United States
Environmental Protection
Agency
Great Lakes National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
EPA-905-R-99-010
October 1999
&EPA Preliminary Investigation
of the Extent of Sediment
Contamination in the
Lower Grand River
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PRELIMINARY INVESTIGATION
OF THE EXTENT OF
SEDIMENT CONTAMINATION
IN THE LOWER GRAND RIVER
TM-99-11
BY
Dr. Richard Rediske
Principal Investigator
And
Carissa Bertin
Jessica Blunt
Dr. Min Qi
R. B. Annis Water Resources Institute
Grand Valley State University
One Campus Drive
Allendale MI 49401
GRANT NUMBER GL985555-01-0
U. S. Environmental Protection Agency
Great Lakes National Program Office
PROJECT OFFICER:
Dr. Marc Tuchman
U. S. Environmental Protection Agency
Great Lakes National Program Office
77 West Jackson Blvd
Chicago IL 60604-3590
October 1999
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Acknowledgements
This work was supported by Grant Number GL985555-01-0 between the Environmental
Protection Agency Great Lakes National Program Office (GLNPO) and Grand Valley State
University. Additional funding was provided by the Robert B. Annis Water Resources
Institute (WRI).
Project Team
EPA Project Officer
Dr. Marc Tuchman USEPA GLNPO
Principal Scientists
Dr. Richard Rediske GVSU Sediment Chemistry
Dr. Min Qi GVSU PCB Congeners
Jeffery Cooper GVSU Sediment Toxicity
Project technical assistance was provided by the following individuals at GVSU:
Carissa Berlin
Jessica Blunt
Alexey Stiop
Mike Sweich
Shana McCrumb
Kane Onwuzulike
Ship support was provided by the crews of the following Research Vessels:
R/VMudpuppy (USEPA) J. Bohnam
R/V D.J. Angus (GVSU) B. Burns
The Gas Chromatograph/Mass Spectrometer used by GVSU for this project was partially
funded by a National Science Foundation Grant (DUE-9650183).
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Table of Contents
List Of Tables ii
List Of Figures iv
Executive Summary 1
1.0 Introduction 2
1.1 Geology Of The Grand River Watershed 2
1.2 Project Objectives And Task Elements 6
1.3 Experimental Design 7
1.4 References 8
2.0 Sampling Locations 10
3.0 Methods 19
3.1 Sampling Methods 19
3.2 Chemical Analysis Methods For Sediment 20
3.3 Chemical Analysis Methods For Culture Water 28
3.4 Quality Assurance/Quality Control Program 28
3.5 Sediment Toxicity 31
3.6 References 35
4.0 Results And Discussions 36
4.1 Sediment Chemistry Of The Harbor Island And The Sag Areas 36
4.2 Sediment Chemistry Of The Grand Haven Area 43
4.3 Sediment Chemistry Of The Spring Lake Area 50
4.4 Sediment Chemistry Of The Middle Bayou Area 57
4.5 Evaluation Of The Sediment Chemistry Of The Lower Grand River 64
4.6 Metals Normalization 78
4.7 Sediment Toxicity Results 83
5.0 Summary 89
6.0 References 89
Appendices 92
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List Of Tables
Table 2.1 Grand River Core Sampling Stations 16
Table 2.2 Grand River Ponar Sampling Stations 18
Table 3.1 Sample Containers, Preservatives, And Holding Times 20
Table 3.2.1 Analytical Methods And Detection Limits 21
Table 3.2.2 Detection Limits For PCB Congeners And DDT Compounds 27
Table 3.2.3 Organic Parameters And Detection Limits 29
Table 3.2.4 Data Quality Objectives For Surrogate Standards Control Limits For Percent
Recovery 30
Table 3.3.1 Analytical Methods And Detection Limits For Culture Water 31
Table 3.5.1 Test Conditions For Conducting A Four Day Sediment Toxicity Test With
Hyalella azteca 33
Table 3.5.2 Recommended Test Conditions For Conducting A Ten Day Sediment
Toxicity Test With Chironomus tentans 34
Table 4.1.1 Inorganic Results For The Sediment Cores Collected From The Harbor Island
And Sag Areas Of The Lower Grand River, October 1997 37
Table 4.1.2 Organic Results For The Sediment Cores Collected From The Harbor Island
And Sag Areas Of The Lower Grand River, October 1997 37
Table 4.2.1 Inorganic Results For The Sediment Cores Collected From The Grand Haven
Area Of The Lower Grand River, October 1997 44
Table 4.2.2 Organic Results For The Sediment Cores Collected From The Grand Haven
Area Of The Lower Grand River, October 1997 44
Table 4.3.1 Inorganic Results For The Sediment Cores Collected From The Spring Lake
Area Of The Lower Grand River, October 1997 51
Table 4.3.2 Organic Results For The Sediment Cores Collected From The Spring Lake
Area Of The Lower Grand River, October 1997 51
Table 4.4.1 Inorganic Results For The Sediment Cores Collected From The Middle Bayou
Area Of The Lower Grand River, October 1997 58
Table 4.4.2 Organic Results For The Sediment Cores Collected From The Middle Bayou
Area Of The Lower Grand River, October 1997 58
Table 4.5.1 Summary Of Recent Sediment Quality Guidelines 64
Table 4.7.1 Inorganic Results For The Ponar Samples Collected For Sediment Toxicity
Evaluation From The Lower Grand River, April 1998 83
Table 4.7.2 Organic Results For The Ponar Samples Collected For Sediment Toxicity
Evaluation From The Lower Grand River, April 1998 83
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Table 4.7.1.1 Summary Qi Hyalella azteca Survival Data Obtained During The 10 Day
Toxicity Test With Grand River Sediments 84
Table 4.7.1.2 Chi-Square Test For Normality Of Hyalella azteca Survival Data 85
Table 4.7.1.3 Dunnett's Test For Hyalella azteca Survival Data 85
Table 4.7.1.4 Steels Many-One Rank Test For Hyalella azteca 10 Day Toxicity Test With
Grand River Sediments 86
Table 4.7.2.1 Summary Of Chironomus tentans Survival Data Obtained During The 10 Day
Toxicity Test With Grand River Sediments, April 1997 Samples 87
Table 4.7.2.2 Chi-Square Test For Normality Of Chironomus tentans Survival Data 87
Table 4.7.2.3 Dunnett's Test For Chironomus tentans Survival Data 88
in
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List Of Figures
Figure 1.1 The Grand River Watershed 4
Figure 1.2 The Lower Grand River Watershed 5
Figure 2.1 Sampling Stations Located In The Harbor Island And Sag Region Of The
Lower Grand River, October 1997 11
Figure 2.2 Sampling Stations Located In The Grand Haven Region Of The Lower Grand
River, October 1997 12
Figure 2.3 Sampling Stations Located In The Spring Lake Region Of The Lower Grand
River, October 1997 13
Figure 2.4 Sampling Stations Located In The Middle Bayou Region Of The Lower
Grand River, October 1997 15
Figure 4.1.1 Total Chromium In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997 38
Figure 4.1.2 Total Mercury In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997 39
Figure 4.1.3 Total Lead In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997 40
Figure 4.1.4 Total PCB In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997 41
Figure 4.1.5 DDE In Core Samples Collected From The Harbor Island And Sag Areas In
The Lower Grand River, October 1997 42
Figure 4.2.1 Total Chromium In The Grand Haven Area Of The Lower Grand River,
October 1997 45
Figure 4.2.2 Total Mercury In The Grand Haven Area Of The Lower Grand River, October
1997 46
Figure 4.2.3 Total Lead In The Grand Haven Area Of The Lower Grand River, October
1997 47
Figure 4.2.4 Total PCBs In The Grand Haven Area Of The Lower Grand River, October
1997 48
Figure 4.2.5 DDE In The Grand Haven Area Of The Lower Grand River, October 1997 49
Figure 4.3.1 Total Chromium In Core Samples Collected From The Spring Lake Area Of
The Lower Grand River, October 1997 52
Figure 4.3.2 Total Mercury In Core Samples Collected From The Spring Lake Area Of The
Lower Grand River, October 1997 53
Figure 4.3.3 Total Lead In Core Samples Collected From The Spring Lake Area Of The
Lower Grand River, October 1997 54
IV
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Figure 4.3.4 Total PCBs In Core Samples Collected From The Spring Lake Area Of The
Lower Grand River, October 1997 55
Figure 4.3.5 DDE In Core Samples Collected From The Spring Lake Area Of The Lower
Grand River, October 1997 56
Figure 4.4.1 Total Chromium In Core Samples From Middle Bayou Area Of The Lower
Grand River, October 1997 59
Figure 4.4.2 Total Mercury In Core Samples Collected From Middle Bayou Area Of The
Lower Grand River, October 1997 60
Figure 4.4.3 Total Lead In Core Samples Collected From Middle Bayou Area Of The
Lower Grand River, October 1997 61
Figure 4.4.5 Total PCBs In Core Samples Collected From Middle Bayou Area Of The
Lower Grand River, October 1997 62
Figure 4.4.6 DDE In Core Samples Collected From Middle Bayou Area Of The Lower
Grand River, October 1997 63
Figure 4.5.1 Total Chromium Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level) 67
Figure 4.5.2 Total Lead Concentrations In Core Samples Taken From The Lower Grand
River, October 1997. (PEL = Probable Effect Level) 68
Figure 4.5.3 Total Mercury Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level) 69
Figure 4.5.4 Total Cadmium Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level) 71
Figure 4.5.5 Total Nickel Concentrations In Core Samples Taken From The Lower Grand
River, October 1997. (PEL = Probable Effect Level) 72
Figure 4.5.6 PCB Concentrations In Core Samples Taken From The Lower Grand River,
October 1997 73
Figure 4.5.7 PCB Congener Distributions For Grand Haven Shoreline, Harbor Island, And
Middle Bayou Regions Of The Lower Grand River, October 1997 75
Figure 4.5.8 PCB Congener Distributions For The Spring Lake And Middle Regions Of
The Lower Grand River, October 1997 76
Figure 4.5.9 DDE Concentrations In Core Samples Taken From The Lower Grand River,
October 1997. (PEL = Probable Effect Level) 77
Figure 4.6.1 The Relationship Between Aluminum And Chromium In Grand River Core
Samples (Middle And Bottom Core Sections Without Significant
Anthropogenic Enrichment), October 1997 80
Figure 4.6.2 The Relationship Between Aluminum And Lead In Grand River Core
Samples (Middle And Bottom Core Sections Without Significant
Anthropogenic Enrichment), October 1997 80
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Figure 4.6.3 The Relationship Between Aluminum And Chromium In Grand River Core
Samples (Regression Line Is From Figure 4.6.1), October 1997 81
Figure 4.6.4 The Relationship Between Aluminum And Lead In Grand River Core
Samples (Regression Line Is From Figure 4.6.2), October 1997 82
VI
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Executive Summary
A preliminary investigation of the nature and extent of sediment contamination in the lower
Grand River was performed. Three areas in the lower Grand River exceeded sediment quality
guidelines for heavy metals and selected organic chemicals. The locations and parameters of
concern are listed below:
Harbor Island (G20). Exceeds sediment PEL values for chromium, lead, nickel, and
DDE in the top core section. Deeper core sections were
extensively contaminated with heavy metals.
Spring Lake (G6). Exceeds sediment PEL values for chromium, lead, cadmium,
nickel, and DDE.
Grand Haven (G12). Exceeds sediment PEL values for chromium and nickel. The
sediments at this location exhibited a statistically significant level
of toxicity to amphipods when compared to the control.
The extent of contaminated sediments in the vicinity of G12 (near the Grand Haven tannery)
appears to be localized in a small area. Some additional sampling of this area would be
necessary to define the extent of the contaminated sediments. The results for Spring Lake
and Harbor Island show these areas to be contaminated with heavy metals and selected
organic compounds. Additional sampling and analysis would be necessary to characterize
the extent of sediment contamination in the areas around Harbor Island and Spring Lake.
Meander core islands appear to play a significant role in the lower Grand River with respect
to the deposition of contaminated sediments. Pockets of contaminated sediments were found
at the downstream tip of Harbor Island (G20), and the unnamed islands near G24 and G17.
These areas serve as sediment deposition zones and indicate the effects of historical
discharges of metals and organic chemicals to the lower Grand River. High water events
however can transport contaminated sediments from these deposits and increase the
contaminant loading to Lake Michigan. Since metals and organic chemicals are associated
with the suspended sediment load, the role of the meander core deposits in contaminant
transport needs to be examined in detail. This investigation examined three of the 12
meander core islands that are located in the lower Grand River.
The normalization of heavy metal data with aluminum was examined for chromium and lead.
Statistically significant correlations between these elements were determined in background
samples (r = 0.73 and 0.75 for Cr and Pb respectively). Plots of the project data set
demonstrate that anthropogenic enrichment of lead and chromium has occurred in a majority
of the top and middle core sections.
Statistically significant (alpha = 0.05) acute toxicity effects were observed in the sediments
of samples G6-P and G12-P on the amphipod, IL azteca, by the Dunnett's test. The PEL
values for chromium and DDE were exceeded at G12-P. PEL values for arsenic and DDE
were exceeded at G6-P. Statistically significant (alpha = 0.05) mortality was not seen on the
midge, C. tentans in the Grand River sediments.
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1.0 Introduction
The Grand River watershed contains the longest river in the State of Michigan and comprises
13% of the entire Lake Michigan drainage basin (Sommers, 1977). A map of the Lower
Grand River is provided in Figure 1.1. Two thirds of this 3.6 million acre watershed is
designated as agricultural with 22% of the total pesticide usage in the Lake Michigan basin
concentrated within its boundaries (GAO, 1993; Hester, 1995). Approximately 300,000 Ibs.
of atrazine alone are applied within the Grand River watershed on an annual basis (Hester,
1995). Since the Grand River watershed includes two of the larger population and industrial
centers in the State of Michigan, there have been significant anthropogenic activities that
have adversely impacted the watershed. Historically, both the Grand Rapids and Lansing
areas were known for large-scale metal finishing and plating industries that contributed
significant amounts of heavy metals to the environment. A large tannery with a historic
discharge to the river is also located in the Grand Haven area. In addition, the lower region
of the Grand River supported a large number of wood processing facilities. High levels of
the wood preservative compound, pentachlorophenol, was recently found in sediments of
Spring Lake and in the navigation channel outside its confluence with the Grand River by the
U.S. Army Corps of Engineers (Bowman, 1995). A second sampling of the area was
however unable to confirm these results. Additional surveys of the sediments in the Grand
River were performed by USAGE in 1996 (DLZ, 1996). Elevated levels of heavy metals and
PAH compounds were detected in these investigations. The USAGE investigations focused
on the evaluation of the sediments for dredging and concentrated on samples collected from
the navigation channels. The sediments in areas outside of the navigation channel have not
been investigated.
Recent studies of the 12 major tributaries of Lake Michigan have found the Grand River to
be one of the most significant contributors of contaminant loads to Lake Michigan (Shafer, et
al., 1995; Hall and Behrendt, 1995; and Cowell, et al., 1995, and Robertson 1997). For most
contaminants, the loading from the Grand River is comparable to that of the Fox River (WI),
yet we know little about sites and sources of contamination in the Grand as compared to the
Fox. For example, preliminary results of the Lake Michigan Mass Balance Study have found
that the Grand River is the largest tributary source to Lake Michigan for lead, DDT
compounds and atrazine and the second largest source for mercury (D. Armstrong, J. Hurley,
and P. Hughes pers. comm.). There is, however, very little data available concerning the
location of contaminant source areas in the Grand River watershed.
1.1 The Geology Of The Grand River Watershed
The geology of the Grand River Watershed was described in a previous report (U.S. Army
Corps of Engineers 1972). From its headwaters in northeastern Hillsdale County at elevation
1040 feet, the Grand River flows northward to Lansing, Michigan, where it makes an abrupt
bend and meanders westerly to Grand Haven where it discharges into Lake Michigan. The
Grand River flows 260 miles through a basin 135 miles long and up to 70 miles in width.
With a drainage area of 5572 square miles, the Grand River basin encompasses all or part of
nineteen counties. A map of the Grand River watershed is shown in Figure 1.1. The
topography of the basin is a result of Pleistocene glaciating with moraines and outwash plains
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dissected by streams. Kettle holes appear sporadically on out wash plains and usually are
filled with water as swamps or lakes. Till plains, moraines, kames, and esker systems of the
Port Huron system are the predominant surface feature with relief of 50 to 60 feet. Pasture
and crop land comprise approximately 63 percent of the basin and another 15 percent is
comprised of forest. The harbor at Grand Haven has a minimum draft of 21 feet, and a
channel 100 feet wide and eight feet deep extends 17 miles upstream. Above this point, the
river is not suitable for commercial navigation.
The Grand River Basin is underlain by two distinct groups of rocks, the younger glacial tills,
and the older bedrock. Glacial deposits are a mixture of rock material from many different
sources. This rock material was picked up, transported and deposited by glaciers or by
waters flowing from the glaciers. The principal glacial deposits in the Grand River basin are
till, moraines, outwash, and glacial lakebeds. The bedrock, that underlies the glacial deposits,
was deposited in large inland seas that covered most of the area of the Great Lakes States.
Bedrock formations are comprised primarily of sandstone, limestone, dolomite and shale, but
include thick beds of salt, gypsum, and anhydrite. After deposition, the bedrock formations
in the Great Lakes were warped into geologic structures that resembles a gigantic set of
shallow bowls. The Grand River Basin overlies the south and southwestern part of this
structure. The bedrock that underlies this basin generally dips gently to the north and east
toward the center of the basin structure causing individual formations to be progressively
deeper in a northerly and easterly direction.
The Grand River Basin evolved during the retreat of the last of the great continental glaciers.
Most of the present surface features of the basin resulted from deposition of the rock
materials from glaciers and subsequent erosion. The basin is underlain by sediments
deposited from glacial lobes that advanced over the basin from the Saginaw Bay and from
Lake Michigan. The two lobes coalesced along a north-south line near the center of Kent
County. The area of coalescence is one of rolling topography. The lower part of the Grand
River Basin is formed on the sediments of former glacial Lake Chicago.
The major portion of the basin is rather flat and featureless. The maximum local relief in the
areas upstream from Maple Rapids, Portland, and Hastings generally ranges from 50 to 75
feet. The areas of minimal relief contain very poorly drained soil. Swamps and marshes
make up a significant part of the Maple, Looking Glass, and Cedar River basins. The upper
reaches of the Flat and Rogue River basins include extensive and numerous swamps,
marshes, and many lakes, as does the middle part of the Thornapple River basin and the
upper part of the Grand River Basin. The upper part of the Maple River includes flatlands
formed on the sediments of ancient glacial lakes. The total relief between Lake Michigan,
which has an altitude of about 580 feet, and the highest point in the basin, which are at
altitudes of about 1170 feet in southern Jackson County, is about 700 feet. The maximum
local relief within the basin ranges from 200 to 275 feet between the banks of the Grand
River and the adjacent highlands. Areas with 200 or more feet of local relief, most of which
are along the Grand River, constitute much less than 5 percent of the total basing area.
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Grand River
Watershed
Watershed Boimdaty
Figure 1.1 The Grand River Watershed
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G1 .. B24
(•) Sampling
Stations
Lower Grand River Sampling Stations
Spring Lake and Grand Haven
Figure 1.2 The Lower Grand River Watershed
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1.2 Project Objectives And Task Elements
The objective of this investigation was to conduct a Phase I assessment of heavy metal and
pesticide contamination in the lower Grand River. Selected samples were analyzed for
chlorinated phenols, PAH compounds, and PCB congeners in areas where industrial releases
may have occurred. In addition, a preliminary assessment of sediment depositional patterns
and sediment toxicity were performed to assist in the analysis of the ecological effects and in
the evaluation of remediation alternatives. Specific objectives and task elements are
summarized below:
• Determine the nature and extent of sediment contamination in the lower Grand River.
- A Phase I investigation was conducted to expand the sediment core sampling
previously performed by the U.S. Army Corps of Engineers. The investigation
included additional spatial coverage in the lower river section and targeted areas of
suspected contamination from industrial and agricultural sources. Twenty-three core
samples were collected in this investigation. Arsenic, barium, cadmium, chromium,
copper, lead, nickel, zinc, aluminum, selenium, iron, calcium, magnesium,
manganese, mercury, TOC, DDT compounds, PCB congeners, and grain size were
analyzed on the sediments in all core samples. Aluminum, iron, magnesium, and
calcium were used to normalize the metals data (Loring, 1991). In addition, a
subgroup of core samples taken from the Spring Lake and areas adjacent to CERCLA
and RCRA sites were analyzed for chlorinated phenols and PAH compounds. Eleven
cores were analyzed for these semivolatile organic compounds.
- Surface sediments were collected in the lower Grand River area with a Ponar dredge
to provide heavy metal concentration information for the toxicity evaluations. Four
sites were selected for toxicity evaluations based on the results of the core sample
analyses.
- Critical measurements were the concentration of arsenic, barium, cadmium,
chromium, copper, lead, nickel, zinc, aluminum, selenium, iron, calcium, magnesium,
manganese, mercury, chlorinated phenols, DDT compounds, PCB congeners and
PAH compounds in sediment samples. Non-critical measurements were total organic
carbon, and grain size.
• Evaluate the toxicity of sediments from sites in the lower Grand River area.
- Sediment toxicity evaluations were performed with Hyalella azteca and Chironomus
tentans on four sediment samples.
- Toxicity measurements in Grand River sediments were evaluated and compared to
the control location. These measurements determined the presence and degree of
toxicity associated with sediments from the Grand River.
- Critical measurements were the determination of lethality during the toxicity tests and
the monitoring of water quality indicators during exposure (ammonia, dissolved
oxygen, temperature, conductivity, pH, and alkalinity).
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1.3 Experimental Design
This investigation was designed to examine specific sites of possible contamination as well
as provide an overall assessment of the nature and extent of sediment contamination in the
lower region of the Grand River. This bifurcated approach allowed the investigation to focus
on specific sites based on historical information in addition to examining the broad-scale
distribution of contamination. To address contamination at specific sites, 16 core samples
were collected from locations likely to have been impacted by significant anthropogenic
activity. The locations were selected to target current and historical point sources and
downstream sites from known industrial and municipal discharges. These sites were
determined by the analysis of historical data and industrial site locations. Analysis of river
flow patterns and depositional areas were then used to select seven locations that would
reflect the general distribution of contaminants.
Sediment samples were collected using the U.S. EPA Research Vessel Mudpuppy and the
GVSU Research Vessel D.J. Angus. The sediment cores were collected with a VibraCore
device with core lengths ranging from 6-8 ft. The core samples were then sectioned in three
equal lengths for chemical analysis. For each core, the analytical parameters included a
general series of inorganic and organic constituents as well as specific chemicals related to a
particular source or area. The general chemical series for each core included the following
heavy metals; arsenic, cadmium, chromium, copper, lead, mercury, nickel, zinc. In addition,
DDT, DDE, ODD, and PCB Congeners were analyzed on all cores. A subset of the 11 core
samples were analyzed for PAH compounds and chlorinated phenols. Basic sediment
chemistry parameters (organic carbon, aluminum, calcium, iron, manganese, magnesium, and
grain size) were also analyzed on each core. Aluminum and other sediment chemistry
parameters were used to normalize sediment metal data for the differentiation of background
levels and anthropogenic sources (Loring 1991, Helmke, et al 1977). The location of the
sampling stations are illustrated in Figure 1.2. Analytical methods were performed according
to the protocols described in SW-846 3rd edition (EPA 1994a).
Chemistry data were then supplemented by laboratory toxicity studies that utilize
standardized exposure regimes to evaluate the effects of contaminated sediment on test
organisms. Six Ponar samples were collected in areas that had elevated levels of
contaminants in the top core sections. Standard EPA methods (1994b) using Chironomus
tentans and Hyalella azteca were used to determine the acute toxicity of sediments from the
Ponar samples.
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1.4 References
Bowman, D. W. 1995. Grand River at Grand Haven Michigan: U.S. Army Corps of
Engineers Tier II Evaluation. June, 1995.
Cowell, S. E., Hurley, J. P., Schafer, M. M. and P. E. Hurley. 1995. Mercury partitioning
and transport in Lake Michigan Tributaries. Presented at 38th Conference.
International Association of Great Lakes Research.
DLZ, 1996. Grand Haven Sediment Sampling and Analysis. Delivery Order #0014.
Prepared for the U.S. Army Corps of Engineers. Detroit District.
EPA, 1994a. Test Methods for Evaluating Solid Waste Physical/Chemical Methods. U.S.
Environmental Protection Agency. SW-846, 3rd Edition.
EPA, 1994b. Methods for Measuring the Toxicity and Bioaccumulation of Sediment-
Associated Contaminants with Freshwater Invertebrates. U. S. Environmental
Protection Agency. EPA/600/R-94/024.
GAO. 1993. Issues Concerning Pesticide Usage in the Great Lakes Watershed. GAO-
RCED-93-128. 39pp.
Hall, D. W. and T. E. Behrendt. 1995. Poly chlorinated byphenyls and pesticides in Lake
Michigan tributaries, 1993-95. Presented at 38th Conference. International
Association of Great Lakes Research.
Helmke, P. A., Koons, R. D., Schomberg, P. J. and I. K. Iskandar. 1977. Determination of
trace element contamination of sediments by multielement analysis of clay-size
fraction. Environ. Sci. Technol. 10:984-988. 23:200-208.
Hester, M. R. 1995. Atlas of Pesticide Usage Trends and Environmental Risk Potentials in
the Grand River Watershed. Pub. #MR-95-3. Water Resources Institute. Grand
Valley State University.
Loring, D. H. 1991. Normalization of heavy-metal data from estuarine and coastal
sediments. ICES J. Mar. Sci. 48:101-115.
Robertson, D. M. 1997. Regionalized loads of suspended sediment and phosphorus to Lakes
Michigan and Superior-High flow and long -term average. Journal of Great Lakes
Research. 23:416-439.
Schropp, S. J., Windom, H. L., Ed. 1988. A Guide to the Interpretation of Metal
Concentrations in Estuarine Sediments. Florida Department of Environmental
Regulation Coastal Zone Management Section.
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Shaffer, M. M., Overdier, J. T., Baldino, R. A., Hurley, J. P. and P. E. Hughes. 1995.
Levels, partitioning, and fluxes of six trace elements in Lake Michigan tributaries.
Presented at 38th Conference. International Association of Great Lakes Research.
Sommers, L. 1977. Atlas of Michigan. Michigan State University Press. East Lansing.
241pp.
U.S. Army Corps of Engineers, 1972. Comprehensive Water Resources Study. The Grand
River Basin. Part II. Detroit District. Appendix C.
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2.0 Sampling Locations
The lower Grand River region included in this investigation covers the Grand Haven/Spring
Lake area in Ottawa County. Samples sites were selected based on proximity to potential
point and non point sources of contamination. The locations of these sites were determined
by review of historical records and communications with the Michigan Department of
Natural Resources and the U.S. Army Corps of Engineers. Samples were collected in areas
of fine sediment deposition. Samples from areas containing rubble and sand were excluded.
A total of 23 core samples and 6 Ponar samples were collected. Locations of each sample
were obtained by differential GPS.
For this project, the lower Grand River was divided into four regions to evaluate potential
source locations and deposition areas:
• Harbor Island and the Sag area
• Grand Haven area
• Spring Lake area
• Middle Bayou area
The Harbor Island and the Sag region is shown in Figure 2.1. This region contains a
meander core island called Harbor Island that contains an old landfill area to the north and a
power generation facility on the southern tip. The main channel of the Grand River flows
around the western side of the island. The eastern channel has a limited flow and is primarily
used for recreational boating. Stations G3 and G4 were selected to investigate potential
sediment contamination from the old landfill and fly ash storage areas. Station G20 was
selected as a sediment deposition area. The Sag region consists of a meander lake that has
been expanded by sand mining activity on the western shore. Station Gl was selected to
examine potential sediment contamination from a large petroleum storage facility located
near the northeastern corner. Stations G2 and G22 were selected to monitor historic
sediment deposition.
The Grand Haven region is located along the southern shoreline of the lower Grand River
(Figure 2.2). Stations G10, Gl 1, G12, and G23 were selected to examine potential sediment
contamination from the tannery located on the southern shore. The municipal wastewater
treatment plant and a brass foundry are also located in this area. Station G24 was located at
the tip of a meander core island in a sediment deposition area. Effects from the tannery
discharge were not anticipated due to river flow. Stations G9, G13, and G15 were also
selected as sediment deposition zones and were located in shallow channels near meander
islands.
The Spring Lake Region is located on the northern shoreline of the lower Grand River
(Figure 2.3). Stations G5, G6, and G7 were located in the Village of Spring Lake. Station
G5 was selected as a control location with residential development as the only potential
impact. Stations G6 and G7 were located near the southern shoreline of Spring Lake in the
area where the USAGE previously detected pentachlorophenol (Bowman 1995). These
10
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0.1 » 01 1X2 M«s
Figure 2.1 Sampling Stations Located In The Harbor Island And Sag Region Of The
Lower Grand River, October 1997.
11
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G12\o-~\.«
"
CM 0 01 02 Mi«
Figure 2.2 Sampling Stations Located In The Grand Haven Region Of The Lower
Grand River, October 1997.
12
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J
0 0.1 O.i Mies
Figure 2.3 Sampling Stations Located In The Spring Lake Region Of The Lower
Grand River, October 1997.
13
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locations were in areas that may be influenced by historical discharges from two metal
finishing facilities (Miller Smith Plating and Burnside Manufacturing). Both of these
facilities are included on the Michigan Department of Environmental Quality's 201 Priority
List of hazardous waste sites because of known groundwater and soil contamination.
Stations G8 and G16 were located on the southern shore of the Village of Spring Lake in the
channel of the Grand River. These stations are also in locations that may be influenced by
the 201 Priority sites described above.
The Middle Bayou region of the lower Grand River (Figure 2.4) is located approximately 2
miles east of the Grand Haven area. Sampling stations G14, G17, G18, and G19 were
located in deposition areas off the main channel. These stations are not located near any
known industrial source and the only anthropogenic impact would be from contaminant
deposition from discharges in Grand Rapids.
The coordinates, depths, and visual descriptions of the sediments for the core sampling
locations described above are presented in Table 2.1. Descriptions for the Ponar samples are
included in Table 2.2. Ponar samples are designated with the letter P (e.g. G12P) to
differentiate this group from the core samples. The Ponar samples were collected from the
same corresponding locations as the sediment cores.
14
-------
0.1 0 t.i Oi Ml*!
Figure 2.4 Sampling Stations Located In The Middle Bayou Region Of The Lower
Grand River, October 1997.
15
-------
Table 2.1 Grand River Core Sampling Stations. (* Field Duplicate Sample).
Station
Gl
G2
G3
G4
G5
G5FD
G6
G7
G8
G9
Date
10/14/97
10/14/97
10/15/97
10/16/97
10/16/97
10/16/97
10/16/97
10/16/97
10/17/97
10/18/97
Depth to
Core
ft/inches
5V
4'6"
2'3"
2'7"
26'8"
26'3"
27'9"
31'2"
3'8"
3'11"
Depth of
Core
inches
55
0-15
15-35
35-55
67
0-22
22-44
44-67
30
0-15
15-30
36
0-18
18-36
70
0-25
25-50
50-70
81
0-27
27-54
54-81
76
0-25
25-50
50-75
62
0-20
20-40
40-62
75
0-23
25-50
50-75
40
0-13
13-26
26-40
Latitude
N
43° 04.7619'
43° 04.6611'
43° 04.3442'
43° 04.4557'
43° 05. 1621'
43° 05. 1621'
43° 04.8388'
43° 04.6643'
43° 04.4692'
43° 04.1913'
Longitude
W
86° 13.9171'
86° 13.9862'
86° 13.9124'
86° 13.6795'
86° 12.2968'
86° 12.2968'
86° 12.3039'
86° 11.9944'
86° 12.4286'
86' 12.2186'
Description
black organic
brown silts
brown silts shell fragments
sandy silt
silt some sand
silts, sand plug at 60"
brown silts
brown silts
black sandy silt
black sandy silt
black organic silts
black silts
black silts
black organic silts
black silts
black silts
black organic silts
black silts
black silts
wood chips, black organic
black organic silts
black organic silts
brown silty clay
brown silty clay
brown silty clay
clay silt
clay silt
clay silt sand on bottom
16
-------
Table 2.1 Grand River Core Sampling Stations (continued)
(* Field Duplicate Sample)
Station
G10
Gil
G12
G13
G14
G15
G16
G17
G18
G19
G20
G20 FD*
Date
10/15/97
10/15/97
10/15/97
10/18/97
10/17/97
10/18/97
10/17/97
10/17/97
10/17/97
10/17/97
10/15/97
10/15/97
Depth to
Core
ft/inches
2'0"
lO'll""
12'11"
2'9"
9'5"
4'8"
9'2"
7' 10"
3'9"
9' 10"
9'9"
9'9"
Depth of
Core
inches
27
0-13
13-27
23
0-11
11-23
11
0-11
63
0-21
21-42
42-63
75
0-25
25-50
50-75
54
0-18
18-36
36-54
10
37
0-12
12-24
24-37
48
0-16
16-32
32-48
29
0-15
15-29
60
0-20
20-40
40-60
61
0-20
20-40
40-61
Latitude
N
43° 04.0637'
43° 04.0704'
43° 03.93 10'
43° 04.1913'
43° 03.4801'
43° 04.2217'
43° 04.4950'
43° 02.6295'
43° 02.0121'
43° 01.5747'
43° 04.0600'
43° 04.0600'
Longitude
W
86° 12.5577'
86° 12.4408'
86° 12.2939'
86' 12.1219'
86° 10.4487'
86° 11.9411'
86° 12.6622'
86° 09.4134'
86° 09.5429'
86° 09.2665'
86° 14.0656'
86° 14.0656'
Description
black organic silts
Sandy silt peat
clay, wood chips
wood chips, black organic
oily organic, hair
brown silts
gray silts
gray silts
black silty clay
silty clay
white/gray clay
silty sand
silty sand
sand and shells
coarse silt sand
black organic sand
black silt
grey silty sand shells
black silty sand
black silty sand
black silty sand oil odor
detritus silt sand
black silty sand
black silts sand
brown silts
brown silts, sand plug at
50"
black silts sand
brown silts
brown silts, sand plug at
50"
17
-------
Table 2.1 Grand River Core Sampling Stations (continued)
(* FIELD DUPLICATE SAMPLE)
Station
G22
G23
G24
Date
10/16/97
10/15/97
10/15/97
Depth to
Core
ft/inches
5'9"
2'6"
TO"
Depth of
Core
inches
110
0-24
24-48
48-72
72-98
98-110
61
0-20
20-40
40-61
55
0-17
17-34
34-55
Latitude
N
43° 04.7919'
43° 04.0640'
43° 03. 8637'
Longitude
W
86° 14.1640'
86°12.6987'
86° 12.1941'
Description
black silts
black silts
black silts
black silts
black silts
3" sand, brown organic
peat, organic silt
gray sand
oily sand
sand silt
oily sand silt
Table 2.2 Grand River Ponar Sampling Stations
Station
G5P
G6P
G7P
G12P
G20P
Date
4/22/98
4/22/98
4/22/98
4/22/98
4/22/98
Depth to
Sample
ft/inches
27'10"
28'09"
29' 11"
13'10"
10"08"
Latitude
N
43° 05. 1598'
43° 04.00489'
43° 04.0690'
43° 03.9286'
43° 04.0596'
Longitude
W
86° 12.2933'
86°12.2820'
86°12.0110'
86° 12.2888'
86° 14.0600'
Description
Black/brown organic silts
Black/brown organic silts
Black/brown organic silts
Oily red/black silts and hair
Black/brown organic silts
18
-------
3.0 Methods
3.1 Sampling Methods
Sediment and benthos samples were collected using the U.S. EPA Research Vessel
Mudpuppy and the GVSU Research Vessel D.J. Angus. Vibra Core methods were used to
collect sediment cores for chemical analysis. A 4 inch lexan core tube was used for
collection. A new core tube was used at each location. The core samples were measured and
sectioned into three equal segments corresponding to top, middle, and bottom. Each section
was then homogenized in a polyethylene pan and split into sub-samples. The visual
appearance of each segment was recorded along with the water depth and core depth.
Ponar samples were collected for toxicity testing and sediment chemistry. For sediment
chemistry and toxicity testing, a standard Ponar sample was deposited into a polyethylene
pan and split into sub-samples. The Ponar was washed with water in between stations.
3.1.2 Sample Containers, Preservatives, And Volume Requirements
Requirements for sample volumes, containers, and holding times are listed in Table 3.1.
All sample containers for sediment chemistry and toxicity testing were purchased precleaned
and certified as Level II by I-CHEM Inc.
19
-------
Table 3.1 Sample Containers, Preservatives, And Holding Times
Matrix
Sediment
Sediment
Sediment
Sediment
Culture
Water
Parameter
Metals
TOC
Container
250 mL Wide
Mouth Plastic
250 mL Wide
Mouth Plastic
Preservation Extraction Analysis
Cool to
Freeze -10UC
Sediment Semi-Volatile 500 mL Amber Cool to 4°C 14 days
Organics Glass
Sediment PCB Congeners 500 mL Amber Cool to 4°C 14 days
DDT Compounds Glass
Grain Size
Toxicity
Alkalinity
Ammonia
Hardness
Conductivity
pH
1 Quart Zip-Lock Cool to 4°C
Plastic Bag
4 liter Wide
Mouth Glass
250 mL Wide
Mouth Plastic
Cool to 4°C
Cool to 4°C
6 months,
Mercury-28 Days
6 months
40 days
40 days
6 months
45 days
24 hrs.
3.2 Chemical Analysis Methods For Sediment
A summary of analytical methods is provided in Table 3.2.1. Instrumental conditions and a
summary of quality assurance procedures are provided in the following sections.
20
-------
Table 3.2.1 Analytical Methods And Detection Limits
SEDIMENT MATRIX
Parameter
Method Description
USEPA Semivolatiles Solvent Extraction and
GC/MS analysis
Analytical
Method
82701,
35501 Extraction
Detection
Limit
Table 3.2.2
Arsenic, Cadmium,
Lead, Selenium
Aluminum, Barium,
Calcium, Chromium,
Copper, Iron,
Magnesium,
Manganese, Nickel,
Zinc
Mercury
Arsenic-Graphite Furnace 70601, O.lOmg/kg
Atomic Absorption Spectroscopy 30521 Digestion
Inductively Coupled Plasma 60101, 2.0mg/kg
Atomic Emission Spectroscopy 30521 Digestion
Mercury Analysis of Soils,
Sludges and Wastes by Manual
Cold Vapor Technique
74711, Prep O.lOmg/kg
Method in 74711
Grain Size
Total Organic
Carbon
Wet Sieve
Combustion/IR
WRI Method
PHY-010
9060
1%
0.1%
1 - SW846 3rd. Ed. EPA 1994.
3.2.1 Sample Preparation For Metals Analysis
For aluminum, arsenic, barium, calcium, cadmium, chromium, copper, iron, magnesium,
manganese, nickel, lead, selenium, and zinc analysis, sediment samples were digested
according to a modified version of EPA SW-846 method 3052 "Microwave Assisted Acid
Digestion of Sediments, Sludges, Soils and Oils". Samples were air-dried prior to digestion.
A Questron (Mercerville, NJ) Q-4000 microwave system was used. The system provided a
controled temperature and pressure in each digestion vessel. Approximately 0.25 g of
sediment was weighed into a teflon liner. 4 mL Type 1 deionized water, 3 mL of
concentrated nitric acid, 6 mL of concentrated hydrochloric acid, and 4 mL of hydrofluoric
acid was added to each sample. Vessels then were capped and placed into the microwave
cavity. The program was set to raise the temperature inside the vessels to 200°C for 20.0
minutes. After completion of the run, vessels were cooled and vented. Then 15 mL of
21
-------
saturated boric acid was added to each sample in place of using hydrogen peroxide. The
vessels were recapped and placed into the microwave cavity. The program was set to raise
the temperature inside the vessels to 180°C for 15.0 minutes. After completion of the second
run, the vessels were cooled and vented. The contents were transferred into 50 mL
centrifuge tubes and brought up to 50 mL with Type I deionized water. Samples were
centrifuged for 5 minutes at 3000 rpm before analysis.
For every 10 samples at least one set of the following quality control samples was prepared:
• Method Blank (4 mL of Type 1 deionized water, 3 mL of nitric acid, 6 mL of
hydrochloric acid, 4 mL of hydrofluoric acid, and 15 mL of boric acid)
• Laboratory Control Spike (Blank Spike)
• Matrix Spike
• Matrix Duplicate
For determining total mercury the samples were prepared by EPA SW-846 method 7471A
"Mercury in Solid and Semisolid Waste". Approximately 0.2 g of wet sediment was
weighed into a 50 mL centrifuge tube. 2.5 mL of Type I deionized water and 2.5 mL of aqua
regia were then added to the tube. Samples were heated in a water bath at 95°C for 2
minutes. After cooling, the volume of the samples was brought up to 30 mL with Type I
deionized water. Then 7.5 mL of 5% potassium permanganate solution was added to each
sample, samples were mixed, and the centrifuge tubes were returned in the water bath for a
period of 30 minutes. Three mL of 12% hydroxylamine chloride solution was added to each
sample after cooling. Finally, the samples were mixed and centrifuged for 5 minutes at 3,000
rpm.
Calibration standards were digested along with the samples. Quality control samples were
prepared as stated previously for every batch of 10 samples or less.
3.2.2 Arsenic Analysis By Furnace
Arsenic was analyzed in accordance with the EPA SW-846 method 7060A utilizing Graphite
Furnace technique. The instrument employed was Perkin Elmer 4110ZL atomic absorption
spectrophotometer. An arsenic Electrodeless Discharge Lamp (EDL) was used as a light
source at wavelength of 193.7 nm. The instrument utilized a Zeeman background correction
that reduces the non-specific absorption caused by some matrix components. The
temperature program is summarized below:
22
-------
Step
1
2
O
4
5
Temp,°C
110
130
1300
2100
2500
Time, sec.
Ramp
1
15
10
0
1
Hold
35
37
20
5
3
Gas Flow,
ml/min
250
250
250
0
250
Read
X
A Pd/Mg modifier was used to stabilize As during the pyrolysis step. The calibration curve
was constructed from four standards and a blank. Validity of calibration was verified with a
check standard prepared from a secondary source. This action was taken immediately after
calibration and after every 10 samples. At least 1 postdigestion spike was performed for
every analytical batch of 20 samples.
3.2.3 Cadmium Analysis By Furnace
Cadmium was analyzed in accordance with the EPA SW-846 method 7060A utilizing
Graphite Furnace technique. The instrument employed was Perkin Elmer 4110ZL atomic
absorption spectrophotometer. A hollow cathode lamp was used as a light source at
wavelength of 228.8 nm. The instrument utilized a Zeeman background correction that
reduces the non-specific absorption caused by some matrix components. The temperature
program is summarized below:
Step
1
2
3
4
5
Temp,°C
110
130
500
1550
2500
Time, sec.
Ramp
1
15
10
0
1
Hold
40
45
20
5
3
Gas Flow,
ml/min
250
250
250
0
250
Read
X
A Pd/Mg modifier was used to stabilize Cd during the pyrolysis step. The calibration curve
was constructed from four standards and a blank. Validity of calibration was verified with a
check standard prepared from a secondary source. This action was taken immediately after
calibration and after every 10 samples. At least 1 postdigestion spike was performed for
every analytical batch of 20 samples.
3.2.4 Lead Analysis By Furnace
Lead was analyzed in accordance with the EPA SW-846 method 7060A utilizing Graphite
Furnace technique. The instrument employed was Perkin Elmer 4110ZL atomic absorption
spectrophotometer. A lead EDL Lamp was used as a light source at wavelength of 283.3 nm.
The instrument utilized a Zeeman background correction that reduces the non-specific
absorption caused by some matrix components. The temperature program is summarized
below:
23
-------
Step
1
2
3
4
5
6
Temp,°C
120
140
200
850
1900
2500
Time, sec.
Ramp
1
5
10
10
0
1
Hold
20
40
10
20
5
3
Gas Flow,
ml/min
250
250
250
250
0
250
Read
X
A Pd/Mg modifier was used to stabilize Pb during the pyrolysis step. The calibration curve
was constructed from four standards and a blank. Validity of calibration was verified with a
check standard prepared from a secondary source. This action was taken immediately after
calibration and after every 10 samples. At least 1 postdigestion spike was performed for
every analytical batch of 20 samples.
3.2.5 Selenium Analysis By Furnace
Selenium was analyzed in accordance with the EPA SW-846 method 7060A utilizing
Graphite Furnace technique. The instrument employed was Perkin Elmer 4110ZL atomic
absorption spectrophotometer. An arsenic EDL Lamp was used as a light source at
wavelength of 196.0 nm. The instrument utilized a Zeeman background correction that
reduces the non-specific absorption caused by some matrix components. The temperature
program is summarized below:
Step
1
2
3
4
5
6
Temp,°C
120
140
200
1300
2100
2450
Time, sec.
Ramp
1
5
10
10
0
1
Hold
22
42
11
20
5
3
Gas Flow,
ml/min
250
250
250
250
0
250
Read
X
A Pd/Mg modifier was used to stabilize Se during the pyrolysis step. The calibration curve
was constructed from four standards and a blank. Validity of calibration was verified with a
check standard prepared from a secondary source. This action was taken immediately after
calibration and after every 10 samples. At least 1 postdigestion spike was performed for
every analytical batch of 20 samples.
24
-------
3.2.6 Metal Analysis By ICP
Aluminum, barium calcium, chromium, copper, iron, magnesium, manganese, nickel and
zinc were analyzed in accordance with EPA SW-846 method 6010A by Inductively Coupled
Plasma Atomic Emission Spectroscopy. Samples were analyzed on a Perkin Elmer P-1000
ICP Spectrometer with Ebert monochromator and cross-flow nebulizer. The following
settings were used:
Element Analyzed
Al
Ba
Ca
Cr
Cu
Fe
Mg
Mn
Ni
Zn
Wavelength, nm
308.2
233.5
315.9
267.7
324.8
259.9
279.1
257.6
231.6
213.9
RF Power:
1300 W
Matrix interferences were supressed with internal standartization utilizing Myers-Tracy
signal compensation. Interelement interference check standards were analyzed in the
beginning and at the end of every analytical run, and indicated absence of this type of
interference at the given wavelength. The calibration curve was constructed from four
standards and a blank and was verified with a check standard prepared from a secondary
source.
3.2.7 Mercury
After the digestion procedure outlined in 3.2.1, sediment samples were analyzed for total
mercury by cold vapor technique according to SW-846 Method 7471. A Perkin Elmer
5100ZL atomic absorption spectrophotometer with FIAS-200 flow injection accessory was
used. Mercury was reduced to an elemental state with stannous chloride solution, and atomic
absorption was measured in a quartz cell at an ambient temperature and a wavelength of
253.7 nm. A mercury electrodeless discharge lamp was used as a light source. The
calibration curve consisted of four standards and a blank and was verified with a check
standard prepared from a secondary source.
3.2.8 Total Organic Carbon
Total Organic Carbon anlysis of sediments was conducted on a Shimadzu TOC-5000 Total
Organic Carbon Analyzer equipped with Solid Sample Accessory SSM-5000A.
An air dried sample was first placed in the oven at 900°C, where all the carbon was
catalyticly converted to CO2 (Total Carbon Analysis). A different portion of the sample was
treated with phosphoric acid at 250°C to displace CO2 from carbonates and bicarbonates
(Inorganic Carbon Analysis). CO2 was measured in the infra-red cell. Total Organic Carbon
content was determined by difference between results of the two analyses.
25
-------
Calibration curves for both analyses were constructed from three standards and a blank.
Glucose was used as a standard compound for Total Carbon Analysis (44% carbon by
weight). For Inorganic Carbon Analysis, sodium carbonate was used (11.11% of carbon by
weight)
3.2.9 Grain Size Analysis
Grain size was performed by wet sieving the sediments. The following mesh sizes were
used: 2mm (granule), 1 mm (very coarse sand), 0.5 mm (coarse sand), 0.25 mm (medium
sand), 0.125 mm (fine sand), 0.063 (very fine sand), and 0.031 (coarse silt).
3.2.10 PCS Congener And DDT Analysis
The sediment samples were extracted for PCB congeners and DDT using SW-846 Method
3050. Sediment samples were air dried for 24 hrs, and then equal amounts of dried soil and
anhydrous sodium sulfate were mixed together. The samples were then extracted using
50 mL of methanol and 100 mL of hexane. The samples were sonicated for 3 minutes, and
then the hexane layer was removed and filtered through anhydrous sodium sulfate. The
process was repeated two more times, adding 50 mL of hexane each time. The hexane extract
was concentrated to 1 mL in the Turbovap, and then run through a chromatography column
packed with 2% deactivated florisil and anhydrous sodium sulfate. Copper turnings cleaned
with 1 M hydrochloric acid were added to remove sulfur. The eluent was concentrated to 1
mL using the Turbovap, and concentrated sulfuric acid was added as a final clean-up step.
Solvent transfer to iso-octane was achieved under a flow of nitrogen gas and condensed to a
final volume of 1 mL.
Sample extracts were analyzed using gas chromatography with a Ni63 electron capture
detector and RTX-5 capillary column. Helium and nitrogen were used as the carrier and
makeup gas, respectively. Instrumental operating conditions were as follows:
Column temperature program:
Injector temperature:
Detector temperature:
Sample volume:
80°C for 2 min., 10°C/min to 160°C,
1.5°C/min to 190°C, 2°C/min to 256°C
and hold at 256°C for 6 min.
260°C
330°C
lul
Table 3.2.3. is a list of PCB congeners and their detection limits. Two surrogate standards,
PCB congeners 46 and 142 were used to monitor extraction efficiency. Acceptance limits for
the surrogates were + 50% for precision and accuracy.
26
-------
Table 3.2.2 Detection Limits For PCB Congeners And DDT Compounds
PCS CONGENER DETECTION LIMIT (UG/KG)
48 1.0
52 1.0
59 1.0
70 1.0
87 1.0
97 1.0
101 1.0
105 1.0
118 1.0
138 1.0
149 1.0
151 1.0
153 1.0
155 1.0
180 1.0
183 1.0
205 1.0
DDT 1.0
ODD 1.0
DDE 1.0
3.2.11 Semivolatiles Analysis
Sediment samples were extracted for semivolatiles analysis using SW-846 Method 3050.
The sediment samples were dried with anhydrous sodium sulfate to form a free flowing
powder. The samples were then serially sonicated 3 times with 1:1 methylene
chloride/acetone and concentrated to a 1 mL volume.
The sample extracts were analyzed by GC/MS on a Finnigan GCQ Mass Spectrometer
according to Method 8270. Instrumental Conditions are itemized below:
MS operating conditions:
Electron energy: 70 volts (nominal)
Mass range: 40-450 amu
Scan time: 820 amu/second, 2 scans/sec
Source temperature: 190°C
Transfer line temperature: 250°C
GC operating conditions:
27
-------
Column temperature program:
Injector temperature program:
Sample volume:
45°C for 6 min., then to 250°C at
10°C/min, then to 300°C at 20°C/min
hold 300°C for 15 min.
250°C
lul
A list of analytes and detection limits is given in Table 3.2.4. Surrogate standards were
utlilized to monitor extraction efficiency. Acceptance criteria for surrogate standards are
given in Table 3.2.5. The GC/MS was calibrated using a 5 point curve. Instrument tuning
was performed by injecting 5 ng of Decafluorotriphenylphosphine and meeting method
acceptance criteria. The MS and MSD samples were analyzed at a 5% frequency.
3.2.12 Hexane Extractable Materials
Hexane extractable Materials (HEM) was analyzed on the Ponar samples by SW-846 Method
6030. The method was modified to use a gravimetric measurement of the hydrocarbon
residue. Wet sediment samples were mixed with anhydrous sodium sulfate until the mixture
was dry and free flowing. The dried sediment was then placed in cellulose thimble and
extracted in a soxhlet apparatus for 24 hours with hexane. After extraction, the hexane was
dried with sodium sulfate and evaporated to approximately 2 mLs in a Kuderna Danish
concentrator with a three-ball Snyder column. The concentrate was then placed in a
preweighed aluminum pan and evaporated on a steam bath to remove the residual hexane.
The pan was then cooled in a dessicator for 12 hours and weighed. For quality control
purposes, a blank, blank spike, matrix spike and matrix spike duplicate were analyzed with
the sample set. Mineral oil was used as the spiking compound. Acceptance limits for
precision and accuracy were + 50%.
3.3 Chemical Analysis Methods for Culture Water
The parameters, methods, and detection limits for the measurements performed on the culture
water used in the sediment toxicity tests are listed in Table 3.3.1. All methods were
th-
performed according to proceedures outlined in Standard Methods 14 Edition (1996).
3.4 Quality Assurance/Quality Control Program
A detailed description of the Quality Assurance/Quality Control program for this project was
described in the Quality Assurance Project Plan.
28
-------
Table 3.2.3 Organic Parameters And Detection Limits
Sediment
(mg/kg)
Semi-Volatile Organic Compounds (8270)
Phenol 0.33
Bis(2-chloroethyl)ether 0.33
2-Chlorophenol 0.33
1,3-Dichlorobenzene 0.33
1,4-Dichlorobenzene 0.33
1,2-Dichlorobenzene 0.33
2-Methylphenol 0.33
4-Methylphenol 0.33
Hexachloroethane 0.33
Isophorone
0.33
2,4-Dimethylphenol 0.33
Bis(2-chloroethoxy)methane 0.33
2,4-Dichlorophenol 0.33
1,2,4-Trichlorobenzene 0.33
Naphthalene 0.33
Hexachlorobutadiene 0.33
4-Chloro-3-methylphenol 0.33
2-Methylnaphthalene 0.33
Hexachlorocyclopentadiene 0.33
2,4,6-Trichlorophenol
0.33
2,4,5-Trichlorophenol 0.33
2-Chloronaphthalene 0.33
Dimethylphthalate 0.33
Acenaphthylene 0.33
Acenaphthene 0.33
Diethylphthalate 0.33
4-Chlorophenyl-phenyl ether 0.33
Fluorene 0.33
4,6-Dinitro-2-methylphenol 1.7
4-Bromophenyl-phenyl ether 0.33
29
-------
Table 3.2.3 Organic Parameters And Detection Limits (continued)
Sediment
(mg/kg)
Semi-Volatile Organic Compounds (8270)
Hexachlorobenzene 0.33
Pentachlorophenol 1.7
Phenanthrene 0.33
Anthracene 0.33
Di-n-butylphthalate 0.33
Fluoranthene 0.33
Pyrene 0.33
Butylbenzylphthalate 0.33
Benzo(a)anthracene 0.33
Chrysene 0.33
Bis(2-ethylhexyl)phthalate 0.33
Di-n-octylphthalate 0.33
Benzo(b)fluoranthene 0.33
Benzo(k)fluoranthene 0.33
Benzo(a)pyrene 0.33
Indeno(l,2,3-cd)pyrene 0.33
Dibenzo(a,h)anthracene 0.33
Benzo(g,h,i)perylene 0.33
3-Methylphenol 0.33
Table 3.2.4 Data Quality Objectives For Surrogate Standards Control Limits For
Percent Recovery
Parameter Control Limit
Nitrobenzene-d5 30%-97%
2-Fluorobiphenyl 42%-99%
o-Terphenyl 60%-101%
Phenol-d6 43%-84%
2-Fluorophenol 33%-76%
2,4,6-Tribromophenol 58%-96%
30
-------
Table 3.3.1 Analytical Methods And Detection Limits For Culture Water
Parameter Method Detection Limit
Specific
Conductance
Alkalinity
Temperature
Dissolved Oxygen
Ammonia Electrode
Hardness
Standard Methods
2510 B.
Standard Methods
2320
Standard Methods
2550
Standard Methods
4500-O G.
Standard Methods
4500-NH3 F.
Standard Methods
2340 C.
NA
10mg/l
NA
0.5 mg/1
0.05 mg/1
10 mg/1
3.5 Sediment Toxicity
The evaluation of the toxicity of the Grand River sediments was conducted using the ten day
survival test for the amphipod Hyalella azteca and the dipteran Chironomus tentans. The
procedures followed are contained in EPA/600/R-94/024, Methods for Measuring the
Toxicity and Bioaccumulation of Sediment-associated Contaminants with Fresh Water
Invertebrates. All sediments were stored at 4°C prior to analysis. Toxicity analysis was
initiated within 30 days of sample collection.
3.5.1 Laboratory Water Supply
A moderately hard well water for H. azteca and C. tentans cultures and maintenance was
employed.
3.5.2 Test Organisms
The original stock of//, azteca was obtained from the Great Lakes Environmental Research
Laboratory in Ann Arbor, Michigan. The H. azteca culture was maintained in four 20 L
glass aquaria using maple leaves as a substrate and food source. The food source was
supplemented with a suspension of Tetramin® fish food. The original stock of C. tentans
was obtained from the University of Michigan Department of Environmental Health in Ann
Arbor, Michigan. The culture of C. tentans was maintained in 36 L glass aquaria using
shredded paper toweling as a substrate and was fed a suspension of Tetrafm® goldfish food.
-------
3.5.3 Experimental Design
Eight replicates per sediment were set up for both H. azteca and C. tentans exposures, with
the sediment from site G-5P designated as the control. In all tests, moderately hard well
water was utilized as the overlying water. The experimental conditions outlined in Tables
3.5.1 and 3.5.2 were used for the toxicity evaluations.
One day prior to the start of the test (day -1), the sediment from each site was mixed
thoroughly and 100 mLs were transferred to each of the eight test chambers. Additionally,
visual observations of the sediments were made. Moderately hard well water was also added
at this time. On day 0, the overlying water was renewed once before the test organisms were
introduced into each of the glass beakers. Measurement of water quality parameters was also
initiated on this day. Ten, 7-14 day old H. azteca and 10 third instar C. tentans larvae were
randomly added to their respective test chambers. At this time the organisms were fed, 1.5
mL YCS for the H. azteca and 1.5 mL Tetrafin® for the C. tentans. The glass beakers were
placed in a rack and transferred to a temperature controlled room (23 + 1°C). The light cycle
was 16 hours on and 8 hours off. Temperature and dissolved oxygen measurements were
taken from one randomly selected beaker for each sediment sample every 12 hours, after
which the overlying water was renewed in all the beakers. Feeding occurred after the
morning renewal. This procedure was repeated daily through day 10, at which point the test
was terminated. On day 0, the overlying water from the beakers was composited from each
sediment sample and 250 mLs were retained for alkalinity, hardness and ammonia analysis.
On the last day the same procedure was carried out. On day 10, the sediments were sieved,
and the surviving test organisms were removed and counted. The biological endpoint for
these sediment tests was mortality. The validity of the test was based on greater than 80%
survival in the control treatment for H. azteca and greater than 70% survival in the control
treatment for the C. tentans. In addition, it was recommended that the hardness, alkalinity,
pH, and ammonia in the overlying water within a treatment should not vary by more than
50% over the duration the test.
32
-------
Table 3.5.1 Test Conditions For Conducting A Ten Day Sediment Toxicity Test With
Hyalella Azteca
1. Test Type: Whole-sediment toxicity test with renewal of overlying
water
2. Temperature (°C): 23 + 1°C
3. Light quality: Wide-spectrum fluorescent lights
4. Illuminance: About 500 to 1000 lux
5. Photoperiod: 16 h light, 8 h darkness
6. Test chamber size: 300 mL high-form lipless beaker
7. Sediment volume: 100 mL
8. Overlying water volume: 175 mL
9. Renewal of overlying
water: 2 volume additions per day (e.g., one volume addition
every 12 hours)
10. Age of test organisms: 7 to 14 days old at the start of the test
11. Numb er of organi sm s
per chamber: 10
12. Number of replicate
chambers per treatment: 8
13. Feeding: Tetramin® fish food, fed 1.5 mL daily to each test
chamber
14. Aeration: None, unless dissolved oxygen in overlying water drops
below 40% of saturation
15. Overlying water: Reconstituted water
16. Overlying water quality: Hardness, alkalinity, conductivity, pH, and ammonia
measured at the beginning and end of a test.
Temperature and dissolved oxygen measured daily.
17. Test duration: 10 days
18. End point: Survival, with greater than 80% in the control.
Test Method 100.1. EPA Publication 600/R-94/024 (July 1994).
33
-------
Table 3.5.2 Recommended Test Conditions For Conducting A Ten Day Sediment
Toxicity Test With Chironomus Tentans
I. Test Type: Whole-sediment toxicity test with renewal of overlying
water
2. Temperature (°C): 23 + 1°C
3. Light quality: Wide-spectrum fluorescent lights
4. Illuminance: About 500 to 1000 lux
5. Photoperiod: 16 h light, 8 h darkness
6. Test chamber size: 300 mL high-form lipless beaker
7. Sediment volume: 100 mL
8. Overlying water volume: 175 mL
9. Renewal of overlying
water: 2 volume additions per day (e.g., one volume addition
every 12 hours)
10. Age of test organisms: Third instar larvae (All organisms must be third instar
or younger with at least 50% of the organisms at third
instar)
11. Numb er of organi sm s
per chamber: 10
12. Number of replicate
chambers per treatment: 8
fEl
13. Feeding: Tetrafin goldfish food, fed 1.5 mL daily to each test
chamber (1.5 mL contains 4.0 mg of dry solids)
14. Aeration: None, unless dissolved oxygen in overlying water drops
below 40% of saturation
15. Overlying water: Reconstituted water
16. Overlying water quality: Hardness, alkalinity, conductivity, pH, and ammonia
measured at the beginning and end of a test.
Temperature and dissolved oxygen measured daily.
17. Test duration: 10 days
18. End point: Survival, with greater than 70% in the control.
Test Method 100.2. EPA Publication 600/R-94/024 (July 1994).
34
-------
3.5.4 Statistical Analysis
Survival data for the toxicity testing were analyzed first for normality and homogeneity
employing Chi Square. The data were then examined using Dunnett's Procedure to
determine whether there was a significant difference in survival between the designated
control sediment and those sediments containing pollutants. The TOXSTAT® 3.5 Computer
Program was used for the statistical evaluations.
3.5.5 Quality Assurance
Sodium chloride was used as a reference toxicant to calibrate the toxicity tests. The results
are provided in Appendix E.
3.6 References
EPA. 1994. Methods for Measuring the Toxicity and Bioaccumulation of Sediment-Associated
Contaminants with Freshwater Invertebrates. EPA Publication 600/R-94/024.
35
-------
4.0 Results And Discussion
The results and discussion section is organized according to four regions of the lower Grand
River. Sections 4.1.1,4.1.2., 4.1.3, and 4.1.4 present the results for Harbor Island and the
Sag area, Grand Haven area, Spring Lake area, and the Middle Bayou area respectively.
These sections are followed by discussions of the sediment chemistry of the entire study area
and the toxicity testing. A summary of the complete project data set is also included in
Appendices A, B, C, D, and E.
4.1 Sediment Chemistry Of The Harbor Island And The Sag Areas
The results of the sediment analyses for selected inorganic parameters from the Harbor Island
and the Sag area are given in Table 4.1.1. The results for selected organic parameters are
presented in Table 4.1.2. Congener specific PCB data, grain size distributions, metals data,
and semivolatile results are included in Appendices A, B, and C. Results for chromium,
mercury, lead, total PCBs and DDE are displayed Figures 4.1.1, 4.1.2, 4.1.3, 4.1.4, and 4.1.5
respectively. Elevated levels of heavy metals, PCB congeners, DDT compounds, and
semivolatiles were not detected in the Sag area. We were unable to collect core samples in
the area northwest of Gl near the petroleum tank farm because the sediments contained strata
that were rich in peat. This peat layer may act as a barrier that prevents the migration of
hydrocarbons from the tank farm area. Evidence of an operational hydrocarbon recovery
system was visible near the tank farm suggesting a localized area of free product existed on
the water table. Sediments from G2 had a coarse particle size (primarily 125-500 urn) and
low results for total organic carbon. This type of sediment would not accumulate metals or
organic contaminants. A deep core of fine grained sediments was collected at station G22.
With the exception of slightly elevated lead levels in the top section (24 mg/kg), most
parameters were at concentrations similar to the other stations in the Sag. Sediment
deposition in the Sag would primarily occur during rain events. The absence of sediment
contamination at G22 may indicate that the station was located outside the deposition zone.
Harbor island stations G3 and G4 were located in an internal pond area between the old
landfill and the power plant. Approximately 50% of the particle size distribution was in the
125-500 um fraction. Hard sediments were encountered at 30"-36". Levels of organic
compounds and metals were low at these stations. In contrast, station G20 contained the
highest levels of metals and organic compounds reported for this investigation. It is located
in a sediment deposition zone at the southern tip of Harbor Island. These sediments were
fine grained (50%-70% < 63 um) and had total organic carbon levels of 4%-6%. Fine
grained sediments would be deposited in this area due to friction induced velocity losses as
the Grand River passes around the meander core island. With the exception of DDE and
cadmium, most parameters were higher in the deeper core sections. Chromium levels of
1071 mg/kg and 1428 mg/kg were found in the 20"-40" and 40"-60" core sections
respectively. Following a similar trend, Mercury levels of 1.44 mg/kg and 4.33 mg/kg were
found at the same core depths. PAH compounds were also elevated in all core sections at
this location. Fluoranthene and pyrene were present at the highest concentrations («2.0
mg/kg).
36
-------
Table 4.1.1 Inorganic Results For The
Island And Sag Areas Of The
Sediment Cores Collected From The Harbor
Lower Grand River, October 1997.
Station
G-l Top
G-lMd
G-l Bot
G-2 Top
G-2Md
G-2 Bot
G-3 Top
G-3 Bot
G-4 Top
G-4 Bot
G-20 Top
G-20 Md
G-20 Bot
G-20D Top
G-20DMd
G-20DBot
G-22 Top
G-22-2
G-22-3
G-22-4
G-22-5
As
mg/kg
10
12
10
3.3
9.2
4.2
5.5
6.2
4.6
1.8
10
14
17
12
13
16
8.9
7.6
5.2
6.3
6.4
Cd
mg/kg
0.56
0.37
0.35
0.25
0.28
0.13
0.69
0.20
0.18
0.03
2.3
0.56
1.2
2.7
0.48
1.0
0.58
0.20
0.20
0.23
0.25
Cr
mg/kg
29
42
26
13
32
12
34
14
24
5
169
1071
1428
209
768
1426
44
29
26
34
38
Cu
mg/kg
14
14
14
7.1
12
4.7
22
6.6
6
0.9
98
267
348
141
233
372
23
10
9
12
12
Hg
mg/kg
0.14
O.I 00
O.10
0.10
0.40
0.10
0.21
0.10
0.10
O.10
0.34
1.44
4.33
0.41
1.27
3.84
0.22
0.10
O.10
0.10
0.10
Ni
mg/kg
42
23
18
13
15
9.3
23
11
7.5
bdl
67
166
214
79
149
210
37
15
15
19
18
Pb
mg/kg
6.4
4.4
5.6
4.8
20
2.8
14
4.2
4.1
1.7
85
184
172
100
154
180
24
2.2
1.8
2.0
2.3
Se
mg/kg
0.5
O.5
0.6
0.5
O.5
0.5
O.5
0.5
0.5
O.5
0.5
0.6
0.6
O.5
0.6
0.6
O.5
0.5
O.5
0.5
0.5
Zn
mg/kg
70
72
58
39
49
18
58
19
30
2.3
262
855
894
311
668
863
88
48
49
58
62
Table 4.1.2 Organic Results For The Sediment Cores Collected From The Harbor
Island And Sag Areas Of The Lower Grand River, October 1997.
Station
G-l Top
G-lMd
G-l Bot
G-2 Top
G-2Md
G-2 Bot
G-3 Top
G-3 Bot
G-4 Top
G-4 Bot
G-20 Top
G-20Md
G-20 Bot
G-20DTop
G-20DMd
G-20DBot
G-22 Top
G-22-2
G-22-3
G-22-4
G-22-5
Total PCBs
ug/kg
30
<1.0
9
11
19
21
2.0
2.0
2.0
1.1
71
107
108
84
124
137
6.2
2.9
2.6
1.1
1.2
DDE
ug/kg
7.6
<1.0
0.8
0.5
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
8.2
3.9
7.3
12.1
12
9.7
1.8
<1.0
<1.0
<1.0
1.3
ODD
ug/kg
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
2.8
14
6.1
3.2
14
13
<1.0
<1.0
<1.0
<1.0
<1.0
DDT
ug/kg
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
Fhenanthrene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.62
0.81
0.72
0.90
1.02
0.66
NA
NA
NA
NA
NA
Anthracene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.08
<0.33
0.11
0.12
0.12
0.09
NA
NA
NA
NA
NA
Fluoranthene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
1.40
2.04
1.96
2.31
2.20
1.73
NA
NA
NA
NA
NA
Pyrene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
1.38
1.60
1.68
2.10
2.10
1.73
NA
NA
NA
NA
NA
Benzo(a)
anthracene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.39
<0.33
0.48
0.51
0.57
0.63
NA
NA
NA
NA
NA
Chrysene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.51
<0.33
0.62
0.64
0.78
0.28
NA
NA
NA
NA
NA
Benzo(b)
fluoranthene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.35
<0.33
<0.33
<0.33
0.85
0.71
NA
NA
NA
NA
NA
Benzo(a)
pyrene
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
NA
NA
NA
NA
0.37
<0.33
0.37
0.48
0.50
0.35
NA
NA
NA
NA
NA
37
-------
\
Depth Cr
0"-22" 13mg/kg
22"-44" 32mg/kg
44"-67" 12mg/kg
Depth Cr
15" 29mg/kg
15"-35" 42mg/kg
35"-55" 26 mg/kg
13
Depth Cr
0"-24" 44 mg/kg
24"-48" 29 mg/kg
48"-72" 26 mg/kg
72"-98" 34 mg/kg
98"-110"38mg/kg
Depth Cr
0"-20" 169 mg/kg
20"-40" 107 mg/kg
40"-60" 1428 mg/kg
:: VT.--.
Depth Cr
0"-15" 34 mg/kg
15"-30" 14 mg/kg
Figure 4.1.1 Total Chromium In Core Samples Collected From The Harbor Island
And Sag Areas In The Lower Grand River, October 1997.
38
-------
u
"*••
Depth
0"-22"
22"-44"
44"-67"
Hg
<0.10mg/kg
0.40 mg/kg
<0.10mg/kg
Depth Hg
0"-15" 0.14 mg/kg
15"-35" <0.10 mg/kg
35"-55" <0.10 mg/kg
Depth
0"-24"
24"-48"
48"-72"
72"-98"
98"-110"
Hg
0.22 mg/kg
<0. 10 mg/kg
<0. 10 mg/kg
<0. 10 mg/kg
<0. 10 mg/kg
Depth Hg
0"-15" .021 mg/kg
15"-30" <0.10 mg/kg
Depth Hg
0"-20" 0.34 mg/kg
20"-40" 1.44 mg/kg
40"-60" 4.33 mg/kg
G20
•1 -1 I.I »
Depth Hg
0"-18" <0.10 mg/kg
18"-36" <0.10 mg/kg
Figure 4.1.2 Total Mercury In Core Samples Collected From The Harbor Island And
Sag Areas In The Lower Grand River, October 1997.
39
-------
Depth Pb
0"-22" 4.8mg/kg
22"-44" 20mg/kg
44"-67" 2.8mg/kg
Depth Pb
0"-24" 24 mg/kg
24"-48" 2.2 mg/kg
48"-72" 1.8 mg/kg
72"-98" 2.0 mg/kg
98"-110" 2.3 mg/kg
Depth Pb
0"-15" 6.4 mg/kg
15"-35" 4.4 mg/kg
35"-55" 5.6 mg/kg
Depth Pb
0"-15" 14 mg/kg
15"-30" 4.2 mg/kg
1 "
Depth
0"-20" 85
20"-40" 184
40"-60" 172
Pb
mg/kg
mg/kg
mg/kg
G20
.1 mg/kg
.7 mg/kg
r ^i^
Figure 4.1.3 Total Lead In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997.
40
-------
Oi 0 01 O.S
Depth Total PCB
0"-22" 12ng/kg
22"-44" 18ng/kg
44"-67" 22 ng/kg
Depth Total PCB
0"-24" <10 ug/kg
24"-48" <10 ug/kg
48"-72" <10 ug/kg
72"-98"
98"-110"
Depth Total PCB
0"-15"
15"-30"
19
Depth Total PCB
0"-20" 70 ng/kg
20"-40" 109 ng/kg
40"-60" 106ng/kg
G20
Depth Total PCB
0"-15" 28 ng/kg
15"-35" <10 ng/kg
35"-55" <10 ug/kg
G3 —*—"
Depth Total PCB
0"-18" <10 ug/kg
18"-36" <10 ug/kg
Figure 4.1.4 Total PCBs In Core Samples Collected From The Harbor Island And Sag
Areas In The Lower Grand River, October 1997.
41
-------
Depth
0"-22"
22"-44" <1 ng/kg
44"-67" <1 ng/kg
Depth DDE
0"-15" 8 ng/kg
15"-35" <1 ng/k
35"-55" <1 ng/k
Depth DDE
0"-24" 2 ng/kg
24"-48"
48"-72" <1 ng/kg
72"-98"
-------
This pattern indicates that historical deposition of sediments with high levels of heavy metals
occurred in this area. It is also possible that contaminated fill materials were deposited in
this area. The high levels of metals may be a result of a combination of historical of erosion
from the old landfill prior to the construction of the power plant and sediment deposition
from sources up stream.
4.2 Sediment Chemistry Of The Grand Haven Area
The results of the sediment analyses for selected inorganic parameters from the Grand Haven
area are given in Table 4.2.1. The results for selected organic parameters are presented in
Table 4.2.2. Congener specific PCB data, grain size distributions, metals data, and
semivolatile results are included in Appendices A, B, and C. Results for chromium, mercury,
lead, total PCBs and DDE are displayed in Figures 4.2.1, 4.2.2, 4.2.3, 4.2.4, and 4.2.5
respectively.
Elevated levels of chromium (877 mg/kg), copper (100 mg/kg), and lead (72 mg/kg) were
detected at Station G12 near the tannery. Historically, the tannery discharged untreated
wastewater into the Grand River. A majority of the sediments in this area consist of coarse
rubble and hard clay. We were able to find a small area of soft sediment that yielded this
sample. The core depth was limited to 11" at this location due to the hard clay bottom. A
slight level of enrichment of metals was noted in the downstream stations G23, G10, and
Gl 1. Sediment cores at G10 and Gl 1 were relatively shallow (27" and 23" respectively)
and hard sediments were encountered below these depths. Copper was the only element that
showed some degree of enrichment in the bottom section of G10 (72 mg/kg). This station
was located downstream from a brass foundry and elevated levels of copper would be
anticipated from this type of operation. Even though high levels of metals were detected near
the tannery, the extent appears to be localized to a small area with limited persistence
downstream. The metals that were historically discharged in this area were probably
transported downstream and deposited in the area of Harbor Island and ultimately in Lake
Michigan.
Station G24 was located on the downstream tip of a meander core island similar to station
G20. The deposition pattern for both stations was similar for heavy metals. As shown in
Figures 4.2.1, 4.2.2, 4.2.3, and 4.4.4, the deeper core sections at this location are enriched
with chromium (134 mg/kg and 226 mg/kg), lead (33 mg/kg and 32 mg/kg) and mercury
(0.35 mg/kg 0.19 mg/kg). Copper, cadmium, nickel, and zinc were also elevated in the
deeper core sections. Since this location is upgradient from the tannery, any deposition of
metals would probably be from sources in the Grand Rapids area. The results from stations
G24 and G20 show the importance of the downstream side of meander core islands as an area
for contaminant deposition. While these areas serve as deposition zones under normal stream
flow, they would tend to be scoured during rain events. The resuspension of sediments in
deposition zones behind meander core islands may be a significant source of contaminant
loadings to Lake Michigan during rain events.
43
-------
Table 4.2.1 Inorganic Results For The Sediment Cores Collected From The Grand
Haven Area Of The Lower Grand River, October 1997.
Station
G-9 Top
G-9Mid
G-9 Bot
G-10 TOD
G-10 Bot
G-llToD
G- 11 Bot
G-12 Top
G-13 Top
G-13 Bot
G-13-2
G-13-3
G-15 TOD
G-15Md
G-15 Bot
G-23 TOD
G-23 Md
G-23 Bot
G-24 Top
G-24 Md
G-24 Bot
As
me/ke
10
6.0
6.4
5.7
6.8
9.3
8.4
6.6
8.7
8.9
6.6
7.4
7.3
10
8.6
12
10
3.8
2.3
5.1
5.2
Cd
me/ke
0.19
0.14
0.16
0.48
0.33
0.87
0.21
1.6
0.49
0.16
0.13
0.11
0.39
0.09
0.02
0.42
0.23
0.04
0.21
1.3
1.5
Cr
me/ke
26
20
24
42
33
27
18
877
36
25
20
20
30
11
7
57
27
10
31
134
226
Cu
me/ke
7.8
5.6
7.5
35
14
13
72
100
28
7.8
6.4
5.7
30
4.3
1
23
9.6
1.7
7.6
58
71
He
me/ke
O.10
O.10
O.10
0.16
O.10
0.36
O.10
0.42
0.31
O.10
0.14
O.10
0.48
0.13
O.10
0.12
O.10
O.10
<0.10
0.35
0.19
Ni
me/ke
14
11
13
18
20
15
12
59
19
15
12
14
20
9.7
6.9
26
19
9.3
18
58
77
Pb
me/ke
3.4
2.9
3.1
11
7.9
8.9
3.8
72
27
3.1
5.1
2.6
27
3.6
1.5
13
6.3
1.8
2.4
33
32
Se
me/ke
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
0.9
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
Zn
me/ke
40
30
34
71
39
64
38
183
79
38
29
31
72
26
10
59
34
2.9
2.9
110
111
Table 4.2.2 Organic Results For The Sediment Cores Collected From The Grand
Haven Area Of The Lower Grand River, October 1997.
Station
G-9 TOD
G-9 Mid
G-9 Bot
G-10 TOD
G-10 Bot
G- 11 TOD
G-l 1 Bot
G-12 TOD
G-13 TOD
G-l 3 Bot
G-13-2
G-13-3
G-15 TOD
G-15 Mid
G-l 5 Bot
G-23 TOD
G-23 Md
G-23 Bot
G-24 TOD
G-24Md
G-24 Bot
Total PCBs
us/ks
2.5
14
9
12
<1.0
25
32
2.1
2.1
10
<1.0
10
1.7
13
38
34
113
13
5
47
32
DDE
UE/ks
<1.0
<1.0
30
1.6
<1.0
20
1.4
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
1.1
<1.0
4.7
<1.0
1.3
<1.0
25
1.0
ODD
us/ks
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
1.2
<1.0
DDT
ua/ks
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
Phenanthrene
ms/ka
NA
NA
NA
NA
NA
NA
NA
140
0.30
<033
<033
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
Anthracene
ma/ka
NA
NA
NA
NA
NA
NA
NA
036
0.10
<033
<033
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
Fluoranthene
ma/ka
NA
NA
NA
NA
NA
NA
NA
290
1.04
<033
0.41
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
Pvrene
ma/ka
NA
NA
NA
NA
NA
NA
NA
2.79
1.32
<033
042
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
BenzolV)
anthracene
ma/ka
NA
NA
NA
NA
NA
NA
NA
1.10
0.70
<033
023
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
Chrvsene
rna/ka
NA
NA
NA
NA
NA
NA
NA
088
0.53
<033
0.15
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
BenzoiVl
fluoranthene
ma/ka
NA
NA
NA
NA
NA
NA
NA
054
0.42
<033
0.13
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
BenzolV)
Dvrene
ma/ka
NA
NA
NA
NA
NA
NA
NA
0.71
0.49
<033
<033
<033
NA
NA
NA
NA
NA
NA
NA
NA
NA
44
-------
Depth Cr
0"-20" 57 mg/kg
20"-40" 27 mg/kg
40"-61" 10 mg/kg
Depth Cr
0"-11" 27 mg/kg
1F-23" 18 mg/kg
Depth Cr
0"-13" 26 mg/kg
13"-26" 20 mg/kg
26"-40" 24 mg/kg
Depth Cr
0"-18" 30 mg/kg
18"-36" 11 mg/kg
36"-54" 7 mg/kg
: i
0.2 MI3S
Cr
36 mg/kg
20 mg/kg
25 mg/kg
Depth Cr
"-13" 42 mg/kg
13"-27" 33 mg/kg
Depth Cr
0"-17" 31 mg/kg
17"-34" 134 mg/kg
34"-55" 226 mg/kg
Figure 4.2.1 Total Chromium In The Grand Haven Area Of The Lower Grand River,
October 1997.
45
-------
Depth
0"-H"
lF-23"
Hg
0.36 mg/kg
<0. 10 mg/kg
Depth Hg
0"-18" 0.48 mg/kg
18"-36" 0.13 mg/kg
54" <0.10 mg/kg
Depth Hg
0"-20" 0.12 mg/kg
20"-40" <0.10 mg/kg
40"-61" <0.10 mg/kg
0.1
C1
Mi.
Hg
<0.10 mg/kg
13"-26" <0.10 mg/kg
26"-40" <0.10
Depth Hg
0"-21" 0.31 mg/kg
21"-42" 0.12 mg/kg
42"-63" <0.10 mg/kg
0"-13" 0.16 mg/kg
13"-27" <0.10 mg/kg
Depth Hg
0"-17" <0.10 mg/kg
17"-34" 0.35 mg/kg
34"-55" 0.19 mg/kg
Depth Hg
0"-H" 0.42 mg/kg
Figure 4.2.2 Total Mercury In The Grand Haven Area Of The Lower Grand River,
October 1997.
46
-------
Depth Pb
0"-20" 13 mg/kg
20"-40" 6.3 mg/kg
40"-61" 1.8 mg/kg
o.i
G 1
»J
Depth Pb
0"-18" 27 mg/kg
18"-36" 3.6 mg/kg
36"-54" 1.5 mg/kg
13" -26"
26"-40"
2.9mg/kg
3.1 mg/kg
Depth Pb
0"-21" 27 mg/kg
21"-42" 3.9 mg/kg
42"-63" 3.1 mg/kg
Depth Pb
0"-13" 11 mg/kg
13"-27" 7.9 mg/kg
Depth Pb
0"-17" 2.4 mg/kg
17"-34" 33 mg/kg
34"-55" 32 mg/kg
Figure 4.2.3 Total Lead In The Grand Haven Area Of The Lower Grand River,
October 1997.
47
-------
Depth Total PCB
<10 ug/kg
18"-36" 14 ug/kg
36"-54" <10
Depth Total PCB
0"-20" 34 ng/kg
20"-40" <10 ng/kg
40"-61" 14 ng/kg
o.i
o.i 0.2 Mies
Depth Total PCB
0"-13" <10 ng/
13"-26" 16 ng/kg
26" -40" <10 ug/kg
Depth Total PCB
0"-H" 20 ug/kg
ll"-23" 15 ug/kg
Depth Total PCB
21" -42" <10 ug/kg
42" -63" <10 ug/kg
Depth Total PCB
0"-13" 12 ug/kg
13"-27" <10 ug/kg
Depth Total PCB
17"-34" 47 ug/kg
34"-55" 3 1 ug/kg
Depth Total PCB
0"-H" <10 ug/kg
Figure 4.2.4 Total PCBs In The Grand Haven Area Of The Lower Grand River,
October 1997.
48
-------
,'1
A
Depth DDE
0"-18"
-------
Stations G9, G13, and G15 were selected as locations of sediment deposition. Station G9
showed no significant enrichment for metals or organic compounds. Stations G13 and G15
showed a small degree of enrichment in the top core sections for lead (27 mg/kg), chromium
(36 mg/kg and 30 mg/kg) and mercury (0.21 mg/kg and 0.48 mg/kg).
4.3 Sediment Chemistry Of The Spring Lake Area
The results of the sediment analyses for selected inorganic parameters from the Spring Lake
area are shown in Table 4.3.1. The results for selected organic parameters are presented in
Table 4.3.2. Congener specific PCB data, grain size distributions, metals data, and
semivolatile results are included in Appendices A, B, and C. Results for chromium, mercury,
lead, total PCBs and DDE are displayed in Figures 4.3.1, 4.3.2, 4.3.3, 4.3.4, and 4.3.5
respectively.
Station G5 served as a control location. Sediments from this area would only be influenced
by residential development and recreational activity. Heavy metals and organic compounds
were not found at elevated concentrations at this station. Stations G6 and G7 were located
along the northern shoreline of Spring Lake near the commercial/industrial area. Station G6
was directly north of two plating facilities. At this station, chromium (313 mg/kg), copper
(100 mg/kg), nickel (99 mg/kg), zinc (268 mg/kg), and lead (100 mg/kg) were all found in
high levels in the top core section. PCB congeners (78 ug/kg), DDE (8 ug/kg) and PAH
compounds (« 3 mg/kg for fluoranthene and pyrene) were also elevated in the top core
section. The middle and bottom core sections did not show significant levels of heavy metals
and organics. Station G7 was located further to the east and upgradient for G6. Chromium
(59 mg/kg), copper (20 mg/kg), and zinc (112 mg/kg) showed a moderate degree of
enrichment at this location. Both stations were located in the area where the USAGE found
high levels of pentachlorophenol during a previous investigation (Bowman 1995).
Pentachlorophenol was not detected at either location during this study. These results
coupled with the fact that a subsequent set of samples collected by the USAGE was unable to
confirm the previous detection of this compound suggests that it is localized in a small area
or its original detection was an artifact. The sediments near to the shoreline at both locations
were covered with wood chips and bark from old sawmills. We were unable to collect core
samples at shallower water depths.
Stations G8 and G16 are located on the northern shoreline of the Grand River directly below
the Village of Spring Lake. Limited deposits of soft sediment were found in this area due to
dredging and marina development. A shallow core of 10" could be collected at G16. A
deeper core was collected at G8 however it was primarily clay. Metals and organic
compounds were not elevated at these stations.
50
-------
Table 4.3.1 Inorganic Results For The Sediment Cores Collected From The Spring
Lake Area Of The Lower Grand River, October 1997.
Station
G-5 Too
G-5 Mid
G-5 Bot
G-5D TOD
G-5D Mid
G-5D Bot
G-6 TOD
G-6 Mid
G-6 Bot
G-7 TOD
G-7 Mid
G-7 Bot
G-8 TOD
G-8 Mid
G-8 Bot
G-16
As
ma/ka
8.4
6.5
5.1
10
6.6
4.4
17
8.0
5.3
7.8
4.5
5.2
8.3
4.9
5.6
4.2
Cd
ma/ka
0.54
0.33
0.27
1.0
0.33
0.29
3.6
0.58
0.30
0.45
0.27
0.26
0.16
0.11
0.12
0.06
Cr
ma/ka
6
43
38
83
42
40
313
54
40
59
37
33
26
18
18
14
Cu
ma/ka
39
16
12
53
17
13
160
22
13
20
11
9.3
7.7
3.3
4.1
2.2
Ha
ma/ka
0.16
0.11
<0.10
0.24
<0.10
<0.10
0.37
0.28
0.11
0.11
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
Ni
ma/ka
29
19
17
26
21
20
99
23
18
30
21
19
14
7.9
9.3
15
Pb
ma/ka
12
5.4
4.7
10
4.9
6.0
100
15
6.5
8.7
4.4
3.7
3.2
3.0
2.5
2.3
Se
ma/ka
<0.5
0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
0.7
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
Zn
ma/ka
89
67
65
105
81
59
268
85
58
112
70
71
40
21
26
17
Table 4.3.2 Organic Results For The Sediment Cores Collected From The Spring Lake
Area Of The Lower Grand River, October 1997.
Station
G-5 Top
G-5 Mid
G-5 Bot
G-5dup Top
G-5duD Mid
G-Sduo Bot
G-6 Top
G-6 Mid
G-6 Bot
G-7 Top
G-7 Mid
G-7 Bot
G-8 Top
G-8 Mid
G-8 Bot
G-16
Total PCBs
U2/k2
5.1
1.1
1.5
35
2.6
5.2
78
10
11
60
5 5
2.4
12
1.7
11
NA
DDE
U2/k2
2.6
<1.0
<1.0
25
<1.0
<1.0
8.4
<1.0
<1.0
1.9
1.9
<1.0
1.4
<1.0
<1.0
NA
ODD
U2/k2
< 0
< 0
< 0
< .0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
NA
DDT
U2*2
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
NA
Phenantbrene
ni2/k2
NA
NA
NA
NA
NA
NA
1.18
0.27
<0.33
<033
<033
<033
NA
NA
NA
NA
Anthracene
II12/k2
NA
NA
NA
NA
NA
NA
<0.33
<033
<0.33
<033
<033
<033
NA
NA
NA
NA
Fluoranthene
rri2/k2
NA
NA
NA
NA
NA
NA
3.14
063
<033
<033
<033
<033
NA
NA
NA
NA
Pvrene
rri2/k2
NA
NA
NA
NA
NA
NA
3.20
056
<0.33
<033
<033
<033
NA
NA
NA
NA
Benzo(a)
anthracene
II12/k2
NA
NA
NA
NA
NA
NA
0.88
0.24
<033
<033
<033
<033
NA
NA
NA
NA
Chrvsene
rri2/k2
NA
NA
NA
NA
NA
NA
<033
035
<033
<033
<033
<033
NA
NA
NA
NA
Benzc/bl
fluoranthene
rri2/k2
NA
NA
NA
NA
NA
NA
097
0.24
<033
<033
<033
<033
NA
NA
NA
NA
Benzofa)
pvrene
II12/k2
NA
NA
NA
NA
NA
NA
0.52
<033
<0.33
<033
<033
<033
NA
NA
NA
NA
51
-------
Depth Cr
0"-25" 6 mg/kg
25"-50" 43 mg/kg
50"-70" 38 mg/kg
Depth Cr
0"-20" 59mg/k
20"-40" 37mg/k
40"-62" 33mg/k
Depth Cr
0"-25" 313 mg/kg
25"-50" 54 mg/kg
50"-75" 40 mg/kg
If-
Depth Cr
"-10" 14mg/kg
Depth Cr
0"-23" 26mg/kg
25"-50" 18mg/kg
50"-75" 18mg/kg
0 0.1 0.2 Wiles
Figure 4.3.1 Total Chromium In Core Samples Collected From The Spring Lake Area
Of The Lower Grand River, October 1997.
52
-------
Depth Hg
0"-25" 0.16 mg/kg
25"-50" 0.11 mg/kg
50"-70" <0.10 mg/kg
Depth Hg
0"-20" 0.11 mg/kg
20"-40" <0.10 mg/kg
40"-62" <0.10 mg/kg
Depth Hg
0"-25" 0.37 mg/kg
25"-50" 0.28 mg/kg
50"-75" 0.11 mg/kg
Depth Hg
0"-10" <0.10 mg/kg
Depth Hg
0"-23" <0.10 mg/kg
25"-50" <0.10 mg/kg
50"-75" <0.10 mg/kg
Figure 4.3.2 Total Mercury In Core Samples Collected From The Spring Lake Area
Of The Lower Grand River, October 1997.
53
-------
Depth Pb
0"-25" 12 mg/kg
25"-50" 5.4 mg/kg
50"-70" 4.7 mg/kg
Depth Pb
0"-10" 2.3 mg/kg
MISS
Depth Pb
0"-20" 8.7 mg/kg
20"-40" 4.4 mg/kg
Depth
0"-25'
25"-50
50"-75
40"-62" 3.7 mg/kg
Depth Pb
0"-23" 3.2mg/k
25"-50" 3.0mg/k
50"-75" 2.5mg/k
Figure 4.3.3 Total Lead In Core Samples Collected From The Spring Lake Area Of
The Lower Grand River, October 1997.
54
-------
u '
o •
Depth Total PCB
0"-25"<10
25"-50"<10
50"-70"<10
Depth Total PCB
0"-20"
20"-40"<10
40"-62"<10 ug/kg
Depth Total PCB
0"-25" 66 ug/kg
25"-50" 10 ug/kg
50"-75" 11 ug/kg
Depth Total PCB
0"-10" <10 ug/kg
Depth Total PCB
0"-23" 12 ug/kg
25"-50"
50"-75" 12 ug/kg
02 IVUes
Figure 4.3.4 Total PCBs In Core Samples Collected From The Spring Lake Area Of
The Lower Grand River, October 1997.
55
-------
n
-*-•
Depth DDE
0"-25" 3
25"-50"
50"-70" <1 ug/kg
Depth DDE
0"-20" 2 ug/kg
20"-40" 2 ug/kg
40"-62" <1 ug/kg
Depth DDE
0"-25" 8 ug/kg
25"-50"
50"-75" <1 ug/kg
Depth
0"-23"
25"-50"
50"-75" <1 ug/kg
0.1 D.2 Ml«a
Figure 4.3.5 DDE In Core Samples Collected From The Spring Lake Area Of The
Lower Grand River, October 1997.
56
-------
4.4 Sediment Chemistry Of The Middle Bayou Area
The results of the sediment analyses for selected inorganic parameters from the Middle
Bayou area are given in Table 4.4.1. The results for selected organic parameters are
presented in Table 4.4.2. Congener specific PCB data, grain size distributions, metals data,
and semivolatile results are included in Appendices A, B, and C. Results for chromium,
mercury, lead, total PCBs and DDE are displayed in Figures 4.4.1, 4.4.2, 4.4.3, 4.4.4, and
4.4.5 respectively.
G17 is another station located at the downstream tip of a meander core island. Chromium
(92 mg/kg and 110 mg/kg), copper (65 mg/kg and 88 mg/kg), lead (30 mg/kg and 43
mg/kg), and zinc (88 mg/kg and 130 mg/kg) were elevated in the top and middle core
sections respectively. The presence of elevated heavy metals in the top core section was not
observed at the other locations near meander core islands. G17 is also located near the outlet
of Dermo Bayou that may be a source of heavy metals. A previous study by Thorpe (1994)
found elevated levels of heavy metals in the sediments of the bayous in this area. The
elevated level of metals was attributed to sediment deposition from the back flow of the
Grand River during rain events. Over the last 10 years, residential development in the bayou
areas has increased overland runoff. This change may be causing movement of
contaminated sediments out of the bayous and into the main channel of the Grand River.
Station G18 showed the enrichment of metals only in the middle core section (16"-32").
Chromium (87 mg/kg), copper (55 mg/kg), lead (58 mg/kg), and zinc (210 mg/kg) were
elevated in this core region. G18 is located in a channel between two islands that would
receive sediment deposition during periods of high flow. Samples collected from G14 and
G19 did not show significant levels of metals.
Levels of heavy metals, PCB congeners, and DDT compounds were lower in this region of
the Grand River than the downstream locations near Grand Haven and Spring Lake. As
mentioned in Section 3, concentrations of metals and organics found at the Middle Bayou
locations would have originated from at least 20 miles upstream from point and nonpoint
discharges. There is no record of localized industrial discharges in the Middle Bayou area.
Potential upstream sources include the metro Grand Rapids area, known industrial sources
east of Grand Rapids, and contributions from the cities of Lansing and Jackson.
57
-------
Table 4.4.1 Inorganic Results For The Sediment Cores Collected From The Middle
Bayou Area Of The Lower Grand River, October 1997.
SamDle ID
G-14 TOD
G-14Mid
G-14 Hot
G-17 TOD
G- 17 Mid
G-17 Hot
G- 18 Top
G- 18 Mid
G- 18 Hot
G- 19 TOD
G- 19 Hot
As
ma/ka
12
16
8.1
10
6.2
8.0
2.6
6.0
3.2
4.2
5.3
Cd
ma/ka
1.0
0.09
0.65
1.8
2.2
0.14
0.14
1.0
0.65
0.23
0.41
Cr
ma/ka
11
13
9
92
110
20
20
87
33
24
39
Cu
ma/ka
3.9
3.9
3.7
65
88
4.4
6.5
55
15
8.2
15
Ha
ma/ka
O.10
<0.10
O.10
<0.10
0.17
<0.10
O.10
1.47
O.10
<0.10
O.10
Ni
ma/ka
9.9
11
8.7
38
37
15
12
60
17
14
20
Pb
ma/ka
0.8
1.0
0.6
30
43
2.0
4.4
58
5.5
6.0
23
Se
ma/ka
0.5
<0.5
0.5
0.5
0.5
O.5
O.5
O.5
O.5
O.5
O.5
Zn
ma/ka
16
18
12
88
130
7.1
4.7
210
14
26
69
Table 4.4.2 Organic Results For The Sediment Cores Collected From The Middle
Bayou Area Of The Lower Grand River, October 1997.
Station
G-14 TOD
G-14 Mid
G-14 Bot
G-17 TOD
G-17 Mid
G-17 Bot
G-18 TOD
G-18 Mid
G-18 Bot
G-19 TOD
G-19 Bot
Total PCBs
ug/kg
2.3
16
1.7
54
35
8
13
9
14
16
19
DDE
ug/kg
1.1
<1.0
<1.0
2.9
2.3
<1.0
2.4
1.2
1.4
2.6
2.0
ODD
ug/kg
<1.0
<1.0
<1.0
1.5
2.9
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
DDT
ug/kg
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
58
-------
t:.l 0 LI Hi Mini
Depth Cr
0"-25" 11 mg/kg
25"-50" 13 mg/kg
50"-75" 9 mg/kg
Depth Cr
0"-12" 92 mg/kg
12"-24" 110 mg/kg
24"-37" 20 mg/kg
Figure 4.4.1 Total Chromium In Core Samples From The Middle Bayou Area Of The
Lower Grand River, October 1997.
59
-------
0.1 D C.1 02 Mloi
Depth Hg
0"-25" <0.10mg/kg
25"-50" <0.10mg/kg
50"-75" <0.10mg/kg
Depth Hg
" <0.10mg/kg
12"-24" 0.17mg/kg
24"-37" <0.10mg/kg
Depth Hg
" <0.10mg/kg
16"-32" 1.47mg/kg
32"-48" <0.10mg/kg
Depth Hg
" <0.10mg/kg
15"-29" <0.10mg/kg
Figure 4.4.2 Total Mercury In Core Samples Collected From The Middle Bayou Area
Of The Lower Grand River, October 1997.
60
-------
0.1 0 ftl 02 htm
Depth Pb
0"-25" 0.8mg/kg
25"-50" l.Omg/kg
50"-75" 0.6mg/kg
Depth Pb
0"-12" 30 mg/k
12"-24" 43 mg/k
24"-37" 2.0 mg/k
Depth Pb
"-16" 4.4mg/kg
16"-32" 58mg/kg
32"-48" 5.5mg/kg
Figure 4.4.3 Total Lead In Core Samples Collected From The Middle Bayou Area Of
The Lower Grand River, October 1997.
61
-------
(XI
0.1 Di
Depth Total PCB
0"-25" <10 ng/k
25"-50" 17 ng/kg
50"-75" <10
Depth Total PCB
0"-12" 38 ng/kg
12"-24" 25 ng/kg
24"-37"<10 ug/kg
Depth Total PCB
0"-16" 12 ug/kg
16"-32" <10 ug/kg
32"-48" 14 ug/kg
Depth Total PCB
0"-15" 15 ug/kg
15"-29" 20 ug/kg
Figure 4.4.5 Total PCBs In Core Samples Collected From The Middle Bayou Area Of
The Lower Grand River, October 1997.
62
-------
0.1 0 ftl 02 htm
Depth DDE
0"-25" 1 ng/kg
25"-50"
50"-75" <1 ng/kg
Depth DDE
0"-12" 3 ng/kg
12"-24" 2 ng/kg
Depth DDE
0"-16" 2 ng/kg
16"-32" 1 ng/kg
32"-48" 1 ug/kg
Depth DDE
0"-15" 3 ug/kg
15"-29" 2 ug/kg
Figure 4.4.6 DDE In Core Samples Collected From The Middle Bayou Area Of The
Lower Grand River, October 1997.
63
-------
4.5 Evaluation Of The Sediment Quality Of The Lower Grand River
There is no single set of guidelines established for evaluating sediment quality. A summary
of recently proposed sediment quality guidelines is provided in Table 4.5.1. These guidelines
Guideline
Arsenic
Cadmium
Chromium
Lead
Mercury
Nickel
Total PCBs
DDE
Guideline
Arsenic
Cadmium
Chromium
Lead
Mercury
Nickel
Total PCBs
DDE
Table 4.5.1 Summary Of Recent Sediment Quality Guidelines
Threshold Effect Levels
Units Long and Morgan (1990) Persaud et al. (1992)
ERL LEL
mg/kg 8.2 6
mg/kg 1.2 0.6
mg/kg 81 26
mg/kg 47 31
mg/kg 0.15 0.2
mg/kg 21 16
ug/kg 23 70
ug/kg * 5
Probable Effect Levels
ERM SEL
mg/kg 70 33
mg/kg 9.6 10
mg/kg 370 110
mg/kg 47 170
mg/kg 0.71 1
mg/kg 52 61
ug/kg 180 5300
ug/kg * 190
Smith etal. (1996)
TEL
5.9
0.6
37.3
35
0.17
18
34
1.4
PEL
17
3.5
90
91.3
0.48
36
277
6.75
TEL=Threshold Effect Level
ERL=Effects Range Low
LEL=Lower Effects Level
ERM=Effects Range Median
PEL=Probable Effect Level
SEL=Severe Effect Level
* Not Calculated
are derived by combining the results of laboratory and field studies that include a variety of
methodological approaches (background levels, equilibrium-partitioning, spiked sediment
bioassays, field surveys, screening level concentrations, apparent effects thresholds, and
bioeffects/contamination co-occurrence analyses) for both freshwater and marine sediments.
These data are used to estimate the range of no effect, possible effect, and probable effect
concentrations of contaminants in sediments. Threshold effect levels estimate the
breakpoint between no effect and possible effect concentrations. The Effects Range Low
(Long et al. 1995), Lower Effect Level (Persaud et al. 1992), and the Threshold Effect Level
(Smith et al. 1996) are all estimates of contaminant concentrations where ecological effects
are not anticipated if the level is below the proposed guideline. The Effects Range Median
64
-------
(Long et al. 1995), Severe Effect Level (Persaud et al. 1992), and the Probable Effect Level
(Smith et al. 1996) are all estimates of contaminant concentrations at which ecological effects
are anticipated if the level is above the proposed guideline. While these guidelines do not
address all site specific conditions that may affect the availability of heavy metals, they are
useful benchmarks for determining sediment quality (USEPA 1992). For the purpose of this
investigation, the Probable Effect Level (PEL) described by Smith et al. (1996) will be used
to evaluate the sediment quality of the lower Grand River. The PEL value represents the
level of a contaminant at which adverse biological effects frequently occur. These values are
based on sediments and organisms found in the Great Lakes and are more indicative of the
conditions found in this investigation. Long et al. (1995) and Persaud et al. (1992) included
both freshwater and saltwater environments in their evaluations.
For comparative purposes, PELs selected as the most representative guideline to evaluate the
potential environmental effects of the Grand River sediments. PELs were derived using
sediments and organisms from the Great Lakes region (Smith et al. 1996 and Ingersoll et al.
1996), that were similar to the environments found in the Grand River. The only potential
problem associated with applying these guidelines to the Grand River sediments was that the
toxicity data for arsenic, cadmium, chromium, copper, lead, nickel, and zinc in the PEL
database were derived from samples analyzed for total extractable metals using a nitric acid
digestion. The samples for the Grand River project were analyzed by a more rigorous total
metals digestion procedure using hydrofluoric acid. The concentration of heavy metals
measured in the Grand River would therefore include the anthropogenic fraction (metals
attached by sorption to the sediment particle surface) and the intrinsic fraction (metals
incorporated in the mineral matrix). The intrinsic metals fraction would have a very limited
potential for bioavailability. Samples with metals concentrations near the PEL value may
therefore have some degree of high bias associated with the analytical method. The Effect
Rang Median (Long and Morgan 1990) data in Table 4.5.1 were derived using a total metals
digestion procedure similar to the analytical method for this project. While these guidelines
are usually higher than the PELs, the ERM data set was developed from marine and estuarine
sediments collected in Florida and the Carolinas. Differences between the two guidelines
therefore reflect the inclusion of variables related to analytical methodology and regional
differences in the respective aquatic environments. In consideration of the strong potential
for regional bias in the ERM data set, the PELs were selected as the benchmark to evaluate
the potential for environmental effects. Additional caution should be used when evaluating
data near the PEL value because of the potential of the analytical method to include a fraction
of metals that are not bioavailable.
The distribution of chromium in the core samples collected in the lower Grand River is
shown in Figure 4.5.1. The stations at Harbor Island (G20), Spring Lake (G6), the Grand
Haven tannery (G12), and meander core island located in the Middle Bayou area (G17) all
exceeded the PEL value of 90 mg/kg for chromium in the top core sections (;«0"-24"). The
middle core section for G17 and the middle and bottom core sections for Harbor Island and
the meander core island (G24) near Grand Haven also exceeded the PEL value of 90 mg/kg.
The spatial distribution of the chromium results suggests that the metal was introduced by
several point sources located in Grand Haven, Spring Lake, and Harbor Island. The
distribution of chromium also shows the importance of upstream sources. Significant
65
-------
chromium deposition at the downstream tips of meander core islands that are located above
potential point sources illustrates the effects of historic upstream discharges.
The distribution of lead in the core samples collected in the lower Grand River is shown in
Figure 4.5.2. Lead follows a similar distribution pattern with potential sources located near
Harbor Island, the Grand Haven tannery, and Spring Lake. The Harbor Island and Spring
Lake stations exceeded the PEL of 91 mg/kg for lead. The middle and bottom core sections
at Harbor Island also exceeded the PEL. In addition, anthropogenic enrichment of lead was
noted in the Middle Bayou area (G18) and meander core island stations G24 and G17. Since
anthropogenic lead can originate from industrial sources and from the release of fuels, its
presence in these core samples is indicative of inputs from both types of discharges.
The distribution of mercury in the core samples collected in the lower Grand River (Figure
4.5.3.) follows a different pattern than lead and chromium. Mercury was not detected on the
top core sections of the Middle Bayou area. Over the last 10 years, the City of Grand Rapids
has initiated an aggressive pollution prevention program to reduce the discharge of mercury.
The absence of mercury in the top sections and its presence in the middle at G18 (1.47
mg/kg) suggests that elevated levels were discharged from upstream locations in the past.
With the exception of Harbor Island (G20), mercury appears to be dispersed in the top core
sections of the remaining study areas. The Grand Haven and Spring Lake areas have
detectable mercury concentrations that range from 0.1 mg/kg to 0.48 mg/kg. Only station
66
-------
Chromium in Top Core Sections
"&
.0
IH
g 40°
u
c
Q
m _ n a U
TJ- W « ^ O
6 6 6 o JiJ
Harbor Island
0
8
6
D _ =
-
l~l r-, _ r-, HI r-,
PEL
n n n • _ fl ,
SI"? §-«?"=p°-?!!2'»Sg''t»?
S6^6666u556656S5656
6
Spring Lake Grand Haven Middle Bayou
Chromium in Middle Core Sections
~ 1000
^)
c
o
£
'c
0 40°
o
O ,nn
1 — 1 i — i
CM
6 o
Harbor Islan
"I
S
6
d
G-20dup
PEL
1 8 1 5 5 * ° S 5 1 S 5 5 5
6
Spring Lake Grand Haven Middle Bayou
Chromium in Bottom Core Sections
"3
0)
c
o
5
C 600
0
o
5 g 3 3
Harbor Island
6
Q.
3
•o
s
6
PEL
8
Spring Lake Grand Haven Middle Bayou
Figure 4.5.1 Chromium Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level).
67
-------
Lead in Top Core Sections
~ 100
u>
^)
c
•° 60 ]
5
o 40
o
o 20
n n D n
O (i (i o
_
Q.
1
n
HI.
esi 19 §• to
PEL
II n
III. ILn
Harbor Island '
Spring Lake
G rand Haven
M iddle Bayou
Lead in Middle Core Sections
u
o
c
o
o
Harbor Island
Spring Lake
G rand Haven
o o
Middle Bayou
Lead in Bottom Core Sections
0)
C
° 100
0)
0
a , = , o , _
-
PEL
In
„ n
V
-------
Mercury in Top Core Sections
0.6
0.5
0.4
0.3
PEL
u
c
o
O
1
I
Harbor Island
Spring Lake
55666
Grand Haven
Middle Bayou
Mercury in Middle Core Sections
ion (mg
c
0)
u
c
o
O
6 6
Harbor Island °
Spring Lake
Grand Haven
Middle Bayou
Mercury in Bottom Core Sections
c 3
o
2
c 2
1 K
C 1'5
0 1
Harbor Islanc
-
6
-
6
PEL
— m
6
Spring Lake Grand Haven Middle Bayou
Figure 4.5.3 Mercury Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level).
69
-------
G15 had a surface zone concentration equivalent to the PEL for mercury (0.48 mg/kg). The
middle and bottom core sections had either very low or non detectable levels of mercury. In
contrast, the bottom section of the Harbor Island station (G20) was heavily contaminated
with mercury (4.3 mg/kg). The levels decreased in the top section to 0.4 mg/kg. These
results suggest heavy historical deposition of mercury in this area. The high concentrations
found in the deeper sections appear to be stable as lower concentrations are found with
decreasing depth. The results however suggest that sediments contaminated with mercury
from historic discharges are still subject to resuspension and deposition in the lower Grand
River. Atmospheric deposition may also contribute to the levels found near the surface.
The distribution of cadmium in the core samples collected in the lower Grand River (Figure
4.5.4.) follows a different pattern than the previous elements. The highest level of cadmium
was found at the Spring Lake station G6 (3.6 mg/kg). The sediment from this location was
the only station to exceed the PEL of 3.5 mg/kg. The Harbor Island station G20 had 2 mg/kg
in the top section and lower levels in the deeper strata. Concentrations of the other heavy
metals were highest in the bottom sections at this location. These results illustrate that the
concentration of cadmium in the recently deposited sediments is higher than historical levels.
While some movement of contaminated sediments can occur from Spring Lake, the
sediments with the greatest potential for mobility appear to be located in the Middle Bayou
area and at the meander core island station G24. The sediments with the highest cadmium
concentrations in the middle and bottom core sections were located at G17 (2.4 mg/kg) and
G24 (1.5 mg/kg) respectively. The top core section at G17 was also elevated (1.8 mg/kg).
Based on these data, the resuspension and transport of sediments from the upper region of the
lower Grand River appears to be the source for observed distribution of cadmium. In
addition, the results suggest that upstream locations were the historical source of much of the
cadmium found in the lower Grand River.
The distribution of nickel in the core samples collected in the lower Grand River (Figure
4.5.5.) follows a pattern similar to chromium. The stations at Harbor Island (Gl, G20, and
G22), Spring Lake (G6), the Grand Haven tannery (G12), and meander core island located in
the Middle Bayou area (G17) all exceeded the PEL value of 36 mg/kg for chromium in the
top core sections. The middle core section for G17 (37 mg/kg) and G18 (60 mg/kg) and the
middle and bottom core sections for Harbor Island (184 mg/kg and 172 mg/kg respectively)
and the meander core island G24 (58 mg/kg and 7 mg/kg respectively) near Grand Haven
also exceeded the PEL value. The spatial distribution of the nickel suggests that the metal
was introduced by several point sources located in Grand Haven, Spring Lake, and Harbor
Island. As observed for chromium, the data suggest that upstream locations contributed
significant levels of nickel to the lower Grand River. Nickel deposition at the downstream
tips of meander core islands located above the point sources illustrates the effects of historic
upstream discharges.
Significant levels of PCBs were not found at the locations that were examined in this
investigation (Figure 4.5.6). The highest PCB level in the top core sections was found near
Harbor Island at G20 (71 ug/kg). This level is well below the PEL of 277 ug/kg.
Concentrations increased with depth at this location to 137 in the bottom core section.
70
-------
Cadmium in Top Core Sections
Harbor Island
Spring Lake
Grand Haven
333333
M iddle Bayou
Cadmium in Middle Core Sections
Harbor Island
Spring Lake
(4 3
Grand Haven
Cadmium in Bottom Core Sections
<4 3 <*
M iddle Bayou
"S
1)
E ,
o
1 °'8
8 '
O
n
nil-
• n n n n • _
nn n n n. •!!••__
n
Harbor Island
Spring Lake
Grand Haven
Middle Bayou
Figure 4.5.4 Cadmium Concentrations In Core Samples Taken From The Lower
Grand River, October 1997. (PEL = Probable Effect Level).
71
-------
Nickel in Top Core Sections
o
40 -
n
n
|-|
n •
n
PEL
. • n
Illlnl
nn
Harbor Island
oo
°
Spring Lake Grand Haven
Nickel in Middle Core Sections
Middle Bayou
Harbor Island
Spring Lake
Grand Haven
Middle Bayou
Nickel in Bottom Core Sections
1
C 150
.0
13
01
o
c
o
DUD
Harbor Islan
__
d
dnpnz-9
PEL
rn n n n
O^3> ^ ot5t5t5ooot5oo
6
Spring Lake Grand Haven Middle Bayou
Figure 4.5.5 Nickel Concentrations In Core Samples Taken From The Lower Grand
River, October 1997. (PEL = Probable Effect Level).
72
-------
Total PCBs in Top Core Sections
'S
=£ 70
O)
3. 60
•43
Concentr
-»• ro w *
3 O O O C
n
~
Trft
Harbor Island o <= Spring Lake Grand Haven Middle Bayou
Total PCBs in Middle Core Sections
j=
ro
t
I
o
o
Harbor Island
Spring Lake
Grand Haven
Middle Bayou
Total PCBs in Bottom Core Sections
o
S
C 60
Ol
O ,.
o 20
II
. • 1 nil
Harbor Island
Spring Lake
Grand Haven
Middle Bayou
Figure 4.5.6 PCB Concentrations In Core Samples Taken From The Lower Grand
River, October 1997.
73
-------
The distribution of the individual PCB congeners in each study area is shown in Figures 4.5.7
and 4.5.8. For these graphs, the samples containing > 10 ug/kg of total PCBs were split into
homolog groups of trichloro, tetrachloro, pentachloro, hexachloro, heptachloro, and
octachloro biphenyls. In addition, the area designated as Grand Haven in the previous
discussions was split into the middle Grand River area (G9, G13, G14, G15, and G24) and
Grand Haven shoreline area (G10, Gl 1, and G23). The Grand Haven Shoreline area would
be primarily influenced by discharges and releases from the local industries and the
wastewater system. The Middle Grand River area consists of sampling stations that would
be influenced by sediment deposition from upstream sources. Figure 4.5.7 shows the PCB
congener distribution for the Grand Haven Shoreline, Harbor Island, and the Middle Bayou
area. These stations show a similar distribution pattern consisting primarily of tetrachloro,
pentachloro and hexachloro congeners. Pentachloro isomers were in the greatest abundance.
This pattern is similar to the distribution described by Anderson et al. (1999) for the PCB
congeners in the suspended solids found in Lake Michigan. The congener distributions for
Spring Lake and the Middle Grand River were different (Figure 4.5.8) showing a greater
weighting for tetrachlorobiphenyl and a lower weighting for hexachlorobiphenyl.
Pentachlorobiphenyl was still the isomer group in greatest abundance. Biodegredation may
have caused the change in congener distribution for the Middle Grand River. The source of
PCBs in this area would be the same as the Middle Bayou that was located 1 Km upstream.
The difference in congener distribution for Spring Lake may also be from biodegradation;
however the possibility of a separate source also exists. Congener distributions for the
Middle Bayou, Harbor Island and the Grand Haven Shoreline suggest that similar aroclor
mixtures were used in all areas or the material originated from upstream sources.
The distribution of DDE in the core samples collected in the lower Grand River (Figure
4.5.9.) follows a different distribution pattern than PCBs. DDT was heavily used in the
lower Grand River Watershed for agricultural and pest control purposes. Extensive DDT
usage was associated with mosquito abatement as the surrounding wetland areas were
developed for residential and commercial use. The persistent degradation product of DDT,
DDE, was found in concentrations in excess of the PEL (6.75 ug/kg) in the Harbor Island
area (Gl at 7.6 ug/kg and G20 at 8.2 ug/kg) and Spring Lake (G6 at 8 ug/kg). The highest
DDE levels were found in the deeper core sections at G20 (10 ug/kg - 12 ug/kg).
In summary, three areas of contaminated sediment in the lower Grand River exceeded PEL
values for heavy metals and selected organic chemicals. The locations and parameters of
concern are listed below:
Harbor Island (G20). Exceeds sediment PEL values for chromium, lead, nickel, and
DDE in the top core section. Deeper core sections were heavily
contaminated with trace metals.
Spring Lake (G6). Exceeds sediment PEL values for chromium, lead, cadmium,
nickel, and DDE.
Grand Haven (G12). Exceeds sediment PEL values for chromium and nickel.
74
-------
Grand Haven Shoreline
Tetra
Penta Hexa
Homolog Group
Hepta
Octa
• G-10Top
dG-11 Top
DG-11 Bot
dG-23Top
• G-23Mid
• G-23 Bot
Harbor Island
30 "
i_ r
PI
i
_
—
~~
-
-i
n n^ nmru
EG--I Top
DG-2Top
ClG-2 Mid
DG-2 Bot
EG-20Top
DG-20 Mid
• G-20 Bot
Tri
Tetra
Penta Hexa
Homolog Group
Hepta
Octa
Middle Bayou
t
Tri
Tetra
Penta Hexa
Homolog Group
Hepta
Octa
lG-14Mid
dG-17Top
dG-17Mid
dG-18Top
IG-18 Bot
dG-19Top
DG-19 Bot
Figure 4.5.7 PCB Congener Distribution For Grand Haven Shoreline, Harbor Island,
And Middle Bayou Regions Of The Lower Grand River, October 1997.
75
-------
Spring Lake
o +
Tri
Tetra
Penta Hexa
Homolog Group
Hepta
Octa
Middle Grand River
• G-9 Mid
DG-13 Bot
ClG-14 Mid
ClG-15 Mid
ClG-24 Mid
• G-24 Bot
Tetra
Penta Hexa
Homolog Group
Hepta
Octa
Figure 4.5.8 PCB Congener Distribution For The Spring Lake And Middle Regions
Of The Lower Grand River, October 1997.
76
-------
DDE in Top Core Sections
14
o
o
12
10
8
XL
PEL
oflffl
JL
^=1
XL
5 6 6 3 §
Harbor Island
Spring Lake
Grand Haven
Middle Bayou
DDE in Middle Core Sections
14
D) 10
C o
.2
£
c
0
o
O
O)
o
5
'c
4
O
O 2
V «!• S
O O o
Harbor Island
n
II
V CM CO ^ C
o 6 6 o [
Harbor Island
PEL
Ii— I
T n
1 ? ° ° ° " ° ° °
Spring Lake Grand Haven Middle Bayou
DDE in Bottom Core Sections
JPEL
• • • n
6 u
Spring Lake Grand Haven Middle Bayou
Figure 4.5.9 DDE Concentrations In Core Samples Taken From The Lower Grand
River, October 1997. (PEL = Probable Effect Level).
11
-------
The extent of contaminated sediments in the vicinity of G12 (near the Grand Haven tannery)
appear to be localized in a small area. Additional sampling and analysis would be necessary
to characterize the extent of sediment contamination in the areas around Harbor Island and
Spring Lake.
Meander core islands appear to play a significant role in the lower Grand River with respect
to the deposition of contaminated sediments. Pockets of contaminated sediments were found
at the downstream tip of Harbor Island (G20), and the unnamed islands near G24 and G17.
These areas serve as sediment deposition zones and indicate the effects of historical
discharges of metals and organic chemicals to the lower Grand River. High water events
however can transport contaminated sediments from these deposits and increase the
contaminant loading to Lake Michigan. Robertson (1997) itemized suspended sediment
loadings from the major tributaries to Lake Michigan and found that the Grand River was the
major source of suspended sediment entering the lake. He estimated that the Grand River
contributed 20% of Lake Michigan's sediment loading during normal flow and during flood
events. Since metals and organic chemicals are associated with the suspended sediment
load, the role of the meander core deposits in contaminant transport needs to be examined in
detail. The resuspension and transport of sediment deposits at meander core islands may be a
significant factor that contributed to the high loading of contaminants from the Grand River
during the Lake Michigan Mass Balance Study (Shaffer, et al., 1995; Hall and Behrendt,
1995; and Cowell, et al., 1995).
4.6 Metals Normalization
Loring (1991) and Schropp et al. (1990) used aluminum to normalize estuarine sediments for
the assessment of anthropogenic enrichment of heavy metals. The concentration of
aluminum in sediments is directly related to clay content. Clay minerals are produced by the
weathering of aluminosilicate minerals that contain background concentrations of heavy
metals. In contrast, trace metals are not typically associated with carbonate and quartz based
minerals. Based on this relationship, the background concentration of trace metals will
increase with the amount of clay minerals present. Loring and Schropp both found that
levels of heavy metals such as chromium and lead increased as part of the natural
background as the sediments contained greater concentrations of clay minerals. Aluminum
was used by both authors to indicate the amount of clay minerals present.
The metals analyses were performed using a hydrofluoric acid digestion (total metals)
procedure that dissolves the aluminosilicate crystal lattice. To determine the relationship
between aluminum heavy metals in the sediments of the lower Grand River, a group of
samples from the middle and bottom core sections was examined. Sediments from the
meander core islands were removed from the data set because the anthropogenic enrichment
discussed in sections 4.4 and 4.5. The remaining data were plotted in Figures 4.6.1 and 4.6.2
for chromium and lead respectively. Significant correlations between aluminum and
chromium and aluminum and lead were obtained (r = 0.73 and r = 0.75 respectively). Based
on these relationships, the natural background concentration of chromium would increase
from 12 mg/kg to 60 mg/kg as the aluminum concentration increased. Lead would follow a
similar pattern and increase within a range of 2 mg/kg to 9 mg/kg.
78
-------
The regression lines for the relationship between aluminum and chromium are plotted along
with all of the sample data in Figure 4.6.3. The data for lead and aluminum are plotted in a
similar manner in Figure 4.6.4. These figures show that considerable anthropogenic
enrichment has occurred for both elements based on the number of samples above the
regression line. Two distinct clusters of data are present in the diagrams for each metal. The
data for chromium shows a small cluster of data points above 400 mg/kg and a larger group
above between 60 mg/kg and 400 mg/kg. The cluster of high level samples come from
suspected point source areas such as Spring Lake, the Grand Haven tannery, and Harbor
Island. The lower level data group includes the sediment deposition zone near meander core
islands and downstream areas from the point sources. Lead follows a similar pattern with a
high level cluster between 100 mg/kg and 200 mg/kg and a lower level cluster between 10
mg/kg and 100 mg/kg. The locations for the high level cluster are again associated with
potential point sources. Enrichment by lead appears to have occurred to a greater extent than
for chromium. This pattern is consistent with the fact that anthropogenic lead can originate
from point sources and from non point sources such as urban runoff and fuel releases from
boat traffic. The normalization of heavy metal data with aluminum therefore appears to
provide a means to determine the extent of anthropogenic enrichment in sediments.
79
-------
10000
20000 30000 40000
Total Aluminum (mg/kg)
50000
60000
Figure 4.6.1 The Relationship Between Aluminum And Chromium In Grand River
Core Samples (Middle And Bottom Core Sections Without Significant
Anthropogenic Enrichment), October 1997.
10000 20000 30000 40000
Total Aluminum (mg/kg)
50000
60000
Figure 4.6.2 The Relationship Between Aluminum And Lead In Grand River Core
Samples (Middle And Bottom Core Sections Without Significant
Anthropogenic Enrichment), October 1997.
80
-------
1SOO
140O
130O
1200
110O
1000
(9
* goo
(9
3
aoo
TOO
eoo
500
40O
aoo
aoo
100
10000 aOOOO 30000
TOTALALUM INUM
40000 SOOOO
eoooo
Figure 4.6.3 The Relationship Between Aluminum And Chromium In Grand River
Core Samples (Regression Line Is From Figure 4.6.1), October 1997.
81
-------
200
180
160
140
I
120
100
80
60
40
1000O 2000O 3000O 4000O 5000O
TOTALAOIM INUM (MGyRG)
6000O 7OOOO
Figure 4.6.4 The Relationship Between Aluminum And Lead In Grand River Core
Samples (Regression Line Is From Figure 4.6.2), October 1997.
82
-------
4.7 Toxicity Testing Results
Toxicity evaluations of the Grand River sediments were initiated on May 12, 1998 and
completed on May 23, 1998. Sediment toxicity was evaluated using Hyalella azteca and
Chironomus tentans. Ponar samples were collected at five locations (with one duplicate) on
April 22, 1998. These locations were selected based on the sediment chemistry results for
the core samples. The results of the inorganic chemical analyses on the sediments selected
for toxicity testing are presented in Table 4.7.1. The organic analytical results are given in
Table 4.7.2. Composite sediment samples collected on the same day from six different sites
were employed in exposing both II azteca and C. tentans over this period.
Table 4.7.1 Inorganic Results For The Ponar Samples Collected For Sediment Toxicity
Evaluation From The Lower Grand River, April 1998.
Station
G5P fControD
G6P
G7P
G12P
G20P
G20PDut>
As
mg/kg
9
22
21
16
15
15
Cd
mg/kg
1.6
1.1
1.1
2.8
2.8
1.4
Cr
mg/kg
13
129
82
890
70
87
Cu
mg/kg
53
62
70
111
352
340
Hg
mg/kg
0.41
0.40
0.35
0.26
0.18
0.24
Ni
mg/kg
35
34
33
43
29
35
Pb
mg/kg
77
67
61
54
55
54
Se
mg/kg
<0.5
0.5
<0.5
0.5
O.5
0.5
Zn
mg/kg
185
191
181
177
192
134
Table 4.7.2 Organic Results For The Ponar Samples Collected For Sediment Toxicity
Evaluation From The Lower Grand River, April 1998.
Station
G5P (Control)
G6P
G7P
G12P
G20P
G20PDup
Total PCBs
ug/kg
38
36
43
35
29
53
DDE
ug/kg
3
12
9
13
3
5
ODD
ug/kg
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
DDT
ug/kg
4
5
4
2
1
<1.0
Phenanthrene
mg/kg
<0.33
1.45
0.56
1.65
0.75
0.55
Anthracene
mg/kg
<0.33
<0.33
<0.33
0.49
<0.33
<0.33
Fluoranthene
mg/kg
O.33
3.55
0.41
3.75
1.20
1.35
Pyrene
mg/kg
O.33
2.98
O.33
3.11
1.10
1.22
Benzo(a)
anthracene
mg/kg
O.33
0.91
O.33
1.34
0.43
0.39
Chrysene
mg/kg
O.33
O.33
O.33
0.95
0.51
0.65
Benzo(b)
fluoranthene
mg/kg
O.33
0.84
O.33
0.73
0.35
0.42
Benzo(a)
pyrene
mg/kg
O.33
0.69
O.33
0.81
0.37
0.33
Temperature and dissolved oxygen measurements were taken daily throughout the duration
of the tests (Appendix D). The test beakers were maintained in a climate controlled room and
little variation in temperature was observed. Dissolved oxygen remained above 40%
saturation in both the II azteca and C, tentans test beakers. Conductivity, hardness,
ammonia and pH were determined at the beginning and on the tenth day of each test and
these data are shown in Appendix D. With the exception of ammonia, these parameters
remained relatively constant, with a variation of less than 50%, from initial to final
measurements for both test species. Ammonia decreased overtime and was < 50% of the
original concentration in all exposures.
83
-------
4.7.1 Hyalella azteca
The evaluation of Grand River's sediment began on May 12, 1998 and the resulting survival
data are presented in Table 4.7.1.1 The survival in the control treatment exceeded the
required 80%. Statistical analyses were performed on the toxicity data and the results are
summarized in Tables 4.7.1.2, 4.7.1.3, and 4.7.1.4. Normality of the data was tested using
the Chi-Square test for normality. The data passed the tests with an alpha value of 0.01.
Dunnett's Test showed a statistically significant (alpha = 0.05) difference on the survival
data, in two out of six sediments when each was compared to the control (G5P). These
samples were collected from Spring Lake (G6P) and near the Grand Haven Tannery (G12P).
Using Steel's many-one rank test (Table 4.7.1.4), sample G12P was determined to be more
toxic to amphipods than the other samples.
Table 4.7.1.1 Summary Of Hyalella azteca Survival Data Obtained During The 10 Day
Toxicity Test With Grand River Sediments.
Sample
ID
G5-P
G6-P
G7-P
G12-P
G20-P
G20-P
DUP
Number of
Organisms
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Replicate
A
10
10
10
9
10
9
10
6
10
9
10
8
B
10
9
10
8
10
8
10
7
10
8
10
8
C
10
8
10
9
10
8
10
7
10
7
10
7
D
10
10
10
10
10
8
10
7
10
6
10
8
E
10
8
10
7
10
9
10
9
10
8
10
9
F
10
10
10
9
10
6
10
7
10
7
10
8
G
10
8
10
8
10
8
10
6
10
8
10
8
H
10
8
10
8
10
9
10
9
10
7
10
7
Survival
Mean
8.875
8.50
8.125
7.25
7.50
7.875
Std Dev
0.9910
0.92582
0.99103
1.1650
0.92582
0.6409
c.v.%
11.1665
10.8920
12.1973
16.0685
12.3443
8.1380
84
-------
Table 4.7.1.2 Chi-Square Test For Normality OfHyalella azteca Survival Data.
CHI-SQUARE TEST FOR NORMALITY
Actual and Expected Frequencies
INTERVAL <-1.5 -1.5to<-0.5 -0.5 to 0.5 >0.5to1.5 >1.5
EXPECTED 3.2160 11.6160 18.3360 11.6160 3.2160
OBSERVED 3 14 14 12 5
Chi-Square = 2.5315 (p-value =
0.6390)
Critical
Chi-Square = 13.277 (alpha = 0.01, df = 4)
= 9.488 (alpha = 0.05, df = 4)
Data PASS normality test (alpha = 0.01).
Table 4.7.1.3 Dunnett's Test For Hyaletta azteca Survival Data.
DUNNETT'S TEST - Ho:ControKTreatment
GROUP
1
2
O
4
5
6
IDENTIFICATION
G5P (Control)
G6P
G7P
G12P
G20P
G20P Dup
MEAN
8.8750
7.5000
8.1250
7.2500
8.5000
7.8750
TSTAT
2.8864
1.5744
3.4112
0.7872
2.0992
SIG
0.05
*
*
Dunnett critical value = 2.3100 (1 Tailed, alpha = 0.05, df [used] = 5,40)
(Actual df= 5,42)
85
-------
Table 4.7.1.4 Steel's Many-One Rank Test For Hyaletta azteca 10 Day Toxicity Test
With Grand River Sediments.
STEEL'S MANY-ONE RANK TEST- Ho: ControKTreatment
GROUP
1
2
3
4
5
6
IDENTIFICATION
G5P (Control)
G6P
G7P
G12P
G20P
G20P Dup
MEAN IN
ORIGINAL
UNITS
8.8750
7.5000
8.1250
7.2500
8.5000
7.8750
RANK
SUM
46.50
57.50
45.00
62.00
50.50
GRIT.
VALUE
46.00
46.00
46.00
46.00
46.00
DF
8.00
8.00
8.00
8.00
8.00
SIG
0.05
*
Critical values are 1 tailed (k = 5)
4.7.2 Chironomus tentans
The midge survival data are presented in Table 4.7.2.1. The survival in the control treatment
exceeded the required 70%. There were no low survival (< 50%) noted in the Grand River
sediments for C. tentans. Statistical analyses were performed on the toxicity data and the
results are summarized in Table 4.7.2.2 and 4.7.2.3. Un-transformed survival data were
evaluated for normality with Chi-squares test for normality at alpha = 0.01. These data were
then analyzed for effects on survival employing Dunnett's Test. No statistically significant
(alpha = 0.05) differences from the control (G5P) were observed in the sediments.
4.7.3 Summary
Statistically significant (alpha = 0.05) acute toxicity effects were observed in the sediments
of samples G6-P and G12-P on the amphipod, II azteca, by the Dunnett's test. Statistical
significant (alpha = 0.05) acute toxicity effects were observed in the sediments at G12-P and
G6-P for H. azteca. The PEL values for chromium and DDE were exceeded at G12-P. The
PEL value for arsenic was exceeded at G7-P however statistically significant mortality was
not observed. Statistically significant mortality was also not observed in assays using the
midge, C. tentans in the Grand River sediments.
86
-------
Table 4.7.2.1 Summary
Day
Of Chironomus Tentans Survival Data Obtained During The 10
Toxicity Test With Grand River Sediments.
Sample
ID
G5P
G6
G7P
G12P
G20P
G20P
Dup
Number of
Organisms
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Replicate
A
10
9
10
9
10
10
10
9
10
10
10
10
B
10
10
10
10
10
9
10
8
10
9
10
10
c
10
9
10
9
10
7
10
10
10
10
10
9
D
10
8
10
8
10
9
10
9
10
10
10
7
E
10
9
10
10
10
9
10
9
10
9
10
9
F
10
10
10
9
10
10
10
10
10
9
10
8
G
10
9
10
8
10
9
10
9
10
10
10
9
H
10
10
10
9
10
8
10
9
10
9
10
10
Survival
Mean
9.250
9.000
8.875
9.125
9.500
9.000
Std Dev
0.7071
0.7559
0.9910
0.6409
0.5345
1.0690
c.v.%
7.6444
8.3992
11.1665
7.0232
5.6266
11.8783
Table 4.7.2.2 Chi-Square Test For Normality Of Chironomus tentans Survival Data.
CHI-SQUARE TEST FOR NORMALITY
INTERVAL
Actual and Expected Frequencies
<-1.5 -1.5to<-0.5 -0.5 to 0.5
>0.5to1.5
EXPECTED
OBSERVED
Chi-Square = 6.3383
3.2160
4
11.6160
8
18.3360
20
(p-value = 0.1753)
11.6160
16
3.2160
0
Critical
Chi-Square= 13.277
= 9.488
(alpha = 0.01 ,df = 4)
(alpha = 0.05, df = 4)
Data PASS normality test (alpha = 0.01).
87
-------
Table 4.7.2.3 Dunnett's Test For Chironomus tentans Survival Data.
DUNNETT'STEST- Ho:ControKTreatment
GROUP
1
2
3
4
5
6
IDENTIFICATION
G5P (control)
G6P
G7P
G12P
G20P
G 20P Dup
MEAN
9.2500
9.0000
8.8750
9.1250
9.5000
9.0000
TSTAT
0.6207
0.9311
0.3104
-0.6207
0.6207
SIG
0.05
Dunnett critical value = 2.3100 (1 Tailed, alpha = 0.05, df [used] = 5,40)
(Actual df= 5,42)
88
-------
5.0 Summary
A preliminary investigation of the nature and extent of sediment contamination in the lower
Grand River was performed. Three areas in the lower Grand River exceeded sediment quality
guidelines for heavy metals and selected organic chemicals. The locations and parameters of
concern are listed below:
Harbor Island (G20). Exceeds sediment PEL values for chromium, lead, nickel, and
DDE in the top core section. Deeper core sections were
extensively contaminated with heavy metals.
Spring Lake (G6). Exceeds sediment PEL values for chromium, lead, cadmium,
nickel, and DDE.
Grand Haven (G12). Exceeds sediment PEL values for chromium and nickel. The
sediments at this location exhibited a statistically significant level
toxicity to amphipods when compared to the control.
The extent of contaminated sediments in the vicinity of G12 (near the Grand Haven tannery)
appears to be localized in a small area. Some additional sampling of this area would be
necessary to define the extent of the contaminated sediments. The results for Spring Lake
and Harbor Island show these areas to be contaminated with heavy metals and selected
organic compounds. Additional sampling and analysis would be necessary to characterize
the extent of sediment contamination in the areas around Harbor Island and Spring Lake.
Meander core islands appear to play a significant role in the lower Grand River with respect
to the deposition of contaminated sediments. Pockets of contaminated sediments were found
at the downstream tip of Harbor Island (G20), and the unnamed islands near G24 and G17.
These areas serve as sediment deposition zones and indicate the effects of historical
discharges of metals and organic chemicals to the lower Grand River. High water events
however can transport contaminated sediments from these deposits and increase the
contaminant loading to Lake Michigan. Since metals and organic chemicals are associated
with the suspended sediment load, the role of the meander core deposits in contaminant
transport needs to be examined in detail. This investigation examined three of the 12
meander core islands that are located in the lower Grand River.
The normalization of heavy metal data with aluminum was examined for chromium and lead.
Statistically significant correlations between these elements were determined in background
samples (r = 0.73 and 0.75 for Cr and Pb respectively). Plots of the project data set
demonstrate that anthropogenic enrichment of lead and chromium has occurred in a majority
of the top and middle core sections.
Statistically significant (alpha = 0.05) acute toxicity effects were observed in the sediments
of samples G6-P and G12-P on the amphipod, H. azteca, by the Dunnett's test. The PEL
values for chromium and DDE were exceeded at G12-P. PEL values for arsenic and DDE
were exceeded at G6-P. Statistically significant (alpha = 0.05) mortality was not seen on the
midge, C. tentans in the Grand River sediments.
89
-------
6.0 References
Anderson, D. 1, Bloem, T. B., Blankenbaker, R. K., Stanko, T.A. 1999. Concentrations of
polychlorinated biphenyls in the water column of the Laurentian Great Lakes: Spring
1993. Journal of Great Lakes Research. 25:160-169.
Bowman, D. W. 1995. Grand River at Grand Haven Michigan: U.S. Army Corps of
Engineers Tier II Evaluation. June, 1995.
Cowell, S. E., Hurley, J. P., Schafer, M. M. and P. E. Hurley. 1995. Mercury partitioning
and transport in Lake Michigan Tributaries. Presented at 38th Conference.
International Association of Great Lakes Research.
Hall, D. W. and T. E. Behrendt. 1995. Polychlorinated byphenyls and pesticides in Lake
Michigan tributaries, 1993-95. Presented at 38th Conference. International
Association of Great Lakes Research.
Helmke, P. A., Koons, R. D., Schomberg, P. J. and I. K. Iskandar. 1977. Determination of
trace element contamination of sediments by multielement analysis of clay-size
fraction. Environ. Sci. Technol. 11:10:984-988. 23:200-208.
Long, E. R., and Morgan, L. G. 1990. The Potential for Biological Effects of Sediment-
Sorbed Contaminants Tested in the National Status and Trends Program. NO AA
Technical Momorandum NOS OMA 52, Seattle, WA.
Loring, D. H. 1991. Normalization of heavy-metal data from estuarine and coastal
sediments. ICES J. Mar. Sci. 48:101-115.
Persaud, D., R. Jaagumagi, and A. Hayton. 1992. Guidelines for the Protection and
Management of Aquatic Sediment Quality in Ontario. ISBN 0-7729-9248-7. Ontario
Ministry of the Environment, Toronto, Canada, 23 p.
Robertson, D. M. 1997. Regionalized loads of suspended sediment and phosphorus to Lakes
Michigan and Superior-High flow and long -term average. Journal of Great Lakes
Research. 23:416-439.
Schropp, S. J. and H. L. Windom. 1988. A Guide to the Interpretation of Metal
Concentrations in Estuarine Sediments. Florida Department of Environmental
Regulation Coastal Zone Management Section.
Schropp, S. J., Lewis, F. G., Windom, H. L. Ryan, J. D., Calder, F. D. and L. C. Burney
1990. Interpretation of metal concentrations in estuarine sediments of Florida using
aluminum as a reference element. Estuaries 13(3):227-235.
90
-------
Shaffer, M. M., Overdier, J. T., Baldino, R. A., Hurley, J. P. and P. E. Hughes. 1995.
Levels, partitioning, and fluxes of six trace elements in Lake Michigan tributaries.
Presented at 38th Conference. International Association of Great Lakes Research.
Smith, S. L., D. D. MacDonald, K. A. Keenleyside, C. G. Ingersoll, and L. J. Field. 1996. A
preliminary evaluation of sediment quality assessment values for freshwater
sediments. J. Great Lakes Res., 22(3): 624-638.
Thorpe, P. 1994. The Identification Of Heavy Metals, Their Movement, and their Impact on
Life in The Lower Grand River, Michigan.., 1992 Summary Report (WRI-MR-94-2).
68pp.
USEPA, 1992. Sediment Classification Methods Compendium. U.S. Environmental
Protection Agency. EPA/823/R-92/006.
91
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Appendix A
Summary Of General Chemistry And Metals Data For Sediments Collected From The
Lower Grand River
-------
Table A-l Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Sediment Core Samples Collected In
The Lower Grand River. October 1997.
Sample ID
G-l TOD
G-lMd
G-l Bot
G-2 TOD
G-2Md
G-2 Bot
G-3 Top
G-3 Bot
G-10 TOD
G-10 Bot
G-ll TOD
G- 11 Bot
G-12 TOD
>2000 am
Weight %
1
0
0
3
0
2
0
0
0
0
1
0
4
200-1000 am
Weight%
1
0
0
1
0
1
0
1
4
1
2
3
2
100-850 urn
Weight %
0
0
0
0
0
0
0
0
2
0
0
1
1
850-500 urn
Weight %
2
0
1
2
1
4
3
1
5
2
2
2
4
500-125 «m
Weight %
36
17
11
70
52
67
52
54
57
51
39
29
45
125-63 urn
Weight %
25
18
13
9
19
13
20
19
18
13
10
11
7
<63wm
Weight %
35
64
75
14
26
13
24
25
13
32
47
54
37
TOC
%
2.5
8
6.4
<1.0
1.5
<1.0
5.4
3.5
5.2
5.3
4.1
5.1
2.8
Solids
%
41
30
33
66
50
62
43
52
42
46
45
52
50
-------
Table A-l (continued). Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Sediment Core Samples
Collected In The Lower Grand River. October 1997.
Sample ID
G-20 Too
G-20 Mid
G-20 Bot
G-20D TOD
G-20DMid
G-20D Bot
G-23 TOD
G-23 Mid
G-23 Bot
G-24 TOD
G-24 Mid
G-24 Bot
G-4 TOD
G-4 Bot
>2000 u m
Weight %
1
1
0
1
2
0
0
0
0
0
0
1
0
0
200-1000 Mm
Weight%
0
1
0
1
1
0
7
1
1
1
0
1
1
0
100-850 u m
Weight %
0
0
0
0
0
0
4
1
0
0
0
1
0
0
850-500 Mm
Weight %
1
1
0
1
1
0
8
4
3
o
J
o
J
5
2
1
500-125 Mm
Weight %
28
16
11
35
17
11
49
45
84
90
87
67
52
50
125-63 Mm
Weight %
16
13
16
14
13
15
15
14
4
o
J
8
5
14
12
<63 Mm
Weight %
53
68
72
48
65
73
16
36
9
2
1
21
30
37
TOC
%
4.1
5.6
5.9
3.8
4.9
5.4
10
10
<1.0
<1.0
<1.0
1.2
1.7
<1.0
Solids
%
37
37
41
39
38
40
33
37
73
73
64
72
64
68
-------
Table A-l (continued). Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Sediment Core Samples
Collected In The Lower Grand River. October 1997.
Sample ID
G-5 TOD
G-5 Mid
G-5 Bot
G-5D Too
G-5D Mid
G-5D Bot
G-6 TOD
G-6 Mid
G-6 Bot
G-7 TOD
G-7 Mid
G-7 Bot
>2000Mm
Weight %
0
0
0
0
0
0
0
0
0
1
0
0
200-1000 wm
Weight%
0
0
0
0
0
0
0
0
0
0
0
0
100-850 Mm
Weight %
0
0
0
0
0
0
0
0
0
0
0
0
850-500 Mm
Weight %
0
1
0
0
1
0
0
0
0
0
1
2
500-125 Mm
Weight %
16
7
o
J
14
10
5
5
10
10
12
8
5
125-63 Mm
Weight %
15
13
5
16
14
9
8
15
18
18
12
8
<63Mm
Weight %
69
78
91
69
76
86
88
75
71
69
78
84
TOC
%
9.7
9.3
7.5
9.2
10.3
7.4
5.7
8.1
6.2
8.6
5
3.5
Solids
%
20
18
27
20
20
29
24
25
27
18
28
35
-------
Table A-l (continued). Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Sediment Core Samples
Collected In The Lower Grand River. October 1997.
Sample ID
G-8 Too
G-8 Mid
G-8 Bot
G-9 TOD
G-9 Mid
G-9 Bot
G-13 TOD
G-13 Bot
G-13-2
G-13-3
G-22 TOD
G-22-2
G-22-3
G-22-4
G-22-5
>2000 u m
Weight %
1
0
1
0
0
0
0
0
2
0
0
0
0
0
0
200-1000 Mm
Weight%
1
1
0
1
0
0
1
1
1
0
1
0
0
0
0
100-850 u m
Weight %
1
0
0
0
0
0
1
0
0
0
0
0
0
1
1
850-500 Mm
Weight %
2
0
o
3
2
1
1
2
1
2
2
2
2
2
2
2
500-125 Mm
Weight %
18
29
29
27
37
18
51
15
41
29
34
17
13
12
11
125-63 Mm
Weight %
27
30
20
23
20
23
18
24
16
21
17
14
15
13
11
<63 Mm
Weight %
51
40
46
47
42
58
26
59
37
47
45
67
69
72
76
TOC
%
4.1
1.7
<1.0
4.1
2.4
1.8
2.4
2.6
1.6
<1.0
5.5
5
4.9
7.6
8.3
Solids
%
39
61
57
48
57
54
52
45
53
57
25
28
24
29
28
-------
Table A-l (Continued). Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Sediment Core
Samples Collected In The Lower Grand River. October 1997.
Sample ID
G-14 TOD
G-14 Mid
G-14 Bot
G-15 Too
G-15 Mid
G-15 Bot
G-16
G-17 TOD
G-17 Mid
G-17 Bot
G-18 TOD
G-18 Mid
G-18 Bot
G-19 TOD
G-19 Bot
>2000 u m
Weight %
1
4
1
1
4
6
22
2
0
7
0
0
0
2
2
200-1000 Mm
Weight%
3
1
2
1
5
7
7
6
1
4
0
0
0
1
1
100-850 u m
Weight %
1
1
1
1
2
3
2
4
0
1
0
0
0
0
0
850-500 Mm
Weight %
4
o
3
4
4
12
16
9
13
o
J
6
1
1
0
1
1
500-125 Mm
Weight %
27
25
24
60
54
65
55
43
81
48
90
77
96
73
66
125-63 Mm
Weight %
19
15
18
12
2
1
4
8
7
9
8
9
2
8
20
<63 Mm
Weight %
46
51
50
21
22
2
1
24
7
25
0
13
1
16
10
TOC
%
<1.0
<1.0
<1.0
1
<1.0
<1.0
<1.0
3.5
1.3
2
<1.0
1.2
<1.0
<1.0
1.2
Solids
%
49
52
45
57
74
76
73
45
48
46
71
77
69
54
52
-------
Table A-2. Grain Size Distribution, Total Organic Carbon (TOC) And % Solids For The Ponar Samples Collected In The
Lower Grand River. April 1998.
Sample ID
G-5P
G-6P
G-7P
G-12P
G-20P
G-20P DUD
>2000 wm
Weight %
0
0
1
4
1
1
200-1000 Mm
Weight%
0
0
0
3
0
0
100-850 Mm
Weight %
0
0
0
2
0
1
850-500 Mm
Weight %
0
0
0
5
1
1
500-125 Mm
Weight %
22
6
12
40
28
33
125-63 Mm
Weight %
11
10
22
15
16
13
<63 Mm
Weight %
67
84
65
31
53
50
TOC
%
8.5
4.3
7.3
3.9
5.1
4.7
Solids
%
22
21
17
45
32
36
-------
Table A-3. Results Of Laboratory Duplicate Analyses For Grain Size Distribution And % Solids For The Lower Grand River
Sediment Samples.
Sample ID
G-2 Bot
G-2 Bot Dup
G-20 Too
G-20 Top Dup
G-24 Mid
G-24MidDuD
G-6 Too
G-6 Top Dup
G-7 TOD
G-7 Top Dup
G-8 Bot
G-8 Bot Dup
G-16
G-16 DUD
G-19 Bot
G- 19 Bot DUD
>2000wm
Weight %
2
1
1
0
0
0
0
0
1
7
1
1
22
20
2
4
200-1000 wm
Weight%
1
1
0
1
0
0
0
0
0
0
0
0
7
4
1
3
100-850 Mm
Weight %
0
0
0
0
0
0
0
0
0
0
0
0
2
1
0
0
850-500 Mm
Weight %
4
3
1
1
3
1
0
0
0
0
3
2
9
11
1
3
500-125 Mm
Weight %
67
65
28
31
87
80
5
3
12
12
29
29
55
50
66
59
125-63 Mm
Weight %
13
16
16
16
8
11
8
12
18
18
20
21
4
9
20
23
<63Mm
Weight %
13
14
53
51
1
7
88
85
69
62
46
47
1
5
10
8
-------
Table A-4. Results Of Laboratory Duplicate Analyses For TOC In The Lower
Grand River Sediment Samples.
Field TOC RPD
ID % wt. %
G-3 Bot 3.5
G-3BotDup 3.9 11%
G-20Bot 5.9
G-20BotDup 5.3 11%
G-5 Md 9.3
G-5MdDup 9.1 2%
G-5 Bot 7.4
G-5BotDup 7.5 1%
G-22-2 5.0
G-22-2 Dup 4.8 4%
G-13 Bot 2.6
G-13BotDup 2.8 7%
G-15 Top 1.0
G-15 Top Dup 1.2 18%
G-17Bot 2.0
G-17BotDup 1.5 29%
G6-P 7.3
G6-P Dup 8.0 9%
A-8
-------
Table A-5 Metals Results For The Sediment Core Samples Collected In The Lower Grand River. October 1997.
Field
Sample ID
(MTop
(MMd
G4Bot
(MTop
&2Md
&2Bot
&3Top
&3Bot
&4Top
&4Bot
&5Top
&5Md
&5Bot
&5D Top
&5DMd
&5DBot
&6Top
&6Md
&6Bot
&7Top
&7Md
&7Bot
&8Top
&8Md
&8Bot
&9Top
&9Md
&9Bot
Concentration, rag/kg
Al
nig/kg
27200
38100
37900
19000
33100
23200
37500
30400
37800
12500
39700
46000
21500
41400
44100
44100
34100
42800
43600
59800
40800
37900
25900
26300
25700
29000
26100
29500
As
nig/kg
10
12
10
3.3
9.2
4.2
5.5
6.2
4.6
1.8
8.4
6.5
5.1
10
6.6
4.4
17
8.0
5.3
7.8
4.5
5.2
8.3
4.9
5.6
9.8
6.0
6.4
Ba
nig/kg
315
327
323
318
389
323
362
366
404
234
328
347
352
336
337
330
355
386
374
450
320
327
296
350
316
291
303
334
Ca
nig/kg
77800
82500
92000
19700
51400
32300
29400
29100
19100
33500
44400
56900
37800
62300
38800
43100
39600
42200
45000
55600
83300
96700
85900
71400
67900
78700
70800
81400
Cd
mg/kg
0.56
0.37
0.35
0.25
0.28
0.13
0.69
0.20
0.18
0.03
0.54
0.33
0.27
0.98
0.33
0.29
3.63
0.58
0.30
0.45
0.27
0.26
0.16
0.11
0.12
0.19
0.14
0.16
Cr
nig/kg
29
42
26
13
32
12
34
14
24
5
6
43
38
83
42
40
313
54
40
59
37
33
26
18
18
26
20
24
Cu
mg/kg
14
14
14
7
12
5
22
7
6
1
39
16
12
53
17
13
160
22
13
20
11
9
8
3
4
8
6
8
Hg
nig/kg
0.14
<0.10
<0.10
<0.10
0.40
<0.10
0.21
<0.10
<0.10
<0.10
0.16
0.11
<0.10
0.24
<0.10
<0.10
0.37
0.24
0.11
0.11
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
Fe
nig/kg
17029
26486
26453
5867
18009
11487
15507
9119
12700
2970
44400
49200
46100
40600
53000
46800
25900
47200
55800
70700
41400
39800
18300
10700
12900
16700
13100
15900
Mg
nig/kg
11700
18300
18400
4040
10300
6980
6090
8760
8180
1280
12800
15300
15500
13100
14600
16300
14500
16000
17300
20800
16300
16800
12800
9810
9970
12800
10400
12300
Mn
nig/kg
335
431
464
126
372
298
180
115
152
97.5
771
798
887
780
923
888
732
715
580
1050
800
932
373
242
265
308
300
392
M
mg/kg
42
23
18
13
15
9
23
11
8
<5
29
19
17
37
21
20
99
23
18
30
21
19
14
8
9
14
11
13
Pb
mg/kg
6
4
6
5
20
3
14
4
4
2
12
5
5
5
5
6
100
15
6
9
4
4
3
3
3
3
3
3
Se
mg/kg
0.39
0.34
0.55
0.11
0.34
0.17
0.47
0.31
0.32
0.03
0.34
0.52
0.38
0.49
0.43
0.46
0.36
0.48
0.44
0.66
0.49
0.37
0.21
0.18
0.24
0.19
0.21
0.22
Zn
nig/kg
70
72
58
39
49
18
58
19
30
2
89
67
65
105
81
59
268
85
58
112
70
71
40
21
26
40
30
34
-------
Table A-5 (continued) Metals Results For The Sediment Core Samples Collected In The Lower Grand River. October 1997.
Field
Sample ID
G-lOTop
G-lOBot
G-llTop
G-llBot
G-12Top
G-13 Top
G-13-2
G-13-3
G-13 Hot
G-14Top
G-14MM
G-14Bot
G-15 Top
G-15Mid
G-15 Hot
G-16
G-17Top
G-17Mid
G-17Bot
G-18Top
G- 18 Mid
G-18Bot
G-19Top
G-19Bot
G-20 Top
G-20Mid
G-20 Hot
G-20D Top
G-20D Mid
G-20D Hot
Concentration, mg/kg
Al
mg/kg
37100
39000
35100
30600
22800
33500
26400
25800
30400
500
319
450
23400
15100
12300
18800
22200
20500
17700
18500
20800
15400
19200
21300
35900
39700
29700
40100
35200
36200
As
mg/kg
5.7
6.8
9.3
8.4
6.6
8.7
6.6
7.4
8.9
12
16
8.1
7.3
10
8.6
4.2
9.7
6.2
8.0
2.6
6.0
3.2
4.2
5.3
10
14
17
12
13
16
Ba
mg/kg
394
405
420
363
353
354
328
297
334
184
201
155
283
210
211
225
291
344
279
385
406
338
387
412
391
437
462
412
429
486
Ca
mg/kg
22000
10600
38200
41000
85000
31000
39900
62600
79400
257000
231000
226000
44600
29500
28600
17900
38900
26600
72200
17700
27600
12800
22400
31700
61800
72100
45500
62400
55400
57700
Cd
mg/kg
0.48
0.33
0.87
0.21
1.55
0.49
0.13
0.11
0.16
0.98
0.09
0.65
0.39
0.09
0.02
0.06
1.83
2.20
0.14
0.14
1.03
0.65
0.23
0.41
2.29
0.56
1.18
2.66
0.48
0.99
Cr
mg/kg
42
33
27
18
877
36
20
20
25
11
13
9
30
11
7
14
92
110
20
20
87
33
24
39
169
1071
1428
209
768
1426
Cu
mg/kg
35
14
13
72
100
28
6
6
8
4
4
4
30
4
1
2
65
88
4
7
55
15
8
15
98
267
348
141
233
372
Hg
mg/kg
0.16
<0.10
0.36
<0.10
0.42
0.31
<0.10
0.14
<0.10
<0.10
<0.10
<0.10
0.48
0.13
<0.10
<0.10
<0.10
0.17
<0.10
<0.10
1.47
<0.10
<0.10
<0.10
0.34
1.44
4.33
0.41
1.27
3.84
Fe
mg/kg
13281
15069
20695
17400
12900
14800
11800
16500
19400
12700
13100
7910
11000
12700
8860
9100
15800
11900
19000
5630
10300
5490
9740
9910
20100
24900
26900
21200
24000
26100
Mg
mg/kg
5900
5800
12200
10500
6950
6610
7490
11300
13800
8220
7710
6770
5550
5410
4260
4860
7880
5240
7820
3630
6010
2780
4510
5120
11200
13500
15200
11600
13200
15000
Mn
mg/kg
232
155
676
710
357
167
235
536
718
588
682
568
226
264
164
176
56
37
104
20
33
22
37
40
545
586
554
585
590
520
Ni
mg/kg
18
20
15
12
59
19
12
14
15
10
11
9
20
10
7
15
32
37
15
12
60
17
14
20
67
166
214
79
149
210
Pb
mg/kg
11
8
9
4
72
27
5
3
3
1
1
1
27
4
2
2
30
43
2
4
58
6
6
23
85
184
172
100
154
180
Se
mg/kg
0.27
0.25
0.36
0.33
0.88
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
0.5
0.56
0.61
0.4
0.55
0.58
Zn
mg/kg
71
39
64
38
183
79
29
31
38
16
18
12
72
26
10
17
88
130
7
5
210
14
26
69
262
855
894
311
668
863
-------
Table A-5 (Continued) Metals Results For The Sediment Core Samples Collected In The Lower Grand River. October 1997.
Field
Sample ID
G-22 Top
G-22-2
G-22-3
G-22-4
G-22-5
G-23 Top
G-23 Mid
G-23 Bot
G-24 Top
G-24 Mid
G-24 Bot
Concentration, mg/kg
Al
mg/kg
26800
10500
16000
22600
25300
27400
26100
2000
2000
21600
21400
As
mg/kg
8.9
7.6
5.2
6.3
6.4
12
9.9
3.8
2.3
5.1
5.2
Ba
mg/kg
260
258
265
281
282
336
306
277
286
373
330
Ca
mg/kg
107000
85700
93300
69800
66300
25100
22500
<2000
<2000
19400
22900
Cd
mg/kg
0.58
0.20
0.20
0.23
0.25
0.42
0.23
0.04
0.21
1.34
1.47
Cr
mg/kg
44
29
26
34
38
57
27
10
31
134
226
Cu
mg/kg
23
10
9
12
12
23
10
2
8
58
71
Hg
mg/kg
0.22
<0.10
<0.10
<0.10
<0.10
0.12
<0.10
<0.10
<0.10
0.35
0.19
Fe
mg/kg
19900
22500
24600
31800
34100
16100
15700
3300
3330
8930
9450
Mg
mg/kg
9940
11700
12600
13400
13500
5480
5970
1490
2760
5190
4790
Mn
mg/kg
403
502
570
648
590
256
170
129
79.8
203
214
Ni
mg/kg
37
15
15
19
18
26
19
9
18
58
77
Pb
mg/kg
24
2
2
2
2
13
6
2
2
33
32
Se
mg/kg
0.27
0.24
0.22
0.4
0.26
0.44
0.29
BDL
0.04
0.41
0.18
Zn
mg/kg
88
48
49
58
62
59
34
3
3
110
111
Table A-6 Metals Results For The Ponar Samples Collected In The Lower Grand River. April 1998.
Field
Sample ID
G-5P
G-6P
G-7P
G-12P
G-20P
G-20PD
Concentration, mg/kg
Al
mg/kg
22700
39000
37800
28600
42600
27200
As
mg/kg
9
22
21
16
15
15
Ba
mg/kg
315
350
355
300
373
289
Ca
mg/kg
112000
113000
126600
61000
95000
52800
Cd
mg/kg
1.6
1.1
1.1
2.8
2.8
1.4
Cr
mg/kg
13
129
82
890
70
87
Cu
mg/kg
53
62
70
111
352
340
Hg
mg/kg
0.41
0.40
0.35
0.26
0.18
0.24
Fe
mg/kg
21100
24000
23800
16100
27000
15700
Mg
mg/kg
10500
13000
12100
8070
13900
7660
Mn
mg/kg
773
1040
892
408
629
200
Ni
mg/kg
35
34
33
43
29
35
Pb
mg/kg
77
67
61
54
55
54
Se
mg/kg
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
Zn
mg/kg
185
191
181
177
192
134
-------
Table A-7. Results Of Laboratory Duplicate And Matrix Spike Analyses For
Metals In The Lower Grand River Sediment Samples.
Aluminum Quality Control Data
Sample
Location
G-l Mid
G-l MidDup
G-2 Hot
G-2 Hot Spk
G-3 Top
G-3 Top Dup
G-ll Top
G-ll Top Spk
G-ll Hot
G-ll Hot Spk
G-l 2 Top
G-l 2 Top Dup
G-20 Hot
G-20 Hot Spk
G-20D Mid
G-20D Mid Spk
G-4 Top
G-4 Top Dup
G-4 Hot
G-4 Hot Dup
G-5 Hot
G-5 Hot Spk
G-5DBot
G-5D Hot Dup
G-6 Top
G-6 Top Spk
G-7 Mid
G-7 Mid Dup
G-7 Top
G-7 Top Dup
G-13-2
G-13-3 Spk
G-l 5 Top
G-l 5 Top Spk
G-l 7 Top
G-l 7 Top Spk
G-5P
G-5P DUP
Concentration
ma/kg
38100
36000
23200
59300
37500
35100
35100
64900
30600
68100
22800
20900
29700
76400
35200
73300
37800
31700
12500
11600
21500
74100
44100
30500
34100
77800
40800
41800
59800
42700
26400
66200
23400
71600
22200
67400
22700
23600
% RPD
6%
7%
9%
18%
7%
36%
2%
33%
4%
%R
90%
75%
94%
117%
95%
132%
109%
100%
120%
113%
Arsenic Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l MidDup
G-2 Hot Spk
G-3 Top
G-3 Top Dup
G-ll Hot
G-ll Hot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-4 Hot
G-4 Hot Dup
G-5D Mid
G-5D Mid Spk
G-5D Hot
G-5D Hot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-13Bot
G-13 Hot Dup
G-l 4 Top
G-l 4 Top Spk
G-14Mid
G-14MidDup
G-l 7 Top
G-l 7 Top Spk
G-17Mid
G-17MidDup
G-6P
G-6P Dup
Concentration
ma/kg
10
12
13
6.0
5.5
5.8
8.4
9.8
6.6
5.8
4.6
5.1
1.8
2.7
6.6
8.0
4.4
4.6
7.8
10.1
4.5
3.9
8.7
10
8.9
9.0
12
15
16
14
9.7
11
6.2
5.0
22
20
% RPD
10%
6%
13%
44%
5%
14%
1%
13%
21%
12%
%R
64%
91%
69%
23%
70%
116%
84%
114%
85%
A-12
-------
Table A-7 (Continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Barium Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Bot
G-ll Bot Spk
G-12 Top
G-12 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-13 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-14 Top
G-14 Top Spk
G-14 Mid
G-14 Mid Dup
G-l 7 Top
G-17 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
ma/ka
315
511
327
324
323
529
362
352
363
559
O £O
353
333
404
539
234
223
337
541
330
363
450
497
320
316
354
515
334
348
184
255
201
148
291
555
344
342
315
508
350
283
373
549
%RPD
1%
3%
6%
5%
10%
10%
1%
4%
30%
1%
21%
%R
98%
103%
98%
68%
102%
81%
36%
132%
97%
88%
Calcium Quality Control Data
Sample
Location
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Top
G-ll Top Spk
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-12 Top Dup
G-20 Bot
G-20 Bot Spk
G-20D Mid
G-20D Mid Spk
G-4 Bot
G-4 Bot Dup
G-5 Bot
G-5 Bot Spk
G-5D Bot
G-5D Bot Dup
G-6 Top
G-6 Top Spk
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Bot
G-l 3 Bot Dup
G-l 3-3
G-13-3 Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 5 Top
G-l 5 Top Spk
G-l 7 Top
G-17 Top Spk
G-17 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P DUP
Concentration
ma/ka
82500
79500
32300
84600
29400
28300
38200
81600
41000
87400
85000
74900
45500
96500
55400
107800
33500
60700
37800
91500
43100
43500
39600
100200
55600
42000
83300
85600
79400
81200
62600
85200
231000
169000
44600
84700
38900
42200
85500
26600
23000
112000
105000
%RPD
4%
4%
13%
58%
1%
28%
3%
2%
31%
15%
6%
%R
131%
109%
116%
128%
131%
134%
152%
57%
100%
1 08%
A-13
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Cadmium Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l Mid Dup
G-2Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-l 1 Bot
G-l 1 Bot Spk
G-12Top
G-12TopDup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5DMid
G-5DMidSpk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-13Bot
G-13BotDup
G-14Top
G-14Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-17Top
G-17Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6PDup
Concentration
mg/kg
0.56
0.59
0.37
0.37
0.13
0.21
0.69
0.76
0.21
0.29
1.55
1.06
0.18
0.24
0.03
0.03
0.33
0.40
0.29
0.30
0.45
0.51
0.27
0.28
0.49
0.62
0.16
0.18
0.98
1.06
0.09
0.10
1.83
1.91
2.20
1.64
1.69
1.76
1.13
1.19
%RPD
5%
1%
10%
37%
16%
3%
4%
10%
15%
29%
5%
%R
80%
82%
69%
74%
58%
128%
79%
87%
74%
Chromium Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l Mid Dup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G- 11 Bot
G- 11 Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5DMid
G-5DMidSpk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-13Bot
G-13BotDup
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-6P
G-6PDup
G-20P
G-20P Spk
Concentration
mg/kg
29
199
42
29
12
197
34
37
18
198
877
765
24
196
0.2
0.8
42
274
40
37
59
207
37
37
36
210
25
26
11
350
13
12
92
246
110
85
82
82
70
275
%RPD
36%
8%
14%
102%
6%
0%
5%
4%
26%
1%
%R
85%
92%
90%
86%
116%
74%
87%
170%
77%
102%
A-14
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Copper Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
mg/kg
13.8
199.3
14.1
14.5
4.7
185.3
22 4
24.0
71.6
184.5
99.7
87.4
6.0
166.1
0.9
1.2
17.3
231.5
13.2
11.2
20.2
182.3
11.4
10.8
28.1
211.1
7.8
8.2
3.9
188.1
3.9
3.5
65.0
236.4
88.4
63.1
53.0
314.0
62.0
61.0
352.0
530.0
%RPD
3%
7%
13%
29%
16%
5%
5%
11%
33%
2%
%R
93%
90%
56%
80%
107%
81%
92%
92%
86%
131%
89%
Iron Quality Control Data
Sample
Location
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Top
G-ll Top Spk
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-20 Bot
G-20 Bot Spk
G-20D Mid
G-20D Mid Spk
G-4 Bot
G-4 Bot Dup
G-5 Bot
G-5 Bot Spk
G-5D Bot
G-5D Bot Dup
G-6 Top
G-6 Top Spk
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Bot
G-l 3 Bot Dup
G-l 3-3
G-l 3-3 Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 5 Top
G-l 5 Top Spk
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-6P
G-6P Dup
Concentration
mg/kg
26486
26635
11487
10150
15507
15693
20695
55000
17400
58900
12900
10600
26900
63000
24000
60300
2970
4070
46100
82800
46800
46400
25900
64800
70700
52100
41400
42500
19400
19900
16500
50700
13100
11700
11000
51900
15800
52600
11900
10800
24000
23600
%RPD
1%
12%
1%
20%
31%
1%
30%
3%
3%
11%
10%
2%
%R
86%
104%
90%
91%
92%
97%
86%
102%
92%
A-15
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Mercury Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-lOBot
G-lOBotSpk
G-ll Top
G-ll TopDup
G-23 Top
G-23 Top Dup
G-23 Mid
G-23 Mid Dup
G-5 Bot
G-5 Bot Spk
G-5D Top
G-5D Top Dup
G-22 Top
G-22 Top Spk
G-22-2
G-22-2 Dup
G-9 Bot
G-9 Bot Spk
G-l 3 Top
G-l 3 Top Dup
G-l 5 Mid
G-l 5 Mid Spk
G-l 5 Bot
G-l 5 Bot Dup
G-l 8 Top
G-l 8 Top Spk
G-l 8 Bot
G-l 8 Bot Dup
Concentration
me/kg
0.14
0.44
<0.1
<0.1
<0.1
0.46
0.36
0.14
0.12
0.34
<0.1
<0.1
<0.1
0.69
0.24
0.29
0.22
0.75
<0.1
<0.1
<0.1
0.26
0.31
0.31
0.13
0.32
0.1
0.1
0.1
0.23
O.I
O.I
%RPD
*
*
87%
64%
*
*
18%
*
*
0.00%
*
*
*
*
* RPD Not Calculated. Sample BDL
%R
106%
1 1 8%
91%
106%
117%
113%
105%
Magnesium Quality Control Data
Sample
Location
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Top
G-ll Top Spk
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-20 Bot
G-20 Bot Spk
G-20D Mid
G-20D Mid Spk
G-4 Bot
G-4 Bot Dup
G-5 Bot
G-5 Bot Spk
G-5D Bot
G-5D Bot Dup
G-6 Top
G-6 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Bot
G-l 3 Bot Dup
G-l 3-3
G-l 3-3 Spk
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 5 Top
G-l 5 Top Spk
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-6P
G-6P Dup
Concentration
mg/kg
18300
18100
6980
27900
6090
6340
12200
32200
10500
33200
6950
5890
15200
35100
13200
32400
1280
1750
15500
33700
16300
15400
14500
33500
16300
16100
13800
13900
11300
29500
8220
7180
7710
6810
5550
27400
7880
34000
5240
4910
13000
11400
%RPD
1%
4%
17%
31%
6%
1%
1%
14%
12%
7%
13%
%R
105%
100%
114%
100%
96%
91%
95%
91%
109%
131%
A-16
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Manganese Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
mg/kg
335
478
431
435
298
448
180
192
710
951
357
288
152
312
97.5
164
923
1210
888
897
1050
1223
800
818
167
339
718
743
588
795
682
672
55.7
266.1
36.9
35.9
773
912
1040
1110
629
873
% RPD
1%
6%
21%
51%
1%
2%
3%
1%
3%
7%
%R
72%
75%
121%
80%
144%
87%
86%
104%
105%
70%
122%
Nickel Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
mg/kg
42.1
210.8
22 9
19.9
9.3
176.2
23
25.1
11.7
178.3
59.2
51.7
7.53
184
21.3
264
20.1
19.6
30.3
183.4
21
22.2
18.5
189.4
15.2
16.3
9.9
257
10.5
11
31.8
194
37.2
31.7
35
277
34.4
36.3
28.7
248
% RPD
14%
9%
14%
3%
6%
7%
5%
16%
5%
%R
84%
83%
83%
88%
121%
77%
85%
124%
81%
121%
110%
A-17
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Lead Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G- 11 Bot
G-ll Bot Spk
G-12 Top
G-l 2 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
mg/kg
6.428
9.06
4.384
6.743
2.849
3.382
14.4
17.53
3.755
6.674
72
63.9
4.1
5.509
1.719
1.533
4.885
7.575
6.012
4.531
8.652
11.43
4.368
4.55
26.6
203.3
3.098
3.474
0.975
1.054
30
198.5
43.2
33.4
76.6
276
66.7
63
55.4
243
% RPD
42%
20%
12%
11%
28%
4%
11%
8%
26%
6%
%R
132%
27%
146%
70%
135%
139%
88%
84%
100%
94%
Zinc Quality Control Data
Sample
Location
G-l Top
G-l Top Spk
G-l Mid
G-l MidDup
G-2 Bot
G-2 Bot Spk
G-3 Top
G-3 Top Dup
G-ll Bot
G-ll Bot Spk
G-12 Top
G-12 Top Dup
G-4 Top
G-4 Top Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 Top
G-7 Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Top
G-l 3 Top Spk
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 Top
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 Top
G-l 7 Top Spk
G-l 7 Mid
G-l 7 Mid Dup
G-5P
G-5P Spk
G-6P
G-6P Dup
G-20P
G-20P Spk
Concentration
mg/kg
70
229
72
70
18
193
58
69
38
239
183
148
30
182
2
3
81
301
59
64
112
260
70
72
79
254
38
39
16
189
18
17
88
257
130
85
185
393
191
189
192
423
% RPD
2%
18%
21%
12%
8%
2%
4%
8%
41%
1%
%R
79%
88%
100%
76%
110%
74%
87%
86%
84%
104%
116%
A-18
-------
Table A-7 (continued). Results Of Laboratory Duplicate And Matrix Spike
Analyses For Metals In The Lower Grand River Sediment Samples.
Selenium Quality Control Data
Sample
Location
G-l TOD
G-l Top Spk
G-l Mid
G-l Mid Dup
G-2 Bot
G-2 Bot Spk
G-3 TOP
G-3 Top Dup
G- 11 Bot
G-ll Bot Spk
G-l 2 Top
G-l 2 Top Dup
G-4 Top
G-4 TOP Spk
G-4 Bot
G-4 Bot Dup
G-5D Mid
G-5D Mid Spk
G-5D Bot
G-5D Bot Dup
G-7 TOP
G-l Top Spk
G-7 Mid
G-7 Mid Dup
G-l 3 Bot
G-l 3 Bot Dup
G-l 4 TOP
G-l 4 Top Spk
G-l 4 Mid
G-l 4 Mid Dup
G-l 7 TOP
G-l 7 TOP Spk
G-l 7 Mid
G-l 7 Mid DUP
G-5P
G-5P DUP
Concentration
mg/kg
0.39
0.9
0.34
0.43
0.17
0.59
0.47
0.33
0.33
0.87
0.88
0.55
0.32
0.86
0.03
0.03
0.43
1.03
0.46
0.42
0.66
1.02
0.49
0.37
<0.5
<0.5
<0.5
5.4
<0.5
<0.5
<0.5
4
<0.5
<0.5
<0.5
<0.5
% RPD
23%
35%
46%
0%
9%
28%
*
*
*
*
%R
102%
84%
108%
108%
120%
72%
108%
80%
RPD not calculated. Sample BDL.
A-19
-------
Appendix B
Summary Of PCB Congener And DDT Compound Data For Sediments Collected
From The Lower Grand River
-------
Table B-l Distribution Of Tri, Tetra, And Penta Chlorinated PCB Congeners In The Sediment Core Samples Collected From
The Lower Grand River. October 1997.
Field Sample
ID
G-1 Top
G-1 Mid
G-1 Bot
G-2 Top
G-2 Mid
G-2 Bot
G-3Top
G-3Bot
G^tTop
G^tBot
G-5Top
G-5 Mid
G-5Bot
G-5dup Top
G-5dup Mid
G-5dup Bot
G-6Top
G-6 Mid
G-6Bot
G-7 Top
G-7 Mid
G-7 Bot
G-8Top
G-8 Mid
G-8Bot
Congener Number
17
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
18
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
1
22
Amount
(ng/g)
3
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
28
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
31
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
32
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
33
Amount
(ng/g)
2
<1
<1
<1
4
4
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
44
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
46
Surrogate
%R
76
136
114
63
62
74
63
64
**
70
63
127
46
81
81
54
89
79
80
92
63
55
50
64
57
48
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
52
Amount
(ng/g)
1
<1
<1
2
1
<1
<1
<1
<1
<1
1
1
1
1
2
1
4
1
8
<1
1
<1
1
1
1
59
Amount
(mg/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
70
Amount
(mg/g)
1
<1
1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
87
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
1
2
<1
<1
<1
<1
<1
<1
<1
<1
2
1
<1
<1
<1
<1
<1
<1
<1
97
Amount
(ng/g)
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
2
1
1
1
<1
<1
<1
<1
<1
101
Amount
(ng/g)
2
1
1
1
1
2
1
1
1
1
1
<1
<1
1
1
2
8
3
2
2
3
1
0
1
0
105
Amount
(ng/g)
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
9
<1
<1
<1
<1
<1
1
<1
1
118
Amount
(ng/g)
9
<1
7
3
5
3
<1
<1
1
<1
1
<1
<1
<1
<1
<1
17
2
<1
2
1
<1
3
<1
3
** Surrogate recovery not available due to matrix interference.
-------
Table B-l (continued). Distribution Of Tri, Tetra, And Penta Chlorinated PCB Congeners In The Sediment Core Samples
Collected From The Lower Grand River. October 1997.
Field Sample
ID
G-9 Top
G-9 Mid
G-9 Bot
G-10Top
G-10Bot
G-11Top
G-11 Bot
G-12Top
G-13Top
G-13-2
G-13-3
G-13Bot
G-14Top
G-14 Mid
G-14Bot
G-15Top
G-15 Mid
G-15Bot
G-17Top
G-17Mid
G-17Bot
G-18Top
G-18 Mid
G-18Bot
G-19Top
G-19Bot
Congener Number
17
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
18
Amount
(ng/g)
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
22
Amount
(ng/g)
<1
<1
<1
<1
<1
3
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
0
1
1
1
3
28
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
31
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
32
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
33
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
44
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
3
<1
<1
5
1
<1
<1
2
0
<1
<1
<1
<1
46
Surrogate
%R
48
95
93
62
52
77
48
89
93
«
68
79
91
81
61
83
84
95
141
54
**
74
73
64
75
127
48
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
52
Amount
(ng/g)
1
3
2
2
<1
1
3
<1
1
<1
1
1
1
1
1
1
<1
1
3
1
<1
1
2
2
2
3
59
Amount
(mg/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
70
Amount
(mg/g)
<1
<1
<1
<1
<1
2
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
3
2
<1
<1
1
1
1
1
87
Amount
(ng/g)
<1
2
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
1
<1
<1
<1
1
3
1
97
Amount
(ng/g)
1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
2
2
<1
<1
<1
<1
<1
<1
101
Amount
(ng/g)
1
6
1
2
1
3
1
1
1
<1
1
1
<1
2
1
1
1
1
5
3
1
1
1
2
1
2
105
Amount
(ng/g)
<1
<1
<1
2
<1
3
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
5
3
<1
1
1
2
2
2
118
Amount
(ng/g)
<1
3
3
1
<1
1
3
<1
<1
<1
3
4
<1
<1
<1
<1
2
<1
4
3
1
2
1
2
1
1
** Surrogate recovery not available due to matrix interference
-------
Table B-l (Continued). Distribution Of Tri, Tetra, And Penta Chlorinated PCB Congeners In The Sediment Core Samples
Collected From The Lower Grand River. October 1997.
Field Sample
ID
G-20 Top
G-20 Mid
G-20 Bot
G-20D Top
G-20D Mid
G-20D Bot
G-22 Top
G-22-2
G-22-3
G-22-4
G-22-5
G-23 Top
G-23 Mid
G-23 Bot
G-24 Top
G-24 Mid
G-24 Bot
Congener Number
17
Amount
(ng/g)
3
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
18
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
3
<1
2
<1
1
<1
22
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
<1
28
Amount
(ng/g)
<1
<1
<1
2
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
31
Amount
(ng/g)
<1
2
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
3
32
Amount
(ng/g)
<1
<1
2
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
2
33
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
44
Amount
(ng/g)
2
6
9
3
9
9
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
8
45
Surrogate
%R
51
120
50
78
133
126
68
57
99
58
56
54
67
75
54
84
115
48
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
2
<1
<1
1
<1
52
Amount
(ng/g)
5
12
15
4
15
22
<1
1
1
<1
1
5
1
2
1
5
10
59
Amount
(mg/g)
<1
1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
70
Amount
(mg/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
4
1
87
Amount
(ng/g)
3
7
8
14
7
8
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
<1
97
Amount
(ng/g)
5
7
7
5
6
7
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
1
101
Amount
(ng/g)
12
13
14
12
16
15
2
1
1
1
1
2
<1
<1
1
4
1
105
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
1
<1
4
1
118
Amount
(ng/g)
14
23
20
17
35
29
<1
1
1
<1
<1
6
2
4
1
4
2
** Surrogate recovery not available due to matrix interference
-------
Table B-2. Distribution Of Hexa, Hepta, And Octa Chlorinated PCB Congeners, Total PCBs, And DDT Compounds In The
Sediment Core Samples Collected From The Lower Grand River. October 1997.
Field Sample
ID
G-l Top
G-lMid
G-l Bot
G-2 Top
G-2Mid
G-2 Bot
G-3 Top
G-3 Bot
G-4 Top
G-4 Bot
G-5 Top
G-5Mid
G-5 Bot
G-5dup Top
G-5dup Mid
G-5dup Bot
G-6 Top
G-6Mid
G-6 Bot
G-7 Top
G-7Mid
G-7 Bot
138
Amount
(ng/g)
0
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
1
<1
1
7
1
1
1
1
1
142
Surrogate
%R
57
111
105
108
67
129
45
62
56
150
56
79
89
47
64
92
97
87
91
83
97
109
Congener Number
149
Amount
(ng/g)
2
<1
<1
1
1
1
<1
<1
<1
<1
1
<1
<1
1
<1
1
5
1
<1
<1
<1
<1
151
Amount
(ng/g)
<1
<1
<1
<1
<1
5
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
<1
<1
<1
<1
<1
153
Amount
(ng/g)
4
<1
<1
4
4
4
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
5
<1
<1
<1
<1
<1
155
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
180
Amount
(ng/g)
0
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
3
<1
<1
<1
<1
<1
183
Amount
(ng/g)
2
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
205
Amount
(ng/g)
2
<1
<1
<1
1
1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
Total
PCBs
Amount
(ng/g)
28
1
9
12
18
22
2
3
2
1
6
1
1
4
3
5
66
10
11
7
6
2
DDT Compounds
ODD
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
DDT
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
DDE
Amount
(ng/g)
8
<1
3
<1
<1
<1
<1
<1
<1
<1
3
<1
<1
3
<1
<1
8
<1
<1
2
2
<1
** Surrogate recovery not available due to matrix interference
-------
Table B-2 (Continued). Distribution Of Hexa, Hepta, And Octa Chlorinated PCB Congeners, Total PCBs, And DDT
Compounds In The Sediment Core Samples Collected From The Lower Grand River. October 1997.
Field Sample
ID
G-8 TOD
G-8 Mid
G-8 Bot
G-9 TOD
G-9 Mid
G-9 Bot
G-10 TOD
G-10 Bot
G-ll TOD
G-ll Bot
G-12 TOD
G-13 TOD
G-13-2
G-13-3
G-13 Bot
G-14 TOD
G-14 Mid
G-14 Bot
G-15 TOD
G-15 Mid
G-15 Bot
G-17 TOD
G-17 Mid
G-17 Bot
138
Amount
(na/a)
<1
<1
<1
<1
1
<1
3
<1
2
<1
<1
1
<1
<1
<1
<1
1
<1
<1
1
1
3
2
1
142
Surroaate
%R
108
78
72
73
67
75
120
69
65
123
54
81
64
81
103
81
85
84
88
120
64
103
50
84
Conaener Number
149
Amount
(na/a)
2
<1
2
<1
1
1
1
<1
<1
<1
<1
<1
<1
1
1
1
2
<1
<1
<1
<1
4
3
<1
151
Amount
(na/a)
1
<1
1
<1
<1
<1
<1
<1
1
2
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
1
1
<1
153
Amount
(na/a)
2
<1
3
<1
<1
1
<1
<1
<1
4
<1
<1
<1
1
1
<1
<1
<1
<1
<1
<1
3
2
<1
155
Amount
(na/a)
<1
<1
<1
<1
<1
<1
1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
180
Amount
(na/a)
<1
<1
<1
<1
<1
<1
0
<1
1
<1
<1
<1
<1
<1
<1
<1
4
<1
<1
<1
<1
1
1
<1
183
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
<1
<1
<1
<1
1
205
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
0
<1
<1
<1
<1
<1
3
<1
0
5
<1
1
1
3
Total
PCBs
Amount
(na/a)
12
2
12
3
16
9
12
1
20
15
2
3
<1
9
10
2
17
2
2
14
4
38
25
9
DDT Compounds
ODD
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
2
3
<1
DDT
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
DDE
Amount
(na/a)
1
<1
<1
<1
<1
3
2
<1
2
1
<1
<1
<1
<1
<1
1
<1
<1
<1
1
<1
3
2
<1
** Surrogate recovery not available due to matrix interference
-------
Table B-2 (Continued). Distribution Of Hexa, Hepta, And Octa Chlorinated PCB Congeners, Total PCBs, And DDT
Compounds In The Sediment Core Samples Collected From The Lower Grand River. October 1997.
Field Sample
ID
G-18 Top
G-18Mid
G-18Bot
G-19 TOD
G-19Bot
G-20 Top
G-20 Mid
G-20 Bot
G-20D TOD
G-20D Mid
G-20D Bot
G-22 Top
G-22-2
G-22-3
G-22-4
G-22-5
G-23 TOD
G-23 Mid
G-23 Bot
G-24 TOD
G-24 Mid
G-24 Bot
138
Amount
fna/a)
0
1
1
1
2
8
6
2
8
2
2
2
<1
<1
<1
<1
1
<1
<1
1
3
<1
142
Surroaate
%R
87
68
50
55
84
76
63
103
122
82
97
109
113
68
74
100
97
78
A A
69
62
92
Congener Number
149
Amount
fna/a)
1
1
1
1
1
4
9
13
5
6
12
2
<1
<1
<1
<1
3
1
<1
1
4
1
151
Amount
fna/a)
1
<1
<1
2
1
<1
2
2
2
3
3
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
153
Amount
fna/a)
4
<1
<1
<1
<1
6
7
5
5
15
13
<1
<1
<1
<1
<1
9
1
3
1
3
<1
155
Amount
fna/a)
<1
<1
<1
<1
2
3
<1
<1
4
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
180
Amount
fna/a)
0
0
1
<1
1
4
6
5
4
1
6
1
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
183
Amount
fna/a)
<1
<1
<1
<1
<1
1
2
1
1
9
5
<1
<1
<1
<1
<1
1
1
2
<1
<1
<1
205
Amount
fna/a)
<1
<1
<1
<1
<1
<1
6
3
<1
1
6
<1
<1
<1
<1
<1
1
<1
<1
<1
<1
1
Total
PCBs
Amount
fna/a)
12
9
14
15
20
70
109
106
86
126
137
7
3
3
1
2
34
8
14
6
47
31
DDT Compounds
DDD
Amount
fna/a)
<1
<1
<1
<1
<1
3
14
6
3
14
13
<1
<1
<1
<1
<1
<1
<1
<1
<1
1
1
DDT
Amount
fna/a)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
DDE
Amount
fna/a)
2
1
1
3
2
8
4
7
12
12
10
2
<1
<1
<1
1
5
<1
1
<1
2
1
** Surrogate recovery not available due to matrix interference
-------
Table B-3. Distribution Of PCB Congeners, Total PCBs, And DDT Compounds In The Ponar Samples Collected From The
Lower Grand River. April 1998.
Field Sample
ID
G5-P
G6-P
G7-P
G12-P
G20-P
G20-P Dup
Congener Number
17
Amount
(na/a)
<1
<1
<1
<1
<1
<1
18
Amount
(na/a)
<1
<1
<1
<1
<1
<1
22
Amount
(na/a)
<1
<1
<1
<1
<1
<1
28
Amount
(na/a)
<1
<1
<1
<1
<1
<1
31
Amount
(na/a)
3
<1
<1
<1
<1
<1
32
Amount
(na/a)
2
<1
<1
<1
<1
<1
33
Amount
(na/a)
<1
<1
<1
<1
<1
<1
44
Amount
(na/a)
8
2
5
13
1
10
46
Surroaate
%R
89
97
82
105
82
78
48
Amount
(na/a)
<1
<1
<1
<1
<1
<1
52
Amount
(na/a)
10
1
1
1
2
2
59
Amount
(ma/a)
<1
<1
<1
<1
<1
<1
70
Amount
(ma/a)
1
<1
<1
<1
<1
<1
87
Amount
(na/a)
<1
14
1
1
11
1
97
Amount
(na/a)
1
2
2
2
3
2
101
Amount
(na/a)
1
4
4
4
3
3
105
Amount
(na/a)
1
<1
<1
<1
<1
<1
Table B-3. Distribution Of PCB Congeners, Total PCBs, And DDT Compounds In The Ponar Samples Collected From The
Lower Grand River. April 1998.
Field Sample
ID
G5-P
G6-P
G7-P
G12-P
G20-P
G20-P DUD
138
Amount
Cng/g)
3
4
3
3
2
<1
142
Surrogate
%R
89
57
140
134
62
77
Congener Number
149
Amount
Cng/g)
2
2
2
2
2
2
151
Amount
Cng/g)
<1
<1
<1
<1
<1
<1
153
Amount
Cng/g)
2
2
3
2
2
2
155
Amount
Cng/g)
<1
<1
<1
<1
<1
<1
180
Amount
Cng/g)
11
8
8
1
1
1
183
Amount
Cng/g)
1
1
1
1
<1
<1
205
Amount
Cng/g)
5
<1
<1
<1
<1
<1
Total
PCBs
Amount
Cng/g)
53
36
43
35
29
29
DDT Compounds
ODD
Amount
Cng/g)
4
5
4
2
1
1
DDT
Amount
Cng/g)
<1
<1
<1
<1
<1
<1
DDE
Amount
Cng/g)
3
12
9
13
3
3
-------
Table B-4. Results Of Matrix Spiked Sample Analyses For The Grand River
Sediments
Initial Concentration
G2 Bot
G3-Bot
G4-Top
G7-Mid
G10-Bot
CIS-Top
52
Amount
(nq/q)
<1
<1
<1
1
<1
<1
44
Amount
(nq/q)
<1
<1
<1
<1
<1
<1
101
Amount
(nq/q)
1
1
<1
3
<1
<1
DDE
Amount
(nq/q)
<1
<1
<1
2
<1
<1
153
Amount
(nq/q)
4
<1
<1
<1
<1
<1
138
Amount
(nq/q)
<1
<1
<1
1
<1
<1
180
Amount
(nq/q)
<1
<1
<1
<1
<1
<1
205
Amount
(nq/q)
1
<1
<1
<1
<1
<1
Concentration After Spike Addition
Sample ID
G2 Bot
G3-Bot
G4-Top
G7-Mid
G10-Bot
G15-Top
52
Amount
(nq/q)
2.35
1.85
2.56
2.06
2.08
1.45
44
Amount
(nq/q)
2.05
2.33
1.93
3.09
2.31
2.00
101
Amount
(nq/q)
1.47
1.42
0.50
1.24
1.42
1.17
DDE
Amount
(nq/q)
1.62
2.4
1.18
2.1
2.6
1.72
153
Amount
(nq/q)
.
1.14
1.60
1.48
1.05
1.73
138
Amount
(nq/q)
0.93
1.48
0.97
1.75
1.44
1.04
180
Amount
(nq/q)
0.91
1.28
0.81
1.48
1.13
0.90
205
Amount
(nq/q)
0.88
0.88
0.85
1.3
0.75
0.65
Amount Spiked
52
Amount
(nq/q)
2.2
44
Amount
(nq/q)
2.2
101
Amount
(nq/q)
1.0
DDE
Amount
(nq/q)
1.5
153
Amount
(nq/q)
1.0
138
Amount
(nq/q)
1.0
180
Amount
(nq/q)
1.1
205
Amount
(nq/q)
1.1
Spiked Recovery
Sample
Location
G2 Bot
G3-Bot
G4-Top
G7-Mid
G10-Bot
G15-Top
Conqener Number
52
Amount
% Recovery
107
84
116
64
65
66
44
Amount
% Recovery
93
106
88
140
105
91
101
Amount
% Recovery
147
142
50
31
142
117
DDE
Amount
% Recovery
108
160
79
60
173
115
153
Amount
% Recovery
0
1
160
148
105
173
138
Amount
% Recovery
93
148
97
88
144
104
180
Amount
% Recovery
83
116
74
135
103
82
205
Amount
% Recovery
0
1
77
118
68
59
-------
Table B-4. Results Of Matrix Duplicate Sample Analyses For The Grand River
Sediments
Field
Sample
ID
G4-Top
G4-Top Dup
G4-Bot
G4-Bot Dup
G22-4
G22-4 Dup
G8-Mid
G8-Mid Dup
G9-Top
G9-Top Dup
G13-Top
G13-TopDup
G15-Top
G15-TopDup
Congener Number
52
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
1
<1
1
1
1
<1
1
<1
44
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
1
<1
1
<1
1
<1
1
101
Amount
(ng/g)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
153
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
138
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
1
<1
1
1
<1
<1
180
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
205
Amount
(ng/g)
1
2
<1
<1
<1
<1
<1
2
<1
1
<1
4
<1
<1
DDE
Amount
(ng/g)
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
B-9
-------
Table B-5. Results Of Method Blanks And Laboratory Control Sample Analyses
For The Grand River Sediments.
Method Blanks
Sample ID
BK1
BK2
BK3
BK4
BK5
BK6
BK7
52
Amount
(na/a)
1
<1
<1
1
<1
<1
1
44
Amount
(na/a)
1
1
<1
<1
1
<1
1
101
Amount
(na/a)
1
<1
1
<1
<1
<1
1
DDE
Amount
(na/a)
1
<1
<1
<1
<1
<1
1
153
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
138
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
180
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
205
Amount
(na/a)
<1
<1
<1
<1
<1
<1
<1
Laboratory Control Samples
Sample ID
LCS1
LCS2
LCS3
LCS4
LCS5
LCS6
LCS7
52
Amount
(na/a)
2.6
2.6
2.5
2.1
2.1
2.3
2.3
44
Amount
(na/a)
2.4
2.5
1.7
1.9
2.3
1.9
2.0
101
Amount
(na/a)
1.6
1.6
1.2
1.3
1.3
1.4
1.5
DDE
Amount
(na/a)
1.6
1.9
1.2
1.7
1.3
1.4
1.9
153
Amount
(na/a)
1.7
2.0
1.3
1.5
1.5
1.6
1.5
138
Amount
(na/a)
1.1
1.1
0.8
0.9
0.9
0.9
0.9
180
Amount
(na/a)
1.0
1.0
0.7
0.8
0.8
0.8
0.9
205
Amount
(na/a)
1.0
1.0
0.7
0.8
0.8
0.9
0.8
Amount Spiked
52
Amount
(na/a)
2.2
44
Amount
(na/a)
2.2
101
Amount
(na/a)
1.0
DDE
Amount
(na/a)
1.6
153
Amount
(na/a)
1.1
138
Amount
(na/a)
1.0
180
Amount
(na/a)
1.1
205
Amount
(na/a)
1.1
Laboratory Control Sample Spiked Recovery
Sample
Location
LCS1
LCS2
LCS3
LCS4
LCS5
LCS6
LCS7
Conaener Number
52
Amount
% Recovery
118
118
114
95
95
105
105
44
Amount
% Recovery
109
114
77
86
105
86
91
101
Amount
% Recovery
160
160
120
130
130
140
150
DDE
Amount
% Recovery
100
119
75
106
81
88
119
153
Amount
% Recovery
155
182
118
136
136
145
136
138
Amount
% Recovery
110
110
80
90
90
90
90
180
Amount
% Recovery
91
91
64
73
73
73
82
205
Amount
% Recovery
91
91
64
73
73
82
73
B-10
-------
Appendix C
Summary Of Semivolatile Organic And TPH Data For Sediments Collected From
The Lower Grand River
-------
Table C-1. Semivolatile Organics Results for Sediment Cores Collected from the Lower Grand River
Station
Core Section
Hexane Extractable Materials
Phenol
Bis(2-chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
4-Methylphenol
Hexachloroethane
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Dimethylphthalate
Acenaphthylene
Acenaphthene
Diethylphthalate
4-Chlorophenyl-phenyl ether
Fluorene
4,6-Dinitro-2-methylphenol
4-Bromophenyl-phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butyl benzylphthalate
Benzo(a)anthracene
Chrysene
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1,2,3-cd)pyrene
Dibenzo(a, h)anthracene
Benzo(g,h,i)perylene
3-Methylphenol
Surrogate Standards
Nitrobenzene-d5
2-Fluorobiphenyl
o-Terphenyl
Phenol-d6
2-Fluorophenol
2,4,6-Tribromophenol
G-1
Top
mg/kg
900
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
78
85
77
70
69
72
G-1
Mid
mg/kg
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
60
79
88
70
74
68
G-1
Bottom
mg/kg
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
62
84
74
68
74
75
G-2
Top
mg/kg
60
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
78
77
70
77
69
88
G-2
Mid
mg/kg
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
71
81
88
63
67
78
G-2
Bottom
mg/kg
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
78
77
70
77
69
88
G-12
Top
mg/kg
2000
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
1.4
0.36
0.33
2.9
2.8
0.33
1.1
0.88
0.33
O.33
0.54
0.33
0.71
O.33
0.33
O.33
O.33
Recovery
62
84
74
68
74
75
G-4
Top
mg/kg
400
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
72
68
66
77
68
68
G-4
Bottom
mg/kg
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
Recovery
75
81
73
69
72
83
C-1
-------
Table C-1 (continued). Semivolatile Organics Results for Sediment Cores Collected from the Lower Grand River
Station
Core Section
Hexane Extractable Materials
Phenol
Bis(2-chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methyl phenol
4-Methyl phenol
Hexachloroethane
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-methyl phenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Dimethylphthalate
Acenaphthylene
Acenaphthene
Diethylphthalate
4-Chlorophenyl-phenyl ether
Fluorene
4,6-Dinitro-2-methylphenol
4-Bromophenyl-phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butyl benzylphthalate
Benzo(a)anthracene
Chrysene
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
3-Methyl phenol
Surrogate Standards
Nitrobenzene-d5
2-Fluorobiphenyl
o-Terphenyl
Phenol-d6
2-Fluorophenol
2,4,6-Tribromophenol
G-20
Top
mg/kg
4000
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.62
0.08
0.33
1.40
1.38
0.33
0.39
0.51
0.33
O.33
0.35
<0.33
0.37
<0.33
<0.33
<0.33
0.33
Recovery
78
84
78
53
77
70
G-20
Mid
mg/kg
6000
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.81
<0.33
0.33
2.04
1.60
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
0.33
Recovery
64
87
66
58
83
57
G-20
Bottom
mg/kg
2000
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.72
0.11
0.33
1.96
1.68
0.33
0.48
0.62
0.33
O.33
<0.33
<0.33
0.37
<0.33
<0.33
<0.33
0.33
Recovery
90
81
79
69
89
71
G-20 Dup
Top
mg/kg
3500
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.90
0.12
0.33
2.31
2.10
0.33
0.51
0.64
0.33
O.33
<0.33
<0.33
0.48
<0.33
<0.33
<0.33
0.33
Recovery
75
73
71
58
73
50
G-20 Dup
Mid
mg/kg
3500
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
1.02
0.12
0.33
2.20
2.10
0.33
0.57
0.78
0.33
O.33
0.85
0.12
0.50
<0.33
<0.33
<0.33
0.33
Recovery
84
87
79
55
82
50
G-20 Dup
Bottom
mg/kg
2000
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.66
0.09
0.33
1.73
1.73
0.33
0.63
0.28
0.33
O.33
0.71
<0.33
0.35
<0.33
<0.33
<0.33
0.33
Recovery
71
90
67
64
76
54
G-8
Top
mg/kg
400
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
0.41
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
Recovery
82
83
62
55
61
58
G-8
Mid
mg/kg
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
Recovery
71
67
58
54
85
57
G-8
Bottom
mg/kg
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
0.33
O.33
0.33
0.33
O.33
0.33
O.33
O.33
0.33
Recovery
90
66
80
52
85
66
C-2
-------
Table C-1 (continued). Semivolatile Organics Results for Sediment Cores Collected from the Lower Grand River
Station
Core Section
Hexane Extractable Materials
Phenol
Bis(2-chloroethyl)ether
2-Chlorophenol
1,3-Dichloro benzene
1,4-Dichloro benzene
1,2-Dichloro benzene
2-Methylphenol
4-Methylphenol
Hexachloroethane
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Dimethylphthalate
Acenaphthylene
Acenaphthene
Diethylphthalate
4-Chlorophenyl-phenyl ether
Fluorene
4,6-Dinitro-2-methylphenol
4-Bromophenyl-phenyl ether
Hexach lorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
Benzo(a)anthracene
Chrysene
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
3-Methylphenol
Surrogate Standards
Nitrobenzene-d5
2-Fluorobiphenyl
o-Terphenyl
Phenol-d6
2-Fluorophenol
2,4,6-Tribromophenol
G-9
Top
mg/kg
200
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
74
82
78
61
64
62
G-9
Mid
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
62
77
69
54
78
53
G-9
Bottom
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
78
74
73
67
61
59
G-22
Top
mg/kg
780
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
89
65
55
65
73
51
G-22
2
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
62
80
78
63
61
53
G-22
3
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
87
61
61
58
72
64
G-22
4
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
74
74
78
64
88
59
G-22
5
mg/kg
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
Recovery
75
67
59
51
80
59
c-:
-------
Table C-1 (continued). Semivolatile Organics Results for Sediment Cores Collected from the Lower Grand River
Station
Core Section
Hexane Extractable Materials
Phenol
Bis(2-chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methyl phenol
4-Methyl phenol
Hexachloroethane
Isophorone
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-methyl phenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
2-Chloronaphthalene
Dimethylphthalate
Acenaphthylene
Acenaphthene
Diethylphthalate
4-Chlorophenyl-phenyl ether
Fluorene
4,6-Dinitro-2-methylphenol
4-Bromophenyl-phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
Benzo(a)anthracene
Chrysene
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
lndeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
3-Methylphenol
Surrogate Standards
Nitrobenzene-d5
2-Fluorobiphenyl
o-Terphenyl
Phenol-d6
2-Fluorophenol
2,4,6-Tribromophenol
G-13
Top
mg/kg
900
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
0.30
0.10
0.33
1.04
1.32
0.33
0.70
0.53
0.33
O.33
0.42
<0.33
0.49
<0.33
<0.33
<0.33
O.33
Recovery
81
89
59
53
73
74
G-13
2
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
0.41
0.42
0.33
O.33
0.33
0.33
O.33
0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
81
85
70
63
65
58
G-13
3
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
79
60
80
54
64
61
G-13
Bottom
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
73
80
58
76
84
76
G-6
Top
mg/kg
1100
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
1.18
<0.33
0.33
3.14
3.20
0.33
0.88
<0.33
0.33
O.33
0.97
<0.33
0.52
<0.33
<0.33
<0.33
O.33
Recovery
64
86
80
58
73
56
G-6
Mid
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
0.27
<0.33
0.33
0.63
0.56
0.33
O.33
0.35
0.33
O.33
0.24
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
87
70
76
66
62
78
G-6
Bottom
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
67
69
77
59
69
63
G-7
Top
mg/kg
800
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
86
67
62
66
65
69
G-7
Mid
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
81
76
77
65
83
69
G-7
Bottom
mg/kg
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
O.33
0.33
O.33
0.33
O.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
<0.33
<0.33
0.33
O.33
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
O.33
Recovery
78
85
77
70
69
72
C-4
-------
Table C-2. Semivolatile Organics Results for Ponar Samples Collected from the Lower Grand River
Station G5-P G6-P G7-P G12-P G20-P G20-P Dup
mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
Phenol O.33 O.33 O.33 O.33 O.33 O.33
Bis(2-chloroethyl)ether <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2-Chlorophenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
1,3-Dichlorobenzene <0.33 <0.33 <0.33 <0.33 <0.33 0.33
1,4-Dichlorobenzene <0.33 <0.33 <0.33 <0.33 <0.33 0.33
1,2-Dichlorobenzene <0.33 <0.33 O.33 <0.33 <0.33 <0.33
2-Methylphenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
4-Methylphenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Hexachloroethane <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Isophorone <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2,4-Dimethylphenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Bis(2-chloroethoxy)methane <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2,4-Dichlorophenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
1,2,4-Trichlorobenzene <0.33 O.33 <0.33 <0.33 <0.33 <0.33
Naphthalene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Hexachlorobutadiene <0.33 <0.33 <0.33 <0.33 <0.33 0.33
4-Chloro-3-methylphenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2-Methylnaphthalene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Hexachlorocyclopentadiene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2,4,6-Trichlorophenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2,4,5-Trichlorophenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
2-Chloronaphthalene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Dimethylphthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Acenaphthylene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Acenaphthene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Diethylphthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
4-Chlorophenyl-phenyl ether <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Fluorene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
4,6-Dinitro-2-methylphenol <1.7 <1.7 <1.7 <1.7 <1.7 <1.7
4-Bromophenyl-phenyl ether <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Hexachlorobenzene <0.33 <0.33 <0.33 <0.33 <0.33 0.33
Pentachlorophenol <1.7 <1.7 <1.7 <1.7 <1.7 <1.7
Phenanthrene <0.33 1.5 0.56 1.6 0.75 0.55
Anthracene <0.33 <0.33 <0.33 0.49 <0.33 <0.33
Di-n-butylphthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Fluoranthene O.33 3.5 0.41 3.7 1.2 1.3
Pyrene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Butylbenzylphthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Benzo(a)anthracene <0.33 0.91 <0.33 1.34 0.43 0.39
Chrysene <0.33 <0.33 O.33 0.95 0.51 0.65
Bis(2-ethylhexyl)phthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Di-n-octylphthalate <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Benzo(b)fluoranthene <0.33 0.84 <0.33 0.73 0.35 0.42
Benzo(k)fluoranthene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Benzo(a)pyrene <0.33 0.69 O.33 0.81 0.37 0.33
lndeno(1,2,3-cd)pyrene O.33 <0.33 <0.33 <0.33 <0.33 O.33
Dibenzo(a,h)anthracene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Benzo(g,h,i)perylene <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
3-Methylphenol <0.33 <0.33 <0.33 <0.33 <0.33 <0.33
Surrogate Standards % % % % % %
Recovery Recovery Recovery Recovery Recovery Recovery
Nitrobenzene-d5 71 84 89 85 60 87
2-Fluorobiphenyl 74 75 62 60 89 71
o-Terphenyl 67 69 57 78 77 79
Phenol-d6 67 74 80 56 62 67
2-Fluorophenol 66 83 68 88 89 68
2,4,6-Tribromophenol 64 76 68 51 55 67
C-5
-------
Table C-3. Semivolatile Organics Matrix Spike and Matrix Spike Duplicate Results.
1,2,4-Trichlorobenzene
Acenaphthene
Pyrene
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
1,2,4-Trichlorobenzene
Acenaphthene
Pyrene
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
1,2,4-Trichlorobenzene
Acenaphthene
Pyrene
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
G-1
Top
Initial
mg/kg
0.33
0.33
0.33
0.33
<1.7
0.33
0.33
0.33
G-8
Top
Initial
mg/kg
0.33
0.33
0.33
0.33
<1.7
0.33
0.33
0.33
G5-P
Top
Initial
mg/kg
0.33
0.33
0.33
0.33
<1.7
0.33
0.33
0.33
G-1 MS
Top
Spiked
Amount
(mg/kg)
5.6
5.6
5.6
5.6
22.4
11.2
11.2
11.2
G-8MS
Top
Spiked
Amount
(mg/kg)
6.7
6.7
6.7
6.7
26.6
13.3
13.3
13.3
G5-P MS
Top
Spiked
Amount
(mg/kg)
6.3
6.3
6.3
6.3
25.2
12.6
12.6
12.6
G-1 MS
Top
Measured
mg/kg
4.3
4.1
4.6
4.8
9.7
7.1
8.8
7.5
G-8MS
Top
Measured
mg/kg
3.9
4.6
5.1
4.2
13
9.3
8.7
8.8
G5-P MS
Top
Measured
mg/kg
4.5
5.2
5.8
4.9
15
8.8
9.3
8.4
G-1MS
Top
%
Recovery
77
73
82
86
43
63
79
67
G-8MS
Top
%
Recovery
59
69
77
63
49
70
65
66
G5-P MS
Top
%
Recovery
71
83
92
78
60
70
74
67
G-1MSD
Top
Spiked
Amount
(mg/kg)
5.6
5.6
5.6
5.6
22.4
11.2
11.2
11.2
G-8MSD
Top
Spiked
Amount
(mg/kg)
6.7
6.7
6.7
6.7
26.6
13.3
13.3
13.3
G5-P MSD
Top
Spiked
Amount
(mg/kg)
6.3
6.3
6.3
6.3
25.2
12.6
12.6
12.6
G-1 MSD
Top
Measured
mg/kg
5.1
5.4
4.9
4.7
9.5
7.5
7.8
7.1
G-8MSD
Top
Measured
mg/kg
4.3
6.1
5.4
5.0
15
10
9.8
9.6
G5-P MSD
Top
Measured
mg/kg
4.6
5.6
5.0
5.8
18
9.1
8.7
7.5
G-1 MSD
Top
%
Recovery
91
96
88
84
42
67
70
63
G-8MSD
Top
%
Recovery
65
92
81
75
56
75
74
72
G5-P MSD
Top
%
Recovery
73
89
79
92
71
72
69
60
RPD
17
27
6
2
2
5
12
5
RPD
10
28
6
17
14
7
12
9
RPD
2
7
15
17
18
3
7
11
C-6
-------
Appendix D
Summary Of Chemical Measurements For The Toxicity Test With Sediments From
The Lower Grand River
-------
HA-980526
Grand River Sediment
Test No:
Toxicant:
Organism: Hvalella azteca
Analyst: sm, jb.rr
Test Start: 05/12/98
1500
Test Stop: 05/23/98 1500
Table D-l. Summary of Initial and Final Chemical Measurements for the
Hyolella azteca Sediment Toxicity Tests
Sample
G5-P
G6-P
G7-P
G12-P
G20-P
G20-P
Dup
Parameter
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
Day
0
7.8
380
120
160
1.1
7.6
350
130
146
1.4
7.5
370
130
167
1.8
7.7
390
130
155
1.6
7.8
350
130
152
1.2
7.7
360
143
163
1.1
10
7.5
350
100
136
0.6
7.4
340
99
132
0.83
7.3
350
122
146
0.65
7.4
340
110
144
0.78
7.5
350
120
144
0.78
7.6
330
134
156
0.74
Difference
(%)
0
8
17
15
45
3
3
24
10
41
3
5
6
13
64
4
13
15
7
51
4
0
8
5
35
1
8
6
4
33
D-l
-------
Test No:
Toxicant:
Organism:
HA-98052601
Grand River Sediment
Hyalella azteca
Analyst: sm, jb. rr
Test Start: 05/12/98 1500
Test Stop: 05/23/98 1500
Table D-2. Summary of the Daily Chemical Measurements for the
Hyalella azteca Sediment Toxicity Tests.
Sample:
G5-P
Temo (°C)
D.O. ma/I
Day (AM)
0
22.0
8.4
1
22.0
8.4
2
22.0
8.4
3
22.0
8.3
4
22.0
8.4
5
22.0
8.4
6
22.0
8.4
7
23.0
8.0
8
23.0
8.2
9
23.0
8.3
10
23.0
8.4
Sample:
G6-P
Temo (°C)
D.O. ma/I
Day (AM)
0
23.0
6.6
1
22.0
6.8
2
22.0
6.3
3
22.0
3.7
4
220
6.4
5
220
6.6
6
22.0
6.8
7
22.0
6.3
8
23.0
6.9
9
23.0
7.0
10
23.0
7.6
Sample:
G7-P
Temo (°C)
D.O. ma/I
Day (AM)
0
22.0
6.8
1
22.0
6.0
2
22.0
6.3
3
22.0
6.7
4
22.0
5.9
5
22.0
6.1
6
22.0
5.3
7
23.0
5.4
8
23.0
6.6
9
23.0
7.2
10
23.0
7.8
Sample:
G12-P
Temp (°C)
D.O. ma/I
Day (AM)
0
220
6.2
1
220
6.3
2
22.0
6.4
3
22.0
6.2
4
220
5.8
5
220
6.3
6
22.0
5.8
7
23.0
6.9
8
23.0
5.4
9
23.0
7.0
10
23.0
7.6
Sample:
G20-P
Temo (°C)
D.O. ma/I
Day (AM)
0
220
6.5
1
220
6.1
2
22.0
6.1
3
22.0
6.3
4
220
6.0
5
220
5.9
6
22.0
5.7
7
23.0
6.2
8
23.0
6.5
9
23.0
7.4
10
23.0
7.3
Sample:
G20-P Dup
Temo (°C)
D.O. ma/I
Day (AM)
0
22.0
5.9
1
22.0
5.8
2
22.0
5.7
3
22.0
5.9
4
22.0
6.3
5
22.0
6.2
6
22.0
6.3
7
23.0
7.0
8
23.0
7.5
9
23.0
7.4
10
23.0
7.5
D-2
-------
HA-980526
Grand River Sediment
Test No:
Toxicant:
Organism: Chironomus tentans
Analyst: sm, jb.rr
Test Start: 05/12/98
1500
Test Stop: 05/23/98 1500
Table D-3. Summary of Initial and Final Chemical Measurements for
the Chironomus tentans Sediment Toxicity Tests
Sample
G5-P
G6-P
G7-P
G12-P
G20-P
G20-P
Dup
Parameter
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
PH
Conductivity (umhos/cm)
Alkalinity (mg/l CaCOS)
Hardness (mg/l CaCOS)
Ammonia (mg/l NH3)
Day
0
7.8
380
120
155
1
7.6
365
140
150
1.3
7.5
370
140
174
1.5
7.6
380
145
155
1.7
7.8
360
145
150
1.1
7.7
370
155
159
1.1
10
7.6
360
100
140
0.6
7.4
350
110
138
0.8
7.4
360
134
158
0.8
7.4
350
115
140
0.68
7.6
350
130
145
0.8
7.6
340
140
142
0.7
Difference
(%)
0
5
17
10
40
3
4
21
8
38
1
3
4
9
47
3
8
21
10
60
3
3
10
3
27
1
8
10
11
36
D-3
-------
Test No:
Toxicant:
Organism:
HA-98052601
Grand River Sediment
Chironomus tentans
Analyst: sm, jb. rr
Test Start:
Test Stop: 05/23/98 1500
05/12/98 1500
Table D-4. Summary of the Daily Chemical Measurements for the
Chironomus tentans Sediment Toxicity Tests
Sample:
G5-P
Temp (°C)
D.O. mg/l
Day (AM)
0
22.0
8.4
1
22.0
8.4
2
22.0
8.4
3
22.0
8.3
4
22.0
8.4
5
22.0
8.4
6
22.0
8.4
7
23.0
8.0
8
23.0
8.2
9
23.0
8.3
10
23.0
8.4
Sample:
G6-P
Temp (°C)
D.O. mg/l
Day (AM)
0
23.0
6.6
1
22.0
6.8
2
22.0
6.3
3
22.0
3.7
4
22.0
6.4
5
22.0
6.6
6
22.0
6.8
7
22.0
6.3
8
23.0
6.9
9
23.0
7.0
10
23.0
7.6
Sample:
G7-P
Temp (°C)
D.O. mg/l
Day (AM)
0
22.0
6.8
1
22.0
6.0
2
22.0
6.3
3
22.0
6.7
4
22.0
5.9
5
22.0
6.1
6
22.0
5.3
7
23.0
5.4
8
23.0
6.6
9
23.0
7.2
10
23.0
7.8
Sample:
G12-P
Temp (°C)
D.O. mg/l
Day (AM)
0
22.0
6.2
1
22.0
6.3
2
22.0
6.4
3
22.0
6.2
4
22.0
5.8
5
22.0
6.3
6
22.0
5.8
7
23.0
6.9
8
23.0
5.4
9
23.0
7.0
10
23.0
7.6
Sample:
G20-P
Temp (°C)
D.O. mg/l
Day (AM)
0
22.0
6.5
1
22.0
6.1
2
22.0
6.1
3
22.0
6.3
4
22.0
6.0
5
22.0
5.9
6
22.0
5.7
7
23.0
6.2
8
23.0
6.5
9
23.0
7.4
10
23.0
7.3
Sample:
G20-P Dup
Temp (°C)
D.O. mg/l
Day (AM)
0
22.0
5.9
1
22.0
5.8
2
22.0
5.7
3
22.0
5.9
4
22.0
6.3
5
22.0
6.2
6
22.0
6.3
7
23.0
7.0
8
23.0
7.5
9
23.0
7.4
10
23.0
7.5
D-4
-------
Appendix E
Summary Of Reference Toxicity Test For The Sediments From The Lower Grand River
-------
1.0 INTRODUCTION
This report contains the reference toxicity methods and data interpretation for the 96 hour
acute tests for Hyalella azteca and Chironomus tentans when exposed to various concentrations
of sodium chloride (NaCl).
2.0 PROCEDURES AND METHODS
Two 96 hour acute static renewal survival tests were performed with both Hyalella azteca
and Chironomus tentans. Methods as outlined in EPA-600/R-94/002 were followed. The
toxicity tests were initiated on June 1, 1998 and completed on June 5, 1998.
2.1 Laboratory Water Supply
A moderately hard well water was employed for H. azteca and C. tentans cultures. The
moderately hard well water was used to make up the various concentrations of sodium chloride
for exposures of//, azteca and C. tentans.
2.2 Test Organisms
H. azteca and C. tentans used in these reference experiments were from the same stock as
those organisms employed in the sediment toxicity tests. The H. azteca used were 7-14 days old
and C. tentans were third instar larvae and 12 to 14 days old.
2.3 Experimental Design
The purpose of this series of tests was to evaluate the "relative sensitivity" of both
organisms to our reference toxicant, sodium chloride. H. azteca were exposed to five different
concentrations of NaCl and one control with 10 replicates, one organism per replicate, for each
treatment. The organisms were fed O.lml of YCS at the beginning of the test and after 48 hours.
Renewal of the exposure solutions occurred after 48 hours. The C. tentans tests followed the
same procedure as described above, except the concentrations of NaCl were different and the
organisms were fed 0.25ml of Tetrafin® (4 g/L suspension) on day 0 and 2. Routine parameters
were measured prior to the transfer of organisms to their respective exposure vessels and at the
end of the test.
2.4 Statistical Analysis
Survival data for all tests were normally distributed according to Chi-square analysis, as a
result, estimated ECso values were calculated using the Probit model.
3.0 RESULTS AND DISCUSSION
Reference toxicity evaluations with both organisms began on June 1, 1998. The results
of the reference toxicity tests are given in Tables E-l-E-4. Statistical analyses are presented in
Tables E-5-E-8. All tests satisfied the validity requirement of 90% survival in the control. The
routine physical-chemical parameters varied little over the test periods, the data are presented in
E-l
-------
Tables E-l and E-2. Fo H. azteca and Tables E-3 and E-4 for C. tentans. Dissolved oxygen for
H. azteca increased over the test period. As expected, conductivity increased with increasing
NaCl concentrations.
3.1 Hyalella azteca
Survival data for this organism are presented in test numbers Tables E-l and E-2. The
Probit model calculated a 96 hour ECso values of 3.72 g/L NaCl with a 95% confidence interval
ranging from 3.20 g/L - 4.31 g/1 NaCl for the first test. An EC50 value of 4.04g/L with a 95%
confidence interval of 3.76 to 4.34g/L NaCl was obtained for the second test. Statistical analyses
are presented in Tables E-5 and E-6.
3.2 Chironomus tentans
Survival and chemistry results are presented in Tables E-3 and E-4 for this organism.
The resulting 96 hour ECso values and 95% confidence intervals were calculated using the Probit
model and are 7.84g/L NaCl, [7.43, 8.28] for the first test and 7.51 g/L NaCl, [6.78, 8.31] for the
second test. Statistical analyses are presented in Tables E-7 and E-8.
4.0 SUMMARY
Separate reference toxicity tests with Hyalella azteca and Chironomus tentans were
carried out with sodium chloride. Both sets of tests proved valid since 90% or greater survival in
the controls was achieved after the four day period. In addition, it was determined that the
amphipod, H. azteca is more sensitive to sodium chloride than the dipteran, C. tentans based on
the EC50.
E-2
-------
Test No.
Toxicant:
HA-RT-60198-1
Sodium Chloride
Test Species: Hyalella azteca
EC Calculation Method: Probit
Table E-l. Summary Of Results Of Reference Toxicity Test #1 For
Hyalella Azteca.
Analyst: SM, JB, RR
Test Start-6/01798 1400
Date/Time:
Test Stop - 6/05/98 1400
Date/Time:
Ohr
Concentration (g/l)
No. of Individuals
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l as CaCOS)
Hardness (mg/l as CaCOS)
Control
10
24
7.9
8.1
280
190
216
2.0
10
24
8.1
8.0
3200
2.8
10
24
8.2
8.0
4700
3.6
10
24
7.8
7.9
6000
4.4
10
24
8.1
8.0
7200
5.2
10
24
8.2
7.9
8500
48 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Control
10
23
8.4
8.1
280
2.0
10
23
8.4
8.0
3300
2.8
10
23
8.4
8.2
4900
3.6
10
23
8.4
8.1
6100
4.4
8
23
8.3
8.0
7300
5.2
7
23
8.3
8.0
8800
96 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
PH
Conductivity (umhos/cm)
Control
10
23
8.6
8.1
310
2.0
9
23
8.4
7.9
3400
2.8
8
23
8.4
7.9
5000
3.6
7
23
8.4
7.9
7100
4.4
3
23
8.4
7.9
7400
5.2
0
23
8.5
7.9
8900
E-2
-------
Test No.
Toxicant:
HA-RT-60198-2
Sodium Chloride
Test Species: Hyalella azteca
EC Calculation Method: Probit
Table E-2. Summary Of Results Of Reference Toxicity Test #2 For
Hyalella Azteca.
Analyst: SM, JB, RR
Test Start-6/01798 1400
Date/Time:
Test Stop - 6/05/98 1400
Date/Time:
Ohr
Concentration (g/l)
No. of Individuals
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l as CaCOS)
Hardness (mg/l as CaCOS)
Control
10
24
7.9
8.1
280
190
216
2.0
10
24
7.9
8.0
3200
2.8
10
24
7.7
7.9
4700
3.6
10
24
7.8
7.9
5900
4.4
10
24
7.9
7.9
7200
5.2
10
24
8.0
7.9
8500
48 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
PH
Conductivity (umhos/cm)
Control
10
23
8.1
8.1
260
2.0
10
23
8.2
8.0
3300
2.8
10
23
8.1
8
4920
3.6
10
23
8.2
7.9
6100
4.4
9
23
8.3
7.9
7450
5.2
6
23
8.1
7.9
9090
96 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Control
10
24
8.4
8.2
320
2.0
10
24
8.4
8.1
3500
2.8
10
24
8.1
8.1
5200
3.6
8
24
8.5
8.1
6500
4.4
3
24
8.3
8.0
7600
5.2
0
24
8.5
8.0
9070
E-4
-------
Test No.
Toxicant:
CT-RT-60198-1
Sodium Chloride
Test Species: Chironomus tentans
EC Calculation Method: Probit
Table E-3. Summary Of Results Of Reference Toxicity Test #1 For
Chironomus Tentans.
Analyst: SM, JB, RR
Test Start-6/01798 1400
Date/Time:
Test Stop - 6/05/98 1400
Date/Time:
Ohr
Concentration (g/l)
No. of Individuals
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l as CaCOS)
Hardness (mg/l as CaCOS)
Control
10
24
7.9
8.1
280
190
216
6.0
10
24
8.2
7.7
8900
7.0
10
24
8.0
7.7
9400
8.0
10
24
8.2
7.7
12000
9.0
10
24
7.8
7.7
1300
10.0
10
24
8.1
7.7
1400
48 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
PH
Conductivity (umhos/cm)
Control
10
24
7.8
8.1
290
6.0
10
24
7.8
8.0
9100
7.0
10
24
7.4
7.9
9600
8.0
10
24
7.4
7.9
12100
9.0
10
24
75
7.9
13000
10.0
6
24
7.4
7.9
14100
96 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Control
10
23
7.6
8.0
210
6.0
10
23
7.7
7.9
9200
7.0
8
23
7.5
7.9
9600
8.0
5
23
7.4
7.7
12700
9.0
1
23
7.7
7.7
13200
10.0
0
23
7.6
7.6
15000
E-5
-------
Test No.
Toxicant:
CT-RT-60198-2
Sodium Chloride
Test Species: Chironomus tentans
EC Calculation Method: Probit
Table E-4. Summary Of Results Of Reference Toxicity Test #2 For
Chironomus Tentans.
Analyst: SM, JB, RR
Test Start-6/01798 1400
Date/Time:
Test Stop - 6/05/98 1400
Date/Time:
Ohr
Concentration (g/l)
No. of Individuals
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Alkalinity (mg/l as CaCOS)
Hardness (mg/l as CaCOS)
Control
10
24
7.9
8.1
280
190
216
6.0
10
23
8.4
7.7
8900
7.0
10
23
8.4
7.7
9400
8.0
10
23
8.4
7.7
12000
9.0
10
24
8.3
7.7
13000
10.0
10
23
8.4
7.7
14000
48 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
pH
Conductivity (umhos/cm)
Control
10
23
7.8
8.1
290
6.0
10
23
7.8
8.0
9000
7.0
10
23
7.4
7.9
9500
8.0
10
23
7.4
8.1
12000
9.0
9
23
7.5
8.0
13000
10.0
4
23
7.4
7.9
14000
96 hr
Concentration (g/l)
No. of Individuals Surviving
Temperature (oC)
Dissolved Oxygen (mg/l)
PH
Conductivity (umhos/cm)
Control
10
23
7.8
7.8
300
6.0
10
23
7.6
7.8
9700
7.0
10
23
7.7
7.8
10000
8.0
4
23
7.6
7.7
12200
9.0
2
23
7.8
7.7
13100
10.0
1
23
7.8
7.6
14800
E-6
-------
Table E-5
HA-RT-60198-1 SODIUM CHLORIDE REFERENCE TEST
96-Hour ECso for Hyalella azteca
SUMMARY STATISTICS ON DATA -- Transform: NO TRANSFORMATION
GRP
1
2
3
4
5
6
IDENTIFICATION
0.0 (control)
2.0 g/L
2.8 g/L
3.6 g/L
4.4 g/L
5.2 g/L
N
10
10
10
10
10
10
MIN
1.0000
1.0000
1.0000
0.0000
0.0000
0.0000
MAX
1.0000
1.0000
1.0000
1.0000
1.0000
0.0000
MEAN
1.0000
1.0000
1.0000
0.9000
0.3000
0.0000
GRP IDENTIFICATI VARIANCE
ON
SD
SEM
c.v. %
1
2
O
4
5
6
0.0 (control)
2.0 g/L
2.8 g/L
3.6 g/L
4.4 g/L
5.2 g/L
0.0000
0.0000
0.0000
0.1000
0.2333
0.0000
0.0000
0.0000
0.0000
0.3162
0.4830
0.0000
0.0000
0.0000
0.0000
0.1000
0.1528
0.0000
0.0000
0.0000
0.0000
35.1364
161.0153
N/A
PROSIT ANALYSIS - USING SMOOTHED PROPORTIONS - Transform: LOG 10 DOSE
NUMBER NUMBER OBSERVED SMOOTHED PREDICTED
DOSE SUBJECTS OBSERVED PROPORTION PROPORTION PROPORTION
2.00
2.80
3.60
4.40
5.20
10
10
10
10
10
9
8
7
3
0
0.9000
0.8000
0.7000
0.3000
0.0000
0.9000
0.8000
0.7000
0.3000
0.0000
0.9538
0.7792
0.5345
0.3233
0.1808
Est. Mu= 0.5782 Est. Sigma = 0.1599
sd= 0.0320 sd= 0.0416
Chi-Square lack of fit = 2.2500 Likelihood lack of fit = 2.2006
Table Chi-square = 11.3449 (alpha = 0.01, df = 3)
Table Chi-square = 7.8147 (alpha = 0.05, df = 3)
E-7
-------
PROBIT EC ESTIMATES -- WITHOUT CONTROL DATA
POINT
EST. END POINT
95% CONFIDENCE
LIMITS
EC10
EC20
EC30
EC40
EC50
EC60
EC70
EC80
EC90
2.3188
2.7265
3.0642
3.3858
3.7168
4.0801
4.5083
5.0667
5.9575
1.7721
2.2214
2.5878
2.9123
3.2055
3.4766
3.7430
4.0364
4.4350
3.0342
3.3464
3.6383
3.9363
4.3096
4.7884
5.4300
6.3602
8.0028
Table E-6
HA-RT-60198-2 SODIUM CHLORIDE REFERENCE TEST
96-Hour ECso for Hyalella azteca
SUMMARY STATISTICS ON DATA -- Transform: NO TRANSFORMATION
GRP
1
2
O
4
5
6
IDENTIFICATION
0.0 (control)
2.0 g/L
2.8 g/L
3.6 g/L
4.4 g/L
5.2 g/L
N
10
10
10
10
10
10
MIN
1.0000
1.0000
1.0000
0.0000
0.0000
0.0000
MAX
1.0000
1.0000
1.0000
1.0000
1.0000
0.0000
MEAN
1.0000
1.0000
1.0000
0.8000
0.3000
0.0000
GRP
1
2
O
4
5
6
IDENTIFICATION
0.0 (control)
2.0 g/L
2.8 g/L
3.6 g/L
4.4 g/L
5.2 g/L
VARIANCE
0.0000
0.0000
0.0000
0.1778
0.2333
0.0000
SD
0.0000
0.0000
0.0000
0.4216
0.4830
0.0000
SEM
0.0000
0.0000
0.0000
0.1333
0.1528
0.0000
c.v. %
0.0000
0.0000
0.0000
52.7046
161.0153
N/A
-------
PROBIT ANALYSIS - USING SMOOTHED PROPORTIONS - Transform: LOG 10 DOSE
DOSE
(g/L)
2.00
2.80
3.60
4.40
5.20
NUMBER
SUBJECTS
10
10
10
10
10
NUMBER
OBSERVED
10
10
8
3
0
OBSERVED
PROPORTION
1.0000
1.0000
0.8000
0.3000
0.0000
SMOOTHED
PROPORTION
1.0000
1.0000
0.8000
0.3000
0.0000
PREDICTED
PROPORTION
1.0000
0.9987
0.8283
0.2441
0.0197
Est. Mu= 0.6066 Est. Sigma = 0.0531
sd= 0.0158 sd= 0.0151
Chi-Square lack of fit = 0.4405 Likelihood lack of fit = 0.6414
Table Chi-square = 11.3449 (alpha = 0.01, df = 3)
Table Chi-square = 7.8147 (alpha = 0.05, df = 3)
PROBIT EC ESTIMATES - WITHOUT CONTROL DATA
POINT EST. END POINT 95% CONFIDENCE
LIMITS
EC10
EC20
EC30
EC40
EC50
EC60
EC70
EC80
EC90
3.4558
3.6469
3.7911
3.9189
4.0423
4.1695
4.3101
4.4806
4.7283
3.0707
3.3135
3.4894
3.6353
3.7634
3.8799
3.9909
4.1052
4.2451
3.8892
4.0138
4.1189
4.2247
4.3419
4.4807
4.6548
4.8903
5.2665
E-9
-------
Table E-7
CT-RT-60198-1 SODIUM CHLORIDE REFERENCE TEST
96-Hour ECso for Chironomus tentans
SUMMARY STATISTICS ON DATA -- Transform: NO TRANSFORMATION
GRP IDENTIFICATI
ON
N
MIN
MAX
MEAN
1
2
3
4
5
6
0.0 (control)
6.0 g/L
7.0 g/L
8.0 g/L
9.0 g/L
10.0 g/L
10
10
10
10
10
10
1.0000
1.0000
0.0000
0.0000
0.0000
0.0000
1.0000
1.0000
1.0000
1.0000
1.0000
0.0000
1.0000
1.0000
0.8000
0.5000
0.1000
0.0000
GRP IDENTIFICATI VARIANCE
ON
SD
SEM
c.v. %
1
2
O
4
5
6
0.0 (control)
6.0 g/L
7.0 g/L
8.0 g/L
9.0 g/L
10.0 g/L
0.0000
0.0000
0.1778
0.2778
0.1000
0.0000
0.0000
0.0000
0.4216
0.5270
0.3162
0.0000
0.0000
0.0000
0.1333
0.1667
0.1000
0.0000
0.0000
0.0000
52.7046
105.4093
316.2278
N/A
PROSIT ANALYSIS - USING SMOOTHED PROPORTIONS - Transform: LOG 10 DOSE
DOSE (g/L)
6.00
7.00
8.00
9.00
10.00
NUMBER
SUBJECTS
10
10
10
10
10
NUMBER
OBSERVE
D
10
8
5
1
0
OBSERVE
D
PROPORTI
ON
1.0000
0.8000
0.5000
0.1000
0.0000
SMOOTHS
D
PROPORTI
ON
1.0000
0.8000
0.5000
0.1000
0.0000
PREDICTS
D
PROPORTI
ON
0.9934
0.8535
0.4277
0.1020
0.0124
Est. Mu= 0.8945
sd= 0.0120
Est. Sigma = 0.0470
sd= 0.0113
Chi-Square lack of fit = 0.6354 Likelihood lack of fit = 0.8044
Table Chi-square = 11.3449 (alpha = 0.01, df = 3)
Table Chi-square = 7.8147 (alpha = 0.05, df = 3)
E-10
-------
PROBIT EC ESTIMATES -- WITHOUT CONTROL DATA
POINT
EST. END POINT
95% CONFIDENCE
LIMITS
EC10
EC20
EC30
EC40
EC50
EC60
EC70
EC80
EC90
6.8279
7.1609
7.4110
7.6316
7.8438
8.0619
8.3019
8.5919
9.0108
6.2499
6.6639
6.9627
7.2109
7.4304
7.6334
7.8310
8.0406
8.3057
7.4594
7.6950
7.8882
8.0769
8.2802
8.5144
8.8010
9.1809
9.7759
Table E-8
CT-RT-60198-2 SODIUM CHLORIDE REFERENCE TEST
96-Hour ECso for Chironomus tentans
SUMMARY STATISTICS ON DATA -- Transform: NO TRANSFORMATION
GRP
1
2
O
4
5
6
IDENTIFICATION
0.0 (control)
6.0 g/L
7.0 g/L
8.0 g/L
9.0 g/L
10.0 g/L
N
10
10
10
10
10
10
MIN
1.0000
1.0000
0.0000
0.0000
0.0000
0.0000
MAX
1.0000
1.0000
1.0000
1.0000
1.0000
1.0000
MEAN
0.9000
0.8000
0.6000
0.4000
0.3000
0.1000
GRP
1
2
O
4
5
6
IDENTIFICATION
0.0 (control)
6.0 g/L
7.0 g/L
8.0 g/L
9.0 g/L
10.0 g/L
VARIANCE
0.1000
0.1778
0.2667
0.2667
0.2333
0.1000
SD
0.3.162
0.4216
0.5164
0.5164
0.4838
0.3162
SEM
0.1000
0.1333
0.1633
0.1633
0.1528
0.1000
C.V. %
35.1364
52.7046
86.8663
129.0994
161.0153
316.2278
E-ll
-------
PROSIT ANALYSIS - USING SMOOTHED PROPORTIONS - Transform: LOG 10 DOSE
NUMBER NUMBER OBSERVED SMOOTHED PREDICTED
DOSE SUBJECTS OBSERVED PROPORTION PROPORTION PROPORTION
(g/L)
6.00
7.00
8.00
9.00
10.00
10
10
10
10
10
8
6
4
O
1
0.8000
0.6000
0.4000
0.3000
0.1000
0.8000
0.6000
0.4000
0.3000
0.1000
0.8053
0.6064
0.4046
0.2443
0.1366
Est. Mu= 0.8757 Est. Sigma = 0.1134
sd= 0.0225 sd= 0.0339
Chi-Square lack of fit = 0.2855 Likelihood lack of fit = 0.2878
Table Chi-square = 11.3449 (alpha = 0.01, df = 3)
Table Chi-square = 7.8147 (alpha = 0.05, df = 3)
PROSIT EC ESTIMATES - WITHOUT CONTROL DATA
POINT EST. END POINT 95% CONFIDENCE
LIMITS
EC10
EC20
EC30
EC40
EC50
EC60
EC70
EC80
EC90
5.3749
6.0292
6.5500
7.0304
7.5112
8.0250
8.6136
9.3575
10.4967
4.2331
5.0372
5.6838
6.2613
6.7873
7.2570
7.6760
8.0855
8.5872
6.8247
7.2167
7.5482
7.8940
8.3123
8.8742
9.6657
10.8295
12.8308
E-12
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