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3 1293 01051

This is to certify that the

thesis entitled

Spatial and Temporal Variations
of Chromium in Sediments
of the Great Lakes

presented by
Sangjo Jeong

has been accepted towards fulfillment
of the requirements for

._Ma.s_te.r_degree in _S_C_1_en§:___° e

Department of Geological Sciences

 

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Spatial and Temporal Variations
of Chromium in Sediments
of the Great Lakes

By

Sangjo Jeong

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Geological Sciences

1994

ABSTRACT

SPATIAL AND TEMPORAL VARIATIONS OF CHROMIUM
IN SEDIIVIENTS OF THE GREAT LAKES

By

Sangjo Jeong

Trace metal loadings are known to have increased in the Great Lakes
ecosystem as a result of anthropogenic inputs. There is little information
specifically addressing chromium loadings. Therefore, the vertical concentration
profiles of chromium in sediment cores were measured from Lakes Superior,
Michigan, and Ontario in an attempt to determine spatial and temporal variations.
Sediment cores were sectioned under air at 0.5 to 1 cm increments to depths of
approximately 40 cm. Chromium was extracted from the sediment by HNO3
digestion in a microwave and its concentration determined in the leachate by
atomic absorption spectroscopy. Sedimentation rates were determined by 210Pb
dating of the sediment cores.

Pre-industrial concentrations of chromium were determined and subtracted
from total chromium concentrations to estimate anthropogenic concentrations.
Chromium inventories and accumulation rates were then determined for each core.
These values were adjusted for sediment focusing using 210Pb derived focusing
factors. Sediment metal accumulation rates were compared to estimated
atmospheric deposition rates obtained from preview studies of the Great Lakes
region

The results are that pre-industrial concentrations of chromium are typical
for soils in the Great Lakes region Only Lake Ontario and Michigan exhibit
anthropogenic enrichments of chromium in the sediments. Sediment profiles in

Lakes Ontario and Mchigan indicate that the rates of anthropogenic chromium
loading to the Great Lakes region is decreasing When compared to sediment
accumulation rates by - ( atmospheric accumulation rate/ focusing-corrected
sediment accumulation rate) x 100 - the following percentages are result : Lake
Superior (6-15%), Lake Michigan (4-11%), and Lake Ontario (2-7%). Focusing
corrected inventories are higher in Lake Ontario than Lake Michigan. However
inventories are similar throughout depositional basins within each lake. The results
are interpreted to indicate that there is a small atmospheric component to
chromium inputs to the Great Lakes and that the relative importance of this input
decreases from Lake Superior to Lake Ontario.

For the hope of peace in the Korean peninsula...

Acknowledgments

Before anything else, I would like to thank to Dr. David T. Long for his
guidance on my research. I would also like to thank committee members Dr.
Grahame J. Larson and Dr. Michael A Velbel for their advice and encouragement

I would like to thank lab friends, Tina Beals, John Kolak, and Bill Sitarz for
their help on this research and my English study. I am grateful to the United States
Environmental Protection Agency, the Great Lakes Protection Fund, and National
Undersea Research Program for their grants. Thanks also to the Korean Army and
the faculty and stafi’ of the department of environmental sciences of Korea Military
Academy for their encouragement to attain my master’s degree.

I am also grateful to my parents and parents-in-law for all their support and
understanding Finally, a special thanks to Soonam as my wife, friend, and advisor
for her support and constant nagging during my experience in America

TABLE OF CONTENTS

List of Tables
List of Figures

1. INTRODUCTION
General Introduction
Statement of Purposes
Hypothesis
Biogeochemistry of Chromium
The Distribution of Chromium in the Environment
Aqueous Geochemistry of Chromium

II. METHODS
Sampling
Sample Treatment
Analysis
Clean Procedures
Quality Assurance and Quality Control Procedures
Lead-210 Dating and Sediment Focusing

III. RESULTS

IV. DISCUSSION
Background Concentrations
Sediment Accumulation Rates for Chromium
Atmospheric Deposition of Chromiuum
Anthropogenic Inventories and Anthropogenic Sediment
Bmden

V. CONCLUSIONS

APPENDICES
Appendix A
Appendix B
Appendix C
Appendix D

REFERENCES

22

38
38
38
42

43
52
54
55
71
74
90

95

Table 1

Table 2

Table 3

Table 4
Table 5

Table 6

Table 7

Table A-1
Table A-2
Table A-3
Table A-4
Table A-5
Table A-6
Table A-7
Table A-8
Table A-9
Table A- 10

Table A- 1 1

LIST OF TABLES

Physical parameters of the Great Lakes.

Background concentrations of chromium in
preliminary backgromrd values for sediments of the
Great Lakes region and in the soils of US.

Sediment accumulation rates for chromium in lakes
Superior, Michigan, and Ontario.

Dry deposition in the Great Lakes.
Wet deposition in the Great Lakes.

Percent atmospheric contribution to accumulation
rates.

Anthropogenic inventories and anthropogenic burdens
of chromium in lakes Michigan and Ontario.

EPA #11 location and description.

EPA #18 location and description.

EPA #19 (LM) location and description.
EPA #19(LO) location and description.
EPA #25a location and description.
EPA #40a location and description.
EPA #6411 location and description.

E 30 location and description.

DTL location and description.

SIE II location and description.

#1383 location and description

vii

39

41

44

45

47

49

55

57

S9

60

61

62

64

66

67

68

69

Table A- 12

Table B-1

Table B-2

Table B-3

Table C-l

Table C-2

Table C-3

Table C-4

Table C-5

Table C-6

Table 07

Table 0-8

Table 09

Table C- 10

Table 0- l 1

Table C- 12

Table C-13

Table C- 14

Table C- 15

Table D

# 1391 location and description.
Replicate result.
Quality assurance: SRM.

The background concentration of chromium in the
sediments of this study.

EPA #11 chromium concentration and porosity data.
EPA #18 chromium concentration and porosity data.

EPA #19(LM) chromium concentration and porosity
data.

EPA #47 s(?)chromium concentration and porosity
data.

EPA #68k chromium concentration and porosity data.

EPA #19(L0) chronrium concentration and porosity
data.

EPA #25a chronrium concentration and porosity data.
EPA #4011 chronrium concentration and porosity data.

EPA #6411 chromium concentration and porosity data.

E 30 chromitun concentration and porosity data.
DTL chromium concentration and porosity data.

SJE II chromium concentration and porosity data.

NOAA #3 chromium concentration and porosity data.

#1383 chromium concentration and porosity data.
#1391 chromium concentration and porosity data.

Inventory calculation.

70

71

72

73

74

75

76

77

78

79

80

81

82

84

85

86

87

88

89

90

Figure 1

Figure 2

Figure 3

Figure4

Figure 5

Figure6

Figure 7

Figure 8

Figure9

Figure 10

Figure 11

Figure 12

Figure 13

LIST OF FIGURES

Basin boundary of the Great Lakes.

Chromium cycling in aquatic environment
(from Richard and Boung, 1991).

Sampling sites and depositional basin of Lake
Superior.

Sampling sites and depositional basin of Lake
Michigan

Sampling sites and depositional basin of Lake Ontario.

Terms used in the depth versus chromium
concentration profiles

Chromium concentration profiles in southem basin of
Lake Michigan.

Chromium concentration profiles in the Algoma basin
of Lake Michigan.

Chromium concentration profiles in the Niagara basin
(EPA #19) and Rochester basin ( E 30) of Lake
Ontario.

Chromium concentration profiles in Niagara basin
(EPA #25a) and Rochester basin (EPA #64a) of
Lake Ontario.

Chromium concentration profiles in the Mississauga
basin (EPA #40a) of Lake Ontario and Chefswct
basin (NOAA #3) of Lake Superior.

Chromium concentration profiles in the Duluth basin
of Lake Superior.

Chromium concentration profiles in the Isle Royale
basin (#1383) and Isle Parisienne basin (#1391) of
Lake Superior.

l3

14

15

16

23

24

25

26

27

28

29

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Figure 19

Figure 20

Figure 21

Figure 22

Chromium concentrations versus year in the southern
basin of Lake Michigan

Chromium concentrations versus year in the Algoma
basin of Lake Michigan

Chromium concentrations versus year in the Niagara
basin (EPA #19) and Rochester basin (E 30) of
Lake Ontario.

Chromium concentrations versus year in the
Mississauga basin (EPA #40a) of Lake Ontario and
Chefswet basin (N 0AA #3) of Lake Superior.

Chromium concentrations versus year in the Duluth
basin of Lake Superior.

Chromium concentrations versus year in the Isle
Royale basin (#1383) and Isle Parisieune basin
(#1391) of Lake Superior.

Background concentration of chromium in the Great
Lakes.

Temporal trends of chromium concentration in the
atmosphere of the Great Lakes region based on the
wet deposition (fiom U. S.E.P.A, 1994).

Chromium inventories of Lake Michigan and Lake
Ontario.

30

31

32

33

34

35

36

46

50

I. Introduction

 

General Introduction

The Great Lakes basin (> 150,000 kmz) contains 20% of world's surface
fresh water (excluding ice); is highly industrialized; and host 20% of the US.
population and 60% of the Canadian population (Berg and Johnson, 1978; Heft,
1993 ). About 40 million people use the Great Lakes as a source of drinking water
and for industrial, commercial, and recreational purposes. The hydrologic and
morphometric features of the Great Lakes are shown in Figure l and Table 1,
respectively.

One of the greatest concerns confronting the Great Lakes region is the
contamination of water and air by persistent toxic substances (Arimoto, 1989).
Heavy metals are toxic environmental pollutants and threaten not only aquatic life,
but the quality of drinking water. High concentrations of trace elements such as
Hg, Pb, and Cd in the surface sediments relative to the subsurface sediments in
Lake Superior, Lake Michigan, and Lake Ontario are believed to be the result of
the recent anthropogenic loading of these elements (Kemp et al., 1978). The
predominant sources of chemical constituents in the Great Lakes are thought to be
derived from the atmosphere (Schmidt and Andrea, 1984; Eisenreich et al., 1986).
Other sources are riverine input, direct industrial and municipal emuents,
groundwater seepage, and coastal erosion

The Great Lakes are particularly susceptible to atmospheric deposition of
contaminants because of large ratios of surface area to basin area, long water
residence times, and their location near and downwind of major industrial or urban

BASIN BOUNDARY

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S 'ERIOR

U.S.

 

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centers (Eisenreich et al., 1981). Over the last 200 years, major sources of
contaminants in the atmosphere of the Great Lakes include pesticides, mining
activities, and fossil fuel combustion (coal and gas).

There is relatively little information specifically applying to chromium
loading in the Great Lakes. Using the sediment profiles of Lake Superior, Lake
Michigan, and Lake Ontario, this study presents spatial and historical distributions
of chromium, magnitude of anthropogenic loading of chromium, and an estimate
of the proportion of atmospheric loading relative to non-atmospheric inputs.

Anthropogenic and natural loads of trace metals to lake sediments have
been estimated for many lakes using vertical profiles of metal concentrations
(Kemp and Thomas, 1976; Galloway and Likens, 1979; Evans and Dillon, 1982;
Kemp et al., 1978; Johnson et al., 1986; Johnson and Nicholls, 1988). Natural
sources for trace metals include glacial and soil deposits occurring in erodable
shorelines and in the tributary watersheds. Contaminants in the sediments are
usually more highly concentrated in the fine particles than in the coarser particles
due to the high surface area of fine particles (Dong et al., 1984). Increase of the
trace metal loading to recent sediment profiles can be usually explained by
derivation from anthropogenic sources including loading from the atmosphere to
undeveloped lakes (Johnson, 1987).

Statement of Purposes

The goal of this study is to determine the spatial and temporal variation of
chromium in the Great Lakes using sediment cores. Sediments are especially
useful for studying the spatial and temporal distribution of trace metals since they
display fairly static sample type rather than the transient samples provided by
water and biota (Mueller et al., 1989).

More specifically, information fi'om chromium concentration profiles in the
sediments, chromium concentration in air and precipitation, and 210Pb data of the
Great Lakes, will be used to:

(1) determine the spatial distribution of anthropogenic chromium loadings,

(2) determine the change in magnitude of historical anthropogenic

chromium inputs,

(3) calculate chromium anthropogenic inventories,

(4) estimate present day sediment-accumulation rate of chromium,

(5) calculate atmospheric deposition rate of chromium, and

(6) estimate the relative proportion of atmospheric deposition to sediment

loadings.

Hypothesis

The main purpose of this research is to determine the extent of the
anthropogenic loading of chromium in the Great Lakes. This knowledge will help
to identify the sources of contaminants. This is essential for understanding the
problems of contaminants in the environment and for efl‘ective restoration It is
hypothesized that the most important source for chromium to the Great Lakes is
atmospheric deposition It is assumed that if this hypothesis is true then the
inventories of chromium should be same throughout the Great Lakes. The
inventory of metal which concentrated in sediments is total mass amounts of metal
in the core. In this study, the anthropogenic inventory will be investigated It is
thought that atmospheric deposition is highly dispersed, afl’ecting near shore and
mid lake areas nearly alike. Thus, the inventory of metals derived from
anthropogenic sources in the sediment should be same throughout the Great Lakes.

Biogeochemistry of Chromium

The Distribution of Chromium in the Environment

Chromium is a common element, present in low concentrations ranging
from less than 0.1 rig/m3 in air to 4 g/kg in soils (World Health Organization,
1988). Chromium concentration in the air of non-industrialized areas is less than
0.1 rig/m3. The background atmospheric chromium concentrations were estimated
at the South Pole, as 5.3 :l: 3.0 pg/m3 with a range of 2.5 to 10 pg/m3 (Zoller et al.,
1974). However, the extensive use of chromium for the production of chrome
alloys, chrome-plated metals, cement, pigments, various chemicals, and the
combustion of many materials increase airborne chromium levels. Most chromium
in the atmosphere exists as particulates (Towill et al., 1978). Due to its high
boiling point, chromium vapor condenses as an oxide on the surface of particles
(Moore and Ramamoorthy, 1984). Depending on the climatic conditions,
atmospheric chromium can be blown over long distances and deposited on land or
water by dry and wet deposition As of 1973, the Great Lakes area received 29%
of the total chromium emissions of United States (Towill et al., 1978).

The most dominant ore mineral of chromium is chromite, FeCr203, and
would theoretically contain 68% chromic oxide (Gephart, 1982). Chromium in the
earth's crust is incorporated in crystal lattice structure of the spinel group and other
silicates such as pyroxenes through the replacement of F 6”, Al3+, and Mg2+ by
Cr3+. The chromium content of natural solids varies according to the type and
nature of underlying parent rocks, geographic region, and age of soil. High
concentrations (average 1800 ppm) of chromium are present in ultramafic and
serpentinite rocks, while low concentrations (about 10 ppm) are found in granite
and limestones. Shales, river suspended matter and soils typically exhibit high

levels of chromium (Robertson, 1975; Salomons and De Groot, 1978). Chromium
in soils is relatively insoluble and its concentrations are constant with depth.

Chromium concentrations in most surface fresh water are low. Kopp and
Kroner (1968) detected dissolved chromium concentration from the surface water
samples in the United States of America ranged from 0 to 112 rig/L with a mean
concentration of 9.7 rig/L. Higher concentrations of chromium were contributed by
run ofl‘ fiom urban and industrialized areas. The principal sources of chromium
emissions which contains relatively toxic form, Cr“, into surface waters are metal
finishing processes such as electroplating In fiesh waters, anthropogenically
introduced soluble Cr“ is reduced to Cr3+, which is far more stable in the aquatic
environment and removed by subsequent sorption to particulates and sediments
(Pfeifi‘er et al., 1980; Moore and Ramamoorthy, 1984).

Aqueous Geochemistry of Chromium

Chromium is a transition series element, a member of periodic group VI a,
and atomic number 24. The ground state of the electron configuration of chromium
is [Argon] 3d54sl. Oxidation states range from ~2 to +6. The most common and
stable oxidation state of chromium in natural environments is Cr3+ derived
primarily from the weathering of ultramafic rocks. Hexavalent chromium in the
environment is mostly derived fi'om human activities.

A number of physical, chemical, and biological processes affect the fate of
chromium in the aquatic environments (Figure 2). The primary types of reactions
that control the distribution of Cr3+ and Cr“+ are oxidation-reduction reactions in
the aquatic environment Under redox conditions, Cr3+ is the most stable
chromium valence or oxidation state in the natural aquatic environments.

Interconversion of Cr3+ and Cr“ can take place in the presence of other redox

 

 

 

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(from Richard and Boung, 1991).

couples such as F e2+ IF e3+, Mn2+/Mn4+, H20/02(aq), NOZ/NO3, 82780423 or
CH4/C02 (Richard and Boung, 1991).

Hexavalent chromium is a strong oxidizing agent in aqueous solution
existing as a component of a complex anion such as chromate (CrO4 '2),
hydrochromate (HCrO4 '), and dichromate (Cr207 '2). The hexavalent chromium
anion forms very soluble, mobile species in the aquatic environment Chromium
(VI) is reduced to chromium (III) with Fe”, dissolved sulfides, and certain organic
matter such as simple amino-acids (Schroeder and Lee, 1975) or humic or fulvic
acid materials (Boyko and Goodgame, 1986). The dissolved F e2+ ions are
generated by weathering of Fe2+containing minerals (biotite, etc.) and some
industrial wastes. Chromium (VI) is mainly reduced in acidic conditions (Grove
and Ellis, 1980; Stollenwerk and Grove, 1985). Chromium (Ill) readily precipitates
as insoluble chromium hydroxides.

Trivalent chromium is oxidized to hexavalent chromium by dissolved
oxygen and manganese oxides. Oxidation rate of Cr3+ at room temperature by
dissolved oxygen is very slow. Most Cr3+ oxidation is related to the amount and
the surface area of manganese oxide in aquatic environments (Eary and Rai, 1987;
Schroeder and Lee, 1975; Takacs, 1988). This oxidation occurs in three steps; (1)
adsorption of Cr3+ onto manganese oxide (MnOz) sin-face sites, (2) oxidation of
Cr3+ to Cr6+ and reduction of Mn4+ to Mn2+, (3) desorption of the reaction
products (Richard and Boung, 1991).

Adsorption is a physicochemical process by which aqueous species adhere
to the surface of particulate matter. Adsorption mechanisms include ion exchange,
electrical double layer ion interactions, surface complexation of hydrolyzable ions,
and surface ionization and complexation (W estall and Hohl, 1980). Although Cr6+
has a strong amnity for organic matter, it is not readily adsorbed to inorganic
materials such as clays, ferric and manganese oxides. Adsorption of hexavalent

10

chromium to hydroxyl-specific surface sites is a surface complexion reaction
(Richard and Boung, 1991). Chromium (V1) is more sfiongly adsorbed on
adsorbents which are positively charged at pH < 7 (Davis and Leckie, 1980).
Amacher et al. (1988) reported that the adsorption of chromate on soils showed an
initial reversible reaction that reached equilibrium within 24 h, but followed that
further adsorption a much slower irreversible reactions. They suggested the latter
step may be related to coprecipitation or internal diffusion

Chromium (III) is strongly adsorbed by Fe and Mn oxides, clay minerals
(Dreiss, 1986; Rai et al., 1984). The adsorption of Cr3+ to clay is 30-300 times
higher than Cr6+ (Griffin et al., 1977). The adsorption of Cr3+ to the soils
increases with pH (Grifin et al., 1977; Rai et al., 1984) and is also organic matter
content (Paya Pe’rez et al., 1988). Adsorption depends on the presence of other
inorganic cations or dissolved organic ligands in solution (Richard and Boung,
1991)

Chromium has a potential to be bioaccumulated in indigenous biota because
it is an essential micronutrient Chromium (v1) is readily adsorbed by tissues due
to the presence as soluble anionic complexes in natural waters (Kuhert et al.,
1976). However, the particulate form of trivalent chromium is less readily
adsorbed by tissues (Sherwood and Wright, 1976). Under common pH/Eh
conditions, chromium precipitates as hydroxides and oxides precipitate, and is thus
not readily bioavailable (Jan and Young, 1978).

Sedimentation and burial are the dominant removal pathway of
contaminants fiom the water column due to the strong afinity of many
contaminants for particulate matter and the long hydraulic residence times of the
Great Lakes (Allan, 1975; F6rstner, 1976; Eadie et al., 1983). Once on the lake
bottom, metals sorbed to sediment can be afl‘ected by early diagenetic processes.
Early diagenesis is chemical and physical changes mostly driven by microbial

ll

processes occurring in a sediment during burial to a few hundred meters (Bemer,
1980). Early diagenetic processes operating above the redox zone are important in
determining potential bioavilability and release elements to the water column
(Matty, 1992). Sediment conditions, however, afl‘ect the distribution and
remobilization of chromium. For example, the distribution of chromium in the
upper portion of sediment is related to Eh-pH condition and selective adsorption
onto Fe hydroxides, MnOz, and organic matter (Mothersill, 1977). The extent of
chemical diagenesis depends on not only the chemical characteristics of
contaminants but the geochemical environment to which the contaminant is
subjected.

In order to interpret the distribution of contaminants in sediments, processes
such as difl‘usion, resuspension, advection, bioturbation, chemical and biological
reactions, and time dependent changes in contaminant flux need to be considered.

II. Methods

 

Sediment cores were collected from Lake Superior (Figure 3), Lake
Michigan (Figure 4), and Lake Ontario (Figure 5) using the box sampling
capabilities of the R/V Lake Guardian (U .S.E.P.A), R/V Seward-Johnson, and
R/S Johnson Sea-Link II (NOAA-NURC) during the summers of 1988, 1990,
1991, 1992, and 1993. Sediment core samples were digested using a microwave—
nitric acid digestion technique. The leachate was analyzed for chromium using
graphite-fumace atomic absorption spectroscopy.

To understand chromium concentration versus sediment depth profiles,
however, some terms need to be defined. Figure 6 is a typical profile of chromium
concentrau'on in sediment versus depth The background depth is the depth in a
core where the concentration of chromium becomes relau'vely constant The
background concentration is the average concentrations of all sample segments
below the background depth. This concentration of chromium in the sediments is
derived fiom natural sources. Peak is the highest anthropogenic chromium
concentration Surficial concentration is concentration of chromium in the
uppermost sectioned interval of the sediment cores. Inventory means that total
mass of chromium in the core by the anthropogenic input The inventory is
corrected by focusing factor using 210Pb.

Sampling

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151 m ’ I '
95 m

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131m

Figure 4. Sampling sites and depositional basin of Lake Michigan.

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Chromium concentration (ug/g)

Figure 6. Terms used in the depth versus chromium concentration profiles.

17

Deep basins within each lake were chosen as sampling sites because these
are the areas of active accumulation of fine-grained sediment and associated
contaminants through the process of sediment focusing Sediment focusing is the
movement of sediment toward deeper zones or quiescent zones of the lake usually
resulting from periodic turbulence (Likens and Davis, 1975), slumping/sliding of
material on slopes, or current erosion/deposition (Hilton et al., 1986). Sediment
samples were obtained by using a stainless steel box coring device (30 cm x 30 cm
x 70 cm). This device was lowered slowly into the sediment in order to obtain
undisturbed sediment samples. Then, PVC core tubes (3") were inserted into the
sediment under vacuum to avoid compacting of the sediment and 5 cm away from
the sides of the box core to avoid contamination from "ledge" efl‘ects. After all
subcore tubes; those for 210Pb, trace metal, and organic analyses, were inserted in
the box core, the bottoms of the tubes were sealed by rubber stopper. The tops of
subcore were covered with polyethylene caps to further prevent contamination of
the sediment core. The sediments were sectioned into 0.5 cm, 1 cm or 2 cm
intervals using a hydraulic extrusion device. The tubes were double stoppered on
the bottom and placed on the extruder to prevent water from coming in contact
with the sediment at the bottom of the core. Sediments in contact with the sides of
core tube were scraped away using a teflon spatula before sectioning The sections
were transferred into individual acid-cleaned polyethylene bottles and fiozen until

sample preparation

Sample Treatment

Trace metals were extracted from sediment by chemical extraction.
InstraTM grade I-INO3 (15M) were used as the chemical leaching agent during

18

sediment digestion in a CEM model 81 microwave with pressure controller. The
extraction method was suggested by Hewitt and Reynolds (1990).

After the frozen samples thawed at room temperature overnight, about 5
' grams of sediment were weighed and dried for 24 hours at 50 °C in a convection
oven. Porosity of the sediment was determined from the wet sample weight and
dry sample weight Dried samples were ground into a fine powder by use of a
ceramic mortar and pestle and 0.50 grams of sample weighed and placed into an
individual 100 ml polyethylene reaction vessel. Ten milliliters of HNO3 were
added to each vessel. Eleven samples and one blank were digested at the same
time. One of the sample vessels was connected with the pressure controlling
device to regulate pressure (150 psig). The microwave program was set to 15
minutes with 100% power; 15 minutes with 0 power and until the pressures were
less than 5 psig After digestion 90 ml of DDW was added to dilute each sample.
The sample leachate, filtered through 0.45pm acid-cleaned Nucleopore membrane
filters, were stored at 4 °C until analysis. 1

Analysis

Leachates were analyzed by graphite-furnace atomic absorption
spectrometry using a Perkin-Elmer Zeeman 5100 with HGA 600 fumace and auto
sampler. The standard solution was made using 1000 ppm :1: 1 % chromium
reference solution of Fisher Scientific. Matrix modifier and calibration blank were
made using 0.05 mg of Mg(NO3)2 and 1 ml of HNO3 dilute in 25 ml of DDW,
respectively (Perkin-Elmer, 1985). The sample was injected into the ftunace
chamber by an automatic pipeting arm The pipet arm collected 5 pl of matrix
modifier, 10 pl of diluent, and 10 ul of sample and injected it onto a L'vov
platform within the furnace chamber. The L'vov platform allows a more uniform

l9

atomization of sample and enables one to acquire more precise results. The
graphite-finnace were controlled by 5 step progams; drying (140 °C, 55 sec),
thermal pretreatment (1550°C, 30 sec ), atomization (2500°C, 10 sec ), clean out
(2630°C, 5 sec), and cool down.

Clean Procedures

All phases of this study were conducted using clean techniques. For
example, the laboratory was supplied with filtered air and sealed against dust and
contaminants from the outside. All materials used in the sample processing such as
bottles, syringes, spatulas, scoops, and reaction vessels were washed 4 times with
DDW from Corning model AG-22 still. These materials were soaked in 10% HCl
(analytical reagent grade) for 24 hours, then rinsed 4 times in DDW. These were
maintained in water bath for 24 hours, then dried in a laminar clean hood supplied
with filtered air from a class 100 filter. These are capped and sealed in plastic bags
for transportation to sampling sites and for storage. All samples and equipment
were handled only with the use of sterile, latex examination type gloves.

Quality Assurance and Quality Control Procedures

The results of quality control procedures are shown in Appendix B. To
evaluate the accuracy of the analytical method and maintain data quality, the
analytical procedure was performed on National Institute of Standards and
Technology (NIST) Standard Reference Material (SRM) #2704 (Bufialo River
Sediment, New York) an inorganic reference material (Epstein et al., 1989). The
certified value for this standard material is 135 i 5 rig/g However, the
concentrations of chromium in these sample results of repeated analyses of SRM
#2704 were significantly lower than the certified value, on the average 87.3 rig/g,
or 65% recovery. The NIST values for chromium in SRM #2704 were based on

20

determination by Instrumental Neutron Activau'on Analysis and Direct-Current
Plasma Emission Spectrometry (Epstein et al., 1989). The digestion methods using
HNO3 and a microwave oven do not extract total amounts of chromium fi'om all
geological materials (Sulcek and Povondra, 1989). However, most of
anthropogenic metals in sediments are associated with organic matter and clay
surfaces (Hewitt and Reynolds, 1990). These results agree with those of Hewitt
and Reynolds (1990) and Rowan and Kalfl (1993). RSD values for SRM #2704 of
this study were < 6%.

The measurement of chromium concentration in each leachate sample was
made three times. The RSDs were required by U.S.E.P.A. to be less than 15% for
the replicates of the sample (Eisenreich et al., 1990). IfRSDs exceeded 15%, the
sample was reanalyzed up to two more times. If the RSD value still exceeded 15%,
the sample was discarded. In addition, one or two samples per sediment core were
subsplit to three samples and analyzed separately. The RSD values of subsplits
were required to be less than 20%. The correlafion coefficient of the standard
calibration curve was required to be greater than 0.95.

Lead-210 Dating and Sediment Focusing

Lead-210 dating is an important and widely used method for determining
the age, sedimentation rates, and the history of anthropogenic inputs of sediments
in lacustrine and near shore marine systems (Shirahata et al., 1980; Evans and
Dillon, 1982; Evans et al., 1986; Beroit and Hemond, 1991). There are two kinds
of 210Pb in sediments; supported and unsupported. Supported 210Pb, produced by
in situ decay of 226Ru, is generally small in concentration and has nearly constant
activity. Unsupported 210Pb is supplied from the atmosphere to sediments. Major
amounts of 222Ru, as the gaseous daughter of 2331}, volatilize from earth crust to

21

the atmosphere. Lead-210, adsorbed to natural aerosols and particles as decay
product of 222Rn, are redistributed with respect to original source material (Junge,
1963; Robbins, 1978). ,

The inventory of metals is afi‘ected by sediment focusing A focusing factor
can be used to normalize the data throughout the Great Lakes region and to
account for variable sedimentation rates between the sampling sites (Rapaport and
Eisenreich, 1988; Eisenreich et al., 1989). The expected 21°Pb inventory from
atmospheric deposition in sediment of the Great Lakes region is 15.5 pCi/cm2
(Golden et al., 1993; Urban et al., 1990; Eisenreich, 1993 personal
communication). The 210Pb inventory is measured in sediments at each sampling
site. Ifthere has been sediment focusing then the 210Pb inventory will be greater
than 15. 5 pCi/cmz. Therefore, the amount of sediment focused into the deposition
site can be determined from the following focusing factor:

FF = 210Pb measured inventory / 21(’Pb expected inventory

The metal inventory at a site is divided by the focusing factor to obtain a
sediment-focused corrected inventory.

A single subcore fiom each box core was sectioned and dated using 21“Pb
methods at the University of Minnesota. Sediments were analyzed using a
modification of the method reported in Eakin and Morrison (1978). Lead-210
radio-isotope dating techniques such as constant flux/constant sedimentation and
constant rate of supply were used to calculate the date of sediment cores, focusing
factors, and sediment accumulation rates. Sedimentation rate through time was
calculated by linear relationship between log unsupported 210Pb activity and
cumulative dry mass with depth (Robbins, 1978).

III. Results

 

Shipboard description of sediment cores (Appendix A) and measured
chromium concentrations (Appendix C) in the sediment are shown as a function of
depth in Figures 7 through 13 and year in Figures 14 through 19.

Pre-industrial (background) concentrations of chromium were determined
and subtracted from total chromium concentrations to estimate the rate and extent
of anthropogenic accumulations. The background concentrations of Lake Mchigan
and Lake Ontario range from 26-38 ug/g Those of Lake Superior are higher that
about 50 ug/g except #1391 (Figure 20).

In the Lakes Michigan and Ontario, the highest concentrations of chromium
are generally in the upper portion of profiles. Surface concentrations in sediment
cores exceeded background concentrations by 1 to 3.6 times in Lakes Michigan
and Ontario. The profiles show that total chromium loading to the sediments has
been decreasing to present

Chromium loading at LM #68k and EPA #40a suddenly increased around
1900, and decreased around 1970. The increasing and decreasing time of
chromium loading around the Great Lakes region was similar.

Chromium concentration profiles from Lake Superior are unlike those in
Lakes Michigan and Ontario. Background concentrations of chromium in Lake
Superior are higher than Lakes Michigan and Ontario; probably due to the
weathering of the metamorphosed rocks of the Canadian shield (Thomas and
Mudroch, 1979). Chromium concentrations at site DTL and SJE II decrease to

22

 

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Superior are higher than Lakes Michigan and Ontario; probably due to the
weathering of the metamorphosed rocks of the Canadian shield (Thomas and
Mudroch, 1979). Chromium concentrations at site DTL and SJE 11 decrease to
present from about 5 cm with no peak concentration. At site #1383, NCAA #3,
and #1391, chromium concentrations are relatively constant through the depth.
Site #1391 has much lower chromium concentration than the other cores because
of the coarser texture of these sediments (Kemp et al., 1978).

The sediment profile of Lake Superior did not show anthropogenic
enrichments of chromium Perhaps, there is no anthropogenic input or
anthropogenic input is significantly lower than backgound concentration of
chromium The variations of chromium concentration in sediment cores could be
the disparity in sediment types. The chromium concentrations of the Duluth basin
were significantly depleted in the top 5 cm of the sediment profiles possibly
because of dilution by taconite tailings. The U. S. Dept. Int. Rept (1969) states that
67,000 ton of tailings daily were released into Lake superior from the Reserve
Mining Company's taconite processing plant at Silver Bay since 1955. Kemp et a1.
(1978) stated that the tailing layer contend high silt (75%), Si, Fe, and Mn
concentrations, but lower concentrations of major trace and nutrient elements.
Unfortunately, the concentration of chromium in the taconite tailings is not known.
Therefore, this interpretation remains as one possibility. The second possibility is
ratio of organic to clastic as a fimction of early diagenesis. The third possibility is
dilution by anthropogenic input with lower chromium content

IV. Discussion

 

Background Concentrations

The ranges of chromium background concentrations in this study are similar
to ranges found by previous researchers (Table 2). The data are also similar to soil
in the Great Lakes region In this study background concentration were highest in
Lake Superior due to the weathering of the metamorphosed rocks of the Canadian
shield. The Canadian shield consists of intrusive igneous and metamorphic rocks.
These contain relatively high concentration of chromium than platform and basin
of lakes Michigan and Ontario. Site #1391 shows much lower chromium
background concentration than the other cores in Lake Superior. However, this
value is similar to that of Lake Michigan because site #1391 is located in Michigan
basin (Figure 20). Background concentrations of chromium in Lake Michigan and
Ontario are similar.

Sediment Accumulation Rates for Chromium

The mass sedimentation rate can be calculated using 210Pb data
Calculations of accumulation rates and dating depth increments in the sediment
help to make interpretation from cores afl‘ected by compaction and early
diagenesis (Norton and Kahl, 1987; Urban et al., 1990). Robbins (1978) states that
the sediment dating of undisturbed, unmixed sediment was determined as follows:

A(z) = As x EXP (-lcz/W)
where

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A(z) = the unsupported 210Pb (part of sediment 210Pb arising from dry or
wet deposition of airborne 210Pb and not supported by soil Ra)
activity

As = the unsupported 210Pb activity at the sediment-water interface

k = the decay constant (0.0311 yearl)

z = the cumulative dry mass of sediment

W = the sedimentation rate (g/cm2 year)

Sediment accumulation rates of chromium were calculated as follows
(Golden et al., 1993):

Accum (pg/m2 year) = Csed x W x 104
where

Accum = chromium accumulation rate (pig/m2 year)

Csed = concentration of chromium in surficial sediment (pg/g dry weight)
W = mass sedimentation rate (g/cm2 year) based on 210Pb dating

104 = units conversion factor (cm2 => m2)

The surface-sediment concentrations of chromium were taken as the
concentration in the topmost 1 or 0.5 cm layers. The accumulation rates of
chromium in the sediment cores were corrected using the focusing factor. The
focusing-corrected sediment accumulation rate can be used in an entire lake. The
sedimentation rates (Table 3) were calculated by Golden et al. (1993). A variable
model was found best to describe sedimentation rates in cores from Lake Superior,
while a constant model was found that to describe sedimentation rates in cores
from Lakes Michigan and Ontario. The present mean accumulation rate of
chromium is highest in Lake Ontario and Iowect in Lake Superior (Table 3).
Present day chromium loadings into the sediments are 5.3 x 105 kg/year, 5.4 x 106
kg/year, and 3.0 x 105 kg/year for Lakes Superior, Michigan, and Ontario,
respectively (Table 3).

 

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42

Atmospheric Deposition of Chromium

An estimate of the relative proportion of recent atmospheric loadings of
chromium sediment can be made by the comparing recent accumulation rates in
surface sediments with atmospheric deposition rates. Atmospheric deposition
consists of both wet and dry depositions. Wet deposition is thought to be more
important than dry particle deposition in the Great Lakes (Mackay et al., 1986;
Eisenreich, 1987; Eisenreich, 1992b). However, dry deposition may be dominant
when the contaminants are associated with large particles (Murphy, 1984). Wet
deposition fluxes were calculated by the following relationship (Eisenreich et al.,
19923).

where
F(wet) = the wet only flux (pig/m2 year)

CTm = the total concentration of chromium in rain (pg/m3)
P = annual precipitation intensity (m/year)

Dry particle deposition was calculated as follows (Eisenreich et al., 1992a):

F(dry)=CT,aierdexfdxC
where

F(dry) = the dry particle flux of chromium (pg/m2 year)

CT,air = the total air concentration of chromium (pg/m3)

Q = the fraction of chemical in the particle phase in the season of interest
Vd = the dry 'cle deposition velocity (0.2 cm/sec

fd = the flammf the year not raining or snowing ( .9)

C = the units correction factor

V

43

The atmospheric dry deposition rates of chromium in the Great Lakes were
calculated from the data sources list on Table 4. Some of the data were given as
less than the detection limit. Therefore, the ranges of mean loadings were
estimated by considering concentrations below detection limits as zero for a
minimum loading or at the detection limit for a maximum loading

The atmospheric wet deposition rates of chromium in the Great Lakes are
calculated from the data of the Great Lakes Atmospheric Deposition (GLAD)
network (U.S.E.P.A, 1994). The data set consists of the atmospheric
measurements of chromium concentrations from over thirty sites around the Great
Lakes region. Chromium concentrations in wet deposition have declined from
1983 to 1991 (Figure 21). This trend is similar to the trends of chromium in the
sediment profiles. The average of chromium concentrations from 1988 to 1991,
was used in the calculates of the wet deposition rates.

Wet deposition rates of chromium are lower than dry deposition rates which
is contrary to previous assumptions. The total atmospheric deposition rate is
highest in Lake Ontario and Lowest in Lake Superior. The relative proportion of
atmospheric contributions to sediment accumulation rates is calculated by dividing
the atmospheric deposition rates by focusing-corrected sediment accumulation
rates (Table 6). The sediment accumulation rates of Lakes Superior, Michigan, and
Ontario are contributed by atmospheric deposition as 6-15%, 4-11%, and 2-7%,
respectively. Atmospheric deposition does not appear to be a major source of
chromium loading into the Great Lakes.

Anthropogenic Inventories and Anthropogenic Sediment Burden
Inventories of anthropogenic chromium in sediment cores were calculated

as follows:

1mg

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48

Inv(ug/cm2)=zi [Csedx(1-®)x p x d]
where

Inv = the chromium inventory in the core (pg/cmz)
Csed = background corrected chromium concentration in sediment

(us/8 dry weight)
Q = volumetric water fraction (porosity)
p = sediment dry density (2.45 g/cm2)
i = number of depth increment
d = thickness of each increment (cm)

The inventories are corrected using the focusing factor. Table 7 and Figure
22 shows the calculated and focusing corrected chromium inventories. All of the
calculations are shown in appendix D. Uncorrected inventories of chromium are
different within basins and between lakes due to the variations in sediment
focusing Focusing corrected inventories of Lake Michigan collapse to similar
value and perhaps also those of Lake Ontario. However, the focusing corrected
inventories between Lake Michigan and Lake Ontario are difi‘erent. This means
that atmospheric deposition of chromium is not important source to the Great
Lakes region or perhaps there is regional gradient of chromium concentration in
the atmosphere of the Great Lakes.

The anthropogenic sediment burdens of chromium to the lakes are
calculated as follows:

ASB (kg) = (Ej Invc)/j x SA
Where

ASB = anthropogenic sediment burden to the lake
j = number of sites

Invc = focusing corrected inventory (kg/m2)

SA = surface area of lake (m2)

49

 

 

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51

Preliminary estimates of anthropogenic chromium loading into the
sediments ofLake Michigan and Lake Ontario are 1.49 x 108 kg, 1.33 x 108 kg
respectively (Table 7). Since the ratio of anthropogenic loading to background
loading is so low, it is dificult to detect anthropogenic loading from Lake Superior

sample cores.

V. Conclusions

 

Sediment cores were obtained from lakes Superior, Michigan, and Ontario
to determine anthropogenic loading histories, chemical inventories, and recent
accumulation rates of chromium. Pre-industrial concentrations of chromium,
which are found to be typical for soil in the area, were determined and subtracted
from the total metal concentrations to estimate anthropogenic loads. Sediment ages
were determined by 210Pb dating Inventories and recent metal accumulation rates,
estimated from recent sediment concentrations, were corrected for sediment
focusing by 210Pb inventories.

Surface concentrations in sediment cores exceed background concentrations
1-3.6 times in Lake Michigan and Lake Ontario. However, the results generally
show that chromium loading rates are decreasing to the present On the other hand,
the trends in Lake Superior are not typical anthropogenic profiles and
anthropogenic inventories could not be calculated F ocusing-corrected inventories
are similar within basin of each lake, but are greater in Ontario than Michigan The
total amount of anthropogenic loading of chromium to the Lake Michigan is 1.49 x
108 kg and Lake Ontario is 1.33 x 108 kg Focusing-corrected sediment
accumulation rates show trends that are similar to those of chromium inventories.
Accumulation rates are lowest for Superior. Atmospheric deposition rates of
chromium were estimated from a variety of sources. The sediment accumulation
rates of Lakes Superior, Michigan, and Ontario are contributed by atmospheric
deposition as 6-15%, 4-11%, and 2-7%, respectively. These results show that the

52

ll"

53

focusing-corrected inventories are similar throughout depositional basins within
each lake. Atmospheric deposition is not major source of chromium input to the

Great Lakes.

Appendices

55

Appendix A

 

Table A-1
Lake Michigan EPA #11
Lat: 42° 22' 36"N, Long 86° 59' 05"W, Depth 131 m
Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Dark gray soupy material

2 1-2 1 Dark gray soupy material

3 2-3 1 Dark gray, less soupy

4 3-4 1 Dark gray, ahnost solid material

5 4-5 1 Dark gray, solid material

6 5-6 1 Upper portion dark gray, lower 0.2 cm
light red color, possible worm burrows
in section

7 6-7 1 Light gray, with tan mottling, some dark
blebs of material (carbon)

8 7-8 1 More rigid, slightly more tan coloration
and mottlingnpossible Fe oxides

9 8-9 1 Upper portion firm, lower portion soupy,
same coloration

10 9-10 1 Sand present in this layer, same color

11 10-11 1 Higher sand content, possible Fe oxides

12 11- 12 1 Light tan upper portion, Redox bands
begin (tilted), yellow redox crust at
base of section

13 12- 12.5 1 Yellow redox crush-cements the
sediment, 1 cm thick, remainder of
section is light tan material, firm

l4 12.5-13.5 1 More redox material, as in 13, light tan
material also remainder of section

15 13.5-14.5 1 Lighttanmaterialwithdarkspecks
(carbon?), redox material at base with
green material (vivianite?)

16 14.5-15 1 Redox crusts (2) each 0.1 cm thick Fe/Mn
oxides, remainder is light tan material

17 15-15.5 1 Tan and gray mottling materialverydry

18 15.5-16.5 1 Some redox, no sand

19 16.5- 17.5 1 Redox layer near bottom of section

20 17. 5- 18.5 1 Thicker redox layer, pockets in middle of

section, dark tan blebs 2 mm across

21
22

23

24

25

18.5-20.5
20.5-22.5

22.5-24.5

24.5-26. 5

26.5-28.5

56

Mottling disappears through section

Redox layer 0.75 cm from section top,
some mottling, remainder is tan

Redox layer, no mottling, tan with some
gray material, Current active redox
layer (color change)

Light gray, several black layers, much
more soupy (anoxic layers)

Same as 24, slightly more black material

Table A-2

Lake Michigan EPA #18

Lat: 42° 44' 44"N, Long 87° 00' 10"W, Depth 151 m

 

Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Gray soupy material, worm burrows

2 1-2 1 Gray soupy material, worm burrows

3 2-3 1 Gray material, less soupy, worm burrows

4 3-4 1 Gray material, less soupy, worm burrows

5 4-5 1 Gray material, ahnost firm, worm
burrows

6 5-6 1 Gray material, firm

7 6-7.5 1.5 Gray material, firm

8 7.5-8.5 1 Gray material, firm

9 8.5-9.5 1 Gray material, firm

10 95-105 1 Gray material, firm

ll 10.5-11.5 1 Slightly lighter gray material, some sand

12 11.5-12.5 1 Mottled gray and tan, some zones of
black material, much more sand

13 12.5-13.5 1 Same as 12

14 13.5-14.5 1 Zones of dry dark material (carbon7),
some mottling, gritty

15 14.5-15.5 1 Less black material, sand content
decreases

16 15.5-16.5 1 Mostly gray, black almost gone, no sand

17 16.5-17.5 1 Afewdarkstreaksinthe light gray
material

18 17.5-18.5 1 Same as 17, mostly firm

19 18.5-19.5 1 No dark streaks, same as 18

20 19.5-20.5 1 Dark band at base, remainder is gray/tan
material

21 20.5-21.5 1 Dark gray material, some sand

22 21.5-22.5 1 Same as 21

23 225-235 1 Dark material abundant, same as 21

24 23.5-24.5 1 Same as 23

25 24.5-25.5 1 Same as 23

26 25.5-27.5 2 Same as 23

27 27.5-29.5 2 Some slight mottling, dark bands at base

Skip 29.5-31.5 2 Material discarded, same as 27

28 31.5-33.5 2 More soupy, less dark material, mostly
light gray with some mottling

29 33.5-35.5 2 Same as 28

 

Skip
3o
31

Skip
32
Skip
33

35.5-37.5
37.5-39.5
39.5-41.5

41.5-43.5
43.5-45.5
45.5-47.5
47.5-49.5

NNN

NNNN

58

Material discarded, same as 29

No dark streaks, all gray material

Mostly very dark material, remainder is
light any

Material discarded, same as 31

Very dark material

Material discarded, same as 32

Very dark material with some tan layers,
bottom of core touches stopper

59

Table A-3

Lake Michigan EPA #19

Lat: 42° 44' OO"N, Long 86° 35' OO"W, Depth 95 m

 

Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Gray soupy material

2 1-2 1 Gray soupy material

3 2-3 1 Gray soupy material, more firm

4 3-4 1 Gray soupy material, more firm

5 4-5 1 Dark gray material, ahnost firm

6 5-6 1 Dark gray to tan material, almost firm

7 6-7 1 Light gray and tan material, firm

8 7-8 1 Same as 7

9 8-9 1 Same as 7 with mottling

10 9-10 1 Lighttanwithincreasing light material,
some sand present

11 10-11 1 Iighttanmaterialwith sand

12 11-12 1 Tan material with rust brown spots (Fe
minerals ?)

13 12-13 1 Darker and more gray, more rust spots

14 13-14 1 Same as 13, fewer rust spots, some other
light mottling

15 14-15 1 Dark tan color deepens to base of sample

16 15-16 1 Redox zone: dark tan band 0.4 cm thick,
dark gray band 0.2 cmthick, rust
brown band 0.4 cm thick-solid crust

17 16-17 1 Drytancrustattop,graywaterymaterial
below (0.6 cm)

18 17-18 1 Graycreamytextured material

19 18-19 1 Same as 18

20 19-20 1 Same as 18 with dark spots of organic
material present

21 20-22 2 Dark gray sandy material with black
streaks at base of section

22 22-24 2 Same as 21 , with a 0.3 cm band of black,
rigid organic material

23 24-26 2 Lighter gray creamy texture with

some dark spots

24 26-28 2 Same as 23 with sand and gravel up to 1
mm in size

25 28-30 2 Darker gray than 24, sand and

gravelup to 1.5 mminsize

 

Table A-4
Lake Ontario EPA #19
Lat: 43° 30' 00"N, Long 79° 25' 00"W, Depth 105 111
Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Tan soupy material, worm burrows

2 1-2 1 Tan soupy material

3 2-3 1 Tan material, less soupy

4 3-4 1 Tan material grades into gray material,
ahnost firm

5 4-5 1 Gray material, slightly watery

6 5-6 1 Gray color darkens to base, some sand

7 6-7 1 Gray material with dark spot, grades into
tan material. slightly gritty

8 7-8 0.5 Tan material grades into gray

9 8-9 0. 5 Dry redox boundary (orange)

10 9-10 1 Gray material with some redox chunks

11 10-11 1 Gray material with some black spots

12 11- 12 l Darker gray material with dry black spots

13 12-13 1 Dark gray with dark spots, shades to
lighter gray with dark black spots

14 13- 14 1 Same as 13, dry at base

15 14-15 1 Mostlydarkmaterial mixedwithlight
any maten'nl

16 15-16 1 Same as 15

17 16-17 1 Same as 16, pockets of water in light gray
material

18 17-18 1 Same as 17

19 18-19 1 Same as 17

20 19-20 1 Light gray shades into dark gray material

21 20-22 1 Same as 17

22 22-24 2 Dark gray grades into watery light gray
material

23 24-26 2 Same as 22

24 26-28 2 Tan to dark tan in color

25 28-30 2 Tan and dark tan material

26 30-32 2 Same as 25

27 32-34 2 Same as 25

28 34-36 2 Same as 25

29 36-38 2 Same as 25

30 38-40 2 Same as 25

Table A-5

Lake Ontario EPA #25a

Lat: 43° 30' 00"N, Long 79° 05' WW, Depth 120 m

 

Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Tan, very soupy material, worm burrows

2 1-2 1 Tan material, less soupy

3 2-3 1 Same as 2

4 3-4 1 Lighter tan material, ahnost firm

5 4-5 1 Same as 4

6 5-6 1 Very dark gray material

7 6-7 1 Same as 6, but darker color

8 7-8 1 Same as 7, with darker spots

9 8-9 1 Same as 8

10 9-10 1 Same as 8, darker color, more black
material

11 10-11 1 Lighter color, more dark spots

12 11-12 1 Sameasll,butverydry

13 12-13 1 Same as 12

14 13- 14 1 More dark material at base

15 14-15 1 Verydarkmaterialatbase

16 15- 16 1 Very dark throughout section, lots of
dark gray material at base

17 16- 17 l Lighter color, with more gray material

18 17-18 1 Same as 17

19 18-19 1 Mostly light tan with some black material,
very creamy

20 19-20 1 Gets darker at base of section

21 20—22 1 Light colored and firm, changes to darker
colored and wet at base

22 22-24 2 Light and dark material mixed, very wet

23 24-26 2 Same as 22, darker at base

24 26-28 2 Same as 22, darker throughout section

25 28-30 2 Same as 22

26 30-32 2 Same as 22

27 32-34 2 Same as 22

28 34-36 2 Same as 22, darker color

29 36-38 2 Same as 28

30 38-40 2 Same as 28

 

62

Table A-6

Lake Ontario EPA #40a

Lat: 43° 37' 00"N, Long; 78° 05' 00"W, Depth 189 m

 

Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Tan flufi; some spots of black material

2 1-2 1 Same as 1, Some gray spots

3 2-3 1 Tan with gray spots, ahnost firm

4 3-4 1 Greenish tan material, very soupy, black
and gray spots at base of section

5 4—5 1 Gray colored material, some chunks of
black material, ahnost firm

6 5-6 1 Same as 5, darker towards base, and
black stufi‘ gets coarser

7 6-7 1 Gray darkens, black chunks get larger

8 7-8 1 Dark gray with tan mottling, color
darkens towards base with black
chunks

9 8-9 1 Mostly tan with black mottling (chunks)

10 9-10 1 Very dark gray to black material

11 10-11 1 Same as 10, black chunks and gray
mottling are present

12 11- 12 1 Fewer black chunks, tan with black
mottling at base of section

13 12-13 1 Same as 12

14 13-14 1 Dark gray color turns to light gray at
base, becomes creamy texture

15 14-15 1 lighter color tan/gray, small black chunks

16 15- 16 1 Gray color with black spots increasing to
the base of section

17 16-17 1 Gray/ tan material darkens towards base
of section, becomes firm

18 17- 18 1 Uniform black material

19 18-19 1 Same as 18, becomes lighter to base

20 19-20 1 Dark gray/ tan with black chunks within
light tan patches

21 20-21 1 Medium tan becomes darker gray at base
of section

22 21-22 1 Medium tan becomes lighter towards base
with lighter patches

23 22-23 1 Light tan at top with black layer 0.1 mm

thick, tan becomes dark to base

24

25
26

27
28
29
Skip
30
Skip
31

"' Remainders of this core are not analyzed.

23-24

24-25

25-26

26-27
27-28
28-29
29-30
30-31
31-32
32-33

p—ay—ap—ap—ap—ap—ap—a

63

Light/dark tan mixture with black
mottling at top, becomes light tan at
base, two thick black layers in section

Light tan with a black layer, darkens to
dark tan color at base

Same as 25, more black material, more
wet

Same as 26

Mixture of light and dark tan material

Same as 28

Material discarded

Creamy light and dark tan material

Material discarded

Light tan changes to dark tan at base,
some kind of grass like material

 

Table A-7
Lake Ontario EPA #64a
Lat: 43° 35' 00"N, Long; 77° 07‘ 00"W, Depth 168 m
Sample # Depth (cm) Thickness (cm) Description

1 0-1 1 Tan soupy material

2 1-2 1 Darker tan soupy material, more firm

3 2-3 1 Same as 2

4 3-4 1 Gray material with some tan mixed in,
almost firm, worm burrows

5 4-5 1 Gray darkens to base, some tan mottling,
few worm burrows

6 5-6 1 Tan mottling in gray upper part, black
material in darker gray at base

7 6-7 1 Gray to dark gray material with black
mottling

8 7-8 1 Same as 8

9 8-9 1 Same as 8

10 9-10 1 Same as 8, more black material

11 10-11 1 Same as 10, some light gray material

12 11-12 1 Same as 11 , much drier, becomes wetter
at base and color lightens

13 12- 13 1 Same as 12, pockets of water and much
more black material at base

14 13- 14 1 Same as 13

15 14-15 1 Light graymixedwithdarkgray and
black spots

16 15-16 1 Same as 15

17 16-17 1 Same as 15, very light gray material also

18 17-18 1 Light and dark material mixed

19 18-19 1 Very light gray with black or dark gray
spots in lower half of section

20 19-20 1 Same as 19

21 20-21 1 Same as 19, drier

22 21-21.75 0.75 Same as 21

23 21.75-22 0.25 Redox zone, orange crust with dark
material mixed in

24 22-23 1 Very light gray material, wetter, not quite
the same material as above redox

25 23-24 1 Same as 24, some pink material

26 24-25 1 Same as 25

27

23
29
3o
31
Skip
32
Skip
33

Skip
34
Skip
35

Skip
36

Skip
37

Skip
38

Skip
39

25-26

26-27
27-28
28-29
29-30
30-31
31-32
32-33
33-34

34-35
35-36
36-37
37-38

38-39
39-40

40-41
41—42

42-43
43-44

44-45
45-46

.—

p—au—as—ay—ag—a—as—ap—a

p—ap—ay—ap—a

p—a

65

Tan gray and blue gray mix, tan gray
material is wetter

Same as 27

Mostly tan gray material, wet

0.25 cm black material

Same as 30

Material discarded

Same as 30

Material discarded

Turns dark at base of section, light gray
and black becomes light gray

Material discarded

Mostly light tan with black specks

Material discarded

Mostly light gray with black material at
base of section

Material discarded

Lots of black material and some pockets
of water in the gray material

Material discarded

Upper part of section is light gray with
black specks, turns black at base

Material discarded

Mixture of light gray and predominantly
black material

Material discarded

Same as 38, slightly lighter color

 

 

Table A-8
Lake Ontario E 30
Lat: 43° 32' 16"N, Long 76° 54' 03"W
Sample # Depth (cm) Thickness (cm) Description

1 0.0-0.5 0.5 Tan sediment

2 0.5-1.0 0.5 Tan sediment

3 1.0-1.5 0.5 Tan sediment

4 1.5-2.0 0.5 Tan sediment

5 2.0-2.5 0.5 Sharp bormdary, tan above

with darker sediment below

6 2.5-3.0 0.5 Dark material and fish bones
7 3.0-3.5 0.5 Dark material and sediment
8 3.5-4.0 0.5 Dark sediment

9 4.0-4.5 0.5 Dark sediment

10 4.5-5.0 0.5 Dark sediment

11 5.0-5.5 0.5 Dark sediment

12 5.5-6.0 0.5 Dark sediment

13 6.0-6.5 0.5 Dark sediment

14 6.5-7.0 0.5 Dark sediment

15 7.0-7.5 0.5 Dark sediment

16 7.5-8.0 0.5 Dark sediment

17 8.0-8.5 0.5 Beginning of tan/ black

layering

18 8.5-9.0 0.5 Tan/ black sedment layering
19 9.0-9.5 0.5 Tan/ black sediment layering
20 9.5-10 0.5 Tan/ black sediment layering
21 10-11 1 Tan/ black sediment layering
22 11- 13 2 Tan/ black sediment layering
23 13-16 3 Tan/ black sediment layering
24 16-18 2 Tan/ black sediment layering

Table A-9

67

Lake Superior DTL

Lat: 46° 50' 50"N, Long 91° 45' 11"W

 

Sample # Depth (cm) Thickness (cm) Description

1 0.0-0.5 0.5 Reddish mud
2 0.5-1.0 0.5 Reddish mud
3 1.0-1.5 0.5 Reddish mud
4 1.5-2.0 0.5 Reddish mud
5 2.0-2.5 0.5 Reddish mud
6 2.5-2.75 0.25 Mud above redox zone
7 2.75-3.0 0.25 Black redox zone
8 3.0-3.1 0.1 Very thin iron redox zone
9 3.1-3.35 0.25 Red layered mud
10 3.35-3.85 0.5 Red layered mud
11 3.85-4.35 0.5 Red layered mud
12 4.35-4.85 0.5 Red layered mud
13 4.85-5.35 0.5 Mud somewhat darker
14 5.35-5.85 0.5 Darker mud
15 5.85-6.35 0.5 A lot ofslag in a dark mud
l6 6.35-7.35 l Slag material in a dark mud
l7 7.35-8.35 l Slag amount decreasing
18 8.35-9.35 1 Little slag material lefi
19 9.35- 10.35 1 Black layer (1 mm thick)
20 10.35-11.35 1 No black layers lefi

Skip 11.35-12.35 1
21 12.35-13.35 1 Dark mud

Skip 13.35-14.35 1
22 14.35-15.35 1 Dark mud

Skip 15.35-16.35 1
23 16.35-17.35 1 Dark mud

Skip 17.35-18.35 1
24 18.35-19.35 1 Dark nmd

 

Table A-lO

68

Lake Superior SJE II

Lat: 47° 02' 00"N, Long: 91° 17' 94"W

 

Sample # Depth (cm) Thickness (cm) Description
1 0.0-0.5 0.5 Brown muddy sediment
2 0.5-1.0 0.5 Brown muddy sediment
3 1.0-1.5 0.5 Brown muddy sediment
4 1.5-2.0 0.5 Brown grading to gray colored sediment
5 2.0-2.5 0.5 Sediment darkening
6 2.5-3.0 0.5 Dark sediment
7 3.0-3.5 0.5 Dark sediment
8 3.5-4.0 0.5 Dark sediment, appears mottled
9 404.25 0.25 Mottled, Mn oxide layer, dark sediment.
10 4.25-4.4 0.15 Redox zone, 4.40 to 4.50 cm increment
was thrown away

11 4.5-5.0 0.5 Slight color change to reddish
12 5.0-5.25 0.25 Reddish colored mud
l3 5.25-5.65 0.4 Better developed redox zone
14 5.65-6.05 0.4 Redox zone with interspaced material
15 6.05-6.55 0.5 Redox zone with wet mud
16 6.55-7.05 0.5 Redox zone ending, wet mud
17 7.05-7.55 0.5 Brown-red uniform mud
18 7.55-8.55 1 Brown-red uniform nrud
19 8.55-9.55 1 Small ( < 1 rmn) black band

Skip 955-1055 1
20 10.55-11.55 1 Darkstreaksinsediment
21 11.55-12.55 1 Mostly lighter sediment
22 12.55-14.55 2 Large dark band( 2 mm thick)

Skip 14.55-16.55 2
23 16.55-18.55 2 Dark material fades out

Skip 18.55-20.55 2
24 20.55-22.55 2 Dark material fades out

 

69

Table A-ll

Lake Superior #1383

Lat: 47° 39' 24" N, Long 87° 57' 98" W

 

 

Sample # Depth (cm) Thickness (cm) Description

1 0.0-1.0 1 Greenish-brown wet fluff

2 1.0-2.0 1 Greenish-brown wet flufl‘

3 2.0-3.0 1 Greenish-brown wet flufi‘, tan

’ contact near base

4 3.0-3.5 0.5 Tan sediment, slightly drier

5 3.5-4.0 0.5 Greenish-black sticky material,
possible start of redox

6 4.0-4.5 0.5 Flaky dry pale orange sediment,
redox boundary

7 4.5-5.5 1 Gray, wet sticky clay

8 5.5-6.5 1 Gray, wet sticky clay

9 6.5-8.5 2 Gray, wet sticky clay

10 8.5- 10.5 2 Gray, wet sticky clay

11 10.5-12.5 2 Gray, wet sticky clay

12 12.5-14.5 2 Gray, wet sticky clay

13 14.5-17.5 3 Gray, wet sticky clay

14 175-205 3 Gray, wet sticky clay

15 20.5-24.5 4 Gray, wet sticky clay

16 24.5-28.5 4 Gray, wet sticky clay

17 28.5-32.5 4 Gray, wet sticky clay

18 32.5-36.5 4 Gray, wet sticky clay

* Remainder of sediment discarded

70

Table A-l2

Lake Superior #1391

Lat: 46° 45' 40" N, Long: 84° 47' 09" W

 

Sample # Depth (cm) Thickness (cm) Description
1 0.0-1.0 1 Brown flufl‘ material
2 1.0-2.0 1 Dark brown sediment
3 2.0-3.0 1 Very dark brown/ sandy
4 3.0-3.5 0. 5 Redox zone, black-red sediment
5 3.5-4.5 1 Light red sediment
6 4. 5-5.5 1 Black material below redox
7 5.5-6.5 1 Light gray/ black sediment
8 6. 5-8.5 2 Light gray/ black sediment
9 85-105 2 Light gray/ black sediment
10 10.5-11.5 1 End ofblack sediment
11 11.5-14.5 3 Gray sediment
_ 12 14.5-16.5 2 Gray sediment
13 16.5-19.5 3 Gray sediment
14 195-235 4 Gray sediment
15 235-285 5 Gray sediment

71

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72

Table B-2

 

Quality assurance: SRM

Sample # Concentrationngg)
EPA#11 93.90
EPA#18 93.90
EPA#19(LM) 88.91
EPA#47s(?) 78.61
EPA#68k 85.92
EPA#19(LO) 93.90
EPA#40A 93.90
EPA#64A 86.82
13.30 79.87
NOAA#3 83.44
DTL 86.09
SJE 11 81.57
#1390 86.22
#1391 85.19

Mean 87.02

73

Table B-3

The background concentration of chromium
in the sediments of this study

Sediment sample # Concentrationhgglg)
EPA#l 1 30.49
EPA#18 27.98

EPA#19(LM) 26.23
LM #47s(?) 34.20
LM #68k 33.05
EPA#19(LO) 35.70
EPA#25a 33.60
EPA #40a 37.66
EPA#64a 29.20
E-30 32.68
NOAA #3 73.00
DTL 49.45
SJE H 63.16
#1390 83.06
#1391 20.00
Mean 40.63
Range 20.00 - 83.06

74

Appendix C
Table 01

EPA #11 chromium concentration and porosity data

Adjustedby Normalizedby

Sample # Map) Age Porosig (%) Confpgzg) M eon. MM
1 0.50 1970.5 84.6 49.73 19.24 24.88
2 1.50 1938.0 82.4 47.92 17.43 23.97
3 2.50 1915.3 82.2 50.89 20.40 25.46
4 3.50 1895.0 79.5 50.32 19.83 25.17
5 4.50 1877.0 79.2 47.23 16.74 23.63
6 5.50 1858.0 77.8 41.59 11.10 20.81
7 6.50 1838.4 77.2 34.93 4.44 17.47
8 7.50 1817.3 73.6 33.25 2.76 16.63
9 8.50 1794.2 73.3 32.97 2.48 16.49
10 9.50 1770.1 73.0 36.01 5.52 18.01
11 10.50 1745.1 66.3 30.09 15.05
12 11.50 67.5 44.40 22.21
13 12.25 68.4 51.11 25.57
14 13.00 64.9 38.27 19.14
15 14.00 ' 61.4 33.27 16.64
16 14.75 64.0 30.66 15.34
17 15.25 66.5 30.49 15.25
18 16.00 65.8 32.29 16.15
19 17.00 63.6 33.39 16.70

20 18.00 64.9 29.98 15.00
21 19.50 66.7 35.35 17.68
22 21.50 66.7 35.96 17.99
23 23.50 65.8 31.73 15.87
24 25.50 64.4 35.79 17.90

N
M

27.50

66.6

39.64

19.83

75

Table C-2

EPA #18 chromium concentration and porosity data

Adjusted by Normalized by
Sample # Deflmm) Age Porgy 1%) gm b_kgd con. focusipg factor
1 0.5 1989.7 94.2 50.81 22.83 20.88
2 1.5 1984.4 93.1 46.38 18.40 19.06
3 2.5 1977.8 91.5 48.43 20.45 19.90
4 3.5 1970.8 90.5 51.68 23.70 21.23
5 4.5 1963.4 89.8 49.93 21.95 20.51
6 5.5 1956.1 89.3 49.47 21.49 20.32
7 6.8 1945.6 89.2 45.19 17.21 18.57
8 8 1938.3 89.2 40.28 12.30 16.55
9 9 1931.0 89.1 39.10 11.12 16.06
10 10 1923.8 88.3 41.33 13.35 16.98
11 11 1916.5 87.5 33.27 5.29 13.67
12 12 1856.5 87.6 37.69 9.71 15.48
13 13 1793.1 87.3 32.43 4.45 13.32
14 14 1776.8 87.2 33.24 5.26 13.66
15 15 87.0 36.25 8.27 14.89
16 16 87.0 30.73 2.75 12.63
17 17 87.0 29.34 1.36 12.05
18 18 26.49 10.88
19 19 29.73 12.21
20 20 30.29 12.44
21 21 27.83 11.43
22 22 31.89 13.10
23 23 31.60 12.98
24 24 27.67 11.37
25 25 29.76 12.23
26 26.5 27.58 11.33
27 28.5 28.90 11.87
28 32.5 28.46 11.69
29 34.5 28.31 11.63
30 38.5 27.64 11.36
31 40.5 26.68 10.96
32 44.5 24.52 10.07
33 48.5 22.86 9.39

 

76

Table C-3

EPA #19(LM) chromium concentration and porosity data

Adjustedby Normalizedby
Sample # Mg) Age Foggy ('Vo) comm Mm, rm} factor

1 0.5 1989.8 94.2 67.24 41.01 55.25
2 1.5 1983.9 93.1 69.07 42.84 56.75
3 2.5 1972.2 91.5 66.06 39.83 54.28
4 3.5 1956.4 90.5 58.23 32.00 47.85
5 4.5 1939.2 89.8 50.81 24.58 41.75
6 5.5 1918.1 89.3 39.02 12.79 32.06
7 6.5 1891.7 89 26.81 0.58 22.03
8 7.5 63.8 19.59 16.10
9 8.5 61.4 18.61 15.29
10 9. 5 66.4 20.88 17.16
11 10.5 63.9 18.84 15.48
12 11.5 70.3 23.64 19.42
13 12.5 73.1 26.31 21.62
14 13.5 72.1 24.76 20.35
15 14.5 71.8 27.17 22.33
16 15.5 71.6 22.76 18.70
17 16.5 71.9 30.13 24.76
18 17.5 71.2 26.72 21.96
19 18.5 73.6 29.37 24.13
20 19.5 75.1 33.84 27.81
21 21 66.7 30.27 24.87
22 23 68.2 33.90 27.86
23 25 68.2 30.90 25.39
24 27 65.6 27.17 22.33
25 29 67.8 27.30 22.43

 

77

Table C-4

EPA #473 (?) chromium concentration and porosity data

Adjustedby Normalizedby

Sample # Mg) Age Porosig (%) MM b_kgg con. fmmg' factor
1 0.25 1990.5 98.4 51.46 17.26 34.31
2 0.75 1986.5 97.3 48.63 14.43 32.42
3 1.25 1981.4 97.5 61.85 27.65 41.23
4 1.75 1975.2 97.0 57.60 23.40 38.40
5 2.25 1969.0 96.6 58.08 23.88 38.72
6 2.75 1962.8 96.7 65.78 31.58 43.85
7 3.25 1955.0 95.4 57.84 23.64 38.56
8 3.75 1945.6 95.2 63.40 29.20 42.27
9 4.50 1936.2 94.9 57.92 23.72 38.61
10 5.50 1924.6 94.1 64.79 30.59 43.19
11 6.50 1910.7 94.2 63.86 29.66 42.57
12 7.50 1896.4 92.1 57.90 23.70 38.60
13 8.50 1881.7 92.7 52.08 17.88 34.72
14 9.50 1867.0 93.1 47.79 13.59 31.86
15 10.50 91.4 46.49 12.29 30.99
16 11.50 93.4 42.13 7.93 28.09
17 12.50 92.3 38.69 4.49 25.79
18 13.50 93.2 38.71 4.51 25.81
19 14.50 93.3 37.07 2.87 24.71

20 15.50 93.6 36.75 2.55 24.50
21 16.50 93.3 35.55 1.35 23.70
22 17.50 91.6 35.38 1.18 23.59
23 18.50 90.8 34.08 22.72
24 19.50 91.2 34.37 22.91
25 23.50 34.16 22.77

. nun IFS." "1

 

78

Table 05

EPA #68k chromium concentration and porosity data

 

 

Adjusted by Normalizedby
§_ample # Bentham) 53.: BMW (%) Configlg) b_kgg con. focusipg factor
1 0.25 1991.4 98.0 43.91 10.86 34.66
2 0.75 1989.3 96.6 51.87 18.82 40.94
3 1.25 1986.6 95.6 54.16 21.11 42.75
4 1.75 1983.4 94.7 57.64 24.59 45.49
5 2.25 1980.1 94.0 59.29 26.24 46.80
6 2.75 1976.8 93.8 63.24 30.19 49.91
7 3.25 1973.0 94.1 61.22 28.17 48.32
8 3.75 1968.7 93.3 62.84 29.79 49.60
9 4.50 1962.3 93.5 61.22 28.17 48.32
10 5.50 1953.4 94.2 52.09 19.04 41.11
11 6.50 1944.0 93.9 47.57 14.52 37.55
12 7.50 1934.6 94.9 43.91 10.86 34.66
13 8.50 1925.2 93.6 37.07 4.02 29.26
14 9.50 1915.6 92.8 38.01 4.96 30.00
15 10.50 1905.7 93.8 39.44 6.39 31.13
16 11.50 1895.9 92.0 33.41 0.36 26.37
17 12.50 1886.0 94.0 38.24 5.19 30.18
18 13.50 1876.0 92.6 34.69 1.64 27.38
19 14.50 1866.0 92.6 33.14 0.09 26.16
20 15.50 1855.7 94.0 32.29 25.49
21 16.50 1845.1 91.6 32.74 25.84
22 17. 50 93.3 36.81 29.05
23 18.50 93.9 33.18 26.19
24 19.50 91.5 36.42 28.75
25 31.88 25.16

 

Table C-6

541319191!

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79

EPA #19(LO) chromium concentration and porosity data

Adjustedby Normalizedby
Mata) Age Form—Mm 99203218) 1.358512% mm

0.5 1989.4 94.2 71.85 39.17 67.78
1.5 1983.8 92.2 73.91 41.23 69.73
2.5 1977.0 90.9 58.66 25.98 55.34
3.5 1969.5 90.6 84.87 52.19 80.07
4.5 1961.8 90.4 88.23 55.55 83.24
5.5 1953.0 87.9 86.76 54.08 81.85
6.5 1942.0 85.0 61.62 28.94 58.13
7.0 1920.0 83.0 39.68 7.00 37.43
7.5 1891.1 81.8 28.95 27.31
8.5 1838.1 83.6 41.97 39.59
9.5 84.5 39.90 37.64
10.5 85.1 35.03 33.05
11.5 84.5 36.33 34.27
12.5 84.3 34.08 32.15
13.5 84.7 34.84 32.87
14.5 84.0 35.87 33.84
15.5 84.7 37.62 35.49
16.5 84.3 35.61 33.59
17.5 84.4 33.51 31.61
18.5 84.5 34.67 32.71
19.5 84.1 33.55 31.65
21.5 83.9 37.36 35.25
23.5 31.40 29.62
25.5 37.74 35.60
27.5 36.38 34.32
29.5 36.22 34.17
31.5 34.51 32.56
35.5 36.61 34.54
37.5 37.75 35.61
39.5 35.53 33.52

 

Table C-7

Sample #

0m\30\\h&WNr—n

80

EPA #258 chromium concentration and porosity data

Adjustedby Normalizedby
Mm) Age Pom__'mLL_1% ._(iismCon mam. W

0.5 89.0 52.63 19.03
1.5 87.0 55.13 21.53
2.5 85.8 58.38 24.78
3.5 84.7 66.85 33.25
4.5 85.2 79.14 45.54
5.5 85.0 108.42 74.82
6.5 85.3 111.62 78.02
7.5 83.6 86.45 52.85
8.5 81.7 86.52 52.92
9.5 80.2 78.86 45.26
10.5 78.0 58.35 24.75
11.5 79.1 51.68 18.08
12.5 78.1 46.68 13.08
13.5 79.3 39.93 6.33
14.5 78.2 38.53 4.93
15.5 78.1 36.17 2.57
16.5 78.6 35.32 1.72
17.5 77.8 34.22 0.62
18.5 77.2 36.37 2.77
19.5 78.0 35.94 2.34
21.0 77.1 34.16 0.56
23.0 77.7 33.31

25.0 78.3 33.10

27.0 77.5 34.06

29.0 77.6 33.45

31.0 77.6 32.79

33.0 76.2 32.26

35.0 77.1 32.22

37.0 78.1 31.99

39.0 77.1 32.93

 

81

Table 08

EPA #40a chromium concentration and porosity data

Adjustedby Normalizedby
Sample # Ming) Age Porosity 1%) Con(1_1g(g) b_kgg eon. focus’pg factor

1 0.5 1990.9 92.3 38.58 0.92 22.63
2 1.5 1988.7 89.5 54.62 16.96 32.04
3 2.5 1985.6 87.8 57.79 20.13 33.89
4 3.5 1981.7 86.9 65.31 27.65 38.30
5 4.5 1977.7 88.0 73.75 36.09 43.26
6 5.5 1974.0 88.9 81.58 43.92 47.85
7 6.5 1970.6 86.7 105.10 67.44 61.64
8 7.5 1967.1 88.3 88.41 50.75 51.85
9 8.5 1963.7 86.7 87.94 50.28 51.58
10 9.5 1959.9 86.6 82.44 44.78 48.35
11 10.5 1955.8 84.4 77.05 39.39 45.19
12 11.5 1951.4 81.9 72.12 34.46 42.30
13 12.5 1946.8 82.7 61.36 23.70 35.99
14 13.5 1937.0 98.4 53.32 15.66 31.27
15 14.5 1927.4 81.2 48.98 11.32 28.73
16 15.5 1917.6 81.3 43.08 5.42 25.27
17 16.5 1907.6 82.6 37.94 0.28 22.25
18 17.5 1897.3 81.4 36.15 21.20
19 18.5 ' 1886.6 83.2 37.66 22.09
20 19.5 1876.1 82.3 37.81 22.18
21 20.5 81.9 38.57 22.62
22 21.5 81.7 38.95 22.84
23 22.5 82.0 43.37 25.44
24 23.5 82.7 41.25 24.19
25 24.5 82.7 39.29 23.04
26 25.5 82.4 51.67 30.30
27 26.5 81.1 40.01 23.47
28 27.5 82.6 38.81 22.76
29 28.5 83.2 37.77 22.15
30 30.5 82.3 37.79 22.16
31 32.5 81.2 41.30 24.22

 

 

Table C-9

82

EPA #64a chromium concentration and porosity data

5.814113%

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0.50
1.50
2.50
3.50
4.50
5.50
6.50
7.50
8.50
9.50
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11.50
12.50
13.50
14.50
15.50
16.50
17.50
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23.50
24.50
25.50
26.50
27.50
28.50
29.50
31.50
33.50
35.50
37.50
39.50

Adjusted by
Age Porosig (7.) Con(1_1g(g) b_kgc_1 con.
93.2 45.22 16.02
90.3 51.43 22.23
89.1 55.10 25.90
91.1 64.74 35.54
90.0 82.95 53.75
89.4 99.26 70.06
87.5 85.51 56.31
85.9 74.32 45.12
83.3 70.73 41.53
84.0 60.35 31.15
82.6 51.29 22.09
82.1 43.63 14.43
82.7 37.87 8.67
80.9 33.74 4.54
80.6 31.41 2.21
79.8 29.92 0.72
80.5 28.58
81.0 29.79
79.9 29.28
76.2 33.83
74.7 30.98
76.1 31.26
75.2 22.23
74.7 32.76
74.1 31.69
73.9 32.49
71.2 29.90
73.7 26.67
75.4 29.80
75.6 31.42
73.0 27.94
74.1 26.00
75.5 31.87
74.4 27.43
74.0 26.84
77.3 27.84

Normalrzed’ by
focusrpg’ factor

83

37 41.50 76.6 24.78
38 43.50 74.7 29.40
39 45.50 74.2 28.06

84

Table 010

E 30 chromium concentration and porosity data

Adjustedby Normalizedby
Sample # Mpg) Ag; Porosig (°/o) Con(t_rg[g) mg con. focusipg factor
1 0.25 1989.6 93.0 33.78 1.10 16.56
2 0.75 1988.1 92.6 55.65 22.97 27.28
3 1.25 1987.4 92.2 54.26 21.58 26.60
4 1.75 1985.7 91.8 72.93 40.25 35.75
5 2.25 1984.3 91.5 81.62 48.94 40.01
6 2.75 1982.5 91.4 77.42 44.74 37.95
7 3.25 1980.8 91.3 113.04 80.36 55.41
8 3.75 1979.4 91.3 117.31 84.63 57.50
9 4.25 1978.0 91.2 114.63 81.95 56.19
10 4.75 1976.2 91.3 82.64 49.96 40.51
11 5.25 1974.8 91.5 79.50 46.82 38.97
12 5.75 1972.7 91.7 81.46 48.78 39.93
13 6.25 1971.3 91.7 77.08 44.40 37.78
14 6.75 1969.9 91.6 77.98 45.30 38.23
15 7.25 1968.5 91.5 73.44 40.76 36.00
16 7.75 1966.8 91.4 67.54 34.86 33.11
17 8.25 1965.4 91.1 59.36 26.68 29.10
18 8.75 1963.3 90.6 55.67 22.99 27.29
19 9.25 1961.9 90.5 59.08 26.40 28.96
20 9.75 1960.1 90.2 56.57 23.89 27.73
21 10.50 1957.7 89.7 51.02 18.34 25.01
22 12.00 1951.0 88.6 43.66 10.98 21.40
23 14.50 1940.6 88.1 34.11 1.43 16.72
24 17.00 1929.7 88.0 32.68 16.02

 

85

Table C-ll

DTL chromium concentration and porosity data

Adjustedby Normalizedby

Sample # Mm) Age Porosity (°/o) Con(1_1g[g) b_kgg eon. focusig factor
1 0.250 1989.3 83.1 30.90 20.88
2 0.750 1986.1 82.4 39.40 26.62
3 1.250 1981.4 82.6 40.53 27.39
4 1.750 1977.1 82.1 39.61 26.76
5 2.250 1973.7 81.3 36.13 24.41
6 2.625 1971.3 80.8 35.87 24.24
7 2.875 1969.7 83.3 35.69 24.11
8 3.050 1968.6 85.2 32.40 21.89
9 3.225 1967.2 81.9 36.30 24.53
10 3.600 1964.3 80.3 43.89 29.66
11 4.100 1960.5 80.9 50.93 34.41
12 4.600 1956.6 81.8 52.73 35.63
13 5.100 1952.8 81.6 49.85 33.68
14 5.600 1947.1 81.8 48.92 33.05
15 6.100 1941.3 82.2 44.81 30.28
16 6.850 1931.1 82.2 43.56 29.43
17 7.850 1916.8 81.7 51.32 34.68
18 8.850 1899.3 81.6 51.45 34.76
19 9.850 1879.6 81.5 50.73 34.28

20 10.850 82.1 49.84 33.68
21 12.850 81.9 48.92 33.05
22 14.850 82.0 50.92 34.41
23 16.850 82.5 49.11 33.18
24 18.850 82.0 49.19 33.24

 

 

86

Table C-12

SJE II chromium concentration and porosity data

Adjustedby Normalizedby

Sample # w Age Porosig (°/o) Con(pg[g) b_kgd eon. focusmg' factor
1 0.25 1988.5 95.0 32.98 26.17
2 0.75 1983.7 82.3 29.31 23.26
3 1.25 1977.9 82.5 32.71 25.96
4 1.75 1972.2 83.1 37.25 29.56
5 2.25 1965.9 83.2 55.63 44.15
6 2.75 1958.0 83.7 60.60 48.10
7 3.25 1947.9 83.9 58.75 46.63
8 3.75 1935.2 84.0 70.05 55.60
9 4.13 1926.8 84.2 70.30 55.79
10 4.28 1921.1 89.8 61.16 48.54
11 4.75 1911.4 83.4 71.66 56.87
12 5.13 1902.3 84.2 64.02 50.81
13 5.45 1892.0 85.6 45.70 36.27
14 5.85 1882.3 84.7 51.41 40.80
15 6.30 1867.4 84.4 60.89 48.33
16 6.80 1851.4 84.4 62.92 49.94
17 7.30 1835.4 84.5 56.41 44.77
18 8.05 84.2 65.38 51.89
19 9.05 83.7 64.21 50.96
20 11.05 82.5 65.68 52.13
21 12.05 83.4 68.71 54.53
22 13.05 83.2 68.49 54.36
23 17.05 83.2 61.85 49.09
24 21.05 83.3 64.83 51.45

 

87

Table C-13

NOAA#3 chromium concentration and porosity data

Adjustedby Normalizedby
_D__Sam le# M6331 Ass W W00 mama W
1 0.25 1988.8 95.0 64.20 56.32
2 0.75 1981.6 93.0 72.90 63.95
3 1.25 1973.3 92.0 66.74 58.54
4 1.75 1963.8 91.0 68.52 60.11
5 2.25 1953.7 91.0 69.57 61.03
6 2.75 1940.9 90.0 68.13 59.76
7 3.25 1925.1 90.0 71.13 62.39
8 3.75 1907.3 89.0 73.16 64.18
9 4.25 1891.4 88.0 74.82 65.63
10 4.75 1875.5 89.0 75.44 66.18
11 5.25 1852.3 88.0 70.17 61.55
12 5.75 1823.4 88.5 76.63 67.22
13 6.25 1800.5 88.0 54.77 48.04
14 6.75 87.0 72.09 63.24
15 7.25 88.0 76.64 67.23
16 7.75 88.0 78.27 68.66
17 8.25 78.46 68.82

Table C-l4

#1383 chromium concentration and porosity data

Adjustedby Normalizedby

Sample # Meg) Age ggosity (%) Con(pg[g) M con. focusing factor
1 0.50 1981.7 72.55 22.60
2 1.50 1967.5 72.13 22.47
3 2.50 1946.0 71.71 22.34
4 3.25 1929.1 78.03 24.31
5 3.75 1889.9 79.57 24.79
6 4.25 1860.7 66.75 20.79
7 5.00 1819.0 84.85 26.43
8 6.00 1698.2 85.28 26.57
9 7.50 88.01 27.42
10 9.50 100.69 31.37
11 11.50 81.58 25.41
12 13.50 83.13 25.90
13 16.00 85.14 26.52
14 19.00 86.48 26.94
15 22.50 83.74 26.09
16 26.50 84.08 26.19
17 30.50 78.34 24.40
18 34.50 81.97 25.54

89

Table C-15

#1391 chromium concentration and porosity data

Adjustedby Normalizedby

Sample # W Agp Porosity (%) Con(1_1g[g) b_kgg eon. focusipg factor
1 0.50 1980.7 90.0 21.63 12.08
2 1.50 1965.2 87.0 18.84 10.53
3 1.50 1944.6 81.0 25.40 14.19
4 3.25 1925.9 80.0 12.83 7.17
5 4.00 1902.2 76.0 10.60 5.92
6 5.00 1867.4 74.0 16.95 9.47
7 6.00 1794.8 74.0 19.52 10.91
8 7.00 71.0 19.68 10.99
9 8.00 72.0 13.73 7.67
10 9.00 71.0 19.90 11.12
11 10.00 72.0 24.61 13.75
12 11.00 72.0 19.47 10.88
13 12.00 71.0 19.24 10.75
14 13.00 72.0 17.14 9.58
15 14.00 72.0 25.34 14.16

Appendix D
Table D
Inventory Calculation
EPA #11 Focusing Factor =1.999
Sample # Con.(1_1g[g) Corr. Cg Porgy m Thickness (m) Qr inventog
1 49.73 19.24 84.60 15.40 1. 0 725. 93
2 47.92 17.43 82.40 17.60 1.0 751. 58
3 50.89 20.40 82.20 17.80 1.0 889.64
4 50.32 19.83 79.50 20.50 1.0 995.96
5 47.23 16.74 79.20 20.80 1.0 853.07
6 41.59 11.10 77.80 22.20 1.0 603.73
7 34.93 4.44 77.20 22.80 1.0 248.02
8 33.25 2.76 73.60 26.40 1.0 178.52
9 32.97 2.48 73.30 26.70 1.0 162.23
10 36.01 5.52 73.00 27.00 1.0 365.15
Total inventory 57.74
Focusing corrected inventory 28.88
EPA #18 Focusing Factor =2.434
Sa_rpp_le# @. (Mg) 0mm 139m}! m mm (a) r '
50 .81 C22. 83 94. 20 5.80 1.0 324.41
2 46. 38 18. 40 93.10 6.90 1.0 311.05
3 48.43 20.45 91.50 8.50 1.0 425.87
4 51.68 23.70 90.50 9.50 1.0 551.62
5 49.93 21.95 89.80 10.20 1.0 548.53
6 49.47 21.49 89.30 10.70 1.0 563.36
7 45.19 17.21 89.18 10.82 1.5 684.33
8 40.28 12.30 89.16 10.84 1.0 326.66
9 39.10 11.12 89.14 10.86 1.0 295.87
10 41.33 13.35 88.31 11.69 1.0 382.35
11 33.27 5.29 87.50 12.50 1.0 162.01
12 37.69 9.71 87.64 12.36 1.0 294.04
13 32.43 4.45 87.33 12.67 1.0 138.13
14 33.24 5.26 87.19 12.81 1.0 165. 08
15 36.25 8.27 87.00 13.00 1.0 263.40
16 30.73 2.75 87.00 13.00 1.0 87. 59
17 29.34 1.36 87.00 13.00 1.0 43.32
18 30.39 2.41 87.00 13.00 1.0 76. 76
19 29.73 1.75 87.00 13.00 1.0 55. 74
20 30.29 2.31 87.00 13.00 1.0 73.57
Total inventory 57 .74

Focusing corrected inventory 23.72

 

91

EPA #19(LM) Focusing Factor =1.217

Sample # Conflglg) Corr. Con Porosity % Thickness (cm) Cr invenm
1 67.24 41.01 94.20 5.80 1.0 582.75
2 69.07 42.84 93.10 6.90 1.0 724.21
3 66.06 39.83 91.50 8.50 1.0 829.46
4 58.23 32.00 90.50 9.50 1.0 744.80
5 50.81 24.58 89.80 10.20 1.0 614.25
6 39.02 12.79 89.30 10.70 1.0 335.29
7 26.81 0.58 89.00 11.00 1.0 15.63

Total inventory 38.46
Focusing corrected inventory 31.61
EPA #475 Focusing Factor =1.50

my: Con.(t_rg[g) 9311. Con Poroeig 2g Thican (cm) gr inventm
1 51.46 17.26 98.40 1.60 0.5 33.83
2 48.63 14.43 97.30 2.70 0.5 47.73
3 61.85 27.65 97.50 2.50 0.5 84.68
4 57.60 23.40 97.00 3.00 0.5 86.00
5 58.08 23.88 96.60 3.40 0.5 99.46
6 65.78 31.58 96.70 3.30 0.5 127.66
7 57.84 23.64 95.40 4.60 0.5 133.21
8 63.40 29.20 95.20 4.80 0.5 171.70
9 57.92 23.72 94.90 5.10 1.0 296.38
10 64.79 30.59 94.10 5.90 1.0 442.18
11 63.86 29.66 94.20 5.80 1.0 421.47
12 57.90 23.70 92.10 7.90 1.0 458.71
13 52.08 17.88 92.70 7.30 1.0 319.78
14 47.79 13.59 93. 10 6.90 1.0 229.74
15 46.49 12.29 91.40 8.60 1.0 258.95
16 42.13 7.93 93.40 6.60 1.0 128.23
18 38.69 4.49 92.30 7.70 1.0 84.70
19 38.71 4.51 93.20 6.80 1.0 75.14

20 37.07 2.87 93.30 6.70 1.0 47.11
21 36.75 2.55 93.60 6.40 1.0 39.98
22 35.55 1.35 93.30 6.70 1.0 22.16
23 35.38 1.18 91.60 8.40 1.0 24.28
Total inventory 36.33
Focusing corrected inventory 24.22

 

 

92

EPA #68k Focusing Factor =1.267

Sample # Con.(i_rg[g) Corr. Con Porosig _D_ry Thickness (cm) Cr invent_o_g
1 43.91 10.86 98.00 2.00 0.5 26.61
2 51.87 18.82 96.60 3.40 0.5 78.39
3 54.16 21.11 95.60 4.40 0.5 113.78
4 57.64 24.59 94.70 5.30 0.5 159.65
5 59.29 26.24 94.00 6.00 0.5 192.86
6 63.24 30.19 93.80 6.20 0.5 229.29
7 61.22 28.17 94.10 5.90 0.5 203.60
8 62.84 29.79 93.30 6.70 0.5 244.50
9 61.22 28.17 93.50 6.50 1.0 448.61
10 52.09 19.04 94.20 5.80 1.0 270.56
11 47.57 14.52 93.90 6.10 1.0 217.00
12 43.91 10.86 94.90 5.10 1.0 135.70
13 37.07 4.02 93.60 6.40 1.0 63.03
14 38.01 4.96 92.80 7.20 1.0 87.49
15 39.44 6.39 93.80 6.20 1.0 97.06
Total inventory 25.68
Focusing corrected inventory 20.27
EPA #19(LO) Focusing Factor = 1.06
M W M min 29! "PM Q_mr inven
1.00 71.85 36.15 94.20 5.80 1.0 513.69
2.00 73.91 38.21 92.20 7.80 1.0 730.19
3.00 58.66 22.96 90.90 9.10 1.0 511.89
4.00 84.87 49.17 90.60 9.40 1.0 1132.39
5.00 88.23 52.53 90.40 9.60 1.0 1235.51
6.00 86.76 51.06 87.90 12.10 1.0 1513.67
7.00 61.62 25.92 85.00 15.00 1.0 952.56
8.00 39.68 3.98 83.00 17.00 0.5 82.88
Total inventory 66.73
Focusing corrected inventory 62.95

 

93

EPA #40 a Focusing Factor =1.705
Sample # Con.(1_1g[g) Corr. Con Porosity Q11 Thickngsg (cm) gr inventpg
l 38.58 0.92 92.3 7.7 1 17.36
2 54.62 16.96 89.5 10.5 1 436.30
3 57.79 20.13 87.8 12.2 1 601.69
4 65.31 27.65 86.9 13.1 1 887.43
5 73.75 36.09 88 12 1 1061.05
6 81.58 43.92 88.9 11.1 1 1194.40
7 105.10 67.44 86.7 13.3 1 2197.53
8 88.41 50.75 88.3 11.7 1 1454.75
9 87.94 50.28 86.7 13.3 1 1638.37
10 82.44 44.78 86.6 13.4 1 1470.13
11 77.05 39.39 84.4 15.6 1 1505.49
12 72.12 34.46 81.9 18.1 1 1528.13
13 61.36 23.70 82.7 17.3 1 1004.52
14 53.32 15.66 98.4 1.6 1 61.39
15 48.98 11.32 81.2 18.8 1 521.40
16 43.08 5.42 81.3 18.7 1 248.32
17 37.94 0.28 82.6 17.4 1 11.94
Total inventory 158.40
Focusing corrected inventory 92.90

 

E30

Sample #

OOQQMQMNt—I

NNNNF-‘I—‘I—It—it—‘F-IF—t—‘I—ir-lc
uni—aoxocoqo‘uttht—c

33.78
55.65
54.26
72.93
81.62
77.42

113.04
117.31
114.63

82.64
79.50
81.46
77.08
77.98
73.44
67.54
59.36
55.67
59.08
56.57
51.02
43.66
34.11

mm

1. 10
22.97
21.58
40.25
48.94
44.74
80.36
84.63
81.95
49.96
46.82
48.78
44.40
45.30
40.76
34.86
26.68
22.99
26.40
23.89
18.34
10.98

1.43

Porosity m
92.95 7.05
92.58 7.80
92.20 8.20
91.80 8.20
91.53 8.47
91.36 8.64
91.25 8.75
91.25 8.75
91.18 8.82
91.29 8.71
91.53 8.47
91.67 8.33
91.67 8.33
91.57 8.43
91.50 8.50
91.36 8.64
91.11 8.89
90.57 9.43
90.52 9.48
90.20 9.80
89.72 10.28
88.56 11.44
88.14 11.86

Total inventory

Focusing Factor =2.04

Thiclcng (cm) Cr invenm

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
1.0
2.0
3.0

Focusing corrected inventory

9.50
219.48
216.77
404.31
507.79
473.53
861.36
907.13
885.43
533.06
485.79
497.76
453.07
467.80
424.41
368.96
290.55
265.57
306.58
286.80
461.91
615.49
124.65

100.68
49.35

 

95

References

Allan RJ. (1975) Natural versus unnatural heavy metal concentrations in lake
sediments in Canada Proc. Internatl. Conf Heavy Metals in the
Environment, 785-808.

Amacher MC., Selim HM, and Iskandar 1K. (1988) Kinetics of chromium(VI)
and cadmium retention in soils: a non linear multireaction model. Soil Sci.
Soc. Am. J. 52, 398-408.

Arimoto R. (1989) Atmospheric deposition of chemical contaminants to the Great
Lakes. Journal of Great Lakes Research 15, 339-356.

 

Barrie LA, Lindberg S.E., Chan W11, Ross HB., Arimoto R, and Church TM
(1987) On the concentration of trace metals in precipitation. Atmospheric
Environment 21, 1133-1135.

Benoit G. and Hemond HF. (1991) Evidence for diffusive redistribution of 210Pb
in lake sediments. Geochimica et Cosmochimica Acta 55, 1963-1975.

Berg NA. and Johnson MG. (1978) Environmental Management Strategy for the
Great Lakes System: Final Report to the International Joint Commission.
The International Reference Group on Great Lakes Pollution fiom Land
Use Activities, Windsor, Ontario.

Bemer RA. (1980) Early Diagenesis, Princeton University Press.

Boyko S.L. and Goodgarne D.M.L. (1986) The interaction of soil fulvic acid and
chromium(VI) produces relatively long-lived, water soluble chromium(V)
species. Inorg. Chim. Acta 123, 189-191.

Chan W.I-L, Tang A.J.S., Lusis MA, Vet R1, and Ro C. (1982) An Analysis of
the Impact of Smelter Emissions on Precipitation Quality and Wet
Deposition in the Sufiury Area: Sucflmry Environmental Stuay Event
Precipitation Network Results. SES 006/82, Ontario Ministry of
Environment, 6th Floor, 40 St. Clair Ave. West, Toronto, Ontario, Canada
M4V 1M2.

96

Connor 1.1. and Shacklette HT. (1975) Background Geochemistry of Some Rocks,
Soils, Plants, and Vegetables in the Conterminous United States. U. S.
Geological Survey Professional Paper 574-F.

Davis J.A. and Leckie 1.0. (1980) Surface ionization and complexation at the
oxide/water interface. 3. Adsorption of anions. J. Colloid Interface Sci. 74,
32-43.

Dong A, Chesters G., and Simsiman G. V. (1984) Metal composition of soil,
sediments, and urban dust and dirt samples fiom the Menomonee River
Watershed, Wisconsin, USA. Water, Air, and Soil Pollution 22, 257-275.

Dreiss SJ. (1986) Chromium migration through sludge treated soils. Groundwater
24, 312-321.

Dutlciewicz V.A, Parekh RR, and Husain L. (1987) An evaluation of regional
elemental signatures relevant to the northeastern United States. Atmospheric
Environment 21, 1033-1044.

Eadie B.J., Robbins J.A, Landrum P.F., Rice C.P., Simmons MS., McCormick
Ml, Eisenreich S.J., Bell G.L., Pickett RL., Johansen K., Rossmann R,
Hawley N., and Voice T. (1983) The cycling of toxic organics in the Great
Lakes: A 3-year status report. NOAA Technical Memorandum ERL
GLERL-45.

Ealdns JD. and Morrison RT. (1978) A new procedure for the determination of
lead-210 in lake and marine sediments. Internat. J. Applied Radiation
Isotopes 29, 531-536.

Eary LE. and Rai D. (1987) Kinetics of chromium(III) oxidation to chromium(VI)
by reaction with manganese dioxide. Environ Sci. Technol. 21, 1187-1193.

Eisenreich S.J., Swackhamer D.L., and Long D.T. (1990) Atmospheric deposition
of toxic contaminants to the Great Lakes: Assessment and importance,
Great Lakes Protection Fund, Grant Proposal.

Eisenreich S.J., Metzer N.A., Urban NR, and Robbins 1A (1986) Response of
atmospheric lead to decreased use of lead in gasoline. Environ. Sci.
Technol. 20, 171-174.

97

Eisenreich S.J., Capel P.D., Robbins J.A, and Bourbonniere R (1989)
Accumulation and diagenesis of chlorinated hydrocarbons in lacustrine
sediments. Environ. Sci. T echnol. 23, 1116-1126.

Eisenreich S.J., and Strachan W.MJ. (1992a) Estimating Atmospheric Deposition
of Toxic Substances to the Great Lakes. A workshop held at the Canada
Centre for Inland Waters, Burlington, Ontario, Jan. 31 through Feb. 2.

Eisenreich S.J., Baker J.E., Franz T., Swanson M, Rapaport RA, Strachan
W.MJ., and Hites RA (1992b) Atmospheric deposition of hydrophobic
organic contaminants to the laurentian Great Lakes. In Fate of Pesticides
and Chemicals in the Environment (ed J.L. Schnoor), pp. 51-78. John
Wiley & Sons, Inc.

Eisenreich S.J., Looney BB, and Thornton JD. (1981) Airborne organic

contaminants in the Great Lakes ecosystem. Environ. Sci. Technol. 15, 30-
38.

Eisenreich SJ. (1982) Atmospheric role in trace metal exchange at the air-water
interface. Journal of Great Lakes Research 8, 243 -256.

Eisenreich SJ. (1987) The chemical limnology of nonpolar organic contaminants:
PCBs in Lake Superior. In Sources and Fates of Aquatic Pollutants (ed
RA Hites and SJ. Eisenreich), pp. 393-469. Adv. Chem Ser. no. 216,
Amer. Chem. Soc., Washington, DC.

Epstein MS., Diamondstone BI, and Gills TE. (1989) A new river sediment
standard reference material. T alanta 36, 141-150.

Evans HE, Dillon P.J., Scholer P.J., and Evans RD. (1986) The use of Pb/Zlon
ratios in lake sediments for estimating atmospheric fallout of stable lead in
south-central Ontario, Canada. Sci. Total Environ. 54, 77-93.

Evans RD. and Dillon RI. (1982) Historical changes in anthropogenic lead fallout
in southern Ontario, Canada. Hydrobiologia 91, 131-137.

F6rstner U. (1976) Lake sediments as indicators of heavy-metal pollution.
Naturwissenschaflen 63, 465-470.

Galloway J.N., Thornton J.D., Norton S.A, Volchok HL., and Mclean RAN.
(1982) Trace metals in atmospheric deposition: 8 review and assessment.
Atmospheric Environment 16, 1677-1700.

98

Galloway J .N. and Likens GE. (1979) Atmospheric enhancement of metal
deposition in Adirondack lake sediments. Limnology and Oceanography
24, 427-433.

Gephart C]. (1982) Relative importance of iron-oxide, manganese-oxide, and
organic material on the adsorption of chromium in natural water sediment
systems. MS. Thesis, Michigan State University.

Golden K. A, Wong C.S., Jeremiason J.D., Eisenreich S.J., Sanders G.,
Swackhamer D.L., Engstrom DR, and Long D.T. (1993) Accumulation
and preliminary inventory of organochlorines in Great Lakes sediments.
contaminated sediments conference, Milwaukee Wise. June 14 through
June 16.

Griflin RA, Au AK, and Frost, RR (1977) Effect of pH on adsorption of
chromium from landfill-leachate by clay minerals. J. Environ. Science and
Health A12, 431-449.

Grove Ill and Ellis B.G. (1980) Extractable chromium as related to soil pH and
applied chromium. Soil Sci. Soc. Am. J. 44, 238-242.

Heft AD. (1993) The Role of A tmospheric Deposition of Contaminant Metals to
the Great Lakes: Deducedfi-om Sediment Cores. MS. Thesis, Michigan
State University.

Hewitt AD. and Reynolds CM (1990) Dissolution of metals fiom soils and
sediments with a microwave-nitric acid digestion technique. Atomic
Spectroscopy 11, 187-192.

Hilton 1, Lishman JP, and Allen P.V. (1986) The dominant processes of
sediment distribution and focusing in a small eutrophic, monomictic lake.
Limnology and Oceanography 31, 125-133.

Jan T.K and Young DR (1978) Chromium speciation in municipal wasterwaters
and seawater. J. Water Pollu. Control Fed, 2327-2336.

Johnson MG, Culp L., and George SE. (1986) Temporal and spatial trends in
metal loadings to sediments of the Turkey Lakes, Ontario. Canadian
Journal of Fisheries and Aquatic Sciences 43, 754-762.

99

Johnson MG., and Nicholls KR (1988) Temporal and spatial trends in metal
loads to sediments of Lake Simcoe, Ontario. Water, Air, and Soil Pollution
39, 337-3 54.

Johnson MG. (1983) Unpublished data.

Johnson MG. (1987) Trace element loadings to sediments of fourteen Ontario
Lakes and correlations with concentrations in fish. Canadian Journal of
Fisheries and Aquatic Sciences 44, 3-13.

Junge C. (1963) Air chemistry and Radioactivity. Academic Press, New York and
London.

Kelly T.J., Czuczwa J.M., Sticksel P.R, Sverdrup GM, Koval P.J., and
Hodanbosi RF. (1991) Atmospheric and tributary inputs of toxic
substances to Lake Erie. Journal of Great Lakes Research 17, 504-516.

Kemp AL.W., Williams J.D.H, Thomas RL. and Gregory ML. (1978) Impact of
man's activities on the chemical composition of the sediments of Lake
Superior and Huron. Water, Air, and Soil pollution 10, 381-402.

Kemp AL.W. and Thomas RL. (1976) Impact of man's activities on the chemical
composition in the sediments of Lakes Ontario, Erie and Huron Water, Air,
Soil Pollution 5, 469-490.

Kopp IF. and Kroner RC. (1968) Trace Metals in Waters of the United States.
Fed Wat Pollut. Control Adm , Div. Pollut Surveillance.

Kuhnert PM, Kuhnert BR, and Stokes RM. (1976) The effect of in vivo
chromium exposure on Na/K' and Mg-ATPase activity in several tissues of
the rainbow trout (Salmo gairdneri). Bull. Environ. Contam Toxicol. 15,
383-3 90.

Leland HV., Shukla SS. and Shimp NP. (1974) Factors afi‘ecting distribution of
lead and other trace elements in sediments of southern Lake Michigan. In
Trace Metals and Metal-Organic Interactions in Natural Waters (ed. P.C.
Singer), pp. 89-129. Ann Arbor Science Publishers, Ann Arbor, Michigan

Likens GE. and Davis MB. (1975) Post-glacial history of Mirror Lake and its
watershed in New Hampshire, USA' An initial report. Verh. International
Verein. Limnology 19, 982-993.

 

 

100

Mackay D., Paterson S., and Schroeder W.H. ( 1986) Model describing the rate of
transfer of organic chemicals between atmosphere and water. Environ Sci.
T echnol. 20, 810-816.

Matty J .M (1992) Influence of Early Diagenesis on the Geochemical Cycling of
Arsenic and Mercury. Ph. D. Thesis, Michigan State University.

Michigan Department of Natural Resources (1990) Air Quality Report. Air Quality
Division, Department of Natural Resources, Michigan.

Michigan Department of Natural Resources (1991) Michigan Annual Air Quality
Report. Air Quality Division, Department of Natural Resources, Michigan.

Moore J.W., and Ramamoorthy S. (1984) Heavy Metals in Natural Waters.
Springer-Veday New York Inc. , New York

Mothersill IS. (1977) Selected element concentrations in the post-glacial
sediments of Thunder Bay, Lake Superior: distribution and methods of
analyses. Can. J. Earth Sci. 14, 1054-1061.

Mudroch A, Sarazin L., and Lomas T. (1988) Summary of surface and
background concentrations of selected elements in the Great Lakes
sediments. Journal of Great Lakes Research 14, 241-251.

Mueller C.S., Ramelow GI, and Beck J.N. (1989) Spatial and temporal variation
of heavy metals in sediment cores from the Calcasieu river/ lake complex.
Water, Air, and Soil Pollution 43, 213-230.

Murphy T]. (1984) Atmospheric inputs of chlorinated hydrocarbones to the Great
Lakes. In Toxic Contaminants in the Great Lakes (ed. 10. Nriagu and MS.
Simmoms), pp. 53-80. John Wiley & Sons, Inc.

Nichols S.J., Manny B.A, Scholesser D.W., and Edsall TA (1991) Heavy metal
contamination of sediments in the upper connecting channels of the Great
Lakes. Hydrobiologia 219, 307-315.

Norton SA and Kahl JS. (1987) A comparison of lake sediments and
ombrotrophic peat deposits as long-term monitors of atmospheric pollution.
In New Approaches to Monitoring Aquatic Ecosystems (ed. T.P Boyle), pp.
40-57. ASTM, Philadelphia.

101

Oldfield F. and Appleby PG. (1984) Empirical testing of (210) Pb-dating models
for lake sediments. In Lake Sediments and Environmental History (ed E.Y.
Haworth and J.W. G. Lund), pp. 91-124. Univer. Minn Press.

Paya Perez AB., GOtz L., Kephalopoulos SD, and Bignoli G. (1988) Sorption of
chromium species on soil. In Heavy Metals in the Hydrocycle (ed M
Astruc and J .N. Lester), pp. 59-66. Selper, London.

Perkin Elmer Corp. (1985) Techniques in Graphite Furnace Atomic Absorption
Spectrophotometry. Ridgefield, CT.

Pfeifi'er W.C., Fiszman M, and Carbonell N. (1980) Fate of chromium in a
tributary of the Iraja River, Rio de Janeiro. Environmental Pollution (Series
B) 1, 117-126.

Rai D., Zachara J.NI, Schwab AP., Schmidt RL., Girvin DC, and Rogers J.E.
(1984) Chemical Attenuation Rates, Coefiicients, and Constants in

Leachate Migration Vol. I, A critical review. Final Report EPRI EA-33 56,
E.P.RI., Palo Alto, Calif.

Rapaport RA and Eisenreich 8.]. (1988) Historical atmospheric inputs of high
molecular weight chlorinated hydrocarbons to eastern North America,
Envir. Sci. T echnol. 22, 931-941.

Richard EC. and Boung, AC.M. (1991) Aqueous geochemistry of chromium: a
review. Water Research 25, 807-816.

Robbins J.A (1978) Geochemical and geophysical applications of radioactive
lead In The Biogeochemistry of Lead in the Environment (ed. J .O. Nriagu),
pp. 285-393. Elsevier/ North-Holland Biomedical Press.

Robertson F .N. (1975) Hexavalent chromium in the groundwater in the Paradise
Valley, Arizona. Groundwater 13, 516-527.

Rowan DJ. and Kalfl J. (1993) Predicting sediment metal concentrations in lakes
without point sources. Water, Air, and Soil Pollution 66, 145-161.

Salomons W. and De Groot AJ. (1978) Pollution history of nace metals in
sediments, as afi‘ected by the Rhine river. In Environmental
Biogeochemistry (ed. W.E Krumbein), pp. 149-162. Ann Arbor Science,
Ann Arbor, Michigan.

 

102

Schmidt J .A and Andren AW. (1984) Deposition of airborne metals into the
Great Lakes. In Toxic Contaminants in the Great Lakes (ed J. O. Nriagu
and MS. Simmoms), pp. 81-104. John Wiley & Sons, Inc.

Schroeder DC. and Lee GE (1975) Potential transformations of chromium in
natural waters. Water, Air, and Soil Pollution 4, 355-365.

Sherwood MJ. and Wright J. L. (1976) Uptake and effects of chromium on marine
fish, In S. Calif Coastal Water Res. Proj. Ann. Rep., pp. 123-128. El
Segundo, Calif.

Shirahata H., Elias RW., Patterson CC, and Koide M (1980) Chronological
variations in concentrations and isotopic compositions of anthropogenic
atmospheric lead in sediments of a remote subalpine pond Geochimica et
Cosmochimica Acta 44, 149-162.

Stollenwerk K. G. and Grove DB. (1985) Adsorption and desorption of hexavalent
chromium in an alluvial aquifer. J. envir. Qual. 14, 150-155.

Sulcek Z. and Povondra P. (1989) Methods of decomposition in inorganic
analysis. CRC Press.

Takacs MJ. (1988) The oxidation of chromium by manganese oxide: The nature
and controls of the reaction. MS. Thesis, Michigan State University.

Thomas RL. and Mudroch A (1979) Small crafl harbours-sediment survey Lakes
Ontario, Erie and Lake St. Clair. Report to Small Craft Harbours Ontario
Region from the Great Lakes Biolimnology Laboratory.

Towill L.E., Shriner C.R, Drmy J.S., Hammons AS., and Holleman J.W. (1978)
Reviews of the environmental efiects of pollutants: III. Chromium. EPA-
600/1-78-023.

U.S.E.P.A (1994) Trends of precipitation loadings to the Great Lakes.
unpublished data.

United States Department of the Interior Report (1969) An Appraisal of Water
Pollution in the Lake Superior Basin. Federal Water Pollution Control
Agency, Great Lake Region.

103

Urban N.R, Eisenreich S.J., Grigal DR, and Schurr K.T. (1990) Mobility and
diagenesis of Pb and 210Pb in peat. Geochimica et Cosmochimica Acta 54,
3329-3346.

Westall J. and Hohl H. (1990) A comparison of electrostatic models for the oxide/
solution interface. Adv. Coll. Interface Sci. 12, 265-294.

World Health Organization (1988) Environmental Health Criteria 61: Chromium.
Geneva.

Zoller W11, Gladney ES, and Duce RA (1974) Atmospheric concentrations and ‘
sources of trace metals at the South Pole. Science 183, 198-200.

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