Current Sediment Quality in the St. Marys River AOC (MI:USA)

i

Current Sediment Quality in the St. Marys River AOC (MI:USA)

FINAL REPORT FOR USEPA-GLNPO GRANT #: GL2002-054

SUBMITTED November 15, 2005

Principle Investigators: Dr. Richard C. Back Dr. Barbara J. Keller Department of Biology Department of Chemistry Oswego State University Lake Superior State University Oswego, NY 13126 Sault Ste. Marie, MI 49783 Phone: 315-312-2623 Phone: 906-635-2438 Fax: 315-312-3059 Fax: 906-635-2266 Email: [email protected] Email: [email protected]

EPA Project Officer:

Marc Tuchman 77 West Jackson Blvd. GL-17J

Chicago, IL 60604 Phone: 312-353-1369

Fax: Email: [email protected]

mailto:[email protected]



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ACKNOWLEDGEMENTS

This work was supported by grant #GL2002-054 from the US Environmental Protection Agency Great Lakes National Program Office (GLNPO) to Lake Superior State University (LSSU). Technical assistance was provided by Emily Grenfell. Dustin Everitt assisted with sample collection. Ship support for the coring operations was provided by GLNPO, and we gratefully acknowledge the J. Bohman and the crew of the R/V Mudpuppy for their assistance. The Inductively Coupled Plasma - Mass Spectrometer used for the metals analysis was obtained through a grant from the National Science Foundation (CHE-0116036) to Lake Superior State University. Any findings, opinions and conclusions, or recommendations expressed in this material are those of the authors, and do not necessarily reflect the views of the National Science Foundation.

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TABLE OF CONTENTS Current Sediment Quality in the St. Marys River AOC (MI:USA) i ACKNOWLEDGEMENTS ii LIST OF FIGURES iv

LIST OF TABLES v

INTRODUCTION 1

METHODS 2

QAPP 2

FIELD SAMPLING 2

ANALYTICAL TECHNIQUES 6

EXCEPTIONS TO QAPP 6

RESULTS AND DISCUSSION 7

SURFICIAL SEDIMENTS 7

SURFICIAL SEDIMENT SUMMARY 24

CORE SAMPLES 25

SEDIMENT CORE SUMMARY 34

CONCLUSIONS 38

LITERATURE CITED 39

APPENDICES 40

Appendix A Quality Assurance Plan 40

Appendix B Grab Sample Data 54

Appendix C Grab Sample Data - PAH's 56

Appendix D Core Data 58

iv

LIST OF FIGURES

Figure 1. Sampling locations in the St. Marys River. ..................................................... 3

Figure 2. Sample locations in the Little Rapids area of the St. Marys River. ................. 4

Figure 3. Sample locations in Munuscong Lake of the St. Marys River. ....................... 5

Figure 4. Dry weight as a percent of wet weight for surficial samples. .......................... 9

Figure 5. Statistical analysis of Dry Weight. .................................................................. 9

Figure 6. Organic carbon (mg g-1 dry weight) for surficial samples. ............................ 10

Figure 7. Statistical analysis of Organic Carbon .......................................................... 10

Figure 8. Total Organic Carbon (TOC) and the Percent Dry Weight. .......................... 11

Figure 9. Total nitrogen for surficial samples. .............................................................. 12

Figure 10. Statistical analysis of Total Nitrogen. ........................................................... 12

Figure 11. Total phosphorus concentration for surficial samples. ................................. 13

Figure 12. Statistical analysis of Total Phosphorus. ...................................................... 13

Figure 13. Total mercury concentration for surficial samples. ....................................... 16

Figure 14. Statistical analysis of Total Mercury ............................................................. 16

Figure 15. Methyl mercury concentration for surficial samples. ..................................... 17

Figure 16. Statistical analysis of Methyl mercury. ......................................................... 17

Figure 17. Chromium concentration for surficial samples. ............................................. 18

Figure 18. Statistical analysis of Chromium .................................................................. 18

Figure 19. Nickel concentration for surficial samples. ................................................... 19

Figure 20. Statistical analysis of Nickel ......................................................................... 19

Figure 21. Copper concentration for surficial samples. ................................................. 20

Figure 22. Statistical analysis of Copper ....................................................................... 20

Figure 23. Zinc concentration for surficial samples. ...................................................... 21

Figure 24. Statistical analysis of Zinc. ........................................................................... 21

Figure 25. Arsenic concentration for surficial samples .................................................. 22

Figure 26. Statistical analysis of Arsenic ....................................................................... 22

Figure 27. Lead concentration for surficial samples. ..................................................... 23

Figure 28. Statistical analysis of Lead ........................................................................... 23

Figure 29. Polyaromatic Hydrocarbons (PAH) in surficial sediment samples. ............... 24

Figure 30. Dry weight, Total Carbon and Total Nitrogen in Core A. ........................... 26

Figure 31. Metal concentrations in Core A .................................................................... 27

Figure 32. Dry weight, Total Carbon and Total Nitrogen in Core B ............................... 29

Figure 33. Metal concentrations in Core B. ................................................................... 30

Figure 34. Dry weight, Total Carbon and Total Nitrogen in Core C ............................... 31

Figure 35. Metal concentrations in Core C .................................................................... 32

Figure 36. Dry weight, Total Carbon and Total Nitrogen in Core D ............................... 33

Figure 37. Metal concentrations in Core D .................................................................... 34

Figure 38. Statistical analysis of DW, TC and TN in cores A-D. .................................... 35

Figure 39. Statistical analysis of metal concentrations in Cores A-D ............................ 36

Figure 40. Unsupported 210Pb distribution with depth in each core. ............................ 37

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LIST OF TABLES

Table 1. Guideline concentrations for selected pollutants in freshwater sediments. For

each parameter, both the USEPA guidelines used in the Stage 1 RAP report for the St. Marys River, and the threshold and probable effect level used by NOAA are presented. ................................................................................................................ 7

Table 2. Surface sediment sampling stations which exceeded either EPA or NOAA guidelines for contaminated freshwater sediments for metals and total phosphorus. Station numbers 1-10 are from the St. Marys River proper, 11-20 are from the Little Rapids area, and 21-40 are from Munuscong Lake. .............................................. 25

1

INTRODUCTION

The St. Marys River is the sole surface outlet from Lake Superior, flowing over 100 km to Lake Huron, and forming part of the international border between Canada (Ontario) and USA (MI). As part of a series of Great Lakes connecting channels, the St. Marys has historically been, and continues to be, vital to shipping and industry. Consequently, the river system has been severely impacted by modifications to the hydrology as well as local industrial and municipal discharges, and was designated in 1985 as an Area of Concern (AOC). Stage 1 of the Remedial Action Plan (RAP) for this AOC, completed in 1991, broadly described the environmental conditions and identified use impairments. Based on the sampling of 125 stations within the river system during 1985, the Stage 1 specifically characterized spatial distribution of heavy metal contaminated sediments. While areas of localized concentrations of heavy metals in sediments are predominantly located on the Canadian side, one fairly localized depositional zone on the US side, an embayment called Munuscong Lake, was shown to have elevated Cr, Ni, Cu, associated with silt/organic sediments. As the St. Marys AOC moves toward the implementation of Stage 2, and actual remediation and regulation, several questions remain regarding sediment contamination. First, while the Canadian stations have been systematically re-sampled (mid-1990’s), the US sites have not. There has been more recent work associated with the Cannelton Industries site in the upper river, and limited sampling of the upper river and Waishkey Bay by the Bay Mills Indian Community. Decisions regarding sediment contamination and any use impairment regarding dredged sediments and degradation of benthos will largely rely on 17-year-old data. While this alone does not forestall the RAP process with respect to sediment contamination, a couple of recent developments do warrant re-investigation and expansion of previous work. In the mid-nineties, earthen levees in the nearshore region of Munuscong Lake were purposely breached, thereby changing the hydrology and likely transporting a pulse of sediment to the lake. These dykes were originally constructed to provide waterfowl hunting opportunities, and retained much of the fine clay derived from the Munuscong River and Little Munuscong River watersheds. These shallow areas undoubtedly also collected organic-rich sediments. The composition, fate and impact of these sediments in Munuscong Lake and the lower St. Marys River are unknown. The original 1985 sampling of the AOC included only 9 stations in Munuscong Lake; an area vital to walleye spawning and heavily utilized by recreational anglers. Secondly, a recurrent impairment in the St. Marys AOC is habitat loss; in particular the limited area of open rapids which now exists. Stage 2 of the RAP will call for either restoration or creation of areas of rapids in the river. Over the last few years, there has been local interest in re-establishing flow through an area of the river historically known as “The Little Rapids”. This largely shallow, rocky area is currently all but excluded from

2

the river flow by a causeway which connects a ferry landing and small island to the larger Sugar Island. More flow could be introduced to this area either by installing more culverts or by replacing the causeway, in whole or part, with an open span bridge. Fisheries biologists concur that allowing more flow through this area would create spawning habitat for walleye, lake sturgeon and lake whitefish while providing recreational fishing opportunities for US citizens. Currently, access to existing rapids below the compensating gates, and the angling opportunities they afford, is limited to the Canadian side of the river. The Little Rapids, which includes some relatively deep, depositional areas, was not previously sampled during the RAP process. The current project sought to revisit a variety of sediment localities within the St. Marys River proper to update sediment contaminant data, and to expand sampling into these additional areas of interest (Munuscong Lake and the Little Rapids). Our primary focus was on surficial sediment contamination, particularly metals shown to be elevated during previous sampling for the Stage 1 of the RAP (Cr, Ni, Cu). Secondarily, sediment core samples were collected within these areas to assess the spatial distribution of the metal contaminants.

METHODS

QAPP The project Quality Assurance Project Plan is attached as Appendix A. Within this plan are the detailed methods used for sampling, documenting, processing and analyzing samples during this project. Here we present the general techniques used for field sampling, sample preparation, and analyses. Finally, any minor deviations from the QAPP are noted. FIELD SAMPLING Sampling of the surficial sediments was accomplished 10SEP (Munuscong Lake), 16SEP (Little Rapids) and 17SEP (St. Marys River proper) of 2003. Ponar grab samples were well mixed and collected directly into respective sample jars. Samples were kept in the dark on ice until returned to the lab, not more than 6 hours. Surface

grab samples were stored at 4 C until further processing. Samples for PAH and TP were immediately prepped and shipped to an outside contractor (Trace Analytical) for analyses. Sediment core samples were collected on 04AUG (Little Rapids) and 05AUG (Munuscong Lake) from the R/V Mudpuppy using GLNPO coring equipment and personnel. Cores were transported to the LSSU Aquatic Research Lab where they were extruded and sectioned within 12 hours of collection using clean technique.

Sediment sections were stored at 4 C until further processing. Sample locations for the St. Marys River proper, the Little Rapids and Munuscong Lake are provided in Figures 1 - 3 respectively.

St. Marys River Sediments QAPP page 3 of 66

Figure 1. Sample locations for surficial sediments (closed circles with numbers) and cores (hatched circles) collected during August and September 2003. Detailed insets for the Little Rapids area (Stations 11-20, Cores A and B) and for Munuscong Lake (Stations 21-40, Cores C and D) are shown in Figures 2 and 3 respectively.


Figure 2. Sample locations for surficial sediments (numbers) and cores (letters) collected during August and September 2003 in the Little Rapids area of the St. Marys River.


Figure 3. Sample locations for surficial sediments (numbers) and cores (letters) collected during August and September 2003 in Munuscong Lake, a large embayment of the St. Marys River.


SAMPLE PREPARATION

Samples were dried to constant mass at 65 C, and homogenized using a ceramic mortar and pestle. Subsamples were collected directly into Teflon vials (Hg and MeHg analyses) or polypropylene mini-centrifuge tubes (TC/TN, 210Pb) and shipped to outside contractors (UW-Madison and UW-Milwaukee, respectively) for analyses. Samples for analysis at LSSU by ICP-MS were prepped and digested according to SW-846, Method 3051A. ANALYTICAL TECHNIQUES Specific procedures used by LSSU or its subcontractors during this project included: Metals – SW-846, Method 3051A – Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils; SW-846, Method 6020A, Inductively Coupled Plasma-Mass Spectrometry Mercury and methyl-mercury – SW-846, Method 7471B – Mercury in Solid or Semisolid Waste (Manual Cold-Vapor Atomic Absorption Fluorescence Technique) PAHs – SW-846, Method 8270D – Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS), sample preparation used one of the following SW-846 methods: 3540, 3541, 3545, 3550, 3560, or 3561 TOC/ TON, TP – TOC/TON was determined by standard CHN analysis on a Perkin Elmer 2400 Series II CHNS/O Analyzer. TP was determined colorimetrically (ascorbic acid/molybdate method) following wet persulfate/autoclave digestion. Sedimentation Rates – Samples from sectioned cores were used to determine sedimentation rates at those sites by the 210Pb procedure commonly employed in the Great Lakes (Robbins and Edgington, 1975), and currently the standard method at the Great Lakes Water Institute, Milwaukee, WI. Metal analysis (ICP-MS) was conducted at LSSU. Separate subcontractors were responsible for specific SOP’s and data quality assurance. EXCEPTIONS TO QAPP The original work plan called for surficial sampling (and analyses) prior to coring to allow directed choice of coring locations. Due to scheduling constraints, however, coring preceded the surface sediment survey. This proved not to be a problem since the coring locations available in those areas to be cored (Little Rapids and Munuscong Lake) were limited by depth and sediment type. Coring proved to be quite difficult in these areas, particularly in Munuscong Lake, due to very low water levels. Limited depth affected both vessel operation and effectiveness of the gravity coring device. At Sites C and D (Munuscong Lake) a vibracore, rather than a gravity core, was used. Extremely difficult vessel operation in Munuscong Lake due to low water levels precluded taking a fifth core.


A final departure from the approved QAPP was a change in analytical lab for the PAH analyses. This was done primarily to expedite sample turn-around. Both labs are certified for the analyses conducted. Additionally, analyses for TP were run by Trace Analytical as opposed to LSSU (as stated in the QAPP) again to expedite sample analysis.

RESULTS AND DISCUSSION

The results and discussion are arranged in two broad sections, one dealing with the surficial sediments, sampled by ponar grab, and one focused on the four cores. Within each section, variables are sequentially considered followed by a summary, or synthesis. In both sections, reference is made to NOAA SQRT (Screening Quick Reference Table) values of Threshold Effect Level (TEL), and Probable Effect Level (PEL) for each of the variables measured, if appropriate. These levels (Buchman, 1999) are presented in Table 1 for the components under consideration here. The TEL is considered the concentration below which adverse effects are rarely encountered, whereas the PEL is the concentration above which adverse effects are frequently encountered. Thus, the NOAA PEL is more generally more conservative than the consensus based Probable Effect Concentration (PEC) (MacDonald et al. 2000). Only in the case of Cu is the NOAA

PEL (197 µg g-1) is above the PEC (149 mg g-1). Also listed in Table 1, for comparison, are the USEPA Interim guidelines for dredged sediments taken from the Stage 1 RAP report for the St. Marys River (St. Marys River RAP Team, 1991).

Table 1. Guideline concentrations for selected pollutants in freshwater sediments. For each parameter, both the USEPA guidelines used in the Stage 1 RAP report for the St. Marys River, and the threshold and probable effect level used by NOAA are presented.

USEPA Guidelines (µg/g)1 NOAA SQRT (µg/g)

2

Parameter Non-Polluted Moderately Polluted

Heavily Polluted

Background Threshold Effects Level

(TEL)

Probable Effects Level

(PEL)

Total P <420 420-650 >650 na3 na na

Chromium <25 25-75 >75 7-13 37.3 90

Nickel <20 20-50 >50 9.9 18 35.9

Copper <25 25-50 >50 10-25 35.7 197

Zinc <90 90-200 >200 7-38 123.1 315

Arsenic <3 3-8 >8 1.1 5.9 17

Cadmium <1 1-6 >6 0.1-0.3 0.596 3.53

Lead <40 40-60 >60 4-17 35 91.3

Mercury <0.3 0.3-0.9 >1 4-51 0.174 0.486 1USEPA Guidelines for the Pollution Classification of Great Lakes Harbor Sediments

2National Oceanic and Atmospheric Administration Screening Quick Reference Table (Buchman 1999)

3Not Available

SURFICIAL SEDIMENTS Percent Dry Weight


As a means to describe the overall character of the sampled sediments, the dry weight percent for each station is presented in Figure 4, and summarized for all stations, and grouped by stations, in Figure 5. Analyses showed that the % dry weight, also considered % solids, is highly variable in the St. Marys River, ranging from 26 to 75% of the bulk sediment wet weight. These results underscore the heterogeneous nature of the sediments throughout the St. Marys River system, as the composition varies dramatically from organic-rich silt to sand and clay. The range of values was more coherent in the Little Rapids (38 to 66%) and Munuscong Lake (51 to 75%) subset of stations, as opposed to the stations from the river proper. Total Organic Carbon

The organic carbon content of surficial sediments ranged from 1.8 to 70 mg g-1 (Figure 6). Both the minimum and maximum values were obtained from stations within the river (Stations 7 and 4 respectively), while those from the Little Rapids and Munuscong Lake

yielded smaller maximum values (39 and 23.5 mg g-1 respectively) as well and narrower ranges (Figure 7). Again the heterogeneity of the river samples, as well as the station locations affect these results. The general inverse correlation found between TOC and % Dry Weight indicated among all samples that the higher organic content was associated with lower percent solids (Figure 8), as would be expected. When analyzed separately, this relationship was very strong for samples from the river (r2 = 0.95, n = 10), less strong for samples from the Little Rapids (r2 = 0.62, n = 10), and very weak for samples from Munuscong Lake (r2 = 0.04, n = 20). Samples from Munuscong Lake showed a narrow range of low organic carbon (3.7 to 23.5 mg g-1) despite an appreciable range of % solids (51 to 75).

Total Nitrogen The total nitrogen content of surficial sediments produced a pattern very similar to that of total organic carbon (Figure 9). Median values for the river samples, the Little Rapids and

Munuscong Lake were 0.49, 0.87 and 0.44 mg g-1 (Figure 10). The maximum values found for each of the groups of samples, however, decreased from 3.96 mg g-1 for the

river samples to 2.37 mg g-1 in the Little Rapids to 1.39 mg g-1 in Munuscong Lake. Total Phosphorus

The total phosphorus content of surficial sediments ranged from 80 to 630 µg g-1 in the

river, from 340 to 560 µg g-1 in the Little Rapids, and from 170 to 560 µg g-1 in Munuscong Lake (Figure 11). Further, samples from Munuscong Lake tended to have as much TP as those from other sites (Figure 12) despite being rather low in organic carbon (cf. Figure 6). While the average TOC’s for the river, Little Rapids and Munuscong Lake samples

were 19.9, 19.4 and 10.9 mg g-1 respectively, the average TP values were 368, 443 and

408 µg g-1 respectively.


Dry Weight

Sites

% o

f W

et

Weig

ht

0

20

40

60

80

100

ALL SMR LR ML

Figure 4. Dry weight as a percent of wet weight for surficial samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40).

Figure 5. Statistical analysis of Dry Weight (% of wet weight) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25

to 75 percentile, the error bars enclose the 10 to 90

percentile, and outliers are shown as filled circles.

Surficial Sediment Dry Mass

Station Number

0 5 10 15 20 25 30 35 40

Dry

Weig

ht

% o

f W

et

Weig

ht

0

20

40

60

80


Organic Carbon

Sites

TO

C (

mg g

-1)

0

20

40

60

80

ALL SMR LR ML

Figure 6. Organic carbon (mg g-1

dry weight) for surficial samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40).

Figure 7. Statistical analysis of Organic Carbon (mg g

-1) determinations on surficial sediment

samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25



Surficial Sediment Carbon

Station Number

0 5 10 15 20 25 30 35 40

Tota

l O

rganic

Carb

on (

mg g

-1)

0

10

20

30

40

50

60

70


Figure 8. Relationship between Total Organic Carbon (TOC) content of surficial sediment samples and the Percent Dry Weight for the Saint Marys River (SMR) stations, the Little Rapids (LR) stations and the Munuscong Lake (ML) Stations.

Percent Dry Weight

20 30 40 50 60 70 80

Tota

l O

rganic

Carb

on

0

20

40

60

80

SMR Stations

LR Stations

ML Stations


Total Nitrogen

Sites

TN

(m

g g

-1)

0

1

2

3

4

5

ALL SMR LR ML

Figure 9. Total nitrogen (mg g-1


Figure 10. Statistical analysis of Total Nitrogen (mg g





Surficial Sediment Nitrogen

Station Number

0 5 10 15 20 25 30 35 40

Tota

l N

itro

gen (

mg g

-1)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0


Total Phosporus

Sites

TP

(g g

-1)

0

100

200

300

400

500

600

700

ALL SMR LR ML

Figure 11. Total phosphorus concentration (µg g-1


Figure 12. Statistical analysis of Total Phosphorus (µg g-1) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25 to 75 percentile, the error bars enclose the 10 to 90 percentile, and outliers are shown as filled circles.

Surficial Sediment Phosphorus

Station Number

0 5 10 15 20 25 30 35 40

Tota

l P

hosphoru

s (

g g

-1)

0

100

200

300

400

500

600

700


Total Mercury

Concentrations of total mercury ranged from 2.5 to 191 ng g-1, and as with other variables showed the greatest range, and highest concentration in the river proper, decreasing in the Little Rapids and Munuscong Lake (Figure 13). The range of sediment total mercury

in Munuscong Lake, for example, was from 3.5 to 36 ng g-1 with a median value of 14.7

ng g-1. Median values were higher in both the river (17.6 ng g-1) and Little Rapids (32.9

ng g-1) samples (Figure 14). Methyl Mercury Concentrations of methyl mercury in surficial sediments ranges from below detection limit

(<0.02 ng g-1) to 1.26 ng g-1 in the river, from 0.08 to 1.17 ng g-1 in the Little Rapids, and

from 0.05 to 0.42 ng g-1 in Munuscong Lake (Figure 15). Note that Station 7, which yielded the below detection limit result, is excluded from Figure 14 and from further

analyses. The overall median for all samples was found to be 0.30 ng g-1, while the

medians for the different sites were 0.440 ng g-1 in the river, 0.605 ng g-1 in the Little

Rapids, and 0.140 ng g-1 for Munuscong Lake (Figure 16). Chromium

Chromium content ranged from 2.7 to 90.2 µg g-1 in the river sediments, a range that

included values found for sediments in the Little Rapids (8.4 to 54.5 µg g-1) and

Munuscong Lake (3.7 to 64.6 µg g-1) sediments (Figure 17). Median values of chromium

in surficial sediments were 19.0, 36.1 and 27.3 µg g-1 for the river, Little Rapids and Munuscong Lake respectively (Figure 18). Nickel

Nickel content ranged from 2.4 to 37.1 µg g-1 in Munuscong Lake, a range which nearly

enveloped results for both the river (1.9 to 13 µg g-1) and Little Rapids (5.6 to 23.1 µg g-1) samples (Figure 19). The median values for nickel concentrations in surficial sediments

were 5.1 µg g-1 for the river, 11.7 µg g-1 for the Little Rapids, and 12.45 µg g-1 for Munuscong Lake (Figure 20). Copper Concentrations of copper in surficial sediments from the river ranged from 2.6 to 48.4

µg g-1, a range which covered values obtained for samples from the Little Rapids (4.8 to

36.9 µg g-1) and Munuscong Lake (2.7 to 29.3 µg g-1) (Figure 21). Median values of

copper were 8.65 µg g-1 for the river, 17.65 µg g-1 for the Little Rapids, and 11.65 µg g-1 for Munuscong Lake (Figure 22). Zinc

Concentrations of zinc in surficial sediments ranged from 6.3 to 146 µg g-1 at the river

sites, from 17 to 106 µg g-1 at the Little Rapids sites, and from 5.2 to 60.1 µg g-1 in

Munuscong Lake (Figure 23). Median values were 24.5, 62 and 33.65 µg g-1 in the river, Little Rapids and Munuscong Lake respectively (Figure 24).


Arsenic

Arsenic content ranged from 0.45 to 3.3 µg g-1 in the river samples, a considerable range

which overlapped values for samples from the Little Rapids (0.54 to 2.8 µg g-1) and

Munuscong Lake (0.47 to 1.2 µg g-1) (Figure 25). Arsenic concentration was generally

consistently low in Munuscong Lake (median = 0.7 µg g-1), while more variable at the Little Rapids and the river sites (Figure 26). The median value of arsenic in the Little

Rapids was more than twice as high (1.8 µg g-1) as that for either the river or Munuscong Lake. Lead

Lead concentrations in surficial sediment samples ranged from 2.6 to 43.4 µg g-1 in the river sediments, a range that nearly included values for sediments in the Little Rapids (3.4

to 30.9 µg g-1) and Munuscong Lake (1.3 to 11.2 µg g-1) (Figure 27). Median values were

11.25 µg g-1, 19.4 µg g-1 and 7.5 µg g-1 for the river, Little Rapids and Munuscong Lake respectively (Figure 28). Cadmium Cadmium was only detected in surficial sediment at one of our stations (Station 4) in the St. Marys River. Cadmium was below detection limit at all other river stations (detection

limits ranged from 0.42 to 0.73 µg g-1). Cadmium was also below detection limits in the

Little Rapids (detection limits ranged from 0.44 to 1.17 µg g-1) and Munuscong Lake

(detection limits ranged from 0.42 to 0.45 µg g-1). Polyaromatic Hydrocarbons (PAH) Analysis of 17 distinct PAH compounds (see methods) at the 40 surficial sediment stations (680 analyses) produced only 67 results above detection limits. At stations where detectable PAH was found (n=11), the sum of all detected PAH was calculated as

“Total PAH” (mg kg-1). Results of total PAH ranged from below detection to 13.2 mg kg-1

in the river, and from below detection to 3.09 mg kg-1 in the Little Rapids (Figure 29). No sample from Munuscong Lake was above detection limit for any of the 17 PAH compounds.


Total Mercury

Sites

Hg (

ng g

-1)

0

50

100

150

200

250

ALL SMR LR ML

Figure 13. Total mercury concentration (ng g-1

dry weight) for surficial samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40). The NOAA SQRT (1999) Threshold Effects Level (TEL) is shown as a dotted reference line.

Figure 14. Statistical analysis of Total Mercury (ng g

-1) determinations on surficial sediment samples

for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25

to 75 percentile, the error bars enclose the 10 to 90 percentile, and

outliers are shown as filled circles.

Surficial Sediment

Total Mercury

Station Number

0 5 10 15 20 25 30 35 40

Hg (n

g g

-1)

0

20

40

60

80

100

120

140

160

180

200


Methyl Mercury

Sites

MeH

g (

ng g

-1)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ALL SMR LR ML

Figure 15. Methyl mercury concentration (ng g-1

dry weight) for surficial samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40). Note that Station 7 results were below detection limit

(<0.02 ng g-1

) and not plotted.

Figure 16. Statistical analysis of Methyl mercury (ng g




percentile, and outliers are shown as filled circles. Note one sample was excluded from the Little Rapids sties as its value was below determination level (<0.02 ng g

-1).

Surficial Sediment

Methyl Mercury

Station Number

0 5 10 15 20 25 30 35 40

MeH

g (

ng g

-1)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


Chromium

Sites

Cr

(g g

-1)

0

20

40

60

80

100

ALL SMR LR ML

Figure 17. Chromium concentration (µg g-1


Figure 18. Statistical analysis of Chromium (µg g

-1) determinations on surficial sediment samples for

all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25



Surficial Sediment

Chromium

Station Number

0 5 10 15 20 25 30 35 40

Cr

(g g

-1)

0

20

40

60

80

100


Nickel

Sites

Ni (

g g

-1)

0

10

20

30

40

ALL SMR LR ML

Figure 19. Nickel concentration (µg g-1


Figure 20. Statistical analysis of Nickel (µg g-1) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25 to 75 percentile, the error bars enclose the 10 to 90 percentile, and outliers are shown as filled circles.

Surficial Sediment

Nickel

Station Number

0 5 10 15 20 25 30 35 40

Ni (

g g

-1)

0

5

10

15

20

25

30

35

40


Copper

Sites

Cu (

g g

-1)

0

10

20

30

40

50

60

ALL SMR LR ML

Figure 21. Copper concentration (µg g-1


Figure 22. Statistical analysis of Copper (µg g-1

) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25



Surficial Sediment Copper

Station Number

0 5 10 15 20 25 30 35 40

Cu (

g g

-1)

0

10

20

30

40

50


Zinc

Sites

Zn (

g g

-1)

0

20

40

60

80

100

120

140

160

ALL SMR LR ML

Figure 23. Zinc concentration (µg g-1


Figure 24. Statistical analysis of Zinc (µg g-1

) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25



Surficial Sediment Zinc

Station Number

0 5 10 15 20 25 30 35 40

Zn (

g g

-1)

0

20

40

60

80

100

120

140

160


Arsenic

Sites

As (

g g

-1)

0.5

1.5

2.5

3.5

0.0

1.0

2.0

3.0

4.0

ALL SMR LR ML

Figure 25. Arsenic concentration (µg g-1

dry weight) for surficial samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40). Note that the NOAA SQRT (1999) Threshold Effects Level (TEL)

is not shown as the value (5.9 µg g-1

) exceeds the axis scale.

Figure 26. Statistical analysis of Arsenic (µg g-1) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25 to 75 percentile, the error bars enclose the 10 to 90 percentile, and outliers are shown as filled circles.

Surficial Sediment Arsenic

Station Number

0 5 10 15 20 25 30 35 40

As (

g g

-1)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5


Lead

Sites

Pb (

g g

-1)

0

10

20

30

40

50

ALL SMR LR ML

Figure 27. Lead concentration (µg g-1


Figure 28. Statistical analysis of Lead (µg g-1) determinations on surficial sediment samples for all samples (ALL, n=40), samples from the St. Marys River proper (SMR, n=10), the Little Rapids (LR, n=10) and Munuscong Lake (ML, n=20). For each sample group, the median value is shown as the bar, the box encloses the 25 to 75 percentile, the error bars enclose the 10 to 90 percentile, and outliers are shown as filled circles.

Surficial Sediment Lead

Station Number

0 5 10 15 20 25 30 35 40

Pb (

g g

-1)

0

10

20

30

40

50


Figure 29. Total Polyaromatic Hydrocarbon (PAH) concentration (mg kg-1

) for surficial sediment samples collected during August and September 2003 from the St. Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40). Analyses were conducted for 15 separate PAH compounds, results shown are the sum of all analyses yielding results above detection limits.

SURFICIAL SEDIMENT SUMMARY For most of the parameters measured, the stations selected in the river proper (“SMR” in Figures 5, 7 and even numbered Figures 10-28) bracketed estimates from the Little Rapids (LR) and Munuscong Lake (ML) stations, the exception being nickel (Figure 20). Results indicated that chromium and nickel continue to be elevated in surficial sediments throughout the St. Marys River system. For chromium, 3 of 10 river stations, 4 of 10 Little Rapids stations, and 8 of 20 Munuscong Lake stations had concentrations above the Threshold Effects Level (TEL). One station in the river, Station 6, exceeded the Probable Effects Level (PEL). Nickel was also elevated above the TEL at 2 of 10 stations in the Little Rapids and 8 of the 20 stations in Munuscong Lake. One station in Munuscong Lake (Station 21) exceeded the PEL for nickel. Overall, 16 stations exceeded the TEL for chromium, 10 for nickel, 2 for copper, and one station for zinc, arsenic and cadmium (Table 2). Results for cadmium from 12 stations were below the method detection limit, however the limit was above the TEL. The actual concentrations at these stations could, therefore, also be above the TEL. The results from the current study are not unlike those compiled for the Stage 1 RAP, which indicated that 44-58% of sites exceeded the Moderately Polluted EPA Standard for

Surficial Sediment

Total PAH

Station Number

0 5 10 15 20 25 30 35 40

PA

H (

mg k

g-1

)

0

2

4

6

8

10

12

14


Cr, and 21-34% exceeded the standard for Ni. Results from this study exceeded the EPA Moderately Polluted standard for chromium at 65% of the sites and for nickel at 25% of the sites. Of the 30 sites sampled in Munuscong Lake and presented in the Stage 1 RAP, 77% exceeded the EPA Moderately Polluted standard for chromium, 37% for nickel and 43% for copper. Applying the EPA Moderately Polluted standard to the 20 stations sampled in Munuscong Lake during the current study, 75% exceeded the standard for chromium, 40% for nickel and 20% for copper.

Table 2. Surface sediment sampling stations which exceeded either EPA or NOAA guidelines for contaminated freshwater sediments for metals and total phosphorus. Station numbers 1-10 are from the St. Marys River proper, 11-20 are from the Little Rapids area, and 21-40 are from Munuscong Lake.

Paramter Stations Exceeding EPA Standard for Moderately Polluted

Stations Exceeding NOAA Threshold Effects Level (TEL)

Stations Exceeding NOAA Probable Effects Levels (PEL)

Total Mercury --- 4 ---

Chromium

2,3,4,6,12,13,14,16,1718,19,21,23,25,26,27 28,29,31,32,34,35,36

37,38,40

3,4,6,13,14,16,17,18 21,23,26,28,35,36,3738

6

Nickel 13,18,21,24,26,28,35

36,37,38 13,18,21,24,26,28,35

36,37,38 21

Copper 4,13,18,21,24,26,28 4,18 ---

Zinc 2,4,6,13,18 4 ---

Arsenic 4,6 --- ---

Cadmium --- 4* ---

Lead 4 4 ---

Total Phosphorus 2,4,5,6,11,12,13,14

17,18,19,23,24,25,26 32,35,36,37,38

na na

*The following stations which yielded results below detection limit, but the detection limit was above the TEL: 2,5,6,11,12,13,14,16,17,18,19,20

CORE SAMPLES As previously stated, coring operations in the targeted areas (Little Rapids and Munuscong Lake) were hampered by extremely low water levels, particularly in Munuscong Lake. Sectioning the cores was also compromised by occasional horizons of rock gravel or large woody debris, signatures of a very dynamic and/or altered sedimentary environment. Core A - Little Rapids Core A was collected from a 6.4m water depth station near the base of the Little Rapids area (Figure 2) using a gravity core. This core was sampled in 1 cm sections from 0 to 10 cm, in 2 cm sections from 10 to 50 cm, and every other 2 cm horizon from 52-54 to 60-62 cm depth. Results are presented as the horizon of the middepth of each sample. This site showed characteristic recent surface deposition and diagenesis evidenced by rapidly decreasing organic carbon and total nitrogen through the first 6 cm (Figure 30b and c).


CORE A - Little Rapids

% Dry Weight

40 50 60 70 80 90

Ho

rizo

n M

idd

ep

th (

cm

)

0

10

20

30

40

50

60

Total Carbon (mg g-1

)

0 5 10 15 20 25 30

0

10

20

30

40

50

60

Total Nitrogen (mg g-1

)

0.0 0.2 0.4 0.6 0.8 1.0 1.2

0

10

20

30

40

50

60a. b. c.

Relatively constant values for organic carbon (0.6 to 0.7%) and total nitrogen (0.01 to 0.02%) were found in the 6 cm to the 18-20 cm section, and again from 28-30 to the 60-62 sections (0.5% C and 0.01% N). There was an abrupt increase in organic carbon and total nitrogen at the 20-22 cm section corresponding to a layer of charcoal in the 20-22 cm section. The 22-24 cm section contained small cobble, samples for carbon and nitrogen were not collected. The 20 to 26 cm zone also corresponded to a change in % dry weight of the sediments from approximately 50% above 20 cm to 65% below 26 cm(Figure 30a), indicating a change in the sedimentary environment.

Figure 30. Dry weight (%), Total Carbon (mg g-1

) and Total Nitrogen (mg g-1

) determined in sequential horizons through Core A. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (62 cm).

Core A yielded estimates of Hg ranging from 6.4 to 119.6 ng g-1 with a median value of 8.6 ng g-1 (Figure 31a). The core showed a slightly elevated mercury near the surface (average 28.7 ng g-1 from 0 to 5 cm) when compared to the rest of the core (average 8.4 ng g-1 from 6 to 60-62 cm, excluding 119.6 ng g-1 value at 20-22 cm). Estimates of chromium ranged from 23.4 to 89.2 µg g-1 (median = 43.2 µg g-1) again with the highest values in the 20-24 cm horizon (89.2 and 85.9 µg g-1 respectively) (Figure 31b). Surficial values were slightly lower (average 29.3 µg g-1 for 0-5 cm) than the rest of the core (average 42.7 µg g-1 for 6 to 60-62 cm excluding the 20-22 and 22-24 sections). Nickel concentrations in Core A ranged from 8.9 to 34.9 µg g-1, with a median value of 29.4 µg g-

1 (Figure 31c). Surface sections (0 to 5 cm, average 13.78 µg g-1 ), and samples from 20 to 28 cm (average 15.85 µg g-1) were lower than other sections in the core (average 30.6


CORE A - Little Rapids

Hg(ng g

-1)

0 50 100

Ho

rizo

n M

idd

ep

th (

cm

)

0

10

20

30

40

50

60

Cr( g g

-1)

0 40 80

Ni( g g

-1)

0 20 40

Cu( g g

-1)

0 20 40

Zn( g g

-1)

0 80 160

As( g g

-1)

0.0 2.0 4.0

Pb( g g

-1)

0 20 40 60

a. b. c. d. e. f. g.

µg g-1). Most of the core sections exceeded the NOAA SQT Threshold Effect Level (TEL) of 18 µg g-1 and were close to the Probable Effect Level (PEL) of 35.9 µg g-1. Copper concentrations (Figure 31d) ranged from 13.6 to 34.8 µg g-1 (median 28.7 µg g-1) with lower values in the surface (0 to 5 cm, average 17.0 µg g-1) and 24-26 and 26-28 cm sections (average 14.3 µg g-1) than the rest of the core (average 29.5 µg g-1). Zinc concentrations were very homogenous through the core (Figure 31e), ranging from 37.2 to 64.2 µg g-1 (median 47.7 µg g-1) with the exception of two sections, 20-22 cm (146.9 µg g-1 ) and 22-24 cm (167.4 µg g-1 ). The average concentration excluding these two horizons was 47.8 µg g-1 (standard deviation of 5.4, n= 31), well below the TEL of 123.1 µg g-1. Estimates of arsenic ranged from 0.54 to 3.63 µg g-1, with a median value of 0.63 µg g-1 (Figure 31f). While arsenic concentrations were slightly elevated in the 0 to 5 cm sections (average 1.0 µg g-1), and considerably higher in the 20-22 cm (2.41 µg g-1), the 22-24 cm (3.63 µg g-1), and the 24-26 cm (1.29 µg g-1) sections, concentrations were very homogenous throughout the other core sections (average 0.62 µg g-1, standard deviation 0.05, n=25). Estimates of lead concentrations ranged from 7.6 to 54.5 µg g-1, with a median value of 9.3 µg g-1 (Figure 31g). As with the arsenic profile, lead is slightly elevated on the 0 to 5 cm sections (average 16.3 µg g-1, and is substantially higher in the

20-22 cm (48.0 µg g-1), the 22-24 cm (54.5 µg g-1), and the 24-26 cm (19.4 µg g-1) sections, concentrations were very homogenous throughout the other core sections

(average 8.9 µg g-1, standard deviation 1.1, n= 25).

Figure 31. Metal concentrations in sequential horizons through Core A. Concentrations for Hg are

ng g-1

, all others are µg g-1

. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (62 cm). For each metal, the NOAA SQRT (1999) Threshold Effects Level (TEL) is shown as a dotted reference line, the Probable Effects Level (PEL) as a dashed reference line if those values are within the axis range.


Sedimentation rate for Core A, calculated from Pb-210 analysis was 0.17 g cm-2y-1. Applying this rate, along with the cumulative midpoint mass of each section, we estimate that the disturbance from 20 to 28 cm observed in sediment moisture (% dry weight) as well as the element concentrations occurred from 105 to 95 years ago (between 1900 and 1910). The surface signal evident from 0 to 5 cm in depth in this core represents deposition that has occurred within the last 25 years. Core B - Little Rapids Core B was collected from a 7.95 m water depth station in a back-water area of the Little Rapids, with only a shallow connection to the river proper (Figure 2) using a gravity core. The core was sampled in 1 cm sections from 0 to 10 cm, 2 cm sections from 10 to 50 cm, and every other 2 cm horizon from 52-54 to 68-70 cm. Results are presented as the middepth of each section. Unlike Core A, taken from a main channel, Core B shows no clear pattern of deposition and diagenesis; the percent dry weight increased with depth (Figure 32a) ranging from 28.5 to 80.6% (median 46.9%). In fact, three distinct regions of sediment were characterized by the solids percent; a zone from 0 to 22 cm (median 41%), a zone from 22 to 48 cm (median 56%), and a zone from 48 to 70 cm (median 69%). These groupings of samples proved to be significantly different (Kruskal-Wallice one-way anova, p<0.001), and likely represent differing periods of sedimentation. Both the organic carbon and total nitrogen showed values increasing from the surface to a broad peak around 12 cm, with a second peak around 48 cm (Figure 32b and c).

Estimates of organic carbon ranged from 5.3 to 33.6 mg g-1 (median 24.8 mg g-1), while

total nitrogen ranged from 0.06 to 2.0 mg g-1 (median 1.2 mg g-1). Core B yielded estimates of total mercury (Figure 33a) which ranged from 4.7 to 67.7

ng g-1 (median 51.0 ng g-1) over most of the core; two horizons had significantly higher

concentrations (187.8 ng g-1 at 4-5 cm, and 227.6 ng g-1 at 7-8 cm). Whether these values represent episodic deposition of mercury, or sample contamination cannot presently be determined. Concentration of chromium (Figure 33b) ranged from 14.6 to

81.6 µg g-1 (median 44.4 µg g-1). As with Core A, most samples from Core B were

elevated above the Threshold Effect Level (TEL) of 37.3 µg g-1, but unlike Core A there was no clear decrease near the surface or peak at depth in Core B. Nickel

concentrations ranged from 8.4 to 31.6 µg g-1 (median 20.1 µg g-1) with 30 of the 34

samples above the TEL of 18 µg g-1 (Figure 33c). Estimates of copper concentration

through Core B ranged from 8.5 to 38.7 µg g-1 (median 28.1 µg g-1), and were generally higher above 25 cm than the rest of the core (Figure 33d). Zinc concentrations ranged

from 5.6 to 142.0 µg g-1 (median 70.8 µg g-1) through the core, with elevated values seen

from 10 to 22 cm (Figure 33e). Arsenic concentrations ranged from 0.5 to 2.8 µg g-1

(median 1.7 µg g-1) with generally higher concentrations through the 10 to 22 cm horizons

(Figure 33f). Concentration of lead ranged from 3.5 to 49.4 µg g-1 (median 24.2 µg g-1),

with 6 sections from 10 to 24 cm exceeding the TEL of 35 µg g-1 (Figure 33g).

Sedimentation rate for Core B, calculated from Pb-210 analysis was 0.24 g cm-2y-1. After correcting for the midpoint accumulated mass, the three zones apparent in the dry weight data correspond to dates 1880 to present, 1718 to 1880, and 1631 to 1718 respectively.


Relatively constant 210Pb in the top 15 cm of Core B indicated a zone of mixing which would influence the accuracy of 210Pb dating estimates, derived from the 20 to 35 cm horizons. Nonetheless, influences of European settlement and industrialization along the

St. Marys should be reflected in the top 20-30 cm of Core B.



) determined in sequential horizons through Core B. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (70 cm).

CORE B - Little Rapids

% Dry Weight

20 30 40 50 60 70 80 90

Hori

zon

M

idde

pth

(cm

)

0

10

20

30

40

50

60

70


)

0 5 10 15 20 25 30 35 40

0

10

20

30

40

50

60

70


)

0.0 0.5 1.0 1.5 2.0 2.5

0

10

20

30

40

50

60

70a. b. c.


Figure 33. Metal concentrations in sequential horizons through Core B. Concentrations for Hg are

ng g-1



Core C - Munuscong Lake Core C was collected from a 1.3 m water depth station on the northern side of Munuscong Lake (Figure 3) using a vibracore. This core was sampled in 1 cm section form 0 to 10 cm, 2 cm sections from 10 to 50 cm, and every other 2 cm horizon from 52-54 to 116-118 cm depth. Results are presented as the middepth of each section. Dry weight of the sediment collected in this core demonstrated rapidly deceasing values through the top 10 cm, from 68% in the 2-3 cm horizon to 53% in the 9-10 cm horizon (Figure 34a). Below 10 cm the dry weight was very constant (mean 51.5, standard deviation 0.97). Both organic carbon (Figure 34b) and total nitrogen (Figure 34c) were

also relatively constant through this core. Organic carbon ranged from 6.6 to 8.2 mg g-1

(median 7.5 mg g-1), nitrogen ranged from 0.68 to 0.90 mg g-1 (median 0.80 mg g-1).

CORE B - Little Rapids

Hg(ng g

-1)

0 100 200

Ho

rizo

n M

idd

ep

th (

cm

)0

10

20

30

40

50

60

70

Cr ( g g

-1)

0 40 80

Ni( g g

-1)

0 20 40

Cu ( g g

-1)

0 20 40

Zn( g g

-1)

0 80 160

As( g g

-1)

0.0 2.0 4.0

Pb( g g

-1)

0 20 40 60

a. b. c. d. e. f. g.




) determined in sequential horizons through Core C. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (118 cm).

Total mercury was low in Core C, ranging from 12.5 to 19.4 ng g-1 (median 15.7 ng g-

1)(Figure 35a). Chromium concentrations ranged from 15.4 to 60.5 µg g-1 (median 46.6

µg g-1), and showed lower values at the surface increasing to 10 cm (Figure 35b).

Estimates of nickel concentrations ranged from 8.2 to 39.7 µg g-1 (median 31.5 µg g-1), and were also lower near surface, increased to 10 cm and remained relatively constant throughout the rest of the core (Figure 35c), near the Probable Effect Level (PEL) of 35.9

µg g-1. Copper also increased though the first 10 cm of Core C, from 7.4 to 15.5 µg g-1,

and peaked at 29.2 µg g-1 in the 48-50 cm horizon (Figure 35d). Zinc concentration

increased from 22.3 to 42.6 µg g-1 through the top 10 cm of Core C, as was consistent

through the rest of the core (Figure 35e), averaging 51.1 µg g-1 (standard deviation 2.9

µg g-1 ). Concentration of arsenic through the core ranged from 0.74 to 0.98 µg g-1

(median 0.86 µg g-1 ) and was fairly constant (mean 0.85, standard deviation 0.06 µg g-

1)(Figure 35f). Lead concentrations increased slightly through the first 10 cm, from 6.5 to

9.1 µg g-1, and remained very constant through the rest of the core (Figure 35g).

CORE C - Munuscong Lake

% Dry Weight

45 50 55 60 65 70

Horizon M

iddepth

(cm

)

0

10

20

30

40

50

60

70

80

90

100

110


)

0 2 4 6 8 10

0

10

20

30

40

50

60

70

80

90

100

110


)

0.0 0.2 0.4 0.6 0.8 1.0

0

10

20

30

40

50

60

70

80

90

100

110a. b. c.


Very low concentrations of unsupported 210Pb through Core C precluded the estimation of sedimentation rate and therefore dates were not assigned to core horizons.

Figure 35. Metal concentrations in sequential horizons through Core C. Concentrations for Hg are

ng g-1



Core D - Munuscong Lake Core D was collected from a 1.7 m water depth station in the central area of Munuscong Lake (Figure 3) using a 5’ vibracore. This core was sampled in 1 cm sections from 0 to 10 cm, and in 2 cm sections from 10 to 40 cm, the total length of the core. Results are presented as the middepth of each section. This site showed an exponential increase in dry weight, from 36.0% in the 0-1 cm section to 79.8% in the 10-12 cm section (Figure 36a). Overall dry weight ranged from 36.0 to 80.2% (median 78.0%), and was very constant below 12 cm (mean 78.3%, standard deviation 0.85). Both organic carbon (Figure 36b) and total nitrogen (Figure 36c) decreased exponentially through the top 12 cm of Core D; organic carbon from 11.9 to 0.53 mg g-1, and total nitrogen from 1.24 to 0.09 mg g-1. Below the 12-14 cm horizon, organic carbon and total nitrogen were quite consistent, averaging 0.52 and 0.09 mg g-1 respectively.

CORE C - Munuscong Lake

Hg(ng g

-1)

0 10 20

Hori

zon

M

idde

pth

(cm

)

0

10

20

30

40

50

60

70

80

90

100

110

Cr( g g

-1)

0 20 40 60

Ni( g g

-1)

0 20 40

Cu( g g

-1)

0 20 40

Zn( g g

-1)

0 20 40 60

As( g g

-1)

0.0 0.5 1.0

Pb( g g

-1)

0 5 10 15

a. b. c. d. e. f. g.


CORE D - Munuscong Lake

% Dry Weight

30 40 50 60 70 80 90

Ho

rizo

n M

idd

ep

th (

cm

)

0

10

20

30

40


)

0 2 4 6 8 10 12 14

0

10

20

30

40


)

0.00.20.40.60.81.01.21.4

0

10

20

30

40a. b. c.



) determined in sequential horizons through Core D. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (42 cm).

Total mercury in Core D ranged from 3.1 to 61.2 ng g-1 (median 8.0 ng g-1), and showed slightly elevated concentrations near the surface, and a peak centered around the 28-30

cm horizon (Figure 37a). Chromium ranged from 10.1 to 23.8 µg g-1 (median 14.0 µg g-1),

nickel ranged from 5.9 to 12.4 µg g-1 (median 9.1 µg g-1), and copper ranged from 4.7 to

13.0 µg g-1 (median 8.8 µg g-1). These three metal showed very similar sediment profiles (Figures 37b-d) with decreasing concentrations from the surface to 5 cm, a broad, but minor increase from 5 to 10 cm, and another broad peak centered around 25 cm. Zinc

concentrations also decreased from the surface (36.2 µg g-1) to, in this case, 10 cm (13.7

µg g-1), and showed a broad peak (up to 31.4 µg g-1) centered around 25 cm (Figure 37e).

Arsenic concentrations were low in Core D, ranging from below detection (<0.46 µg g-1) to

0.80 µg g-1 (median of detected values 0.51 µg g-1), and generally followed the pattern of Cr, Ni and Cu near the surface (Figure 37f). Lead concentrations ranged from 2.4 to 27.9

µg g-1 (median 3.7 µg g-1), and also tended to decrease through the upper 5 cm of the core (Figure 37g). Lead concentration in the 7-8 cm horizon abruptly increased to 27.9

µg g-1, and corresponded with the broad, less severe increases in Cr, Ni, Cu and As through the 5 to 10 cm zone.


Figure 37. Metal concentrations in sequential horizons through Core D. Concentrations for Hg are

ng g-1


. For each 2 cm section, the middepth of that horizon is plotted from the sediment surface (0 cm) to the maximum depth cored (42 cm). Missing values for As (n=6) were

below detection limit (<0.46 µg g-1

). For each metal, the NOAA SQRT (1999) Threshold Effects Level (TEL) is shown as a dotted reference line, the Probable Effects Level (PEL) as a dashed reference line if those values are within the axis range.

Sedimentation rate for Core D, calculated from 210Pb analysis was 0.34 g cm-2y-1. Applying this rate, along with the cumulative midpoint mass of each section, we estimate that the top 5 cm represents approximately 50 years before present, that the peak in Pb concentration occurred some 80 years before present, and that the deeper, broader peak observed for Ni, Cu, and Zn occurred 200 to 270 years ago.

SEDIMENT CORE SUMMARY

General Characteristics The four cores collected for this study represent a disparate group of profiles, most likely illustrating the natural heterogeneity nature of the St. Marys River confounded by episodic and localized perturbations. The two areas targeted for coring, the Little Rapids and Munuscong Lake are somewhat removed from the river yet are still influenced by its sediment loading. The Little Rapids historically derived flow from the main river channel until a causeway was built to Sugar Island in the 1950’s. Depositional environments would have collected sediment differently before an after the construction of the earthen

CORE D - Munuscong Lake

Hg

(ng g-1

)

0 40 80

Hori

zon

M

idde

pth

(cm

)

0

10

20

30

40

Cr( g g

-1)

0 20 40

Ni( g g

-1)

0 8 16

Cu ( g g

-1)

0 8 16

Zn( g g

-1)

0 20 40

As( g g

-1)

0.0 0.5 1.0

Pb( g g

-1)

0 10 20 30

a. b. c. d. e. f. g.


Perc

ent

Dry

Weig

ht

20

40

60

80

100

Org

anic

Carb

on (

mg g

-1)

0

10

20

30

40

Core

Tota

l N

itro

gen (

mg g

-1)

0.0

0.5

1.0

1.5

2.0

2.5

A B C D

causeway, which does currently allow a limited amount of flow into the Little Rapids area. Munuscong Lake, on the other hand, derives much of its sediment load from the Munuscong River watershed, a landscape currently dominated by agriculture and fine grained soils (clay). The large surface area of Munuscong Lake and its shallow depth allow for nearly continuous mixing during the ice-free periods of the year. In general, core samples from the Little Rapids showed a great deal more variability in dry weight than those from the Munuscong Lake cores (Figure 38a), suggesting much more mixing during and after deposition. Differences observed between Core C and Core D in Munuscong Lake are likely due to prevalence of silt and sand, respectively, through the cores. The high, and highly variable, organic carbon and total nitrogen concentrations through Core B (Figure 38b and c) indicate both high inputs and rapid burial.

Figure 38. Statistical analysis of Dry Weight (%), Organic Carbon (mg g-1

) and Total Nitrogen (mg g-

1) for all horizons sampled in each core. For each sample group (core), the median value is shown

as the bar, the box encloses the 25 to 75 percentile, the error bars enclose the 10 to 90 percentile,

and outliers are shown as filled circles.


Metals Metal concentrations were generally higher in the cores from the Little Rapids than from Munuscong Lake (Figure 39). Both the proximity of the Little Rapids to point sources in the upper river, and dilution of the Munuscong Lake sediments with uncontaminated sediments from the Munuscong watershed could contribute to this pattern. Within Munuscong Lake, metal concentrations were higher, and more variable in Core C than in Core D. Higher concentrations in Core C are most likely correlated with the higher organic content at this station, a pattern observed for Cr, Ni, Zn and Cu during the 1985 sampling for the RAP (St. Marys River RAP Team. 1991).

Figure 39. Statistical analysis of metal concentrations (µg g-1

) for all horizons sampled in each core. For each sample group (core), the median value is shown as the bar, the box encloses the 25

to 75

percentile, the error bars enclose the 10 to 90 percentile, and outliers are shown as filled circles. Note that y-axes range is the same for each plot for graphical clarity.

Stratigraphic Analyses The application of 210Pb dating of sediment cores from rivers and streams is difficult in general, and is exacerbated in the present study by the lack of corroborating radiometric measures (137Cs, for example). Models predicting sedimentation rate from 210Pb stratigraphy rely, in general, on the assumption of uniform sedimentation over the last several hundred years (Robbins and Edington 1975). The St. Marys River has undergone tremendous alterations in flow (and presumably sedimentation) regimes with the construction of a compensating gates, power canal, locks and shipping channels, dredging of channels, and installation of causeways for road surfaces. Core A, from the Little Rapids, best displayed the pattern of sediment accumulation required for sound application of 210Pb. Exponential decline of unsupported 210Pb from the sediment water interface (Figure 40a) allows reasonable estimate (r2=0.92) of

sedimentation. The estimate of 0.17 g cm-2y-1 found here agrees favorably with estimates

from Lake George ranging from 0.19 to 0.22 g cm-2y-1 (Hesselberg and Hamdy 1987)

Core D Munuscong Lake

0

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based on 137Cs stratigraphy. While we do not have 137Cs data to corroborate our 210Pb estimates, the large disturbance 20 to 28 cm down in Core A correlates very well with the construction of the power canal through Sault Ste. Marie, MI during the 1890’s which may represent the single largest disturbance upstream from the Little Rapids sites. Unsupported 210Pb in Core B (Figure 40b) indicates mixing through the first 15 cm of the sediment; sedimentation rate estimates relied on exponential decline from 15 to 30 cm. Such mixing at the sediment-water interface can be due to bioturbation, resuspension and settling of local sediment, or increased erosion in the watershed. The sedimentation rate estimate here should be viewed with caution. The lack of unsupported 210Pb through Core C (Figure 40c) probably represents very high delivery of inorganic particle from the watershed followed by high scouring and possibly net erosion from that area of Munuscong Lake. Such processes would obliterate the sequential sedimentation and burial processes upon which stratigraphic dating method rely. . Figure 40. Unsupported

210Pb distribution with depth in each core. Note that a common y-axis is

used for comparison, and that x-axis tick marks have equivalent spacing, also to allow for comparison.

a.

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a. b. c. d.


CONCLUSIONS

Chromium and nickel contamination of surficial sediments remains a persistent problem throughout the St. Mary River system. The current study focused on two areas of particular interest, undersampled in previous studies. Both the Little Rapids and Munuscong Lake are potential sites of restoration efforts within the river. Our results show that 13 of the 16 sites which exceeded TEL for chromium, and all 10 sites which exceeded the TEL for Ni were from either the Little Rapids or Munuscong Lake. Results from the cores indicate that historical contamination of surface sediments is being buried in the Little Rapids area of the river, and is likely resuspended and redeposited in Munuscong Lake.


LITERATURE CITED

Buchman, M.F. 1999. NOAA Quick Screening Reference Tables. NOAA HAZMAT

Report 99-1. Seattle WA, Coastal Protection and Restoration Division, National Oceanic and Atmospheric Administration. 12p.

Hesselberg, R.J. and Y. Hamdy. 1987. Current and historical contamination of sediment

in the St. Marys River. UGLCCS Sediment Workgroup Report. 17p. MacDonald, D.D., C.G. Ingersoll and T.A. Berger. 2000. Development and evaluation of

consensus-based sediment quality guidelines for freshwater ecosystems. Arch. Environ. Contam. Toxicol. 39:20-31.

Robbins, J.A. and D.N. Edgington. 1975. Determination of recent sedimentation rates in

Lake Michigan using Lead-210 and Cesium-137. Geochim. Cosmochim. Acta 39:285-304.

St. Marys River RAP Team. 1991. The St. Marys River Area of Concern. Environmental

Conditions and Problem Definitions: Remedial Action Plan Stage 1. Ontario Ministry of the Environment and Michigan Department of Natural Resources. 393 p.


APPENDICES

Appendix A. A4. Project/Task Organization The project, “Current Sediment Quality in the St. Marys River AOC”, represents an effort by

researchers at Lake Superior State University in Sault Ste. Marie (MI) to update and expand the

dataset regarding sediment contamination in the St. Marys River.

The organization and responsibilities for this project are outlined in Figure 1. The two individuals

primarily responsible for accomplishing the objectives of this project are Richard Back, Ph.D., a

biologist/limnologist and Barbara Keller, Ph.D., an environmental/analytical chemist, both from

Lake Superior State University (LSSU).

The U.S. EPA is responsible for awarding the grant to Lake Superior State University, providing

for the R/V Mudpuppy, and the equipment for coring and sectioning the samples. U.S. EPA QA

manager will provide external QA support.

Lake Superior State University's Environmental Analysis Laboratory is responsible for providing physical and chemical analysis of the sediment samples submitted for metals (excluding mercury), TOC, TON, and TP. This lab is responsible for QA/QC and lab data reduction for these sample analyses (Lab Manager: Dr. Barb Keller 906-635-2438). KARLaboratories, Inc., an EPA certified laboratory is responsible for providing chemical analysis of the samples submitted for PAH. This lab is responsible for QA/QC and lab data reduction for these sample analyses. Samples for total and methyl mercury will be analyzed under a sub-contract to the University of Wisconsin-Madison Environmental Chemistry and Technology Program, which will be responsible for QA/QC and lab data reduction for these samples. The subcontract will be administered by Dr. Helen Manolopoulos, 608-265-5086. Core sections for radio-dating will be analyzed under subcontract to the University of Wisconsin-Milwaukee Great Lakes Water Institute, which will be responsible for QA/QC and lab reduction data for these samples. The subcontract will be administered by Dr. J. Val Klump, 414-382-1700.


Figure 1. Flow chart showing the organization and responsibility for the project entitled

“Current Sediment Quality in the St. Marys River Area of Concern” (GL2002-054).

GLNPO

Project Manager M. Tuchman M. Tuchman

GLNPO

QA Manager

LSSU Project Directors R. Back and B. Keller

Field Sampling

LSSU ICP-MS Metals, TOC / TON TP,

Porosity, Grain Size

EPA Certified Contract Laboratory

PAH Analyses

Subcontracts

UW-Milwaukee Water Institute 210

Pb Core Dating

UW-Madison EC&T Program Mercury Analysis

Laboratory Analyses

Surface Sediments

Coring R/V

Mudpuppy


A5. Problem Definition/Background The St. Marys River is the sole surface outlet from Lake Superior, flowing over 100 km to Lake Huron, and forming part of the international border between Canada (Ontario) and USA (MI). As part of a series of Great Lakes connecting channels, the St. Marys River has historically been, and continues to be, vital to shipping and industry. Consequently, the river system has been severely impacted by modifications to the hydrology as well as local industrial and municipal discharges, and was designated in 1985 as an Area of Concern (AOC).

Stage 1 of the Remedial Action Plan (RAP) for this AOC, completed in 1991, broadly described

the environmental conditions and identified use impairments. Based on the sampling of 125

stations within the river system during 1985 (Figure 2), the Stage 1 specifically characterized

spatial distribution of heavy metal contaminated sediments. While areas of localized

concentrations of heavy metals in sediments are predominantly located on the Canadian side, one

fairly localized depositional zone on the US side, an embayment called Lake Munuscong, was

shown to have elevated Cr, Ni, Cu associated with silt/organic sediments.

As the St. Marys AOC moves toward the completion of Stage 2, now in draft, and actual

remediation and regulation, several questions remain regarding sediment contamination. First,

while the Canadian stations have been systematically re-sampled (mid 1990's), the US sites have

not. This means that any decisions that are made regarding sediment contamination and any use

impairment regarding dredged sediments and degradation of benthos will largely rely on 17-year-

old data. Secondly, a recurrent impairment in the St. Marys AOC is habitat loss; in particular the

limited rapids which now exist. Stage 2 of the RAP will call for either restoration or creation of

areas of rapids in the river. Over the last few years, there has been local interest in re-establishing

flow through an area of the river historically known as "The Little Rapids". This area, which

includes some relatively deep, depositional areas, was not previously sampled during the RAP

process.

A6. Project/Task Description This investigation will provide detailed sampling of surface sediments and cored sediments in

several areas of the St. Marys AOC. All sampling sites will be mapped using the Global

Positioning System (GPS). First, surface sediment samples will be collected from a) 10 previously

sampled sites, b) 10 sites within Little Rapids area, and c) 20 sites within the Lake Munuscong

area. These surface samples will be collected from small boats using a Ponar grab. Samples will

be collected and stored using clean technique, and subsamples will be characterized for physical

properties (porosity, grain size distribution), nutrient concentrations (TOC, TON, TP), and

contaminant concentrations (metals, Hg, methyl-Hg, PAH). Subsamples will also be cataloged

and archived for future reference.

Secondly, this investigation will collect cores from 5 additional stations which will be sectioned,

analyzed as above, and radiodated to ascertain sedimentation rate and history of contamination.

The 5 coring sites will include two sites in the Little Rapids, which will allow us to determine the

potential for sediment and contaminant transport should flow through that area be increased, and

three sites in Lake Munuscong, which will allow us to determine to what extent recent

sedimentation has buried previous contaminants and what the potential from transport from those

areas would be during any remediation or restoration.


Figure 2. Sampling sites from the Stage 1of the St. Marys River Remedial Action Plan. During the

current study, ten of these sites will be re-sampled to provide temporal analysis. Ten additional

samples will be taken in the Little Rapids (A) and 20 in Lake Munuscong (B); areas with limited

previous sampling.

A

B


Work Schedule and Required Reports:

Task Date Installation of LSSU ICP-MS 08/2002 ICPMS Training 05/2003 QAPP 05/2003 Field Sampling of Surface Sediments 06/2003 Sample Preparation and Analyses 07/2003 Coring of Selected Sites 08/2003 Sample Preparation and Analyses 08/2003 Draft Report 12/2003 Final Report 02/2004 A7. Data Quality Objectives for Measurement Data The overall quality assurance objective for this project is to ensure that the characterization data is

of known and acceptable quality with location of samples precisely identified. The quality

assurance program plan for this project is designed to accomplish the following objectives:

establish the QA/QC criteria used to control and assess the data that is collected in this

project

provide comparable sampling, preparation, and analytical methods

when possible utilize EPA approved methods containing QA/QC protocol that allows

for verification of the quality of the data

when EPA approved methods are not available, utilize written standard operating

procedures or published reference methods

perform field and on-site laboratory system audits to ensure that all activities are

properly performed and that discrepancies when identified are resolved

evaluate the data and document the results in a final report to GLNPO

The raw data for this program will be collected in several phases that consist of sediment sampling,

sediment analysis, and sediment mapping. Uncertainty in the data measurements will occur at

each phase. However, it is hoped that the amount of uncertainty that occurs will be held to

minimum by through adherence to this QAPP. The data quality objectives (DQOs) for this

program are controlled by the overall uncertainty associated with the sediment sampling

population, the analytical measurements that are made on the samples, and the uncertainty that is

associated with mapping the locations. These many sources of uncertainty make it difficult to

delineate the specific DQOs for this program. Therefore, this QAPP focuses on Measurement

Quality Objectives (MQOs) for the field sampling phase and the sample preparation and analysis

phases of data collection. The MQOs are defined by:

detection limits – the lowest concentration of an analyte that a specified analytical

method can reliably detect

accuracy – the difference between an observed value and the "true" value of the

measured parameter


precision – the level of agreement among multiple measurements of the same parameter

that is being measured

representativeness – the degree to which the data collected accurately represents the

population of interest

comparability – the similarity of analytical methods and data from related projects

across other AOC’s

The major objective of this project is to confirm, or re-establish contaminant levels in sediments

presented in the RAP Stage 1 for the St. Marys River Area of Concern. Metals found to be

elevated in a significant number of sites were As, Cd, Cr, Cu, Ni, Pb, and Zn. To this end,

detection limit issues should not seriously constrain our results since the classification as

moderately or heavily polluted is based on limits which are orders of magnitude above detection

limits listed below. This is to say that our purpose is to determine if the patterns of moderately and

heavily contaminated sites is similar to the nearly 20 year-old dataset the Stage 2 RAP is now

working from. This is not to imply that we are not committed to obtain the most accurate estimates

at low, or non-contaminated, sites. For example, Pb concentrations in sediments less than 40

mg/kg are considered to be non-polluted. Using this limit, a sample mass of 0.1 g, and 100 mL

final digestate volume we could expect to see 40 ppb. Our method detection limit for lead on the

LSSU ICP-MS is < 0.08 ppb.

IDL MDL IDL MDL

Element 1/30/2003 1/30/2003 Element 1/30/2003 1/30/2003

Mass ppb ppb Mass ppb ppb

Be-9 0.008 <0.1 As-75 0.07 <0.2

Na-23 2.8 <5 Se-82 0.24 <1.0

Mg-24 0.44 <3 Mo-98 0.01 <0.07

K-39 3.4 <4 Ag-107 0.01 <0.07

Ca-44 4.9 <5 Ag-109 0.01 <0.05

V-51 0.01 <0.5 Cd-111 0.008 <0.03

Cr-52 0.03 <0.1 Cd-114 0.006 <0.02

Cr-53 0.02 <0.09 Sb-121 0.01 <0.07

Mn-55 0.01 <0.03 Sb-123 0.009 <0.05

Fe-57 1.5 <4 Ba-135 0.01 <0.04

Co-59 0.007 <0.04 Ba-137 0.009 <0.1

Ni-60 0.006 <0.06 Tl-203 0.007 <0.05

Ni-61 0.13 <0.60 Tl-205 0.007 <0.03

Cu-63 0.03 <0.09 Pb-206 0.01 <0.08

Cu-65 0.025 <0.09 Pb-207 0.009 <0.08

Zn-66 0.13 <0.6 Pb-208 0.007 <0.03

Zn-68 0.13 <0.4

A8. Special Training Requirements/Certification Both project directors will receive training specific to the newly installed ICP-MS. This training

will be conducted for one week at the Agilent Technologies training facility in Wilmington, DE.

While no project funds are directed to this training, the benefits to the quality assurance of the

proposed analyses are noteworthy.


A9. Documentation and Record Records and documentation regarding all facets of this project will be maintained by the Project

Directors at LSSU. Field records and raw data will be housed indefinitely, corrected and reduced

data will be housed in the St. Marys River Binational Public Advisory Commission office at

LSSU. Final data will also be posted to the LSSU website with linked with the BPAC website. A

final report will be submitted to the Project Director.

While there is great public interest in the quality of the St. Marys River environment, publicly

posted data will be filtered to provide accurate information without unnecessary technical detail.

To this end, the lay public will have access to general summary data and trends, while more

detailed information, including QA/QC information and tabular data will be available to registered

academic and agency users.

Contracted work, including sample analysis, data reporting and interpretation will be completed

within 6 months of sample delivery.

B. Measurement/Data Acquisition B1. Sampling Process Designs This investigation will provide detailed sampling of surface sediments in two particular areas of

the St. Marys Area of Concern. Surface sediment samples will be collected at 1) 10 sites that were

previously sampled during Stage 1 of the Remedial Action Plan; 2) 10 sites from the Little Rapids

area; and 3) 20 sites from Lake Munuscong area (Figure 2). Surficial sediments will be collected

with a petite Ponar grab and visually inspected for integriaty before sample is collected. The

criteria for rejecting a particular grab sample, and conducting another will be based on whether the

sample is intact, upright and minimally disturbed by the sampling process. One sample will be

collected from each station, from a homogenized grab sample. Sites will be selected on two

criteria: spatial distribution and substrate type; for each of the three sets of samples (previously

sampled, Little Rapids and Lake Munuscong) we want to gather information for as broad a survey

of sites as possible. Selection of previously sampled sites will have an additional criterion of

previous determination of contamination; we want to revisit sites along a gradient of established

human impact. All surficial sites will be sampled once during the late summer, within 14 days of

one another.

Three of the 5 sectioned core sediment samples will be collected at three sites in Lake Munuscong

area and 2 of the 5 sectioned core sediment samples will be collected at two sites in the Little

Rapids area. Two of the Lake Munuscong coring sites will be located along the northern shore, an

area previously shown to have elevated metal concentrations, the third site will be chosen toward

the western margin of the lake in a depositional zone from the Munuscong River. Coring in the

Little Rapids area will be very dependent on availability of suitable substrate, and the coring sites

will be chosen form the limited depositional zones. Sites will be cored once during the second

week in August 2003.

The following samples/measurements are to be taken as part of this project:


Matrix: Surface sediment grab samples and sediment core sections.

Measurements:

Physical - porosity

grain size distribution

Chemical - Organic: Polyaromatic Hydrocarbons

Total Organic Carbon

Total Organic Nitrogen

Methyl Mercury

- Inorganic:

Total Phosphorus

Cadmium

Chromium

Copper

Nickel

Lead

Zinc

Arsenic

Total Mercury

Position - Global Positioning System

We consider the samples for metal analysis (ICP-MS) to be critical for the objectives of this study.

Additionally accurate location information is equally critical. Other variables are considered to be

needed or of ancillary importance. For example, radiodating of cores will provide additional

information regarding sedimentation rates and burial of surficial sediments, but our primary

concern is with the surficial sediments themselves. Likewise, information on TN, TOC, Hg, etc.

will add to our understanding of the composition of the sediments of the St. Marys River, but since

these elements were not found to be elevated in previous samplings, they are not considered

crtitical to the long-term remediation of the sediments in the AOC.

B2. Sampling Methods Requirements Sediment surface sample collection on LSSU's Aquatic Research Laboratory boat will consist of

using a Ponar grab to collect the surface sediments. The sediment samples will be processed

immediately on deck. The sample will be homogenized, placed in 250 mL wide-mouth

polypropylene jars, labeled, and preserved until delivered to the laboratory for processing and

analysis. Sampling tools will be properly decontaminated with water and brushes prior to each

sample.

Sediment core collection on the R/V Mudpuppy will consist of using a modified push core or mini-box corer designed to collect cores up to 1 meter in length from sites of limited water depth. Cores will be immediately processed on deck. The processing crew will section the initial surface 0 – 10 cm in 1 cm intervals, then every 2 cm to either the maximum core depth or 1 m. The sectioned sample will be homogenized, placed in 250 mL wide-mouth polypropylene jars, labeled, and preserved on ice until delivered to the laboratory for subsequent processing. Sampling tools (plastic spatulas) will be properly decontaminated with water and brushes prior to each sample.

Processing, preparation, holding times and preservation for each analyte can be found in the

pertinent EPA Laboratory Methods listed below in section B.4, or in SOP’s for each subcontracted


lab (forthcoming). After each sample is subsampled for the different analyses, remaining material

will be archived.

Changes in the sampling regime or schedule due to weather/boat conditions or sample

integrity/field conditions will be the responsibility of the craft operator/captain or chief scientist

respectively.

B3. Sampling Handling and Custody Requirements Strict "chain-of-custody" procedures for the samples will not be adhered to because the intended

use of the data is not for litigation or enforcement action. All sediment collection,

homogenization, and splits will be done under the direct supervision of U.S. EPA or LSSU

personnel. All sediment samples will be transported or shipped to the appropriate laboratory by

LSSU personnel. Samples will be held on ice in coolers prior to delivery to the laboratory for

analysis or other processing.

Field label identification and documentation will be done according to appropriate LSSU laboratory protocols. A field log will be kept by LSSU personnel documenting the sample id, location, date, time, analysis, and comments. Field records shall consist of bound field notebooks with pre-numbered pages, sample collection forms, sample location (in GPS electronic format) maps, and sample analysis request forms. All records will be written in indelible ink.

B4. Analytical Methods Requirements For this project the MQOs are established for the specific laboratory analytical measurements in

the pertinent SOP (see the specific EPA methods listed below) that is used by the laboratory to

analyze the sample. These SOPs address such things as:

equipment/instrumentation

operating procedures

sample management

reagent/standard preparation

general laboratory techniques

test methods

method detection limits

equipment calibration and maintenance

QA/QC (for accuracy & precision)

corrective action

data reduction and validation

49

Specifically, the SOPs that this project will use include:

Metals – SW-846, Method 3051A – Microwave Assisted Acid Digestion of

Sediments, Sludges, Soils, and Oils; SW-846, Method 6020A, Inductively Coupled

Plasma-Mass Spectrometry

Mercury and methyl-mercury – SW-846, Method 7471B – Mercury in Solid or

Semisolid Waste (Manual Cold-Vapor Atomic Absorption Fluorescence Technique)

PAHs –SW-846, Method 8270D – Semivolatile Organic Compounds by Gas

Chromatography/Mass Spectrometry (GC/MS), sample preparation will be using one

of the following SW-846 methods: 3540, 3541, 3545, 3550, 3560, or 3561

TOC/ TON, TP – TOC/TON will be determined by standard CHN analysis on a

Perkin Elmer 2400 Series II CHNS/O Analyzer. TP will be determined

colorimetrically (ascorbic acid/molybdate method) following wet persulfate/autoclave

digestion.

Sedimentation Rates - Samples from sectioned cores will be used to determine

sedimentation rates at those sites by the 210

Pb procedure commonly employed in the

Great Lakes (Robbins, JA and DN Edgington (1975) Determination of recent

sedimentation rates in Lake Michigan using Pb-210 and Cs-137. Geochim.

Cosmochim. Acta. 39:285-304), and currently the standard method at the Great Lakes

Water Institute, Milwaukee, WI.

B5. Quality Control Requirements Field Samples -

Control samples are introduced into the field process to monitor the performance of the system.

Daily control samples will be included during the field events. These control will include blanks

(trip, equipment, and laboratory) and duplicates. One of each of these types of blanks will be

included for each matrix type per day. The trip blank will be collected to accompany the PAH

samples. Additionally, for every twenty samples (or for every sampling event if less than twenty

samples are collected), enough sample will be collected for at least one sample so as to allow the

laboratory to prepare one matrix spike and one matrix duplicate for each analytical method

employed. In summary, the following control samples will be collected:

field duplicate (one per day per matrix type)

equipment rinsate (one per day per matrix type)

trip blank (one per day, PAH samples only)

matrix spike (one per 20 samples per matrix type or one per matrix type per day if less

samples are collected)

matrix duplicate (one per 20 samples per matrix type or one per matrix type per day if less

samples are collected)

Laboratory Analyses -

To produce data of known quality, the participating laboratories must analyze QC samples that

are known to the laboratory staff that can be used by the analysts to assess and control the

analytical measurement uncertainty. The specific method SOPs (listed above) include the

specifications for each QC sample including acceptance limits and frequency of QC sample use

50

requirements. The various types of QC samples for the chemical parameters include initial

calibration verification, ongoing continuing calibration verification, analytical replicates, field

duplicates, reagent blanks, reference materials, matrix spikes, and surrogate spikes for organic

analyses.

B6. Instrument/Equipment Testing Inspection and Maintenance Requirements All LSSU instrumentation is maintained following manufacturers’ recommendations. The

critical instrument, the ICP-MS, is under manufacturer’s service contract for the duration of this

project. System performance on all instruments is assessed through continuous log book entries

describing ongoing QA/QC results.

B7. Instrument Calibration and Frequency Instrument calibration procedures and frequency are referenced in the pertinent methods. Global

Positioning System (GPS) location calibration is under the direction of USEPA GLNPO (during

R/V/ Mudpuppy work) and LSSU personnel (during all other sampling), including QA/QC

checks to ensure accurate positioning.

B8. Inspection/Acceptance Requirements for Supplies and Consumables The project directors (LSSU), or sub-contractors (UW-Madison, UW-Milwuakee) will have

authority to accept supplies and consumables as suitable for the purposes of this project

consistent with the requirements of each particular sample type and analysis.

B9. Data Acquisition Requirements (Non-direct Measurements) The project directors (LSSU) are currently trying to obtain actual position data for previously

sampled St. Marys River stations. Currently, we have the approximate locations entered in

our database from a digitized scan for the Stage 1 Report. While these points are probably

representative of the original stations, there could be several hundred meters of error in re-

occupying previous sampled stations.

B10. Data Management Sampling sequencing, as dictated by particular SOP’s, is largely controlled through instrument-

resident software. Raw data from instruments will be transferred to Microsoft Excel 2002 for

additional reduction and cursory assessment. Statistical analyses will be performed using Systat

10.2 for Windows. Reduced and filtered data will be placed in Microsoft Access database. GPS

and spatial information will be collected and processed using Trimble Pathfinder and ArcView

software packages.

The final data repository for this project is a St. Marys AOC sediments database that will be

developed at Lake Superior State University and housed on a secure server in Crawford Hall.

The database will be accessible to the general public, government agencies, etc. through a link

located on the St. Marys River Binational Public Advisory Committee (BPAC) web page. The

database will combine source input information with sediment pollutant data, field sampling

data, and location GIS/GPS data.

C. Assessment/Oversight

C1. Assessments and Response Actions The assessment of data accuracy is based on the ongoing calibration check samples and the use

of certified reference materials, standard reference materials, or standards for the inorganic and

organic analyses. Duplicate measurements will be used to assess precision of the analyses and

51

matrix spike and surrogate spike recoveries will be used to assess the accuracy of inorganic and

organic analyses.

Field sampling data is assessed through on-site audits and verification of the field QA/QC

protocol required by the QAPP. Because of the nature of the institution (no graduate students,

post-docs, technicians, etc.) one or both of the project directors will be personally involved in

every aspect of the field and laboratory work ongoing at LSSU. As a result of this intimate

involvement, the project will essentially have real time auditing to insure QAPP compliance.

Undergraduate assistants will be marginally involved and constantly supervised by one of the

project directors during sample preparation and analysis. Further, the PI’s will review data files

monthly to guarantee QA/QC. The project directors will, therefore, be responsible for any

corrective actions required during analyses at LSSU, each individual contractor will be

responsible for outside analyses according to their lab’s internal QA program.

A final written summary of the QA activities and final results will be provided to the funding

agency along with the laboratory QA approved datasets.

C2. Reports to Management A draft report will be submitted by the project directors to the EPA Project Manager in

December, 2003 for review and comments. This draft will have incorporated information from

the subcontractors. A final project report detailing the project results, QA/QC verification and

budget accounting will be submitted to the EPA project manager in February, 2004.

Additionally, the principal investigators will submit technical manuscripts for publication in

referred journals and post results the LSSU Website, with links from the St. Marys River BPAC

Website.

D. Data Validation and Usability

D1. Data Review, Validation and Verification Requirements The criteria used to accept or reject data based on quality will follow each individual SOP. If

sample data are determined to be unacceptable, samples will be re-processed and analyzed.

D2. Validation and Verification Methods Laboratory quality assurance is implemented through laboratory performance and system audits.

The audit includes the submittal of evaluation samples to each participating laboratory. The

laboratory performance on these evaluation samples can then be assessed by the funding agency

(EPA) or its representative. On-site audits by the funding agency (EPA) or its representative

may be used to evaluate the individual laboratory systems.

An initial set of evaluation samples will be sent to each participating laboratory prior to the

analysis of any samples. The results of these samples will allow for the evaluation of the

laboratory for timeliness of sample analysis, the ability of the laboratory to follow the required

quality assurance requirements specified by the method SOPs and this QAPP, and the ability of

the laboratory to accurately perform the required analyses. Subsequent evaluation samples will

be submitted with routine samples to ensure that the laboratory is continuing to accurately

perform the required analyses.

52

System audits of both the laboratory and field operations may include an on-site audit by the

funding agency (EPA) or its representative to ensure that all personnel are adhering to the

protocols specified in this QAPP. Data will be verified by:

obtaining and evaluating the complete raw dataset, including data from routine

samples, QA/QC samples, instrument calibration, etc.

checking the QA/QC for each dataset to insure that it meets the requirements set forth

in this QAPP

checking the calculations and the final results

checking for transcription errors

reviewing logbooks to verify such things holding time violations, proper sample

collection and preservation, consistent use of the same descriptive terms and reporting

units, and consistent use of station coordinates (latitude and longitude).

In lieu of on-site audits by the funding agency or its representatives, the project directors will

compile and maintain audit information regarding field and laboratory procedures. As stated

above, since one or the other director will be completing all of the LSSU work, this project

essentially has real-time auditing. R.C. Back will be responsible for auditing the 210

Pb and

Mercury subcontracts, B.J. Keller will be responsible for auditing the PAH subcontract.

Should any audit reveal departure from this QAPP, the responsible party indicated above will

identify cause and impact, and take necessary action such as: request additional QA/QC

validation, or that samples be reanalyzed.

In instances where there is recurrent problems with the quality of a particular variable or sample,

which might arise from unforeseen matrix effects or intereferences, and it is determined by the

responsible party that the issue cannot be resolved, that data will be discarded from the dataset

with accompanying explanation.

D3. Reconciliation with Data Quality Objectives Precision:

Precision of the sampling procedures and the analytical procedures will be estimated using field

duplicates of sediment samples. The duplicate results will be used to calculate the relative

percent difference (RPD) as:

RPD (%) = [(C1 – C2) x 100%] [(C1 + C2) 2]

where C1 = larger of the two observed values

C2 = smaller of the two observed values

Accuracy: Matrix spikes shall be used to calculate the percent recovery (%R) as follows:

%R = [(S – U) C] x 100%

53

where: S = measured concentration in the spiked aliquot

U = measured concentration in the unspiked aliquot

C = actual concentration of the spike that was added

Method Detection Limits (MDL):

Method detection limits establish the lower limits of reliable analysis for each method that is

used. MDL is defined as:

MDL = (t) x s

where:

s = standard deviation of replicate analysis

t = Student's t value for a 99% confidence level and a standard deviation

estimate with n – 1 degrees of freedom (t = 3.14 for 7 replicates).

54

Appendix B. Results of the analyses surficial sediment (grab samples) from the Saint Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40).

STN DW TOC TN TP HgT MeHg

% mg/g mg/g ug/g ng/g ng/g

1 73.7 4.56 0.21 230 16.14 0.26

2 41.0 48.75 2.16 480 54.54 0.80

3 64.3 9.05 0.45 340 16.77 0.36

4 26.4 69.95 3.96 630 191.44 0.54

5 62.6 20.27 0.65 430 79.52 0.44

6 50.7 29.49 0.94 525 113.26 1.26

7 74.9 1.84 0.18 80 2.50

8 69.8 3.20 0.25 320 9.22 0.16

9 65.8 6.75 0.53 350 18.52 0.43

10 62.0 5.41 0.43 300 12.34 0.65

11 62.0 14.37 0.77 440 29.53 0.52

12 65.0 17.45 0.76 440 26.43 0.51

13 44.2 22.31 1.32 520 66 1

14 37.9 26.45 2.02 560 51.19 0.81

15 66.5 2.57 0.13 340 3.66 0.08

16 58.7 10.00 0.59 390 28.91 0.53

17 51.3 26.83 1.38 420 43.32 1.03

18 43.4 38.71 2.37 560 101.18 1.17

19 57.1 20.61 0.97 420 35.94 0.68

20 60.8 14.81 0.77 340 29.81 0.53

21 57.8 5.21 0.28 370 14.27 0.13

22 67.9 6.72 0.47 360 12.42 0.15

23 68.4 23.48 0.36 440 16.38 0.10

24 59.9 4.89 0.38 480 14.86 0.11

25 52.4 10.34 0.95 510 26.53 0.27

26 50.6 12.25 1.39 470 36 0

27 60.2 9.86 0.70 360 16.68 0.17

28 56.0 8.17 0.21 390 14.54 0.08

29 55.0 12.15 1.18 370 19.51 0.42

30 54.0 13.07 1.28 400 25.63 0.24

31 54.3 11.25 1.20 400 25.21 0.33

32 57.5 10.23 0.67 480 9.69 0.34

33 70.2 3.75 0.40 170 3.50 0.09

34 66.0 10.61 0.20 330 8.54 0.07

35 56.1 17.85 0.32 480 15.50 0.06

36 56.9 14.17 0.42 420 13.65 0.07

37 54.6 17.54 0.70 560 27.34 0.16

38 59.0 11.55 0.29 550 11.04 0.13

39 74.7 7.83 0.25 320 6.33 0.05

40 59.6 7.80 0.47 310 9.61 0.16

55

Appendix B (cont.). Results of the analyses surficial sediment (grab samples) from the Saint Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40).

STN Cr Ni Cu Zn As Cd Pb

ug/g ug/g ug/g ug/g ug/g ug/g ug/g

1 5.0 3.3 8.5 20.0 0.51 <.432 9.9

2 27.8 12.2 26.2 112.2 3.14 <.694 25.5

3 42.4 3.9 5.9 24.1 0.69 <.436 12.6

4 58.2 13.0 48.4 146.6 3.35 0.8 43.4

5 21.3 7.1 10.6 55.2 2.18 <.678 14.5

6 90.2 9.1 22.2 92.4 2.98 <.726 29.2

7 2.7 1.9 2.6 6.3 0.72 <.418 2.6

8 10.9 4.7 6.0 7.5 0.60 <.433 3.9

9 16.7 5.4 8.8 25.0 0.64 <.433 5.5

10 9.1 3.6 5.8 20.4 0.45 <.421 5.3

11 24.7 9.5 15.4 58.8 1.87 <.695 18.6

12 28.4 10.5 18.4 47.4 2.81 <.706 20.2

13 53 20 28 106 2.38 <.730 31

14 44.9 16.6 24.5 81.1 2.18 <.712 25.1

15 8.4 5.6 4.8 17.0 0.54 <.439 3.4

16 44.2 17.5 17.9 56.1 1.17 <.675 11.4

17 43.7 12.9 17.4 67.9 1.81 <.716 26.4

18 54.5 23.1 36.9 101.6 2.45 <.737 30.0

19 26.7 10.3 12.8 44.3 1.42 <.679 13.0

20 24.7 9.6 16.1 65.2 1.48 <1.172 12.5

21 64.6 37.1 29.2 54.9 0.85 <.443 10.5

22 16.2 9.3 10.0 30.8 0.67 <.433 7.0

23 26.5 11.7 11.3 33.1 0.73 <.444 6.3

24 50.2 32.8 29.3 55.3 0.77 <.426 8.9

25 26.7 13.5 14.5 31.9 0.73 <.439 7.9

26 38 23 27 42 0.74 <.432 11

27 25.1 11.6 11.8 29.8 0.71 <.443 6.5

28 57.0 35.3 26.6 51.3 0.74 <.441 9.1

29 25.8 10.0 10.4 30.9 0.81 <.435 10.0

30 22.0 8.1 8.3 26.1 0.75 <.424 8.6

31 27.4 12.5 15.9 34.2 0.77 <.427 8.8

32 26.7 11.5 11.5 30.2 0.64 <.428 5.0

33 3.7 2.4 2.7 5.2 0.47 <.435 1.3

34 27.3 10.2 9.1 26.4 0.62 <.440 4.3

35 57.4 32.5 26.6 60.1 0.68 <.431 9.2

36 44.4 25.3 20.4 48.6 0.69 <.437 7.3

37 42.7 21.8 10.1 40.5 0.69 <.433 7.7

38 39.5 27.0 13.0 44.1 1.16 <.437 7.1

39 13.0 7.8 6.2 20.0 0.59 <.445 3.7

40 29.3 12.4 11.2 35.0 0.68 <.432 5.2

56

Appendix C. Results of the analysis of Polyaromatic Hydrocarbons (PAH) in surficial sediment (grab samples) from the Saint Marys River (Stations 1-10), the Little Rapids (Stations 11-20) and Munuscong Lake (Stations 21-40). All concentrations are mg/kg, undetected are designated “u”, and the summed concentration is shown as “sum”.

STN sum 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

1 1.7 u u u u u u u 0.5 0.4 u 0.5 0.4 u u u u u

2 7.9 1.3 u u u u 0.9 u 1.2 1 0.6 0.8 0.7 0.9 0.5 u u u

3 2.3 u u u u u u u 0.7 0.6 0.3 0.4 0.4 u u u u u

4 13 2.0 u u u u u u 2.1 1.9 1.1 1.5 1.6 1.9 1.1 u u u

5 8.6 1.4 u u u u 0.7 u 1.3 1.1 0.7 0.9 0.9 0.6 0.6 0.3 u u

6 12.9 1.7 u u u u 1.0 0.4 2.0 1.8 1.1 1.3 1.4 0.7 0.9 0.4 u 0.4

7 0 u u u u u u u u u u u u u u u u u





12 2.8 0.5 u u u u 0.3 u 0.7 0.6 u 0.3 0.4 u u u u u

13 3.1 0.4 u u u u u u 0.8 0.6 u 0.4 0.5 0.4 u u u u




17 0.4 u u u u u u u 0.4 u u u u u u u u u

18 1.1 u u u u u u u 0.4 0.4 u u u 0.3 u u u u























57

Appendix C (cont.) Code of PAH compounds listed as columns 1-17 above. 1 Naphthalene 2 2-Methylnaphthalene 3 Acenaphthylene 4 Acenaphthene 5 Fluorene 6 Phenanthrene 7 Anthracene 8 Fluoranthene 9 Pyrene 10 Benzo[a]anthracene 11 Chrysene 12 Benzo[b]fluoranthene 13 Benzo[k]fluoranthene 14 Benzo[a]pyrene 15 Indeno[1,2,3-cd]pyrene 16 Dibenzo[a,h]anthracene 17 Benzo[g,h,i]perylene

58

Appendix D. Results from the analysis of core sections. Separate cores are identified as A-D, as in text, and each horizon sampled is indicated as its middepth (MID) in cm.

CORE MID DW TOC TN HGT Cr Ni Cu Zn As Pb Cd

% mg/g mg/g ng/g ug/g ug/g ug/g ug/g ug/g ug/g ug/g

A 0.5 46.38 19.31 0.74 33.14 28.9 13.7 16.8 45.8 0.97 15.1 <.427

A 1.5 55.71 16.94 0.74 29.58 29.5 14.4 17.9 42.7 1.04 14.6 <.448

A 2.5 63.71 18.05 0.70 21.03 23.4 11.2 15.4 39.9 0.96 16.0 <.426

A 3.5 66.34 17.57 0.69 28.40 27.2 12.2 16.3 45.6 1.15 18.1 <.431

A 4.5 57.92 13.76 0.54 21.37 37.6 17.4 18.4 51.7 1.04 18.0 <.439

A 5.5 49.55 6.52 0.19 8.82 48.6 34.1 30.8 57.3 0.66 9.7 <.440

A 6.5 49.54 6.20 0.16 6.95 50.0 34.9 30.2 51.6 0.57 9.8 <.424

A 7.5 49.83 6.56 0.18 7.94 49.3 34.6 30.2 51.2 0.54 9.5 <.428

A 8.5 50.30 6.41 0.17 8.62 50.0 34.9 30.0 51.1 0.61 8.8 <.444

A 9.5 50.59 6.43 0.17 8.59 47.8 33.8 29.1 51.4 0.56 8.6 <0.432

A 11.0 50.80 6.89 0.18 7.60 50.0 34.2 28.7 55.7 0.60 8.8 <.442

A 13.0 51.41 6.79 0.17 8.06 46.7 32.6 28.3 46.5 0.59 8.3 <.434

A 15.0 51.42 7.03 0.18 6.94 46.4 31.9 27.6 47.7 0.58 8.4 <.426

A 17.0 51.88 7.60 0.17 7.98 43.3 30.0 26.1 45.6 0.63 7.9 <.431

A 19.0 49.48 7.45 0.24 12.44 46.7 31.8 28.3 64.2 0.73 10.8 <.424

A 21.0 47.48 26.11 1.12 119.58 89.2 23.3 32.1 146.9 2.41 48.0 0.6

A 23.0 63.10 85.9 17.3 28.7 167.4 3.63 54.5 0.7

A 25.0 82.80 26.4 8.9 13.6 42.2 1.29 19.4 <.704

A 27.0 73.36 25.9 13.9 15.0 37.2 0.63 9.5 <.433

A 29.0 68.64 5.23 0.17 12.39 47.0 30.8 30.7 48.4 0.72 12.3 <.438

A 31.0 68.24 5.55 0.16 8.96 37.6 25.0 28.3 45.3 0.66 9.4 <.449

A 33.0 67.79 5.09 0.13 8.03 47.9 31.5 30.2 50.7 0.66 8.8 <.437

A 35.0 67.28 5.28 0.15 6.55 42.1 29.2 34.8 46.0 0.62 8.1 <.436

A 37.0 67.23 6.04 0.14 8.14 36.0 25.2 26.7 41.9 0.58 9.5 <.439

A 39.0 66.77 11.35 41.1 28.1 27.8 42.8 0.56 7.9 <.428

A 41.0 67.34 8.63 38.7 27.2 28.8 43.3 0.59 7.7 <.439

A 43.0 67.82 5.27 0.15 7.24 38.2 26.9 29.0 46.2 0.56 7.7 <.431

A 45.0 67.74 5.35 0.10 6.37 42.9 29.9 31.0 46.0 0.59 8.2 <.437

A 47.0 67.56 5.15 0.10 6.79 37.4 26.2 26.9 49.3 0.60 7.6 <.436

A 49.0 65.68 4.95 0.10 7.44 44.2 31.1 29.8 48.6 0.67 9.3 <.442

A 53.0 64.35 4.55 0.10 43.2 31.3 31.3 49.1 0.66 8.9 <.437

A 57.0 67.59 5.10 0.10 40.8 29.4 29.7 44.4 0.61 8.5 <.431

A 61.0 65.83 5.85 0.10 44.1 33.1 31.4 52.5 0.64 9.2 <.440

59

Appendix D (cont.). Results from the analysis of core sections. Separate cores are identified as A-D, as in text, and each horizon sampled is indicated as its middepth (MID) in cm. CORE MID DW TOC TN HGT Cr Ni Cu Zn As Pb Cd


B 0.5 28.54 24.83 1.81 49.20 44.2 23.6 32.6 75.8 1.98 24.9 <.434

B 1.5 33.48 25.47 1.78 53.26 40.4 18.2 30.4 72.2 1.68 24.3 <.438

B 2.5 35.53 26.23 1.81 60.15 40.7 18.5 32.3 90.9 1.63 26.1 <.446

B 3.5 36.87 25.93 1.90 52.84 45.4 19.0 34.0 75.6 1.71 26.9 0.5

B 4.5 38.56 26.33 1.83 187.83 44.6 18.4 34.4 77.8 1.79 26.9 0.5

B 5.5 40.61 24.53 1.68 46.62 40.7 18.3 31.4 72.5 1.84 24.6 0.5

B 6.5 42.26 24.76 1.63 48.22 38.7 17.8 30.7 73.8 1.83 24.1 0.5

B 7.5 42.47 25.46 1.66 227.64 42.6 18.9 33.1 84.6 1.94 26.8 0.5

B 8.5 42.23 26.60 1.67 56.87 45.7 20.0 34.2 89.9 2.11 30.4 0.6

B 9.5 41.84 31.45 1.85 67.73 49.4 18.8 35.9 93.1 2.46 33.3 0.6

B 11.0 40.38 32.31 1.97 49.2 20.4 36.6 107.2 2.40 37.2 0.7

B 13.0 39.81 31.57 2.00 53.6 26.0 38.7 120.6 2.64 46.1 0.8

B 15.0 43.12 27.07 1.67 49.0 20.3 31.1 117.8 2.78 39.9 0.7

B 17.0 43.92 28.88 1.61 44.6 20.4 32.9 119.8 2.78 44.6 0.7

B 19.0 45.89 16.66 0.77 47.4 27.8 29.4 83.5 1.55 26.1 <.438

B 21.0 41.38 28.09 1.32 81.6 25.3 33.1 142.0 2.70 49.4 0.7

B 23.0 47.13 33.36 1.33 72.8 19.9 26.8 114.5 2.55 46.2 0.6

B 25.0 60.21 10.60 0.40 47.1 22.6 16.8 56.3 1.13 18.4 <.419

B 27.0 48.06 26.70 1.14 79.0 20.7 25.0 69.4 1.90 23.5 0.5

B 29.0 56.05 8.43 0.38 58.5 31.6 19.2 61.4 1.01 15.4 <.436

B 31.0 59.01 6.02 0.30 41.5 24.7 17.8 51.2 0.90 14.7 <.435

B 33.0 58.97 5.85 0.28 46.0 29.5 23.1 60.0 0.83 13.1 <.427

B 35.0 56.88 5.28 0.23 13.09 42.6 27.9 18.9 56.3 0.85 13.0 <.445

B 37.0 57.88 7.06 0.23 42.2 27.3 19.2 49.4 0.80 12.9 <.433

B 39.0 55.88 9.80 0.40 48.6 31.4 20.4 54.6 0.81 13.8 <.434

B 41.0 55.34 7.67 0.36 46.4 29.5 19.5 53.0 0.78 13.5 <.432

B 43.0 53.84 21.49 0.62 37.4 18.8 20.2 44.0 0.90 13.9 <.450

B 47.0 46.59 33.62 1.24 34.5 28.7 32.1 63.0 2.67 26.0 1.0

B 49.0 61.76 18.55 0.68 19.9 10.6 17.4 44.6 1.14 16.5 <.434

B 53.0 80.60 18.4 12.9 10.3 11.1 0.53 4.5 <.438

B 57.0 71.70 8.30 0.15 21.9 13.5 12.6 12.2 0.56 6.0 <.447

B 61.0 66.31 9.13 0.14 32.6 18.0 15.9 36.1 0.55 7.1 <.427

B 65.0 63.33 9.37 0.14 39.8 19.4 17.7 42.1 0.55 7.9 <.443

B 69.0 75.12 8.59 0.06 4.66 14.6 8.4 8.5 5.6 0.52 3.5 <.422

60

Appendix D (cont.). Results from the analysis of core sections. Separate cores are identified as A-D, as in text, and each horizon sampled is indicated as its middepth (MID) in cm.

CORE MID DW TOC TN HGT Cr Ni Cu Zn As Pb Cd


C 0.5 51.19 8.17 0.86 19.41 16.5 8.9 8.6 28.5 0.94 9.8 <.447

C 1.5 66.80 7.19 0.75 17.64 15.4 8.2 7.4 22.3 0.95 6.5 <.435

C 2.5 67.62 7.39 0.78 15.73 15.7 8.6 8.9 24.8 0.96 6.5 <.439

C 3.5 67.53 7.54 0.79 14.31 16.7 9.0 8.9 31.6 0.94 6.3 <.424

C 4.5 66.94 7.67 0.82 13.92 17.2 9.8 8.9 26.4 0.92 6.2 <.436

C 5.5 65.95 7.58 0.75 15.54 18.4 10.2 9.8 27.8 0.89 6.8 <.429

C 6.5 63.45 7.67 0.75 16.12 25.9 12.5 11.6 28.2 0.88 8.0 <.426

C 7.5 62.35 7.31 0.74 15.71 28.6 12.3 11.7 32.2 0.87 8.2 <.443

C 8.5 60.51 6.87 0.68 17.35 30.4 13.2 11.5 13.2 0.85 7.9 <.423

C 9.5 56.82 7.30 0.76 14.22 35.8 16.4 13.4 39.3 0.81 8.5 <.445

C 11.0 52.75 7.57 0.81 41.3 27.3 15.5 42.6 0.81 9.1 <.440

C 13.0 52.17 7.24 0.79 43.2 28.3 22.5 44.5 0.87 9.2 <.441

C 15.0 51.07 7.15 0.80 48.0 31.5 22.8 49.3 0.75 9.8 <.444

C 17.0 50.88 7.48 0.85 44.3 30.0 22.7 47.6 0.74 9.2 <.431

C 19.0 50.76 7.48 0.85 45.1 30.2 22.4 51.0 0.75 9.2 <.421

C 21.0 50.11 7.70 0.90 46.7 31.1 22.2 49.3 0.78 9.2 <.447

C 23.0 50.80 7.50 0.80 45.7 31.4 22.4 50.7 0.75 9.2 <.426

C 25.0 50.39 7.90 0.90 41.9 28.3 21.8 56.1 0.77 8.5 <.426

C 27.0 50.14 7.90 0.90 42.5 29.4 22.9 52.9 0.81 8.6 <.428

C 29.0 50.38 7.85 0.85 43.2 29.8 22.2 53.5 0.79 8.7 <.437

C 31.0 50.82 7.60 0.80 47.5 32.1 14.9 51.0 0.84 9.1 <.471

C 33.0 50.94 7.00 0.80 49.6 32.4 14.6 49.2 0.84 9.4 <.461

C 35.0 50.77 7.55 0.85 49.1 32.4 14.0 49.8 0.84 9.6 <.428

C 37.0 50.75 7.50 0.85 51.9 33.0 14.6 50.9 0.92 9.8 <.452

C 39.0 50.71 7.50 0.90 50.3 33.5 14.2 48.9 0.82 9.6 <.432

C 41.0 51.09 7.50 0.85 50.1 33.0 14.5 50.5 0.89 9.8 <.452

C 43.0 50.84 7.50 0.85 51.4 32.8 14.1 50.0 0.91 9.7 <.462

C 45.0 50.94 7.80 0.90 51.2 32.7 14.2 50.8 0.84 9.8 <.448

C 47.0 51.45 7.55 0.80 50.1 32.2 14.4 49.1 0.90 9.5 <.429

C 49.0 51.46 7.80 0.90 60.5 39.7 29.2 58.5 0.89 9.7 <.414

C 53.0 51.98 7.20 0.80 50.6 33.1 24.3 50.4 0.87 9.6 <.460

C 57.0 51.69 7.50 0.85 51.2 32.2 23.8 51.6 0.85 9.8 <.457

C 61.0 52.39 6.60 0.75 49.6 32.6 14.1 48.9 0.89 9.4 <.452

C 65.0 52.54 6.90 0.75 49.6 32.4 14.6 48.5 0.85 9.4 <.459

C 69.0 51.69 7.50 0.80 44.6 31.3 23.0 48.6 0.79 9.2 <.453

C 73.0 52.37 6.95 0.80 45.6 31.7 23.3 49.6 0.81 9.3 <.469

C 77.0 52.36 6.90 0.80 47.2 31.6 23.6 54.5 0.81 9.5 <.441

C 81.0 52.19 7.10 0.80 46.5 32.0 23.6 56.9 0.87 9.5 <.447

C 85.0 52.81 6.90 0.75 45.8 31.2 23.6 52.1 0.90 9.5 <.471

C 89.0 52.97 6.80 0.75 47.2 32.0 24.0 56.3 0.92 9.7 <.475

C 93.0 49.28 6.60 0.80 46.7 31.5 24.3 50.8 0.90 9.6 <.455

C 97.0 52.76 7.20 0.80 46.9 32.1 25.1 52.6 0.85 9.5 <.482

C 109.0 52.69 7.00 0.80 48.7 33.1 25.1 51.6 0.94 9.8 <.476

C 117.0 52.77 7.10 0.90 12.52 47.5 33.1 24.8 50.5 0.98 10.0 <.473

61

Appendix D (cont.). Results from the analysis of core sections. Separate cores are identified as A-D, as in text, and each horizon sampled is indicated as its middepth (MID) in cm. CORE MID DW TOC TN HGT Cr Ni Cu Zn As Pb Cd


D 0.5 35.93 11.94 1.24 26.77 23.8 11.2 9.3 36.2 0.80 6.6 <.437

D 1.5 52.11 8.73 0.96 43.52 14.9 8.6 7.0 34.0 0.57 5.1 <.442

D 2.5 61.71 6.48 0.71 32.64 13.2 7.6 5.9 25.7 0.53 4.5 <.432

D 3.5 68.76 5.41 0.59 10.16 11.4 6.4 5.1 22.7 0.53 3.9 <.438

D 4.5 74.67 4.07 0.47 8.65 10.1 5.9 4.7 30.2 0.54 3.7 <.448

D 5.5 76.42 3.12 0.34 7.62 11.4 6.3 5.5 19.0 0.59 4.2 <.428

D 6.5 76.65 10.04 15.4 8.2 8.1 16.0 0.64 4.6 <.432

D 7.5 77.50 2.77 0.33 8.04 15.2 8.0 8.0 23.1 0.59 27.9 <.431

D 8.5 78.21 2.36 0.28 12.40 14.0 7.9 7.6 16.4 0.55 3.9 <.431

D 9.5 78.78 1.76 0.20 7.16 12.6 6.9 6.6 13.7 0.48 3.2 <.431

D 11.0 79.84 1.36 0.16 4.11 11.8 7.5 7.4 13.7 <.457 2.7 <.453

D 13.0 80.17 0.53 0.09 11.94 10.5 6.9 6.7 13.2 <.445 2.4 <.440

D 17.0 79.94 0.37 0.06 3.12 13.0 8.5 8.2 12.9 <.444 2.9 <.440

D 19.0 79.53 0.41 0.07 4.16 13.9 9.2 9.0 6.3 <.442 3.2 <.438

D 21.0 79.49 0.41 0.07 5.28 18.6 11.0 10.3 28.9 <.454 3.9 <.450

D 23.0 78.02 0.47 0.10 7.17 23.1 12.1 12.8 29.2 0.49 4.5 <.434

D 25.0 77.96 0.55 0.12 6.54 23.2 12.4 13.0 31.4 0.51 4.5 <.453

D 27.0 77.90 0.53 0.12 7.98 21.1 11.6 11.5 25.5 0.46 4.0 <.431

D 29.0 78.39 0.53 0.11 61.21 15.6 10.2 10.5 17.3 0.47 3.4 <.431

D 31.0 78.11 0.46 0.10 39.92 16.2 10.6 11.0 22.6 0.47 3.6 <.440

D 33.0 77.62 0.45 0.10 5.00 16.5 11.0 11.6 18.7 0.47 3.7 <.430

D 35.0 77.35 0.46 0.10 25.62 16.0 10.5 11.0 19.2 0.45 3.6 <.436

D 37.0 77.22 0.42 0.10 4.51 14.0 9.5 9.5 16.3 <.443 3.1 <.439

D 39.0 78.02 0.41 0.09 6.64 13.5 9.1 9.4 20.5 0.45 3.1 <.433

D 41.0 77.95 1.35 0.08 17.23 13.7 9.5 8.8 17.2 0.43 3.1 <.427

Current Sediment Quality in the St. Marys River AOC (MI:USA)

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Transcript of Current Sediment Quality in the St. Marys River AOC (MI:USA)