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Scientific Investigations Report 2005-5034

Mercury in the Grand Calumet River/
Indiana Harbor Canal and Lake Michigan,
Lake County, Indiana,
August 2001 and May 2002

By Martin R. Risch


Abstract

Water samples from the Grand Calumet River/Indiana Harbor Canal and Lake Michigan in Lake County, Indiana, were collected and analyzed for mercury. Sampling was done with ultra-clean protocols, and mercury was analyzed by low-level methods during seasons of contrasting weather and streamflow conditions in August 2001 and May 2002. Total mercury concentrations in all the Grand Calumet River/Indiana Harbor Canal samples exceeded the 1.3 nanogram per liter Indiana water-quality standard for waters within the Great Lakes system. Total mercury concentrations in the Lake Michigan samples did not exceed the Indiana water-quality standard. Total mercury and methylmercury concentrations were larger in more samples collected during the wet-weather streamflow conditions in May 2002 than in samples collected during the dry-weather streamflow conditions in August 2001. The largest total mercury concentrations were in samples collected from the West Branch Grand Calumet River near wetlands and municipal-effluent outfalls (17.2 nanograms per liter) and in samples collected from the Indiana Harbor Canal near the confluence of the East Branch and West Branch Grand Calumet River (16.0 nanograms per liter).
Particulate total mercury was the predominant form of total mercury detected in samples from the Grand Calumet River/Indiana Harbor Canal. Methylmercury concentrations were no more than 1.5 percent of the total mercury concentrations in August 2001 and no more than 6.2 percent in May 2002. Nearly all methylmercury was particulate and was correlated to concentrations of dissolved solids, total organic carbon, and sulfate. The estimated composition of most of the suspended solids in the water samples from the Grand Calumet River/ Indiana Harbor Canal was sediment larger than medium clay containing minimal organic carbon and plant matter. Total mercury loads in the Indiana Harbor Canal during the time of water sampling were as large as 703 milligrams per hour in August 2001 and 542 milligrams per hour in May 2002. As much as 21 percent of the instantaneous mercury load in some stream reaches could have come from ground-water discharge. Data from this study have implications for a Total Maximum Daily Load (TMDL) for mercury in the Grand Calumet River/Indiana Harbor Canal. Comparisons of data from this study with historical data do not show substantial changes in the distribution of mercury in the study area from 1994 through 2002. Treated municipal effluent had larger mercury concentrations than industrial effluent and presents a potential for larger mercury loads that could be controlled to achieve a TMDL, based on concentration. Mercury in ground-water discharge may be difficult to control to achieve a TMDL because of its diffuse and widespread distribution.


Contents

Abstract

Introduction

Purpose and Scope

Mercury in the Environment

Description of the Study Area

Previous Investigations of Mercury in the Study Area

Mercury in Surface Water

Mercury in Fish, Sediment, Atmospheric Deposition, and Ground Water

Methods

Study Design

Sampling Locations

Sampling Procedures

Equipment and Supplies

Watercraft and Vehicles

Sample Collection

Water-Quality Analysis

Quality Control

Streamflow

Mercury in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan

Total Mercury and Methylmercury

Mercury in Environmental Samples

Mercury in Quality-Control Field-Blank Samples

Factors Affecting Mercury Concentrations and Mercury Transport

Weather and Streamflow

Suspended Sediment and Suspended Fine Particulates

Natural Variability of Mercury Concentrations

Water-Quality Constituents

Total Mercury Loads

Implications for a Total Maximum Daily Load

Comparisons with Historical Data

Mercury in Effluent Samples

Mercury in Ground-Water Discharge

Inputs of Mercury

Summary and Conclusions

Acknowledgments

References Cited

Appendixes

1–1.—1–6. Tables of total mercury and methylmercury concentrations; estimated loads of combined total mercury; water-quality characteristics, physical properties, and major ions; unfiltered total mercury and water-quality characteristics of effluent samples; total mercury in field-blank samples; and variability of selected constituents in sequential duplicate samples, Grand Calumet River/Indiana Harbor Canal and Lake Michigan, Lake County, Indiana, August 2001

2–1.—2–6. Tables of total mercury and methylmercury concentrations; estimated loads of combined total mercury; water-quality characteristics, physical properties, and major ions; unfiltered total mercury and water-quality characteristics of effluent samples; total mercury in field-blank samples; and variability of selected constituents in sequential duplicate samples, Grand Calumet River/Indiana Harbor Canal and Lake Michigan, May 2002

3–1. Table of U.S. Geological Survey National Water Information System site-identification numbers for locations sampled in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan, August 2001 and May 2002

Figures

1.–2. Illustrations showing—

1. Sources of mercury and mercury cycling in aquatic ecosystems

2. Accumulation and magnification of mercury in the food chain

3.–5. Maps showing—

3. Study area for mercury in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan in Lake County, Indiana, August 2001 and May 2002

4. Locations of Indiana monitoring stations for mercury in wet deposition during 2001 and 2002

5. Sampling locations for mercury in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan, August 2001 and May 2002

6. Illustration showing peristaltic-pump apparatus for mercury sampling, August 2001 and May 2002

7. Photograph showing watercraft and U.S. Geological Survey personnel during mercury sampling, August 2001

8.–9. Maps showing—

8. Combined total mercury concentrations in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan, August 2001 and May 2002

9. Estimated loads of combined total mercury during the time of sampling at selected locations in the Grand Calumet River/Indiana Harbor Canal, August 2001 and May 2002

Tables

1. Mercury concentrations and mercury wet-deposition rates for National Atmospheric Deposition Program Mercury Deposition Network monitoring stations in Indiana and North America

2. Locations for mercury sampling in the Grand Calumet River/Indiana Harbor Canal and Lake Michigan, Lake County, Indiana, August 2001 and May 2002

3. Constituents, containers, treatment, and preservation for sampling during August 2001 and May 2002 in Lake County, Indiana

4. Analytical methods for supplementary constituents in water samples during August 2001 and May 2002 in Lake County, Indiana

5. Ranges of combined total mercury and methylmercury concentrations in water samples from groups of sampling locations on the Grand Calumet River/Indiana Harbor Canal and Lake Michigan, Lake County, Indiana, August 2001 and May 2002

6. Ranges of combined methylmercury as a percentage of combined total mercury in water samples from groups of sampling locations, August 2001 and May 2002

7. Ranges of particulate total mercury as a percentage of combined total mercury in water samples from groups of sampling locations, August 2001 and May 2002

8. Streamflow at 10 sampling locations and suspended-sediment concentration in water samples, August 2001 and May 2002

9. Suspended-sediment concentrations in sequential duplicate water samples from five sampling locations, May 2002

10. Proportions of suspended fine particulates, particulate organic carbon, and plant pigments in seston of water samples from groups of sampling locations, August 2001 and May 2002

11. Ranges of concentrations of dissolved solids, total organic carbon, and sulfate in water samples from groups of sampling locations, August 2001 and May 2002

12. Estimated loads of combined total mercury during the time of sampling at eight sampling locations, August 2001 and May 2002

13. Concentrations of total mercury in water samples from seven sampling locations, July 1999, August 2001, and May 2002

14. Maximum estimated loads of total mercury in ground-water discharges to stream reaches and maximum instantaneous loads of total mercury at eight sampling locations, August 2001 and May 2002


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