Preliminary Investigation of the Extent of Sediment Contamination in Manistee Lake  (Grant # GL-985906-01 / AWRI Publication # TM-2001-7)

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This work was supported by Grant Number 985906-01 from the Environmental Protection Agency Great Lakes National Program Office (GLNPO) to the Annis Water Resources Institute (AWRI) at Grand Valley State University Principle Scientists  Dr. Richard Rediske GVSU  Dr. John Gabrosek GVSU  Dr. Cynthia Thompson GVSU  Dr. Peter Meier U of M  Project technical assistance was provided by the following individuals at GVSU:  Shanna McCrumb  Mike Sweik  Eric Andrews  Betty Doyle  Tonya Cnossen	Questions or Comments Contact: Marc Tuchman, Project Officer U.S. Environmental Protection Agency Great Lakes National Program Office 77 W. Jackson Boulevard [G-17J] Chicago, Illinois  60604 Telephone:  (312) 353-1369 Fax: (312) 353-2018 Ship support was provided by the crews of the following Research Vessels: R/V Mudpuppy (USEPA) J. Bohnam  The Gas Chromatograph/Mass Spectrometer used by GVSU for this project was partially funded by a National Science Foundation Grant (DUE-9650183).
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Executive Summary
A preliminary investigation of the nature and extent of sediment contamination in Manistee Lake was performed. The investigation utilized the sediment quality triad approach with integrated assessments of chemistry, toxicity, and benthic macroinvertebrates. Diverse populations of benthic macroinvertebrates and limited evidence of anthropogenic chemical contamination were found in the control locations near the Manistee and Little Manistee Rivers (upper northeast and lower southeast sections of the lake). The remainder of Manistee Lake was characterized by depauperate benthic communities and sediments impacted by the influx of contaminated groundwater and the presence of oils and polycyclic aromatic hydrocarbons (PAH). The influx of contaminated groundwater and brines from surface discharge were evident by the presence of chemical stratification in the lower hypolimnion. A layer (approximately 5') of water with high specific conductance was present at the bottom of the lake in July 1998. High levels of chloride were also found in the sediments. Areas of intense brine intrusion were found one mile north of the Martin Marietta facility where abandon brine wells and transmission pipelines were located across the lake from Hardy Salt. The chloride levels in the remaining stations suggested a more diffuse venting of contaminated groundwater and the formation of a density gradient in the sediments. Chloride concentrations increased with sediment depth.

Sediment oil contamination and the detection of elevated levels of PAH compounds indicated extensive hydrocarbon pollution was still present in Manistee Lake. The levels reported for oils were similar to the amounts found in 1975. Of the 12 sites investigated in areas of anthropogenic impact, 10 locations exceeded the Probable Effect Concentrations (PECs) for individual PAH compounds. The highest level of PAH compounds was near Morton Chemical (M-13: 29.4 mg/kg) and the highest level of oil was found near Manistee Drop Forge (M-6: 26,000 mg/kg). Elevated levels of metals were found at all stations however concentrations were below the PEC guidelines. Resin acids were found to be distributed throughout Manistee Lake. The highest levels were found in the 20"-40" core section downstream from the old PCA outfall. The distribution of resin acids in the surficial sediments also supported the hypothesis of a diffuse venting of groundwater from the PCA site. Resin acids were not detected in the fish samples collected. The diffuse nature of the groundwater influx, the presence chemical stratification during the summer, and the high levels of oil contamination in the sediments create conditions that limit the exposure of fish populations to these chemicals.

Sediment toxicity to amphipods and midges was observed at M-6 and M-13. These stations had the highest levels of hydrocarbon oils and PAH compounds. Amphipod toxicity was measured at five additional sites, all containing levels of individual PAH compounds exceeding PEC concentrations.

A variety of statistical techniques were employed to examine the difference between the control population and locations impacted by the PCA groundwater plume and the salt brine companies. The results showed a clear difference between diversity and trophic status with respect to the controls and the impacted sites. ANOVA results confirmed that the impacted populations were less diverse and dominated by pollution tolerant organisms. The ANOVA results also suggested that the brine-impacted sites as a group, have benthic macroinvertebrate populations with a lower trophic status than benthos collected in the area influenced by the PCA/Martin Marietta groundwater plume.

Introduction
Manistee Lake is a large drowned river mouth (929 acres) that is directly connected to Lake Michigan by a navigation channel (Figure 1.1). The main basin of the lake is characterized by steep banks and water contours with a maximum depth of 49 feet. An extensive wetland complex is located in the northern part of the lake in the area where the Manistee River enters the system. Wetlands are also located in the southern basin of the lake near the confluence of the Little Manistee River. Water flows in a northwesterly direction in Manistee Lake up to the channel area across from the Manistee River wetlands. At this point, the water flows westward to Lake Michigan. The watershed has a drainage basin of over 2000 square miles and contains an important fishery in this region of the Great Lakes. While most rivers in this watershed are classified as relatively pristine trout streams, substantial anthropogenic activities have adversely affected Manistee Lake. For over 125 years, industrial discharges from lumbering, leather tanning, brine extraction, and pulp/cardboard production facilities have impacted water quality and contaminated the sediments. Investigations conducted by the Michigan Water Resources Commission (Surber 1953) and the Michigan Department of Natural Resources (Grant 1975) found depauperate benthic macroinvertebrate communities in a majority of Manistee Lake. The only locations that contained pollution intolerant organisms were at the mouths of the Little Manistee and the Manistee River. The Packaging Corporation of America (PCA) Superfund Site is of particular concern due to an extensive groundwater discharge of Kraft black liquor that enters the southeastern basin of the lake. Process water from the Kraft operations was discharged into a series of eight unlined lagoons approximately 2500 ft from the lake. These lagoons are hydraulically connected to Manistee Lake by a sand/gravel aquifer that ranges from 40 - 200 ft thick (FTCH 1991). From 1951 to 1976, approximately 7 billion gallons of effluent and process wastes were discharged into the lagoons. A detailed investigation of the groundwater discharge from the lagoons was conducted in August 1993 (Camp, Dresser & McKee and Battelle Great Lakes Environmental Center 1993). Sediment pore water and groundwater collected from wells installed beneath the lake bottom (50 - 200 ft) was found to be toxic to Ceriodaphnia dubia. Toxicity of sediments from this area and the extent of impact on the current benthic community have not been evaluated.

Resin acids have been identified as one of the more toxic components of Kraft effluents (Zanella 1983 and Sunito et al. 1988). This group of compounds has been shown to be toxic to fish (Leach and Thankore 1976 and Johnsen et al. 1997) and to exhibit estrogenic activity in trout (Mellenen et al. 1996). Nimi and Lee (1992) found certain resin acids to bioaccumulate in caged fish studies. Burggraaf et al. (1996) found similar levels of bioaccumulation in mussels. Since resin acids were previously reported in groundwater and sediment samples near a Kraft mill (Wilkins et al. 1996 and Travendale et al. 1995), it is of ecological importance to evaluate the extent of contamination of these compounds in the sediments and biota of Manistee Lake.

In addition to the area near PCA Superfund Site, other locations in Manistee Lake are affected by historic and current discharges from several salt brine extraction facilities and foundry operations. Many of these facilities have initiated remediation programs to eliminate and/or reduce the amount of contamination entering the lake. Since the last assessment of the lake was conducted in 1975, it is important to examine the current nature and extent of sediment contamination and the status of the health of the benthic community. This project utilized a series of sampling stations that are in the area influenced by the groundwater discharge plume from the PCA lagoons. In addition, a group of sediment sampling stations that reflect deposition areas near historic industrial locations, wastewater treatment outfalls, and Michigan 307 sites were examined. The study protocol followed the sediment quality triad approach (McDonald 1991) and focused on sediment chemistry, sediment toxicity, and the health of the benthic macroinvertebrate community. The information from this investigation will be important for the determination of areas that may require further delineation and the prioritization of remedial action and habitat restoration activities.

History Of Anthropogenic Activities In Manistee Lake
Manistee Lake has been impacted by industrial activity since 1841 when the first sawmill was constructed on the shore (Grant 1975). The abundance of timber resources led to the construction of many sawmills and ancillary industries such as leather tanneries and pulp mills. The first pulp mill was built in 1917, after the depletion of the areas white pine trees resulted in the closing of the remaining sawmills. Wet-lap processing was used for pulp production until 1949 when the plant was converted to a neutral sulfide operation. This change resulted in the production of Kraft black liquor that was discharged directly to Manistee Lake. After numerous fish kills and odor complaints, the pulp mill discontinued the direct discharge of this material and constructed a series of eight unlined lagoons on the opposite side of the lake. Black liquor and other waste products were discharged to the lagoons from 1951 to 1976. The lagoons were closed in 1976 due to problems associated with groundwater discharges entering Manistee Lake. The mill is currently operated by the Packaging Corporation of America (PCA) and the lagoons are in the process of final closure under the Superfund Program.

In addition to the long-term impact of the pulp/box mill, industries related to the extraction and processing of salt brine have also discharged contaminants to the lake. The first brine extraction well was installed in 1881. Since then, Hardy Salt and Morton Salt have constructed facilities to extract and purify salt brine on the shores of Manistee Lake. Chemical brines containing bromide, calcium, magnesium, and potassium are also extracted and processed. Brine discharges from abandon wells, NPDES outfalls, and seeps continue to flow into Manistee Lake. Martin Marietta operates a production facility located on the southeast lakeshore. The Martin Marietta facility is located down gradient from the PCA lagoons and a combined plume of contaminated groundwater enters Manistee Lake at this location.

Petroleum hydrocarbons have also been discharged into the lake by a number of industries. PCA used kerosene as a pitch control agent and was forced to eliminate its discharge to Manistee Lake in 1967 due to fish tainting. Oil spills were reported at Manistee Drop Forge on several occasions in addition to a large release of fuel oil that was recently remediated by soil and sediment removal. In addition to discharges from industries, petroleum releases from shipping may also contribute to hydrocarbon levels in the sediments. Large vessels frequently enter Manistee Lake to transport coal for the power plant and to pick up process chemicals from the brine facilities.

Project Objectives And Task Elements
The objective of this investigation was to conduct a Category II assessment of sediment contamination in Manistee Lake. Specific objectives and task elements are summarized below:

Develop a target list of resin acids for the PCA Superfund Site. A sample of contaminated groundwater was collected from the PCA Site and analyzed for a group of resin acids by GC/MS.Based on a review of the literature, the following resin acid compounds were selected: abietic acid, dehydroabietic acid, chlorodehydroabietic acid, dichlorodehydroabietic acid, neoabietic acid, pimaric acid, and isopimeric acid. Critical measurements were the resin acids.

Determine the nature and extent of sediment contamination in Manistee Lake. A Phase II investigation was conducted to examine the nature and extent of sediment contamination in Manistee Lake. Core samples were collected to provide an historical perspective of sediment contamination. The investigation was directed at known sources of contamination in the lake and provided expanded coverage in the area of the PCA Superfund site. Arsenic, barium, cadmium, chromium, copper, lead, nickel, zinc, selenium, mercury, total organic carbon (TOC), semivolatile organics, resin acids, and grain size were analyzed in all core samples. Surface sediments were collected from Manistee Lake with a Ponar to provide chemical data for the sediments used in the toxicity evaluations and for the analysis of the benthic macroinvertebrate communities. The Ponar samples were analyzed for the same parameters as the sediment cores. Critical measurements were the concentration of arsenic, barium, cadmium, chromium, copper, lead, nickel, zinc, selenium, mercury, semivolatile organics, and resin acids in sediment samples. Non-critical measurements were total organic carbon, and grain size.

Evaluate the toxicity of sediments from sites in the lower Manistee Lake area. Sediment toxicity evaluations were performed with Hyalella azteca and Chironomus tentans. Toxicity measurements in Manistee Lake sediments were evaluated and compared with the two control locations. These measurements determined the presence and degree of toxicity associated with sediments from Manistee Lake.  Critical measurements were the determination of lethality during the toxicity tests and the monitoring of water quality indicators during exposure (ammonia, dissolved oxygen, temperature, conductivity, pH, and alkalinity).

Determine the abundance and diversity of benthic invertebrates in Manistee Lake. Sediment samples were collected with a Ponar in Manistee Lake. The abundance and diversity of the benthic invertebrate communities were evaluated and compared with the two control locations. Critical measurements included the abundance and species composition of benthic macroinvertebrates.

Determine the degree of bioaccumulation of resin acids in fish from Manistee Lake. Fish samples were collected from Manistee Lake Size, age, species, and sex of the fish were determined.  Resin acids were analyzed in the fish tissue. The final analyte list was determined by reviewing the results of the sediment samples. Critical measurements were the target list of resin acids.

Experimental Design
This investigation was designed to examine specific sites of possible contamination as well as provide an overall assessment of the nature and extent of sediment contamination in Manistee Lake. This bifurcated approach allowed the investigation to focus on specific sites based on historical information in addition to examining the broad-scale distribution of contamination. To address contamination at specific sites, 10 core samples were collected from locations likely to have been impacted by significant anthropogenic activity. The locations were selected to target current and historical point sources and downstream sites from known industrial and municipal discharges. These sites were determined by the analysis of historical data and industrial site locations. Analysis of lake depositional areas was then used to select two locations that would reflect the general distribution of contaminants. 

Sediment samples were collected using the U.S. EPA Research Vessel R/V Mudpuppy. The sediment cores were collected with a VibraCore device with core lengths ranging from 6-8 ft. The core samples were then sectioned in three lengths for chemical analysis. Ponar samples were also collected at these locations to provide an assessment of the near surface zone sediments. For each core, the analytical parameters included a general series of inorganic and organic constituents as well as specific chemicals related to a particular source or area. The general chemical series for each core included the following heavy metals; arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc. In addition, resin acids were analyzed on all cores. The location of the study area is shown in Figure 1.2. Analytical methods were performed according to the protocols described in SW-846 3rd edition (EPA 1994a). 

Chemistry data were then supplemented by laboratory toxicity studies that utilized standardized exposure regimes to evaluate the effects of contaminated sediment on test organisms. Six Ponar samples were collected in areas that had elevated levels of contaminants in the top core sections. Standard EPA methods (1994b) using Chironomus tentans and Hyalella azteca were used to determine the acute toxicity of sediments from the Ponar samples.

References
Burggraaf, S., Langdon, A.G., Wilkins, A.L., and D.S. Roper. 1996. Accumulation and depuration of resin acids and fichtelite by the freshwater mussel Hyridella menziesi. Environmental Toxicology and Chemistry 15(3):369-375.

Camp, Dresser, and McKee and Battelle Great Lakes Environmental Center. 1993. Packaging Corporation of America/Manistee Lake Site. 118 pp.

EPA, 1994a. Test Methods for Evaluating Solid Waste Physical/Chemical Methods. U.S. Environmental Protection Agency. SW-846, 3rd Edition.

EPA, 1994b. Methods for Measuring the Toxicity and Bioaccumulation of Sediment-Associated Contaminants with Freshwater Invertebrates. U.S. Environmental Protection Agency. EPA/600/R-94/024.

Grant, J. 1975. Water Quality and Biological Survey of Manistee Lake. Michigan Department of Natural Resources. Pub. 4833-9310. 56pp.

Johnsen, K., Mattsson, K., Tana, J., Stuthridge, T.R., Hemming, J., and K.J. Lehtinen. 1995. Uptake and elimination of resin acids and physiological responses in rainbow trout exposed to total mill effluent from an integrated newsprint mill. Environmental Toxicology and Chemistry 14(9):1561-1568.

Leach, J. M. and A. N. Thakore. 1976. Toxic constituents in mechanical pulping effluents. Tappi 59:129-132.

Mellanen, P., T. Petenen, J. Lehtimaki, S. Makela, G. Bylund, B. Holmbom, E. Mannila, A. Oikari, and R. Santti. 1996. Wood-derived estrogens: studies in vitro with breast cancer cell lines and in vivo in trout. Toxicol-Appl-Pharmacol 136(2):381-8.

Nimi, A. J. and H. B. Lee. 1992. Free and conjugated concentration of nine resin acids in rainbow trout (Oncorhynchus mykiss) following waterborne exposure. Environmental Toxicology and Chemistry 11:1403-1407.

Sunito, L. R., Shiu, W. Y., and D. Mackay. 1988. A review of the nature and properties of chemicals present in pulp mill effluents. Chemosphere 17:1249-1290.

Surber, E. 1953. A Biological Survey of the Effects of Pollution on Manistee Lake. September 15, 1953. Michigan Water Resources Commission.

Tavendale, M. H., Wilkins, A. L., Langdon, A. G., Mackie, K. L., Stuthridge, T. R., and P. N. McFarlane. 1995. Analytical methodology for the determination of freely available bleached Kraft mill effluent-derived organic constituents in recipient sediments. Environ. Science and Technology 29(5).

Wilkins, A. L., Davidson, J. A. C., Langdon, A. G., and C. H. Hendy. 1996. Sodium, calcium, and resin acid levels in ground water and sediments from two sites adjacent to the Tarawera River, New Zealand. Bulletin of Environmental Contamination and Toxicology 58:575-581.

Wilkins, A. L., Singh-Thandi, M., and A. G. Langdon. 1996. Pulp mill sourced organic compounds and sodium levels in water and sediments from the Tarawera River, New Zealand. Bulletin of Environmental Contamination and Toxicology 57:434-441.

Zanella, E. 1983. Effect of pH on acute toxicity of dehydroabietic acid and chlorinated dehydroabietic acid to fish and Daphnia. Bulletin of Environmental Contamination and Toxicology 30:133-40.

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