Chapter 14
Maumee Area of Concern Sediment Screening Survey, Toledo, Ohio 1
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Thomas J. Balduf , Jeff Wander , Philip A. Williams , Brent Kuenzli , and Patrick J. Heider
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Division of Surface Water and Division of Emergency and Remedial Response, Ohio Environmental Protection Agency, Northwest District Office, 347 North Dunbridge Road, Bowling Green, OH 43402
The Maumee Bay, located in the western basin of Lake Erie, was once known as the most prolific fish spawning ground in Lake Erie. The heavy metal and organic chemical contamination caused by agriculture and heavy industry such as oil refining, petrochemical, metal fabricating, auto parts and manufacturing resulted in the Maumee Bay being listed as an Area of Concern (AOC) in 1985 by the International Joint Commission. In September, 1994, during the initial reconnaissance of sediment quality in the Ottawa River, Ohio, both screening and standard methods were used to analyze 29 sediment core samples. Total Polynuclear Aromatic Hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were quantified to parts per million (ppm) level by enzyme immunoassay using a variation of EPA 4020 and 4035 draft methods. Contract Laboratory Program (CLP) analysis of the same samples for the parameters followed standard Statement of Work (SOW). This study indicates that immunoassays are valuable screening devices for PAHs and PCBs, especially when used with periodic laboratory confirmation sampling
The Maumee Bay is located in the western basin of Lake Erie (northwest section of Ohio and the southeast section of Michigan). It was once known as the most prolific fish spawning ground in Lake Erie. This area included what was known as the Great Black Swamp, which contained a faunal association requiring water free of clayey silts and containing aquatic vegetation. Habitat and water quality degradation began as far back as 1850, due to the effects of dams, channelization, over-fishing and pollution. 3
Corresponding author
0097-6156/96/0646-0155$15.00/0 © 1996 American Chemical Society
In Environmental Immunochemical Methods; Van Emon, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Downloaded by UNIV MASSACHUSETTS AMHERST on October 11, 2012 | http://pubs.acs.org Publication Date: October 23, 1996 | doi: 10.1021/bk-1996-0646.ch014
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ENVIRONMENTAL IMMUNOCHEMICAL METHODS
The heavy metal and organic chemical contamination caused by agriculture and heavy industry such as oil refining, petrochemical, metal fabricating, auto parts and manufacturing resulted in the Maumee Bay being listed as an AOC in 1985 by the International Joint Commission. It is one of 43 areas with pollution problems so severe that the 14 identified beneficial uses in the Great Lakes Water Quality Agreement are impaired. Because the Maumee River is the largest tributary to the Great Lakes, this pollution is readily carried into Lake Erie, contaminating water and sediment. In the spring of 1991, the Ohio Environmental Protection Agency (EPA) produced the "Fish Tissue, Bottom Sediment, Surface Water, Organic and Metal Chemical Evaluation and Biological Community Evaluation" for the Ottawa River and Tenmile Creek, a tributary in the Maumee AOC. These data documented the pollution problems and identified areas needing further analysis, including grossly contaminated surface sediments. This report led to the Ohio Department of Health issuing a fish consumption/contact advisory for the Ottawa River from River Mile 8.8 to Lake Erie in April 1991. This advisory was based on the detection of extremely elevated levels of (PCBs) in sediments and fish tissues. A few highlights in this report include: A) Extensive PCB contamination in the lower 10 miles of the Ottawa River. PCBs were detected in all media sampled within the Ottawa River, with Ohio Water Quality Standard violations noted in both surface water and fish tissue samples. The highest PCB concentration (1,200 ppm) was documented in sediment sampled from a portion of the former river channel which now serves as a drainage swale for a storm water discharge into the Ottawa River. The highest total PCB levels in fish tissue occurred at River Mile 5.2, where common carp fillets and whole body PCB concentrations were 65 ppm and 84 ppm, respectively. Theses fish tissue samples had to be disposed of as Toxic Substance Control Act (TSCA) waste because they exceeded the regulator levels. B) A wide range of pesticides were detected in the fish tissue and sediment samples. Most pesticides appeared to be in low concentrations. However, heptachlor epoxide and dieldrin were considered extremely elevated. C) Five heavy metal contaminants (barium, cadmium, chromium, lead, and selenium) were measured in fish tissue fillet and whole body composite samples from the 1990 sampling sites. Eleven heavy metal elements were detected in the sediments from the Ottawa River between 1986 and 1990. D) Biological community results show non-attainment of the Warmwater Habitat aquatic life use designation for nearly the entire sampling area of the Ottawa River. Based on 1986 and 1990 Ohio E P A sampling results, the Ottawa River is in violation of Ohio Water Quality Standards. The severe water quality noted in this document along with the health advisory prompted the first Ohio EPA sediment screening survey to be conducted in the Ottawa River.
In Environmental Immunochemical Methods; Van Emon, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
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14. BALDUF ET AL.
Maumee AOC Sediment Screening Survey
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The Division of Surface Water (DSW) and the Division of Emergency and Remedial Response (DERR) worked together during the various stages of this screening survey. The DSW focused their efforts on establishing a baseline of current water quality conditions in the AOC. Their efforts included the collection and chemical/physical analysis of the surface water samples and the chemical analysis of sediments at several stations throughout the AOC. DERR began their study efforts by initiating site inspections at 21 identified uncontrolled/unregulated hazardous waste disposal sites known within the Ottawa River watershed. In September 1994 the Ohio E P A Maumee Area of Concern (AOC) Project team consisting of personnel from Ohio EPA, DSW and DERR began the initial reconnaissance of sediment quality in the Ottawa River, Ohio. In this reconnaissance both screening and standard methods were used to analyze 29 subsamples from 18 sediment cores. For screening, 12 metals were quantified at part-per-million (ppm) levels with energy dispersive X-ray fluorescence (EDXRF) and organics (total PCBs and PAHs) were quantified at part-per-billion (ppb) to ppm levels by enzyme immunoassay, using a variation of EPA 4020 and 4035 (1) draft methods. CLP analysis of the same samples for the parameters followed standard CLP SOW E P A methods (2). The goal of this survey was to conduct the initial portion (Step 1) of a sediment screening survey to collect field data supported by laboratory confirmational data to be used to evaluate the extent of PCB, P A H and heavy metals contamination within the Ottawa River health advisory zone. This was to be accomplished by using field screening methods (with laboratory confirmation) to provide a broad survey of 8.8 miles of the Ottawa River. The survey is to determine the broad distribution of contamination in the sediment within the health advisory zone and to determine, within the constraints of this initial sediment sampling, the extent of the contamination , not to determine responsible parties. However the information obtained through this survey may aid in the direction of future remedial investigatory actions taken within the health advisory zone of the Ottawa River. Table I is a summary of the 29 replicate sub-samples collected from various depths of the 18 cores that were analyzed by both CLP laboratory methods and by immunoassay methods for PCB, the constituent of most concern with respect to the use of immunoassay as a field screening method. Table I and Figure 1 displays the correlation between the laboratory methods and the field screening methods. The data shown in this table have undergone validation procedures by a third party contractor. The validation results for semivolatiles, pesticides and PCB were developed in accordance with the U S EPA Contract Laboratory Program National Functional Guidelines for Organic Data Review, February 1994. The validation results for metals were developed in accordance with the U.S. E P A Contract Laboratory Program National Functional Guidelines for Inorganic Data Review, February 1994. All samples were analyzed by the laboratory using Contract Laboratory Program protocols with full packages as a deliverable. The results from this screening survey were submitted to the U.S.EPA, Region 5, Immunoassay Assessment Team for their review of the immunoassay process. Hopefully, these data will demonstrate, to the Team, the information necessary to gain their confidence in this field screening methodology.
In Environmental Immunochemical Methods; Van Emon, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
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Table I.
Data from laboratory and field analysis of sediment at the Maumee A O C , Toledo, Ohio
ΟΕΡΑ SAMPLE #
ROSS LAB SAMPLE #
PCB FIELD (ppm)
PCB LAB. (ppm)
TOC (ppm)
0R1/4.9/9-15
101
3.9
6
56800
0R1/4.9/15-34
102
2.1
0.11
34000
OR1/6.0/0-6
103
244
1300
130000
OR1/6.0/30-57
104
1045
2000
112000
OR1/4.2/6-23
105
9.6
5
59400
OR1/4.2/23-40
106
8.4
0.79
54700
0R1/3.4/8-19
107
1.2
0.79
0100
0R1/3.4/19-41
108
5.8
0.17
120000
OR1/5.8/0-6
109
11
37
81200
OR1/6.4/0-6
110
2.7
3.7
37700
OR1/7.9/0-6
111
0.67
0.53
41200
OR1/7.4/0-6
0.65
28000
112
0.35
0R1/6.9/8-21
113
2.7
8.6
42700
0R1/6.9/21-31
114
1.3
0.7
40900
OR1/9.0/6-23
115
6.1
2.7
66400
0R1/10.0/0-6
116
4.7
10
43200
0R1/1.6/12-27
117
3.6
0.3
74000
OR1/1.6/0-12
118
1.1
0.62
60400
0R1/6.1/0-16
119
1.7
3.8
33800
OR1/6.1/16-50
120
