Re-Examination of Mercury Pollution
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Journal of GeocHemical Exploration, 29 (1987) 1-12 Elsevier Science Publishers B.V., Amsterdam — Printed in The Netherlands Environmental geochemical studies Re-Examination of Hg Pollution in the Ashtabula Area, Ashtabula County, Ohio* ROBERT A. ANDERSON1 and ERNEST H. CARLSON Department of Geology, Kent State University, Kent, OH 44242, U.S.A. (Received May 14,1986) ABSTRACT ' Andersen, RA. and Cartson, E.H., 1987. Re-examination of Hg pollution in the Ashtabula area, Ashtabula County, Ohio. In: R.G. Garrett (Editor), Geochemical Exploration 1985. JgGeochem. Explor., 29:1-12. Environmental concern about Hg pollution in Lake Erie peaked in 1970 with most, investiga- tions being directed to the west end of the lake and problems associated with Lake Si.' Clair. The Ohio Geological Survey subsequently (1970-1971) collected and analyzed stream and lake sedi- ments in the vicinity of several industrial areas that border Lake Erie and reported indications of Hg pollution along the lower reaches of the Ashtabula River. Neither the intensity, nor the center, of the contamination was recognized in that study. In 1970, however, the state began to monitor the levels of Hg in the industrial effluent of the area. During a re-investigation of pollution at Ashtabula, 68 sediment samples were collected across an area of 90 km2 in the late spring and early summer of 1982. The Hg that was released by heating the samples on a hot plate for one minute at 290 °C was determined with a gold-film Hg detector. "£"££^ Mercury concentrations in the sediments had a median (background) value of 24.4 ppb and a &:•*£« mean content of 422 ppb, and exhibited a lognormal distribution that was bimodal. Three samples that ranged from 1550 to 20,600 ppb Hg are considered anomalous and come from the drainage of Fields Brook. Although no single industrial operation could be targeted as a source, high Hg levels apparently are due to the past accumulation of industrial waste. Mean Hg levels in the Ashtabula River samples from south and north of the junction with Fields Brook were 42.8 and 118.5 ppb Hg, respectively, indicating that contamination of the latter had occurred. The Lake Erie samples (mean ppb Hg) can be separated by the mouth of the Ashtabula River and the depth of the lake bottom as follows: west side (9.7),east side (59.8); and shoreline (15.8), nearshore (64.5). The six-fold increase on the eastern side of the harbor relative to the western side is believed to be due to the direction of the longshore currents which, in the Ashtabula area, run from southwest to northeast. The four-fold increase in Hg levels in nearshore sediments rel- ative to those from the shoreline is due to preferential concentration in the finer size fraction. The Hg levels obtained for nearshore sediments just east of the Ashtabula River are six times higher •Contribution No. 299, Department of Geology, Kent State University. 'Present address: 2916 Fairview Drive, Ashtabula, OH 44004, U.S.A. 0375-6742/87/S03.50 © 1987 Elsevier Science Publishers B.V. !• .' X**PlMHtt. lMSi.'i.Vit »"."« «..S»"-U' • ' V.'., than those reported earlier by the Geological Survey, suggesting that accumulation of Hg may have occurred. INTRODUCTION The accumulation of Hg in the environment from industrial wastes has become a worldwide problem due to the toxic character of that element (D'ltri and D'ltri, 1977). Environmental concern about industrial Hg pollution in Lake Erie peaked in 1970, when high levels discovered at the western end of the lake could be traced to contamination from Lake St. Clair (Fig. 1). In the Ashtabula area at that time, reports confirmed that Hg-rich waste water had been dumped into ponds and ditches entering Fields Brook and Lake Erie (The Star-Beacon, 1970a, b, c). The Ohio Geological Survey subsequently (1970- 1971) collected and analyzed stream and lake sediment from the Ashtabula region, as well as from several other industrial areas that border on the south- ern shore of Lake Erie (Stith, 1973). Although signs of Hg pollution along the lower reaches of the Ashtabula River were documented in that study, neither the intensity nor the center of the contamination was recognized. A few years later local residents expressed concern to one of the investigators (H.A.A.) about high levels of Hg that reportedly were encountered in old drainage pipelines at Fields Brook. An additional problem was the quality of municipal water, which is drawn from the lake through an aqueduct on the west side of the harbor. Although industrial effluent at Ashtabula continues to be discharged into Fields Brook and Lake Erie (Fig. 2), Hg loads today are maintained at minimal levels as specified in discharge permits issued under the authority of the Clean Water Act (Ohio Environmental Protection Agency, unpublished data). Undesirable amounts of Hg, therefore, may still be enter- ing the lake from old disposal sites or past spills at Ashtabula, even though the discharge of toxic constituents from other areas along the lake has been reduced greatly over the past 15 years (Herdendorf and Stuckey, 1979). The purpose of the present study was to determine the extent and source of Hg contami- nation in the drainage sediment of Ashtabula and adjacent parts of Lake Erie v^y^$^;V:;;~y . by means of a detailed program of sampling and analysis. The Ashtabula area is situated within the southern part of the Lake Plains province and is underlain by glaciolacustrine silts and clays which, in turn, rest on glacial till. Both surface drainage and groundwater generally flow north- ward into the Lake Erie basin. Fields Brook runs westerly through the indus- trial district of Ashtabula Township before it enters a residential area at the eastern city limits and empties into the Ashtabula River, the latter draining into the lake at Ashtabula Harbor. The shore at Ashtabula trends east-north- east and is characterized by bluffs up to 20 m high and deep stream channels, exposing the glacial deposits and the underlying Devonian black shales. * 4^r$>r-">;. ;=;, •'• '•"' -•'V'.Vi.rV'fr.rv. '•^£^i*3»rp?TT£rs>;;'?X :'&£2HEt9;&&:il4 '$8 S'.t.' ?V ;.'.-' V 1 •S^ii'JLr •- ~ ' ••^K* Fig. 1. Map of Lake Erie showing the location of the Aahtabula area. SAMPLE COLLECTION, PREPARATION AND ANALYSIS Sixty-eight grab samples were collected across a region of 90 km2 during the late spring and early summer of 1982 (Fig. 2; Tables 1 and 2). As the complex of industrial and chemical plants is situated in the central part of the study area, the drainage there and in the surrounding vicinity contains the highest density of sample sites. The bodies of water that were sampled and the corre- sponding number of sites visited were as follows: Fields Brook (5), Red Brook (5), Whitman Creek (5), the Ashtabula River (22), Lake Erie (27), ponds (2) and drainage ditches (2). Most stream sediment samples were collected from active portions of the channels near road crossings. Lake Erie shoreline samples (16) were gathered at average water depths of 0.3 m, while nearshore ones (11) were obtained at depths ranging from 1.5 to 4.7 m. Nearshore sedi- ment, which provides about a meter of veneer west of the harbor and a few centimeters on the east side, was obtained by scuba diving. The samples typi- cally were dark brown to gray, organic, sandy muds except for the shoreline sediment which consisted of gray and brown sands (Tables 1 and 2). The samples were air-dried, sieved to — 80 mesh (—177 /on) and stored in tightly capped vials for analysis. The weight of the material analyzed varied according to the Hg content and ranged from 1.0 to less than 0.1 g. A partial extraction technique was selected in the present study because Hg in the Ash- tabula sediment is believed to be bonded loosely. The precision of ±20%, as measured by the relative standard deviation, was surprisingly good for an apparatus that was readily portable. The Hg was released by heating the sam- ples on a hot plate for one minute at 290 °C and the resulting vapor analyzed with a Jerome Instrument Corporation Model 301, gold-film Hg detector (McNerney, 198la, b). The amount of Hg yielded by this method is propor- tional to the concentration in the samples, being about 40% of the total on average. The instrument has an absolute sensitivity of 1.0 ng of Hg (McNerney, 1983). All samples were run at least twice with the mean values being recorded. / A K E ERIE ••#•;.•. #*, •.] ._'.- - .^r.*•**'• jmi TABLE 1 Location and description of the stream, ditch and pond samples Station Location Sample deacriptkm MeanHg oo. content (ppb) A-l Ashtabula River on north side of State Road bridge Brownish -gray sandy mud 13.4 A-2 Aahtabula River on east tide of Ohio Rout* 11 overpass Brownish -gray Mndy mud 4.0 A-3 Ashtabula River near nwuth of Hubbard Run Brownish-gray sandy mud 93 A-4 Aahtabula River south of Norfolk «od Western railroad bridge Brownish-gray sandy mud 90.5 A-5 Aahtabula River north of Norfolk and Western railroad bridge Brown sandy mud 6.6 A -6 Ash tabula River north of Ohio Route 20 Brownish-gray mud 68.2 A-7 AahtabukRrw on weat side of Hannon Hill bridge Brown organic mud 90.5 A-8 Aahtabula River on Moth side of Bast 24th St. bridge Brown sandy mud 4.2 A-9 Asbtabula River on northeaat «de of But 24th St. bridge Brown organic mud 16.6 A- 10 Ashtabula River on northwest tide of But 24th St bridge Black organic mud 32.9 A-ll Ashtabula Rivw on south side of Fields Brook mouth Black organic mud 111 A-12 Ashtabula River at month at FieUi Brook Gray organic mud 63J A-13 Aahtabula River north of Pena Central railroad bridge Brown organic mud 296 A-H Ashtabula River south of Ashtabula Yacht Club Brown organic mud 46.3 A-16 AshtabuU River south <rf fith St.