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Concerns about possible effects of lead-mining activities on the water quality of federally protected streams located in southeastern Missouri prompted a suite of multidisciplinary studies to be conducted by the U.S. Geological Survey. As part of this investigation, a series of biological studies were initiated in 2001 for streams in the current mining region and the prospecting area. In this report, results are examined for trace elements and other selected chemical measurements in sediment, surface water, and sediment interstitial (pore) water sampled between 2002 and 2005 in association with these biological studies. Compared to reference sites, fine sediments collected downstream from mining areas were enriched in metals by factors as large as 75 for cadmium, 62 for cobalt, 171 for nickel, 95 for lead, and 150 for zinc. Greatest metal concentrations in sediments collected in 2002 were from sites downstream from mines on Strother Creek, Courtois Creek, and the West Fork Black River. Sediments from sites on Bee Fork, Logan Creek, and Sweetwater Creek also were noticeably enriched in lead. Sediments in Clearwater Lake, at least 75 kilometers downstream from mining activity, had metal concentrations that were 1.5 to 2.1 times greater than sediments in an area of the lake with no upstream mining activity. Longitudinal sampling along three streams in 2004 indicated that sediment metal concentrations decreased considerably a few kilometers downstream from mining activities; however, in Strother Creek some metals were still enriched by a factor of five or more as far as 13 kilometers downstream from the Buick tailings impoundment. Compared with 2002 samples, metals concentrations were dramatically lower in sediments collected in 2004 at an upper West Fork Black River site, presumably because beneficiation operations at the West Fork mill ceased in 2000. Concentrations of metals and sulfate in sediment interstitial (pore) waters generally tracked closely with metal concentrations in sediments. Metals, including cobalt, nickel, lead, and zinc, were elevated substantially in laboratory-produced pore waters of fine sediments collected near mining operations in 2002 and 2004. Passive diffusion samplers (peepers) buried 4 to 6 centimeters deep in riffle-run stream sediments during 2003 and 2005 had much lower pore-water metal concentrations than the laboratory-produced pore waters of fine sediments collected in 2002 and 2004, but each sampling method produced similar patterns among sites. The combined mean concentration of lead in peeper samples from selected sites located downstream from mining activities for six streams was about 10-fold greater than the mean of the reference sites. In most instances, metals concentrations in surface water and peeper water were not greatly different, indicating considerable exchange between the surface water and pore water at the depths and locations where peepers were situated. Passive sampling probes used to assess metal lability in pore waters of selected samples during 2004 sediment toxicity tests indicated that most of the filterable lead in the laboratory-prepared pore water was relatively non-labile, presumably because lead was complexed by organic matter, or was present as colloidal species. In contrast, large percentages of cobalt and nickel in pore water appeared to be labile. Passive integrative samplers deployed in surface water for up to 3 weeks at three sites in July 2005 confirmed the presence of elevated concentrations of labile metals downstream from mining operations on Strother Creek and, to a lesser extent, Bee Fork. These samplers also indicated a considerable increase in metal loadings occurred for a few days at the Strother Creek site, which coincided with moderate increases in stream discharges in the area. Introduction Southeastern Missouri has been a primary producer of lead (Pb) since the early 1700s (Mining and Quarry World, 2004). Mining ceased in 1972 in the Old Lead Belt (fig. 1, inset) where large quantities of metal-enriched tailings eroded into area streams. Contamination of fish and other aquatic biota, alteration of fish and invertebrate communities, and public health advisories against human consumption of lead-contaminated fish have resulted (Czarneski, 1985; Schmitt and others, 1993). Since the 1960s, most lead mining in Missouri shifted to a new district, the Viburnum Trend, also known as the New Lead Belt. This area remains a primary producer of lead, and a secondary producer of zinc (Zn); copper (Cu) and silver (Ag) also are produced in small quantities (Missouri Department of Natural Resources, 2004). Viburnum Trend deposits also Assessment of Elemental Concentrations in Streams of the New Lead Belt in Southeastern Missouri, 2002–05 By William G. Brumbaugh, Thomas W. May, John M. Besser, Ann L. Allert, and Christopher J. Schmitt contain considerable quantities of cobalt(Co) and nickel(Ni) bearing minerals (Jessey, 1981), but there is no production of those metals (Shedd, 2004; Kuck, 2004). In fact, lead production in Missouri has been identified as a primary loss pathway in the materials flow of cobalt in the United States (Shedd, 1993). Mining in the Viburnum Trend has developed concurrently with increased environmental regulation and improved technology for metal recovery and pollution control. Studies conducted in the 1970s reported amelioration of adverse biological effects on stream biota, and attributed these changes to processes such as recycling wastewater from mining and beneficiation (milling and flotation concentration) and the development of passive wastewater treatment systems with increased retention time (Ryck and Whitley, 1974; Wixson, 1977). However, mining in the Viburnum Trend has not necessarily proceeded without environmental questions (Duchrow, 1983). Through the early 1980s, most instances of water-quality degradation associated with active lead-zinc mines in Missouri were attributed to catastrophic or intermittent releases from tailings or settling ponds during heavy rainfall events (U.S. Environmental Protection Agency, 1994). Limited U.S. Geological Survey (USGS) investigations conducted during the 1990s suggested that lead and/or zinc concentrations in sediments were potentially harmful to aquatic organisms at some locations (Petersen and others, 1998). With time, mining activity in the Viburnum Trend has progressed from north to south as ore deposits were depleted and new mines opened. Most of these mines have been developed on lands adjacent to the Mark Twain National Forest, federally-owned lands that are managed for forestry, mining, and recreation (U.S. Department of Agriculture, 2005). Beginning in the late 1970s, prospecting for new ore was conducted primarily in two exploration areas about 30 kilometers south of the Viburnum Trend (Kleeschulte and Seeger, 2003). This activity has raised concerns about possible adverse environmental effects of mining on the water quality and aquatic biota of nearby high-quality streams that are federally protected and managed as National Parks, National Scenic Rivers, and National Forests. In the karst landscape of southeastern Missouri, metals and other substances associated with mining activities potentially could enter surface streams and subsurface waterways that recharge springs (Kleeschulte, 2000). Consequently, concerns about possible effects of mining activities on the water quality of federally-protected streams located in this region of Missouri prompted a series of multidisciplinary studies conducted by the USGS that began in October, 2000 (Kleeschulte, 2003). Purpose and Scope This report presents results of chemical measurements performed on surface-water, sediment, and sediment porewater samples collected between 2002 and 2005 in association with USGS biological studies conducted at sites near mining and exploration regions in southeastern Missouri. Biological studies are described in part by Besser and others (2006), and Schmitt and others (2007a, 2007b). The primary objectives of this report are to assess the magnitude, geographic range, temporal variation, and bioavailability of mining-related metals in water and sediment, and to provide baseline data for locations in exploration areas. Materials and Methods Chronology of Sites and Sampling Matrices Biologic sampling was initiated in 2001, sampling of sediment and water began in 2002, and sampling of all matrices continued through July 2005. Sampling sites are shown in figures 1 and 2; the sampling matrices that were collected for each year and site are summarized in table 1. Descriptions of sampling sites potentially affected by mining activities are listed in table 2. Sampling conducted from 2001 to 2003 included a broad geographic area, whereas sampling conducted in 2004 and 2005 was limited to a few streams, but with more sampling locations in each stream. A brief summary of the chemical measurements performed on the abiotic components associated with these biological studies follows. Fine sediment samples were collected from Clearwater Lake (fig. 1) in July 2002, and from streams in the Black River Basin upstream from Clearwater Lake in July 2002, and August 2004. Composite samples of these sediments were transported to the laboratory for toxicity testing with sediment (2002 and 2004) and sediment interstitial (pore) water (2002). Sediments from the 2002 collection were analyzed for total recoverable metals of cadmium (Cd), Cu, Ni, Pb, Zn, thallium (Tl), acid-volatile sulfide (AVS), and simultaneously extracted metals (SEM) including Cd, Cu, Ni, Pb and Zn. Overlying water and pore water also were sampled periodically during the toxicity tests and analyzed for selected metals. For 2004 sediments, analyses included Cd, Co, Ni, Pb and Zn in sediments, laboratory-prepared pore waters, and in porewater sampling probes. Pore waters obtained from the 2004 sediments also were analyzed for selected major and min

Assessment of elemental concentrations in streams of the New Lead Belt in southeastern Missouri, 2002-05