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An assessment of organic chemicals and aquatic toxicity in streams located near Milwaukee, Wisconsin, indicated high potential for adverse impacts on aquatic organisms that could be related to organic waste compounds (OWCs). OWCs used in agriculture, industry, and households make their way into surface waters through runoff, leaking septic-conveyance systems, regulated and unregulated discharges, and combined sewage overflows, among other sources. Many of these compounds are toxic at elevated concentrations and (or) known to have endocrine-disrupting potential, and often they occur as complex mixtures. There is still much to be learned about the chronic exposure effects of these compounds on aquatic populations. During 2006–9, the U.S. Geological Survey, in cooperation with the Milwaukee Metropolitan Sewerage District (MMSD), conducted a study to determine the occurrence and potential toxicity of OWCs in different stream compartments and flow regimes for streams in the Milwaukee area. Samples were collected at 17 sites and analyzed for a suite of 69 OWCs. Three types of stream compartments were represented: water column, streambed pore water, and streambed sediment. Water-column samples were subdivided by flow regime into stormflow and base-flow samples. One or more compounds were detected in all 196 samples collected, and 64 of the 69 compounds were detected at least once. Base-flow samples had the lowest detection rates, with a median of 12 compounds detected per sample. Median detection rates for stormflow, pore-water, and sediment samples1 were more than double that of base-flow samples. Compounds with the highest detection rates include polycyclic aromatic hydrocarbons (PAHs), insecticides, herbicides, and dyes/pigments. 1 U.S. Geological Survey, Wisconsin Water Science Center 2 U.S. Geological Survey, Iowa Water Science Center 3 Wisconsin State Laboratory of Hygiene 4 Milwaukee Metropolitan Sewerage District Elevated occurrence and concentrations of some compounds were detected in samples from urban sites, as compared with more rural sites, especially during stormflow conditions. These include the PAHs and the domestic wastewater-indicator compounds, among others. Urban runoff and storm-related leaks of sanitary sewers and (or) septic systems may be important sources of these and other compounds to the streams. The Kinnickinnic River, a highly urbanized site, had the highest detection rates and concentrations of compounds of all the sampled sites. The Milwaukee River near Cedarburg— one of the least urban sites—and the Outer Milwaukee Harbor site had the lowest detection rates and concentrations. Aquatic-toxicity benchmarks were exceeded for 12 of the 25 compounds with known benchmarks. The compounds with the greatest benchmark exceedances were the PAHs, both in terms of exceedance frequency (up to 93 percent for some compounds in sediment samples) and magnitude (concentrations up to 1,024 times greater than the benchmark value). Other compounds with toxicity-benchmark exceedances include Bis(2-ethylhexyl) phthalate (a plasticizer), 2-Methylnapthalene (a component of fuel and oil), phenol (an antimicrobial disinfectant with diverse uses), and 4-Nonylphenol (sum of all isomers; a detergent metabolite, among other uses). Analyzed as a mixture, the suite of PAH compounds were found to be potentially toxic for most non-base-flow samples. Bioassay tests were conducted on samples from 14 streams: Ceriodaphnia dubia in base-flow samples, Ceriodaphnia dubia and Hyallela azteca in pore-water samples, and Hyallela azteca and Chironomus tentans in sediment samples. The greatest adverse effect was observed in tests with Chironomus tentans from sediment samples. The weight of Chironomus tentans after exposure to sediments decreased with increased OWC concentrations. This was most evident in the relation between PAH results and Chironomus tentans bioassay results for the majority of samples; however, solvents and flame retardants appeared to be important for one site each. These results for PAHs were consistent with assessment of PAH potency factors for sediment, indicating that PAHs were likely to have adverse effects on aquatic organisms in many of the streams studied. 2 Organic Waste Compounds in Streams: Occurrence and Aquatic Toxicity, Southeast Wisconsin, 2006–9 Introduction The occurrence and effects of organic waste compounds (OWCs) in streams has garnered increasing attention in recent years, both within the scientific community and in the popular press (Kolpin and others, 2002; Richardson and Ternes, 2005; Blue, 2012). OWCs are natural or synthetic chemicals derived from domestic, agricultural, and industrial wastewater sources. OWCs include fire retardants, fuel by-products, polycyclic aromatic hydrocarbons (PAHs), herbicides, antimicrobial disinfectants, and flavors and fragrances, among others. These compounds enter the environment through a number of pathways, including washing into streams from impervious surfaces and agricultural fields, industrial discharges into the air or water, leaching into the groundwater from unlined landfills, discharges from wastewater-treatment plants, combined sewer overflows, leaking septic systems, and leaking municipal sanitary and storm sewer systems (Kolpin and others, 2002; Gilliom and others, 2006; Phillips and others, 2012). Numerous recent studies have focused on the health effects of OWCs on aquatic communities (Thorpe and others, 2001; U.S. Environmental Protection Agency, 2003; Barber and others, 2007; Vandenberg and others, 2012; Kemble and others, 2013). Although environmental concentrations tend to be low (generally, in the range of micrograms per liter or nanograms per liter), exposure is often chronic, spanning entire life cycles. Many of the OWCs sampled in this study are known or suspected endocrine-disrupting chemicals (EDCs), meaning they possess hormone-like activity that can disrupt normal endocrine function. EDCs have been shown to disrupt sexual development, brain development, and the immune system, among others (Vandenberg and others, 2012). In aquatic environments, EDCs and other OWCs usually occur as complex mixtures, which may have additive or synergistic effects (Sumpter and Jobling, 1995; Marinovich and others, 1996; Thorpe and others, 2001; U.S. Environmental Protection Agency, 2003; Vandenberg and others, 2012). Chronic, multigenerational exposure of low-concentration mixtures of OWCs may result in incremental and irreversible impacts to aquatic communities (Daughton and Ternes, 1999). In 2006, the U.S. Geological Survey (USGS) and the Milwaukee Metropolitan Sewerage District (MMSD) began a cooperative study of OWCs in Milwaukee area streams and in the Milwaukee Harbor. The goal of the study was to provide an assessment of OWCs and toxicity in different stream compartment and flow regimes, including surface water during base flow and stormflow, streambed pore water, and streambed sediment. During 2006–9, 196 samples were collected from 17 sites: 14 stream sites, 2 harbor sites, and 1 stream/harbor transition site (table 1; fig. 1). Water samples were analyzed for 69 OWCs; sediment samples were analyzed for 57 OWCs. Additionally, water column, pore-water, and sediment samples from the 14 stream sites were analyzed for aquatic toxicity (AqT) using bioassays. This study can assist watershed managers in prioritizing management and remediation efforts by describing OWC occurrences at different sites and in different stream compartments and flow regimes, and by identifying frequently occurring compounds and their potential toxicity to aquatic communities. Purpose and Scope This report presents results of an assessment of OWCs and AqT in different stream compartments (stream water, sediment pore water, and bed sediment) and flow regimes (stormflow and base flow) in aquatic ecosystems within the MMSD service area. Occurrence and concentrations of OWCs are analyzed by sampling site, stream compartment, and flow regime. AqT is assessed by comparing measured concentrations to benchmark values, and by bioassays. This study was part of the Watercourse Corridor Study—Phase III, a cooperative effort among the MMSD, WDNR, SEWRPC, USGS, and local universities. Data from this study builds on data collected during 2004–5 as part of the Watercourse Corridor Study— Phase II (Thomas and others, 2007). Description of Study Area Most sampling sites were within the MMSD planning area. In total, 17 sites were sampled: 14 stream sites, 2 sites in the Milwaukee Harbor (Middle Harbor Milwaukee Outer Harbor Site (OH-03) and Middle Outside Harbor Breakwater Lake Site (OH-14)), and 1 stream/harbor transition site (Milwaukee River at the mouth at Jones Island (MRJ)). The stream/harbor transition site, MRJ, receives water from the Milwaukee, Kinnickinnic, and Menomonee River watersheds, as well as Lake Michigan. Basin-drainage areas of the stream sites (including MRJ) range from 9.56 to 872 square miles (mi2), with annual mean discharges from 13.2 to 735 cubic feet per second (ft3/s) (Scudder Eikenberry and others, 2010; U.S. Geological Survey, 2011). The sampled basins span a broad range of land uses and urban influence, with 10.4 to 96.0 percent urban land use. Of the harbor sites, OH-14 is located outside the break wall and OH-03 is located inside the break wall, approximately midway between the break wall and the mouth of the Milwaukee River.

scientific investigations report

Organic waste compounds in streams: Occurrence and aquatic toxicity in different stream compartments, flow regimes, and land uses in southeast Wisconsin, 2006–9