The potential for polycyclic aromatic hydrocarbon (PAH)-related effects in benthic organisms is commonly estimated from organic carbon-normalized sediment concentrations based on equilibrium partitioning (EqP). Although this approach is useful for screening purposes, it may overestimate PAH bioavailability by orders of magnitude in some sediments, leading to inflated exposure estimates and potentially unnecessary remediation costs. Recently, passive samplers have been shown to provide an accurate assessment of the freely dissolved concentrations of PAHs, and thus their bioavailability and possible biological effects, in sediment porewater and overlying surface water. We used polyethylene passive sampling devices (PEDs) to measure freely dissolved porewater and water column PAH concentrations at 55 Great Lakes (USA/Canada) tributary locations. The potential for PAH-related biological effects using PED concentrations were estimated with multiple approaches by applying EqP, water quality guidelines, and pathway-based biological activity based on in vitro bioassay results from ToxCast. Results based on the PED-based exposure estimates were compared with EqP-derived exposure estimates for concurrently collected sediment samples. The results indicate a potential overestimation of bioavailable PAH concentrations by up to 960-fold using the EqP-based method compared with measurements using PEDs. Even so, PED-based exposure estimates indicate a high potential for PAH-related biological effects at 14 locations. Our findings provide an updated, weight-of-evidence-based site prioritization to help guide possible future monitoring and mitigation efforts. Environ Toxicol Chem 2024;43:1509-1523. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Human sewage contaminates waterways, delivering excess nutrients, pathogens, chemicals, and other toxic contaminants. Contaminants and various sewage indicators are measured to monitor and assess water quality, but these analytes vary in their representation of sewage contamination and the inferences about water quality they support. We measured the occurrence and concentration of multiple microbiological (n = 21) and chemical (n = 106) markers at two urban stream locations in Milwaukee, Wisconsin, USA over two years. Five-day composite water samples (n = 98) were collected biweekly, and sewage influent samples (n = 25) were collected monthly at a Milwaukee, WI water reclamation facility. We found the vast majority of markers were not sensitive enough to detect sewage contamination. To compare analytes for monitoring applications, five consistently detected human sewage indicators were used to evaluate temporal patterns of sewage contamination, including microbiological (pepper mild mottle virus, human Bacteroides, human Lachnospiraceae) and chemical (acetaminophen, metformin) markers. The proportion of human sewage in each stream was estimated using the mean influent concentration from the water reclamation facility and the mean concentration of all stream samples for each sewage indicator marker. Estimates of instream sewage pollution varied by marker, differing by up to two orders of magnitude, but four of the five sewage markers characterized Underwood Creek (mean proportions of human sewage ranged 0.0025 % - 0.075 %) as less polluted than Menomonee River (proportions ranged 0.013 % - 0.14 %) by an order of magnitude more. Chemical markers correlated with each other and yielded higher estimates of sewage pollution than microbial markers, which exhibited greater temporal variability. Transport, attenuation, and degradation processes can influence chemical and microbial markers differently and cause variation in human sewage estimates. Given the range of potential human and ecological health effects of human sewage contamination, robust characterization of sewage contamination that uses multiple lines of evidence supports monitoring and research applications.

Human sewage contamination of waterways is a major issue in the United States and throughout the world. Models were developed for estimation of two human-associated fecal-indicator and three general fecal-indicator bacteria (HIB and FIB) using in situ optical field-sensor data for estimating concentrations and loads of HIB and FIB and the extent of sewage contamination in the Menomonee River in Milwaukee, Wisconsin. Three commercially available optical sensor platforms were installed into an unfiltered custom-designed flow-through system along with a refrigerated automatic sampler at the Menomonee River sampling location. Ten-minute optical sensor measurements were made from November 2017 to December 2018 along with the collection of 153 flow-weighted discrete water samples (samples) for HIB, FIB, dissolved organic carbon (DOC), and optical properties of water. Of those 153 samples, 119 samples were from event-runoff periods, and 34 were collected during low-flow periods. Of the 119 event-runoff samples, 43 samples were from event-runoff combined sewer overflow (CSO) influenced periods (event-CSO periods). Models included optical sensor measurements as explanatory variables with a seasonal variable as an interaction term. In some cases, separate models for event-CSO periods and non CSO-periods generally improved model performance, as compared to using all the data combined for estimates of FIB and HIB. Therefore, the CSO and non-CSO models were used in final estimations for CSO and non-CSO time periods, respectively. Estimated continuous concentrations for all bacteria markers varied over six orders of magnitude during the study period. The greatest concentrations, loads, and proportion of sewage contamination occurred during event-runoff and event-CSO periods. Comparison to water quality standards and microbial risk assessment benchmarks indicated that estimated bacteria levels exceeded recreational water quality criteria between 34 and 96% of the entire monitoring period, highlighting the benefits of high-frequency monitoring compared to traditional grab sample collection. The application of optical sensors for estimation of HIB and FIB markers provided a thorough assessment of bacterial presence and human health risk in the Menomonee River.

In a study of 44 diverse sampling sites across 16 Great Lakes tributaries, 110 pharmaceuticals were detected of 257 monitored. The present study evaluated the ecological relevance of detected chemicals and identified heavily impacted areas to help inform resource managers and guide future investigations. Ten pharmaceuticals (caffeine, nicotine, albuterol, sulfamethoxazole, venlafaxine, acetaminophen, carbamazepine, gemfibrozil, metoprolol, and thiabendazole) were distinguished as having the greatest potential for biological effects based on comparison to screening‐level benchmarks derived using information from two biological effects databases, the ECOTOX Knowledgebase and the ToxCast database. Available evidence did not suggest substantial concern for 75% of the monitored pharmaceuticals, including 147 undetected pharmaceuticals and 49 pharmaceuticals with screening‐level alternative benchmarks. However, because of a lack of biological effects information, screening values were not available for 51 detected pharmaceuticals. Samples containing the greatest pharmaceutical concentrations and having the highest detection frequencies were from Lake Erie, southern Lake Michigan, and Lake Huron tributaries. Samples collected during low‐flow periods had higher pharmaceutical concentrations than those collected during increased‐flow periods. The wastewater‐treatment plant effluent content in streams correlated positively with pharmaceutical concentrations. However, deviation from this correlation demonstrated that secondary factors, such as multiple pharmaceutical sources, were likely present at some sites. Further research could investigate high‐priority pharmaceuticals as well as those for which alternative benchmarks could not be developed. Environ Toxicol Chem 2022;41:2221–2239. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For the present study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes (USA/Canada) tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations with established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and with high-throughput toxicity screening data from the US Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several PAHs. Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. The results provide a screening-level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur. Environ Toxicol Chem 2022;41:1016-1041. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Relations between spectral absorbance and fluorescence properties of water and human-associated and fecal indicator bacteria were developed for facilitating field sensor applications to estimate wastewater contamination in waterways. Leaking wastewater conveyance infrastructure commonly contaminates receiving waters. Methods to quantify such contamination can be time consuming, expensive, and often nonspecific. Human-associated bacteria are wastewater specific but require discrete sampling and laboratory analyses, introducing latency. Human sewage has fluorescence and absorbance properties different than those of natural waters. To assist real-time field sensor development, this study investigated optical properties for use as surrogates for human-associated bacteria to estimate wastewater prevalence in environmental waters. Three spatial scales were studied: Eight watershed-scale sites, five subwatershed-scale sites, and 213 storm sewers and open channels within three small watersheds (small-scale sites) were sampled (996 total samples) for optical properties, human-associated bacteria, fecal indicator bacteria, and, for selected samples, human viruses. Regression analysis indicated that bacteria concentrations could be estimated by optical properties used in existing field sensors for watershed and subwatershed scales. Human virus occurrence increased with modeled human-associated bacteria concentration, providing confidence in these regressions as surrogates for wastewater contamination. Adequate regressions were not found for small-scale sites to reliably estimate bacteria concentrations likely due to inconsistent local sanitary sewer inputs.

Polycyclic aromatic hydrocarbons (PAHs) are among the most widespread and potentially toxic contaminants in Great Lakes (USA/Canada) tributaries. The sources of PAHs are numerous and diverse, and identifying the primary source(s) can be difficult. The present study used multiple lines of evidence to determine the likely sources of PAHs to surficial streambed sediments at 71 locations across 26 Great Lakes Basin watersheds. Profile correlations, principal component analysis, positive matrix factorization source-receptor modeling, and mass fractions analysis were used to identify potential PAH sources, and land-use analysis was used to relate streambed sediment PAH concentrations to different land uses. Based on the common conclusion of these analyses, coal-tar-sealed pavement was the most likely source of PAHs to the majority of the locations sampled. The potential PAH-related toxicity of streambed sediments to aquatic organisms was assessed by comparison of concentrations with sediment quality guidelines. The sum concentration of 16 US Environmental Protection Agency priority pollutant PAHs was 7.4-196 000 µg/kg, and the median was 2600 µg/kg. The threshold effect concentration was exceeded at 62% of sampling locations, and the probable effect concentration or the equilibrium partitioning sediment benchmark was exceeded at 41% of sampling locations. These results have important implications for watershed managers tasked with protecting and remediating aquatic habitats in the Great Lakes Basin. Environ Toxicol Chem 2020;39:1392-1408. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

The spatial distribution, concentration, particle size, and polymer compositions of microplastics in Lake Michigan and Lake Erie sediment were investigated. Fibers/lines were the most abundant of the five particle types characterized. Microplastic particles were observed in all samples with mean concentrations for particles greater than 0.355 mm of 65.2 p kg(-1) in Lake Michigan samples (n = 20) and 431 p kg(-1) in Lake Erie samples (n = 12). Additional analysis of particles with size 0.12500.3549 mm in Lake Erie resulted in a mean concentration of 631 p kg(-1). The majority of polymers in Lake Michigan samples were poly(ethylene terephthalate) (PET), high-density polyethylene (HDPE), and semisynthetic cellulose (S.S. Cellulose), and in Lake Erie samples were S.S. Cellulose, polypropylene (PP), and poly(vinyl chloride) (PVC). Polymer density estimates indicated that 85 and 74% of observed microplastic particles have a density greater than 1.1 g cm(-3) for Lake Michigan and Lake Erie, respectively. The current study provided a multidimensional dataset on the spatial distribution of microplastics in benthic sediment from Lake Michigan and Lake Erie and valuable information for assessment of the fate of microplastics in the Great Lakes.

Microplastic contamination was studied along a freshwater continuum from inland streams to the Milwaukee River estuary to Lake Michigan and vertically from the water surface, water subsurface, and sediment. Microplastics were detected in all 96 water samples and 9 sediment samples collected. Results indicated a gradient of polymer presence with depth: low-density particles decreased from the water surface to the subsurface to sediment, and high-density particles had the opposite result. Polymer identification results indicated that water surface and subsurface samples were dominated by low-density polypropylene particles, and sediment samples were dominated by more dense polyethylene terephthalate particles. Of the five particle-type categories (fragments, films, foams, pellets/beads, and fibers/lines), fibers/lines were the most common particle-type and were present in every water and sediment sample collected. Fibers represented 45% of all particles in water samples and were distributed vertically throughout the water column regardless of density. Sediment samples were dominated by black foams (66%, identified as styrene-butadiene rubber) and to a lesser extent fibers/lines (29%) with approximately 89% of all of the sediment particles coming from polymers with densities greater than 1.1 g cm-3. Results demonstrated that polymer density influenced partitioning between the water surface and subsurface and the underlying surficial sediment and the common practice of sampling only the water surface can result in substantial bias, especially in estuarine, harbor, and lake locations where water surface concentrations tend to overestimate mean water column concentrations.

Fecal contamination from sewage and agricultural runoff is a pervasive problem in Great Lakes watersheds. Most work examining fecal pollution loads relies on discrete samples of fecal indicators and modeling land use. In this study, we made empirical measurements of human and ruminant-associated fecal indicator bacteria and combined these with hydrological measurements in eight watersheds ranging from predominantly forested to highly urbanized. Flow composited river samples were collected over low-flow ( n = 89) and rainfall or snowmelt runoff events ( n = 130). Approximately 90% of samples had evidence of human fecal pollution, with highest loads from urban watersheds. Ruminant indicators were found in ∼60-100% of runoff-event samples in agricultural watersheds, with concentrations and loads related to cattle density. Rain depth, season, agricultural tile drainage, and human or cattle density explained variability in daily flux of human or ruminant indicators. Mapping host-associated indicator loads to watershed discharge points sheds light on the type, level, and possible health risk from fecal pollution entering the Great Lakes and can inform total maximum daily load implementation and other management practices to target specific fecal pollution sources.

Hydrologic, seasonal, and spatial variability of sewage contamination was studied at six locations within a watershed upstream from water reclamation facility (WRF) effluent to define relative loadings of sewage from different portions of the watershed. Fecal pollution from human sources was spatially quantified by measuring two human-associated indicator bacteria (HIB) and eight human-specific viruses (HSV) at six stream locations in the Menomonee River watershed in Milwaukee, Wisconsin from April 2009 to March 2011. A custom, automated water sampler, which included HSV filtration, was deployed at each location and provided unattended, flow-weighted, large-volume (30-913 L) sampling. In addition, wastewater influent samples were composited over discrete 7 day periods from the two Milwaukee WRFs. Of the 8 HSV, only 3 were detected, present in up to 38% of the 228 stream samples, while at least 1 HSV was detected in all WRF influent samples. HIB occurred more often with significantly higher concentrations than the HSV in stream and WRF influent samples ( p < 0.05). HSV yield calculations showed a loss from upstream to the most-downstream sub-watershed of the Menomonee River, and in contrast, a positive HIB yield from this same sub-watershed emphasizes the complexity in fate and transport properties between HSV and HIB. This study demonstrates the utility of analyzing multiple HSV and HIB to provide a weight-of-evidence approach for assessment of fecal contamination at the watershed level, provides an assessment of relative loadings for prioritizing areas within a watershed, and demonstrates how loadings of HSV and HIB can be inconsistent, inferring potential differences in fate and transport between the two indicators of human fecal presence.

Great Lakes tributaries are known to deliver waterborne pathogens from a host of sources. To examine the hydrologic, land cover, and seasonal patterns of waterborne pathogens (i.e. protozoa (2), pathogenic bacteria (4) human viruses, (8) and bovine viruses (8)) eight rivers were monitored in the Great Lakes Basin over 29 months from February 2011 to June 2013. Sampling locations represented a wide variety of land cover classes from urban to agriculture to forest. A custom automated pathogen sampler was deployed at eight sampling locations which provided unattended, flow-weighted, large-volume (120 1630 L) sampling. Human and bovine viruses and pathogenic bacteria were detected by real-time qPCR in 16%, 14%, and 1.4% of 290 samples collected while protozoa were never detected. The most frequently detected pathogens were: bovine polyomavirus (11%), and human adenovirus C, D, F (9%). Human and bovine viruses were present in 16.9% and 14.8% of runoff-event samples (n = 189) resulting from precipitation and snowmelt, and 13.9% and 12.9% of low-flow samples (n = 101), respectively, indicating multiple delivery mechanisms could be influential. Data indicated human and bovine virus prevalence was different depending on land cover within the watershed. Occurrence, concentration, and flux of human viruses were greatest in samples from the three sampling locations with greater than 25% urban influence than those with less than 25% urban influence. Similarly, occurrence, concentration, and flux of bovine viruses were greatest in samples from the two sampling locations with greater than 50 cattle/km(2) than those with less than 50 cattle/km2. In seasonal analysis, human and bovine viruses occurred more frequently in spring and winter seasons than during the fall and summer. Concentration, occurrence, and flux in the context of hydrologic condition, seasonality, and land use must be considered for each watershed individually to develop effective watershed management strategies for pathogen reduction. Published by Elsevier Ltd.

Organic compounds used in agriculture, industry, and households make their way into surface waters through runoff, leaking septic-conveyance systems, regulated and unregulated discharges, and combined sewer overflows, among other sources. Concentrations of these organic waste compounds (OWCs) in some Great Lakes tributaries indicate a high potential for adverse impacts on aquatic organisms. During 2010–13, 709 water samples were collected at 57 tributaries, together representing approximately 41% of the total inflow to the lakes. Samples were collected during runoff and low-flow conditions and analyzed for 69 OWCs, including herbicides, insecticides, polycyclic aromatic hydrocarbons, plasticizers, antioxidants, detergent metabolites, fire retardants, non-prescription human drugs, flavors/fragrances, and dyes. Urban-related land cover characteristics were the most important explanatory variables of concentrations of many OWCs. Compared to samples from nonurban watersheds (<15% urban land cover) samples from urban watersheds (>15% urban land cover) had nearly four times the number of detected compounds and four times the total sample concentration, on average. Concentration differences between runoff and low-flow conditions were not observed, but seasonal differences were observed in atrazine, metolachlor, DEET, and HHCB concentrations. Water quality benchmarks for individual OWCs were exceeded at 20 sites, and at 7 sites benchmarks were exceeded by a factor of 10 or more. The compounds with the most frequent water quality benchmark exceedances were the PAHs benzo[a]pyrene, pyrene, fluoranthene, and anthracene, the detergent metabolite 4-nonylphenol, and the herbicide atrazine. Computed estradiol equivalency quotients (EEQs) using only nonsteroidal endocrine-active compounds indicated medium to high risk of estrogenic effects (intersex or vitellogenin induction) at 10 sites. EEQs at 3 sites were comparable to values reported in effluent. This multifaceted study is the largest, most comprehensive assessment of the occurrence and potential effects of OWCs in the Great Lakes Basin to date.

By transforming fixed nitrogen (N) into nitrogen gas, the biochemical processes that support denitrification provide a function critical to maintaining the integrity of ecosystems subjected to increased loading of N from anthropogenic sources. The Louisiana coastal region receives high nitrate (NO3−) concentrations (>100µM) from the Mississippi–Ohio–Missouri River Basin and is also an area undergoing high rates of wetland loss. Ongoing and anticipated changes in the Louisiana coastal region promise to alter biogeochemical cycles including the net rate of denitrification by ecosystems. Projecting what these changes could mean for coastal water quality and natural resources requires an understanding of the magnitude and patterns of variation in denitrification rates and their connection to estuarine water quality at large temporal and spatial scales under current conditions. We compile and review denitrification rates reported in 32 studies conducted in a variety of habitats across coastal Louisiana during the period 1981– 2008. The acetylene inhibition and 15N flux were the preferred techniques (95%); most of the studies used sediment slurries rather than intact sediment cores. There are no estimates of denitrification rates using the N2/Ar ratio and isotope pairing techniques, which address some of the problems and limitations of the acetylene inhibition and 15N flux techniques. These studies have shown that sediments from estuaries, lakes, marshes, forested wetlands, and the coastal shelf region are capable of high potential denitrification rates when exposed to high NO3− concentrations (>100µM). Maximum potential denitrification rates in experimental and natural settings can reach values >2500µmolm2h−1. The lack of contemporary studies to understand the interactions among critical nitrogen transformations (e.g., organic matter mineralization, immobilization, aquatic plant assimilation, nitrification, nitrogen fixation, dissimilatory nitrate reduction to ammonium (DNRA) and anaerobic ammonium oxidation (annamox) limits our understanding of nitrogen cycling in coastal Louisiana, particularly the role of respiratory and chemolithoautotrophic denitrification in areas undergoing wetland restoration.