Correlating effluent concentrations and bench-scale experiments to assess the transformation of endocrine active compounds in wastewater by UV or chlorination disinfection.

Transformation of endocrine active compounds (EACs) by either chlorination (Cl-D) or UV disinfection (UV-D) was studied by field sampling and bench-scale validation studies. Field testing assessed concentration of 13 EACs in effluent at two Chicago area 250 MGD wastewater reclamation plants (WRP) over two years. One WRP uses chlorination/dechlorination while the other employs UV disinfection. Target compounds included bupropion, carbamazepine, citalopram, duloxetine, estradiol, estrone, fluoxetine, nonylphenol, norfluoxetine, norsertraline, paroxetine, sertraline, and venlafaxine. Concentrations of 9/13 target compounds were partially reduced after disinfection (5-65% reduction). None of the target compounds were fully transformed by either chlorination or UV treatment at the WRP scale. In bench-scale experiments each compound was spiked into deionized water or effluent and treated in a process mimicking plant-scale disinfection to validate transformations. Correlation was observed between compounds that were transformed in bench-testing and those that decreased in concentration in post-disinfection WRP effluent (10/13 compounds). A survey of potential reaction products was made. Chlorination of some amine containing compounds produced chloramine by-products that reverted to the initial form after dechlorination. Transformation products produced upon simulated UV disinfection were more diverse. Laboratory UV-induced transformation was generally more effective under stirred conditions, suggesting that indirect photo-induced reactions may predominate over direct photolysis.

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: I. Patterns of occurrence.

Human activities introduce a variety of chemicals to the Laurentian Great Lakes including pesticides, pharmaceuticals, flame retardants, plasticizers, and solvents (collectively referred to as contaminants of emerging concern or CECs) potentially threatening the vitality of these valuable ecosystems. We conducted a basin-wide study to identify the presence of CECs and other chemicals of interest in 12 U.S. tributaries to the Laurentian Great Lakes during 2013 and 2014. A total of 292 surface-water and 80 sediment samples were collected and analyzed for approximately 200 chemicals. A total of 32 and 28 chemicals were detected in at least 30% of water and sediment samples, respectively. Concentrations ranged from 0.0284 (indole) to 72.2 (cholesterol) µg/L in water and 1.75 (diphenhydramine) to 20,800 µg/kg (fluoranthene) in sediment. Cluster analyses revealed chemicals that frequently co-occurred such as pharmaceuticals and flame retardants at sites receiving similar inputs such as wastewater treatment plant effluent. Comparison of environmental concentrations to water and sediment-quality benchmarks revealed that polycyclic aromatic hydrocarbon concentrations often exceeded benchmarks in both water and sediment. Additionally, bis(2-ethylhexyl) phthalate and dichlorvos concentrations exceeded water-quality benchmarks in several rivers. Results from this study can be used to understand organism exposure, prioritize river basins for future management efforts, and guide detailed assessments of factors influencing transport and fate of CECs in the Great Lakes Basin.

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: II. Biological consequences of exposure.

The Laurentian Great Lakes contain one fifth of the world's surface freshwater and have been impacted by human activity since the Industrial Revolution. In addition to legacy contaminants, nitrification and invasive species, this aquatic ecosystem is also the recipient of Contaminants of Emerging Concern (CECs) with poorly understood biological consequences. In the current study, we documented the presence, concentrations, and biological effects of CECs across 27 field sites in six Great Lakes tributaries by examining over 2250 resident and caged sunfish (Lepomis ssp.) for a variety of morphological and physiological endpoints and related these results to CEC occurrence. CEC were ubiquitous across studies sites and their presence and concentrations in water and sediment were highest in effluent dominated rivers and downstream of municipal wastewater treatment plant discharges. However, even putative upstream reference sites were not free of CEC presence and fish at these sites exhibited biological effects consistent with CEC exposure. Only the Fox River exhibited consistent adverse biological effects, including increased relative liver size, greater prominence of hepatocyte vacuoles and increased plasma glucose concentrations. Canonical Redundancy Analysis revealed consistent patterns of biological consequences of CEC exposure across all six tributaries. Increasing plasma glucose concentrations, likely as a result of pollutant-induced metabolic stress, were associated with increased relative liver size and greater prominence of hepatocyte vacuoles. These indicators of pollutant exposure were inversely correlated with indicators of reproductive potential including smaller gonad size and less mature gametes. The current study highlights the need for greater integration of chemical and biological studies and suggests that CECs in the Laurentian Great Lakes Basin may adversely affect the reproductive potential of exposed fish populations.

Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions.

Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds, with the highest concentrations occurring in streams with the greatest WWTP effluent content. Biomarkers of endocrine disruption in the fish indicated long-term exposure to estrogenic chemicals in the wastewater impacted urban waterways.

Environmental estrogens in an urban aquatic ecosystem: I. Spatial and temporal occurrence of estrogenic activity in effluent-dominated systems.

The present study investigated occurrence of environmental estrogens (EEs) in waterways managed by the Metropolitan Water Reclamation District of Greater Chicago ('District') - one of the largest and most complex water districts in the United States. The objectives of the study were: (i) to document spatial and temporal occurrence of EEs in the Chicago Area Waterways (CAWs); (ii) to determine whether water reclamation plant (WRP) effluents contribute to estrogenic pollution of the receiving streams; (iii) to determine whether the mandated water quality monitoring data could be used to predict estrogenic pollution in the receiving streams; and (iv) to determine whether snow melt, storm runoff and combined sewer overflows may also be contributors of estrogenic activity to these systems. The estrogenic potency of the waterways was assessed using a cell-based reporter gene assay. The water quality data was readily available as part of the District's regular monitoring program. Our findings indicate that EEs are commonly found in the CAWs, and that WRP effluents are one of, but not the only important contributor to estrogenic activity. Mean estrogenic activities in CAWs (11ng estradiol equivalents (EEQs/L)) are well within the values reported for other urban areas and WRP effluents. The estrogenic activity exhibited significant seasonal variation with highest values noted during the spring and summer months. When comparing the mean estrogenic activity of general use waters, secondary contact waters and WRP effluents, we found that general use waters had significantly lower estrogenic activity (ca 5ng EEQ/L) than the other two matrices (ca 15 and 17ng EEQ/L respectively). Our analyses indicate that estrogenic activity of the waterways was not reliably associated with mandated water quality parameters, and that such measurements may not be useful for predicting estrogenic activity, especially so in the complex urban systems. One of the prominent findings of this study is that EEs do not follow predictable spatial patterns - many of the upstream sites in the heavily urbanized areas had levels of estrogenic activity comparable to those found in the effluents and downstream locations. Our data suggest that surface runoff and snow melt are estrogenic (0-9ng EEQ/L), and given that their estrogenic activities are similar to those of their receiving waterways (0-7ng EEQ/L), we conclude that these non-WRP sources are important contributors to estrogenic activity of the CAWs.

Environmental estrogens in an urban aquatic ecosystem: II. Biological effects.

Urban aquatic ecosystems are often overlooked in toxicological studies even though they serve many ecosystem functions and sustain fish populations despite large-scale habitat alterations. However, urban fish populations are likely exposed to a broad range of stressors, including environmental estrogens (EEs) that may affect anatomy, physiology and reproduction of exposed fish. Although significant progress has been made in establishing ecological consequences of EE exposure, these studies have focused largely on hydrologically simple systems that lack the complexity of urban aquatic environments. Therefore, the objective of this study was to assess the occurrence and biological effects of EEs across a large urbanized aquatic ecosystem. A multi-pronged study design was employed relying on quantitative determination of select EEs by liquid chromatography tandem mass spectrometry and repeated biological monitoring of wild-caught and caged fish for indications of endocrine disruption. Over three years, EEs were measured in aqueous samples (n=42 samples) and biological effects assessed in >1200 male fish across the 2000km(2) aquatic ecosystems of the Greater Metropolitan Area of Chicago, IL. Our study demonstrated that in addition to water reclamation plant (WRP) effluents, non-WRP sources contribute significant EE loads to the aquatic ecosystem. While resident and caged male fish responded with the induction of the egg-yolk protein vitellogenin, an indicator of EE exposure, neither resident nor caged sunfish exhibited prevalent histopathological changes to their reproductive organs (i.e., intersex) that have been reported in other studies. Vitellogenin induction was greater in spring than the fall and was not correlated with body condition factor, gonadosomatic index or hepatosomatic index. Exposure effects were not correlated with sites downstream of treated effluent discharge further affirming the complexity of sources and effects of EEs in urban aquatic ecosystems.