Optimized suspect screening approach for a comprehensive assessment of the impact of best management practices in reducing micropollutants transport in the Potomac River watershed.

The vast number of chemicals potentially reaching aquatic environment pose a challenge in maintaining the quality of water resources. However, best management practices to improve water quality are typically focused on reducing nutrient transport without assessing how these practices may impact the occurrence of micropollutants. The potential for co-management of nutrients and organic micropollutants exists, but few studies have comprehensively evaluated the suite of contaminants associated with different water quality management practices (riparian zone restoration, stormwater management, etc.). Furthermore, most studies dealing with the determination of micropollutants in environmental samples include only a limited number of target analytes, leaving many contaminants undetected. To address this limitation, there has been a gradual shift in environmental monitoring from using target analysis to either suspect screening analysis (SSA) or non-targeted analysis (NTA), which relies on accurate mass measurements, mass spectral fragmentation patterns, and retention time information obtained using liquid chromatography coupled to high-resolution mass spectrometry. The work presented in this paper focuses on a wide-scope detection of micropollutants in surface water samples from the Potomac River watershed (United States). An in-house database composed of 1039 compounds based on experimental analysis of primary standards was established, and SSA workflow was optimized and applied to determine the presence of micropollutants in surface water. A total of 103 micropollutants were detected in the samples, some of which are contaminants that were not previously monitored and belong to various classes such as pharmaceuticals, personal care products, per-and polyfluoroalkyl substances and other persistent industrial chemicals. The impact of best management practices being implemented for nitrogen and phosphorus reductions were also assessed for their potential to reduce micropollutant transport. This work illustrates the advantages of suspect screening methods to determine a large number of micropollutants in environmental samples and reveals the potential to co-manage a diverse array of micropollutants based on shared transport and transformation mechanisms in watersheds.

Evidence that watershed nutrient management practices effectively reduce estrogens in environmental waters.

We evaluate the impacts of different nutrient management strategies on the potential for co-managing estrogens and nutrients in environmental waters of the Potomac watershed of the Chesapeake Bay. These potential co-management approaches represent agricultural and urban runoff, wastewater treatment plant effluent, and combined sewer overflow replacements. Twelve estrogenic compounds and their metabolites were analysed by gas chromatography-mass spectrometry. Estrogenic activity (E2Eq) was measured by in vitro bioassay. We detected estrone E1 (0.05-6.97 ng L-1) and estriol E3 (below detection-8.13 ng L-1) and one conjugated estrogen (estrone-3-sulfate E1-3S; below detection-8.13 ng L-1). E1 was widely distributed and positively correlated with E2Eq, water temperature, and dissolved organic carbon (DOC). Among nonpoint sources, E2Eq, and concentrations of E1, soluble reactive phosphorus (SRP) and total dissolved nitrogen (TDN) decreased by 51-61%, 77-82%, 62-64%, 4-16% in restored urban and agricultural streams with best management practices (BMPs) relative to unrestored streams without BMPs. In a wastewater treatment plant (Blue Plains WWTP), >94% of E1, E1-3S, E3, E2Eq and TDN were removed while SRP increased by 305% during nitrification/denitrification as a part of advanced wastewater treatment. Consequently, E1 and TDN concentrations in WWTP effluents were comparable or even lower than those observed in the receiving stream or river waters, and the effects of wastewater discharges on downstream E1 and TDN concentrations were minor. Highest E2Eq value and concentrations of E1, E3, and TDN were detected in combined sewer overflow (CSO). This study suggests that WWTP upgrades with biological nutrient removal, CSO management, and certain agricultural and urban BMPs for nutrient controls have the potential to remove estrogens from point and nonpoint sources along with other contaminants in streams and rivers.

Delayed Release of Intracellular Microcystin Following Partial Oxidation of Cultured and Naturally Occurring Cyanobacteria.

Oxidation processes can provide an effective barrier to eliminate cyanotoxins by damaging cyanobacteria cell membranes, releasing intracellular cyanotoxins, and subsequently oxidizing these toxins (now in extracellular form) based on published reaction kinetics. In this work, cyanobacteria cells from two natural blooms (from the United States and Canada) and a laboratory-cultured Microcystis aeruginosa strain were treated with chlorine, monochloramine, chlorine dioxide, ozone, and potassium permanganate. The release of microcystin was measured immediately after oxidation (t ≤ 20 min), and following oxidant residual quenching (stagnation times = 96 or 168 h). Oxidant exposures (CT) were determined resulting in complete release of intracellular microcystin following chlorine (21 mg-min/L), chloramine (72 mg-min/L), chlorine dioxide (58 mg-min/L), ozone (4.1 mg-min/L), and permanganate (391 mg-min/L). Required oxidant exposures using indigenous cells were greater than lab-cultured Microcystis. Following partial oxidation of cells (oxidant exposures ≤ CT values cited above), additional intracellular microcystin and dissolved organic carbon (DOC) were released while the samples remained stagnant in the absence of an oxidant (>96 h after quenching). The delayed release of microcystin from partially oxidized cells has implications for drinking water treatment as these cells may be retained on a filter surface or in solids and continue to slowly release cyanotoxins and other metabolites into the finished water.

External Standard Calibration Method To Measure the Hydroxyl Radical Scavenging Capacity of Water Samples.

The hydroxyl radical (•OH) scavenging capacity is a useful parameter for the design and operation of an advanced oxidation process (AOP) in water treatment. The scavenging capacity may change with time, and it would be useful to continuously measure this change to be able to optimize AOP doses. In this study, we first reviewed current methods for scavenging capacity measurement to identify strengths and weaknesses of each method. This information helped guide the design of an external calibration method to allow straightforward laboratory and field measurement of •OH scavenging capacity. The method used low-pressure UV/H2O2 as the •OH generation system, methylene blue (MB) as the probe compound, and isopropyl alcohol (IPA) as the standard. By monitoring, offline, the color decay of MB in a series of IPA solutions with different scavenging capacity, a calibration curve was established between the color decay rate and the scavenging capacity. The measured color decay in real water samples can then be used with this external calibration to estimate their scavenging capacity. Work was undertaken to ensure that the process would be robust under a wide range of water quality conditions. Parallel tests using this method compared with the benchmark methods confirmed its robustness and accuracy.

Mathematical modeling of biologically active filtration (BAF) for potable water production applications.

In this study, a modeling framework was developed to simulate biologically active filtration (BAF) headloss buildup in response to organic removal and nitrification. This model considered not only the biofilm growth on the BAF media but also the particle deposition in the BAF bed. In addition, the model also took temperature effect into consideration. It was calibrated and validated with data collected from a pilot-scale study used for potable water reuse and a full-scale facility used for potable water treatment. The model prediction provided insights that biofilm growth rather than particle deposition primarily contributes to the headloss buildup. Therefore, biofilm control is essential for managing headloss buildup and reducing the backwash frequency. Model simulation indicated that the BAF performance in terms of pollutant removal per unit headloss is insensitive to the BAF bed depth but can be effectively improved by increasing the media size. The partial biofilm coverage of the media is confirmed in this study and was mathematically verified to be a prerequisite for the model fitness.

Varied influence of microcystin structural difference on ELISA cross-reactivity and chlorination efficiency of congener mixtures.

Enzyme-linked immunosorbent assay (ELISA) is an antibody-based analytical method that has been widely applied in water treatment utilities for the screening of toxic cyanobacteria metabolites such as microcystins (MCs). However, it is unknown how the minor structural difference of MCs may impact their chlorination kinetics and measurement via ELISA method. It was found in this study that, regardless of the experimental conditions (n = 21), there was no MC-YR or MC-LY residual, while different removal rates of other MCs were observed (MC-RR > MC-LR > MC-LA âˆ¼ MC-LF) as measured by liquid chromatography tandem mass spectrometry (LC-MS/MS), which was consistent with the relative reactivity of the amino acid variables with free chlorine. The removal of total MCs was generally lower as measured by ELISA than by LC-MS/MS. By incorporating both analytical results, existence of ADDA-containing byproducts or byproducts that had a higher sensitivity toward the ELISA kit was demonstrated, after excluding the contribution of the cross-reactivity of the parent MCs. It should be noted, however, that the cross-reactivities of MCs could be influenced not only by MC congeners, but also by other conditions such as mixtures and the applied ELISA kit.

Effect of advanced oxidation on N-nitrosodimethylamine (NDMA) formation and microbial ecology during pilot-scale biological activated carbon filtration.

Water treatment combining advanced oxidative processes with subsequent exposure to biological activated carbon (BAC) holds promise for the attenuation of recalcitrant pollutants. Here we contrast oxidation and subsequent biofiltration of treated wastewater effluent employing either ozone or UV/H2O2 followed by BAC during pilot-scale implementation. Both treatment trains largely met target water quality goals by facilitating the removal of a suite of trace organics and bulk water parameters. N-nitrosodimethylamine (NDMA) formation was observed in ozone fed BAC columns during biofiltration and to a lesser extent in UV/H2O2 fed columns and was most pronounced at 20 min of empty bed contact time (EBCT) when compared to shorter EBCTs evaluated. While microbial populations were highly similar in the upper reaches, deeper samples revealed a divergence within and between BAC filtration systems where EBCT was identified to be a significant environmental predictor for shifts in microbial populations. The abundance of Nitrospira in the top samples of both columns provides an explanation for the oxidation of nitrite and corresponding increases in nitrate concentrations during BAC transit and support interplay between nitrogen cycling with nitrosamine formation. The results of this study demonstrate that pretreatments using ozone versus UV/H2O2 impart modest differences to the overall BAC microbial population structural and functional attributes, and further highlight the need to evaluate NDMA formation prior to full-scale implementation of BAC in potable reuse applications.

UV/H2O2 degradation of endocrine-disrupting chemicals in water evaluated via toxicity assays.

Due to rising concern regarding the presence of endocrine-disrupting chemicals (EDCs) in surface water and groundwater throughout the United States, Asia and Europe, treatment of these chemicals in drinking water and wastewater to protect human health and the environment is an area of great interest. Many conventional treatment schemes are relatively ineffective in removing EDCs from water and wastewater. This is concerning because these chemicals are biologically active at very low concentrations and effects of mixtures are relatively unknown. 17-alpha-oestradiol (E2) and 17-beta-ethinyl-oestradiol (EE2), suspected EDCs, were degraded significantly by the UV/H2O2 AOP. The UV/H2O2 processes using either low or medium pressure lamps were degraded EDCs by between 80 and 99.3% at a 15 ppm H2O2 concentration and a UV dose of 1,000 mJ/cm2. Significantly greater removal was noted when the removal was based on total oestrogenic activity using a yeast oestrogen screen (YES) assay. These data indicated that a dose of less than 200 mJ/cm2 completely removed oestrogenic activity in lab water. Values for natural waters were slightly higher. A steady state model was developed to determine EDC destruction efficiency in waters of differing quality. The model effectively predicted destruction in water, where concentrations of all scavenging species were known. Based on these results it was concluded than complete destruction of oestrogenic activity was possible under practical advanced oxidation conditions for a variety of water qualities.

Destruction of estrogenic activity in water using UV advanced oxidation.

The transformation of the steroidal Endocrine Disrupting Compounds (EDCs), 17-beta-estradiol (E2) and 17-alpha-ethinyl estradiol (EE2) by direct UV photolysis and UV/H(2)O(2) advanced oxidation was studied from the perspective of the removal of estrogenic activity associated with the compounds. First, experiments were performed to link the oxidation of E2 and EE2 with subsequent reduction in estrogenic activity. No statistically significant difference between removal rates was observed, implying that the oxidation products of E2 and EE2 are not as estrogenic (measured by the Yeast Estrogen Screen (YES)) as the parent compounds. Utilizing the YES, 90% removal of estrogenic activity of E2 and EE2 at environmentally relevant concentrations ( approximately 3 microg L(-1)) was achieved using a combination of 5 mg L(-1) H(2)O(2) and a UV fluence of less than 350 mJ cm(-2). Thus, these compounds, when considered at environmentally relevant levels, are significantly degraded at much lower UV fluences than previously thought. A steady state OH radical model was used to predict oxidation of EE2 in laboratory and natural waters.

Biological assessments of a mixture of endocrine disruptors at environmentally relevant concentrations in water following UV/H2O2 oxidation.

Numerous studies have investigated degradation of individual endocrine disrupting compounds (EDCs) in lab or natural waters. However, natural variations in water matrices and mixtures of EDCs in the environment may confound analysis of the treatment efficiency. Because chemical based analytical methods cannot represent the combined or synergistic activities between water quality parameters and/or the EDC mixtures at environmentally relevant concentrations (microg L(-1)-ng L(-1)), bioanalytical assessments of residual estrogenic activity in treated water were used to evaluate the performance of the UV based advanced oxidation process for estrogenic contaminants in water. Four EDCs including estradiol (E(2)), ethinyl estradiol (EE(2)), bisphenol-A (BPA) and nonylphenol (NP) were spiked individually or as a mixture at mug L(-1)-ng L(-1) in laboratory or natural river water. The removal rates of estrogenic activity were quantitatively evaluated by in vitro yeast estrogen screen (YES) and in vivo Vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). UV in combination with 10 ppm H(2)O(2) as an oxidation process was capable of decreasing in vitro and in vivo estrogenic activity, however, in vivo estrogenic activity of the EDC mixture in natural water was not completely removed at UV fluence up to 2000 mJ cm(-2). The removal rates of in vitro estrogenic activity of the EDC mixtures were lower than those observed for single compounds, and slower in natural waters, likely due to lower steady-state concentrations of hydroxyl radicals (*OH) in the presence of *OH scavengers from the water matrix and EDC mixture.

Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2.

Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios.

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation.

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.

Degradation of endocrine disrupting chemicals bisphenol A, ethinyl estradiol, and estradiol during UV photolysis and advanced oxidation processes.

The degradation of three endocrine disrupting chemicals (EDCs), bisphenol A, ethinyl estradiol, and estradiol, was investigated via ultraviolet (UV) radiation photolysis and the UV/hydrogen peroxide advanced oxidation process (AOP). These EDCs have been detected at low levels in wastewaters and surface waters in both the United States and European countries, can cause adverse effects on humans and wildlife via interactions with the endocrine system, and thus must be treated before entering the public drinking water supply. Because many EDCs can only be partially removed with conventional water treatment systems, there is a need to evaluate alternative treatment processes. For each EDC tested, direct UV photolysis quantum yields were derived for use with both monochromatic low-pressure (LP) UV lamps and polychromatic medium-pressure (MP) UV lamps and second-order hydroxyl radical rate constants were developed. These parameters were utilized to successfully model UV treatment of the EDCs in laboratory and natural waters. The polychromatic MP UV radiation source was more effective for direct photolysis degradation as compared to conventional LP UV lamps emitting monochromatic UV 254 nm radiation. However, in all cases the EDCs were more effectively degraded utilizing UV/H2O2 advanced oxidation as compared to direct UV photolysis treatment.