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Several studies have demonstrated that air-bubbling and foam fractionation techniques can efficiently remove long-chain PFAS from contaminated water. However, removing short-chain PFAS is challenging due to its lower surface activity and inability to form self-assembly structures at the air-water interface. In this study, we tested various additives, including salts, surfactants, and polymers, to improve short-chain PFAS (e.g., perfluorobutanesulfonic acid (PFBS) and perfluorobutanoic acid (PFBA)) removal in non-foaming solutions using a bench-scale system. We found that in the presence of cetyltrimethylammonium chloride (CTAC) and salt, air-bubbling can significantly remove 0.5 μg L -1 of PFBS and PFBA in deionized water by >99% (15 min) and 81% (60 min), respectively. The decline of surface tension and the formation of thin foam-like layers during bubbling, controlled by the concentration of CTAC, significantly improved the removal of short-chain PFAS. Adding anionic and neutral surfactants showed no removal of short-chain PFAS during bubbling, suggesting the importance of the electrostatic interactions between short-chain PFAS and the cationic CTAC. We observed a 1:1 M ratio between CTAC and PFBS removed from the solution, suggesting the formation of ion pairs in the solution and enhancing the surface activity of the overall neutral (PFAS-CTAC) complex. A mass balance of the system revealed that the primary mechanism by which PFAS was removed from non-foaming waters was through aerosol generation (70-100%). Using the optimized condition, PFAS mixtures (short- and long-chain PFAS, including five recently regulated PFAS by USPEA, 2 nM each) in deionized water and natural groundwater were successfully removed to below detection (>99% removal; <2 ng L -1 ), except for PFBA (25-73% removal). These results provide an improved understanding of the mechanism by which PFAS is removed during foam fractionation and highlight the need for capturing aerosols enriched with PFAS to prevent secondary contamination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) enter the marine food web, accumulate in organisms, and potentially have adverse effects on predators and consumers of seafood. However, evaluations of PFAS in meso-to-apex predators, like sharks, are scarce. This study investigated PFAS occurrence in five shark species from two marine ecosystems with contrasting relative human population densities, the New York Bight (NYB) and the coastal waters of The Bahamas archipelago. The total detected PFAS (∑PFAS) concentrations in muscle tissue ranged from 1.10 to 58.5 ng g -1 wet weight, and perfluorocarboxylic acids (PFCAs) were dominant. Fewer PFAS were detected in Caribbean reef sharks ( Carcharhinus perezi ) from The Bahamas, and concentrations of those detected were, on average, ∼79% lower than in the NYB sharks. In the NYB, ∑PFAS concentrations followed: common thresher ( Alopias vulpinus ) > shortfin mako ( Isurus oxyrinchus ) > sandbar ( Carcharhinus plumbeus ) > smooth dogfish ( Mustelus canis ). PFAS precursors/intermediates, such as 2 H ,2 H ,3 H ,3 H -perfluorodecanoic acid and perfluorooctanesulfonamide, were only detected in the NYB sharks, suggesting higher ambient concentrations and diversity of PFAS sources in this region. Ultralong-chain PFAS (C ≥ 10) were positively correlated with nitrogen isotope values (δ 15 N) and total mercury in some species. Our results provide some of the first baseline information on PFAS concentrations in shark species from the northwest Atlantic Ocean, and correlations between PFAS, stable isotopes, and mercury further contextualize the drivers of PFAS occurrence.

Background: The application of wastewater-based epidemiology to track the outbreak and prevalence of coronavirus disease (COVID-19) in communities has been tested and validated by several researchers across the globe. However, the RNA-based surveillance has its inherent limitations and uncertainties., Objective: This study aims to complement the ongoing wastewater surveillance efforts by analyzing other chemical biomarkers in wastewater to help assess community response (hospitalization and treatment) during the pandemic (2020-2021)., Methods: Wastewater samples (n = 183) were collected from the largest wastewater treatment facility in Suffolk County, NY, USA and analyzed for COVID-19 treatment drugs (remdesivir, chloroquine, and hydroxychloroquine (HCQ)) and their human metabolites. We additionally monitored 26 pharmaceuticals including common over-the-counter (OTC) drugs. Lastly, we developed a Bayesian model that uses viral RNA, COVID-19 treatment drugs, and pharmaceuticals data to predict the confirmed COVID-19 cases within the catchment area., Results: The viral RNA levels in wastewater tracked the actual COVID-19 case numbers well as expected. COVID-19 treatment drugs were detected with varying frequency (9-100%) partly due to their instability in wastewater. We observed a significant correlation (R = 0.30, p < 0.01) between the SARS-CoV-2 genes and desethylhydroxychloroquine (DHCQ, metabolite of HCQ). Remdesivir levels peaked immediately after the Emergency Use Authorization approved by the FDA. Although, 13 out of 26 pharmaceuticals assessed were consistently detected (DF = 100%, n = 111), only acetaminophen was significantly correlated with viral loads, especially when the Omicron variant was dominant. The Bayesian models were capable of reproducing the temporal trend of the confirmed cases., Impact: In this study, for the first time, we measured COVID-19 treatment and pharmaceutical drugs and their metabolites in wastewater to complement ongoing COVID-19 viral RNA surveillance efforts. Our results highlighted that, although the COVID-19 treatment drugs were not very stable in wastewater, their detection matched with usage trends in the community. Acetaminophen, an OTC drug, was significantly correlated with viral loads and confirmed cases, especially when the Omicron variant was dominant. A Bayesian model was developed which could predict COVID-19 cases more accurately when incorporating other drugs data along with viral RNA levels in wastewater., (© 2023. The Author(s).)

The widespread detection of per- and polyfluoroalkyl substances (PFAS) in environmental compartments across the globe has raised several health concerns. Destructive technologies that aim to transform these recalcitrant PFAS into less toxic, more manageable products, are gaining impetus to address this problem. In this study, a 9 MeV electron beam accelerator was utilized to treat a suite of PFAS (perfluoroalkyl carboxylates: PFCAs, perfluoroalkyl sulfonates, and 6:2 fluorotelomer sulfonate: FTS) at environmentally relevant levels in water under different operating and water quality conditions. Although perfluorooctanoic acid and perfluorooctane sulfonic acid showed >90% degradation at <500 kGy dose at optimized conditions, a fluoride mass balance revealed that complete defluorination occurred only at/or near 1000 kGy. Non-target and suspect screening revealed additional degradation pathways differing from previously reported mechanisms. Treatment of PFAS mixtures in deionized water and groundwater matrices showed that FTS was preferentially degraded (∼90%), followed by partial degradation of long-chain PFAS (∼15-60%) and a simultaneous increase of short-chain PFAS (up to 20%) with increasing doses. The increase was much higher (up to 3.5X) in groundwaters compared to deionized water due to the presence of PFAS precursors as confirmed by total oxidizable precursor (TOP) assay. TOP assay of e-beam treated samples did not show any increase in PFCAs, confirming that e-beam was effective in also degrading precursors. This study provides an improved understanding of the mechanism of PFAS degradation and revealed that short-chain PFAS are more resistant to defluorination and their levels and regulation in the environment will determine the operating conditions of e-beam and other PFAS treatment technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

We assessed the competitive adsorption between long-chain and short-chain PFAS and the impact of coexisting ions to understand the mechanisms leading to the early breakthrough of short-chain PFAS from granular activated carbon (GAC) filters. Three pairs of short-chain and long-chain PFAS representing different functional groups were studied using GAC (Filtrasorb 400) in batch systems. In bisolute systems, the presence of long-chain PFAS decreased the adsorption of short-chain PFAS by 30-50% compared to their single solute adsorption capacity (0.22-0.31 mmol/g). In contrast to the partial decrease observed in bisolute systems, the addition of long-chain PFAS to GAC pre-equilibrated with short-chain PFAS completely desorbed all short-chain PFAS from GAC. This suggested that the outermost adsorption sites on GAC were preferentially occupied by short-chain PFAS in the absence of competition but were prone to displacement by long-chain PFAS. The presence of inorganic/organic ions inhibited the adsorption of short-chain PFAS (up to 60%) but had little to no impact on long-chain PFAS, with the inhibitory trend inversely correlated with K ow values. Study results indicated that the displacement of short-chain PFAS by long-chain PFAS and charge neutralization are important mechanisms contributing to the early breakthrough of short-chain PFAS from GAC systems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

1,4-Dioxane is a recalcitrant pollutant in water and is ineffectively removed during conventional water and wastewater treatment processes. In this study, we demonstrate the application of nitrifying sand filters to remove 1,4-dioxane from domestic wastewater without the need for bioaugmentation or biostimulation. The sand columns were able to remove 61 ± 10% of 1,4-dioxane on average (initial concentration: 50 μg/L) from wastewater, outperforming conventional wastewater treatment approaches. Microbial analysis revealed the presence of 1,4-dioxane degrading functional genes (dxmB, phe, mmox, and prmA) to support biodegradation being the dominant degradation pathway. Adding antibiotics (sulfamethoxazole and ciprofloxacin), that temporarily inhibited the nitrification process during the dosing period, showed a minor effect in 1,4-dioxane removal (6-8% decline, p < 0.05), suggesting solid resilience of the 1,4-dioxane-degrading microbial community in the columns. Columns amended with sodium azide significantly (p < 0.05) depressed 1,4-dioxane removal in the early stage of dosing but followed by a gradual increase of the removal over time to >80%, presumably due to a shift in the microbial community toward azide-resistant 1,4-dioxane degrading microbes (e.g., fungi). This study demonstrated for the first time the resilience of the 1,4-dioxane-degrading microorganisms during antibiotic shocks, and the selective enrichment of efficient 1,4-dioxane-degrading microbes after azide poisoning. Our observation could provide insights into designing better 1,4-dioxane remediation strategies in the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

1,4-Dioxane is a contaminant of emerging concern that has been commonly detected in groundwater. In this study, a stable and robust 1,4-dioxane degrading enrichment culture was obtained from uncontaminated soil. The enrichment was capable to metabolically degrade 1,4-dioxane at both high (100 mg L -1 ) and environmentally relevant concentrations (300 μg L -1 ), with a maximum specific 1,4-dioxane degradation rate (q max ) of 0.044 ± 0.001 mg dioxane h -1 mg protein -1 , and 1,4-dioxane half-velocity constant (K s ) of 25 ± 1.6 mg L -1 . The microbial community structure analysis suggested Pseudonocardia species, which utilize the dioxane monooxygenase for metabolic 1,4-dioxane biodegradation, were the main functional species for 1,4-dioxane degradation. The enrichment culture can adapt to both acidic (pH 5.5) and alkaline (pH 8) conditions and can recover degradation from low temperature (10°C) and anoxic (DO < 0.5 mg L -1 ) conditions. 1,4-Dioxane degradation of the enrichment culture was reversibly inhibited by TCE with concentrations higher than 5 mg L -1 and was completely inhibited by the presence of 1,1-DCE as low as 1 mg L -1 . Collectively, these results demonstrated indigenous stable and robust 1,4-dioxane degrading enrichment culture can be obtained from uncontaminated sources and can be a potential candidate for 1,4-dioxane bioaugmentation at environmentally relevant conditions. KEY POINTS: •1,4-Dioxane degrading enrichment was obtained from uncontaminated soil. • The enrichment culture could degrade 1,4-dioxane to below 10 μg L -1 . •Low K s and low cell yield of the enrichment benefit its application in bioremediation., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Many environmentally relevant poly-/perfluoroalkyl substances (PFASs) including perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) exist in different isomeric (branched and linear) forms in the natural environment. The isomeric distribution of PFASs in the environment and source waters is largely controlled by the source of contamination and varying physicochemical properties imparted by their structural differences. For example, branched isomers of PFOS are relatively more reactive and less sorptive compared to the linear analogue. As a result, the removal of branched and linear PFASs during water treatment can vary, and thus the isomeric distribution in source waters can influence the overall efficiency of the treatment process. In this paper, we highlight the need to consider the isomeric distribution of PFASs in contaminated matrices while designing appropriate remediation strategies. We additionally summarize the known occurrence and variation in the physicochemical properties of PFAS isomers influencing their detection, fate, toxicokinetics, and treatment efficiency.

Advanced oxidation processes (AOPs) are popular technologies employed across the U.S. for wastewater reclamation and drinking water treatment of recalcitrant chemicals. Although there is consensus about the ineffectiveness of AOPs to treat perfluoroalkyl substances (PFASs; not polyfluoro compounds by definition here), there is a lack of field data demonstrating their impact on the transformation of unknown PFAS precursors during groundwater treatment. In this study, the fate of PFASs in seven pilot-scale AOPs, including four different technologies (UV/H 2 O 2 , UV/Cl 2 , UV/TiO 2 , and O 3 /H 2 O 2 ), was assessed at four drinking water systems across New York State (NYS), USA. Seven of 18 PFASs were detected in the influent at concentrations ranging from below method detection to 64 ng/L. Across all systems, all detected PFASs showed an increase in concentration after treatment presumably due to unknown precursor transformation with specific increases for perfluorobutane sulfonate (PFBS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and perfluorononanoic acid (PFNA) averaging 405 (range: 0 - 1220) %, 1.0 (-7 - 9) %, 3.8 (0 - 9.5) %, 3.3 (-11 - 13) %, 14 (0 - 48) %, 13 (3 - 25) %, and 2 (0 - 5.2) %, respectively. The increase in PFAS concentration was dependent on UV and oxidant dose, further confirming that transformation reactions were occurring due to AOPs similar to a total oxidizable precursor assay. At one of the sites, PFOA levels exceeded the current NYS drinking water standard of 10 ng/L after, but not before treatment, highlighting the importance of considering the potential impact of AOP on treated water quality when designing treatment systems for regulatory compliance. The increase in PFAS concentration in the AOP systems positively correlated (r = 0.91) with nitrate levels in groundwater, suggesting that onsite septic discharges may be an important source of PFAS contamination in these unsewered study areas. Results from this pilot-scale demonstration reveal that hydroxyl radical-based AOPs, although ineffective in treating PFASs, can help to reveal the true extent of PFAS contamination in source waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In recent decades, the rate of introduction of non-indigenous macroalgae has increased. While invasive seaweeds often outcompete native species for substrata, their direct effects on marine life are rarely described. Here, we describe 'red water' events caused by the decay of blooms of the invasive red seaweed, Dasysiphonia japonica, in Great South Bay, NY, USA, and the ability of water from such events to induce rapid and significant mortality in larval and juvenile fish (Menidia beryllina, Menidia menidia, and Cyprinodon variegatus) and larval bivalves (Mercenaria mercenaria and Crassostrea virginica). All species studied experienced significant (p<0.05) reductions in survival when exposed to macroalgae in a state of decay, seawater in which the alga was previously decayed, or both. Both bivalve species experienced 50-60% increases in mortality when exposed to decaying D. japonica for ∼ one week, despite normoxic conditions. Among fish, significant increases (40-80%) in mortality were observed after 24 h exposure to decayed D. japonica and one-week exposures caused, on average, 90% mortality in larval M. beryllina, 50% mortality in juvenile (∼3 cm) M. menidia, and 50% mortality in larval C. variegatus. All fish and bivalve mortality occurred under normoxic conditions (dissolved oxygen (DO) >7 mg L -1 ) and low ammonium levels (< 20 µM), with the exception of C. variegatus, which expired under conditions of decayed D. japonica coupled with reduced DO caused by the alga. Screening of water with decayed D. japonica using liquid chromatography-mass spectrometry revealed compounds with mass-to-charge ratios matching caulerpin, a known algal toxin that causes fish and shellfish mortality, and several other putative toxicants at elevated levels. Collectively, the high levels of mortality (50-90%) of larval and juvenile fish and bivalves exposed to decaying D. japonica under normoxic conditions coupled with the observation of 'red water' events in estuaries collectively indicate the red seaweed, D. japonica, can create harmful algal blooms (HABs)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Characterizing the occurrence of organic contaminants (OCs) of environmental health concern in municipal sewage sludges is essential for safe handling and disposal of these abundant materials. This meta-analysis aimed to (i) summarize the extent of studies performed on the chemical composition of sewage sludges from China and the U.S., the world's two largest chemical producers, (ii) identify chemical groups of priority concern, (iii) quantitatively compare chemical abundance in sludge between nations, (iv) determine longitudinal contaminant accumulation trends in sludge, and (v) identify data gaps with regard to OC concentrations in sludge. A literature search was conducted on concentrations of OCs in U.S. sludges produced during treatment of domestic and industrial wastewater and compared statistically to contaminant levels in Chinese sludge abstracted from a recently established database. Longitudinal trends of OC occurrence were interpreted in the context of national chemical production, usage statistics, and regulations. A total of 105 studies on OCs in U.S. sewage sludge were found, while a total of 159 had been found in China. Among 1175 OCs monitored for, 23% of all analytes had been monitored in both countries (n = 269), 41% (n = 480) in China only, and the remaining 36% (n = 426) in the U.S. only. On average, concentrations of OCs were 4.0 times higher in U.S. than in Chinese sewage sludge, with the highest detection being observed for alkylphenol ethoxylates. Data from a new binational database on toxic OCs in sewage sludges suggest and reiterates the need for additional chemical monitoring in both countries, risk assessments for emerging OCs contained in sludges destined for application on land, and stronger enforcement of sludge disposal restrictions in China, where as much as 40% of sludge is currently being dumped improperly., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Dr. Halden and Mr. Steele are co-founders of AquaVitas LLC, an Arizona State University startup company that works in the intellectual space touched upon by this study. Dr. Halden is founder of Arizona State University Foundation's OneWaterOneHealth, a nonprofit project providing wastewater-based health assessments to underserved US communities., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Wound healing is a complicated physiological process that comprises various steps, including hemostasis, inflammation, proliferation, and remodeling. The wound healing process is significantly affected by coexisting disease states such as diabetes, immunosuppression, or vascular disease. It can also be impacted by age, repeated injury, or hypertrophic scarring. These comorbidities can affect the rate of wound closure, the quality of wound closure, and tissues' function at the affected sites. There are limited options to improve the rate or quality of wound healing, creating a significant unmet need. Advances in nucleic acid research and the human genome project have developed potential novel approaches to address these outstanding requirements. In particular, the use of microRNA, short hairpin RNA, and silencing RNA is unique in their abilities as key regulators within the physiologic machinery of the cell. Although this innovative therapeutic approach using ribonucleic acid (RNA) is an attractive approach, the application as a therapeutic remains a challenge due to site-specific delivery, off-target effects, and RNA degradation obstacles. An ideal delivery system is essential for successful gene delivery. An ideal delivery system should result in high bioactivity, inhibit rapid dilution, controlled release, allow specific activation timings facilitating physiological stability, and minimize multiple dosages. Currently, these goals can be achieved by inorganic nanoparticle (NP) (e.g., cerium oxide, gold, silica, etc.) based delivery systems. This review focuses on providing insight into the preeminent research carried out on various RNAs and their delivery through NPs for effective wound healing. This article is categorized under: Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Therapeutic Approaches and Drug Discovery > Emerging Technologies Biology-Inspired Nanomaterials > Nucleic Acid-Based Structures., (© 2021 Wiley Periodicals LLC.)

The presence of pharmaceuticals and personal care products (PPCPs) in the environment is primarily the result of discharge of waste, including from onsite wastewater treatment systems (OWTSs) which are employed by 25% of homes in the United States. However, the occurrence and removal of PPCPs in OWTSs is not well understood, particularly given the large diversity in PPCP compounds as well as in OWTS designs. In this study, we monitored 26 different PPCPs in 13 full-scale nitrogen removing biofilters (NRBs), an innovative/alternative type of OWTS that utilizes an overlying sand layer and an underlying woodchip/sand layer to simultaneously remove nitrogen and other wastewater-derived contaminants. The specific objectives of this study were (i) to measure the occurrence of PPCPs in septic tank effluent (STE) that served as an influent to NRBs, (ii) to quantify PPCP removal in three types of NRB configurations (n = 13), and (iii) to evaluate PPCP removal with depth and environmental conditions in NRBs. Aqueous samples were taken during 42 separate sampling events during 2016 - 2019 and analyzed by liquid chromatography tandem mass spectrometry. Analysis of the STE samples yielded detection of 23 of the 26 PPCPs, with caffeine being the most abundant and frequently detected compound at 52,000 ng/L (range: 190 - 181,000 ng/L), followed by acetaminophen and paraxanthine at 47,500 ng/L (190 - 160,000 ng/L), and 34,300 ng/L (430 - 210,000 ng/L), respectively. Cimetidine, fenofibrate, and warfarin were the only compounds not detected. The average removal of PPCPs by NRBs ranged from 58% to >99% for the various compounds. PPCP removal as a function of depth in the systems showed that 50 to >99% of the observed removal was achieved within the top oxic layer (0 - 46 cm) of the NRBs for 19 analytes. Seven of the compounds had >85% removal by the same depth. These results indicate that NRBs are effective at removing PPCPs and that a large portion of the removal is achieved within the oxic nitrifying layer of the NRBs. Overall, the removal of PPCPs in NRBs was comparable (n = 8) or better (n = 15) than that observed for conventional wastewater treatment plants., (Copyright © 2021. Published by Elsevier Ltd.)

The presence and release of 1,4-dioxane to groundwater from onsite-wastewater treatment systems (OWTS), which represent 25% of the total wastewater treatment in the U.S., has not been studied to date. In this study we monitored 1,4-dioxane in six septic tank effluents (STE) and receiving OWTS installed at residences on Long Island (LI), NY, for a period of 15 months. We specifically evaluated the performance of Nitrogen Removing Biofilters (NRBs) as an innovative/alternative-OWTS, consisting of a top sand layer and a bottom woodchip/sand layer, to simultaneously remove nitrogen and 1,4-dioxane. 1,4-Dioxane levels in STE (mean: 1.49 μg L -1 ; range: 0.07-8.45 μg L -1 ; n = 37) were on average > 15 times higher than tap water from these residences, demonstrating that 1,4-dioxane primarily originated from the use of household products. NRBs were effective in removing both 1,4-dioxane and total nitrogen with an overall removal efficiency of 56 ± 20% and 88 ± 12%, respectively. The majority of 1,4-dioxane removal (~80%) occurred in the top oxic layer of the NRBs. The detection of functional genes (dxmB, prmA, and thmA), which encode for metabolic and co-metabolic 1,4-dioxane degradation, in NRBs provides the first field evidence of aerobic microbial degradation of 1,4-dioxane occurring in a wastewater system. Given that there are ~500,000 conventional OWTS on LI, the 1,4-dioxane discharge to groundwater from residential wastewater was estimated at 195 ± 205 kg yr -1 , suggesting high risk of contamination to shallow aquifers. The results also demonstrate that installation of NRBs can reduce 1,4-dioxane to levels even lower than the NY State drinking water standard of 1 μg L -1 ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Extensive use of per- and polyfluoroalkyl substances (PFAS) has caused their ubiquitous presence in natural waters. One of the standard practices for PFAS removal from water is adsorption onto granular activated carbon (GAC); however, this approach generates a new waste stream, i.e., PFAS-laden GAC. Considering the recalcitrance of PFAS molecules in the environment, inadequate disposal (e.g., landfill or incineration) of PFAS-laden GAC may let PFAS back into the aquatic cycle. Therefore, developing approaches for PFAS-laden GAC management present unique opportunities to break its forever circulation within the aqueous environment. This comprehensive review evaluates the past two decades of research on conventional thermal regeneration of GAC and critically analyzes and summarizes the literature on regeneration of PFAS-laden GACs. Optimized thermal regeneration of PFAS-laden GACs may provide an opportunity to employ existing regeneration infrastructure to mineralize the adsorbed PFAS and recover the spent GAC. The specific objectives of this review are (i) to investigate the role of physicochemical properties of PFAS on thermal regeneration, (ii) to assess the changes in regeneration yield as well as GAC physical and chemical structure upon thermal regeneration, and (iii) to critically discuss regeneration parameters controlling the process. This literature review on the engineered regeneration process illustrates the significant promise of this approach that can break the endless environmental cycle of these forever chemicals, while preserving the desired physicochemical properties of the valuable GAC adsorbent.

In this study, a semi-batch, bench-scale UV/hydrogen peroxide (UV/H 2 O 2 ) advanced oxidation process system was used to investigate how typical groundwater quality parameters (pH, alkalinity, natural organic matter (NOM), nitrate, and iron) influence the treatment of 1,4-dioxane. Deionized (DI) water spiked with 1,4-dioxane (100 μg L -1 ), treated using H 2 O 2 (10 mg L -1 ) in a commercially available UV system (40 W low-pressure lamp) showed an UV fluence-based first-order rate constant (k') and electrical energy-per-order (EEO) of 4.32✕10 -3  cm 2 -mJ -1 and 0.15 kWh-m -3 -order -1 , respectively. The most abundant byproduct generated in spiked-DI water was oxalic acid (up to 55 μg L -1 ), followed by formic and acetic acids. The k' showed no significant difference at pH ranging from 5 to 7 and at low alkalinity concentrations (<20 mg-CaCO 3 L -1 ), typical of sandy aquifers. The k' declined by up to 85% with increasing NOM concentration. Elevated production (up to ∼400% increase) of aldehydes and organic acids was observed in NOM-spiked water, implying that NOM is a significant byproduct precursor during UV/H 2 O 2 treatment. High NO 3 - concentration (10 mg-N L -1 ) in source water reduced the k' by 25%, while no significant impact was observed at lower concentrations (<2 mg-N L -1 ). Addition of Fe(II) at 0.5 mg-L -1 resulted in an instantaneous Fenton-reaction-assisted removal of ∼10% 1,4-dioxane in the presence of H 2 O 2 , but did not enhance the performance of UV/H 2 O 2 treatment over time. In contrast, both Fe(II) and Fe(III) addition lowered the k' by 15-27%. The decline of k' observed in these experiments was attributed to reduced UVT (Fe), . OH radical scavenging (pH), or both (NO 3 - , NOM). Treatment of groundwater samples collected from three 1,4-dioxane-contaminated wells located in Long Island, NY, showed k' values of 13-40% lower than what was observed for DI water due to radical scavenging from a combination of high NO 3 - and NOM in the samples. A multiple linear-regression model, developed using water quality data as model input, showed good agreement with field observations (paired t-test: p > 0.05) in predicting k' for the removal of 1,4-dioxane from groundwater. This study provides the first systematic evaluation of the impacts of groundwater quality on UV/H 2 O 2 process to remove environmentally relevant levels of 1,4-dioxane and reports standardized performance-related parameters to aid in the design and evaluation of full-scale systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Access to near-real time opioid use data is essential to the effective management of the U.S. opioid crisis. Current narcotic data collection methods are limited by time delay and would be complimented by a rapid data acquisition technique. Use of wastewater-based epidemiology (WBE) analysis may offer access to near real-time data on opioid consumption but application in the United States has been limited. From 2015 to 2017, monthly 24-h time-weighted composite samples of municipal raw wastewater from two Midwestern U.S. cities were routinely analyzed using liquid chromatography-tandem mass spectrometry for morphine, codeine, oxycodone, heroin, fentanyl, and select opioid metabolites. Concentrations of opioids (ng/L) in raw wastewater from City 1 and 2, respectively, were: morphine (713 ± 38; 306 ± 29; detection frequency (DF): 100%), oxycodone (17.8 ± 1.1; 78 ± 6; DF: 100%), codeine (332 ± 37; 100 ± 27; DF: 93%), heroin (41 ± 16; 9 ± 11; DF: 81%), and fentanyl (1.7 ± 0.2; 1.0 ± 0.5; DF: 62%). Average opioid consumption rates estimated using WBE ranged between 9 and 2590 mg/day/1000 persons. Anticipated overdoses and overdose-deaths calculated from analyte concentrations in wastewater forecasted 200 opioid-related overdoses/year and 39 opioid related overdose-deaths/year across the two cities during the year 2016, which aligned well with observed coroner-reported opioid deaths. This long-term U.S. screening study of opioids in wastewater was the first to utilize wastewater epidemiological data to estimate the number of expected overdose and overdose-deaths, and to identify detectable levels of the powerful synthetic opioid fentanyl in community wastewater consistently over the course of one whole year., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Wastewater-based epidemiology (WBE), an emerging tool for monitoring public health in near real-time, is used extensively in Europe but applications to U.S. populations are still scarce. In this longitudinal study, raw wastewater was collected monthly from three U.S. cities as 24-h weekday composites and analyzed for evidence of alcohol and tobacco consumption. Over the 11-month sampling period, biomarkers of stimulant use were detected in wastewater by isotope dilution liquid chromatography tandem mass spectrometry in units of μg/L (ethyl sulfate, 1.6-25.1; nicotine, 0.6-26.7; cotinine, 0.2-3.8; and 3‑hydroxycotinine, 0.3-3.8). Average consumption rates in the three communities were calculated using detected biomarker levels in conjunction with wastewater flow rates, metabolic excretion factors, and population size data. Computed average per-capita consumption rates estimated for the sub-population aged 15 and above for alcohol (13.4 ± 5.6 L/y/person) and daily consumption of nicotine by smokers (14.2 ± 3.6 cigarettes/d/person) were in good agreement with U.S. survey data (9.0 L/y/person; 14.2 cigarettes/d/smoker). The WBE approach also captured impacts of temporal population influx on substance consumption patterns. This first U.S. WBE study to track recreational use of stimulants longitudinally and concurrently in multiple American cities highlights opportunities for collecting robust public health information from wastewater anonymously, economically and in near real-time., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Ten infrequently monitored antibiotics in biosolids were examined in archived American sewage sludges (n = 79) collected as part of the 2006/2007 U.S. Environmental Protection Agency (EPA) Targeted National Sewage Sludge Survey. This study inspected the occurrence of amoxicillin, ampicillin, erythromycin, furazolidone [proxy metabolite: 3-(2-nitrobenzylidenamino)-2-oxazolidinone (NP-AOZ)], nalidixic acid, oxolinic acid, oxytetracycline, spiramycin, sulfadimidine, and sulfadimethoxine in sewage sludges after nearly a decade in frozen storage. Six antibiotics were detected at the following average concentrations (ng/g dry weight): amoxicillin (1.0), nalidixic acid (19.1), oxolinic acid (2.7), erythromycin (0.6), oxytetracycline (4.5), and ampicillin (14.8). The remaining four were not detected in any samples (

Phosphorus (P) is an important and often limiting element in terrestrial and aquatic ecosystem. A lack of understanding of its distribution and structures in the environment limits the design of effective P mitigation and recovery approaches. Here we developed a robust method employing size exclusion chromatography (SEC) coupled to an ICP-MS to determine the molecular weight (MW) distribution of P in environmental samples. The most abundant fraction of P varied widely in different environmental samples: (i) orthophosphate was the dominant fraction (93-100%) in one lake, two aerosols and DOC isolate samples, (ii) species of 400-600 Da range were abundant (74-100%) in two surface waters, and (iii) species of 150-350 Da range were abundant in wastewater effluents. SEC-DOC of the aqueous samples using a similar SEC column showed overlapping peaks for the 400-600 Da species in two surface waters, and for >20 kDa species in the effluents, suggesting that these fractions are likely associated with organic matter. The MW resolution and performance of SEC-ICP-MS agreed well with the time integrated results obtained using conventional ultrafiltration method. Results show that SEC in combination with ICP-MS and DOC has the potential to be a powerful and easy-to-use method in identifying unknown fractions of P in the environment., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Single particle inductively coupled plasma mass spectrometry (spICP-MS) was used to detect Ti-containing particles in heavily-used bathing areas of a river (Salt River) and five swimming pools. Ti-containing particle concentrations in swimming pools ranged from 2.8 × 10 3 to 4.4 × 10 3 particles/mL and were an order of magnitude lower than those detected in the Salt River. Measurements from the Salt River showed an 80% increase in Ti-containing particle concentration over baseline concentration during peak recreational activity (at 16:00 h) in the river. Cloud point extraction followed by transmission electron microscopy with energy dispersive X-ray analysis confirmed presence of aggregated TiO 2 particles in river samples, showing morphological similarity to particles present in an over-the-counter sunscreen product. The maximum particle mass concentration detected in a sample from the Salt River (659 ng/L) is only slightly lower than the predicted no effect concentration for TiO 2 to aquatic organisms (< 1 μg/L).

In the present study, 40 freshwater sediments collected near 14 wastewater treatment plants (WWTPs) across the United States were analyzed for eight N-nitrosamines by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Three N-nitrosamines were detected for the first time in freshwater sediments in units of ng/g dry weight at the specified detection frequency: N-nitrosodibutylamine (NDBA; 0.2-3.3; 58%), N-nitrosodiphenylamine (NDPhA; 0.2-4.7; 50%), and N-nitrosopyrrolidine (NPYR; 3.4-19.6; 18%). At least one N-nitrosamine was detected in 70% (28/40) of sediments analyzed. Non-detect values in units of ng/g dw were obtained for N-nitrosodimethylamine (NDMA; <10.2), N-nitrosomethylethylamine (NMEA; <1.7), N-nitrosodiethylamine (NDEA; <3.9), N-nitroso-di-n-propylamine (NDPA; <1.7), and N-nitrosopiperidine (NPIP; <3.6). Principal component analysis specifically points to two of multiple potential pathways explaining N-nitrosamine occurrences in sediment: NDBA and NDPhA were positively correlated with bulk water ammonia and pH levels, and NPYR with sediment content of organic carbon and iron. Interestingly, N-nitrosamine occurrences up- and downstream of WWTPs were statistically indistinguishable (p>0.05). This is the first report on the occurrence of the carcinogenic N-nitrosamines NDBA, NDPhA, and NPYR in U.S. freshwater sediments. Discovery of this phenomenon warrants further research on the compounds' origin, environmental persistence, aquatic toxicity, and risks posed., (Copyright © 2016. Published by Elsevier B.V.)

The production of sewage sludge is increasing in China but with unsafe disposal practices, causing potential risk to human health and the environment. Using literature from the past 30 years (N = 159), we conducted a meta-analysis of organic contaminants (OCs) in Chinese sludge. Most data were available from developed and populated regions, and no data were found for Tibet. Since 1987, 35 classes of chemicals consisting of 749 individual compounds and 1 mixture have been analyzed, in which antibiotics and polycyclic aromatic hydrocarbons (PAHs) were the most targeted analytes. For 13 classes of principal OCs (defined as chemicals detected in over five studies) in sludge, the median (expressed in nanograms per gram dry weight) was the highest for phthalate esters (27 900), followed by alkylphenol polyethoxylates (12 000), synthetic musks (5800), antibiotics (4240), PAHs (3490), ultraviolet stabilizers (670), bisphenol analogs (160), organochlorine pesticides (110), polybrominated diphenyl ethers (100), pharmaceuticals (84), hormones (69), perfluorinated compounds (21), and polychlorinated biphenyls (15). Concentrations of PAHs in sludges collected between 1998 and 2012 showed a decreasing trend. Study findings suggest the need for a Chinese national sewage sludge survey to identify and regulate toxic OCs, ideally employing both targeted as well as nontargeted screening approaches.

A model was developed to assess the impact of adding acids and bases to processed municipal sewage sludge (MSS) to mobilize contaminants, facilitating their removal from sludge by flushing prior to land application. Among 312 organic contaminants documented to occur in U.S. MSS, 71 or 23% were identified as ionizable organic contaminants (IOCs), contributing a disproportionately large fraction of 82% of the total mass of sludge-borne contaminants. Detected IOCs included 57 pharmaceuticals and personal care products, 12 perfluorinated compounds, one surfactant and one pesticide. Annually, about 2000t of IOCs were estimated to be released to U.S. soils via land-application of MSS. A partitioning model developed to assess the impact of pH on hydrophobic sorption revealed that between 36 and 85% of the mass of individual classes of IOCs potentially could be desorbed from MSS via pH adjustment and flushing. Thus, modeling results suggest that a sequential pH treatment [acidic (~pH2) followed by basic (~pH12) treatment] has the potential to reduce the burden of harmful IOCs in MSS applied on U.S. land by up to 40±16t annually. This approach may serve as a cost-effective treatment process that can be implemented easily in existing sludge treatment infrastructure in the U.S. and worldwide, serving to significantly improve the quality of MSS destined for land application., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In response to limited phosphorus (P) reserves worldwide, several countries have demonstrated the prospect of recovering significant amounts of P from wastewater treatment plants (WWTPs). This technique uses enhanced biological P removal (EBPR) to concentrate P in sludge followed by chemical precipitation of P as struvite, a usable phosphate mineral. The present study models the feasibility of this enhanced removal and recovery technique in a WWTP in Arizona with design parameters typical of infrastructure in the United States. A mass balance was performed for existing treatment processes and modifications proposed to estimate the quantity of P that could be recovered under current and future flow conditions. Modeling results show that about 71 to 96% of the P being lost potentially could be recovered as struvite. About 491 ± 64 t yr of struvite may be recovered after process modification, which corresponds to $150,000 ± $20,000 yr in P sales to fertilizer industries. The process was projected to be economically feasible, with a payback period of 45 ± 30 yr in the studied WWTP and a much shorter duration of 3 ± 1 yr for WWTPs already using an EBPR process. Furthermore, modeling results suggest that P recovery can improve the quality of biosolids by favorably reducing the P:N ratio. Implementation of this strategy at US WWTPs may increase national security by reducing dependence of limited P resources. Considering all aspects of the recovery process with respect to environmental, economic, and social implications, the examined technique is concluded to represent a cost-attractive and sustainable method for P management in US WWTPs., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

As health concerns over bisphenol A (BPA) in consumer products are mounting, this weak estrogen mimicking compound is gradually being replaced with structural analogs, whose environmental occurrence and estrogen risks are not well understood yet. We used high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to determine the concentrations of eight bisphenol analogs in 76 sewage sludge samples collected by the U.S. Environmental Protection Agency (EPA) in 2006/2007 from 74 wastewater treatment plants (WWTPs) in 35 states. Bisphenols were detected at the following concentration ranges (ng/g dry weight) and detection frequencies: BPA (6.5-4700; 100%); bisphenol S (BPS; <1.79-1480; 84%); bisphenol F (BPF; <1.79-242; 68%); bisphenol AF (BPAF; <1.79-72.2; 46%); bisphenol P (BPP; <1.79-6.42; <5%), bisphenol B (BPB; <1.79-5.60; <5%), and bisphenol Z (BPZ; <1.79--66.7; <5%). Bisphenol AP (BPAP) was not detected in any of the samples (<1.79 ng/g dw). Concentrations of BPA in sewage sludge were an order of magnitude higher than those reported in China but similar to those in Germany. The calculated 17β-estradiol equivalents (E2EQ) of bisphenols present in sludge samples were 7.74 (0.26-90.5) pg/g dw, which were three orders of magnitude lower than the estrogenic activity contributed by natural estrogens present in the sludge. The calculated mass loading of bisphenols through the disposal of sludge and wastewater was <0.02% of the total U.S. production. As the usage of BPA is expected to decline further, environmental emissions of BPS, BPF, and BPAF are likely to increase in the future. This study establishes baseline levels and estrogenic activity of diverse bisphenol analogs in sewage sludge., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Traditionally, hazardous chemicals have been regulated in the U.S. on a one-by-one basis, an approach that is slow, expensive and can be inefficient, as illustrated by a decades-long succession of replacing one type of organohalogen flame retardants (OHFRs) with another one, without addressing the root cause of toxicity and associated public health threats posed. The present article expounds on the need for efficient monitoring strategies and pragmatic steps in reducing environmental pollution and adverse human health impacts. A promising approach is to combine specific bioassays with state-of-the-art chemical screening to identify chemicals and chemical mixtures sharing specific modes of action (MOAs) and pathways of toxicity (PoTs). This approach could be used to identify and regulate hazardous chemicals as classes or compound families, featuring similar biological end-points, such as endocrine disruption and mutagenicity. Opportunities and potential obstacles of implementing this approach are discussed.

Epoxy resins incorporating bisphenol A diglycidyl ether (BADGE) and novolac glycidyl ether (NOGE) are used in a wide range of applications, including adhesives, structural and electrical laminates. However, little is known about the occurrence of BADGE, NOGE, and their derivatives in the environment. Using liquid chromatography-tandem mass spectrometry, BADGE, bisphenol F glycidyl ether (BFDGE), 3-ring NOGE, and eight of their derivatives (BADGE·2 H2O, BADGE·H2O, BADGE·HCl·H2O, BADGE·2 HCl, BADGE·HCl, BFDGE·2 H2O, and BFDGE·2 HCl) were determined in archived biosolid samples collected from 68 wastewater treatment plants (WWTPs) from the northeastern, midwestern, western, and southern regions of the USA. BADGE·2 H2O was the most frequently detected (DR = 99%) and the most abundant compound found (median: 93.6 ng/g dry weight [dw]) in this family. The highest total concentrations of target chemicals, ranging from 83.6 to 2490 ng/g dw, were found in biosolids collected from the northeastern United States. The sum of geometric mean (GM) concentration of BADGE, NOGE, and their derivatives in biosolids increased with the treatment capacity of WWTPs. Based on the measured concentrations in biosolids and predicted mass in wastewater, it was estimated that approximately 3.5% of the total production of BADGEs was emitted through WWTP discharges.

Important antibiotics in human medicine have been used for many decades in animal agriculture for growth promotion and disease treatment. Several publications have linked antibiotic resistance development and spread with animal production. Aquaculture, the newest and fastest growing food production sector, may promote similar or new resistance mechanisms. This review of 650+ papers from diverse sources examines parallels and differences between land-based agriculture of swine, beef, and poultry and aquaculture. Among three key findings was, first, that of 51 antibiotics commonly used in aquaculture and agriculture, 39 (or 76%) are also of importance in human medicine; furthermore, six classes of antibiotics commonly used in both agriculture and aquaculture are also included on the World Health Organization's (WHO) list of critically important/highly important/important antimicrobials. Second, various zoonotic pathogens isolated from meat and seafood were observed to feature resistance to multiple antibiotics on the WHO list, irrespective of their origin in either agriculture or aquaculture. Third, the data show that resistant bacteria isolated from both aquaculture and agriculture share the same resistance mechanisms, indicating that aquaculture is contributing to the same resistance issues established by terrestrial agriculture. More transparency in data collection and reporting is needed so the risks and benefits of antibiotic usage can be adequately assessed.

Processed municipal sewage sludges (MSS) are an abundant, unwanted by-product of wastewater treatment, increasingly applied to agriculture and forestry for inexpensive disposal and soil conditioning. Due to their high organic carbon and lipid contents, MSS not only is rich in carbon and nutrients but also represents a "sink" for recalcitrant, hydrophobic, and potentially bioaccumulative compounds. Indeed, many organics sequestered and concentrated in MSS meet the US Environmental Protection Agency's definition of being persistent, bioaccumulative, and toxic (PBT). In a strategic effort, our research team at the Biodesign Institute has created the National Sewage Sludge Repository (NSSR), a large repository of digested MSSs from 164 wastewater treatment plants from across the USA, as part of the Human Health Observatory (H2O) at Arizona State University (ASU). The NSSR likely represents the largest archive of digested MSS specimens in the USA. The present study summarizes key findings gleaned thus far from analysis of NSSR samples. For example, we evaluated the content of toxicants in MSS and computed estimates of nationwide inventories of mass produced chemicals that become sequestrated in sludge and later are released into the environment during sludge disposal on land. Ongoing efforts document co-occurrence of a variety of PBT compounds in both MSS and human samples, while also identifying a large number of potentially harmful MSS constituents for which human exposure data are still lacking. Finally, we summarize future opportunities and invite collaborative use of the NSSR by the research community. The H2O at ASU represents a new resource and research tool for environmental scientists and the larger research community. As illustrated in this work, this repository can serve to (i) identify and prioritize emerging contaminants, (ii) provide spatial and temporal trends of contaminants, (iii) inform and evaluate the effectiveness of environmental policy-making and regulations, and (iv) approximate, ongoing exposures and body burdens of mass-produced chemicals in human society.

The World Health Organization recently proposed the inclusion of brominated congeners in addition to chlorinated congeners when computing the toxic equivalency (TEQ) of dioxin-like compounds (DLCs) in assessments of human health risks. In the present study, 12 polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were analyzed by gas chromatography/high resolution mass spectrometry in the composited, archived biosolids that were collected in 32 U.S. states and the District of Columbia from 94 wastewater treatment plants by the United States Environmental Protection Agency in its 2001 national sewage sludge survey. Two PBDDs and five PBDFs were detected in the biosolids composites at varying frequencies (40-100%) with a total mean concentration of 10,000 ng/kg dry weight (range: 630-42,800), of which 1,2,3,4,6,7,8-hepta-BDF constituted about 95% by mass. Relative to commercial polybrominated diphenyl ether (PBDE) formulations, the ratio of PBDD/Fs to PBDEs in biosolids was 55-times higher (∼ 0.002% vs ∼ 0.11%), which indicates potential PBDE transformation or possibly additional sources of PBDD/Fs in the environment. The TEQ contribution of PBDD/Fs was estimated at 162 ng/kg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (range: 15-672), which is equivalent to 75% (range: 12-96%) of the total TEQ in biosolids. The TEQ of DLCs released annually to U.S. soils as a result of the land application of biosolids was estimated at 720 g (range: 530-1600 g). Among all known DLCs determined in biosolids, brominated analogs contributed 370% more TEQ than did chlorinated congeners, which indicates the need to include brominated DLCs in the exposure and risk assessment of land-applied biosolids.

An outdoor mesocosm study was conducted in Baltimore, Maryland, to explore the fate of thirteen perfluoroalkyl substances (PFASs) over the course of three years in biosolids/soil mixtures (1:2) exposed to ambient outdoor conditions. Analysis by liquid chromatography tandem mass spectrometry showed perfluorooctanoate (PFOA) to be the most abundant analyte found early in the soil weathering experiment at 24.1 ng/g dry weight (dw), followed by perfluoroundecanoate (PFUnDA) and perfluorodecanoate (PFDA) at 18.4 and 17.4 ng/g dw, respectively. Short-chain perfluorinated carboxylates (PFCAs; C4-C8) showed observable loss from biosolids/soil mixtures, with experimentally determined first-order half-lives in soil ranging from 385 to 866 days. Perfluorooctane sulfonate (PFOS), perfluorononaoate (PFNA) and PFUnDA levels in biosolids/soil mixtures remained stable, while other long-chain PFCAs [PFDA, perfluorododecanoate (PFDoDA)] and perfluorooctane sulfonamide (PFOSA) levels increased over time, presumably due to the breakdown of unidentified precursors in a process analogous to that reported previously for wastewater treatment plants. This study informs risk assessment initiatives by furnishing data on the environmental persistence of PFASs while also constituting the first report on in situ production of long-chained PFASs in terrestrial environments., (Copyright © 2014 Elsevier Inc. All rights reserved.)

We determined national baseline levels and release inventories of 77 traditional and novel brominated flame retardants (BFRs) in biosolids composites (prepared from 110 samples) from the U.S. Environmental Protection Agency's 2001 national sewage sludge survey (NSSS). Additionally, analyses were performed on archived samples from a 3-year outdoor mesocosm study to determine the environmental persistence of BFRs in biosolids-amended soil. The total polybrominated diphenylether (PBDE) concentration detected in biosolids composites was 9400 ± 960 μg/kg dry weight, of which deca-BDE constituted 57% followed by nona- and penta-BDE at 18 and 13%, respectively. The annual mean loading rate estimated from the detected concentrations and approximate annual biosolids production and disposal numbers in the U.S., of the sum of PBDEs and non-BDE BFRs was calculated to be 47,900-60,100 and 12,900-16,200 kg/year, of which 24,000-36,000 and 6400-9700 kg/year are applied on land, respectively. Mean concentration of PBDEs were higher in the 2001 samples compared to levels reported in EPA's 2006/7 Targeted NSSS, reflecting on-going efforts in phasing-out PBDEs in the U.S. In outdoor soil mesocosms, >99% of the initial BFRs mass in the biosolids/soil mixtures (1:2) persisted over the monitoring duration of three years. Estimates of environmental releases may be refined in the future by analyzing individual rather than composited samples, and by integrating currently unavailable data on disposal of biosolids on a plant-specific basis. This study informs the risk assessment of BFRs by furnishing national inventories of BFR occurrence and environmental release via biosolids application on land., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The occurrence of eight carcinogenic N-nitrosamines in biosolids from 74 wastewater treatment plants (WWTPs) in the contiguous United States was investigated. Using liquid chromatography-tandem mass spectrometry, seven nitrosamines [(N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine, N-nitrosodi-n-propylamine (NDPA), N-nitrosodibutylamine, N-nitrosopyrrolidine, N-nitrosopiperidine (NPIP), and N-nitrosodiphenylamine (NDPhA)] were detected with varying detection frequency (DF) in 88% of the biosolids samples (n = 80), with five of the seven being reported here for the first time in biosolids. While rarely detected (DF 3%), NDMA was the most abundant compound at an average concentration of 504 ± 417 ng/g dry weight of biosolids. The most frequently detected nitrosamine was NDPhA (0.7-147 ng/g) with a DF of 79%, followed by NDPA (7-505 ng/g) and NPIP (51-1185 ng/g) at 21% and 11%, respectively. The DF of nitrosamines in biosolids was positively correlated with their respective n-octanol-water partition coefficients (R(2) = 0.65). The DF and sum of mean concentrations of nitrosamines in biosolids increased with the treatment capacity of WWTPs. Given their frequent occurrence in nationally representative samples and the amount of U.S. biosolids being applied on land as soil amendment, this study warrants more research into the occurrence and fate of nitrosamines in biosolids-amended soils in the context of crop and drinking water safety.

Thousands of chemicals have been identified as contaminants of emerging concern (CECs), but prioritizing them concerning ecological and human health risks is challenging. We explored the use of sewage treatment plants as chemical observatories to conveniently identify persistent and bioaccumulative CECs, including toxic organohalides. Nationally representative samples of sewage sludge (biosolids) were analyzed for 231 CECs, of which 123 were detected. Ten of the top 11 most abundant CECs in biosolids were found to be high-production volume chemicals, eight of which representing priority chemicals, including three flame retardants, three surfactants and two antimicrobials. A comparison of chemicals detected in nationally representative biological specimens from humans and municipal biosolids revealed 70% overlap. This observed co-occurrence of contaminants in both matrices suggests that the analysis of sewage sludge can inform human health risk assessments by providing current information on toxic exposures in human populations and associated body burdens of harmful environmental pollutants.

Using liquid chromatography tandem mass spectrometry, we determined the first nationwide inventories of 13 perfluoroalkyl substances (PFASs) in U.S. biosolids via analysis of samples collected by the U.S. Environmental Protection Agency in the 2001 National Sewage Sludge Survey. Perfluorooctane sulfonate [PFOS; 403 ± 127 ng/g dry weight (dw)] was the most abundant PFAS detected in biosolids composites representing 32 U.S. states and the District of Columbia, followed by perfluorooctanoate [PFOA; 34 ± 22 ng/g dw] and perfluorodecanoate [PFDA; 26 ± 20 ng/g dw]. Mean concentrations in U.S. biosolids of the remaining ten PFASs ranged between 2 and 21 ng/g dw. Interestingly, concentrations of PFOS determined here in biosolids collected prior to the phase-out period (2002) were similar to levels reported in the literature for recent years. The mean load of ∑PFASs in U.S. biosolids was estimated at 2749-3450 kg/year, of which about 1375-2070 kg is applied on agricultural land and 467-587 kg goes to landfills as an alternative disposal route. This study informs the risk assessment of PFASs by furnishing national inventories of PFASs occurrence and environmental release via biosolids application on land., (Copyright © 2013 Elsevier B.V. All rights reserved.)

We determined the first nationwide inventories of alkylphenol surfactants in U.S. sewage sludges (SS) using samples from the U.S. Environmental Protection Agency's 2001 national SS survey. Additionally, analysis of archived 3-year outdoor mesocosm samples served to determine chemical fates in SS-amended soil. Nonylphenol (NP) was the most abundant analyte (534 ± 192 mg/kg) in SS composites, followed by its mono- and di-ethoxylates (62.1 ± 28 and 59.5 ± 52 mg/kg, respectively). The mean annual load of NP and its ethoxylates in SS was estimated at 2408-7149 metric tonnes, of which 1204-4289 is applied on U.S. land. NP compounds showed observable loss from SS/soil mixtures (1:2), with mean half-lives ranging from 301 to 495 days. Surfactant levels in U.S. SS ten-times in excess of European regulations, substantial releases to U.S. soils, and prolonged half-lives found under field conditions, all argue for the U.S. to follow Europe's move from 20 years ago to regulate these chemicals., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The antimicrobial agents triclosan (TCS), triclocarban (TCC) and their associated transformation products are of increasing concern as environmental pollutants due to their potential adverse effects on humans and wildlife, including bioaccumulation and endocrine-disrupting activity. Analysis by tandem mass spectrometry of 24 paired freshwater bed sediment samples (top 10 cm) collected by the U.S. Geological Survey near 12 wastewater treatment plants (WWTPs) in Minnesota revealed TCS and TCC concentrations of up to 85 and 822 ng/g dry weight (dw), respectively. Concentrations of TCS and TCC in bed sediments collected downstream of WWTPs were significantly greater than upstream concentrations in 58% and 42% of the sites, respectively. Dichloro- and non-chlorinated carbanilides (DCC and NCC) were detected in sediments collected at all sites at concentrations of up to 160 and 1.1 ng/g dw, respectively. Overall, antimicrobial concentrations were significantly higher in lakes than in rivers and creeks, with relative abundances decreasing from TCC>TCS>DCC>NCC. This is the first statewide report on the occurrence of TCS, TCC and TCC transformation products in freshwater sediments. Moreover, the results suggest biological or chemical TCC dechlorination products to be ubiquitous in freshwater environments of Minnesota, but whether this transformation occurs in the WWTP or bed sediment remains to be determined., (Copyright © 2012 Elsevier B.V. All rights reserved.)

This study evaluates the impact of urban growth in the Las Vegas Valley (LVV), Nevada, USA on salinity of the Colorado River. In the past thirty eight years the LVV population has grown from 273,288 (1970) to 1,986,146 (2008). The wastewater effluents and runoff from the valley are diverted back to the Colorado River through the Las Vegas Wash (LVW). With the growth of the valley, the salinity released from urban areas has increased the level of TDS in the wastewater effluents, ultimately increasing the TDS in the Colorado River. The increased usage of water softeners in residential and commercial locations is a major contributor of TDS in the wastewater effluents. Controlling TDS release to the Colorado River is important because of the 1944 Treaty signed between the USA and Mexico. In addition, the agriculture salinity damage cost for the Colorado River has been estimated to be more than $306 a million per year using 2004 salinity levels. With the expected growth of LVV in coming years the TDS release into Lake Mead will increase over time. For this purpose, it is important to investigate future TDS release into the Colorado in anticipation of potential TDS reducing measures to be adopted. In this research, a dynamic simulation model was developed using system dynamics modeling to carry out water and TDS mass balances over the entire LVV. The dynamic model output agreed with historic data with an average error of 2%. Forecasts revealed that conservation efforts can reduce TDS load by 16% in the year 2035 when compared to the current trend. If total population using water softeners can be limited to 10% in the year 2035, from the current 30% usage, TDS load in the LVW can be reduced by 7%., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Selective ion-exchange resins are very effective to remove perchlorate from contaminated waters. However, these resins are currently incinerated after one time use, making the ion-exchange process incomplete and unsustainable for perchlorate removal. Resin bioregeneration is a new concept that combines ion-exchange with biological reduction by directly contacting perchlorate-laden resins with a perchlorate-reducing bacterial culture. In this research, feasibility of the bioregeneration of perchlorate-laden gel-type anion-exchange resin was investigated. Bench-scale bioregeneration experiments, using a fluidized bed reactor and a bioreactor, were performed to evaluate the feasibility of the process and to gain insight into potential mechanisms that control the process. The results of the bioregeneration tests suggested that the initial phase of the bioregeneration process might be controlled by kinetics, while the later phase seems to be controlled by diffusion. Feasibility study showed that direct bioregeneration of gel-type resin was effective in a fluidized-bed reactor, and that the resin could be defouled, reused, and repeatedly regenerated using the method applied in this research., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)