Accumulation of Per- and Polyfluoroalkyl Substances (PFAS) in Coastal Sharks from Contrasting Marine Environments: The New York Bight and The Bahamas.

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 2H,2H,3H,3H-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 (δ15N) 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.

Cationic surfactant-assisted foam fractionation enhances the removal of short-chain perfluoroalkyl substances from impacted water.

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.

Application of electron beam technology to decompose per- and polyfluoroalkyl substances in water.

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.

Monitoring of over-the-counter (OTC) and COVID-19 treatment drugs complement wastewater surveillance of SARS-CoV-2.

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.

Coexisting ions and long-chain per- and polyfluoroalkyl substances (PFAS) inhibit the adsorption of short-chain PFAS by granular activated carbon.

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 Kow 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.

1,4-Dioxane removal in nitrifying sand filters treating domestic wastewater: Influence of water matrix and microbial inhibitors.

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.

Characterization of 1,4-dioxane degrading microbial community enriched from uncontaminated soil.

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 (qmax) of 0.044 ± 0.001 mg dioxane h-1 mg protein-1, and 1,4-dioxane half-velocity constant (Ks) 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 Ks and low cell yield of the enrichment benefit its application in bioremediation.

The invasive red seaweed, Dasysiphonia japonica, forms harmful algal blooms: Mortality in early life stage fish and bivalves and identification of putative toxins.

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).

The Need for Testing Isomer Profiles of Perfluoroalkyl Substances to Evaluate Treatment Processes.

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.

Hydroxyl-radical based advanced oxidation processes can increase perfluoroalkyl substances beyond drinking water standards: Results from a pilot study.

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/H2O2, UV/Cl2, UV/TiO2, and O3/H2O2), 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.

Comparative meta-analysis of organic contaminants in sewage sludge from the United States and China.

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.

Occurrence and removal of PPCPs from on-site wastewater using nitrogen removing biofilters.

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.

Thermal Regeneration of Spent Granular Activated Carbon Presents an Opportunity to Break the Forever PFAS Cycle.

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.

Removal of 1,4-dioxane during on-site wastewater treatment using nitrogen removing biofilters.

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.

Impact of groundwater quality and associated byproduct formation during UV/hydrogen peroxide treatment of 1,4-dioxane.

In this study, a semi-batch, bench-scale UV/hydrogen peroxide (UV/H2O2) 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 H2O2 (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 cm2-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-CaCO3 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/H2O2 treatment. High NO3- 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 H2O2, but did not enhance the performance of UV/H2O2 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 (NO3-, 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 NO3- 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/H2O2 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.

Long-term tracking of opioid consumption in two United States cities using wastewater-based epidemiology approach.

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 ±â€¯38; 306 ±â€¯29; detection frequency (DF): 100%), oxycodone (17.8 ±â€¯1.1; 78 ±â€¯6; DF: 100%), codeine (332 ±â€¯37; 100 ±â€¯27; DF: 93%), heroin (41 ±â€¯16; 9 ±â€¯11; DF: 81%), and fentanyl (1.7 ±â€¯0.2; 1.0 ±â€¯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.

Alcohol and nicotine consumption trends in three U.S. communities determined by wastewater-based epidemiology.

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 3­hydroxycotinine, 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 ±â€¯5.6 L/y/person) and daily consumption of nicotine by smokers (14.2 ±â€¯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.

U.S. nationwide reconnaissance of ten infrequently monitored antibiotics in municipal biosolids.

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 (

Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water 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.

Detection and Sizing of Ti-Containing Particles in Recreational Waters Using Single Particle ICP-MS.

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 × 103 to 4.4 × 103 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 TiO2 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 TiO2 to aquatic organisms (< 1 µg/L).