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.

Molecular Insights into MpAGO1 and Its Regulatory miRNA, miR11707, in the High-Temperature Acclimation of Marchantia polymorpha.

As a model plant for bryophytes, Marchantia polymorpha offers insights into the role of RNA silencing in aiding early land plants navigate the challenges posed by high-temperature environments. Genomic analysis revealed unique ARGONAUTE1 ortholog gene (MpAGO1) in M. polymorpha, which is regulated by two species-specific microRNAs (miRNAs), miR11707.1 and miR11707.2. Comparative studies of small RNA profiles from M. polymorpha cellular and MpAGO1 immunoprecipitation (MpAGO1-IP) profiles at various temperatures, along with analyses of Arabidopsis AGO1 (AtAGO1), revealed that MpAGO1 has a low selectivity for a diverse range of small RNA species than AtAGO1. Protein structural comparisons revealed no discernible differences in the guide strand small RNA recognition middle domain, MID domain, of MpAGO1 and AtAGO1, suggesting the complexity of miRNA species specificity and necessitating further exploration. Small RNA profiling and size exclusion chromatography have pinpointed a subset of M. polymorpha miRNAs, notably miR11707, that remain in free form within the cell at 22°C but are loaded into MpAGO1 at 28°C to engage in RNA silencing. Investigations into the mir11707 gene editing (mir11707ge) mutants provided evidence of the regulation of miR11707 in MpAGO1. Notably, while MpAGO1 mRNA expression decreases at 28°C, the stability of the MpAGO1 protein and its associated miRNAs is essential for enhancing the RNA-inducing silencing complex (RISC) activity, revealing the importance of RNA silencing in enabling M. polymorpha to survive thermal stress. This study advances our understanding of RNA silencing in bryophytes and provides groundbreaking insights into the evolutionary resilience of land plants to climatic adversities.

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.

In Operando X-ray Spectroscopic and DFT Studies Revealing Improved H2 Evolution by the Synergistic Ni-Co Electron Effect in the Alkaline Condition.

The different electrolyte conditions, e.g., pH value, for driving efficient HER and OER are one of the major issues hindering the aim for electrocatalytic water splitting in a high efficiency. In this regard, seeking durable and active HER electrocatalysts to align the alkaline conditions of the OER is a promising solution. However, the success in this strategy will depend on a fundamental understanding about the HER mechanism at the atomic scale. In this work, we have provided thorough understanding for the electrochemical HER mechanisms in KOH over Ni- and Co-based hollow pyrite microspheres by in operando X-ray spectroscopies and DFT calculations, including NiS2, CoS2, and Ni0.5Co0.5S2. We discovered that the Ni sites in hollow NiS2 microspheres were very stable and inert, while the Co sites in hollow CoS2 microspheres underwent reduction and generated Co metallic crystal domains under HER. The generation of Co metallic sites would further deactivate H2 evolution due to the large hydrogen desorption free energy (-1.73 eV). In contrast, the neighboring Ni and Co sites in hollow Ni0.5Co0.5S2 microspheres exhibited the electronic interaction to elevate the reactivity of Ni and facilitate the stability of Co without structure or surface degradation. The energy barrier in H2O adsorption/dissociation was only 0.73 eV, followed by 0.06 eV for hydrogen desorption over the Ni0.5Co0.5S2 surface, revealing Ni0.5Co0.5S2 as a HER electrocatalyst with higher durability and activity than NiS2 and CoS2 in the alkaline medium due to the synergy of neighboring Ni and Co sites. We believe that the findings in our work offer a guidance toward future catalyst design.

Dual Regulation of Cytochrome P450 Gene Expression by Two Distinct Small RNAs, a Novel tasiRNA and miRNA, in Marchantia polymorpha.

The miR390-derived TAS3 trans-acting short-interfering RNAs (tasiRNAs) module represents a conserved RNA silencing pathway in the plant kingdom; however, its characterization in the bryophyte Marchantia polymorpha is limited. This study elucidated that MpDCL4 processes MpTAS3 double-stranded RNA (dsRNA) to generate tasiRNAs, primarily from the 5'- and 3'-ends of dsRNA. Notably, we discovered a novel tasiRNA, tasi78A, which can negatively regulate a cytochrome P450 gene, MpCYP78A101. Additionally, tasi78A was abundant in MpAGO1, and transient expression assays underscored the role of tasi78A in repressing MpCYP78A101. A microRNA, miR11700, also regulates MpCYP78A101 expression. This coordinate regulation suggests a role in modulating auxin signaling at apical notches of gemma, influencing the growth and sexual organ development of M. polymorpha and emphasizing the significance of RNA silencing in MpCYP78A101 regulation. However, phylogenetic analysis identified another paralog of the CYP78 family, Mp1g14150, which may have a redundant role with MpCYP78A101, explaining the absence of noticeable morphological changes in loss-of-function plants. Taken together, our findings provide new insights into the combined regulatory roles of miR390/MpTAS3/miR11700 in controlling MpCYP78A101 and expand our knowledge about the biogenesis and regulation of tasiRNAs in M. polymorpha.

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.

Associations between total mercury, trace minerals, and blood health markers in Northwest Atlantic white sharks (Carcharodon carcharias).

The ecology and life-histories of white sharks make this species susceptible to mercury bioaccumulation; however, the health consequences of mercury exposure are understudied. We measured muscle and plasma total mercury (THg), health markers, and trace minerals in Northwest Atlantic white sharks. THg in muscle tissue averaged 10.0 mg/kg dry weight, while THg in blood plasma averaged 533 µg/L. THg levels in plasma and muscle were positively correlated with shark precaudal length (153-419 cm), and THg was bioaccumulated proportionally in muscle and plasma. Nine sharks had selenium:mercury molar ratios in blood plasma >1.0, indicating that for certain individuals the potential protective effects of the trace mineral were diminished, whereas excess selenium may have protected other individuals. No relationships between plasma THg and any trace minerals or health markers were identified. Thus, we found no evidence of negative effects of Hg bioaccumulation, even in sharks with very high THg.

Sodium Alginate-Aldehyde Cellulose Nanocrystal Composite Hydrogel for Doxycycline and Other Tetracycline Removal.

A novel composite hydrogel bead composed of sodium alginate (SA) and aldehyde cellulose nanocrystal (DCNC) was developed for antibiotic remediation through a one-step cross-linking process in a calcium chloride bath. Structural and physical properties of the hydrogel bead, with varying composition ratios, were analyzed using techniques such as BET analysis, SEM imaging, tensile testing, and rheology measurement. The optimal composition ratio was found to be 40% (SA) and 60% (DCNC) by weight. The performance of the SA-DCNC hydrogel bead for antibiotic remediation was evaluated using doxycycline (DOXY) and three other tetracyclines in both single- and multidrug systems, yielding a maximum adsorption capacity of 421.5 mg g-1 at pH 7 and 649.9 mg g-1 at pH 11 for DOXY. The adsorption mechanisms were investigated through adsorption studies focusing on the effects of contact time, pH, concentration, and competitive contaminants, along with X-ray photoelectron spectroscopy analysis of samples. The adsorption of DOXY was confirmed to be the synergetic effects of chemical reaction, electrostatic interaction, hydrogen bonding, and pore diffusion/surface deposition. The SA-DCNC composite hydrogel demonstrated high reusability, with more than 80% of its adsorption efficiency remaining after five cycles of the adsorption-desorption test. The SA-DCNC composite hydrogel bead could be a promising biomaterial for future antibiotic remediation applications in both pilot and industrial scales because of its high adsorption efficiency and ease of recycling.

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 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.

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).

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.

Risk assessment for seafood consumers exposed to mercury and other trace elements in fish from Long Island, New York, USA.

We determined concentrations of Hg, Pb, Cd, Cr, As, Ni, Ag, Se, Cu, and Zn in muscle tissue of six commonly consumed Long Island fish species (black seabass, bluefish, striped bass, summer flounder, tautog, and weakfish, total sample size = 1211) caught off Long Island, New York in 2018 and 2019. Long-term consumption of these coastal fish could pose health risks largely due to Hg exposure; concentrations of the other trace elements were well below levels considered toxic for humans. By combining the measured Hg concentrations in the fish (means ranging from 0.11 to 0.27 mg/kg among the fish species), the average seafood consumption rate, and the current US EPA Hg reference dose (0.0001 mg/kg/d), it was concluded that seafood consumption should be limited to four fish meals per month for adults for some fish (bluefish, tautog) and half that for young children. Molar ratios of Hg:Se exceeded 1 for some black seabass, bluefish, tautog, and weakfish.

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.

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.

Effects of methylmercury on the early life stages of an estuarine forage fish using two different dietary sources.

Marine fish accumulate methylmercury (MeHg) to elevated concentrations, often higher than in freshwater systems. As a neurotoxic compound, high MeHg tissue concentrations could affect fish behavior which in turn could affect their populations. We examined the sublethal effects of MeHg on larvae of the Sheepshead minnow (Cyprinodon variegatus), an estuarine fish, using artificial or natural diets with varying MeHg concentrations (0-4.8 ppm). Larvae were fed control and MeHg-contaminated diets at low or normal (10% of their body mass) daily food rations from 7 to 29 days when they reached juvenile stage. Growth, respiration, swimming activity and prey capture ability were assessed. Food ration affected Hg toxicity in our study. Natural diets containing 3.2 ppm MeHg had no impacts on growth and swimming in fish that were fed normal food rations but depressed growth and swimming at low food rations. MeHg toxicity did not differ between artificial and natural foods, however fish accumulated more MeHg from the former. Artificial food containing 4.8 ppm MeHg only affected prey capture after 21 days of exposure. Sheepshead minnows, a forage fish species occupying a low trophic level in coastal waters, can be MeHg tolerant, especially when food is abundant, and can serve as an enriched Hg source for higher trophic level predators.

Metal concentrations in coastal sharks from The Bahamas with a focus on the Caribbean Reef shark.

Over the last century anthropogenic activities have rapidly increased the influx of metals and metalloids entering the marine environment, which can bioaccumulate and biomagnify in marine top consumers. This may elicit sublethal effects on target organisms, having broad implications for human seafood consumers. We provide the first assessment of metal (Cd, Pb, Cr, Mn, Co, Cu, Zn, As, Ag, and THg) and metalloid (As) concentrations in the muscle tissue of coastal sharks from The Bahamas. A total of 36 individual sharks from six species were evaluated, spanning two regions/study areas, with a focus on the Caribbean reef shark (Carcharhinus perezi), and to a lesser extent the tiger shark (Galeocerdo cuvier). This is due their high relative abundance and ecological significance throughout coastal Bahamian and regional ecosystems. Caribbean reef sharks exhibited some of the highest metal concentrations compared to five other species, and peaks in the concentrations of Pb, Cr, Cu were observed as individuals reached sexual maturity. Observations were attributed to foraging on larger, more piscivorous prey, high longevity, as well a potential slowing rate of growth. We observed correlations between some metals, which are challenging to interpret but may be attributed to trophic level and ambient metal conditions. Our results provide the first account of metal concentrations in Bahamian sharks, suggesting individuals exhibit high concentrations which may potentially cause sublethal effects. Finally, these findings underscore the potential toxicity of shark meat and have significant implications for human consumers.

Metal Organic Framework-Polyethersulfone Composite Membrane for Iodine Capture.

A variety of metal organic frameworks (MOFs) were synthesized and evaluated for their iodine adsorption capacity. Out of the MOFs tested, ZIF-8 showed the most promising result with an iodine vapor uptake of 876.6 mg/g. ZIF-8 was then incorporated into a polymer, polyethersulfone (PES), at different proportions to prepare mixed matrix membranes (MMMs), which were then used to perform further iodine adsorption experiments. With a mixing ratio of 40 wt % of ZIF-8, the iodine adsorption capacity reached 1387.6 mg/g, wherein an astounding 60% improvement in adsorption was seen with the MMMs prepared compared to the original ZIF-8 powder.