Prairie pothole lakes (PPLs) are glacially derived, ecologically important water bodies found in central North America and represent a unique setting in which extensive agriculture occurs within wetland ecosystems. In the Prairie Pothole Region (PPR), elevated pesticide use and increasing hydrologic connectivity have raised concerns about the impact of nonpoint source agricultural pollution on the water quality of PPLs and downstream aquatic systems. Despite containing high dissolved organic matter (DOM) levels, the photoreactivity of the PPL water and the photochemical fate of pesticides entering PPLs are largely unknown. In this study, the photodegradation of sixteen pesticides was investigated in PPL waters sampled from North Dakota, under simulated and natural sunlight. Enhanced pesticide removal rates in the irradiated PPL water relative to the control buffer pointed to the importance of indirect photolysis pathways involving photochemically produced reactive intermediates (PPRIs). The steady-state concentrations of carbonate radical, hydroxyl radical, singlet oxygen, and triplet-excited state DOM were measured and second-order rate constants for reactions of pesticides with these PPRIs were calculated. Results from this study underscore the role of DOM as photosensitizer in limiting the persistence of pesticides in prairie wetlands through photochemical reactions.
Water utilities are increasingly considering indirect and direct potable reuse of municipal wastewater effluents. Disinfection byproducts (DBPs), particularly N-nitrosamines, are key contaminants of potential health concern for potable reuse. This study quantified the concentrations of N-nitrosamines and a suite of regulated and unregulated halogenated DBPs across five U.S. potable reuse Full Advanced Treatment trains incorporating microfiltration, reverse osmosis, and UV-based advanced oxidation. Low μg/L concentrations of trihalomethanes, haloacetic acids, dichloroacetonitrile, and dichloroacetamide were detected in the secondary or tertiary wastewater effluents serving as influents to potable reuse treatment trains, while the concentrations of N-nitrosamines were more variable (e.g., <2-320 ng/L for N-nitrosodimethylamine). Ozonation promoted the formation of N-nitrosamines, haloacetaldehydes, and haloacetamides, but biological activated carbon effectively reduced concentrations of these DBPs. Application of chloramines upstream of microfiltration for biofouling control increased DBP concentrations to their highest levels observed along the treatment trains. Reverse osmosis rejected DBPs to varying degrees, ranging from low for some (e.g., N-nitrosamines, trihalomethanes, and haloacetonitriles) to high for other DBPs. UV-based advanced oxidation eliminated N-nitrosamines, but only partially removed halogenated DBPs. Chloramination of the treatment train product waters under simulated distribution system conditions formed additional DBPs, with concentrations often equaling or exceeding those in the treatment train influents. Overall, the concentration profiles of DBPs were fairly consistent within individual treatment trains for sampling campaigns separated by months and across different treatment trains for the same sampling time window. Weighting DBP concentrations by their toxic potencies highlighted the potential significance of haloacetonitriles, which were not effectively removed by reverse osmosis and advanced oxidation, to the DBP-associated toxicity in potable reuse waters.
The disposal and leaks of hydraulic fracturing wastewater (HFW) to the environment pose human health risks. Since HFW is typically characterized by elevated salinity, concerns have been raised whether the high bromide and iodide in HFW may promote the formation of disinfection byproducts (DBPs) and alter their speciation to more toxic brominated and iodinated analogues. This study evaluated the minimum volume percentage of two Marcellus Shale and one Fayetteville Shale HFWs diluted by fresh water collected from the Ohio and Allegheny Rivers that would generate and/or alter the formation and speciation of DBPs following chlorination, chloramination, and ozonation treatments of the blended solutions. During chlorination, dilutions as low as 0.01% HFW altered the speciation toward formation of brominated and iodinated trihalomethanes (THMs) and brominated haloacetonitriles (HANs), and dilutions as low as 0.03% increased the overall formation of both compound classes. The increase in bromide concentration associated with 0.01-0.03% contribution of Marcellus HFW (a range of 70-200 μg/L for HFW with bromide = 600 mg/L) mimics the increased bromide levels observed in western Pennsylvanian surface waters following the Marcellus Shale gas production boom. Chloramination reduced HAN and regulated THM formation; however, iodinated trihalomethane formation was observed at lower pH. For municipal wastewater-impacted river water, the presence of 0.1% HFW increased the formation of N-nitrosodimethylamine (NDMA) during chloramination, particularly for the high iodide (54 ppm) Fayetteville Shale HFW. Finally, ozonation of 0.01-0.03% HFW-impacted river water resulted in significant increases in bromate formation. The results suggest that total elimination of HFW discharge and/or installation of halide-specific removal techniques in centralized brine treatment facilities may be a better strategy to mitigate impacts on downstream drinking water treatment plants than altering disinfection strategies. The potential formation of multiple DBPs in drinking water utilities in areas of shale gas development requires comprehensive monitoring plans beyond the common regulated DBPs.
Wastewater surveillance of SARS-CoV-2 RNA is increasingly being incorporated into public health efforts to respond to the COVID-19 pandemic. In order to obtain the maximum benefit from these efforts, approaches to wastewater monitoring need to be rapid, sensitive, and relatable to relevant epidemiological parameters. In this study, we present an ultracentrifugation-based method for the concentration of SARS-CoV-2 wastewater RNA and use crAssphage, a bacteriophage specific to the human gut, to help account for RNA loss during transit in the wastewater system and sample processing. With these methods, we were able to detect, and sometimes quantify, SARS-CoV-2 RNA from 20 mL wastewater samples within as little as 4.5 hours. Using known concentrations of bovine coronavirus RNA and deactivated SARS-CoV-2, we estimate recovery rates of approximately 7-12% of viral RNA using our method. Results from 24 sewersheds across Upstate New York during the spring and summer of 2020 suggested that stronger signals of SARS-CoV-2 RNA from wastewater may be indicative of greater COVID-19 incidence in the represented service area approximately one week in advance. SARS-CoV-2 wastewater RNA was quantifiable in some service areas with daily positives tests of less than 1 per 10,000 people or when weekly positive test rates within a sewershed were as low as 1.7%. crAssphage DNA concentrations were significantly lower during periods of high flow in almost all areas studied. After accounting for flow rate and population served, crAssphage levels per capita were estimated to be about 1.35 × 10 11 and 2.42 × 10 8 genome copies per day for DNA and RNA, respectively. A negative relationship between per capita crAssphage RNA and service area size was also observed likely reflecting degradation of RNA over long transit times. Our results reinforce the potential for wastewater surveillance to be used as a tool to supplement understanding of infectious disease transmission obtained by traditional testing and highlight the potential for crAssphage co-detection to improve interpretations of wastewater surveillance data.
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