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Differences in neonicotinoid and metabolite sorption to activated carbon are driven by alterations to the insecticidal pharmacophore

Widespread application of neonicotinoids has led to their proliferation in waters. Despite low neonicotinoid hydrophobicity, our prior studies implicated granular activated carbon (GAC) in neonicotinoid removal. Based on known receptor binding characteristics, we hypothesized that the insecticidal pharmacophore influences neonicotinoid sorption. Our objectives were to illuminate drivers of neonicotinoid sorption for parent neonicotinoids (imidacloprid, clothianidin, thiamethoxam, and thiacloprid) and pharmacophore-altered metabolites (desnitro-imidacloprid and imidacloprid urea) to GAC, powdered activated carbon, and carbon nanotubes (CNTs). Neonicotinoid sorption to GAC was extensive and largely irreversible, with significantly greater sorption of imidacloprid than desnitro-imidacloprid. Imidacloprid and imidacloprid urea (electronegative pharmacophores) sorbed most extensively to nonfunctionalized CNTs, whereas desnitro-imidacloprid (positive pharmacophore) sorbed most to COOH-CNTs, indicating the importance of charge interactions and/or hydrogen bonding between the pharmacophore and carbon surface. Water chemistry parameters (temperature, alkalinity, ionic strength, and humic acid) inhibited overall neonicotinoid sorption, suggesting that pharmacophore-driven sorption in real waters may be diminished. Analysis of a full-scale drinking water treatment plant GAC filter influent, effluent, and spent GAC attributes neonicotinoid/metabolite removal to GAC under real-world conditions for the first time. Our results demonstrate that the neonicotinoid pharmacophore not only confers insecticide selectivity but also impacts sorption behavior, leading to less effective removal of metabolites by GAC filters in water treatment.

Environmental Science and Technology↗

Vertical distribution of microplastics in the water column and surficial sediment from the Milwaukee River basin to Lake Michigan

Microplastic contamination was studied along a freshwater continuum from inland streams to the Milwaukee River estuary to Lake Michigan, and vertically from the water surface, water subsurface and sediment. Microplastics were detected in all 96 water samples and nine sediment samples collected. Results indicated a gradient of polymer presence with depth: low-density particles decreased from water surface to subsurface to sediment, and high-density particles had the opposite result. Polymer identification results indicated water surface and subsurface samples were dominated by low-density polypropylene particles and sediment samples were dominated by more dense polyethylene terephthalate particles. Of the five particle-type categories (fragments, films, foams, pellets/beads and fibers/lines), fibers/lines were the most common particle type and were present in every water and sediment sample collected. Fibers represented 45% of all particles in water samples and were distributed vertically throughout the water column regardless of density. Sediment samples were dominated by black foams (66%, identified as styrene-butadiene rubber, SBR) and to a lesser extent fibers/lines (29%) with approximately 89% of all the sediment particles coming from polymers with densities greater than 1.1 g cm-3. Results demonstrated polymer density influenced partitioning between water surface and subsurface and the underlying surficial sediment and the common practice of sampling only the water surface can result in substantial bias, especially in estuarine, harbor and lake locations where water surface concentrations tend to overestimate mean water column concentrations.

Wisconsin↗

Measurement of in situ rates of selenate removal by dissimilatory bacterial reduction in sediments

A radioisotope method for measurement of bacteria respiratory reduction of selenate to elemental selenium in aquatic sediments was devised. Sediments were labeled with [75Se]selenate, incubated, and washed, and 75Se0(s) was determined as counts remaining in the sediments. Core profiles of selenate reduction, sulfate reduction, and denitrification were made simultaneously in the sediments of an agricultural wastewater evaporation pond. Most of the in situ selenate reduction (85%) and all the denitrificatation activities were confined to the upper 4-8 cm of the profile, whereas sulfate reduction was greatest below 8 cm (89% of total). The integrated areal rate of selenate reduction was 301 mol m-2 day-1, which results in a turnover of water column selenate in 82.4 days.

Environmental Science & Technology↗

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology↗

Methane emissions from artificial waterbodies dominate the carbon footprint of irrigation: A study of transitions in the food-energy-water-climate nexus (Spain, 1900-2014)

Irrigation in the Mediterranean region has been used for millennia and has greatly expanded with industrialization. Irrigation is critical for climate change adaptation, but it is also an important source of greenhouse gas emissions. This study analyzes the carbon (C) footprint of irrigation in Spain, covering the complete historical process of mechanization. A 21-fold total, 6-fold area-based, and 4-fold product-based increase in the carbon footprint was observed during the 20th century, despite an increase in water use efficiency. CH 4 emissions from waterbodies, which had not previously been considered in the C footprint of irrigation systems, dominated the emission budget during most of the analyzed period. Technologies to save water and tap new water resources greatly increased energy and infrastructure demand, while improvements in power generation efficiency had a limited influence on irrigation emissions. Electricity production from irrigation dams may contribute to climate change mitigation, but the amount produced in relation to that consumed in irrigation has greatly declined. High uncertainty in CH 4 emission estimates from waterbodies stresses a need for more spatially resolved data and an improved empirical knowledge of the links between water quality, water level fluctuations, and emissions at the regional scale.

Environmental Science & Technology↗

Occurrence of neonicotinoid insecticides in finished drinking water and fate during drinking water treatment

Neonicotinoid insecticides are widespread in surface waters across the agriculturally-intensive Midwestern US. We report for the first time the presence of three neonicotinoids in finished drinking water and demonstrate their general persistence during conventional water treatment. Periodic tap water grab samples were collected at the University of Iowa over seven weeks in 2016 (May-July) after maize/soy planting. Clothianidin, imidacloprid, and thiamethoxam were ubiquitously detected in finished water samples and ranged from 0.24-57.3 ng/L. Samples collected along the University of Iowa treatment train indicate no apparent removal of clothianidin and imidacloprid, with modest thiamethoxam removal (~50%). In contrast, the concentrations of all neonicotinoids were substantially lower in the Iowa City treatment facility finished water using granular activated carbon (GAC) filtration. Batch experiments investigated potential losses. Thiamethoxam losses are due to base-catalyzed hydrolysis at high pH conditions during lime softening. GAC rapidly and nearly completely removed all three neonicotinoids. Clothianidin is susceptible to reaction with free chlorine and may undergo at least partial transformation during chlorination. Our work provides new insights into the persistence of neonicotinoids and their potential for transformation during water treatment and distribution, while also identifying GAC as an effective management tool to lower neonicotinoid concentrations in finished drinking water.

Environmental Science & Technology Letters↗

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

California↗

Relationship between mercury accumulation in young-of-the-year yellow perch and water-level fluctuations

A three-year (2001−2003) monitoring effort of 14 northeastern Minnesota lakes was conducted to document relationships between water-level fluctuations and mercury bioaccumulation in young-of-the-year (YOY) yellow perch ( Perca flavescens ) collected in the fall of each year at fixed locations. Six of those lakes are located within or adjacent to Voyageurs National Park and are influenced by dams on the outlets of Rainy and Namakan lakes. One site on Sand Point Lake coincides with a location that has nine years of previous monitoring suitable for addressing the same issue over a longer time frame. Mean mercury concentrations in YOY yellow perch at each sampling location varied significantly from year to year. For the 12-year monitoring site on Sand Point Lake, values ranged from 38 ng gww - 1 in 1998 to 200 ng gww - 1 in 2001. For the 14-lake study, annual mean concentrations ranged by nearly a factor of 2, on average, for each lake over the three years of record. One likely factor responsible for these wide variations is that annual water-level fluctuations are strongly correlated with mercury levels in YOY perch for both data sets.

Environmental Science & Technology↗

Isotopically modified nanoparticles for enhanced detection in bioaccumulation studies

This work presents results on synthesis of isotopically enriched (99% 65 Cu) copper oxide nanoparticles and its application in ecotoxicological studies. 65 CuO nanoparticles were synthesized as spheres (7 nm) and rods (7 × 40 nm). Significant differences were observed between the reactivity and dissolution of spherical and rod shaped nanoparticles. The extreme sensitivity of the stable isotope tracing technique developed in this study allowed determining Cu uptake at exposure concentrations equivalent to background Cu concentrations in freshwater systems (0.2–30 μg/L). Without a tracer, detection of newly accumulated Cu was impossible, even at exposure concentrations surpassing some of the most contaminated water systems (>1 mg/L).

Environmental Science & Technology↗

Nitrogen enrichment during soil organic matter burning and molecular evidence of maillard reactions

Wildfires in forested watersheds dramatically alter stored and labile soil organic matter (SOM) pools and the export of dissolved organic matter (DOM). Ecosystem recovery after wildfires depends on soil microbial communities and revegetation and therefore is limited by the availability of nutrients, such as nitrogen-containing and labile, water-soluble compounds. However, SOM byproducts produced at different wildfire intensities are poorly understood, leading to difficulties in assessing wildfire severity and predicting ecosystem recovery. In this work, water-extractable organic matter (WEOM) from laboratory microcosms of soil burned at discrete temperatures was characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to study the impacts of fire temperature on SOM and DOM composition. The molecular composition derived from different burn temperatures indicated that nitrogen-containing byproducts were enriched with heating and composed of a wide range of aromatic features and oxidation states. Mass difference-based analysis also suggested that products formed during heating could be modeled using transformations along the Maillard reaction pathway. The enrichment of N-containing SOM and DOM at different soil burning intensities has important implications for ecosystem recovery and downstream water quality.

Environmental Science and Technology↗

A reconnaissance study of herbicides and their metabolites in surface water of the midwestern united states using immunoassay and gas chromatography/mass spectrometry

Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.

Environmental Science & Technology↗

A fresh look at road salt: Aquatic toxicity and water-quality impacts on local, regional, and national scales

A new perspective on the severity of aquatic toxicity impact of road salt was gained by a focused research effort directed at winter runoff periods. Dramatic impacts were observed on local, regional, and national scales. Locally, samples from 7 of 13 Milwaukee, Wisconsin area streams exhibited toxicity in Ceriodaphnia dubia and Pimephales promelas bioassays during road-salt runoff. Another Milwaukee stream was sampled from 1996 to 2008 with 72% of 37 samples exhibiting toxicity in chronic bioassays and 43% in acute bioassays. The maximum chloride concentration was 7730 mg/L. Regionally, in southeast Wisconsin, continuous specific conductance was monitored as a chloride surrogate in 11 watersheds with urban land use from 6.0 to 100%. Elevated specific conductance was observed between November and April at all sites, with continuing effects between May and October at sites with the highest specific conductance. Specific conductance was measured as high as 30 800 ??S/cm (Cl = 11 200 mg/L). Chloride concentrations exceeded U.S. Environmental Protection Agency (USEPA) acute (860 mg/L) and chronic (230 mg/L) water-quality criteria at 55 and 100% of monitored sites, respectively. Nationally, U.S. Geological Survey historical data were examined for 13 northern and 4 southern metropolitan areas. Chloride concentrations exceeded USEPA water-quality criteria at 55% (chronic) and 25% (acute) of the 168 monitoring locations in northern metropolitan areas from November to April. Only 16% (chronic) and 1% (acute) of sites exceeded criteria from May to October. At southern sites, very few samples exceeded chronic water-quality criteria, and no samples exceeded acute criteria. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Bacterial pathogen gene abundance and relation to recreational water quality at seven Great Lakes beaches

Quantitative assessment of bacterial pathogens, their geographic variability, and distribution in various matrices at Great Lakes beaches are limited. Quantitative PCR (qPCR) was used to test for genes from E. coli O157:H7 ( eae O157 ), shiga-toxin producing E. coli ( stx2 ), Campylobacter jejuni ( mapA ), Shigella spp. ( ipaH ), and a Salmonella enterica -specific ( SE ) DNA sequence at seven Great Lakes beaches, in algae, water, and sediment. Overall, detection frequencies were mapA > stx2 > ipaH > SE > eae O157 . Results were highly variable among beaches and matrices; some correlations with environmental conditions were observed for mapA , stx2 , and ipaH detections. Beach seasonal mean mapA abundance in water was correlated with beach seasonal mean log 10 E. coli concentration. At one beach, stx2 gene abundance was positively correlated with concurrent daily E. coli concentrations. Concentration distributions for stx2 , ipaH , and mapA within algae, sediment, and water were statistically different (Non-Detect and Data Analysis in R). Assuming 10, 50, or 100% of gene copies represented viable and presumably infective cells, a quantitative microbial risk assessment tool developed by Michigan State University indicated a moderate probability of illness for Campylobacter jejuni at the study beaches, especially where recreational water quality criteria were exceeded. Pathogen gene quantification may be useful for beach water quality management.

Environmental Science & Technology↗

High-resolution remote sensing of water quality in the San Francisco Bay-Delta Estuary

The San Francisco Bay–Delta Estuary watershed is a major source of freshwater for California and a profoundly human-impacted environment. The water quality monitoring that is critical to the management of this important water resource and ecosystem relies primarily on a system of fixed water-quality monitoring stations, but the limited spatial coverage often hinders understanding. Here, we show how the latest technology in visible/near-infrared imaging spectroscopy can facilitate water quality monitoring in this highly dynamic and heterogeneous system by enabling simultaneous depictions of several water quality indicators at very high spatial resolution. The airborne portable remote imaging spectrometer (PRISM) was used to derive high-spatial-resolution (2.6 × 2.6 m) distributions of turbidity, and dissolved organic carbon (DOC) and chlorophyll-a concentrations in a wetland-influenced region of this estuary. A filter-passing methylmercury vs DOC relationship was also developed using in situ samples and enabled the high-spatial-resolution depiction of surface methylmercury concentrations in this area. The results illustrate how high-resolution imaging spectroscopy can inform management and policy development in important inland and estuarine water bodies by facilitating the detection of point- and nonpoint-source pollution, and by providing data to help assess the complex impacts of wetland restoration and climate change on water quality and ecosystem productivity.

California↗

Large shift in source of fine sediment in the upper Mississippi River

Although sediment is a natural constituent of rivers, excess loading to rivers and streams is a leading cause of impairment and biodiversity loss. Remedial actions require identification of the sources and mechanisms of sediment supply. This task is complicated by the scale and complexity of large watersheds as well as changes in climate and land use that alter the drivers of sediment supply. Previous studies in Lake Pepin, a natural lake on the Mississippi River, indicate that sediment supply to the lake has increased 10-fold over the past 150 years. Herein we combine geochemical fingerprinting and a suite of geomorphic change detection techniques with a sediment mass balance for a tributary watershed to demonstrate that, although the sediment loading remains very large, the dominant source of sediment has shifted from agricultural soil erosion to accelerated erosion of stream banks and bluffs, driven by increased river discharge. Such hydrologic amplification of natural erosion processes calls for a new approach to watershed sediment modeling that explicitly accounts for channel and floodplain dynamics that amplify or dampen landscape processes. Further, this finding illustrates a new challenge in remediating nonpoint sediment pollution and indicates that management efforts must expand from soil erosion to factors contributing to increased water runoff.

Environmental Science & Technology↗

Evaluation of passive diffusion bag samplers, dialysis samplers, and nylon-screen samplers in selected wells at Andersen Air Force Base, Guam, March-April 2002

During March-April 2002, the U.S. Geological Survey, Earth Tech, and EA Engineering, Science, and Technology, Inc., in cooperation with the Air Force Center for Environmental Excellence, tested diffusion samplers at Andersen Air Force Base, Guam. Samplers were deployed in three wells at the Main Base and two wells at Marianas Bonins (MARBO) Annex as potential ground-water monitoring alternatives. Prior to sampler deployment, the wells were tested using a borehole flowmeter to characterize vertical flow within each well. Three types of diffusion samplers were tested: passive diffusion bag (PDB) samplers, dialysis samplers, and nylon-screen samplers. The primary volatile organic compounds (VOCs) tested in ground water at Andersen Air Force Base were trichloroethene and tetrachloroethene. In most comparisons, trichloroethene and tetrachloroethene concentrations in PDB samples closely matched concentrations in pumped samples. Exceptions were in wells where the pumping or ambient flow produced vertical translocation of water in a chemically stratified aquifer. In these wells, PDB samplers probably would be a viable alternative sampling method if they were placed at appropriate depths. In the remaining three test wells, the trichloroethene or tetrachloroethene concentrations obtained with the diffusion samplers closely matched the result from pumped sampling. In all of the tests, the regenerated cellulose dialysis samplers produced lower VOC concentrations than the passive diffusion bag samplers and most of the pumped results. The source of the difference is unknown, but a possible explanation may be the biodegradation of the dialysis membrane during the 22 to 23 days of deployment. Chloride concentrations in nylon-screen samplers were compared with chloride concentrations in dialysis and pumped samples to test inorganic-solute diffusion into the samplers across a range of concentrations. The test showed that the results from nylon-screen samplers might have underestimated chloride concentrations at depths with elevated chloride concentrations. The reason for the discrepancy in this investigation is unknown, but may be related to nylon-screen-mesh size, which was smaller than that used in previous investigations.

Andersen Air Force Base, Guam↗

Nitrate in groundwater of the United States, 1991-2003

An assessment of nitrate concentrations in groundwater in the United States indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high N inputs. During 1991-2003, 5101 wells were sampled in 51 study areas throughout the U.S. as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program. The well networks reflect the existing used resource represented by domestic wells in major aquifers (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations were highest in shallow groundwater beneath agricultural land use in areas with well-drained soils and oxic geochemical conditions. Nitrate concentrations were lowest in deep groundwater where groundwater is reduced, or where groundwater is older and hence concentrations reflect historically low N application rates. Classification and regression tree analysis was used to identify the relative importance of N inputs, biogeochemical processes, and physical aquifer properties in explaining nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that dissolved iron concentrations explained most of the variation in groundwater nitrate concentration, followed by manganese, calcium, farm N fertilizer inputs, percent well-drained soils, and dissolved oxygen. Overall, nitrate concentrations in groundwater are most significantly affected by redox conditions, followed by nonpoint-source N inputs. Other water-quality indicators and physical variables had a secondary influence on nitrate concentrations.

Environmental Science & Technology↗

Relation of usage to the occurrence of cotton and rice herbicides in three streams of the Mississippi delta

During the 1995 growing season water samples were collected from three streams in the Mississippi delta and were analyzed for selected cotton and rice herbicides and metabolites. The purpose of the study was to relate the use of these herbicides to their occurrence in streams of the delta, to describe how the geochemistry of these herbicides affects their occurrence, and to report the occurrence of selected metabolites. The total concentration of eight herbicides and their metabolites exceeded 5 μg/L throughout most of the growing season with a median total of 15 μg/L. The order of occurrence was molinate > fluometuron > cyanazine > metolachlor > norflurazon > atrazine > prometryn > propanil. The distribution and duration of the total herbicide concentration found in this study are much different from that found in regional studies of herbicides in the U.S. Midwest. In the Midwest, the total herbicide concentration in surface water showed a sharp peak during the spring immediately after application of herbicides to crops, followed by a gradual decrease. In the Mississippi delta, the total herbicide concentration in surface water was more sustained, with multiple peaks due to different application times and postemergent applications to cotton and rice.

Environmental Science & Technology↗