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David A. Alvarez

Publications and source records attributed to David A. Alvarez.

At least 19 recordsLinked to original sources

Targeted quantitation of 6ppd-quinone in fish tissue samples with liquid chromatography-tandem mass spectrometry

The tire additive transformation product N -(1,3-dimethylbutyl)- N’ -phenyl- p -phenylenediamine-quinone (6PPD-quinone) has recently garnered global attention due to its acute toxicity to some salmonids, such as coho salmon ( Oncorhynchus kisutch ), and its ubiquitous presence in urban stormwater systems. In the present study, we developed and compared the extraction efficiency of two sample preparation methodologies for quantification of 6PPD-quinone among two fish tissue sample types that included fillet of smallmouth bass ( Micropterus dolomieu ) and whole-body samples of O. kisutch fry subjected to in vivo exposure tests with 6PPD-quinone. The two sample preparation methods tested included an accelerated solvent extraction (ASE) approach and a sonication extraction approach. Both sample preparation methods included identical purification steps for the crude sample extracts with enhanced matrix removal cartridges. The purified sample extracts were subjected to targeted analysis of 6PPD-quinone using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The results showed that extractions made with the reported ASE method demonstrated significantly higher absolute recovery (80–96%) of the extracted internal standard, [ 13 C 6 ]-6PPD-quinone, than sonication-based extractions (74–80%) in both fish tissue sample types. The proposed ASE method shows acceptable limits of quantification (0.37–0.67 ng g −1 ), linearity (R 2 > 0.996), and repeatability (RSD ≤ 9%). This work advances research capabilities for investigations on the toxicokinetic processes of 6PPD-quinone in biological samples.

Environmental Toxicology and Chemistry

Per- and polyfluoroalkyl substances in surface water and sediment in Great Lakes tributaries and relations with watershed attributes

Per- and polyfluoroalkyl substances (PFAS) are chemicals of emerging concern that potentially pose risks to human and environmental health. In May–Oct 2018, sediment and passively collected surface water samples were collected from 62 tributary sites of the Laurentian Great Lakes with site catchments spanning various land cover types. Discrete samples of sediment collected manually and time-integrated surface water samples collected with polar organic chemical integrative samplers (POCIS) were analyzed for 23 and 34 PFAS, respectively. Concentrations of individual PFAS in sediment and surface water varied immensely among sites from below detection to 20,800 ng kg −1 and 247 ng L −1 , respectively. Of all target compounds, PFOS was the most frequently detected in sediment (56 of 62 sites) and had the highest median concentration (132 ng kg −1 ). PFOA, PFHxS, PFOS, PFHpA, and PFNA (full chemical names are listed in online supplementary material Table S2) were detected in all 60 surface water sites, with median estimated concentrations of 5.9, 5.2, 4.6, 3.7, and 1.3 ng L −1 , respectively. Compounds with 8–13 fluorinated carbons comprised a larger proportion of sediment PFAS than compounds with 4–7 fluorinated carbons, whereas compounds with 4–7 fluorinated carbons comprised a greater proportion of PFAS in surface waters. Watershed attributes, including urban land cover, airports per catchment area, and wastewater treatment plants flow percentage were significantly ( p < 0.05) and positively related with PFAS sum concentrations in sediment and (or) surface water. Collectively, these results, albeit with some uncertainty in the estimated concentrations, highlight the relation PFAS occurrence has with human activities and documents widespread low-level PFAS contamination across the Great Lakes basin.

Great Lakes

Potential for biological effects of per- and polyfluoroalkyl substances in Great Lakes tributaries and associations with land cover and wastewater effluent

Surface water concentrations of per- and polyfluoroalkyl substances (PFAS) and potential for resulting biological effects were estimated in a study using polar organic chemical integrative samplers (POCIS) from 60 tributary sites within 20 watersheds in the Great Lakes Basin in 2018. Sites represented a range of urban to agricultural, forested, and wetland land uses and included a gradient of wastewater treatment effluent from zero to 44% of annual streamflow. Several sites also had airport influence. Twenty-one of 32 targeted PFAS compounds were detected in POCIS samplers, of which, 16 had available POCIS sampling rates, enabling time-weighted water concentration estimates and comparison with available effects data. Estimated water concentrations were compared with published water quality guidelines (available for nine PFAS), effect concentrations reported in primary literature within the ECOTOX Knowledgebase for apical endpoints (10 PFAS) and nonapical endpoints (10 PFAS), and in vitro high-throughput screening data from the U.S. Environmental Protection Agency Toxicity Forecaster (ToxCast; 14 PFAS). Based on a conservative evaluation approach that was also weighted for persistence and limitations in available toxicological information, five individual PFAS, including perfluorooctanesulfonic acid, perfluorohexanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanoic acid, and perfluorononanoic acid were identified as warranting additional investigation. Possible increased potency of PFAS mixtures over individual chemical effects, estimated by summation of exposure-activity ratios (EARs) for chemicals that influence common ToxCast assays and specified gene targets, indicated that EAR values increased up to 5.6-fold over individual chemicals, with up to 14 chemicals contributing to mixture effect predictions. Potential for biological effects from PFAS, as estimated by summed exposure-activity ratios, were correlated with urban land use and the proportion of streamflow contributed by wastewater effluent.

Great Lakes tributaries

Investigating the chemical space coverage of multiple chromatographic and ionization methods using non-targeted analysis on surface and drinking water collected using passive sampling

Multiple non-targeted analysis tools were used to look for a broad range of possible chemical contaminants present in surface and drinking water using liquid chromatography separation and high-resolution mass spectrometry detection, including both quadrupole time of flight (Q-ToF) and Orbitrap instruments. Two chromatographic techniques were evaluated on an LC-Q-ToF with electrospray ionization in both positive and negative modes: (1) the traditionally used reverse phase C18 and (2) the hydrophilic interaction liquid chromatography (HILIC) aimed to capture more polar contaminants that may be present in water. Multiple ionization modes were evaluated with an LC-Orbitrap, including electrospray (ESI) and atmospheric pressure chemical ionization (APCI), also in both positive and negative modes. A suspect screening library of over 1300 possible environmental contaminants, including pesticides, pharmaceuticals, personal care products, illicit drugs/drugs of abuse, and various anthropogenic markers was made with experimentally collected data with the LC-Q-ToF with both column types, with 227 chemicals being retained by the HILIC column. The non-targeted methods using multiple chromatographic and ionization modes were applied to environmental water samples collected with polar organic chemical integrative samplers (POCIS), including surface water upstream and downstream from wastewater effluent discharge, and the downstream drinking water intake and treated drinking water for three distinct sampling events. For the LC-Q-ToF, 442 chemical features were detected on the C18 column and 91 with the HILIC column in the POCIS extracts, while 556 features were found on the Orbitrap workflow by ESI and 131 features detected by APCI. Over 100 chemicals were tentatively identified by suspect screening and database searching. The comprehensive and systematic evaluation of these methods serve as a step in characterizing the chemical space covered when utilizing different chromatography and ionization methods, or different instrument workflows on complex environmental mixtures.

Science of the Total Environment

Pesticides in surface water downstream of and near agricultural and developed land in Hawai‘i, 2015–19

Pesticides and pesticide degradates (herein referred to as pesticides) in surface water were assessed at 78 sites on 4 Hawaiian Islands (Kauaʻi, Oʻahu, Maui, and Island of Hawaiʻi) during 2015–19. Each site was downstream of or near agricultural land, developed land, or both. Most (58) sites were streams; the remaining sites were canals, ditches, anchialine pools, coastal ponds, and the nearshore ocean. Pesticides in water at each site were assessed by collection of one to four water samples, by a weeks-long deployment of a passive sampler, or both. Passive-sampler extracts and water samples, which consisted of fair-weather samples and storm samples, were analyzed for as many as 253 pesticides that consisted of 129 herbicides, 101 insecticides, and 23 fungicides. A total of 117 pesticides were detected in water. Of these, 30 pesticides were detected at more than 20 percent of their assessment sites and thus were considered “common” pesticides. The common pesticides included 17 herbicides (ametryn, atrazine, bentazon, bromacil, diuron, hexazinone, metolachlor, propazine, simazine, triclopyr, prometryn, and degradates of atrazine [4], diuron, hexazinone, and prometryn); 8 insecticides (carbaryl, dinotefuran, fipronil, flubendiamide, imidacloprid, methoxyfenozide and 2 degradates of fipronil); and 5 fungicides (azoxystrobin, metalaxyl, propiconazole, a degradate of chlorothalonil, and a degradate of thiophanate-methyl and benomyl). Common pesticides typically were present more frequently in storm samples than in fair-weather samples. A mixture of two or more pesticides was detected in 86 percent of the water samples and in water during every passive-sampler deployment. About 92 percent of all pesticide detections had concentrations less than 100 nanograms per liter. Pesticide concentrations were less than Federal aquatic-life benchmarks (ALBs) for vertebrates and typically were less than ALBs for invertebrates, nonvascular plants, and vascular plants. Acute ALBs were exceeded by acetochlor, atrazine, carbaryl, chlorpyrifos, cis-permethrin, diazinon, diuron, halosulfuron methyl, and imidacloprid in storm samples at one to four sites. ALBs for invertebrates were exceeded by clothianidin, diazinon, fipronil, and imidacloprid in fair-weather samples, during passive-sampler deployments, or both at 1 to 17 sites. Federal drinking water standards were available for only five pesticides detected in water, and the standard for atrazine was exceeded in one storm sample. Pesticide concentrations did not exceed any Federal human-health benchmarks, but many of the detected pesticides did not have a benchmark.

Hawaii

Fish health altered by contaminants and low water temperatures compounded by prolonged regional drought in the Lower Colorado River Basin, USA

The goal of this study was to assess health of male Common Carp (carp, Cyprinus carpio ) at four sites with a wide range in environmental organic contaminant (EOC) concentrations and water temperatures in Lake Mead National Recreation Area NV/AZ, US, and the potential influence of regional drought. Histological and reproductive biomarkers were measured in 17–30 carp at four sites and 130 EOCs in water per site were analyzed using passive samplers in 2010. Wide ranges among sites were noted in total EOC concentrations (>10Xs) and water temperature/degree days (10Xs). In 2007/08, total polychlorinated biphenyls (tPCBs) in fish whole bodies from Willow Beach (WB) in the free-flowing Colorado River below Hoover Dam were clearly higher than at the other sites. This was most likely due to longer exposures in colder water (12–14 °C) and fish there having the longest lifespan (up to 54 years) for carp reported in the Colorado River Basin. Calculated estrogenicity in water exceeded long-term, environmentally safe criteria of 0.1–0.4 ng/L by one to three orders of magnitude at all sites except the reference site. Low ecological screening values for four contaminants of emerging concern (CEC) in water were exceeded for one CEC in the reference site, two in WB and Las Vegas Bay and three in the most contaminated site LVW. Fish health biomarkers in WB carp had 25% lower liver glycogen, 10Xs higher testicular pigmented cell aggregates and higher sperm abnormalities than the reference site. Sperm from LVW fish also had significantly higher fragmentation of DNA, lower motility and testis had lower percent of spermatozoa, all of which can impair reproduction. Projections from a 3D water quality model performed for WB showed that EOC concentrations due to prolonged regional drought and reduced water levels could increase as high as 135%. Water temperatures by late 21st century are predicted to rise between 0.7 and 2.1 °C that could increase eutrophication, algal blooms, spread disease and decrease dissolved oxygen over 5%.

Arizona, Nevada

Potential hazards of polycyclic aromatic hydrocarbons in Great Lakes tributaries using water column and porewater passive samplers and sediment wquilibrium partitioning

The potential for polycyclic aromatic hydrocarbon (PAH)-related effects in benthic organisms is commonly estimated from organic carbon-normalized sediment concentrations based on equilibrium partitioning (EqP). Although this approach is useful for screening purposes, it may overestimate PAH bioavailability by orders of magnitude in some sediments, leading to inflated exposure estimates and potentially unnecessary remediation costs. Recently, passive samplers have been shown to provide an accurate assessment of the freely dissolved concentrations of PAHs, and thus their bioavailability and possible biological effects, in sediment porewater and overlying surface water. We used polyethylene passive sampling devices (PEDs) to measure freely dissolved porewater and water column PAH concentrations at 55 Great Lakes (USA/Canada) tributary locations. The potential for PAH-related biological effects using PED concentrations were estimated with multiple approaches by applying EqP, water quality guidelines, and pathway-based biological activity based on in vitro bioassay results from ToxCast. Results based on the PED-based exposure estimates were compared with EqP-derived exposure estimates for concurrently collected sediment samples. The results indicate a potential overestimation of bioavailable PAH concentrations by up to 960-fold using the EqP-based method compared with measurements using PEDs. Even so, PED-based exposure estimates indicate a high potential for PAH-related biological effects at 14 locations. Our findings provide an updated, weight-of-evidence–based site prioritization to help guide possible future monitoring and mitigation efforts.

Illinois, Indiana, Michigan, Minnesota, New York,

De facto water reuse: Investigating the fate and transport of chemicals of emerging concern from wastewater discharge through drinking water treatment using non-targeted analysis and suspect screening

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K -means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Environmental Science & Technology

Degradation kinetics of veterinary antibiotics and estrogenic hormones in a claypan soil

Veterinary antibiotics and estrogens are excreted in livestock waste before being applied to agricultural lands as fertilizer, resulting in contamination of soil and adjacent waterways. The objectives of this study were to 1) investigate the degradation kinetics of the VAs sulfamethazine and lincomycin and the estrogens estrone and 17β-estradiol in soil mesocosms, and 2) assess the effect of the phytochemical DIBOA-Glu, secreted in eastern gamagrass (Tripsacum dactyloides) roots, on antibiotic degradation due to the ability of DIBOA-Glu to facilitate hydrolysis of atrazine in solution assays. Mesocosm soil was a silt loam representing a typical claypan soil in portions of Missouri and the Central United States. Mesocosms (n = 133) were treated with a single target compound (antibiotic concentrations at 125 ng g−1 dw, estrogen concentrations at 1250 ng g−1 dw); a subset of mesocosms treated with antibiotics were also treated with DIBOA-Glu (12,500 ng g−1 dw); all mesocosms were kept at 60% water-filled pore space and incubated at 25 °C in darkness. Randomly chosen mesocosms were destructively sampled in triplicate for up to 96 days. All targeted compounds followed pseudo first-order degradation kinetics in soil. The soil half-life (t0.5) of sulfamethazine ranged between 17.8 and 30.1 d and ranged between 9.37 and 9.90 d for lincomycin. The antibiotics results showed no significant differences in degradation kinetics between treatments with or without DIBOA-Glu. For estrogens, degradation rates of estrone (t0.5 = 4.71–6.08 d) and 17β-estradiol (t0.5 = 5.59–6.03 d) were very similar; however, results showed that estrone was present as a metabolite in the 17β-estradiol treated mesocosms and vice-versa within 24 h. The antibiotics results suggest that sulfamethazine has a greater potential to persist in soil than lincomycin. The interconversion of 17β-estradiol and estrone in soil increased their overall persistence and sustained soil estrogenicity. This study demonstrates the persistence of these compounds in a typical claypan soil representing portions of the Central United States.

Chemosphere

Temporal variability and sources of PFAS in the Rio Grande, New Mexico through an arid urban area using multiple tracers and high-frequency sampling

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment but sources are not well defined for temporal and spatial aspects within an urban environment, and especially for an arid urban environment subject to seasonal short term high-intensity precipitation events. A focused diel sampling was conducted in the summer of 2021 to assess the temporal and spatial variability of PFAS in the Rio Grande near Albuquerque, New Mexico and showed an order of magnitude increase of PFAS as it flows through the Albuquerque urban area. Discrete samples were collected at two different locations on the Rio Grande in addition to wastewater treatment plant (WWTP) effluent that discharges directly to the Rio Grande between the sampling locations. Short-term high-intensity precipitation events occurred during the study period and mobilized PFAS from urban runoff. Dissolved organic matter composed of tryptophan-like organic substances and refined fuel and fuel byproducts, characteristic of an urban signature, were also related to the precipitation events. The PFAS in discharge from the WWTP was consistent over a 24-h period with slight differences in some compounds. Wastewater presence on the Rio Grande downstream of the WWTP was evidenced by a gadolinium anomaly as well as increases in several other trace elements, total dissolved nitrogen, and fluorescence indicators, in addition to PFAS. PFAS varied depending on source contribution, where urban runoff was associated with PFOA, PFOS, and PFBA, whereas PFHxA and PFPeA were associated with wastewater effluent. In addition, passive polar organic chemical integrative samplers (POCIS) using hydrophilic-lipid balance (HLB) sorption media were deployed for a month at two locations on the Rio Grande to assess longer term PFAS concentrations. The POCIS results show some compounds (PFPeA and PFHpA) were greater than the average concentration from discrete samples, whereas other compounds (PFHxA, PFOA, PFDA, and PFNA) were lower in the POCIS, and PFOS was very similar between the two. The POCIS did not detect PFBA, which may be related to the HLB media not performing well for short chain PFAS compounds. The results show promise for integrative samplers utilizing sorbent media. More detailed investigation of the spatial and temporal variability of water chemistry on the Rio Grande as it flows through Albuquerque could provide information applicable to urban areas worldwide.

New Mexico

PCB source assessment in the lower Clinton River, Clinton River Area of Concern, Mount Clemens, Michigan

Polychlorinated biphenyls (PCBs), some of the earliest “forever chemicals,” were used for decades in the United States before 1979 when PCB manufacturing was banned. High PCB concentrations were found recently in the lower Clinton River in the Great Lakes drainage. To determine the possible existence, location, and significance of a current source of PCBs, the U.S. Geological Survey (USGS) deployed passive water samplers (SPMDs, semipermeable membrane devices) in the river at 15 sites for 1 month in 2019 near outfalls of interest and other locations. USGS also deployed passive stream sediment samplers at a subset of four sites during the same period and collected bank sediment samples at a subset of four sites. Sediment from nearby catch basins was also collected. Samples were assayed for 209 individual PCB congeners, and patterns in total and individual congeners were evaluated; ancillary sediment data included grain size, total organic carbon, and moisture. U.S. Army Corps of Engineers (USACE) data for total PCBs and 209 PCB congeners in surficial sediment samples collected in 2019 were also evaluated. In general, total PCBs were highest in streambed sediment, followed by catch basin sediment, bank sediment, and then water as estimated from SPMDs. Total PCBs in sediment were low in all catch basins but one (sample CB19–02) that drains from an historical landfill area to one of two adjacent outfalls of interest: the outfall for a nearby wastewater treatment plant and adjacent outfall MTC–R–060, where the highest total PCBs in USGS stream sediment samples were found (site 14, sample 14STRM; 1,260,000 picograms per gram). Also, the SPMD at site 14 was the only water sample with more “light” (three or fewer chlorine atoms) than “heavy” (four or more chlorine atoms) PCB congeners, and the passive sediment sample had the highest proportion of light PCBs in USGS sediment samples. Light PCB congeners degrade more quickly than heavy PCB congeners and results may indicate that one or more current sources of PCBs are contributing to total PCBs in sediment at four river sites. Of 209 possible PCB congeners assayed, 117 congeners were detected in water samples; 155 and 154 congeners were detected in USGS and USACE sediment samples, respectively. PCBs 28, 73, 31, and 18 (highest to lowest) contributed most toward total PCBs in water samples overall; PCBs 20/28, 31, 52, and 44/47/65 contributed most toward total PCBs for sediment in USGS stream samples overall and USACE samples overall; these rankings were also true for catch basins overall except for PCB–31. After omitting coeluting congeners to allow further comparison, 5 key PCB congeners are in the top 20 congeners across all assay groups: 17, 31, 52, 95, and 118. The importance of these congeners in multiple assays aligns with their importance as components of certain Aroclors. Sediment from the high PCB catch basin (sample CB19–02) had a different pattern of top congeners than the other catch basins, and multivariate analyses indicated a high degree of similarity in its overall congener pattern with that of the highest PCB sediment sample (sample 14STRM) collected by the outfalls for the catch basin and the wastewater treatment plant. Similarities in overall congener patterns across sample media as determined by multivariate analyses confirmed some site linkages and the possibility of more than one source of PCBs to the reach. Furthermore, equilibrium partitioning calculations indicated that water concentrations as estimated by SPMDs were high enough to result in the PCB concentrations measured in USGS passive sediment samples but not USACE surficial sediment samples when normalized by organic carbon. However, the SPMDs and passive sediment samples reflect only one month of contribution to the river and higher concentrations would be expected to result with years of PCB accumulation. PCBs contributed to the river water by outfalls could eventually partition to sediment in the reach. Thus, the river could have a current source or sources of PCBs, perhaps one or more outfalls near four sites. Additional investigation is needed to better define the relative significance of each outfall and areas in nearby drainage systems that may be contributing PCBs to outfalls and the river.

Michigan

Uptake of per- and polyfluoroalkyl substances by fish, mussel, and passive samplers in mobile laboratory exposures using groundwater from a contamination plume at a historical fire training area, Cape Cod, Massachusetts

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L –1 in reference groundwater and 6100 to 15,000 ng L –1 in contaminated groundwater. Biotic concentration factors (CF b ) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg –1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CF b generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CF b between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CF b = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CF b , and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Massachusetts

Vegetative buffer strips show limited effectiveness for reducing antibiotic transport in surface runoff

Vegetative buffer strips (VBS) have been demonstrated to effectively reduce loads of sediment, nutrients, and herbicides in surface runoff, but their effectiveness for reducing veterinary antibiotic (VA) loads in runoff has not been well documented. The objective of this study was to determine the effectiveness of VBS vegetation and width on surface runoff loads of the VAs sulfamethazine (SMZ) and lincomycin (LIN). Experimental design of the plots (1.5 × 25 m) was a two-way factorial with four vegetation treatments (tall fescue [ Festuca aruninacea Schreb.]; tall fescue with switchgrass [ Panicum virgatum L.] hedge; warm-season native grass mix; and continuous fallow control), and four buffer widths (0, 2, 5, and 9 m). Turkey litter spiked with SMZ and LIN was applied to the source area (upper 7 m) of each plot, and runoff was collected at each width. Runoff was generated with a rotating boom simulator. Results showed VA loads in runoff at the 0-m sampler ranged from 3.8 to 5.9% of applied, and overall VA transport in runoff was predominately in the dissolved phase (90% for SMZ and 99% for LIN). Among vegetation treatments, only tall fescue significantly reduced loads of SMZ and LIN compared with the control, with load reductions of ∼30% for both VAs. Estimated field-scale reductions in VA loads showed that source-to-buffer area ratios (SBARs) of 10:1 to 20:1 reduced VA loads by only 7 to 16%. Overall, the grass VBS tested here were less effective at reducing SMZ and LIN loads in surface runoff than has been previously demonstrated for sediment, nutrients, and herbicides.

Journal of Environmental Quality

Prioritizing pesticides of potential concern and identifying potential mixture effects in Great Lakes tributaries using passive samplers

To help meet the objectives of the Great Lakes Restoration Initiative with regard to increasing knowledge about toxic substances, 223 pesticides and pesticide transformation products were monitored in 15 Great Lakes tributaries using polar organic chemical integrative samplers. A screening-level assessment of their potential for biological effects was conducted by computing toxicity quotients (TQs) for chemicals with available US Environmental Protection Agency (USEPA) Aquatic Life Benchmark values. In addition, exposure activity ratios (EAR) were calculated using information from the USEPA ToxCast database. Between 16 and 81 chemicals were detected per site, with 97 unique compounds detected overall, for which 64 could be assessed using TQs or EARs. Ten chemicals exceeded TQ or EAR levels of concern at two or more sites. Chemicals exceeding thresholds included seven herbicides (2,4-dichlorophenoxyacetic acid, diuron, metolachlor, acetochlor, atrazine, simazine, and sulfentrazone), a transformation product (deisopropylatrazine), and two insecticides (fipronil and imidacloprid). Watersheds draining agricultural and urban areas had more detections and higher concentrations of pesticides compared with other land uses. Chemical mixtures analysis for ToxCast assays associated with common modes of action defined by gene targets and adverse outcome pathways (AOP) indicated potential activity on biological pathways related to a range of cellular processes, including xenobiotic metabolism, extracellular signaling, endocrine function, and protection against oxidative stress. Use of gene ontology databases and the AOP knowledgebase within the R-package ToxMixtures highlighted the utility of ToxCast data for identifying and evaluating potential biological effects and adverse outcomes of chemicals and mixtures. Results have provided a list of high-priority chemicals for future monitoring and potential biological effects warranting further evaluation in laboratory and field environments. Environ Toxicol Chem 2023;42:340–366. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes tributaries

Identifying chemicals and mixtures of potential biological concern detected in passive samplers from Great Lakes tributaries using high-throughput data and biological pathways

Waterborne contaminants were monitored in 69 tributaries of the Laurentian Great Lakes in 2010 and 2014 using semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS). A risk-based screening approach was used to prioritize chemicals and chemical mixtures, identify sites at greatest risk for biological impacts, and identify potential hazards to monitor at those sites. Analyses included 185 chemicals (143 detected) including polycyclic aromatic hydrocarbons (PAHs), legacy and current-use pesticides, fire retardants, pharmaceuticals, and fragrances. Hazard quotients were calculated by dividing detected concentrations by biological effect concentrations reported in the ECOTOX Knowledgebase (toxicity quotients) or ToxCast database (exposure–activity ratios [EARs]). Mixture effects were estimated by summation of EAR values for chemicals that influence ToxCast assays with common gene targets. Nineteen chemicals—atrazine, N,N -diethyltoluamide, di(2-ethylhexyl)phthalate, dl-menthol, galaxolide, p-tert-octylphenol, 3 organochlorine pesticides, 3 PAHs, 4 pharmaceuticals, and 3 phosphate flame retardants—had toxicity quotients >0.1 or EARs for individual chemicals >10 –3 at 10% or more of the sites monitored. An additional 4 chemicals (tributyl phosphate, triethyl citrate, benz[ a ]anthracene, and benzo[ b ]fluoranthene) were present in mixtures with EARs >10 –3 . To evaluate potential apical effects and biological endpoints to monitor in exposed wildlife, in vitro bioactivity data were compared to adverse outcome pathway gene ontology information. Endpoints and effects associated with endocrine disruption, alterations in xenobiotic metabolism, and potentially neuronal development would be relevant to monitor at the priority sites. The EAR threshold exceedance for many chemical classes was correlated with urban land cover and wastewater effluent influence, whereas herbicides and fire retardants were also correlated to agricultural land cover. Environ Toxicol Chem 2021;40:2165–2182. Published 2021. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes

Movement of synthetic organic compounds in the food web after the introduction of invasive quagga mussels (Dreissena bugensis) in Lake Mead, Nevada and Arizona, USA

Introductions of dreissenid mussels in North America have been a significant concern over the last few decades. This study assessed the distribution of synthetic organic compounds (SOCs) in the food web of Lake Mead, Nevada/Arizona, USA and how this distribution was influenced by the introduction of invasive quagga mussels. A clear spatial gradient of SOC concentrations in water was observed between lake basins downstream of populated areas and more rural areas. Within the food web, trophic magnification factors (TMF) indicated statistically significant biomagnification for nine, and biodilution for two, of 22 SOCs examined. The highest value recorded was for PCB 118 (TMF, 5.14), and biomagnification of methyl triclosan (TMF, 3.85) was also apparent. Biodilution was observed for Tonalide® (0.06) and Galaxolide® (0.38). Total SOC concentration in quagga mussels was higher than in three pelagic fishes. Also, 19 of 20 SOC examined in Largemouth Bass ( Micropterus salmoides ) had substantially lower concentrations in 2013, when quagga mussels had become well established, than in 2007/08, soon after quagga mussels were introduced. Estimates of SOC concentrations in the water column and quagga mussels suggest that a considerable portion (~10.5%) of the SOC mass in the lake has shifted from the pelagic to the benthic environments due to quagga mussel growth. These observations suggest that benthic species, such as the endangered Razorback Sucker, may be experiencing increased risk of SOC exposure. In addition, stable isotope analysis (carbon and nitrogen) indicated a decrease in the nutritional value of zooplankton to consumers (e.g., Razorback Sucker larvae) since quagga mussels became established. These changes could affect Razorback Sucker larval survival and recruitment. Results from this study strongly suggest that the introduction of quagga mussels has greatly altered the dynamics of SOCs and other processes in the food web of Lake Mead.

Arizona, Nevada

Physical and chemical stressors on algal, invertebrate, and fish communities in 14 Milwaukee area streams, 2004–2013

In 2004, the U.S. Geological Survey (USGS) began sampling 14 wadable streams in urban or urbanizing watersheds near Milwaukee, Wisconsin. The overall goal of the study is to assess the health of the aquatic communities in the Milwaukee Metropolitan Sewerage District planning area to inform current and future watershed management. In addition to collection of biological data on aquatic communities, physical and chemical data were also collected to evaluate effects of potential environmental stressors on the aquatic communities. This fact sheet summarizes the primary results of the study from 2004 to 2013. Detailed information is described in Scudder Eikenberry and others (2020a), and all data are available in Scudder Eikenberry and others (2020b; https://doi.org/10.5066/P9FWMODL ).

Wisconsin

Ecological status of aquatic communities in selected streams in the Milwaukee Metropolitan Sewerage District planning area of Wisconsin, 2004–13

A total of 14 wadable streams in urban or urbanizing watersheds near Milwaukee, Wisconsin, were sampled in 2004, 2007, 2010, and 2013 to assess the ecological status of aquatic communities (biota), including benthic algae and invertebrates, and fish. To assess temporal variation, additional community sampling was also done at a subset of three sites in 2011 and 2012. Relative abundances of each type of organism were used to calculate biological metrics, such as richness and diversity, percentages of intolerant and tolerant organisms, and indexes of biotic integrity for invertebrates and fish. Selected environmental (physical and chemical) data in the streams were collected to evaluate potential relations to the biota and the ecological health of the stream. Physical and chemical data included land use/land cover, stream discharge from U.S. Geological Survey (USGS) streamgages (except at 2 creeks that were not gaged), stream habitat, microhabitat at invertebrate collection locations, water quality (except at 2 creeks that were not gaged), field measurements of several water-quality constituents, measures of benthic algal biomass, and toxicity and chemical tests on extracts from passive samplers deployed at a subset of 6 sites. Relative abundances of organisms and biological metrics were compared among sampling years and with environmental metrics to evaluate the ecological status of these streams and determine primary stressors on the aquatic communities, with the aim of helping resource managers understand and work toward improving the ecological health of these and other urban and urbanizing rivers in the study area. Biological metrics for most sites indicated some level of diminished ecological status when compared across all sampled sites and when compared with rating scales for selected metrics. The least degraded sites among all those sampled—indicated by aggregate bioassessments for algae, invertebrates, and fish metrics and in order starting with the best overall condition—were the Milwaukee River near Cedarburg, Menomonee River at Menomonee Falls, Jewel Creek, and Milwaukee River at Milwaukee. The most degraded sites were Menomonee River at Wauwatosa, Root River at Greenfield, Lincoln Creek, and the Kinnickinnic River. Differences in aggregate bioassessments indicate that aquatic communities at the Menomonee River at Wauwatosa site and the Root River at Greenfield site were worse in 2013 than in 2004; however, Oak Creek and Honey Creek sites were better. In 2013, several sites had less than 30-percent pollution-sensitive diatoms indicating degraded algal assemblages. Invertebrate metrics for most of the 14 sites in 2013 were lower than in 2004 and indicate that invertebrate assemblages at most sampled sites were more degraded in 2013. Tolerant fish taxa made up more than 40 percent of assemblages at most sites and nearly 100 percent of assemblages at four sites. At times, in some smaller streams, too few fish were captured to compute an Index of Biotic Integrity with confidence, and invertebrates provided a better means for assessing the ecological status and water quality. With these few exceptions, the use of all three groups of biota provided the most robust assessments at the 14 sites in 2004–13. Physical and chemical stressors were correlated to adverse effects on aquatic biota at the sampled streams. Passive samplers were deployed at a subset of six sites in 2013. Microtox results indicated there was little or no toxicity at the Milwaukee River near Cedarburg site and at the Oak Creek site, slight toxicity at the Lincoln Creek and Honey Creek sites, and moderate toxicity at the Milwaukee River at Milwaukee site and the Little Menomonee River site; however, based on cytochrome-P450 reporter gene system toxicity tests, potential toxicity from hydrophobic organic contaminants was measured at all six sites. For all 14 sites, physical and chemical stressors related to urbanization correlated with biological metrics for algae, invertebrates, and fish. Most stressors for aquatic biota reflected an urban signature. Stressors related to ecological condition in our study were chemical and physical, such as developed land, impervious surface in the watershed, urban land in a buffer area around the stream (a 100-foot [30-meter]-wide area on each side of the stream, and maximum instantaneous discharge normalized by drainage area (a measure of flood and scour effects). Chemical stressors included low waterborne concentrations of dissolved oxygen and high concentrations of chloride, zinc and other metals, nutrients (nitrite and phosphorus), and fecal coliform bacteria. Although algae, invertebrates, and fish did not always demonstrate a significant response to the same stressors, higher abundances of high total phosphorus-indicator diatoms, lower ratings for invertebrate biotic integrity indexes and percentages of mayflies-stoneflies-caddisflies, and lower values for fish biotic integrity indexes underscored possible adverse effects of even low levels of developed land. Developed land is typically associated with more rapid runoff, which washes chemicals from impervious surfaces into area waterways and degrades stream habitat for aquatic communities. However, with respect to at least chloride from road salt, diatoms tolerant to dissolved salts were significantly lower with as little as 1-percent mixed forest in the watershed. Lower percentages of urban land in the stream buffer correlated with healthier aquatic assemblages of algae, invertebrates, and fish. The assessment of algal, invertebrate, and fish assemblages coupled with physical and chemical data were highly useful in evaluating the ecological status of aquatic communities at the 14 sites and for determining environmental stressors that may be contributing to reduced stream condition. Some of the stressors could potentially be removed or lessened with stream rehabilitation or changes in watershed management.

Wisconsin