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Michelle L. Hladik

Publications and source records attributed to Michelle L. Hladik.

At least 37 records · Page 2Linked to original sources

Assessing potential collateral effects on amphibians from insecticide applications for flea control and plague mitigation

Ideal disease mitigation measures for wildlife are safe and benign for target species, non-target organisms, the environment, and humans. Identifying collateral (i.e., unintended) effects is a key consideration in implementing such actions. Deltamethrin dust and fipronil-laced baits represent a group of insecticides that target fleas (pulicides) and are used to control flea (Siphonaptera) vectors of the plague bacterium Yersinia pestis to protect prairie dogs ( Cynomys spp.) and their plague-susceptible obligate predators, endangered black-footed ferrets ( Mustela nigripes ). A variety of animals use prairie dog burrows as refuge, which potentially exposes them to deltamethrin, and to fipronil and its metabolites in fecal pellets excreted by prairie dogs and other mammals that have eaten fipronil baits. We assessed the potential effects of deltamethrin and fipronil residues on survival, body mass, and activity of western tiger salamanders ( Ambystoma mavortium ), a burrow-inhabiting amphibian. Pulicides were applied at realistic concentrations in mesocosms mimicking burrows. Treatments included (1) deltamethrin dust and non-treated prairie dog fecal pellets, (2) prairie dog fecal pellets containing fipronil and fipronil sulfone, and (3) un-treated prairie dog fecal pellets as controls. All 29 salamanders survived the experiment. We did not detect pulicide residues in any control salamanders. Fipronil sulfone was detected in tissues from 3 of 10 salamanders in the fipronil treatment and deltamethrin was detected in tissues from 9 of 11 salamanders in the deltamethrin treatment. Salamanders were observed outside of burrows more frequently after treatments than before. Deltamethrin concentrations in whole body samples correlated positively with the amount of time salamanders were inside burrows. Acute, lethal effects were not detected, but uptake of deltamethrin and, to a lesser extent fipronil sulfone, into salamander tissues indicated the potential for long-term effects on this non-target species. Identifying potential collateral effects is an important aspect of evaluating mitigation actions implemented to protect endangered species.

PLoS ONE↗

Occurrence of pesticides in Oregon coastal waters

Pesticides are used globally for a wide range of applications including agricultural, forestry, roadsides, freshwater systems, and personal use. While pesticides have ensured efficient crop production, they are frequently transported away from application sites and are found in almost all terrestrial and aquatic environments. Pesticides are frequently detected in watersheds and rivers, but there is limited research on pesticide presence in United States (U.S.) marine environments. To address these data gaps, this study documents pesticide occurrence in U.S. coastal waters, providing new understanding of pesticide contamination in offshore environments. Polar organic chemical integrative samples (POCIS) were deployed at five sites along the Oregon, U.S. coast to examine the occurrence of pesticides. Between two and seven different pesticides were detected at every site, with herbicides diuron, and atrazine, and fungicides carbendazim, propiconazole, and tebuconazole being the most frequently detected at three sites. The prevalence of herbicides and fungicides in coastal waters indicates a connection between terrestrial pesticide practices and marine contamination. These findings provide new insights into the presence of pesticides in coastal nearshore and offshore waters and suggest that a comprehensive monitoring effort could enhance our understanding of sources, transport, and pesticide risks for marine species both nearshore and offshore.

Oregon↗

6PPD-quinone in water from the Sacramento-San Joaquin Delta, California, 2018-2024

The Sacramento-San Joaquin Delta (Delta) is an expansive river delta supplying a large portion of California’s fresh water for agriculture and residential use, and it is also an area of critical habitat for numerous state and federally listed species of concern. In many locations, urban stormwater flows directly into the Delta. 6PPD-quinone (6PPD-Q), an ozonation byproduct of a tire antiozonant 6PPD, has been shown to enter surface water via these pathways and can cause various toxicological effects, including acute urban mortality syndrome to coho salmon ( Oncorhynchus kisutch ) at low levels (LC 50 = 41 and 95 ng/L for juveniles and adults, respectively). Here, we quantified 6PPD-Q in 61 archived Delta water extracts collected between 2018 and 2024 and found concentrations up to 21 ng/L. Currently, no 6PPD-Q presence and/or quantitative data is available for this complex and diverse ecosystem. Little is known regarding long-term storage of 6PPD-quinone in solvent extracts, so 6PPD-Q observations document its presence in the study area and provide evidence that further sampling may be warranted to better quantify environmental concentrations. Consistent with the general understanding of 6PPD-Q transport, all detections observed were in samples collected during or immediately after a precipitation event. This work provides environmentally relevant concentration data to complement ongoing toxicological investigations of 6PPD-Q in Delta organisms and suggests there are research opportunities for a more robust survey of 6PPD-Q inputs into the Delta.

California↗

The effects of imidacloprid and polyester microfibers on the larval development of the endangered sunflower star

Sea star wasting syndrome (SSWS) has affected numerous species of sea star, with populations of Pycnopodia helianthoides (Brandt, 1835) left most at risk. As their populations are struggling to recover, it is important to gain a better understanding of the impacts that the multiple stressors in their habitats can have on their populations. Contaminant stressors in particular are of increasing importance, as aquatic organisms can be exposed to a dynamic range of contaminants from nearby anthropogenic activity that may affect their future recovery efforts. This study is the first to quantify the effects of contaminant stressors on the larvae of P. helianthoides . We exposed P. helianthoides larvae to the neonicotinoid insecticide imidacloprid and polyester microfibers, both individually and in combination, at environmentally relevant concentrations (10 ng/L and 25 fibers/L, respectively) to measure the effects of these contaminants on their early life stages. Imidacloprid exposure resulted in stomach malformation in 10% of larvae and increased mortality during early development (p < 0.001), and all treatments resulted in increased larval lengths relative to controls (p < 0.001). During settlement, imidacloprid resulted in more rapid settlement responses than in the controls (p < 0.01). These findings highlight the need for further research investigating the effects of contaminant stressors to endangered organisms during reintroduction, as well as a more comprehensive understanding of the effects of pesticides to non-target organisms.

Environmental Toxicology and Chemistry↗

Neonicotinoid exposure causes behavioral impairment and delayed mortality of the federally threatened American burying beetle, Nicrophorus americanus

Among the most immediate drivers of American burying beetle ( Nicrophorus americanus Olivier) declines, nontarget toxicity to pesticides is poorly understood. Acute, episodic exposure to neonicotinoid insecticides at environmentally relevant concentrations is linked to negative impacts on beneficial terrestrial insect taxa. Beyond mortality, behavioral indicators of toxicity are often better suited to assess sublethal effects of residual concentrations in the environment. First, Nicrophorus spp. congeners were used to generate and identify a low-dose exposure rate (lethal dose 10%; LD10) from an acute, 24-hour exposure and the concentration-series was confirmed by LC–MS/MS. Next, we evaluated the effects of single and repeated low-dose (LD10 = 58.9 ng/beetle) imidacloprid exposure on N . americanus behavior (10 minutes post-dose) and mortality (10 days post-dose). Behavior parameters were analyzed using EthoVision-XT. Control N . americanus were significantly less mobile, demonstrating death-feigning, an anti-predator behavior. Single LD10 dosed N . americanus were hyperactive, traveling over 4 times farther (total distance; p = 0.03) and faster (mean velocity; p = 0.02) than controls. Single and repeated LD10 dosed N . americanus extended their wings without taking flight and flipped on their backs. All control N . americanus survived 10 days post-dose; single LD10 and repeated LD10 exhibited 30% and 50% mortality, respectively. A single LD10 exposure event was sufficient to significantly elicit greater movement and high predation risk behaviors, whereas repeated LD10 exposure did not worsen behavioral impairment but increased mortality over time. Collectively, generalized linear mixed effects models indicated that distance traveled, velocity, and extended wings were significant predictors of mortality. Recently reclassified, the federally threatened N . americanus may be at greater risk to insecticide exposure than previously thought and vulnerable to episodic, low-dose neonicotinoid exposure.

Nebraska, Oklahoma↗

Characterizing pyrethroid and fipronil concentrations in biosolids

Pesticides are prevalent in wastewater, yet few studies have measured pesticides in biosolids and aqueous media from samples collected concurrently. Seventeen California wastewater treatment plants (WWTPs) were sampled in May 2020. Biosolids samples were analyzed for 27 analytes, and paired aqueous samples (influent and effluent) were analyzed for 23 analytes. Analytes included fipronil and its transformation products (fiproles), pyrethroids, novaluron, and several other pesticides with down-the-drain transport potential. Of the 27 compounds analyzed in biosolids samples, 16 were detected in at least one sample, and 10 had a detection frequency (DF) of at least 25 %. Fipronil sulfone, fipronil sulfide, and fipronil were the most frequently detected fiproles (DF = 100 %, 94 %, and 67 %, respectively); permethrin was the most frequently detected pyrethroid (DF = 100 %), followed by bifenthrin (DF = 94 %), cyhalothrin (DF = 89 %), and etofenprox (DF = 78 %). To elucidate fipronil transformation pathways within the treatment system, data from the three sample types were compared; findings were generally consistent with transformation pathways reported previously (e.g., some fiproles were rarely detected in influent or biosolids, but frequently detected in effluent, indicating their formation during the treatment process). No correlations were found between WWTP characteristics and pesticide concentrations in biosolids. The fraction of organic carbon ( f OC ) of each biosolids sample was measured, and a statistically significant negative correlation was observed between f OC and some fiproles, but not fipronil; possible explanations are discussed. Additional analysis for two major agricultural pesticides (bifenthrin and permethrin) indicated that estimated mass loads of these pesticides in biosolids applied to land as a soil amendment are minimal (approximately 2 to 3 orders of magnitude lower) compared to inputs from agricultural applications. This study provides insight on the magnitude of pesticides entering the environment via land-applied biosolids; existing regulations surrounding agricultural pesticide applications are expected to also be protective of the relatively low inputs from biosolids.

Science of the Total Environment↗

Pesticide contamination detected across five wildlife refuges in the Sacramento Valley of California

An important goal for the applied ecological sciences is to understand the extent to which the biodiversity on conserved or managed lands is exposed to anthropogenic stressors. Among the various categories of conserved lands in the United States, the National Wildlife Refuge System is focused on the protection and management of native wildlife and plant populations. Refuge lands can be associated with wetlands and, especially in California, tend to be near areas of intense human use, including agriculture. The proximity of refuges to cultivated lands results in potential exposure to pesticide drift, which increases the possibility of non-target effects on plants and wildlife. We used a passive sampler approach to quantify aerial pesticide deposition during 28 days in spring of 2023, across five refuges in the Sacramento Valley of California. Pesticides were detected across all refuges and plots within the study area, with 36 individual compounds identified, including insecticides, herbicides, and fungicides, from 176 silicone bands from 49 plots. Distance to agriculture was not an important predictor in our models for most indices of contamination. However, our models revealed that the nearest crop type was an important mediator of the importance of distance to agriculture, as fungicide contamination decreased with distance to agriculture only when orchards were the nearest crop type. The overall lack of distance effects suggests that the interior of refuges in the study area do not necessarily provide more protection from pesticides than refuge edges, although larger refuges could offer more protection. We currently lack information on how the level of contamination found herein is biologically relevant to wildlife, and ongoing monitoring efforts have found productive communities of insects in the study area. The results of this study provide a foundation for future investigations on refuges to analyze impacts of specific pesticide compounds on plants and wildlife.

California↗

Identifying organic contaminants at trespass cannabis grows on federal land in California, USA

Despite the legalization of recreational cannabis in California, USA, illegal cannabis cultivation remains pervasive, partly through the establishment of illegal cultivation on public lands (trespass grows). These operations often illegally divert water for irrigation and perform unauthorized applications of chemical fertilizers and pesticides. This work investigates a broad suite of these chemicals, focusing on their persistence in topsoil and presence in water and bed sediment in adjacent streams. Quantitative analyses of pesticides were conducted (183 compounds in water; 176 in topsoil/bed sediment), supplemented by qualitative nontargeted screening at three trespass grows that had no active cultivation for 8 months to 2 years. Targeted multi-residue analysis of topsoil detected the insecticides bifenthrin, cyfluthrin, malathion and imidacloprid (with concentrations up to 38 ng/g dry weight, d.w.), and the fungicides fluopyram, myclobutanil, and triadimefon (concentrations up to 8.1 ng/g d.w.). No pesticides were detected in the companion water or streambed sediment samples from adjacent streams. In addition, no water samples were found to have measurable estrogenic activity. Nontargeted screening uncovered additional pesticides (i.e., spiromesifen, trinexapac) in the topsoil and cannabis-related compounds (i.e., cannabidol, delta9-tetrahydrocannabinol) in both topsoil and streambed sediment suggesting the likelihood of offsite transport of cannabis related compounds. Phthalate plasticizers, rubber-related compounds, pharmaceuticals and personal care product chemicals were detected in topsoil, water, and streambed sediment and may be related to extensive irrigation infrastructure installed at these trespass grows. This work begins to establish a contaminant profile associated with illegal cannabis growing activities, providing a foundation for future research focused on their potential ecological impacts.

California↗

Land application of biosolid, livestock, and drilling wastes to US farmland: A potential pathway for the redistribution of contaminants in the environment

In the United States (U.S.), waste byproducts generated from the treatment of municipal waste (biosolids), production of livestock (livestock waste), and drilling of oil and gas wells (drilling waste) are commonly applied to agricultural lands. Although this can be a cost-effective reuse/disposal practice, there is limited research on the potential for contaminant exposures and effects on ecosystems, wildlife, and human health from such land applications. In this study, we conducted extensive chemical, microbial, and toxicity analyses of biosolid, livestock, and drilling wastes just prior to land application on agricultural lands at 34 sites across the U.S. Twenty-two analytical methods were used to determine potential contaminant exposures profiles for 452 organic and 114 inorganic chemicals, nine microbial groups, estrogenicity, and cytotoxicity. Analytical results document unique and substantial chemical, microbial, and toxicity profiles for these land-applied wastes. Of the three waste byproducts, biosolids contained the greatest concentrations of household chemicals, pesticides, pharmaceuticals, per-/polyfluoroalkyl substances, calcium, and phosphorus. Livestock waste contained the greatest concentrations of total and leachable dissolved organic carbon, biogenic hormones, mycotoxins, plant estrogens, total inorganic nitrogen, and potassium. Drilling waste contained the greatest concentrations of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes), polycyclic aromatic hydrocarbons, rare-earth elements, barium, strontium, and uranium–thorium series radioisotopes. Biosolid and livestock wastes had greater culturable heterotrophic bacteria, halophilic bacteria, Escherichia coli ( E. coli ), enterococci, and staphylococci concentrations, and greater microbial diversity than drilling waste. Bioassay analyses indicated that exposure to contaminants in livestock wastes and biosolids could result in estrogenic effects, whereas exposure to contaminants in drilling waste could result in cytotoxic effects. Our study documents that current reuse/disposal practices for biosolid, livestock, and drilling wastes on agricultural lands could provide a potential pathway for the redistribution of unique and complex contaminant mixtures into the environment that have bioactive, endocrine disrupting, and carcinogenic characteristics. Results of this study provide a snapshot of chemical compositions and concentrations that can be used to inform the development of best-management practices to help maximize beneficial reuse of these wastes and minimize risk to the environment and human health.

Environmental Science: Processes & Impacts↗

In situ allelopathic expression by the invasive amphibious plant, Ludwigia hexapetala (water primrose) across habitat types, seasons, and salinities

Broad infestations of invasive, non-native vegetation have transformed wetlands around the world. Ludwigia hexapetala is a widespread, amphibious invasive plant with a creeping growth habit in open water and an erect growth habit in terrestrial habitats. In the upper San Francisco Estuary of California, L. hexapetala is increasingly terrestrializing into marshes and this expansion may be facilitated by allelopathy. We conducted the first field-based study on L. hexapetala allelopathy to determine whether (1) three allelochemicals known to be exuded by L. hexapetala are expressed in situ, (2) the allelochemicals are detectable in leaves, soil, and water, and (3) allelopathic expression varies by season, salinity, and growth habit (open water “patch” vs. terrestrial marsh “interface” locations). Water, soil, and L. hexapetala leaves were collected in two freshwater sites and two oligohaline sites in the upper San Francisco Estuary in summer 2021, fall 2021, and spring 2022. Myricitrin and quercitrin, known allelochemicals, and salipurposid, a newly identified polyphenol, were detected in water, soil, and leaves. There were significant differences in allelochemical concentrations under fresh versus oligohaline conditions in water and soil, but not leaves. All three allelochemicals generally had higher concentrations in patch versus interface locations, suggesting that L. hexapetala allelopathy plays a greater competitive role in open water than terrestrial habitats. Leaf concentrations of each allelochemical varied seasonally; however, both myricitrin and salipurposid had heightened concentrations in spring. These results suggest that herbicide application in early spring may be most effective in controlling L. hexapetala terrestrialization from open water to marshes.

California↗

Pesticide concentrations of surface water and suspended sediment in Yolo By-Pass and Cache Slough Complex, California, 2019–2021

Managed flow pulses in the north Sacramento-San Joaquin Delta are an adaptive management tool used in efforts to enhance food availability in delta smelt ( Hypomesus transpacificus ) habitat as part of the North Delta Food Subsidies Action. The California Department of Water Resources (DWR) monitors non-managed seasonal and local flow pulses and managed flow pulses from agricultural drainage or main stem Sacramento River water redirected through Yolo By-Pass. Augmented flow pulses are hypothesized to improve net positive flow during summer and fall in Yolo By-Pass and enhance plankton availability in delta smelt habitat in Cache Slough complex. However, flow pulses may also result in unintended negative effects of increased pesticides that are transported through Yolo By-Pass. Here, we evaluate pesticides in surface water and suspended sediment correlated with flow pulses in Yolo By-Pass during the 2019–21 calendar years. Surface-water and suspended-sediment samples were collected by DWR personnel. Water samples were analyzed at the U.S. Geological Survey Organic Chemistry Research Laboratory in Sacramento, California, for a suite of as many as 178 current-use pesticides and pesticide degradates using gas chromatography with mass spectrometry (GC/MS), gas chromatography with tandem mass spectrometry, and liquid chromatography with tandem mass spectrometry. Suspended sediments filtered from water samples were analyzed for a suite of as many as 173 current-use pesticides and pesticide degradates. There were 52 different current-use pesticides and pesticide degradates detected in water samples collected throughout the study. Concentrations ranged from below method detection limits to 4,070 nanograms per liter. Five different compounds in water samples were detected with concentrations above U.S. Environmental Protection Agency aquatic life benchmarks. In suspended-sediment samples collected throughout the study, eight different current-use pesticides and pesticide degradates were detected. Total pesticide concentrations were highest at surface-water sites in the northern end of Yolo By-Pass and decreased farther downstream during the same sampling events. Total pesticide concentrations generally were higher for most surface-water sites immediately before or during the managed flow pulse in 2019 versus after the flow pulse. Finally, mean total pesticide concentrations for each surface-water site generally were higher during all of 2019 than 2021, regardless of sampling period.

California↗

Evaluating the reliability of environmental concentration data to characterize exposure in environmental risk assessments

Environmental risk assessments often rely on measured concentrations in environmental matrices to characterize exposure of the population of interest—typically, humans, aquatic biota, or other wildlife. Yet, there is limited guidance available on how to report and evaluate exposure datasets for reliability and relevance, despite their importance to regulatory decision-making. This paper is the second of a four-paper series detailing the outcomes of a Society of Environmental Toxicology and Chemistry Technical Workshop that has developed Criteria for Reporting and Evaluating Exposure Datasets (CREED). It presents specific criteria to systematically evaluate the reliability of environmental exposure datasets. These criteria can help risk assessors understand and characterize uncertainties when existing data are used in various types of assessments and can serve as guidance on best practice for the reporting of data for data generators (to maximize utility of their datasets). Although most reliability criteria are universal, some practices may need to be evaluated considering the purpose of the assessment. Reliability refers to the inherent quality of the dataset and evaluation criteria address the identification of analytes, study sites, environmental matrices, sampling dates, sample collection methods, analytical method performance, data handling or aggregation, treatment of censored data, and generation of summary statistics. Each criterion is evaluated as “fully met,” “partly met,” “not met or inappropriate,” “not reported,” or “not applicable” for the dataset being reviewed. The evaluation concludes with a scheme for scoring the dataset as reliable with or without restrictions, not reliable, or not assignable, and is demonstrated with three case studies representing both organic and inorganic constituents, and different study designs and assessment purposes. Reliability evaluation can be used in conjunction with relevance evaluation (assessed separately) to determine the extent to which environmental monitoring datasets are “fit for purpose,” that is, suitable for use in various types of assessments. Integr Environ Assess Manag 2024;00:1–23. © 2024 Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Integrated Environmental Assessment and Management↗

Comparing modern identification methods for wild bees: Metabarcoding and image-based morphological taxonomic assignment

With the decline of bee populations worldwide, studies determining current wild bee distributions and diversity are increasingly important. Wild bee identification is often completed by experienced taxonomists or by genetic analysis. The current study was designed to compare two methods of identification including: (1) morphological identification by experienced taxonomists using images of field-collected wild bees and (2) genetic analysis of composite bee legs (multiple taxa) using metabarcoding. Bees were collected from conservation grasslands in eastern Iowa in summer 2019 and identified to the lowest taxonomic unit using both methods. Sanger sequencing of individual wild bee legs was used as a positive control for metabarcoding. Morphological identification of bees using images resulted in 36 unique taxa among 22 genera, and >80% of Bombus specimens were identified to species. Metabarcoding was limited to genus-level assignments among 18 genera but resolved some morphologically similar genera. Metabarcoding did not consistently detect all genera in the composite samples, including kleptoparasitic bees. Sanger sequencing showed similar presence or absence detection results as metabarcoding but provided species-level identifications for cryptic species (i.e., Lasioglossum ). Genus-specific detections were more frequent with morphological identification than metabarcoding, but certain genera such as Ceratina and Halictus were identified equally well with metabarcoding and morphology. Genera with proportionately less tissue in a composite sample were less likely to be detected using metabarcoding. Image-based methods were limited by image quality and visible morphological features, while genetic methods were limited by databases, primers, and amplification at target loci. This study shows how an image-based identification method compares with genetic techniques, and how in combination, the methods provide valuable genus- and species-level information for wild bees while preserving tissue for other analyses. These methods could be improved and transferred to a field setting to advance our understanding of wild bee distributions and to expedite conservation research.

PLoS ONE↗

Determinants of spring migration departure dates in a New World sparrow: Weather variables reign supreme

Numerous factors influence the timing of spring migration in birds, yet the relative importance of intrinsic and extrinsic variables on migration initiation remains unclear. To test for interactions among weather, migration distance, parasitism, and physiology in determining spring departure date, we used the Dark-eyed Junco ( Junco hyemalis ) as a model migratory species known to harbor diverse and common haemosporidian parasites. Prior to spring migration departure from their wintering grounds in Indiana, USA, we quantified the intrinsic variables of fat, body condition (i.e., mass ~ tarsus residuals), physiological stress (i.e., ratio of heterophils to lymphocytes), cellular immunity (i.e., leukocyte composition and total count), migration distance (i.e., distance to the breeding grounds) using stable isotopes of hydrogen from feathers, and haemosporidian parasite intensity. We then attached nanotags to determine the timing of spring migration departure date using the Motus Wildlife Tracking System. We used additive Cox proportional hazard mixed models to test how risk of spring migratory departure was predicted by the combined intrinsic measures, along with meteorological predictors on the evening of departure (i.e., average wind speed and direction, relative humidity, and temperature). Model comparisons found that the best predictor of spring departure date was average nightly wind direction and a principal component combining relative humidity and temperature. Juncos were more likely to depart for spring migration on nights with largely southwestern winds and on warmer and drier evenings (relative to cooler and more humid evenings). Our results indicate that weather conditions at take-off are more critical to departure decisions than the measured physiological and parasitism variables.

Ecology and Evolution↗

Methods of analysis—Determination of pesticides in filtered water and suspended sediment using liquid chromatography- and gas chromatography-tandem mass spectrometry

The widespread application of pesticides in agricultural and urban areas leads to their presence in surface waters. Presence of these biologically active chemicals in environmental waters potentially has adverse effects on nontarget organisms. To better understand the environmental fate of these contaminants, a robust method to capture chemicals with wide-ranging physicochemical properties has been developed. The method was developed by the U.S. Geological Survey’s Organic Chemistry Research Laboratory to monitor pesticides, pesticide degradates, and other agrochemicals in environmental surface waters throughout the country. The analysis involves a multiresidue method to determine 183 pesticides and pesticide degradates in filtered water samples and 178 pesticides and pesticide degradates in paired suspended sediment samples. After the filtration of whole water, contaminants are individually measured in the filtered water and the collected suspended sediment. Filtered water is extracted via solid-phase extraction, whereas suspended sediment is extracted using an ultrasonication, solid-liquid extraction. Samples are analyzed by liquid chromatography-tandem mass spectrometry using an electrospray ionization source in positive and negative modes and analyzed by gas chromatography-tandem mass spectrometry using an advanced electron ionization source in positive mode. Instrument parameters were optimized for the highest sensitivity, and at least two transitions (quantifier and qualifier) were monitored for each analyte. Recoveries in test filtered water ( n =9; 183 analytes) from the American River, California, and suspended sediment ( n =9; 178 analytes) samples fortified at 15 nanograms per liter (ng/L) ranged from 70.1 to 121.0 and 71.1 to 117.0 percent in water and suspended sediment filter samples, respectively. Method detection limits of pesticides and pesticide degradates ranged from 0.5 to 10.6 ng/L in water and 0.7 to 11.8 ng/L in suspended sediment filters. Reporting limits were 1.1–21.1 ng/L and 1.5–23.7 ng/L in water and filter samples, respectively. The developed method is applied to surface-water samples for the analysis of pesticides, pesticide degradates, and other agrochemicals.

Techniques and Methods↗

Multigenerational, indirect exposure to pyrethroids demonstrates potential compensatory response and reduced toxicity at higher salinity in estuarine fish

Estuarine environments are critical to fish species and serve as nurseries for developing embryos and larvae. They also undergo daily fluctuations in salinity and act as filters for pollutants. Additionally, global climate change (GCC) is altering salinity regimes within estuarine systems through changes in precipitation and sea level rise. GCC is also likely to lead to an increased use of insecticides to prevent pests from damaging agricultural crops as their habitats and mating seasons change from increased temperatures. This underscores the importance of understanding how insecticide toxicity to fish changes under different salinity conditions. In this study, larval Inland Silversides ( Menidia beryllina ) were exposed to bifenthrin (1.1 ng/L), cyfluthrin (0.9 ng/L), or cyhalothrin (0.7 ng/L) at either 6 or 10 practical salinity units (PSU) for 96 h during hatching, with a subset assessed for end points relevant to neurotoxicity and endocrine disruption by testing behavior, gene expression of a select suite of genes, reproduction, and growth. At both salinities, directly exposed F0 larvae were hypoactive relative to the F0 controls; however, the indirectly exposed F1 larvae were hyperactive relative to the F1 control. This could be evidence of a compensatory response to environmentally relevant concentrations of pyrethroids in fish. Effects on development, gene expression, and growth were also observed. Overall, exposure to pyrethroids at 10 PSU resulted in fewer behavioral and endocrine disruptive effects relative to those observed in organisms at 6 PSU.

Environmental Science and Technology↗

Pesticides in small volume plasma samples: Method development and application to smallmouth bass (Micropterus dolomieu) from the Chesapeake Bay watershed, USA

Nontarget organisms are exposed to pesticides following applications in agricultural and urban settings, potentially resulting in deleterious effects. Direct measurements of pesticides in biological tissues may aid in characterizing exposure, accumulation, and potential toxicity versus analyses in environmental media alone (e.g., water, soil, and air). Plasma represents a nonlethal sampling medium that can be used to assess recent exposures to contaminants. Herein, a method was developed to test the extraction of 210 pesticides and their transformation products in small volume plasma samples (100 μL). Plasma samples were protein precipitated with 0.5 % formic acid in acetonitrile added to the sample (ratio of 3.5:1). Pass-through solid phase extraction was used for sample matrix and lipid removal and samples were analyzed by liquid chromatography and gas chromatography with tandem mass spectrometry. Recoveries of 70.0–129.8 % were achieved for 182 pesticides and degradates across the low (25 ng mL −1 ), medium (100 ng mL −1 ), and high (250 ng mL −1 ) spike levels. Method detection levels ranged 0.4–13.0 ng mL −1 . Following development, the method was applied to smallmouth bass ( Micropterus dolomieu ) plasma samples (n = 10) collected from adults in the Chesapeake Bay watershed. Individual plasma samples resulted in four to seven analytes detected with summed concentrations ranging 16.4–95.0 ng mL −1 . Biological multiresidue pesticide methods help elucidate recent exposures of bioactive compounds to nontarget organisms.

Chesapeake Bay watershed↗

Temporal concentrations of Quaternary ammonium compounds in wastewater treatment effluents during the COVID-19 pandemic, 2020–2021

Quaternary ammonium compounds (QAC) are high production chemicals used in many commercial and household disinfection products. During the SARS-CoV-2 (COVID-19) pandemic, QACs were included on lists of COVID-19 disinfectants. Increased QAC use could lead to higher levels of QACs in wastewater treatment plant (WWTP) effluents, which could subsequently be released into the environment. To evaluate QACs in WWTP effluent, three WWTPs in the northeastern United States were monitored from May 2020 through August 2021. Target QACs included six benzylalkyldimethyl ammonium compounds (BAC), three dialkyldimethyl ammonium compounds (DADMAC), two ethylbenzylalkyldimethyl ammonium compounds (EBAC), and benzethonium. At least one QAC was detected in every sample with individual concentrations up to 1600 ng L −1 . BAC-C 14 was detected most frequently, found in 93% of effluent samples; BAC-C 12 , BAC-C 16 , EBAC-C 12 and EBAC-C 14 were all detected in greater than 80% of samples. Few temporal patterns were observed in QAC concentrations with respect to weekly COVID-19 cases: at WWTP 2, DADMAC-C 8 :C 10 and DADMAC-C 10 were positively correlated, and DADMAC-C 8 negatively correlated. There were several seasonal trends at WWTP 1, including significant differences of ƩDADMAC, which were higher in fall than summer; ƩBAC was higher during the fall than both spring and summer; and ƩQAC where higher during the fall than spring.

Chemosphere↗