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Geology topics

Michael S. Gross

Publications and source records attributed to Michael S. Gross.

11 recordsLinked to original sources

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

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

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

Persistence of pesticide residues in weathered avian droppings

Avian droppings (combination of fecal matter and urates) provide a non-lethal and non-invasive matrix for measuring pesticide exposures. In the field, droppings may be collected days or weeks after excretion and the persistence of pesticide residues in weathered droppings is not known. Thus, we studied the effects of weathering on pesticide residues in droppings. Domestic chicken ( Gallus gallus domesticus ) hens were used as a representative species for Order Galliformes. We collected droppings from hens before they were exposed to the pesticides (reference or pre-dose droppings ). Thereafter, the hens were orally administered encapsulated wheat seeds coated with Raxil® PRO Shield (containing the active ingredients imidacloprid, prothioconazole, metalaxyl, and tebuconazole) for consecutive 7 days. During this time, their droppings were collected on days 3, 5, and 8 from the start of the exposure period (post-dose droppings ). The pre-dose and post-dose droppings were weathered for up to 30 days in autumn and spring in shrubsteppe habitat. Droppings were analyzed using HPLC coupled to triple quad LC/MS for parent compound and metabolite residues. No pesticide or its metabolite residues were detected in the weathered reference droppings. No parent pesticide compounds were detected in weathered post-dose droppings but imidacloprid metabolites, imidacloprid-5-hydroxy and imidacloprid-olefin, and the prothioconazole metabolite, desthio-prothioconazole, were detected in all post-dose weathered samples from both seasons. The active ingredients metalaxyl and tebuconazole and their metabolites were not detected in any of the samples. Our results suggest that, depending on the pesticide, its concentration, and the environmental conditions, residues of some pesticides can be detected in droppings weathered for at least 30 days. Knowledge of pesticide persistence in weathered droppings can help refine the quality and quantity of fecal samples that are collected for monitoring pesticide exposures to birds.

Environmental Research

Multiresidue extraction of current-use pesticides from complex solid matrices using energized dispersive guided extraction with analysis by gas and liquid chromatography tandem mass spectroscopy

The development of sample processing techniques that recover a broad suite of pesticides from solid matrices, while mitigating coextracted matrix interferences, and reducing processing time is beneficial for high throughput analyses. The objective of this study was to evaluate the effectiveness of an automated extraction system for pesticide analyses in solid environmental samples. An Energized Dispersive Guided Extraction (EDGE) system was used to evaluate two different extraction solvents in optimizing the extraction of 210 pesticides and pesticide transformation products. A graphitized carbon cleanup step was implemented, and three elution solvents were evaluated separately for analyte recoveries. Recoveries between 70 and 130% were achieved for 167 compounds in a test soil using acetonitrile as an extraction solvent and carbon cleanup with acetonitrile and dichloromethane elutions. Nine field samples (soil, sediment, and biosolids) were extracted using the newly developed method and were compared with a previously validated pressurized liquid extraction (PLE) method using an Accelerated Solvent Extraction (ASE) system. Concentrations obtained from the two methods were comparable (linear R 2 > 0.999), suggesting similar performance between the EDGE and PLE extractions in complex matrices. The new method provided slightly better sensitivities in comparison to the PLE method, ranging from 0.09 to 2.56 ng g −1 . The method presented here significantly reduces extraction setup and runtimes while also minimizing the volume of carcinogenic solvents ( e.g. , dichloromethane) used in the laboratory and presents a sensitive multiresidue method for a wide range of pesticides in solid matrices.

Chemosphere

Evaluation of ELISA for the analysis of imidacloprid in biological matrices: Cross-reactivities, matrix interferences, and comparison to LC-MS/MS

Imidacloprid is among the most used pesticides worldwide and there are toxicity concerns for nontarget organisms. Accurate and sensitive methods are necessary to quantitate imidacloprid concentrations in biological matrices to better understand their fate and effects. Here we evaluated an enzyme-linked immunosorbent assay (ELISA) kit for the analysis of imidacloprid in biological samples. Following the dosing of Japanese quail ( Coturnix japonica ) with imidacloprid-treated wheat seeds, plasma, liver, and fecal matter samples were analyzed by ELISA and compared to previous analyses that employed liquid chromatography-tandem mass spectrometry (LC-MS/MS). Imidacloprid metabolites—5-OH-imidacloprid, imidacloprid-olefin, imidacloprid-urea, desnitro-imidacloprid, and 6-chloronicotinic acid—were tested for their cross-reactivity to antibodies within the commercial imidacloprid ELISA kit. The two major metabolites, 5-OH-imidacloprid and imidacloprid-olefin, showed cross-reactivities of 0.93–26 %. ELISA and LC-MS/MS results were positively correlated but there was poor agreement in concentrations: plasma and fecal matter imidacloprid concentrations were higher by ELISA, whereas liver imidacloprid concentrations were higher by LC-MS/MS. Matrix interferences observed in analyses were minimized by the application of matrix-matched calibration curves. ELISA provided an effective screening tool for imidacloprid in these biological matrices, but the presence of cross-reactants confounded results. Confirmation of ELISA results by more selective techniques (e.g., LC-MS/MS) is suggested for complex samples.

Chemosphere

Exposure to crop production alters cecal prokaryotic microbiota, inflates virulome and resistome in wild prairie grouse

Chemically intensive crop production depletes wildlife food resources, hinders animal development, health, survival, and reproduction, and it suppresses wildlife immune systems, facilitating emergence of infectious diseases with excessive mortality rates. Gut microbiota is crucial for wildlife's response to environmental stressors. Its composition and functionality are sensitive to diet changes and environmental pollution associated with modern crop production. In this study we use shotgun metagenomics (median 8,326,092 sequences/sample) to demonstrate that exposure to modern crop production detrimentally affects cecal microbiota of sharp-tailed grouse ( Tympanuchus phasianellus : 9 exposed, 18 unexposed and greater prairie chickens ( T. cupido ; 11, 11). Exposure to crop production had greater effect on microbiota richness ( t = 6.675, P < 0.001) and composition (PERMANOVA r 2 = 0.212, P = 0.001) than did the host species ( t = 4.762, P < 0.001; r 2 = 0.070, P = 0.001) or their interaction ( t = 3.449; r 2 = 0.072, both P = 0.001), whereas sex and age had no effect. Although microbiota richness was greater in exposed ( T. cupido chao1 = 152.8 ± 20.5; T. phasianellus 115.3 ± 17.1) than in unexposed (102.9 ± 15.1 and 101.1 ± 17.2, respectively) birds, some beneficial bacteria dropped out of exposed birds' microbiota or declined and were replaced by potential pathogens. Exposed birds also had higher richness and load of virulome (mean ± standard deviation; T. cupido 24.8 ± 10.0 and 10.1 ± 5.5, respectively; T. phasianellus 13.4 ± 6.8/4.9 ± 2.8) and resistome ( T. cupido 46.8 ± 11.7/28.9 ± 10.2, T. phasianellus 38.3 ± 16.7/18.9 ± 14.2) than unexposed birds ( T. cupido virulome: 14.2 ± 13.5, 4.5 ± 4.2; T. cupido resistome: 31.6 ± 20.2 and 13.1 ± 12.0; T. phasianellus virulome: 5.2 ± 4.7 and 1.4 ± 1.5; T. phasianellus resistome: 13.7 ± 16.1 and 4.0 ± 6.4).

Nebraska

Uptake, metabolism, and elimination of fungicides from coated wheat seeds in Japanese quail (Coturnix japonica)

Pesticides coated to the seed surface potentially pose an ecological risk to granivorous birds that consume incompletely buried or spilled seeds. To assess the toxicokinetics of seeds treated with current-use fungicides, Japanese quail (Coturnix japonica) were orally dosed with commercially coated wheat seeds. Quail were exposed to metalaxyl, tebuconazole, and fludioxonil at either a low (0.07, 0.03, and 0.03 mg/kg body weight) or high dose (0.2, 0.09, and 0.1 mg/kg body weight). Fungicides were rapidly absorbed and distributed to tissues. Tebuconazole was metabolized into t-butylhydroxy-tebuconazole. All compounds were eliminated to below detection limits within 24 h. The high detection frequencies observed in fecal samples potentially offers a noninvasive matrix to monitor pesticide exposure. Summing total body burden across plasma, tissue, and fecal samples, less than 9% of the administered dose was identified as the parent fungicide, demonstrating the importance to monitor both active ingredients and their metabolites in biological samples.

Journal of Agricultural and Food Chemistry

Toxicokinetics of imidacloprid-coated wheat seeds in Japanese quail (Coturnix japonica) and an evaluation of hazard

Birds are potentially exposed to neonicotinoid insecticides by ingestion of coated seeds during crop planting. Adult male Japanese quail were orally dosed with wheat seeds coated with an imidacloprid (IMI) formulation at either 0.9 mg/kg body weight (BW) or 2.7 mg/kg BW (~3 and 9% of IMI LD50 for Japanese quail, respectively) for 1 or 10 days. Quail were euthanized between 1 and 24 h post-exposure to assess toxicokinetics. Analysis revealed rapid absorption (1 h) into blood, and distribution to brain, muscle, kidney and liver. Clearance to below detection limits occurred at both dose levels and exposure durations in all tissues within 24 h. Metabolism was extensive, with 5-OH-IMI and IMI-olefin detected at greater concentrations than IMI in tissues and fecal samples. There was no lethality or overt signs of toxicity at either dose level. Furthermore, no evidence of enhanced expression of mRNA genes associated with hepatic xenobiotic metabolism, oxidative DNA damage or alterations in concentrations of corticosterone and thyroid hormones was observed. Application of the toxicokinetic data was used to predict IMI residue levels in liver with reasonable results for some field exposure and avian mortality events. It would appear that some affected species are either consuming larger quantities of seeds or exhibit differences in ADME or sensitivity than predicted by read-across from these data.

Environmental Science & Technology