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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

A novel method to characterise levels of pharmaceutical pollution in large scale aquatic monitoring campaigns

Much of the current understanding of pharmaceutical pollution in the aquatic environment is based on research conducted in Europe, North America and other select high-income nations. One reason for this geographic disparity of data globally is the high cost and analytical intensity of the research, limiting accessibility to necessary equipment. To reduce the impact of such disparities, we present a novel method to support large-scale monitoring campaigns of pharmaceuticals at different geographical scales. The approach employs the use of a miniaturised sampling and shipping approach with a high throughput and fully validated direct-injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry method for the quantification of 61 active pharmaceutical ingredients (APIs) and their metabolites in tap, surface, wastewater treatment plant (WWTP) influent and WWTP effluent water collected globally. A 7-day simulated shipping and sample stability assessment was undertaken demonstrating no significant degradation over the 1–3 days which is typical for global express shipping. Linearity (r 2 ) was consistently ≥0.93 (median = 0.99 ± 0.02), relative standard deviation of intra- and inter-day repeatability and precision was <20% for 75% and 68% of the determinations made at three concentrations, respectively, and recovery from Liquid Chromatography Mass Spectrometry grade water, tap water, surface water and WWTP effluent were within an acceptable range of 60–130% for 87%, 76%, 77% and 63% of determination made at three concentrations respectively. Limits of detection and quantification were determined in all validated matrices and were consistently in the ng/L level needed for environmentally relevant API research. Independent validation of method results was obtained via an interlaboratory comparison of three surface-water samples and one WWTP effluent sample collected in North Liberty, Iowa (USA). Samples used for the interlaboratory validation were analysed at the University of York Centre of Excellence in Mass Spectrometry (York, UK) and the U.S. Geological Survey National Water Quality Laboratory in Denver (Colorado, USA). These results document the robustness of using this method on a global scale. Such application of this method would essentially eliminate the interlaboratory analytical variability typical of such large-scale datasets where multiple methods were used.

Applied Sciences

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

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

Environmental Science and Technology

Using high resolution satellite and telemetry data to track flooded habitats, their use by waterfowl, and evaluate effects of drought on waterfowl and shorebird bioenergetics in California

Wetland managers in the Central Valley of California, a dynamic hydrological landscape, require information regarding the amount and location of existing wetland habitat to make decisions on how to best use water resources to support multiple wildlife objectives, particularly during drought. Scientists from the U.S. Geological Survey Western Ecological Research Center (WERC), Point Blue Conservation Science (Point Blue), and the U.S. Fish and Wildlife Service (USFWS) partnered to learn how wetland and flooded agricultural habitats used by waterfowl and shorebirds change during the non-breeding season (July–April) particularly during drought. During extreme drought conditions, the ability to provide sufficient water for wildlife often depends on the timing of water deliveries to managed wetlands and winter-flooded crop fields and decisions on whether to fallow croplands. Waterfowl and shorebirds could be particularly affected by these decisions because they typically rest and feed in flooded habitats. Poor habitat conditions resulting from spatially or temporally suboptimal water deliveries (that is, mismatch between waterfowl habitat needs and timing and location of flooded habitats) could reduce waterfowl hunting opportunities and body condition. Point Blue scientists developed a system for near real-time tracking of habitats used by waterfowl, shorebirds, and some other wetland-dependent “waterbirds” ( www.pointblue.org/watertracker ) and to assess the impacts of drought on habitat availability and on waterfowl and shorebird bioenergetics. The WERC researchers linked these data with near real-time tracking (telemetry) data of duck locations throughout the Valley. The team used these two datasets to relate duck locations to open-water characteristics and to learn how waterfowl use habitats under spatially and temporally changing conditions during drought and non-drought periods. We found that recent extreme drought (2013–15) significantly changed the timing and magnitude of flooding and consequently reduced the availability of habitats used by waterfowl and shorebirds more than other recent historic droughts 2000–11. Drought reduced irrigations of moist soil seed plants and thus there was lower food energy available for waterfowl. Analyses using bioenergetics models indicated that, overall, extreme drought increased food energy deficits (total number of deficit days) for shorebirds and waterfowl. Our analysis indicated a strong direct relationship between duck locations and classified habitat derived from open-water data during the wintering period (October–March). This result helps confirm the application of dynamic water data to identify flooded areas that provide waterfowl habitat. Presence of open water at a 1-hectare resolution can be used effectively to identify flooded landscape areas available as habitat for ducks. Our discoveries from evaluating use of space by ducks also indicated that nighttime feeding locations of ducks were concentrated nearby primary roosts and that foraging distances could depend on hydrologic dynamics of location (Suisun Marsh versus California excluding Suisun Marsh) and time of season (early, middle, late). Other results indicated that some areas on the California landscape with extremely reliable water supplies could receive consistent use by ducks year after year (in essence, almost drought proof). The Water Tracker is set up to automatically track wetland habitat and food availability each year and is making these data available to water and wetland managers. Results from this research are a significant step toward understanding how waterfowl and shorebird habitats can be optimally managed on the landscape to support desired populations of these migratory birds during extreme drought.

California

Development and Application of Pyrolysis Gas Chromatography/Mass Spectrometry for the Analysis of Bound Trinitrotoluene Residues in Soil

TNT (trinitrotoluene) is a contaminant of global environmental significance, yet determining its environmental fate has posed longstanding challenges. To date, only differential extraction-based approaches have been able to determine the presence of covalently bound, reduced forms of TNT in field soils. Here, we employed thermal elution, pyrolysis, and gas chromatography/mass spectrometry (GC/MS) to distinguish between covalently bound and noncovalently bound reduced forms of TNT in soil. Model soil organic matter-based matrixes were used to develop an assay in which noncovalently bound (monomeric) aminodinitrotoluene (ADNT) and diaminonitrotoluene (DANT) were desorbed from the matrix and analyzed at a lower temperature than covalently bound forms of these same compounds. A thermal desorption technique, evolved gas analysis, was initially employed to differentiate between covalently bound and added 15N-labeled monomeric compounds. A refined thermal elution procedure, termed "double-shot analysis" (DSA), allowed a sample to be sequentially analyzed in two phases. In phase 1, all of an added 15N-labeled monomeric contaminant was eluted from the sample at relatively low temperature. In phase 2 during high-temperature pyrolysis, the remaining covalently bound contaminants were detected. DSA analysis of soil from the Louisiana Army Ammunition Plant (LAAP; ???5000 ppm TNT) revealed the presence of DANT, ADNT, and TNT. After scrutinizing the DSA data and comparing them to results from solvent-extracted and base/acid-hydrolyzed LAAP soil, we concluded that the TNT was a noncovalently bound "carryover" from phase 1. Thus, the pyrolysis-GC/MS technique successfully defined covalently bound pools of ADNT and DANT in the field soil sample.

Environmental Science & Technology

An open source database for the synthesis of soil radiocarbon data: ISRaD version 1.0

Radiocarbon is a critical constraint on our estimates of the timescales of soil carbon cycling that can aid in identifying mechanisms of carbon stabilization and destabilization and improve the forecast of soil carbon response to management or environmental change. Despite the wealth of soil radiocarbon data that have been reported over the past 75 years, the ability to apply these data to global-scale questions is limited by our capacity to synthesize and compare measurements generated using a variety of methods. Here, we present the International Soil Radiocarbon Database (ISRaD; http://soilradiocarbon.org , last access: 16 December 2019), an open-source archive of soil data that include reported measurements from bulk soils, distinct soil carbon pools isolated in the laboratory by a variety of soil fractionation methods, samples of soil gas or water collected interstitially from within an intact soil profile, CO 2 gas isolated from laboratory soil incubations, and fluxes collected in situ from a soil profile. The core of ISRaD is a relational database structured around individual datasets (entries) and organized hierarchically to report soil radiocarbon data, measured at different physical and temporal scales as well as other soil or environmental properties that may also be measured and may assist with interpretation and context. Anyone may contribute their own data to the database by entering it into the ISRaD template and subjecting it to quality assurance protocols. ISRaD can be accessed through (1) a web-based interface, (2) an R package (ISRaD), or (3) direct access to code and data through the GitHub repository, which hosts both code and data. The design of ISRaD allows for participants to become directly involved in the management, design, and application of ISRaD data. The synthesized dataset is available in two forms: the original data as reported by the authors of the datasets and an enhanced dataset that includes ancillary geospatial data calculated within the ISRaD framework. ISRaD also provides data management tools in the ISRaD-R package that provide a starting point for data analysis; as an open-source project, the broader soil community is invited and encouraged to add data, tools, and ideas for improvement. As a whole, ISRaD provides resources to aid our evaluation of soil dynamics across a range of spatial and temporal scales. The ISRaD v1.0 dataset is archived and freely available at https://doi.org/10.5281/zenodo.2613911 (Lawrence et al., 2019).

Earth System Science Data

Effects of prescribed fire timing on vigor of the invasive forb sericea lespedeza (Lespedeza cuneata), total forage biomass accumulation, plant-community composition, and native fauna on tallgrass prairie in the Kansas Flint Hills

The predominant grazing-management practice of the Kansas Flint Hills involves annual prescribed burning in March or April with postfire grazing by yearling beef cattle at a high stocking density from April to August. There has been a dramatic increase in sericea lespedeza ( Lespedeza cuneata [Dumont] G. Don) coincident with this temporally focused use of prescribed fire in the Flint Hills region. The species is an aggressive invader and a statewide noxious weed in Kansas. Control has generally been attempted using repeated herbicide applications. This approach has not limited proliferation of sericea lespedeza and resulted in collateral damage to nontarget flora and fauna. Alternative timing of prescribed fire has not been evaluated for its control. Our objectives for this 4-yr experiment were to (1) document the effects of prescribed burning during early April, early August, or early September on vigor of sericea lespedeza, standing forage biomass, and basal cover of native graminoids, forbs, and shrubs and (2) measure responses to fire regimes by grassland bird and butterfly communities. Whole-plant dry mass, basal cover, and seed production of sericea lespedeza were markedly less ( P < 0.01) in areas treated with prescribed fire in August or September compared with April. Forage biomass did not differ ( P ≥ 0.43) among treatments when measured during July; moreover, frequencies of bare soil, litter, and total basal plant cover were not different ( P ≥ 0.29) among treatments. Combined basal covers of C4 grasses, C3 grasses, annual grasses, forbs, and shrubs also did not differ ( P ≥ 0.11) between treatments. Densities of grasshopper sparrow ( Ammodramus savannarum ), dickcissel ( Spiza americana ), and eastern meadowlark ( Sturnella magna ) were not negatively affected ( P > 0.10) by midsummer or late-summer fires relative to early-spring fires. There were no differences ( P > 0.10) in densities of grassland-specialist butterfly species across fire regimes. Under the conditions of our experiment, prescribed burning during summer produced no detrimental effects on forage production, desirable nontarget plant species, grassland birds, or butterfly communities but had strong suppressive effects on sericea lespedeza. Additional research is warranted to investigate how to best incorporate late-summer prescribed fire into common grazing-management practices in the Kansas Flint Hills.

Kansas

Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO 3 − ) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl 18 O 3 − ) using 18 O water (H 2 18 O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO 3 − was 2 ng L −1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO 3 − in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO 3 − analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO 4 − ) occurrence were analyzed using the proposed method and ClO 3 − was found to co-occur with ClO 4 − at concentrations ranging from <2 ng L −1 in precipitation from Texas and Puerto Rico to >500 mg kg −1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO 3 − in some natural groundwater samples (<0.1 μg L −1 ) analyzed in this work may indicate lower stability when compared to ClO 4 − in the subsurface. The high concentrations of ClO 3 − in caliches and soils (3−6 orders of magnitude greater) as compared to precipitation samples indicate that ClO 3 − , like ClO 4 − , may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Environmental Science & Technology

Plant community context controls short- vs. medium-term effects of pre-emergent herbicides on target and non-target species after fire

Questions: Selective herbicide application is a common restoration strategy to control exotic invaders that interfere with native plant recovery after wildfire. Whether spraying with preemergent or bioherbicides releases native plants from competition with exotics (“spray-and-release” strategy) and can make communities resistant to re-invasion by exotic annual grasses (e.g., cheatgrass, medusahead), without risks to non-target native plants or secondary invasion, is a major question for land managers of semiarid plant communities. Location: Sagebrush steppe of southwest Idaho, USA Methods We applied chemical herbicides (imazapic, rimsulfuron) and weed-suppressive bacteria ( Pseudomonas fluorescens strains MB906 and D7) to three sagebrush-steppe communities after fire.We measured plant cover prior to burning and for four years (five for exotic annual grasses) post-treatment. Results Both chemical herbicides significantly reduced exotic annual grass cover in all communities in the first post-spraying year, but rimsulfuron plots were re-invaded after 1-2 years, while imazapic plots continued to resist re-invasion 4 and even 5 years post-spraying, well after the herbicide should have degraded. We did not detect any increase in native perennial grass cover with either herbicide, and herbicides had both positive and negative effects on individual bunchgrass basal diameter, depending on species and plant community. Rimsulfuron was more damaging than imazapic to shallow-rooted perennial bunchgrasses. Moss and lichen cover, key components of soil integrity, increased with chemical herbicide treatments in some communities. Both herbicides increased secondary invaders (exotic forbs or grasses), which varied by plant community and herbicide. Weed-suppressive bacteria treatments had no significant effects on cover of any functional group. Conclusions While short-term effects of chemical herbicides that target exotic annual grasses were relatively consistent and predictable, longer-term effects were specific to the herbicide and plant community. The “spray and release” strategy may confer resistance to re-invasion by exotic annual grasses if herbicides prevent re-invasion for an extended period.

Idaho

Climate refugia for Pinus spp. in topographic and bioclimatic environments of the Madrean sky islands of México and the United States

Climate refugia, or places where habitats are expected to remain relatively buffered from regional climate extremes, provide an important focus for science and conservation planning. Within high-priority, multi-jurisdictional landscapes like the Madrean sky islands of the United States and México, efforts to identify and manage climate refugia are hindered by the lack of high-quality and consistent transboundary datasets. To fill these data gaps, we assembled a bi-national field dataset ( n = 1416) for five pine species ( Pinus spp.) and used generalized boosted regression to model pine habitats in relation to topographic variability as a basis for identifying potential microrefugia at local scales in the context of current species’ distribution patterns. We developed additional models to quantify climatic refugial attributes using coarse scale bioclimatic variables and finer scale seasonal remote sensing indices. Terrain metrics including ruggedness, slope position, and aspect defined microrefugia for pines within elevation ranges preferred by each species. Response to bioclimatic variables indicated that small shifts in climate were important to some species (e.g., P. chihuahuana, P. strobiformis ), but others exhibited a broader tolerance (e.g., P. arizonica ). Response to seasonal climate was particularly important in modeling microrefugia for species with open canopy structure and where regular fires occur (e.g., P. engelmannii and P. chihuahuana ). Hotspots of microrefugia differed among species and were either limited to northern islands or occurred across central or southern latitudes. Mapping and validation of refugia and their ecological functions are necessary steps in developing regional conservation strategies that cross jurisdictional boundaries. A salient application will be incorporation of climate refugia in management of fire to restore and maintain pine ecology.

Arizona, Chihuahua, New Mexico, Sonora

Combining local, landscape, and regional geographies to assess plant community vulnerability to invasion impact

Invasive species science has focused heavily on the invasive agent. However, management to protect native species also requires a proactive approach focused on resident communities and the features affecting their vulnerability to invasion impacts. Vulnerability is likely the result of factors acting across spatial scales, from local to regional, and it is the combined effects of these factors that will determine the magnitude of vulnerability. Here, we introduce an analytical framework that quantifies the scale-dependent impact of biological invasions on native richness from the shape of the native species–area relationship (SAR). We leveraged newly available, biogeographically extensive vegetation data from the U.S. National Ecological Observatory Network to assess plant community vulnerability to invasion impact as a function of factors acting across scales. We analyzed more than 1000 SARs widely distributed across the USA along environmental gradients and under different levels of non-native plant cover. Decreases in native richness were consistently associated with non-native species cover, but native richness was compromised only at relatively high levels of non-native cover. After accounting for variation in baseline ecosystem diversity, net primary productivity, and human modification, ecoregions that were colder and wetter were most vulnerable to losses of native plant species at the local level, while warmer and wetter areas were most susceptible at the landscape level. We also document how the combined effects of cross-scale factors result in a heterogeneous spatial pattern of vulnerability. This pattern could not be predicted by analyses at any single scale, underscoring the importance of accounting for factors acting across scales. Simultaneously assessing differences in vulnerability between distinct plant communities at local, landscape, and regional scales provided outputs that can be used to inform policy and management aimed at reducing vulnerability to the impact of plant invasions.

Ecological Applications

Effects of watershed densities of animal feeding operations on nutrient concentrations and estrogenic activity in agricultural streams

Application of manures from animal feeding operations (AFOs) as fertilizer on agricultural land can introduce nutrients and hormones (e.g. estrogens) to streams. A landscape-scale study was conducted in the Shenandoah River watershed (Virginia, USA) in order to assess the relationship between densities of AFOs in watersheds of agricultural streams and in-stream nutrient concentrations and estrogenic activity. The effect of wastewater treatment plants (WWTPs) on nutrients and estrogenic activity was also evaluated. During periods of high and low flow, dissolved inorganic nitrogen (DIN) and orthophosphate (PO4-P) concentrations were analyzed and estrogens/estrogenic compounds were extracted and quantified as17β-estradiol equivalents (E2Eq) using a bioluminescent yeast estrogen screen. Estrogenic activity was measurable in the majority of collected samples, and 20% had E2Eq concentrations > 1 ng/L. Relatively high concentrations of DIN (> 1000 μg/L) were also frequently detected. During all sampling periods, there were strong relationships between watershed densities of AFOs and in-stream concentrations of DIN (R2 = 0.56–0.81) and E2Eq (R2 = 0.39–0.75). Relationships between watershed densities of AFOs and PO4-P were weaker, but were also significant (R2 = 0.27–0.57). When combined with the effect of watershed AFO density, streams receiving WWTP effluent had higher concentrations of PO4-P than streams without WWTP discharges, and PO4-P was the only analyte with a consistent relationship to WWTPs. The results of this study suggest that as the watershed density of AFOs increases, there is a proportional increase in the potential for nonpoint source pollution of agricultural streams and their receiving waters by nutrients, particularly DIN, and compounds that can cause endocrine disruption in aquatic organisms.

Science of the Total Environment

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

RNA-seq reveals potential gene biomarkers in fathead minnows (Pimephales promelas) for exposure to treated wastewater effluent

Discharged wastewater treatment plant (WWTP) effluent greatly contributes to the generation of complex mixtures of contaminants of emerging concern (CECs) in aquatic environments which often contain neuropharmaceuticals and other emerging contaminants that may impact neurological function. However, there is a paucity of knowledge on the neurological impacts of these exposures to aquatic organisms. In this study, caged fathead minnows ( Pimephales promelas ) were exposed in situ in a temperate-region effluent-dominated stream ( i.e. , Muddy Creek) in Coralville, Iowa, USA upstream and downstream of a WWTP effluent outfall. The pharmaceutical composition of Muddy Creek was recently characterized by our team and revealed many compounds there were at a low microgram to high nanogram per liter concentration. Total RNA sequencing analysis on brain tissues revealed 280 gene isoforms that were significantly differentially expressed in male fish and 293 gene isoforms in female fish between the upstream and downstream site. Only 66 (13%) of such gene isoforms overlapped amongst male and female fish, demonstrating sex-dependent impacts on neuronal gene expression. By using a systems biology approach paired with functional enrichment analyses, we identified several potential novel gene biomarkers for treated effluent exposure that could be used to expand monitoring of environmental effects with respect to complex CEC mixtures. Lastly, when comparing the results of this study to those that relied on a single-compound approach, there was relatively little overlap in terms of gene-specific effects. This discovery brings into question the application of single-compound exposures in accurately characterizing environmental risks of complex mixtures and for gene biomarker identification.

Iowa

Simulating long-term effectiveness and efficiency of management scenarios for an invasive grass

Resource managers are often faced with trade-offs in allocating limited resources to manage plant invasions. These decisions must often be made with uncertainty about the location of infestations, their rate of spread and effectiveness of management actions. Landscape level simulation tools such as state-and-transition simulation models (STSMs) can be used to evaluate the potential long term consequences of alternative management strategies and help identify those strategies that make efficient use of resources. We analyzed alternative management scenarios for African buffelgrass ( Pennisetum ciliare syn. Cenchrus ciliaris ) at Ironwood Forest National Monument, Arizona using a spatially explicit STSM implemented in the Tool for Exploratory Landscape Scenario Analyses (TELSA). Buffelgrass is an invasive grass that is spreading rapidly in the Sonoran Desert, affecting multiple habitats and jurisdictions. This invasion is creating a novel fire risk and transforming natural ecosystems. The model used in this application incorporates buffelgrass dispersal and establishment and management actions and effectiveness including inventory, treatment and post-treatment maintenance. We simulated 11 alternative scenarios developed in consultation with buffelgrass managers and other stakeholders. The scenarios vary according to the total budget allocated for management and the allocation of that budget between different kinds of management actions. Scenario results suggest that to achieve an actual reduction and stabilization of buffelgrass populations, management unconstrained by fiscal restrictions and across all jurisdictions and private lands is required; without broad and aggressive management, buffelgrass populations are expected to increase over time. However, results also suggest that large upfront investments can achieve control results that require relatively minimal spending in the future. Investing the necessary funds upfront to control the invasion results in the most efficient use of resources to achieve lowest invaded acreage in the long-term.

Arizona

Routine determination of sulfonylurea, imidazolinone, and sulfonamide herbicides at nanogram-per-liter concentrations by solid-phase extraction and liquid chromatography/mass spectrometry

Sulfonylurea (SU), imidazolinone (IMI), and sulfonamide (SA) herbicides are new classes of low-application-rate herbicides increasingly used by farmers. Some of these herbicides affect both weed and crop species at low dosages and must be carefully used. Less is known about the effect of these compounds on non-crop plant species, but a concentration of 100 ng/l in water has been proposed as the threshold for possible plant toxicity for most of these herbicides. Hence, analytical methods must be capable of detecting SUs, IMIs, and SAs at concentrations less than 100 ng/l in ambient water samples. The authors developed a two-cartridge, solid-phase extraction method for isolating 12 SU, 3 IMI, and 1 SA herbicides by using high-performance liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS) to identify and quantify these herbicides to 10 ng/l. This method was used to analyze 196 surface- and ground-water samples collected from May to August 1998 throughout the Midwestern United States, and more than 100 quality-assurance and quality-control samples. During the 16 weeks of the study, the HPLC/ESI-MS maintained excellent calibration linearity across the calibration range from 5 to 500 ng/l, with correlation coefficients of 0.9975 or greater. Continuing calibration verification standards at 100-ng/l concentration were analyzed throughout the study, and the average measured concentrations for individual herbicides ranged from 93 to 100 ng/l. Recovery of herbicides from 27 reagent-water samples spiked at 50 and 100 ng/l ranged from 39 to 92%, and averaged 73%. The standard deviation of recoveries ranged from 14 to 26%, and averaged 20%. This variability reflects multiple instruments, operators, and the use of automated and manual sample preparation. Spiked environmental water samples had similar recoveries, although for some herbicides, the sample matrix enhanced recoveries by as much as 200% greater than the spiked concentration. This matrix enhancement was sample- and compound-dependent. Concentrations of herbicides in unspiked duplicate environmental samples were typically within 25% of each other. The results demonstrate the usefulness of HPLC/ESI-MS for determining low-application-rate herbicides at ambient concentrations.

Science of Total Environment

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

Trends in plant cover derived from vegetation plot data using ordinal zero-augmented beta regression

Questions Plant cover values in vegetation plot data are bounded between 0 and 1, and cover is typically recorded in discrete classes with non-equal intervals. Consequently, cover data are skewed and heteroskedastic, which hampers the application of conventional regression methods. Recently developed ordinal beta regression models consider these statistical difficulties. Our primary question is whether we can detect species trends in vegetation plot time series data with this modelling approach. A second question is whether trends in cover have additional value compared to trends in occurrence, which are easier to assess for practitioners. Location The Netherlands, Western Europe. Methods We used vegetation plot data collected from 10,000 fixed plots which were surveyed once every four years during 1999–2022. We used the ordinal zero-augmented beta regression (OZAB) model, a hierarchical model consisting of a logistic regression for presence and an ordinal beta regression for cover. We adapted the OZAB model for longitudinal data and produced estimates of cover and occurrence for each four-year period. Thereafter we assessed trends in cover and in occurrence across all periods. Results We found evidence of a trend in cover in 318 out of the 721 species (44%) with sufficient data. Most species showed similar directional trends in occurrence and percent cover. No trend in occurrence was detected for 64 species that had evidence of a trend in cover. Declining species had stronger relative changes in cover than in occurrence. Conclusions Our model enables researchers to detect trends in cover using longitudinal vegetation plot data. Cover trends often corroborated trends in occurrence, but we also regularly found trends in cover even in the absence of evidence for trends in occurrence. Our approach thus contributes to a more complete picture of (changes in) vegetation composition based on large monitoring data sets.

Journal of Vegetation Science