Per- and polyfluorinated alkyl substances (PFAS) in Pennsylvania surface waters: A statewide assessment, associated sources, and land-use relations.

The objectives of this study are to identify per- and polyfluoroalkyl substances (PFAS) in Pennsylvania surface waters, corresponding associations with potential sources of PFAS contamination (PSOC) and other parameters, and compare raw surface water concentrations to human and ecological benchmarks. Surface water samples from 161 streams were collected in September 2019 and were analyzed for 33 target PFAS and water chemistry. Land use and physical attributes in upstream catchments and geospatial counts of PSOC in local catchments are summarized. The hydrologic yield of the sum of 33 PFAS (∑PFAS) for each stream was computed by normalizing each site's load by the drainage area of the upstream catchment. Utilizing conditional inference tree analysis, the percentage of development (>7.58 %) was identified as a primary driver of the ∑PFAS hydrologic yields. When percentage of development was removed from analysis, ∑PFAS yields were closely related to surface water chemistry associated with landscape alteration (e.g., development or agricultural cropland), such as concentrations of total nitrogen, chloride, and ammonia, but also to count of water pollution control facilities (agricultural, industrial, stormwater, and/or municipal waste pollution abatement facilities). In oil and gas development regions, ∑PFAS yields were associated with combined sewage outfalls. Sites surrounded by ≥2 electronic manufacturing facilities had elevated ∑PFAS yields (median = 241 ng/s/km2). Study results are critical to guide future research, regulatory policy, best practices that will mitigate PFAS contamination, and the communication of human health and ecological risks associated with PFAS exposure from surface waters.

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 R2 > 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.

Comparing imidacloprid, clothianidin, and azoxystrobin runoff from lettuce fields using a soil drench or treated seeds in the Salinas Valley, California.

Neonicotinoid insecticide use has increased over the last decade, including as agricultural seed treatments (application of chemical in a coating to the seed prior to planting). In California, multiple crops, including lettuce, can be grown using neonicotinoid treated seeds or receive a direct neonicotinoid soil application (drenching) at planting. Using research plots, this study compared pesticide runoff in four treatments: (1) imidacloprid seed treatment; (2) clothianidin seed treatment; (3) imidacloprid drench and an azoxystrobin seed treatment; and (4) a control with no pesticidal treatment. Neonicotinoid and azoxystrobin concentrations were measured in surface water runoff during six irrigations events in the 2020 growing seasons. Results showed runoff concentrations up to 1308 (±1200) ng L-1 for imidacloprid drench treatment, 431 (±100) ng L-1 for clothianidin seed treatment, 135 (±60) ng L-1 for imidacloprid seed treatment, and 13 (±10) ng L-1 for azoxystrobin seed treatment (treatments averaged). The percent of applied mass in runoff over the entire sampling period varied by compound; the imidacloprid seed treatment and drench were similar (0.015 and 0.019%, respectively) to the clothianidin seed treatment (0.036%) while the azoxystrobin seed treatment was much higher (15%). Although the proportion of imidacloprid in runoff was similar for imidacloprid treatments, the mass applied during soil drench was > 4x the amount applied from the imidacloprid seed treatment. Surface soils were collected before planting and at the end of the trial. The neonicotinoids were detected in soil throughout the study and average maximum concentrations were 9-13 ng g-1; azoxystrobin was detected in only two soils at concentrations up to 0.57 ng g-1. These results elucidate the comparative mass runoff resulting from planting treated seed and soil drench applications and highlight the value of additional work to characterize off-site transport from the many commodities that may be utilizing treated seeds.

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.

Widespread Use of the Nitrification Inhibitor Nitrapyrin: Assessing Benefits and Costs to Agriculture, Ecosystems, and Environmental Health.

Agricultural production and associated applications of nitrogen (N) fertilizers have increased dramatically in the last century, and current projections to 2050 show that demands will continue to increase as the human population grows. Applied in both organic and inorganic fertilizer forms, N is an essential nutrient in crop productivity. Increased fertilizer applications, however, create the potential for more N loss before plant uptake. One strategy for minimizing N loss is the use of enhanced efficiency fertilizers, fortified with a nitrification inhibitor, such as nitrapyrin. In soils and water, nitrapyrin inhibits the activity of ammonia monooxygenase, a microbial enzyme that catalyzes the first step of nitrification from ammonium to nitrite. Potential benefits of using nitrification inhibitors range from reduced nitrate leaching and nitrous oxide emissions to increased crop yield. The extent of these benefits, however, depends on environmental conditions and management practices. Thus, such benefits are not always realized. Additionally, nitrapyrin has been shown to transport off-field, and it is unknown what effects environmental nitrapyrin could have on nontarget organisms and the ecological nitrogen cycle. Here, we review the agronomic and environmental benefits and costs of nitrapyrin use and present a series of research questions and considerations to be addressed with future nitrification inhibitor research.

Fate and transport of nitrapyrin in agroecosystems: Occurrence in agricultural soils, subsurface drains, and receiving streams in the Midwestern US.

Nitrapyrin is a nitrification inhibitor that is co-applied with nitrogen fertilizer in agroecosystems. There is limited information on the fate of nitrapyrin after it is applied to agricultural soils. Over the course of one year (March 2016 to June 2017), 192 water samples from seven streams across Iowa and Illinois were analyzed for nitrapyrin, its metabolite 6­chloropicolinic acid (6­CPA), and three widely used herbicides acetochlor, atrazine, and metolachlor. Additional environmental samples were collected and analyzed in spring 2017: 63 water samples from eight subsurface drains in Illinois, and 33 soil samples from a field in Iowa that received direct application of nitrapyrin. Nitrapyrin was detected in all seven streams (56% detection) with concentrations ranging from less than LOD to 1200 ng/L; 6­CPA was detected in six of the seven streams (13% detection) with concentrations ranging from less than LOD to 13 ng/L. Nitrapyrin was detected in 10% of the subsurface drain samples with concentrations ranging from less than LOD to 12 ng/L; 6­CPA was detected in six of the eight subsurface drains and in 33% of drain samples with concentrations ranging from less than LOD to 6 ng/L. Nitrapyrin was detected in 67% of the soil samples collected, and concentrations ranged from less than LOD to 42 ng/g. Generally, all three herbicides were detected more frequently and at higher concentrations than nitrapyrin in the streams, subsurface drains, and soils. The environmental fate of nitrapyrin after application is dominated by sorption to soil and off-field transport via leaching and overland flow.

Uptake of Three Antibiotics and an Antiepileptic Drug by Wheat Crops Spray Irrigated with Wastewater Treatment Plant Effluent.

With rising demands on water supplies necessitating water reuse, wastewater treatment plant (WWTP) effluent is often used to irrigate agricultural lands. Emerging contaminants, like pharmaceuticals and personal care products (PPCPs), are frequently found in effluent due to limited removal during WWTP processes. Concern has arisen about the environmental fate of PPCPs, especially regarding plant uptake. The aim of this study was to analyze uptake of sulfamethoxazole, trimethoprim, ofloxacin, and carbamazepine in wheat ( L.) plants that were spray-irrigated with WWTP effluent. Wheat was collected before and during harvest, and plants were divided into grain and straw. Subsamples were rinsed with methanol to remove compounds adhering to surfaces. All plant tissues underwent liquid-solid extraction, solid-phase extraction cleanup, and liquid chromatography-tandem mass spectrometry analysis. Residues of each compound were present on most plant surfaces. Ofloxacin was found throughout the plant, with higher concentrations in the straw (10.2 ± 7.05 ng g) and lower concentrations in the grain (2.28 ± 0.89 ng g). Trimethoprim was found only on grain or straw surfaces, whereas carbamazepine and sulfamethoxazole were concentrated within the grain (1.88 ± 2.11 and 0.64 ± 0.37 ng g, respectively). These findings demonstrate that PPCPs can be taken up into wheat plants and adhere to plant surfaces when WWTP effluent is spray-irrigated. The presence of PPCPs within and on the surfaces of plants used as food sources raises the question of potential health risks for humans and animals.

Vadose Zone Transport of Natural and Synthetic Estrogen Hormones at Penn State's "Living Filter" Wastewater Irrigation Site.

The increase in endocrine-disrupting compounds in the environment has generated research focused on the behavior of these compounds in natural soil and water ecosystems. To understand how estrogens behave in the soil environment as a result of 25+ yr of wastewater irrigation, soils from Penn State's "Living Filter" wastewater irrigation site were extracted and analyzed for two natural estrogens (17ß-estradiol and estrone) and one synthetic estrogen (17α-ethynylestradiol). Soil estrogen concentrations were compared for two independent variables: type of land cover and sampling time. Soils were sampled from cropped and forested land areas, and soils were sampled 2 d and 3 wk after a single 12-h effluent irrigation event. A nonirrigated control site was sampled to provide natural background data. For 17ß-estradiol, the nonirrigated mean concentration was 0.68 ± 0.11 ng cm, and the irrigated values, including samples from both land areas and time frames, ranged from 0.99 ± 0.11 to 1.82 ± 0.69 ng cm. For estrone, the nonirrigated mean concentration was 2.36 ± 0.22 ng cm, and the irrigated values, including samples from both land areas collected and time frames, ranged from 2.18 ± 0.20 to 6.24 ± 3.14 ng cm. The 17α-ethynylestradiol nonirrigated mean concentration was 0.47 ± 0.40 ng cm. The irrigated values, including samples from both land areas and time frames, ranged from 0.25 ± 0.06 to 1.37 ± 0.39 ng cm. This study found that time of sampling, land cover, and irrigation can affect estrogen concentrations in soils, resulting in levels that exceed natural background and require improvements in management practices.