USGS Science⌕ Search
Home/Archive/USGS

USGS · 70242020

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

Gabrielle Pecora Black·Emily E. Woodward·Corey Sanders·Michael S. Gross·Michelle L. Hladik
View original source ↗Export metadata ↓

Abstract

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.

Explore related subjects

ChemosphereArticle

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Gabrielle Pecora Black, Emily E. Woodward, Corey Sanders, Michael S. Gross, Michelle L. Hladik. 2023. 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. https://doi.org/10.1016/j.chemosphere.2023.138550

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related USGS reports

USGS2025

Exposure to the Polychlorinated biphenyl mixture Aroclor 1254 elicits neurological and cardiac developmental effects in early life stage zebrafish (Danio rerio)

The goal of this study was to compare the bioaccumulation of the PCB mixture Aroclor 1254 in zebrafish to cardiac and neurologic outcomes. The establishment of effect concentrations (ECs) for cardiac and neurotoxic effects of PCBs in early life stage fish is challenging due to a lack of measured PCB concentrations in test media (e.g., fish tissue), the lack of standard exposure methods, and the propensity of PCBs to adsorb to test glassware and materials resulting in discrepancies in ECs from different studies with similar endpoints. Reporting tissue concentrations in test organisms will allow for standardization across different tests and thus may improve estimations of effect thresholds. Early life stage zebrafish ( Danio rerio ) are a common environmental toxicological model well represented within the literature, making them ideal for comparisons across multiple studies. Embryos were exposed at 6 h post fertilization (hpf) to aqueous Aroclor 1254 for 96 h with or without renewal in addition to a PCB 126 positive control for cardiotoxicity. PCB concentrations were measured in both exposure solutions and tissue samples. Measured concentrations of Aroclor 1254 in test solutions ranged from 8.7% to 870% of nominal concentrations. Heart rate, pericardial edema, and neurological endpoints (eye tremors) were measured in 102 hpf larvae. Pericardial edema was not present in Aroclor 1254-treated zebrafish but was observed in those exposed to PCB-126. Concentration-dependent bradycardia was observed in zebrafish exposed to Aroclor 1254 and PCB-126. Similarly, a concentration-dependent increase in eye tremor behavior was observed in embryos exposed to Aroclor 1254. Data produced by this study demonstrate novel toxicological effects of Aroclor 1254 and highlight the importance of measuring PCBs in both exposure and receptor media.

Chemosphere↗
USGS2024

Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe–Al–Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation. AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO 3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems. The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Pennsylvania↗
USGS2024

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

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

Chemosphere↗