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At least 73 records · Page 4Linked to original sources
USGS2017

Using silver and bighead carp cell lines for the identification of a unique metabolite fingerprint from thiram-specific chemical exposure

Conservation biology often requires the control of invasive species. One method is the development and use of biocides. Identifying new chemicals as part of the biocide registration approval process can require screening millions of compounds. Traditionally, screening new chemicals has been done in vivo using test organisms. Using in vitro (e.g., cell lines) and in silico (e.g., computer models) methods decrease test organism requirements and increase screening speed and efficiency. These methods, however, would be greatly improved by better understanding how individual fish species metabolize selected compounds. We combined cell assays and metabolomics to create a powerful tool to facilitate the identification of new control chemicals. Specifically, we exposed cell lines established from bighead carp and silver carp larvae to thiram (7 concentrations) then completed metabolite profiling to assess the dose-response of the bighead carp and silver carp metabolome to thiram. Forty one of the 700 metabolomic markers identified in bighead carp exhibited a dose-response to thiram exposure compared to silver carp in which 205 of 1590 metabolomic markers exhibited a dose-response. Additionally, we identified 11 statistically significant metabolomic markers based upon volcano plot analysis common between both species. This smaller subset of metabolites formed a thiram-specific metabolomic fingerprint which allowed for the creation of a toxicant specific, rather than a species-specific, metabolomic fingerprint. Metabolomic fingerprints may be used in biocide development and improve our understanding of ecologically significant events, such as mass fish kills.

Chemosphere↗
USGS2018

Stability of mercury concentration measurements in archived soil and peat samples

Archived soil samples can provide important information on the history of environmental contamination and by comparison with recently collected samples, temporal trends can be inferred. Little previous work has addressed whether mercury (Hg) concentrations in soil samples are stable with long-term storage under standard laboratory conditions. In this study, we have re-analyzed using cold vapor atomic adsorption spectroscopy a set of archived soil samples that ranged from relatively pristine mountainous sites to a polluted site near a non-ferrous metal smelter with a wide range of Hg concentrations (6 - 6485 µg kg-1). Samples included organic and mineral soils and peats with a carbon content that ranged from 0.2 to 47.7%. Soil samples were stored in polyethylene bags or bottles and held in laboratory rooms where temperature was not kept to a constant value. Mercury concentrations in four subsets of samples were originally measured in 2000, 2005, 2006 and 2007, and re-analyzed in 2017, i.e. after 17, 12, 11 and 10 years of storage. Statistical analyses of either separated or lumped data yielded no significant differences between the original and current Hg concentrations. Based on these analyses, we show that archived soil and peat samples can be used to evaluate historical soil mercury contamination.

Chemosphere↗
USGS2020

Influence of remediation on sediment toxicity within the Grand Calumet River, Indiana, USA

The Grand Calumet River (GCR), located in northern Indiana, is contaminated due to a wide range of historical industrial activities. This study was conducted to determine the influence of sediment remediation within the GCR on concentrations of chemical contaminants and toxicity to sediment-dwelling organisms. Between 2005 and 2016, sediments with high concentrations of metals and toxic organic compounds were remediated through a combination of removal, addition of activated carbon and organoclay amendments, and capping with sand or relatively uncontaminated sediment. Short-term and long-term sediment toxicity tests with the amphipod Hyalella azteca, the midge Chironomus dilutus, and the mussel Lampsilis siliquoidea were conducted with samples collected in 2013, 2015, and 2017, from 29 sites, including both remediated and non-remediated sites. Sediment chemistry and toxicity data for three groups of remediated sites (US Steel, West Branch, and East Branch) were compared to samples from contaminated but unremediated sites and to relatively uncontaminated reference sites. In general, remediated sediments had lower levels of PAHs, PCBs and metals, although sediments from the US Steel area still had elevated levels of PAH, PCB and chromium. Sediments from the three remediated sites and from reference sites showed significantly reduced toxic effects in short-term sediment bioassays, compared to unremediated sites. Variation in the long-term success of remediation may reflect site-specific factors such as the type of remediation and the potential for recontamination from uncontrolled sources.

Indiana↗
USGS2021

Elemental and radionuclide exposures and uptakes by small rodents, invertebrates, and vegetation at active and post-production uranium mines in the Grand Canyon watershed

The effects of breccia pipe uranium mining in the Grand Canyon watershed (Arizona) on ecological and cultural resources are largely unknown. We characterized the exposure of biota to uranium and co-occurring ore body elements during active ore production and at a site where ore production had recently concluded. Our results indicate that biota have taken up uranium and other elements (e.g., arsenic, cadmium, copper, molybdenum, uranium) from exposure to ore and surficial contamination, like blowing dust. Results indicate the potential for prolonged exposure to elements and radionuclides upon conclusion of active ore production. Mean radium-226 in deer mice was up to 4 times greater than uranium-234 and uranium-238 in those same samples; this may indicate a potential for, but does not necessarily imply, radium-226 toxicity. Soil screening benchmarks for uranium and molybdenum and other toxicity thresholds for arsenic, copper, selenium, uranium (e.g., growth effects) were exceeded in vegetation, invertebrates, and rodents ( Peromyscus spp. , Thomomys bottae, Tamias dorsalis, Dipodomys deserti ). However, the prevalence and severity of microscopic lesions in rodent tissues (as direct evidence of biological effects of uptake and exposure) could not be definitively linked to mining. Our data indicate that land managers might consider factors like species, seasonal changes in environmental concentrations, and bioavailability, when determining mine permitting and remediation in the Grand Canyon watershed. Ultimately, our results will be useful for site-specific ecological risk analysis and can support future decisions regarding the mineral extraction withdrawal in the Grand Canyon watershed and elsewhere.

Arizona↗
USGS2021

Retrospective analysis of estrogenic endocrine disruption and land-use influences in the Chesapeake Bay watershed

The Chesapeake Bay is the largest estuary in the United States and its watershed includes river drainages in six states and the District of Columbia. Sportfishing is of major economic interest, however, the rivers within the watershed provide numerous other ecological, recreational, cultural and economic benefits, as well as serving as a drinking water source for millions of people. Consequently, major fish kills and the subsequent finding of estrogenic endocrine disruption (intersex or testicular oocytes and plasma vitellogenin in male fishes) raised public and management concerns. Studies have occurred at various sites within the Bay watershed to document the extent and severity of endocrine disruption, identify risk factors and document temporal and spatial variability. Data from these focal studies, which began in 2004, were used in CART (classification and regression trees) analyses to better identify land use associations and potential management practices that influence estrogenic endocrine disruption. These analyses emphasized the importance of scale (immediate versus upstream catchment) and the complex mixtures of stressors which can contribute to surface water estrogenicity and the associated adverse effects of exposure. Both agricultural (percent cultivated, pesticide application, phytoestrogen cover crops) and developed (population density, road density, impervious surface) land cover showed positive relationships to estrogenic indicators, while percent forest and shrubs generally had a negative association. The findings can serve as a baseline for assessing ongoing restoration and management practices.

Chesapeake Bay river watersheds↗
USGS2021

Terrestrial ecological risk analysis via dietary exposure at uranium mine sites in the Grand Canyon watershed (Arizona, USA)

The U.S. Department of the Interior recently included uranium (U) on a list of mineral commodities that are considered critical to economic and national security. The uses of U for commercial and residential energy production, defense applications, medical device technologies, and energy generation for space vehicles and satellites are known, but the environmental impacts of uranium extraction are not always well quantified. We conducted a screening-level ecological risk analysis based on exposure to mining-related elements via diets and incidental soil ingestion for terrestrial biota to provide context to chemical characterization and exposures at breccia pipe U mines in northern Arizona. Relative risks, calculated as hazard quotients (HQs), were generally low for all biological receptor models. Our models screened for risk to omnivores and insectivores (HQs>1) but not herbivores and carnivores. Uranium was not the driver of ecological risk; arsenic, cadmium, copper, and zinc were of concern for biota consuming ground-dwelling invertebrates. Invertebrate species composition should be considered when applying these models to other mining locations or future sampling at the breccia pipe mine sites. Dietary concentration thresholds (DCTs) were also calculated to understand food concentrations that may lead to ecological risk. The DCTs indicated that critical concentrations were not approached in our model scenarios, as evident in the very low HQs for most models. The DCTs may be used by natural resource and land managers as well as mine operators to screen or monitor for potential risk to terrestrial receptors as mine sites are developed and remediated in the future.

Arizona↗
USGS2021

Isotopic composition of natural and synthetic chlorate (δ18O, Δ17O, δ37Cl, 36Cl/Cl): Methods and initial results

Natural chlorate (ClO 3 − ) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO 3 − , we developed and tested methods to determine the multi-dimensional isotopic compositions (δ 18 O, Δ 17 O, δ 37 Cl, 36 Cl/Cl) of ClO 3 − and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ 18 O = +7.0 to +11.1‰, Δ 17 O = +5.7 to +6.4‰, δ 37 Cl = −1.4 to +1.3‰, and 36 Cl/Cl = 48 × 10 −15 to 104 × 10 −15 . Chlorate from Death Valley samples had δ 18 O = −6.9 to +1.6‰, Δ 17 O = +0.4 to +2.6‰, δ 37 Cl = +0.8 to +1.0‰, and 36 Cl/Cl = 14 × 10 −15 to 44 × 10 −15 . Positive Δ 17 O values of natural ClO 3 − indicate that its production involved reaction with O 3 , while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ 17 O and δ 18 O values of natural ClO 3 − are positively correlated, as are those of ClO 4 − and NO 3 − from the same localities, possibly indicating variation in the relative contributions of O 3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO 3 − could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars.

Chemosphere↗
USGS2021

Neither microcystin, nor nodularin, nor cylindrospermopsin directly interact with human toll-like receptors

Various stressors including temperature, environmental chemicals, and toxins can have profound impacts on immunity to pathogens. Increased eutrophication near rivers and lakes coupled with climate change are predicted to lead to increased algal blooms. Currently, the effects of cyanobacterial toxins on disease resistance in mammals is a largely unexplored area of research. Recent studies have suggested that freshwater cyanotoxins can elicit immunomodulation through interaction with specific components of innate immunity, thus potentially altering disease susceptibility parameters for fish, wildlife, and human health owing to the conserved nature of the vertebrate immune system. In this study, we investigated the effects of three microcystin congeners (LR, LA, and RR), nodularin-R, and cylindrospermopsin for their ability to directly interact with nine different human Toll-like receptors (TLRs)—key pathogen recognition receptors for innate immunity. Toxin concentrations were verified by LC/MS/MS prior to use. Using an established HEK293-hTLR NF-κB reporter assay, we concluded that none of the tested toxins (29–90 nM final concentration) directly interacted with human TLRs in either an agonistic or antagonistic manner. These results suggest that earlier reports of cyanotoxin-induced NF-κB responses likely occur through different surface receptors to mediate inflammation.

Chemosphere↗
USGS2021

Co-transport of biogenic nano-hydroxyapatite and Pb(II) in saturated sand columns: Controlling factors and stochastic modeling

Biogenic nano-hydroxyapatite (bio-nHAP) has recently gained great interest in many domains, especially in the remediation of heavy metal-contaminated soil, due to its high reactivity, low cost, and eco-friendly nature. The co-transport and reaction of bio-nHAP with Pb(II) in saturated porous media, however, are not well understood. This work investigated the effects of ionic strength (IS), ionic composition (IC), dissolved organic matter (DOM), and flow velocity on transport-reaction dynamics of Pb(II) and bio-nHAP by combining column breakthrough experiments and model simulations. Results showed that the mobility of Pb(II) was significantly enhanced with increasing IS/IC but less affected by flow velocity during the transport-reaction process of bio-nHAP and Pb(II) in the saturated sand column; while the transport of bio-nHAP was restricted by increasing IS/IC but facilitated by increasing velocity. IC, IS, and velocity only slightly affected the reaction kinetics between Pb(II) and bio-nHAP, likely due to the fast reaction rate between Pb(II) and bio-nHAP and precipitation of pyromorphite. The transport dynamics of bio-nHAP and Pb(II) were significantly changed by DOM, and this effect depended strongly on the type of DOM with different molecular weights. Breakthrough curves of Pb(II) and bio-nHAP exhibited apparent “anomalous”, sub-diffusive transport behaviors, which could be well quantified by a novel tempered fractional derivative bimolecular reaction equation (T-FBRE). Our findings highlighted the accurate simulation of the co-transport and reaction of bio-nHAP with Pb(II) using T-FBRE and had a great benefit for risk assessment and remediation strategy development for Pb(II) contaminated soil.

Chemosphere↗
USGS2021

Development of a simulated lung fluid leaching method to assess the release of potentially toxic elements from volcanic ash

Freshly erupted volcanic ash contains a range of soluble elements, some of which can generate harmful effects in living cells and are considered potentially toxic elements (PTEs). This work investigates the leaching dynamics of ash-associated PTEs in order to optimize a method for volcanic ash respiratory hazard assessment. Using three pristine (unaffected by precipitation) ash samples, we quantify the release of PTEs (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn) and major cations typical of ash leachates (Mg, Na, Ca, K) in multiple simulated lung fluid (SLF) preparations and under varying experimental parameters (contact time and solid to liquid ratio). Data are compared to a standard water leach (WL) to ascertain whether the WL can be used as a simple proxy for SLF leaching. The main findings are: PTE concentrations reach steady-state dissolution by 24 h, and a relatively short contact time (10 min) approximates maximum dissolution; PTE dissolution is comparatively stable at low solid to liquid ratios (1:100 to 1:1000); inclusion of commonly used macromolecules has element-specific effects, and addition of a lung surfactant has little impact on extraction efficiency. These observations indicate that a WL can be used to approximate lung bioaccessible PTEs in an eruption response situation. This is a useful step towards standardizing in vitro methods to determine the soluble-element hazard from inhaled ash.

Chemosphere↗
USGS2021

Foraging in marine habitats increases mercury concentrations in a generalist seabird

Methylmercury concentrations vary widely across geographic space and among habitat types, with marine and aquatic-feeding organisms typically exhibiting higher mercury concentrations than terrestrial-feeding organisms. However, there are few model organisms to directly compare mercury concentrations as a result of foraging in marine, estuarine, or terrestrial food webs. The ecological impacts of differential foraging may be especially important for generalist species that exhibit high plasticity in foraging habitats, locations, or diet. Here, we investigate whether foraging habitat, sex, or fidelity to a foraging area impact blood mercury concentrations in western gulls ( Larus occidentalis ) from three colonies on the US west coast. Cluster analyses showed that nearly 70% of western gulls foraged primarily in ocean or coastal habitats, whereas the remaining gulls foraged in terrestrial and freshwater habitats. Gulls that foraged in ocean or coastal habitats for half or more of their foraging locations had 55% higher mercury concentrations than gulls that forage in freshwater and terrestrial habitats. Ocean-foraging gulls also had lower fidelity to a specific foraging area than freshwater and terrestrial-foraging gulls, but fidelity and sex were unrelated to gull blood mercury concentrations in all models. These findings support existing research that has described elevated mercury levels in species using aquatic habitats. Our analyses also demonstrate that gulls can be used to detect differences in contaminant exposure over broad geographic scales and across coarse habitat types, a factor that may influence gull health and persistence of other populations that forage across the land-sea gradient.

California, Oregon↗
USGS2022

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↗
USGS2022

Enhanced bioremediation of RDX and co-contaminants perchlorate and nitrate using an anaerobic dehalogenating consortium in a fractured rock aquifer

The potential neurotoxic and carcinogenic effects of the explosives compound RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) on human health requires groundwater remediation strategies to meet low cleanup goals. Bioremediation of RDX is feasible through biostimulation of native microbes with an organic carbon donor but may be less efficient, or not occur at all, in the presence of the common co-contaminants perchlorate and nitrate. Laboratory tests compared biostimulation with bioaugmentation to achieve anaerobic degradation of RDX, perchlorate, and nitrate; a field pilot test was then conducted in a fractured rock aquifer with the selected bioaugmentation approach. Insignificant reduction of RDX, perchlorate, or nitrate was observed by the native microbes in microcosms, with or without biostimulation by addition of lactate. Tests of the RDX-degrading ability of the microbial consortium WBC-2, originally developed for dehalogenation of chlorinated volatile organic compounds, showed first-order biodegradation rate constants ranging from 0.57 to 0.90 per day (half-lives 1.2 to 0.80 days). WBC-2 sustained degradation without daughter product accumulation when repeatedly amended with RDX and lactate for a year. In microcosms with groundwater containing perchlorate and nitrate, RDX degradation began without delay when bioaugmented with 10% WBC-2. Slower RDX degradation occurred with 3% or 5% WBC-2 amendment, indicating a direct relation with cell density. Transient RDX daughter compounds included methylene dinitramine, MNX, and DNX. With WBC-2 amendment, nitrate concentrations immediately decreased to near or below detection, and perchlorate degradation occurred with half-lives of 25 to 34 days. Single-well injection tests with WBC-2 and lactate showed that the onset of RDX degradation coincided with the onset of sulfide production, which was affected by the initial perchlorate concentration. Bioegradation rates in the pilot injection tests agreed well with those measured in the microcosms. These results support bioaugmentation with an anaerobic culture as a remedial strategy for sites contaminated with RDX, nitrate, and perchlorate.

New Mexico↗
USGS2022

Temporal variability in TiO2 engineered particle concentrations in rural Edisto River

Titanium dioxide (TiO 2 ) is widely used in engineered particles including engineered nanomaterial (ENM) and pigments, yet its occurrence, concentrations, temporal variability, and fate in natural environmental systems are poorly understood. For three years, we monitored TiO 2 concentrations in a rural river basin (Edisto River, < 1% urban land cover) in South Carolina, United States. The total concentrations of Ti, Nb, Al, Fe, Ce, and La in the Edisto River trended higher during spring/summer compared to autumn/winter. Upward trending Ti/Nb ratio in the spring/summer compared to near-background autumn/winter ratios of 255.7 ± 8.9 indicated agricultural preparation and growing-season-related increases in TiO 2 engineered particles. In contrast, downward trending of the Ti/Al and Ti/Fe ratios in the spring and summer compared to the near-background autumn/winter ratios of 0.05 indicated greater mobilization of Fe and Al, relative to Ti during spring/summer. Surface-water concentrations of TiO 2 engineered particles varied between 0 and 128.7 ± 3.9 μg TiO 2 L −1 . Increases in TiO 2 concentrations over the spring/summer were associated with increases in phosphorus, orthophosphate, nitrate, ammonia, anthropogenic gadolinium, water temperature, suspended sediments, organic carbon, and alkalinity, and with decreases in dissolved oxygen. The association between these contaminants together with the timing of the increases in their concentrations is consistent with diffuse wastewater sources, such as reuse application overspray, biosolids fertilization, leaking sewers, or septic tanks, as the driver of instream concentrations; however, other diffuse sources cannot be ruled out. The findings of this study indicate spatially-distributed (non-point source) releases can result in high concentrations of TiO 2 engineered particles, which may pose higher risks to rural stream aquatic ecosystems during the agricultural season. The results illustrate the importance of monitoring seasonal variations in engineered particles concentrations in surface waters for a more representative assessment of ecosystem risk.

South Carolina↗
USGS2023

Prevalence of neonicotinoid insecticides in paired private-well tap water and human urine samples in a region of intense agriculture overlying vulnerable aquifers in eastern Iowa

A pilot study among farming households in eastern Iowa was conducted to assess human exposure to neonicotinoids (NEOs). The study was in a region with intense crop and livestock production and where groundwater is vulnerable to surface-applied contaminants. In addition to paired outdoor (hydrant) water and indoor (tap) water samples from private wells, urine samples were collected from 47 adult male pesticide applicators along with the completions of dietary and occupational surveys. Estimated Daily Intake (EDI) were then calculated to examine exposures for different aged family members. NEOs were detected in 53% of outdoor and 55% of indoor samples, with two or more NEOs in 13% of samples. Clothianidin was the most frequently detected NEO in water samples. Human exposure was ubiquitous in urine samples. A median of 10 different NEOs and/or metabolites were detected in urine, with clothianidin, nitenpyram, thiamethoxam, 6-chloronicotinic acid, and thiacloprid amide detected in every urine samples analyzed. Dinotefuran, imidaclothiz, acetamiprid- N -desmethyl, and N -desmethyl thiamethoxam were found in ≥70% of urine samples. Observed water intake for study participants and EDIs were below the chronic reference doses (CRfD) and acceptable daily intake (ADI) standards for all NEOs indicating minimal risk from ingestion of tap water. The study results indicate that while the consumption of private well tap water provides a human exposure pathway, the companion urine results provide evidence that diet and/or other exposure pathways (e.g., occupational, house dust) may contribute to exposure more than water contamination. Further biomonitoring research is needed to better understand the scale of human exposure from different sources.

Iowa↗
USGS2023

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↗
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↗