Nitrate-Stimulated Release of Naturally Occurring Sedimentary Uranium.

Groundwater uranium (U) concentrations have been measured above the U.S. EPA maximum contaminant level (30 µg/L) in many U.S. aquifers, including in areas not associated with anthropogenic contamination by milling or mining. In addition to carbonate, nitrate has been correlated to uranium groundwater concentrations in two major U.S. aquifers. However, to date, direct evidence that nitrate mobilizes naturally occurring U from aquifer sediments has not been presented. Here, we demonstrate that the influx of high-nitrate porewater through High Plains alluvial aquifer silt sediments bearing naturally occurring U(IV) can stimulate a nitrate-reducing microbial community capable of catalyzing the oxidation and mobilization of U into the porewater. Microbial reduction of nitrate yielded nitrite, a reactive intermediate, which was further demonstrated to abiotically mobilize U from the reduced alluvial aquifer sediments. These results indicate that microbial activity, specifically nitrate reduction to nitrite, is one mechanism driving U mobilization from aquifer sediments in addition to previously described bicarbonate-driven desorption from mineral surfaces, such as Fe(III) oxides.

Photodegradation of a mixture of five pharmaceuticals commonly found in wastewater: Experimental and computational analysis.

Photochemical transformation of pharmaceuticals plays an important role in their natural attenuation, especially in lagoon-based wastewater treatment plants and surface waters receiving substantial sunlight. In this study, the photodegradation of five important pharmaceuticals was studied in samples obtained from a wastewater treatment plant and surface water sources. Batch photodegradation studies for a mixture of pharmaceuticals (diclofenac, sulfamethoxazole, acetaminophen, carbamazepine and gemfibrozil) were carried out in a photochemical reactor. Multiple aliquots of samples removed from the reactor during the experiment were analyzed through high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector. Intermediate products formed due to photodegradation were identified by ultra-high-performance liquid chromatography coupled with a time-of-flight mass spectrometry (UHPLC-MS/MS). Diclofenac and sulfamethoxazole were found to undergo direct photodegradation due to strong light absorption, whereas the indirect route of photosensitized degradation in the presence of dissolved organic matter (DOM) and model humic acid was significant for acetaminophen, carbamazepine, and gemfibrozil. The reactive radicals such as hydroxyl (OH•), singlet oxygen (1O2) and excited states of DOM (*DOM) were predominantly responsible for the indirect photodegradation of acetaminophen, gemfibrozil and carbamazepine, respectively. Computational analysis revealed that chlorine and carbon atoms belonging to the benzene ring of diclofenac were more reactive to radical attack. Sulfamethoxazole photodegradation occurred through oxidation of the NH2 group. Acetaminophen was more susceptible to electrophilic radical attack at the O-11, and N-7 positions and carbon atoms ortho to the phenolic oxygen and the amine group. The double bonds between C-7, C-8 and C-13 were the most reactive sites for carbamazepine that participated in the phototransformation pathway. Organic matter plays a critical role in the photodegradation of emerging contaminants. The coupling of DFT calculations with UHPLC-MS/MS analysis provided insights on key functional groups participating in the phototransformation pathway. Thus, both parent pharmaceuticals and the photodegradation intermediates should be considered during wastewater treatment.

Reaction Steps in Heterogeneous Photocatalytic Oxidation of Toluene in Gas Phase-A Review.

A review of the current literature shows there is no clear consensus regarding the reaction mechanisms of air-borne aromatic compounds such as toluene by photocatalytic oxidation. Potential oxidation reactions over TiO2 or TiO2-based catalysts under ultraviolet and visible (UV/VIS) illumination are most commonly considered for removal of these pollutants. Along the pathways from a model pollutant, toluene, to final mineralization products (CO2 and H2O), the formation of several intermediates via specific reactions include parallel oxidation reactions and formation of less-reactive intermediates on the TiO2 surface. The latter may occupy active adsorption sites and causes drastic catalyst deactivation in some cases. Major hazardous gas-phase intermediates are benzene and formaldehyde, classified by the International Agency for Research on Cancer (IARC) as Group 1 carcinogenic compounds. Adsorbed intermediates leading to catalyst deactivation are benzaldehyde, benzoic acid, and cresols. The three most typical pathways of toluene photocatalytic oxidation are reviewed: methyl group oxidation, aromatic ring oxidation, and aromatic ring opening.

Human Health Risk Assessment of the Photocatalytic Oxidation of BTEX over TiO2/Volcanic Glass.

This study demonstrates rapid photocatalytic oxidation of a benzene, toluene, ethylbenzene, and xylene (BTEX) mixture over TiO2/volcanic glass. The assessment of the photocatalytic oxidation of BTEX was conducted under conditions simulating those found in indoor environments affected by aromatic hydrocarbon release. We show, under UV-A intensities of 15 mW/cm2 and an air flow rate of 55 m3/h, that low ppmv levels of BTEX concentrations can be reduced to below detectable levels. Solid-phase microextraction technique was employed to monitor the levels of BTEX in the test chamber throughout the photocatalytic oxidation, lasting approximately 21 h. Destruction of BTEX from the gas phase was observed in the following sequence: o-xylene, ethylbenzene, toluene, and benzene. This study identified sequential degradation of BTEX, in combination with the stringent regulatory level set for benzene, resulted in the air quality hazard indexes (Total Hazard Index and Hazard Quotient) remaining relatively high during the process of photocatalytic oxidation. In the practical application of photocatalytic purification, it is crucial to account for the slower oxidation kinetics of benzene. This is of particular importance due to not only its extremely low exposure limits, but also due to the classification of benzene as a Group 1 carcinogenic compound by the International Agency for Research on Cancer (IARC). Our study underscores the importance of taking regulatory considerations into account when using photocatalytic purification technology.

Source apportionment and health risk assessment of nitrate in foothill aquifers of Western Ghats, South India.

The present research reports the level of nitrate (NO3-), associated health risks and possible sources of contamination in groundwater from south India. Many samples (32%) are above or approaching the recommended level of NO3- for safe drinking water. The correlation analysis indicates different sources of NO3- contamination in different regions rather than a common origin. The isotopic measurements provide information about potential nitrogen sources contributing NO3- to the groundwater. Based on isotope analysis, the sources of NO3- in the groundwater of this region are likely to be from (a) septic sewage (b) organic nitrogen (animal and livestock excreta) (c) sewage (domestic & chemical fertilizers). Among the sample analyzed sewage, manure and septic sewage contribute 46%, 23% and 31% NO3- to groundwater. The HQ > 1 indicates non-carcinogenic health risk due to consumption of high NO3- in drinking water. Among the studied age groups, infants are exposed to higher risk than children and adults. Results indicate that groundwater of this region is polluted with NO3- due to anthropogenic activities. Continuous consumption of such water may pose serious health risk to the residents.

Targeted Method for Quantifying Air-Borne Pesticide Residues from Conventional Seed Coat Treatments to Better Assess Exposure Risk During Maize Planting.

Agricultural seed-coat treatments are prone to drift as seed coatings may scuff off and become incorporated into field particles during planting. Vacuum planters release exhaust and kick up field dust, laden with systemic pesticides that blow across the landscape, is taken up, and later expressed in the nectar and pollen of surrounding plants. Offsite movements and nontarget exposure to systemic pesticides need attention and determining how and at what exposure levels pollinators are exposed is of critical importance. Unfortunately, this requires extensive and costly instrumental analyses. Here, we describe dust sampling and a modified, rapid method based on liquid chromatography in tandem with mass spectrometry-based method for quantification of a broad array of agrochemicals in captured dust particles. This method increases ability to detect potential exposure to multiple agrochemicals and allows researchers to better address critical knowledge gaps in the environmental fate, off-target movement, and persistence of conventional seed treatments.

Stockpiling versus Composting: Effectiveness in Reducing Antibiotic-Resistant Bacteria and Resistance Genes in Beef Cattle Manure.

Manure storage methods can affect the concentration and prevalence of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) in cattle manure prior to land application. The objective of this study was to compare stockpiling and composting with respect to their effectiveness in reducing ARB and ARGs in beef cattle manure in a field-scale study. Field experiments were conducted in different seasons with different bulking agents for composting. For both the winter-spring cycle and the summer-fall cycle, ARB concentrations declined below the limit of quantification rapidly in both composting piles and stockpiles; however, ARB prevalence was significantly greater in the composting piles than in the stockpiles. This was likely due to the introduction of ARB from bulking agents. There was no significant change in ARG concentrations between initial and final concentrations for either manure storage treatment during the winter-spring cycle, but a significant reduction of the ARGs erm(B), tet(O), and tet(Q) over time was observed for both the composting pile and stockpile during the summer-fall cycle. Results from this study suggest that (i) bulking agent may be an important source of ARB and ARGs for composting; (ii) during cold months, the heterogeneity of the temperature profile in composting piles could result in poor ARG reduction; and (iii) during warm months, both stockpiling and composting can be effective in reducing ARG abundance. IMPORTANCE Proper treatment of manure is essential to reduce the spread of antibiotic resistance and protect human health. Stockpiling and composting are two manure storage methods which can reduce antibiotic-resistant bacteria and resistance genes, although few field-scale studies have examined the relative efficiency of each method. This study examined the ability of both methods in both winter-spring and summer-fall cycles, while also accounting for heterogeneity within field-scale manure piles. This study determined that bulking agents used in composting could contribute antibiotic-resistant bacteria and resistance genes. Additionally, seasonal variation could hinder the efficacy of composting in colder months due to heterogeneity in temperature within the pile; however, in warmer months, either method of manure storage could be effective in reducing the spread of antibiotic resistance.

Transmission Routes of the Microbiome and Resistome from Manure to Soil and Lettuce.

The land application of animal manure can introduce manure microbiome and resistome to croplands where food crops are grown. The objective of this study was to characterize the microbiome and resistome on and in the leaves of lettuce grown in manured soil and identify the main transmission routes of microbes and antibiotic resistance genes (ARGs) from soil to the episphere and endosphere of lettuce. Shotgun metagenomic results show that manure application significantly altered the composition of the microbiome and resistome of surface soil. SourceTracker analyses indicate that manure and original soil were the main source of the microbiome and resistome of the surface soil and rhizosphere soil, respectively. Manure application altered the microbiome and resistome in the episphere of lettuce (ADONIS p < 0.05), and surface soil accounted for ∼81% of the microbes and ∼62% of the ARGs in episphere. Manure application had limited impacts on the microbiome and resistome in the endosphere (ADONIS p > 0.05). Our results show that manure-borne microbes and ARGs reached the episphere primarily through surface soil and some epiphytic microbes and ARGs further entered the endosphere. Our findings can inform the development of pre- and postharvest practices to minimize the transmission of manure-borne resistome from food crops to consumers.

Ferrihydrite Reduction Increases Arsenic and Uranium Bioavailability in Unsaturated Soil.

Redox driven mobilization and plant uptake of contaminants under transiently saturated soil conditions need to be clarified to ensure food and water quality across different irrigation systems. We postulate that solid-phase iron reduction in anoxic microsites present in the rhizosphere of unsaturated soil is a key driver for mobilization and bioavailability of contaminants under nonflooded irrigation. To clarify this, two major crops, corn and soybean differing in iron uptake strategies, were grown in irrigated synthetic soil under semiarid conditions with gravimetric moisture content ∼12.5 ± 2.4%. 2-line ferrihydrite, which was coprecipitated with uranium and arsenic, served as the only iron source in soil. Irrespective of crop type, reduced iron was detected in pore water and postexperiment rhizosphere soil confirming ferrihydrite reduction. These results support the presence of localized anoxic microsites in the otherwise aerobic porous bulk soil causing reduction of ferrihydrite and concomitant increase in plant uptake of comobilized contaminants. Our findings indicate that reactive iron minerals undergo reductive dissolution inside anoxic microsites of primarily unsaturated soil, which may have implications on the mobility of trace element contaminants such as arsenic and uranium in irrigated unsaturated soils, accounting for 55% of the irrigated area in the US.

Influence of Setback Distance on Antibiotics and Antibiotic Resistance Genes in Runoff and Soil Following the Land Application of Swine Manure Slurry.

The environmental spread of antibiotics and antibiotic resistance genes (ARGs) from the land application of livestock wastes can be a potential public health threat. The objective of this study was to assess the effects of setback distance, which determines how close manure may be applied in relation to surface water, on the transport of antibiotics and ARGs in runoff and soil following land application of swine manure slurry. Rainfall simulation tests were conducted on field plots covered with wheat residues, each of which contained an upslope manure region where slurry was applied and an adjacent downslope setback region that did not receive slurry. Results show that all three antibiotics (chlortetracycline, lincomycin, and tiamulin) and seven out of the ten genes tested (erm(B), erm(C), intI1, tet(O), tet(Q), tet(X), and the 16S rRNA gene) decreased significantly in runoff with increased setback distance. Only blaTEM, chlortetracycline, and tiamulin decreased significantly in surface soil with increased setback distance, while the other analytes did not exhibit statistically significant trends. By using linear regression models with field data, we estimate that a setback distance between 34-67 m may allow manure-borne antibiotics and ARGs in runoff to reach background levels under the experimental conditions tested.

Assessment of Gene Expression Biomarkers in the Chilean Pencil Catfish, Trichomycterus areolatus, from the Choapa River Basin, Coquimbo Chile.

The objective of this study was to describe changes in the gene expression in the Chilean catfish, Trichomycterus areolatus, based on their geographic location within the Choapa River. Genes of choice included those that are biomarkers of exposure to metals, oxidative stress, and endocrine disruption. Male and female T. areolatus were sampled from four sites in January 2015 differently impacted by human activities. In males, but not females, hepatic gene expression of heat shock protein (HSP70) and cytochrome P450 1A (CYP1A) were significantly elevated at the site adjacent to the small city of Salamanca, relative to the other sites. In females, hepatic HSP70, the aryl hydrocarbon receptor (AHR), and the estrogen responsive genes, vitellogenin (VTG) and estrogen receptor alpha (ERα), were significantly lower at the site located furthest downstream. A similar downstream pattern of lower expression levels also was found in ovarian tissue for the genes, HSP70 and ERα. Gill gene expression showed a unique pattern in females as levels of metallothionein were elevated at the site furthest downstream. While analytical chemistry of water samples provided limited evidence of agrichemical contamination, the gene expression data are consistent with an exposure to agrichemicals and metals. T. areolatus may be a valuable sentinel organism and its use as a bioindicator species in some rivers within Chile can provide considerable insight, particularly in situations analytical chemistry is limited by environmental constraints.

Comparative evaluation of machine learning models for groundwater quality assessment.

Contamination from pesticides and nitrate in groundwater is a significant threat to water quality in general and agriculturally intensive regions in particular. Three widely used machine learning models, namely, artificial neural networks (ANN), support vector machines (SVM), and extreme gradient boosting (XGB), were evaluated for their efficacy in predicting contamination levels using sparse data with non-linear relationships. The predictive ability of the models was assessed using a dataset consisting of 303 wells across 12 Midwestern states in the USA. Multiple hydrogeologic, water quality, and land use features were chosen as the independent variables, and classes were based on measured concentration ranges of nitrate and pesticide. This study evaluates the classification performance of the models for two, three, and four class scenarios and compares them with the corresponding regression models. The study also examines the issue of class imbalance and tests the efficacy of three class imbalance mitigation techniques: oversampling, weighting, and oversampling and weighting, for all the scenarios. The models' performance is reported using multiple metrics, both insensitive to class imbalance (accuracy) and sensitive to class imbalance (F1 score and MCC). Finally, the study assesses the importance of features using game-theoretic Shapley values to rank features consistently and offer model interpretability.

Microbial Transformation of A Sulfonamide Antibiotic Under Various Background Nutrient Conditions.

Certain microbes can biotransform antibiotics. Little is known about these microbes or the biotransformation processes. The objective of this study was to determine the effects of background nutrient conditions on a sulfonamide degrading culture and on its biotransformation of sulfadiazine (SDZ) with respect to transformation kinetics and transformation products. The mixed culture capable of degrading SDZ consisted primarily of three genera, Brevibacterium, Castellaniella and Leucobacter. The maximum biotransformation rate was 4.55 mg L-1 d-1 in the absence of background nutrients. Among the three background nutrient conditions tested, diluted R2A medium lead to the highest maximum SDZ biotransformation rates, followed by humic acid and glucose. 2-aminopyrimidine was the major SDZ biotransformation product under the background nutrient conditions tested, while another previously reported biotransformation product, sulfanilic acid, was further degraded by the mixed culture. The findings from this study can help improve our estimation of the fate of antibiotics in the environment.

Affinity extraction of emerging contaminants from water based on bovine serum albumin as a binding agent.

Affinity sorbents using bovine serum albumin as a binding agent were developed and tested for the extraction of environmental contaminants from water. Computer simulations based on a countercurrent distribution model were also used to study the behavior of these sorbents. Several model drugs, pesticides, and hormones of interest as emerging contaminants were considered in this work, with carbamazepine being used as a representative analyte when coupling the albumin column on-line with liquid chromatography and tandem mass spectrometry. The albumin column was found to be capable of extracting carbamazepine from aqueous solutions that contained trace levels of this analyte. Further studies of the bovine serum albumin sorbent indicated that it had higher retention under aqueous conditions than a traditional C18 support for most of the tested emerging contaminants. Potential advantages of using these protein-based sorbents included the low cost of bovine serum albumin and its ability to bind to a relatively wide range of drugs and related compounds. It was also shown how simulations could be used to describe the elution behavior of the model compounds on the bovine serum albumin sorbents as an aid in optimizing the retention and selectivity of these supports for use with liquid chromatography or methods such as liquid chromatography with tandem mass spectrometry.

Detection, Occurrence and Fate of Emerging Contaminants in Agricultural Environments.

A total of 75 papers published in 2017 were reviewed ranging from detailed descriptions of analytical methods, to fate and occurrence studies, to ecological effects and sampling techniques for a wide variety of emerging contaminants likely to occur in agricultural environments. New methods and studies on veterinary pharmaceuticals, steroids, antibiotic resistance genes, and engineered nanoparticles agricultural environments continue to expand our knowledge base on the occurrence and potential impacts of these compounds. This review is divided into the following sections: Introduction, Analytical Methods, Fate and Occurrence, Pharmaceutical Metabolites, Anthelmintics, Antibiotic Resistence Genes, and Engineered Nanomaterials.

Occurrence of Antibiotics in an Agricultural Watershed in South-Central Idaho.

The polar organic compound integrative sampler (POCIS) is a tool that has been effectively used to passively sample organic pollutants over long periods in aquatic environments. In this study, POCIS were used to investigate the spatial and temporal occurrence of 21 antibiotics in irrigation return flows and upstream sites of an intensively managed agricultural watershed in south-central Idaho. The antibiotic metabolite, erythromycin-HO, and the antibiotics monensin, oxytetracycline, sulfadimethoxine, sulfamethazine, sulfamethoxazole, trimethoprim, and tylosin were detected at frequencies ranging from 3.1 to 62.5%, with monensin having the highest rate of detection. The fact that monensin was the most frequently detected compound indicates that it is entering return flows in runoff from fields that had received livestock manure or wastewater. Antibiotics (except oxytetracycline, sulfamethazine, and tylosin) were also detected at an upstream site that consisted of diverted Snake River water and is the source of irrigation water for the watershed. Therefore, even cropped soils that are not treated with manure are still receiving low-level antibiotics during irrigation events. This study provides the first set of evidence that surface waters within this agricultural watershed contain antibiotic residues associated with veterinary and human uses.

Evaluation of Fecal Indicators and Pathogens in a Beef Cattle Feedlot Vegetative Treatment System.

Runoff from open-lot animal feeding areas contains microorganisms that may adversely affect human and animal health if not properly managed. One alternative to full manure containment systems is a vegetative treatment system (VTS) that collects runoff in a sediment basin and then applies it to a perennial vegetation (grass) treatment area that is harvested for hay. Little is known regarding the efficacy of large-scale commercial VTSs for the removal of microbial contaminants. In this study, an active, pump-based VTS designed and built for a 1200-head beef cattle feedlot operation was examined to determine the effects of repeated feedlot runoff application on fecal indicator microorganisms and pathogens over short-term (2 wk) and long-term (3 yr) operations and whether fecal bacteria were infiltrating into deeper soils within the treatment area. In a short-term study, fecal bacteria and pathogen numbers declined over time in soil. Measurements of total coliforms and Enterococcus counts taken on control soils were not effective as fecal indicators. The repeated application of manure-impacted runoff as irrigation water did not enrich the pathogens or fecal indicators in the soil, and no evidence was seen to indicate that pathogens were moving into the deeper soil at this site. These results indicate that large-scale, active VTSs reduce the potential for environmental contamination by manure-associated bacteria. Also, this study has implications to full-containment systems that apply runoff water to land application areas (cropland) and the fate of pathogens in the soils of land application sites.

Detection, Occurrence and Fate of Emerging Contaminants in Agricultural Environments.

A total of 79 papers published in 2016 were reviewed ranging from detailed descriptions of analytical methods, to fate and occurrence studies, to ecological effects and sampling techniques for a wide variety of emerging contaminants likely to occur in agricultural environments. New methods and studies on veterinary pharmaceuticals, steroids, antibiotic resistance genes, cyanotoxins, and potential effects of biochar use in agricultural environments continue to expand our knowledge base on the occurrence and potential impacts of these compounds. This review is divided into the following sections: Introduction, Analytical Methods, Steroid Hormones, Anthelmintics, Antibiotic Fate and Occurrence, Antibiotic Resistance Genes, Cyanotoxins, and Implications of Biochar in Agricultural Environments.

Stereoselective Degradation of Estradiol and Trenbolone Isomers in Alluvial Sediment.

Stereoisomers of estradiol (E2) or trenbolone (TB) can occur together in the environment receiving human or livestock wastes. However, the effect of their co-occurrence on persistence has not been well elucidated. A sandy and a silt loam sediment were used to establish microcosms with α- and ß-isomers of E2 or TB spiked individually and together. Sediments were sampled periodically and analyzed for E2 and TB isomers and their transformation products using derivatization gas chromatography-mass spectrometry. Results showed that stereoselective degradation was significant for E2 in both sediments and TB in the sandy sediment with ß-isomers decaying more rapidly than α-isomers. In the sandy sediment containing limited natural organic carbon and nutrients, co-occurrence of both isomers of either E2 or TB decreased the dissipation rates. In the silt loam sediment with abundant organic matter and nutrients, the decay rates of both isomers were not changed in the presence of the other isomer. Estrone (E1) and trendione (TD) were detected as primary metabolites of E2 and TB isomers, respectively. The formation and decay profiles of E1 were similar in both sediments with 92-100% of E2 transformed to E1. The TD profiles were different across sediments with ∼100% of TB transformed to TD except in the sandy sediment where 51-60% of 17α-TB was converted to TD. These results indicate that the transformation processes of steroid hormone are stereoselective in sediment and co-occurrence of stereoisomers can prolong steroid persistence and thus pose greater environmental risk.