Black Carbon Impacts on Paraburkholderia xenovorans Strain LB400 Cell Enrichment and Activity: Implications toward Lower-Chlorinated Polychlorinated Biphenyls Biodegradation Potential.

Volatilization of lower-chlorinated polychlorinated biphenyls (LC-PCBs) from sediment poses health threats to nearby communities and ecosystems. Biodegradation combined with black carbon (BC) materials is an emerging bioaugmentation approach to remove PCBs from sediment, but development of aerobic biofilms on BC for long-term, sustained LC-PCBs remediation is poorly understood. This work aimed to characterize the cell enrichment and activity of biphenyl- and benzoate-grown Paraburkholderia xenovorans strain LB400 on various BCs. Biphenyl dioxygenase gene (bphA) abundance on four BC types demonstrated corn kernel biochar hosted at least 4 orders of magnitude more attached cells per gram than other feedstocks, and microscopic imaging revealed the attached live cell fraction was >1.5× more on corn kernel biochar than GAC. BC characteristics (i.e., sorption potential, pore size, pH) appear to contribute to cell attachment differences. Reverse transcription qPCR indicated that BC feedstocks significantly influenced bphA expression in attached cells. The bphA transcript-per-gene ratio of attached cells was >10-fold more than suspended cells, confirmed by transcriptomics. RNA-seq also demonstrated significant upregulation of biphenyl and benzoate degradation pathways on attached cells, as well as revealing biofilm formation potential/cell-cell communication pathways. These novel findings demonstrate aerobic PCB-degrading cell abundance and activity could be tuned by adjusting BC feedstocks/attributes to improve LC-PCBs biodegradation potential.

Acid- and Base-Mediated Hydrolysis of Dichloroacetamide Herbicide Safeners.

Safeners are used extensively in commercial herbicide formulations. Although safeners are regulated as inert ingredients, some of their transformation products have enhanced biological activity. Here, to fill gaps in our understanding of safener environmental fate, we determined rate constants and transformation products associated with the acid- and base-mediated hydrolysis of dichloroacetamide safeners AD-67, benoxacor, dichlormid, and furilazole. Second-order rate constants for acid- (HCl) and base-mediated (NaOH) dichloroacetamide hydrolysis (2.8 × 10-3 to 0.46 and 0.3-500 M-1 h-1, respectively) were, in many cases (5 of 8), greater than those reported for their chloroacetamide herbicide co-formulants. In particular, the rate constant for base-mediated hydrolysis of benoxacor was 2 orders of magnitude greater than that of its active ingredient co-formulant, S-metolachlor. At circumneutral pH, only benoxacor underwent appreciable hydrolysis (5.3 × 10-4 h-1), and under high-pH conditions representative of lime-soda softening, benoxacor's half-life was 13 h─a timescale consistent with partial transformation during water treatment. Based on Orbitrap LC-MS/MS analysis of dichloroacetamide hydrolysis product mixtures, we propose structures for major products and three distinct mechanistic pathways that depend on the system pH and compound structure. These include base-mediated amide cleavage, acid-mediated amide cleavage, and acid-mediated oxazolidine ring opening. Collectively, this work will help to identify systems in which hydrolysis contributes to the transformation of dichloroacetamides, while also highlighting important differences in the reactivity of dichloroacetamides and their active chloroacetamide co-formulants.

Exposure and Transport of Alkaloids and Phytoestrogens from Soybeans to Agricultural Soils and Streams in the Midwestern United States.

Phytotoxins are naturally produced toxins with potencies similar/higher than many anthropogenic micropollutants. Nevertheless, little is known regarding their environmental fate and off-field transport to streams. To fill this research gap, a network of six basins in the Midwestern United States with substantial soybean production was selected for the study. Stream water (n = 110), soybean plant tissues (n = 8), and soil samples (n = 16) were analyzed for 12 phytotoxins (5 alkaloids and 7 phytoestrogens) and 2 widely used herbicides (atrazine and metolachlor). Overall, at least 1 phytotoxin was detected in 82% of the samples, with as many as 11 phytotoxins detected in a single sample (median = 5), with a concentration range from below detection to 37 and 68 ng/L for alkaloids and phytoestrogens, respectively. In contrast, the herbicides were ubiquitously detected at substantially higher concentrations (atrazine: 99% and metolachlor: 83%; the concentrations range from below detection to 150 and 410 ng/L, respectively). There was an apparent seasonal pattern for phytotoxins, where occurrence prior to and during harvest season (September to November) and during the snow melt season (March) was higher than that in December-January. Runoff events increased phytotoxin and herbicide concentrations compared to those in base-flow conditions. Phytotoxin plant concentrations were orders of magnitude higher compared to those measured in soil and streams. These results demonstrate the potential exposure of aquatic and terrestrial organisms to soybean-derived phytotoxins.

Occurrence and Spatiotemporal Dynamics of Pharmaceuticals in a Temperate-Region Wastewater Effluent-Dominated Stream: Variable Inputs and Differential Attenuation Yield Evolving Complex Exposure Mixtures.

Effluent-dominated streams are becoming increasingly common in temperate regions and generate complex pharmaceutical mixture exposure conditions that may impact aquatic organisms via drug-drug interactions. Here, we quantified spatiotemporal pharmaceutical exposure concentrations and composition mixture dynamics during baseflow conditions at four sites in a temperate-region effluent-dominated stream (upstream, at, and progressively downstream from effluent discharge). Samples were analyzed monthly for 1 year for 109 pharmaceuticals/degradates using a comprehensive U.S. Geological Survey analytical method and biweekly for 2 years focused on 14 most common pharmaceuticals/degradates. We observed a strong chemical gradient with pharmaceuticals only sporadically detected upstream from the effluent. Seventy-four individual pharmaceuticals/degradates were detected, spanning 5 orders of magnitude from 0.28 to 13 500 ng/L, with 38 compounds detected in >50% of samples. "Biweekly" compounds represented 77 ± 8% of the overall pharmaceutical concentration. The antidiabetic drug metformin consistently had the highest concentration with limited in-stream attenuation. The antihistamine drug fexofenadine inputs were greater during warm- than cool-season conditions but also attenuated faster. Differential attenuation of individual pharmaceuticals (i.e., high = citalopram; low = metformin) contributed to complex mixture evolution along the stream reach. This research demonstrates that variable inputs over multiple years and differential in-stream attenuation of individual compounds generate evolving complex mixture exposure conditions for biota, with implications for interactive effects.

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.

Polymeric Nanofiber-Carbon Nanotube Composite Mats as Fast-Equilibrium Passive Samplers for Polar Organic Contaminants.

To improve the performance of polymeric electrospun nanofiber mats (ENMs) for equilibrium passive sampling applications in water, we integrated two types of multiwalled carbon nanotubes (CNTs; with and without surface carboxyl groups) into polyacrylonitrile (PAN) and polystyrene (PS) ENMs. For 11 polar and moderately hydrophobic compounds (-0.07 ≤ logKOW ≤ 3.13), 90% of equilibrium uptake was achieved in under 0.8 days (t90% values) in nonmixed ENM-CNT systems. Sorption capacity of ENM-CNTs was between 2- and 50-fold greater than pure polymer ENMs, with equilibrium partition coefficients (KENM-W values) ranging from 1.4 to 3.1 log units (L/kg) depending on polymer type (hydrophilic PAN or hydrophobic PS), CNT loading (i.e., values increased with weight percent (wt %) of CNTs), and CNT type (i.e., greater uptake with carboxylated CNTs composites). During field deployment at Muddy Creek in North Liberty, Iowa, optimal ENM-CNTs (PAN with 20 wt % carboxylated CNTs) yielded atrazine concentrations in surface water with a 40% difference relative to analysis of a same-day grab sample. We also observed a mean percent difference of 30 (±20)% when comparing ENM-CNT sampler results to grab sample data collected within 1 week of deployment. With their rapid, high capacity uptake and small material footprint, ENM-CNT equilibrium passive samplers represent a promising alternative to complement traditional integrative passive samplers while offering convenience over large volume grab sampling.

Photochemical Transformations of Dichloroacetamide Safeners.

Dichloroacetamide safeners are commonly added to commercial chloroacetamide herbicide formulations and widely used worldwide, but their environmental fate has garnered little scrutiny as a result of their classification as "inert" ingredients. Here, we investigated the photolysis of dichloroacetamide safeners to better understand their persistence and the nature of their transformation products in surface waters. High-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize photoproducts. Of the four commonly used dichloroacetamide safeners, only benoxacor undergoes direct photolysis under simulated natural sunlight ( t1/2 ∼ 10 min). Via a photoinitiated ring closure, benoxacor initially yields a monochlorinated intermediate that degrades over longer irradiation time scales to produce two fully dechlorinated diastereomers and a tautomer, which further photodegrade over several days to a structurally related aldehyde confirmed via NMR. Dichlormid, AD-67, and furilazole were more slowly degraded by indirect photolysis in the presence of the photosensitizers nitrate, nitrite, and humic acid. Reactive entities involved in these reactions are likely hydroxyl radical and singlet oxygen based on the use of selective quenchers. These safeners also directly photolyzed under higher energy ultraviolet (UV) light, suggesting their potential transformation in engineered systems using UV for disinfection. The finding that dichloroacetamide safeners can undergo photolysis in environmental systems over relevant time scales demonstrates the importance of evaluating the fate of this class of "inert" agrochemicals.

Evaluation of Mechanistic Models for Nitrate Removal in Woodchip Bioreactors.

Woodchip bioreactors (WBRs) are increasingly being applied to remove nitrate from runoff. In this study, replicate columns with aged woodchips were subjected to a range of measured flow rates and influent nitrate concentrations with an artificial stormwater matrix. Dissolved oxygen (DO), nitrate, and dissolved organic carbon (DOC) were measured along the length of the columns. A multispecies reactive transport model with Michaelis-Menten kinetics was developed to explain the concentration profiles of DO, nitrate, and DOC. Four additional models were developed based on simplifying assumptions, and all five models were tested for their ability to predict nitrate concentrations in the experimental columns. Global sensitivity analysis and constrained optimization determined the set of parameters that minimized the root-mean-squared error (RMSE) between the model and the experimental data. A k-fold validation test revealed no statistical difference in RMSE for predicting nitrate concentrations between a zero-order model and the other multispecies reactive transport models tested. Additionally, the multispecies reactive transport models demonstrated no significant differences in predicting DO and DOC concentrations. These results suggest that denitrification in an aged woodchip bioreactor at constant temperature can effectively be modeled using zero-order kinetics when nitrate concentrations are >2 mg-N L-1. A multispecies model may be used if predicting DOC or DO concentrations is desired.

Plant Assimilation Kinetics and Metabolism of 2-Mercaptobenzothiazole Tire Rubber Vulcanizers by Arabidopsis.

2-Mercaptobenzothiazole (MBT) is a tire rubber vulcanizer found in potential sources of reclaimed water where it may come in contact with vegetation. In this work, we quantified the plant assimilation kinetics of MBT using Arabidopsis under hydroponic conditions. MBT depletion kinetics in the hydroponic medium with plants were second order (t1/2 = 0.52 to 2.4 h) and significantly greater than any abiotic losses (>18 times faster; p = 0.0056). MBT depletion rate was related to the initial exposure concentration with higher rates at greater concentrations from 1.6 µg/L to 147 µg/L until a potentially inhibitory level (1973 µg/L) lowered the assimilation rate. 9.8% of the initial MBT mass spike was present in the plants after 3 h and decreased through time. In-source LC-MS/MS fragmentation revealed that MBT was converted by Arabidopsis seedlings to multiple conjugated-MBT metabolites of differential polarity that accumulate in both the plant tissue and hydroponic medium; metabolite representation evolved temporally. Multiple novel MBT-derived plant metabolites were detected via LC-QTOF-MS analysis; proposed transformation products include glucose and amino acid conjugated MBT metabolites. Elucidating plant transformation products of trace organic contaminants has broad implications for water reuse because plant assimilation could be employed advantageously in engineered natural treatment systems, and plant metabolites in food crops could present an unintended exposure route to consumers.

Rapid Phytotransformation of Benzotriazole Generates Synthetic Tryptophan and Auxin Analogs in Arabidopsis.

Benzotriazoles (BTs) are xenobiotic contaminants widely distributed in aquatic environments and of emerging concern due to their polarity, recalcitrance, and common use. During some water reclamation activities, such as stormwater bioretention or crop irrigation with recycled water, BTs come in contact with vegetation, presenting a potential exposure route to consumers. We discovered that BT in hydroponic systems was rapidly (approximately 1-log per day) assimilated by Arabidopsis plants and metabolized to novel BT metabolites structurally resembling tryptophan and auxin plant hormones; <1% remained as parent compound. Using LC-QTOF-MS untargeted metabolomics, we identified two major types of BT transformation products: glycosylation and incorporation into the tryptophan biosynthetic pathway. BT amino acid metabolites are structurally analogous to tryptophan and the storage forms of auxin plant hormones. Critical intermediates were synthesized (authenticated by (1)H/(13)C NMR) for product verification. In a multiple-exposure temporal mass balance, three major metabolites accounted for >60% of BT. Glycosylated BT was excreted by the plants into the hydroponic medium, a phenomenon not observed previously. The observed amino acid metabolites are likely formed when tryptophan biosynthetic enzymes substitute synthetic BT for native indolic molecules, generating potential phytohormone mimics. These results suggest that BT metabolism by plants could mask the presence of BT contamination in the environment. Furthermore, BT-derived metabolites are structurally related to plant auxin hormones and should be evaluated for undesirable biological effects.

Root exudate enhanced contaminant desorption: an abiotic contribution to the rhizosphere effect.

Despite reports in the literature of superior contaminant degradation in the root-zone of plants, this phenomenon, known as the rhizosphere effect, is poorly understood. We investigated whether root exudates could enhance desorption of residual pollutants, thus improving bioavailability and subsequent biodegradation potential. Root exudates were harvested from three species of hydroponically grown plants, and artificial root exudates (AREs) were created using a literature recipe. Aliquots of the exudates were metabolized by soil bacteria to investigate whether biotransformed exudates exhibited different chemical characteristics or had different effects on contaminant bioavailability than 'raw exudates.' Slurries of naphthalene-aged soil containing raw exudates had a significantly lower soil-water distribution coefficient (Kd) than slurries with metabolized exudates or no-exudate controls, exhibiting median reductions of 50% and 55%, respectively. Raw exudates had a significantly lower surface tension while not increasing overall solubility, indicating the presence of surface-active compounds below the critical micelle concentration; this is a newly observed mechanism of the rhizosphere effect. Exudate samples were characterized by specific UV absorbance, spectral slope, fluorescence index, and excitation-emission matrices. Substantial changes in organic carbon character pre- and postmetabolism, and between harvested exudates and AREs, suggest that AREs are not chemically representative of plant root exudates. Overall, we present evidence that enhanced contaminant desorption in the presence of exudates provides an abiotic contribution to the rhizosphere effect.

Microbial Biotransformation Products and Pathways of Dichloroacetamide Herbicide Safeners.

Dichloroacetamide safeners are common ingredients in commercial herbicide formulations. We previously investigated the environmental fate of dichloroacetamides via photolysis and hydrolysis, but other potentially important, environmentally relevant fate processes remain uncharacterized and may yield products of concern. Here, we examined microbial biotransformation of two dichloroacetamide safeners, benoxacor and dichlormid, to identify products and elucidate pathways. Using aerobic microcosms inoculated with river sediment, we demonstrated that microbial biotransformations of benoxacor and dichlormid proceed primarily, if not exclusively, via cometabolism. Benoxacor was transformed by both hydrolysis and microbial biotransformation processes; in most cases, biotransformation rates were faster than hydrolysis rates. We identified multiple novel products of benoxacor and dichlormid not previously observed for microbial processes, with several products similar to those reported for structurally related chloroacetamide herbicides, thus indicating potential for conserved biotransformation mechanisms across both chemical classes. Observed products include monochlorinated species such as the banned herbicide CDAA (from dichlormid), glutathione conjugates, and sulfur-containing species. We propose a transformation pathway wherein benoxacor and dichlormid are first dechlorinated, likely via microbial hydrolysis, and subsequently conjugated with glutathione. This is the first study reporting biological dechlorination of dichloroacetamides to yield monochlorinated products in aerobic environments.

Functional Group Properties and Position Drive Differences in Xenobiotic Plant Uptake Rates, but Metabolism Shares a Similar Pathway.

Plant uptake of xenobiotic compounds is crucial for phytoremediation (including green stormwater infrastructure) and exposure potential during crop irrigation with recycled water. Experimentally determining the plant uptake for every relevant chemical is impractical; therefore, illuminating the role of specific functional groups on the uptake of trace organic contaminants is needed to enhance predictive power. We used benzimidazole derivatives to probe the impact of functional group electrostatic properties and position on plant uptake and metabolism using the hydroponic model plant Arabidopsis thaliana. The greatest plant uptake rates occurred with an electron-withdrawing functional group at the 2 position; however, uptake was still observed with an electron-donating group. An electron-donating group at the 1 position significantly slowed uptake for both benzimidazole- and benzotriazole-based molecules used in this study, indicating possible steric effects. For unsubstituted benzimidazole and benzotriazole structures, the additional heterocyclic nitrogen in benzotriazole increased plant uptake rates compared to benzimidazole. Analysis of quantitative structure-activity relationship parameters for the studied compounds implicates energy-related molecular descriptors as uptake drivers. Despite significantly varied uptake rates, compounds with different functional groups yielded shared metabolites, including an impact on endogenous glutathione production. Although the topic is complex and influenced by multiple factors in the field, this study provides insights into the impact of functional groups on plant uptake, with implications for environmental fate and consumer exposure.

Transcriptome signatures of wastewater effluent exposure in larval zebrafish vary with seasonal mixture composition in an effluent-dominated stream.

Wastewater treatment plant (WWTP) effluent-dominated streams provide critical habitat for aquatic and terrestrial organisms but also continually expose them to complex mixtures of pharmaceuticals that can potentially impair growth, behavior, and reproduction. Currently, few biomarkers are available that relate to pharmaceutical-specific mechanisms of action. In the experiment reported in this paper, zebrafish (Danio rerio) embryos at two developmental stages were exposed to water samples from three sampling sites (0.1 km upstream of the outfall, at the effluent outfall, and 0.1 km below the outfall) during base-flow conditions from two months (January and May) of a temperate-region effluent-dominated stream containing a complex mixture of pharmaceuticals and other contaminants of emerging concern. RNA-sequencing identified potential biological impacts and biomarkers of WWTP effluent exposure that extend past traditional markers of endocrine disruption. Transcriptomics revealed changes to a wide range of biological functions and pathways including cardiac, neurological, visual, metabolic, and signaling pathways. These transcriptomic changes varied by developmental stage and displayed sensitivity to variable chemical composition and concentration of effluent, thus indicating a need for stage-specific biomarkers. Some transcripts are known to be associated with genes related to pharmaceuticals that were present in the collected samples. Although traditional biomarkers of endocrine disruption were not enriched in either month, a high estrogenicity signal was detected upstream in May and implicates the presence of unidentified chemical inputs not captured by the targeted chemical analysis. This work reveals associations between bioeffects of exposure, stage of development, and the composition of chemical mixtures in effluent-dominated surface water. The work underscores the importance of measuring effects beyond the endocrine system when assessing the impact of bioactive chemicals in WWTP effluent and identifies a need for non-targeted chemical analysis when bioeffects are not explained by the targeted analysis.

Fate of naphthalene in laboratory-scale bioretention cells: implications for sustainable stormwater management.

Bioretention cells are increasingly popular in low-impact development as a means to sustainably mitigate the environmental problems associated with stormwater runoff. Yet, much remains to be known regarding the removal and ultimate fate of pollutants such as petroleum hydrocarbons in bioretention cells. In this work, laboratory-scale bioretention cells were constructed inside sealed glass columns. The columns were periodically spiked with (14)C-naphthalene over a 5-month period and the fate of this representative hydrocarbon and the influence of vegetation on naphthalene fate was studied. Three column setups were used: one planted with a legume (Purple Prairie Clover, Dalea purpureum), one planted with grass (Blue-Joint Grass, Calamagrostis canadensis), and one unplanted (i.e., control). Overall naphthalene removal efficiency was 93% for the planted columns and 78% for the control column. Adsorption to soil was the dominant naphthalene removal mechanism (56-73% of added naphthalene), although mineralization (12-18%) and plant uptake (2-23%) were also important. Volatilization was negligible (<0.04%). Significant enrichment of naphthalene-degrading bacteria occurred due to contaminant exposure and plant growth as evidenced by increased biodegradation activity and increased naphthalene dioxygenase gene concentrations in the bioretention media. This research suggests that bioretention is a viable solution for sustainable petroleum hydrocarbon removal from stormwater, and that vegetation can enhance overall performance and stimulate biodegradation.

White Rot Fungi Produce Novel Tire Wear Compound Metabolites and Reveal Underappreciated Amino Acid Conjugation Pathways.

There is increasing concern about tire wear compounds (TWCs) in surface water and stormwater as evidence grows on their toxicity and widespread detection in the environment. Because TWCs are prevalent in stormwater, there is a need to understand fate and treatment options including biotransformation in green infrastructure (e.g., bioretention). Particularly, fungal biotransformation is not well-studied in a stormwater context despite the known ability of certain fungi to remove recalcitrant contaminants. Here, we report the first study on fungal biotransformation of the TWCs acetanilide and hexamethoxymethylmelamine (HMMM). We found that the model white rot fungus, Trametes versicolor, removed 81.9% and 69.6% of acetanilide and HMMM, respectively, with no significant sorption to biomass. The bicyclic amine 1,3-diphenylguanidine was not removed. Additionally, we identified novel TWC metabolites using semi-untargeted metabolomics via high-resolution mass spectrometry. Key metabolites include multiple isomers of HMMM biotransformation products, melamine as a possible "dead-end" product of HMMM (verified with an authentic standard), and a glutamine-conjugated product of acetanilide. These metabolites have implications for environmental toxicity and treatment. Our discovery of the first fungal glutamine-conjugated product highlights the need to investigate amino acid conjugation as an important pathway in biotransformation of contaminants, with implications in other fields including natural products discovery.

The use of recycled materials in a biofilter to polish anammox wastewater treatment plant effluent.

Anammox is gaining popularity for treating wastewater containing high-strength ammonia due to lower energy demand compared to conventional nitrification-denitrification processes; however, anammox is reported to increase nitrate loads in the effluent. The objective of this study was to assess the applicability of recycled materials [recycled concrete aggregate (RCA) and rice husks (RH)] as a polishing step to improve anammox reactor effluent quality. Anammox effluents were separately passed through two single-stage columns containing RCA and RH, and one two-stage column (50% RCA, 50% RH) to quantify total N, ammonia, nitrate, nitrite, and phosphate removal efficiencies. Langmuir isotherm experiments were conducted to quantify nitrate, nitrite, and phosphate sorption capacities in the columns. The RCA column exhibited the highest phosphate sorption capacity (0.074 mg/g), while the RH column exhibited higher nitrite and nitrate adsorption (0.063 mg/g and 0.023 mg/g respectively). We created a Hydrus-1D model to estimate pseudo-first-order reaction rates in the columns. Because RCA media can form metal-phosphate precipitates, the fastest phosphate reaction rate (1.58 min-1) occurred in the RCA column. The two-stage column demonstrated the greatest overall removals for all nutrients, and removal rates were consistent throughout the experimental period. The two-stage column achieved 15% total N, 94% ammonia-N, 38% nitrate-N, 75% nitrite-N, and 27% phosphate removal. The maximum nitrite, nitrate, and phosphate adsorption capacities in the two-stage column were 0.030 mg/g, 0.017 mg/g, and 0.014 mg/g respectively. This is the first study to demonstrate that recycled materials can successfully be integrated into a biofilter as an effluent polishing step to remove nutrients from anammox wastewater.

Rapid plant uptake of isothiazolinone biocides and formation of metabolites by hydroponic Arabidopsis.

Isothiazolinones biocides are water-soluble, low molecular weight, nitrogenous compounds widely used to prevent microbial growth in a variety of applications including personal care products and building façade materials. Because isothiazolinones from buildings wash off and enter stormwater, interactions with terrestrial plants may represent an important part of the environmental fate of these compounds (e.g., in green stormwater infrastructure). Using the model plant Arabidopsis thaliana grown hydroponically, we observed rapid (≥99% within 24 hours), plant-driven removal of four commonly used isothiazolinones: benzisothiazolinone (BIT), chloromethylisothiazolinone, methylisothiazolinone, and octylisothiazolinone. No significant differences in uptake rate occurred between the four compounds; therefore, BIT was used for further detailed investigation. BIT uptake by Arabidopsis was concentration-dependent in a manner that implicates transporter-mediated substrate inhibition. BIT uptake was also minimally impacted by multiple BIT spikes, suggesting constituently active uptake. BIT plant uptake rate was robust, unaffected by multiple inhibitors. We investigated plant metabolism as a relevant removal process. Proposed major metabolites that significantly increased in the BIT-exposure treatment compared to the control included: endogenous plant compounds nicotinic acid (confirmed with a reference standard) and phenylthioacetohydroximic acid, a possible amino acid-BIT conjugate, and two accurate masses of interest. Two of the compounds (phenylthioacetohydroximic acid and TP 470) were also present in increased amounts in the hydroponic medium after BIT exposure, possibly via plant excretion. Upregulation of endogenous plant compounds is environmentally significant because it demonstrates that BIT impacts plant biology. The rapid plant-driven isothiazolinone removal observed here indicates that plant-isothiazolinone processes could be relevant to the environmental fate of these stormwater compounds.

Combining Experimental Sorption Parameters with QSAR to Predict Neonicotinoid and Transformation Product Sorption to Carbon Nanotubes and Granular Activated Carbon.

We recently discovered that transformation of the neonicotinoid insecticidal pharmacophore alters sorption propensity to activated carbon, with products adsorbing less than parent compounds. To assess the environmental fate of novel transformation products that lack commercially available standards, researchers must rely on predictive approaches. In this study, we combined computationally derived quantitative structure-activity relationship (QSAR) parameters for neonicotinoids and neonicotinoid transformation products with experimentally determined Freundlich partition constants (log K F for sorption to carbon nanotubes [CNTs] and granular activated carbon [GAC]) to model neonicotinoid and transformation product sorption. QSAR models based on neonicotinoid sorption to functionalized/nonfunctionalized CNTs (used to generalize/simplify neonicotinoid-GAC interactions) were iteratively generated to obtain a multiple linear regression that could accurately predict neonicotinoid sorption to CNTs using internal and external validation (within 0.5 log units of the experimentally determined value). The log K F,CNT values were subsequently related to log K F,GAC where neonicotinoid sorption to GAC was predicted within 0.3 log-units of experimentally determined values. We applied our neonicotinoid-specific model to predict log K F,GAC for a suite of novel neonicotinoid transformation products (i.e., formed via hydrolysis, biotransformation, and chlorination) that do not have commercially available standards. We present this modeling approach as an innovative yet relatively simple technique to predict fate of highly specialized/unique polar emerging contaminants and/or transformation products that cannot be accurately predicted via traditional methods (e.g., pp-LFER), and highlights molecular properties that drive interactions of emerging contaminants.