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Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H 2 ) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H 2 photolysis on the hydrated electron (e aq - ) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of e aq - ([e aq - ] ss ). Results showed that VUV/H 2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant ( k deF ) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of e aq - via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to e aq - by H 2 , which was supported by a linear correlation between the predicted [e aq - ] ss and experimentally observed k deF . The k deF value increased from pH 9 to 12, which was attributed to the speciation of the H · /e aq - pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.

Many contaminants of emerging concern (CECs) have reactive functional groups and may readily undergo biotransformations, such as methylation and demethylation. These transformations have been reported to occur during human metabolism and wastewater treatment, leading to the propagation of CECs. When treated wastewater and biosolids are used in agriculture, CECs and their transformation products (TPs) are introduced into soil-plant systems. However, little is known about whether transformation cycles, such as methylation and demethylation, take place in higher plants and hence affect the fate of CECs in terrestrial ecosystems. In this study, we explored the interconversion between four common CECs (acetaminophen, diazepam, methylparaben, and naproxen) and their methylated or demethylated TPs in Arabidopsis thaliana cells and whole wheat seedlings. The methylation-demethylation cycle occurred in both plant models with demethylation generally taking place at a greater degree than methylation. The transformation rate of demethylation or methylation was dependent on the bond strength of R-CH 3 , with demethylation of methylparaben or methylation of acetaminophen being more pronounced. Although not explored in this study, these interconversions may exert influences on the behavior and biological activity of CECs, particularly in terrestrial ecosystems. The study findings demonstrated the prevalence of transformation cycles between CECs and their methylated or demethylated TPs in higher plants, contributing to a more complete understanding of risks of CECs in the human-wastewater-soil-plant continuum.

The karst forest is one of the extremely sensitive and fragile ecosystems in southwest China, where the biogeochemical cycling of mercury (Hg) is largely unknown. In this study, we investigated the litterfall deposition, accumulation, and soil migration of Hg in an evergreen-deciduous broadleaf karst forest using high-resolution sampling and stable isotope techniques. Results show that elevated litterfall Hg concentrations and fluxes in spring are due to the longer lifespan of evergreen tree foliage exposed to atmospheric Hg 0 . The hillslope has 1-2 times higher litterfall Hg concentration compared to the low-lying land due to the elevated atmospheric Hg levels induced by topographical and physiological factors. The Hg isotopic model suggests that litterfall Hg depositions account for ∼80% of the Hg source contribution in surface soil. The spatial trend of litterfall Hg deposition cannot solely explain the trend of Hg accumulation in the surface soil. Indeed, soil erosion enhances Hg accumulation in soil of low-lying land, with soil Hg concentration up to 5-times greater than the concentration on the hillslope. The high level of soil Hg migration in the karst forest poses significant ecological risks to groundwater and downstream aquatic ecosystems.

Contaminants of emerging concern (CECs) in the environment undergo various transformations, leading to the formation of transformation products (TPs) with a modified ecological risk potential. Although the environmental significance of TPs is increasingly recognized, there has been relatively little research to understand the influences of such transformations on subsequent ecotoxicological safety. In this study, we used four pairs of CECs and their methylated or demethylated derivatives as examples to characterize changes in bioaccumulation and acute toxicity in Daphnia magna , as a result of methylation or demethylation. The experimental results were further compared to quantitative structure-activity relationship (QSAR) predictions. The methylated counterpart in each pair generally showed greater acute toxicity in D. magna , which was attributed to their increased hydrophobicity. For example, the LC 50 values of methylparaben (34.4 ± 4.3 mg L -1 ) and its demethylated product (225.6 ± 17.3 mg L -1 ) differed about eightfold in D. magna . The methylated derivative generally exhibited greater bioaccumulation than the demethylated counterpart. For instance, the bioaccumulation of methylated acetaminophen was about 33-fold greater than that of acetaminophen. In silico predictions via QSARs aligned well with the experimental results and suggested an increased persistence of the methylated forms. The study findings underline the consequences of simple changes in chemical structures induced by transformations such as methylation and demethylation and highlight the need to consider TPs to achieve a more holistic understanding of the environmental fate and risks of CECs.

Carbonaceous materials are often proposed for use in restoring soils or sediments contaminated with hydrophobic organic contaminants (HOCs). However, the contamination of most sites is a result of historical events, where HOCs have resided in the solid compartment for many years or decades. The prolonged contact time, or aging, leads to reduced contaminant availability and likely diminished effectiveness of using sorbents. In this study, three different carbonaceous sorbents, i.e., biochars, powdered activated carbon, and granular activated carbon, were amended to a Superfund site marine sediment contaminated with DDT residues from decades ago. The amended sediments were incubated in seawater for up to 1 year, and the freely dissolved concentration ( C free ) and the biota-sediment accumulation factors (BSAFs) for a native polychaete ( Neanthes arenaceodentata ) were measured. Even though the bulk sediment concentrations were very high (6.4-154.9 μg/g OC), both C free and BSAFs were very small, ranging from nd to 1.34 ng/L and from nd to 0.024, respectively. The addition of carbonaceous sorbents, even at 2% (w/w), did not consistently lead to reduced DDT bioaccumulation. The limited effectiveness of carbonaceous sorbents was attributed to the low DDT availability due to prolonged aging, highlighting the need for considering contaminant aging when using sorbents for remediation.

Due to the detection frequencies and measured concentrations in surface water, the type I pyrethroid insecticide, bifenthrin, has been of particular concern within the Sacramento-San Joaquin Delta in California. Concentrations have been detected above levels previously reported to impair neuroendocrine function and induce neurotoxicity to several species of salmonids. Metabolomic and transcriptomic studies indicated impairment of cellular signaling within the brain of exposed animals and potential alteration of lipid metabolism. To better understand the potential impacts of bifenthrin on brain lipids, juvenile rainbow trout ( Oncorhynchus mykiss ) were exposed to mean bifenthrin concentrations of 28 or 48 ng/L for 14 days, and non-targeted lipidomic profiling in the brain was conducted. Brain tissue sections were also assessed for histopathological insult following bifenthrin treatment. Bifenthrin-exposed trout had a concentration-dependent decrease in the relative abundance of triglycerides (TGs) with levels of phosphatidylcholines (PCs) and phosphatidylethanolamines (PEs) significantly altered following 48 ng/L bifenthrin exposure. An increased incidence of histopathological lesions, such as focal hemorrhages and congestion of blood vessels, was noted in the brains of bifenthrin-treated animals, suggesting an association between altered lipid metabolism and neuronal cell structure and integrity.

Bifenthrin (BF) is a widely used pyrethroid that has been frequently detected in surface waters. Previous studies indicated that BF had antiestrogenic activity in zebrafish embryos but estrogenic activity in posthatch fish. To determine whether age-related differences in metabolism contribute to the endocrine effects in developing fish, embryos from zebrafish and Japanese medaka were exposed to BF before and after liver development. Since the commercial mixture of BF is an isomer-enriched product containing two enantiomers (1 R - cis -BF and 1 S - cis -BF), enantioselective metabolism was also evaluated. The estrogenic metabolite, 4-hydroxybifenthrin (4-OH-BF) was identified in zebrafish embryos, and formation was higher in animals after liver development (>48 hpf). Treatments with β-glucuronidase indicated that 4-OH-BF underwent conjugation in embryos. Formation was reduced by cotreatment of the cytochrome P450 (CYP450) inhibitor, ketoconazole. Formation of 4-OH-BF was greater when treated with 1 R - cis -BF compared to the S -enantiomer. However, metabolites were not observed in medaka embryos. These data indicate enantioselective oxidation of BF to an estrogenic metabolite occurs in zebrafish embryos and, since it is increased after liver development, may partially explain estrogenic activity observed in older animals. The lack of activity in medaka suggests species-specific effects with BF metabolism and may influence risk assessment strategies in wildlife.

Waste paper, an essential substitute for wood and other plant-based fibers in paper making, is an indispensable part of the circular economy; yet, the impacts of China's ban on global waste paper cycles have not been well understood. We modeled the evolution of the global waste paper trade network during 1995-2019. We found that the cumulative trade volume of global waste paper reached 1010 million tons in the last 25 years and showed a downward trend since 2015. The global import center of waste paper experienced a transfer from Europe to East Asia and then to Southeast Asia. The ban has stimulated some developed countries to reduce the exports of unsorted waste paper since 2017, but for many major importers their changes in waste paper trade patterns were related to waste paperboard, which was not banned by China, suggesting that this import change trend may be inevitable and irrespective of China's ban. Besides, India has replaced China to become a new import hub of unsorted waste paper. Our results lay a foundation for exploring the evolution of the future global solid waste cycle under the background of zero import of solid waste increasingly implemented by China and many other developing countries.

Shellfish aquaculture has been proposed to abate eutrophication because it can remove nutrients via shellfish filter-feeding. Using a three-dimensional physical-biogeochemical model, we investigate how effective oyster aquaculture can alleviate eutrophication-driven hypoxia off the Pearl River Estuary. Results show that oysters reduce sediment oxygen consumption and thus hypoxia, by reducing both particulate organic matter directly and regenerated nutrients that support new production of organic matter. The hypoxia reduction is largest when oysters are farmed within the upper water of the low-oxygen zone, and the reduction increases with increasing oyster density although oyster growth becomes slower due to food limitation. When oysters are farmed upstream of the hypoxic zone, the farming-induced hypoxia reduction is small and it declines with increasing oyster density because the nutrients released from the farm can increase downstream organic matter production. An oyster farming area of 10 to 200 km 2 yields a hypoxic volume reduction of 10% to 78%, equaling the impact of reducing 10% to 60% of river nutrient input. Our results demonstrate that oyster aquaculture can mitigate eutrophication and hypoxia, but its effectiveness depends on the farming location, areal size, and oyster density, and optimal designs must take into account the circulation and biogeochemical characteristics of the specific ecosystem.

Plasticizers, due to the widespread use of plastics, occur ubiquitously in the environment. The reuse of waste resources (e.g., treated wastewater, biosolids, animal waste) and other practices (e.g., plastic mulching) introduce phthalates into agroecosystems. As a detoxification mechanism, plants are known to convert phthalates to polar monophthalates after uptake, which are followed by further transformations, including conjugation with endogenous biomolecules. The objective of this study was 2-fold: to obtain a complete metabolic picture of the widely used di- n -butyl phthalate (DnBP) by using a suite of complementary techniques, including stable isotope labeling, 14 C tracing, and high-resolution mass spectrometry, and to determine if conjugates are deconjugated in human microsomes to release bioactive metabolites. In Arabidopsis thaliana cells, the primary initial metabolite of DnBP was mono- n -butyl phthalate (MnBP), and MnBP was rapidly metabolized via hydroxylation, carboxylation, glycosylation, and malonylation to seven transformation products. One of the conjugates, MnBP-acyl-β-d-glucoside (MnBP-Glu), was incubated in human liver (HLM) and intestinal (HIM) microsomes and was found to undergo rapid transformations. Approximately 15% and 10% of MnBP-Glu were deconjugated to the free form MnBP in HIM and HLM, respectively. These findings highlight that phthalates, as diesters, are susceptible to hydrolysis to form monoesters that can be readily conjugated via a phase II metabolism in plants. Conjugates may be deconjugated to release bioactive compounds after human ingestion. Therefore, an accurate assessment of the dietary exposure of phthalates and other contaminants must consider plant metabolites, especially including conjugates, to better predict their potential environmental and human health risks.

The pyrethroid insecticide, bifenthrin, is frequently measured at concentrations exceeding those that induce acute and chronic toxicity to several invertebrate and fish species residing in the Sacramento-San Joaquin Delta of California. Since the brain is considered to be a significant target for bifenthrin toxicity, juvenile steelhead trout ( Oncorhynchus mykiss ) were treated with concentrations of bifenthrin found prior to (60 ng/L) and following (120 ng/L) major stormwater runoff events with nontargeted metabolomics used to target transcriptomic alterations in steelhead brains following exposure. Predicted responses were involved in cellular apoptosis and necrosis in steelhead treated with 60 ng/L bifenthrin using the software Ingenuity Pathway Analysis. These responses were predominately driven by decreased levels of acetyl-l-carnitine (ALC), docosahexaenoic acid (DHA), and adenine. Steelhead treated with 120 ng/L bifenthrin had reductions of lysophosphatidylcholines (LPC), lysophosphatidylethanolamines (LPE), and increased levels of betaine, which were predicted to induce an inflammatory response. Several genes predicted to be involved in apoptotic ( caspase 3 and nrf 2) and inflammatory ( miox ) pathways had altered expression following exposure to bifenthrin. There was a significantly increased expression of caspase 3 and miox in fish treated with 120 ng/L bifenthrin with a significant reduction of nrf 2 in fish treated with 60 ng/L bifenthrin. These data indicate that bifenthrin may have multiple targets within the brain that affect general neuron viability, function, and signaling potentially through alterations in signaling fatty acids.

Soil is a primary sink for plastics, but the influence of microplastics as carriers on terrestrial cycling of persistent contaminants is poorly understood as compared to aquatic systems. Studies to date have disregarded the potential fact that microplastics are generally contaminated before their entry into soil. In this study, earthworm Eisenia fetida was incubated for 28 d in a soil amended with five common types of microplastics precontaminated with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) to elucidate contaminant transfer. Accumulation of HOCs in E. fetida varied greatly among different plastic types and HOCs. The freely dissolved concentration ( C free ) of HOCs showed that desorption of HOCs from microplastics into soil was closely related to plastic types and HOC hydrophobicity and was much slower for polystyrene or polypropylene than polyethylene. Biodynamic model analysis suggested that ingestion of microplastics could act as a significant pathway for some microplastics, likely due to HOCs on the plastics being in an "over-equilibrium" state. This was in contrast with mixing clean microplastics into HOC-contaminated soil, where the microplastics decreased bioaccumulation. Therefore, whether microplastics serve as facilitators or inhibitors of HOC bioaccumulation depends on the fugacity gradient of HOCs between microplastics and soil, which highlights the importance of considering the sequence of contamination between the plastics and soil. These findings also question the validity of short-term experiments because of the generally very slow partition kinetics of HOCs on plastics.

Few studies have considered the effect of co-occurring heavy metals on plant accumulation of hydrophobic organic compounds (HOCs), and less is known about the role of intermolecular interactions. This study investigated the molecular mechanisms of Cu/Zn effects on hydroponic uptake of four deuterated polycyclic aromatic hydrocarbons (PAHs- d 10 ) by spinach ( Spinacia oleracea L.). Both solubility enhancement experiment and quantum mechanical calculations demonstrated the existence of [PAH-Cu(H 2 O) 0-4 ] 2+ and [2·PAH-Cu(H 2 O) 0-2 ] 2+ via cation-π interactions when Cu 2+ concentration was ≤100 μmol/L. Notably, PAH- d 10 concentrations in both roots and shoots increased significantly with Cu 2+ concentration. This was because the formation of phytoavailable PAH-Cu 2+ complexes decreased PAH- d 10 hydrophobicity and consequently decreased their sorption onto dissolved organic carbon (DOC, i.e., root exudates), thereby increasing phytoavailable concentrations and uptake of PAHs- d 10 . X-ray absorption near-edge structure analysis showed that PAH-Cu 2+ complexes could enter defective spinach roots via apoplastic pathway. However, Zn 2+ and PAHs- d 10 cannot form the cation-π interactions because of the high desolvation penalty of Zn 2+ . Actually, Zn 2+ decreased the spinach uptake of PAHs- d 10 due to the increase of DOC induced by Zn. This work provides molecular insights into how metals could selectively affect the plant uptake of HOCs and highlights the importance of considering the HOC phytoavailability with coexisting metals.

Ecotoxicological risks of neonicotinoid insecticides are raising significant concerns, including their potential role in bee population declines. Neonicotinoids are water-soluble, systemic insecticides, and exposure of nontarget organisms such as pollinators occurs mainly through residues in nectar and pollens of flowering plants. To better elucidate the underlying mechanisms for such nontarget exposure, it is highly valuable to develop analytical capabilities for in vivo monitoring of neonicotinoids in live plants. In this study, we developed a novel biomimetic water-swelling solid-phase microextraction (SPME) probe, with limits of detection for neonicotinoids as low as 0.03 ng mL -1 , and applied it for in vivo detection of seven neonicotinoids in plant sap. The preparation of this fiber was simple and free of stringent or complex physical-chemical reactions. Equilibrium in neonicotinoid accumulation on the fiber was reached in <10 min, allowing for near instantaneous sampling. The water-swelling fiber displayed much greater sampling capacity than the commercially available polydimethylsiloxane and polyacrylate fibers, good reproducibility (RSD of inter- and intrafiber <8.9% and 7.8%, respectively), and antibiofouling property (no loss in performance after 20 use cycles). After treating lettuce ( Lactuca sativa L.) by foliar spray and soybean ( Glycine max M.) by seed soaking, the in vivo assays provided a wealth of information, including changes in levels and distribution of neonicotinoids over time in the same plants. Kinetics and distribution patterns suggested that after treatment at the same level, neonicotinoids differed significantly in their levels in the sap. The in vivo sampling and monitoring of neonicotinoids in live plants may provide unique and much needed information in achieving breakthrough understanding of the connection between neonicotinoid use and pollinator exposure.

Insecticides such as pyrethroids and fipronil are used in large amounts in both agricultural and urban settings and have the potential to elicit toxicity to nontarget aquatic organisms. In California, like in many other regions of the world, urban centers are located along the coast, and it is documented that urban-use insecticides enter the marine environment, where little is known about their occurrence and consequences. In this study, we measured the spatial distribution of pyrethroids and fipronil (and its metabolites) on the Palos Verdes Shelf off the coast of Los Angeles. Total pyrethroid levels ranged from nd to 170 μg/kg (dry weight), and fipronil sulfide levels ranged from 1.8 to 5.6 μg/kg. Two pyrethroids were traced to wastewater effluent discharge, while two others and fipronil sulfide were traced to to surface runoff. Toxicity units (TUs) were estimated for benthic invertebrates, which ranged from no toxicity (nt) to 146 for total pyrethroids, and 0.09 to 1.6 and 4.2 to 75 for fipronil sulfide, depending on the indicator species. Therefore, near-shore deposition of urban-use insecticides due to wastewater discharge and surface runoff poses a significant risk to marine benthic invertebrates and highlights the importance of monitoring near-shore ocean environments and developing mitigation strategies to reduce seaward movement.

Organophosphate esters (OPEs) have been in use as flame retardants for many decades, with their actual usage varying over time. Knowledge of the emission history of OPEs is valuable for improving our prediction of their environmental loadings and associated risks. In this study, concentrations and compositions of 10 OPEs were measured in three dated sediment cores from the Palos Verdes Shelf (PVS) off the coast of Los Angeles, which has been impacted by wastewater treatment plant (WWTP) effluents for over a century. The total OPE concentrations varied from 0.68 to 1064 ng/g along the sediment profile, with two apparent peaks. The first peak occurred in the 1970s, coinciding with peak emissions from WWTPs. The second peak appeared in the 2000s and was possibly attributed to increased consumption of OPEs as replacement flame retardants. Since downward movement of OPEs in the PVS sediment bed was retarded by their slow desorption, the reconstructed history likely provided an accurate picture of OPE emissions in Southern California and North America. These findings suggest that the near-shore marine sediments affected by WWTP effluents could serve as an environmental proxy documenting history in OPE use and emissions.

Active samplers for ambient monitoring of trace contaminants in surface water are highly desirable, but their use is often constrained by power supply. Here, we proposed a novel solution by coupling an improved osmotic pump (OP) with a solid-phase extraction (SPE) cartridge to construct a power-free active sampler for organic contaminants. The OP simply consisted of two cylindrical chambers separated by a reverse osmosis membrane. We, for the first time, added ion-exchange resins into the OP inlet chamber and successfully constructed OPs with a smooth and constant flow. In the OP-SPE sampler, water was continuously drawn through the SPE cartridge at a constant flow, and time-weighted average concentration over the sampling course may be easily calculated from the amount of target analytes retained on the SPE cartridge and water collected in the sampler. The OP-SPE samplers were deployed in a river to detect herbicides, and the measured concentrations were largely in agreement with the average of 11 daily spot samples. Given that a wide range of SPE cartridges are available for different classes of organic contaminants, this approach is versatile and may find widespread applications for in situ sampling of surface water under different conditions, including poorly accessible locations.

Agricultural use of treated wastewater, biosolids, and animal wastes introduces a multitude of contaminants of emerging concerns (CECs) into the soil-plant system. The potential for food crops to accumulate CECs depends largely on their metabolism in plants, which at present is poorly understood. Here, we evaluated the metabolism of naproxen and ibuprofen, two of the most-used human drugs from the Profen family, in Arabidopsis thaliana cells and the Arabidopsis plant. The complementary use of high-resolution mass spectrometry and 14 C labeling allowed the characterization of both free and conjugated metabolites, as well as nonextractable residues. Naproxen and ibuprofen, in their parent form, were conjugated quickly and directly with glutamic acid and glutamine, and further with peptides, in A. thaliana cells. For example, after 120 h, the metabolites of naproxen accounted for >90% of the extractable chemical mass, while the intact parent itself was negligible. The structures of glutamate and glutamine conjugates were confirmed using synthesized standards and further verified in whole plants. Amino acid conjugates may easily deconjugate, releasing the parent molecule. This finding highlights the possibility that the bioactivity of such CECs may be effectively preserved through direct conjugation, a previously overlooked risk. Many other CECs are also carboxylic acids, such as the profens. Therefore, direct conjugation may be a common route for plant metabolism of these CECs, making it imperative to consider conjugates when assessing their risks.

Passive samplers for moderately hydrophobic organic compounds (MHOCs) (i.e., log K ow ranging from 2 to 5) are under-developed compared to those that target polar or strongly hydrophobic compounds. The goal of this study was to identify a suitable polymer and develop a robust and sensitive film-based passive sampler for MHOCs in aquatic systems. Poly(methyl methacrylate) (PMMA) exhibited the highest affinity for fipronil and its three metabolites (i.e., fipronils) (log K ow 2.4-4.8) as model MHOCs compared with polyethylene and nylon films. In addition, a 30-60 min treatment of PMMA in ethyl ether was found to increase its sorption capacity by a factor of 10. Fipronils and 108 additional compounds (log K ow 2.4-8.5) reached equilibrium on solvent-treated PMMA within 120 h under mixing conditions and their uptake closely followed first-order kinetics. PMMA-water partition coefficients and K ow revealed an inverse parabolic relationship, with vertex at log K ow of 4.21 ± 0.19, suggesting that PMMA was ideal for MHOCs. The PMMA sampler was tested in an urban surface stream, and in spiked sediment. The results demonstrated that PMMA film, after a simple solvent swelling treatment, may be used as an effective passive sampler for determining C free of MHOCs in aquatic environments.

Pesticides are commonly applied around residential homes, but their occurrence on exterior surfaces (e.g., pavement) has not been thoroughly evaluated. We collected 360 dust samples from curbside gutters, sidewalks, and street surfaces at 40 houses in southern California to evaluate pesticide occurrence on urban paved surfaces as well as their spatial and temporal distributions. Pesticides and select degradates were ubiquitously detected in dust, with the median concentration of total target analytes at 85 μg kg -1 . A total of 75% of samples contained at least five pesticides. As a result of recurring pesticide applications, concentrations increased throughout the summer. The pyrethroids bifenthrin and permethrin accounted for 55% of total pesticides detected in the dust. The highest concentrations in dust were found on the sidewalk and in the gutter. Relative to indoor environments, human exposure risk to pesticides on paved surfaces was estimated to be lower, with the highest potential oral and dermal exposure predicted to be 38 ng day -1 for permethrin. The ubiquitous detection of pesticides on residential outdoor surfaces and the fact that the exterior concentrations did not correlate to the indoor areas highlight the necessity to measure pesticides in both indoor and outdoor areas for complete residential pesticide risk assessment.

During soil fumigation, it is ideal to mitigate soil fumigant emissions, ensure pest control efficacy, and speed up the recovery of the soil microorganism population established postapplication. However, no current fumigant emission reduction strategy can meet all these requirements. In the present study, replicated soil columns were used to study the effect of biochar derived from rice husk (BR) and green waste (BG) applied to the soil surface on 1,3-dichloropropene (1,3-D) and chloropicrin (CP) emissions and soil gas distribution, and on microorganism population re-establishment. Relative to fumigated bare soil (no emission reduction strategy), high-density polyethylene (HDPE), and ammonium thiosulfate (ATS) treatments, BR gave dramatic emission reductions for both fumigants with no obvious emission peak, whereas BG was very effective only for 1,3-D. With BR application, the concentration of fumigant in the soil gas was higher than in the bare soil and ATS treatment. After the soil column experiment, mixing the BR with the fumigated soil resulted in higher soil respiration rates than were observed for HDPE and ATS treatments. Therefore, biochar amendment to the soil surface may be an effective strategy for fumigant emission reduction and the recovery of soil microorganism populations established postapplication.

Many pesticides have been identified as endocrine-disrupting chemicals (EDCs) due to their ability to bind sex-steroid hormone receptors. However, little attention has been paid to the ability of pesticides to interfere with other steroid hormone receptors such as glucocorticoid receptor (GR) that plays a critical role in metabolic, endocrine, immune, and nervous systems. In this study, the glucocorticoidic and antiglucocorticoidic effects of 34 pesticides on human GR were investigated using luciferase reporter gene assay. Surprisingly, none of the test chemicals showed GR agonistic activity, but 12 chemicals exhibited apparent antagonistic effects. Bifenthrin, λ-cyhalothrin, cypermethrin, resmethrin, o,p'-DDT, p,p'-DDT, methoxychlor, ethiofencarb, and tolylfluanid showed remarkable GR antagonistic properties with RIC20 values lower than 10(-6) M. The disruption of glucocorticoid-responsive genes in H4IIE and J774A.1 cells was further evaluated on these 12 GR antagonists. In H4IIEcells, four organochlorine insecticides, bifenthrin, and 3-PBA decreased cortisol-induced PEPCK gene expression, while o,p'-DDT and methoxychlor inhibited cortisol-stimulated Arg and TAT gene expression. Cypermethrin and tolyfluanid attenuated cortisol-induced TAT expression. In J774A.1 cells, λ-cyhalothrin, resmethrin, 3-PBA, o,p'-DDT, p,p'-DDT, p,p'-DDE, methoxychlor- and tolylfluanid-reduced cortisol-stimulated GILZ expression. Furthermore, molecular docking simulation indicated that different interactions may stabilize the binding between molecules and GR. Our findings suggest that comprehensive screening and evaluation of GR antagonists and agonists should be considered to better understand the health and ecological risks of man-made chemicals such as pesticides.

Phthalate esters (PAEs) are large-volume chemicals and are found ubiquitously in soil as a result of widespread plasticulture and waste disposal. Food plants such as vegetables may take up and accumulate PAEs from soil, potentially imposing human health risks through dietary intake. In this study, we carried out a cultivation study using lettuce, strawberry, and carrot plants to determine the potential of plant uptake, translocation, and metabolism of di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) and their primary metabolites mono-n-butyl phthalate (MnBP) and mono(2-ethylhexyl) phthalate (MEHP). All four compounds were detected in the plant tissues, with the bioconcentration factors (BCFs) ranging from 0.16 ± 0.01 to 4.78 ± 0.59. However, the test compounds were poorly translocated from roots to leaves, with a translocation factor below 1. Further, PAEs were readily transformed to their monoesters following uptake. Incubation of PAEs and monoalkyl phthalate esters (MPEs) in carrot cell culture showed that DnBP was hydrolyzed more rapidly than DEHP, while the monoesters were transformed more quickly than their parent precursors. Given the extensive metabolism of PAEs to monoesters in both whole plants and plant cells, metabolism intermediates such as MPEs should be considered when assessing human exposure via dietary intake of food produced from PAE-contaminated soils.

Hydroxylated polybrominated diphenyl ethers (HO-PBDEs) are emerging endocrine-disrupting compounds that are widely present in the marine environment. The origin of HO-PBDEs is generally attributed to metabolism of PBDEs and natural production in the environment. However, it is unclear how HO-PBDEs are produced naturally. Here we report the formation of HO-PBDEs from simple bromophenols (BPs) [e.g., 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP)] under the catalysis of bromoperoxidase (BPO) isolated from the common marine red alga Corallina officinalis. Experiments at room temperature showed that BPO readily catalyzes the conversion of 2,4-DBP and 2,4,6-TBP to HO-PBDEs in the presence of Br(-) and H2O2. From analysis of the original forms and their corresponding methylated derivatives, the reaction products were tentatively identified as 2'-HO-BDE-121 and 4'-HO-BDE-121. The formation of HO-PBDEs was likely resulted from the coupling of bromophenoxy radicals generated by the oxidation of BPs via BPO-mediated processes. The presence of Br(-) in the reaction favored the conversion. The production of HO-PBDEs was found to be pH-dependent, and a higher yield was obtained at pH 6.5. In view of the abundance of BPs and C. officinalis in the marine environment, bioconversion of BPs mediated by BPO may be a potential route for the natural production of HO-PBDEs.

Global water shortage is placing an unprecedented pressure on water supplies. Treated wastewater is a valuable water resource, but its reuse for agricultural irrigation faces a roadblock: the public concern over the potential accumulation of contaminants of emerging concern (CECs) into human diet. In the present study, we measured the levels of 19 commonly occurring pharmaceutical and personal care products (PPCPs) in 8 vegetables irrigated with treated wastewater under field conditions. Tertiary treated wastewater without or with a fortification of each PPCP at 250 ng/L, was used to irrigate crops until harvest. Plant samples at premature and mature stages were collected. Analysis of edible tissues showed a detection frequency of 64% and 91% in all vegetables from the treated wastewater and fortified water treatments, respectively. The edible samples from the two treatments contained the same PPCPs, including caffeine, meprobamate, primidone, DEET, carbamazepine, dilantin, naproxen, and triclosan. The total concentrations of PPCPs detected in edible tissues from the treated wastewater and fortified irrigation treatments were in the range of 0.01-3.87 and 0.15-7.3 ng/g (dry weight), respectively. Annual exposure of PPCPs from the consumption of mature vegetables irrigated with the fortified water was estimated to be only 3.69 μg per capita. Results from the present study showed that the accumulation of PPCPs in vegetables irrigated with treated wastewater was likely limited under field conditions.

Many cases of severe environmental contamination arise from historical episodes, where recalcitrant contaminants have resided in the environment for a prolonged time, leading to potentially decreased bioavailability. Use of bioavailable concentrations over bulk chemical levels improves risk assessment and may play a critical role in determining the need for remediation or assessing the effectiveness of risk mitigation operations. In this study, we applied the principle of isotope dilution to quantify bioaccessibility of legacy contaminants DDT and PCBs in marine sediments from a Superfund site. After addition of 13C or deuterated analogues to a sediment sample, the isotope dilution reached a steady state within 24 h of mixing. At the steady state, the accessible fraction (E) derived by the isotope dilution method (IDM) ranged from 0.28 to 0.89 and was substantially smaller than 1 for most compounds, indicating reduced availability of the extensively aged residues. A strong linear relationship (R2=0.86) was found between E and the sum of rapid (Fr) and slow (Fs) desorption fractions determined by sequential Tenax desorption. The IDM-derived accessible concentration (Ce) was further shown to correlate closely with tissue residue in the marine benthic polychaete Neanthes arenaceodentata exposed in the same sediments. As shown in this study, the IDM approach involves only a few simple steps and may be readily adopted in laboratories equipped with mass spectrometers. This novel method is expected to be especially useful for historically contaminated sediments or soils, for which contaminant bioavailability may have changed significantly due to aging and other sequestration processes.

Nonylphenol (NP), a well-known environmental estrogen with numerous isomers, is frequently found in surface water and sediments. Recent studies showed that NP isomers exhibited different estrogenicity. However, at present little information is available on its isomer-specific degradation in the bed sediment, which is the primary sink of NP in surface aquatic systems. In this study, we investigated the biodegradability of 19 NP isomers in two river sediments under oxic and anoxic conditions. Under oxic conditions, the half-lives of NP isomers in an upper river sediment ranged from 0.9 to 13.2 d. Under reduced conditions, the persistence of NP isomers generally increased, with negligible dissipation under strongly reduced conditions. In the well-aerated sediment, NP isomers with short side chain and/or bulky α-substituents were found to be more recalcitrant to degradation. Moreover, when a total of 57 molecular descriptors were examined, the degree of branching as quantified by IDWbar was found to result in the best linear correlation with half-lives of NP isomers (R(2) = 0.88). These results indicated that the isomer-specificity of NP in environmental processes should be considered, and that simple molecular descriptors may be used to identify the more recalcitrant isomers, thus allowing prioritization in the evaluation of environmental fate and risks of NP isomers.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are of significant concern because of their enhanced toxicological effects compared to PBDEs. Research to date has attributed the origin of OH-PBDEs to biological metabolism of PBDEs and natural production in the environment. However, it is unclear how OH-PBDEs are formed naturally. In this study, we explored the formation of OH-PBDEs via the oxidative transformation of simple bromophenols (BPs, e.g., 4-BP, 2,4-DBP, and 2,4,6-TBP) by birnessite (δ-MnO2). Results showed that OH-PBDEs were readily produced by δ-MnO2 with BPs as precursors. For example, oxidation of 2,4-DBP by δ-MnO2 yielded 2'-OH-BDE-68 and 2',5'-OH-BDE-25. Other OH-PBDEs, such as 6-OH-BDE-13, 2',5'-OH-BDE-3, 4'-OH-BDE-121, and 2',5'-OH-BDE-69, were detected from the reaction with 4-BP and 2,4,6-TBP. The formation of OH-PBDEs likely resulted from the oxidative coupling of bromophenoxy radicals. Mild acidic conditions enhanced while coexisting cations (e.g., Na(+), Mg(2+), and Ca(2+)) suppressed the transformation. Given the ubiquity of BPs and δ-MnO2, oxidation of BPs by δ-MnO2 and other metal oxides is likely an abiotic route for the formation of OH-PBDEs in the environment.

Chiral insecticide paichongding (IPP) is one of the prospective substitutes for imidacloprid used in China due to its higher activity against imidacloprid-resistant insects. However, little is known about the fate of IPP in soils, including especially the different behaviors among its stereoisomers. In this study, four stereoisomers of IPP were separated and applied in flooded soils. Kinetics of mineralization, extractable residues, and bound residues showed diastereoselectivity in IPP degradation, with enantiomers (5S,7R)-IPP (IPP-SR) and (5R,7S)-IPP (IPP-RS) being more readily mineralized and preferentially bound to soils than enantiomers (5R,7R)-IPP (IPP-RR) and (5S,7S)-IPP (IPP-SS). The overall mineralization was rather limited and did not exceed 4% of the spiked rate. Concurrent to the decreases of extractable residues, the fraction of bound residues increased with time and reached about 34% of the applied radioactivity for (14)C-IPP-SR and (14)C-IPP-RS as compared to about 23% for (14)C-IPP-RR or (14)C-IPP-SS. Soil properties such as organic matter content and pH likely contributed to the variability. Relatively rapid formation of bound residue suggests that IPP may be quickly detoxified in flooded paddy soil, decreasing the potential for off-site transport such as leaching or runoff, especially for enantiomers IPP-SR and IPP-RS.

Solid-phase microextraction (SPME) is a biomimetic tool ideally suited for measuring bioavailability of hydrophobic organic compounds (HOCs) in sediment and soil matrices. However, conventional SPME sampling requires the attainment of equilibrium between the fiber and sample matrix, which may take weeks or months, greatly limiting its applicability. In this study, we explored the preloading of polydimethylsiloxane fiber with stable isotope labeled analogs (SI-SPME) to circumvent the need for long sampling time, and evaluated the performance of SI-SPME against the conventional equilibrium SPME (Eq-SPME) using a range of sediments and conditions. Desorption of stable isotope-labeled analogs and absorption of PCB-52, PCB-153, bifenthrin and cis-permethrin were isotropic, validating the assumption for SI-SPME. Highly reproducible preloading was achieved using acetone-water (1:4, v/v) as the carrier. Compared to Eq-SPME that required weeks or even months, the fiber concentrations (Cf) under equilibrium could be reliably estimated by SI-SPME in 1 day under agitated conditions or 20 days under static conditions in spiked sediments. The Cf values predicted by SI-SPME were statistically identical to those determined by Eq-SPME. The SI-SPME method was further applied successfully to field sediments contaminated with PCB 52, PCB 153, and bifenthrin. The increasing availability of stable isotope labeled standards and mass spectrometry nowadays makes SI-SPME highly feasible, allowing the use of SPME under nonequilibrium conditions with much shorter or flexible sampling time.

The antiepileptic drug carbamazepine (CBZ) is one of the most frequently detected human pharmaceuticals in wastewater effluents and biosolids. Soil is a primary environmental compartment receiving CBZ through wastewater irrigation and biosolid application. In this study, we explored the transformation of CBZ to biologically active intermediates in soil. Both (14)C labeling and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were used to track transformation kinetics and identify major degradation intermediates. Through 120 days of incubation under aerobic conditions, mineralization of CBZ did not exceed 2% of the spiked rate in different soils. Amendment of biosolids further suppressed mineralization. The fraction of non-extractable (i.e., bound) residue also remained negligible (<5%). On the other hand, CBZ was transformed to a range of degradation intermediates, including 10,11-dihydro-10-hydroxycarbamazepine, carbamazepine-10,11-epoxide, acridone-N-carbaldehyde, 4-aldehyde-9-acridone, and acridine, of which acridone-N-carbaldehyde was formed in a large fraction and appeared to be recalcitrant to further degradation. Electrocyclization, ring cleavage, hydrogen shift, carbonylation, and decarbonylation contributed to CBZ transformative reactions in soil, producing biologically active products. The persistence of the parent compound and formation of incomplete intermediates suggest that CBZ has a high risk for off-site transport from soil, such as accumulation into plants and contamination of groundwater.

Pesticides such as pyrethroids have been frequently found in runoff water from urban areas and the offsite movement is a significant cause for aquatic toxicities in urban streams and estuaries. To better understand the origination of pesticide residues in urban runoff, we investigated the association of pyrethroid residues with loose particles in runoff water from concrete surfaces after treatment with commercial products of bifenthrin and permethrin. In runoff water generated from simulated precipitations after 1 to 89 d exposure under dry outdoor conditions, over 80% of the pesticides was found on particles >0.7 μm for most treatments. The solid-water partitioning coefficient (K(d)) on day 1 was estimated to be 2.4 × 10(3) to 1.1 × 10(5) L/kg for permethrin and bifenthrin on these solids. Except for solid formulations, the pesticide-laden particles likely originated from dust particles preexisting on the concrete before treatment and the disintegration of the surficial concrete matter through weathering. We consequently tested a simple sponge-wipe method to collect and analyze the loose particles on concrete. Concurrent analyses (n = 30) showed an excellent linear correlation between the amount of pesticides transferrable to runoff water and that on the wipe (R(2) = 0.78, slope = 1.13 ± 0.11, P < 0.0001). The fact that the linear relationship has a slope close to 1.0 suggests that this method may be used to predict pesticide residues available for contaminating runoff water before runoff actually occurs. The importance of loose particles should be considered when developing practices to mitigate pesticide runoff contamination from urban residential areas.

Insecticides are commonly used around homes for controlling insects such as ants, termites, and spiders. Such uses have been linked to pesticide contamination and toxicity in urban aquatic ecosystems. Fipronil is a relatively new and popular urban-use insecticide that has acute toxicity to arthropods at low-ppb levels. In this study, we collected runoff water from 6 large communities, each consisting of 152 to 460 single-family homes, in Sacramento County and Orange County, California, and evaluated the occurrence of fipronil and its biologically active derivatives over 26 months under dry weather conditions. Statistical modeling showed that the levels of fipronil and derivatives in the runoff water were both spatially and temporally correlated. More than 10-fold differences were observed between the Sacramento and Orange County sites, with the much higher levels for Orange County (southern California) coinciding with heavier use. The median concentrations of combined fipronil and derivatives for the Orange County sites were 204-440 ng L(-1), with the 90th percentile levels ranging from 340 to 1170 ng L(-1). These levels frequently exceeded the LC50 values for arthropods such as mysid shrimp and grass shrimp. The highest levels occurred from April to October, while decreases were seen from October to December and from January to March, likely reflecting seasonal use patterns and the effect of rain-induced washoff. Fipronil and fipronil sulfone (oxidation derivative) each accounted for about 35% of the total concentrations, with desulfinyl fipronil (a photolytic product) contributing about 25%. Results of this study clearly established residential drainage as a direct source for pesticide contamination in urban waterways, and for the first time, identified fipronil as a new and widespread contaminant with potential ecotoxicological significance.

Polybrominated diphenyl ethers (PBDEs) are a class of widely used brominated flame retardants with strong hydrophobicity. Due to their strong affinity for organic matter, accurate measurement of adsorption coefficients for PBDEs using conventional batch methods can be confounded by biases caused by their sorption to dissolved organic carbon (DOC). In this study, sorption isotherms were constructed for BDE-47 and BDE-99 in sediments by using different methods to measure the aqueous phase concentration Cw. Upon centrifugation, Cw measured by automated solid-phase microextraction (Cw-SPME) was consistently smaller than by liquid-liquid extraction (Cw-LLE), suggesting substantial association of PBDEs with DOC. Significant underestimations (1.2-106-fold) of sediment-water partition coefficient Kd occurred when Cw was measured by LLE. The log KDOC values derived from the SPME measurements ranged from 5.10 to 8.02 for eight congeners from BDE-28 to BDE-183, suggesting a strong tendency for PBDEs to complex with DOC. This study showed that PBDE congeners have larger sorption coefficients than would be measured by the conventional method. The high affinity to DOC also means a potential for DOC-facilitated transport, thus enhancing the environmental mobility of PBDEs.

Use of pesticides around residential homes is linked to contamination of urban waterways, where impervious surfaces like concrete are considered as sources or facilitators of the contamination. However, the fate of pesticides on urban hard surfaces is poorly understood. We characterized sorption and desorption of permethrin, the most used pyrethroid insecticide, on concrete surfaces, to understand its availability for contaminating runoff water. Sorption of (14)C-permethrin to concrete was rapid, and the sorption isotherm was linear, with surface area-normalized K(d) of 1.91 ± 0.1 mL/cm(2). When small permethrin-treated concrete cubes (14 × 14 × 8 mm) were subjected to 300 h sequential desorption, both the parent compound and total (14)C showed an initial rapid desorption, followed by prolonged slow desorption. Meanwhile, permethrin became more resistant to desorption as the pesticide contact time on the concrete increased. When desorption was performed 1 and 7 d after the treatment, the desorbed permethrin after 300 h was 34.1 ± 3.2% and 23.7 ± 1.1% of the spiked amount, respectively, as compared to 56.2 ± 6.1% for the freshly spiked samples. The decreased desorption was partially attributed to permethrin decomposition on the alkaline concrete. However, even after 300 h, over 20% of the applied (14)C still remained in the concrete. Therefore, when pesticide-treated concrete surfaces come in contact with runoff water, elevated concentrations may be expected initially, while the extended desorption implies a potential for sustained contamination.

Despite their strong hydrophobicity, recent studies showed widespread occurrence of pyrethroid in downstream surface waters bodies. In this work, the effect of dissolved organic carbon (DOC) on the sorption and desorption of pyrethroids in sediment was evaluated to understand the role of DOC in facilitating pyrethroid transport. Presence of DOC from three sources at 38 ± 2 mg L⁻¹ in the aqueous phase decreased pesticide sorption to a sediment by 1.7 to 38.9 times and increased their desorption by 1.2 to 41.4 times. The effect on pyrethroid sorption to the sediment was linear. In addition, interactions between DOC and pyrethroids, when taking place prior to the contact with sediment, decreased sorption of some pyrethroids even further, implying that DOC-pyrethroid complexs were relatively stable in solution. DOC sources with higher contents of carboxylic and phenolic groups were found to have a higher potential to associate with pyrethroids. The DOC-water partition coefficients (K(DOC)) obtained by solid-phase microextraction measurement were significantly correlated (P < 0.01) with K(d) values measured for the sediment. These results provide evidence that DOC increases the distribution of pyrethroids from the sediment to the solution phase and plays an important role in mobilizing pyrethroids in runoff and surface streams.

Pirimiphos-methyl (PMM) is a widely used pesticide that can be released into the atmosphere in the gas phase and the condensed phase. The reaction of suspended PMM particles with ozone is investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a scanning mobility particle sizer (SMPS). The reactions are conducted in an 180 L reaction chamber. The identification of particulate products detected with VUV-ATOFMS is proposed on the basis of GC-MS analysis of PMM ozonation products in methylene dichloride solution. The heterogeneous reactive rate constant of PMM with azelaic acid as matrix under room temperature (293 +/- 2 K) is (1.97 +/- 0.25) x 10(-17) cm(3) molecules(-1) s(-1). The corresponding lifetime at 100 ppbv of ozone is 5.2 +/- 0.66 h, and the reactive uptake coefficient (gamma) for ozone on PMM particles is (8.5 +/- 1.1) x 10(-4). Additionally, ozonation of PMM vapor is conducted, and the rapid formation of secondary organic aerosol (SOA) is observed in the homogeneous ozonation of gas-phase PMM. The experimental results indicate that ozone is an important atmospheric oxidant for the transformation of PMM in the atmosphere.

Birnessite (delta-MnO2) is a naturally occurring soil and sediment component that has been shown to oxidize organic compounds containing phenolic or aniline moieties. In this study, for the first time we explored the oxidation reaction of tetrabromobisphenol A (TBBPA), the most heavily used brominated flame retardant, with MnO2. TBBPA rapidly dissipated from the reaction solution and the process was accompanied by the dissolution of Mn2+. Dissipation of 50% of TBBPA occurred in less than 5 min in a system (pH 4.5) containing 625 microM MnO2 and 3.50 microM TBBPA at 21 degrees C, and the removal further increased to as high as 90% when the reaction was prolonged to 60 min. Analysis of initial reaction kinetics showed that the reaction orders with respect to TBBPA, MnO2, and H+ were 1.0, 0.8, and 0.25, respectively. Higher initial concentrations of TBBPA and MnO2 both enhanced the reaction. In addition, reaction rates increased as pH decreased. A retarded first-order model was found to closely describe the long-term reaction kinetics (R2 > or = 0.99), from which initial half-lives of TBBPA under different reaction conditions were estimated. A total of 7 reaction products were identified and a tentative reaction scheme was proposed. This study suggests that oxidative transformation of TBBPA by MnO2 may play an important role in the natural attenuation of TBBPA. The reaction may be further optimized for treatment of TBBPA-containing wastewater or remediation of TBBPA-polluted environmental matrices.

Hydrophobic contaminants partition between water and sorbent phases such as dissolved organic matter (DOM) in environmental matrices. Consideration of bioavailability increasingly requires the measurement of freely dissolved concentration (Cfree) in addition to the total chemical concentration (Ctotal). However, current practices require the use of separate methods and samples to derive Cfee and Ctotal, and no method affords simultaneous measurementof both concentrations. We employed a method by coupling solid-phase microextraction (SPME) with the use of an isotope-labeled internal standard and gas chromatography-mass spectrometer (GC-MS) for detection. The method was demonstrated using 8 pyrethroids as model compounds and 13C-cis-permethrin as the labeled internal standard. Analysis of 4 spiked sediment porewater and 4 field-contaminated samples showed that Ctotal obtained by this method was in close agreementwith the spiked concentrations or the total concentrations measured after whole-sample solvent extraction, while Cfree was only a small fraction of Ctotal, suggesting pronounced association of these compounds with DOM. The method displayed good reproducibility with average relative standard deviation <20%, and high sensitivity with method detection limits in the range of 1-5 ng L(-1). The method uses a small sample volume (<20 mL, as opposed to 1 L for conventional analysis), and is solventless and fast. The concurrent measurements also allow for estimation of K(DOC), a key parameter that is difficult to derive otherwise. The simultaneous determination of Cfree and Ctotal provides information for better relating chemical concentrations with potential ecotoxicological effects.

Pollutants in agricultural irrigation return flow (tailwater) constitute a significant nonpoint source of pollution in intensive agricultural regions such as the Central Valley of California. Constructed wetlands (CWs) represent a feasible mitigation option to remove pollutants including pesticides in the tailwater. In this study, we evaluated two CWs in the Central Valley for their performance in removing pyrethroid and organophosphate insecticides under field-scale production conditions. Both CWs were found to be highly effective in reducing pyrethroid concentrations in the tailwater, with season-average concentration reductions ranging from 52 to 94%. The wetlands also reduced the flow volume by 68-87%, through percolation and evapotranspiration. When both concentration and volume reductions were considered, the season-average removal of pyrethroids ranged from 95 to 100%. The primary mechanism for pyrethroid removal was through sedimentation of pesticide-laden particles, which was influenced by hydraulic residence time and vegetation density. Temporal analysis indicates a potential efficiency threshold during high flow periods. The season-average removal of chlorpyrifos ranged 52-61%. The wetlands, however, were less effective at removing diazinon, likely due to its limited sorption to sediment particles. Analysis of pesticide partitioning showed that pyrethroids were enriched on suspended particles in the tailwater. Monitoring of pesticide association with suspended solids and bed sediments suggested an increased affinity of pyrethroids for lighter particles with the potential to move further downstream before subject to sedimentation. Results from this study show that flow-through CWs, when properly designed, are an effective practice for mitigating hydrophobic pesticides in the irrigation tailwater.

Microbial degradation is the most important removal process for hydrophobic organic compounds (HOCs) in soil or sediment, and chemical availability is often a governing factor. However, the availability of HOCs in the sorbed forms is still a topic of debate. In this study, we applied rigorous kinetics analysis to the relationship between the freely dissolved concentration (Cfree) of phenanthrene (PHE) measured by polydimethylsiloxane (PDMS) fibers and its degradation by a PAH degrading bacterium PYR-1 under a range of soil conditions. In solutions of soils with varying organic carbon (OC) contents, Cfree of PHE decreased from 28.63 +/- 2.15 to 0.79 +/- 0.04 microg L(-1) when the soil OC content changed from 0.23 to 7.1%. Correlation analysis between Cfree and PHE mineralization rates revealed that the bacterium quickly exhausted the PHE pool available for equilibrium distribution, including Cfree and the reversibly sorbed fraction, after which the sequestered pool was utilized. In addition, unlike changes in Cfree, degradation rates of total PHE only varied by a factor of 1.6-2.1 over the same soil OC range. Regression analysis using a multivariate relationship showed that soil OC content and porosity properties such as soil surface area had a compounded effect on the microbial availability of PHE in these soils. The kinetics analysis using Cfree, as proposed in this study, may be applied to other HOCs to gain a better understanding of microbial availability under various conditions.

Availability is an important factor regulating the fate and toxic effects of hydrophobic organic compounds (HOCs) in soil and sediment. Many methods have been proposed for measuring HOC availability, but ambiguity exists in the selection of methods or method conditions. In this study, using pyrethroid insecticides as model HOCs, we measured their desorption kinetics from black carbon (BC)-amended sediments and used comprehensive statistical analysis to understand the dependence of the derived parameters on desorption intervals. Fitting of data from Tenax-aided depletive desorption to a three-phase model gave estimates of 11-13, 28-33, and 57-60% pyrethroid distribution in the rapid (F(rapid)), slow (F(s)), and very slow (F(vs)) desorption fractions, respectively. The desorbed fraction after 24 h, or F(24h), essentially equaled to F(rapid), while the desorbed fraction after 6 h (F(6h)) was only about half of F(rapid), suggesting that the practice of using F(6h) in lieu of F(rapid) would lead to inaccurate assessment of availability. In contrast, Pearson correlation coefficients for the desorbed fractions and uptake into polydimethylsiloxane (PDMS) fibers decreased with increasing desorption intervals, with F(6h) giving the most agreeable measurements. Therefore, while F(rapid) estimated from depletive desorption reflects the total chemical accessibility, desorbed fractions after short intervals likely provide a measure for the immediate availability, much like PDMS fibers. The use of desorbed fractions after short intervals (e.g., F(6h)) to approximate F(rapid) may give estimates substantially different from F(rapid) and therefore should be avoided.

The prevalent use of soil fumigants has resulted in air pollution in some agricultural regions. Our previous research showed that application of thiosulfate fertilizers at the soil surface may offer an effective and economical approach to reduce the emission of halogenated fumigants via a chemical remediation process. In this fumigant emission-reduction strategy, volatile 1,3-dichloropropene (1,3-D) reacts with thiosulfate to generate a nonvolatile Bunte salt (thiosulfate derivative of 1,3-D). However, the decomposition of the Bunte salt may be associated with the production of perceptible odors. This study investigated the stability of this reaction product in different environmental media. Hydrolysis experiments demonstrated that the thiosulfate derivative was relatively stable in neutral and moderately acidic aqueous solutions. In contrast, the thiosulfate derivative was readily converted to a dialkyl disulfide via a base hydrolysis process in pH 10 buffer solution. In a strongly acidic solution, a mercaptan and a dialkyl disulfide compound were detected as two primary hydrolysis products. In soil, this initial reaction product underwent a series of biotic conversions to generate several volatile or semivolatile organic sulfur compounds. The formation and distribution of four volatile/semivolatile products in the air and soil were detected in different soils treated with the thiosulfate derivative of 1,3-D. This study indicated that odors occurring in soil treated with halogenated fumigants and thiosulfate fertilizers might arise from the generation and release of these and other volatile/semivolatile organic sulfur products. The environmental fate and effects of such volatile/semivolatile sulfur compounds should be considered in the application of sulfur-containing fertilizers in fumigated fields.

Despite the fact that the biological processes of chiral compounds are enantioselective, the endocrine disruption activity and uptake of chiral contaminants with respect to enantioselectivity has so far received limited research. In this study, the estrogenic potential and uptake of the enantiomers of a newer pyrethroid insecticide, bifenthrin (BF), were investigated. Significant differences in estrogenic potential were observed between the two enantiomers in the in vitro human breast carcinoma MCF-7 cell proliferation assay (i.e., the E-SCREEN assay) and the in vivo aquatic vertebrate vitellogenin enzyme-linked immunosorbent assay (ELISA). In the E-SCREEN assay, the relative proliferative effect ratios of 1S-cis-BF and 1R-cis-BF were 74.2% and 20.9%, respectively, and the relative proliferative potency ratios were 10% and 1%, respectively. The cell proliferation induced by the two BF enantiomers may be through the classical estrogen response pathway via the estrogen receptor (ER), as the proliferation induced by the enantiomers could be completely blocked when combined with 10-6 mol/L of the ER antagonist ICI 182,780. Measurement of vitellogenin induction in Japanese medaka (Oryzias latipes) showed that, at an exposure level of 10 ng/mL, the response to 1S-cis-BF was about 123 times greater than thattothe Renantiomer. Significant selectivity also occurred in the uptake of BF enantiomers in the liver and other tissues of J. medaka. These results together suggest that assessment of the environmental safety of chiral insecticides should consider enantioselectivity in acute and chronic ecotoxicities such as endocrine disruption.

Many important environmental pollutants are strongly adsorbing hydrophobic compounds. Because of their potential to adsorb to dissolved organic matter (DOM), their partition coefficient Kd may be underestimated by the conventional approach due to incomplete phase separation. In this study, solid-phase microextraction (SPME) was compared with liquid-liquid partition (LLP) for measuring Kd of bifenthrin and permethrin isomers on sediments. Due to its selective detection of the freely dissolved concentration, SPME gave Kd values 0.6-4.4-fold greater than those obtained by LLP in creek and field sediments and 3.6-21.7-fold greater in nursery runoff sediments. Underestimation by the conventional method was attributed to adsorption to DOM that was not excluded from the aqueous phase by centrifugation. The degree of underestimation was dependent on the source and amount of DOM and may be generally significant for compounds that have DOM adsorption coefficient (KDOM) > 10(4). This study provides evidence that the existing Kd values for many hydrophobic pollutants may be underestimated, and SPME may be a viable, efficacious tool for evaluating the underestimation.

Recent monitoring shows that the majority of urban streams in the United States are contaminated by pesticide residues, and the contamination is mainly due to runoff from residential landscapes. In this study we evaluated the effect of landscape planting on persistence of the herbicides 2,4-D and dicamba in soil under laboratory conditions. The herbicides exhibited substantially different persistence in the same soil type that had been subjected to different planting practices for about 6 years. In the 0-10 cm surface layer, the half-life of 2,4-D was 30.7 d in soil under trees, which was about 20 times longer than in soil planted with turf grass (1.6 d). The difference in 2,4-D persistence was closely correlated to the number of 2,4-D-degrading bacteria that had evolved in the soils. The half-life of dicamba was much longer in soil under a tree canopy (149 d) than in mulched soil (7.9 d). The rate of dicamba degradation was proportional to soil organic matter content. This study indicates that planting practices can modify soil chemical properties and microbial activity and may further affect pesticide runoff potential by influencing pesticide degradation. Characterizing pesticide behavior as a function of planting covers may improve our understanding of pesticide runoff in urban environments and also help to identify strategies for minimizing pesticide contamination to urban streams.

Plastic tarps currently used during soil fumigation to control emissions have been shown to be permeable to fumigant vapors, resulting in appreciable losses to the atmosphere. New low-permeability films are being developed to reduce fumigant emissions and increase efficacy. A rapid, reliable, and sensitive method is required to measure the permeability of various films that may be used in new management practices. This manuscript presents an approach for estimating the mass transfer coefficient (h) of fumigant compounds across agricultural films. The h is a measure of the resistance to diffusion which, unlike other measures of permeability, is a property of the film-chemical combination and independent of the concentration gradient across the film. This method uses static sealed cells; fumigant vapor is spiked to one side of the film and the concentrations on both sides of the film are monitored until equilibrium. An analytical model is fitted to the data to obtain h. This model relies on a mass balance approach and includes sorption to and diffusion across the film membrane. The method was tested using two polyethylene films and a very low-permeability film and showed that the method produces a sensitive and reproducible measure of film permeability.