High-performance plastic-derived metal-free catalysts for organic pollutants degradation via Fenton-like reaction.

The preparation of waste plastics-derived catalysts is an effective strategy for the waste reclamation. However, plastic-derived material is unsuitable for wastewater purification due to its small specific surface area (SSA) and inadequate active sites (such as N/O sites). Herein, we synthesized graphene-like nanosheets using g-C3N4 as the self-sacrificing soft template and plastic as the carbon precursor. Consequently, this strategy greatly promoted the efficiencies of the emerging organic pollutants degradation with the SSA and N content of the plastic-derived biochar increasing up to 1043.4 m2/g and 17.53 at.%, respectively. In detail, 100 % sulfadiazine (SD) removal could be achieved in 180 s via the activation of peroxymonosulfate (PMS) and the catalytic activity is far higher than previous research. Mechanism experiments corroborated that such a striking performance was attributed to the generation of SO4•-, O2•- and 1O2. Meanwhile, kinds of plastic precursors, even medical waste (i.e., masks, gauze, operating caps and degreasing cotton) were also applicable. And the practical application of the plastic-derived catalyst was further demonstrated by treating pollutants in a continuous flow mode with in situ fabricated membrane. This work provides valuable insights into waste plastics processing and water pollutants removal.

o-Semiquinone Radical and o-Benzoquinone Selectively Degrade Aniline Contaminants in the Periodate-Mediated Advanced Oxidation Process.

Advanced oxidation processes (AOPs) often employ strong oxidizing inorganic radicals (e.g., hydroxyl and sulfate radicals) to oxidize contaminants in water treatment. However, the water matrix could scavenge the strong oxidizing radicals, significantly deteriorating the treatment efficiency. Here, we report a periodate/catechol process in which reactive quinone species (RQS) including the o-semiquinone radical (o-SQ•-) and o-benzoquinone (o-Q) were dominant to effectively degrade anilines within 60 s. The second-order reaction rate constants of o-SQ•- and o-Q with aniline were determined to be 1.0 × 108 and 4.0 × 103 M-1 s-1, respectively, at pH 7.0, which accounted for 21% and 79% of the degradation of aniline with a periodate-to-catechol molar ratio of 1:1. The major byproducts were generated via addition or polymerization. The RQS-based process exhibited excellent anti-interference performance in the degradation of aniline-containing contaminants in real water samples in the presence of diverse inorganic ions and organics. Subsequently, we extended the RQS-based process by employing tea extract and dissolved organic matter as catechol replacements as well as metal ions [e.g., Fe(III) or Cu(II)] as periodate replacements, which also exhibited good performance in aniline degradation. This study provides a novel strategy to develop RQS-based AOPs for the highly selective degradation of aniline-containing emerging contaminants.

Molecularly imprinted polymer sheathed mesoporous silica tube as SPME fiber coating for determination of tobacco-specific nitrosamines in water.

Tobacco-specific nitrosamines (TSNAs) are probably carcinogenic disinfection byproducts eliciting health risk concerns. The determination and surveillance of TSNAs in water is still cumbersome due to the lack of advanced sample preparation methods. Herein, we prepared a solid phase microextraction (SPME) fiber coated with the molecularly imprinted polymer (MIP) sheathed mesoporous silica tube (MST) composite material, and developed a highly efficient, selective, and sensitive method for the determination of five TSNAs in water. Benefiting from the TSNAs-specific recognition of MIP and the increased specific surface area derived from MST, the MIP@MST fiber exhibited excellent extraction performance for TSNAs, which was much superior to the commercially available SPME fibers. By coupling to high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), the outstanding analytical merits such as low method detection limits (ranging 0.1-6.7 ng L-1) and good reproducibility (intra-fiber and inter-fiber relative standard deviations ranging 4.1 %-11.6 % and 3.5 %-12.2 %, respectively) were achieved with the consumption of 8 mL water sample and 100 µL methanol solvent in 50 min. The feasibility of the SPME-HPLC-MS/MS method was demonstrated in tap water and chloraminated source water, with relative recoveries for the five TSNAs ranging from 85.2 % to 108.5 %. In result, none of the TSNAs were found in the tap water samples, while 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-Butanol (NNAL) were detected in the chloraminated source water samples. The rapid and convenient SPME-HPLC-MS/MS method developed in this study offers a powerful tool for monitoring TSNAs in water.

Sea-urchin-like covalent organic framework as solid-phase microextraction fiber coating for sensitive detection of trace pyrethroid insecticides in water.

Pyrethroid insecticides residues in water pose a critical threat to the environment from widespread production and overuse. Therefore, it is of major relevance to develop a sensitive and efficient method to detect pyrethroid insecticides in water. In this paper, a covalent organic framework (COF) with NHCO as the structural unit was synthesized using a simple condensation reaction of TTL (NH2) and TDBA (COOH). Various characterization results and density functional theory (DFT) calculations demonstrated that multiple interactions synergistically promoted the adsorption of pyrethroid insecticides on COFTDBA-TTL. Based on the excellent extraction capability of COFTDBA-TTL, efficient detection of 11 pyrethroid insecticides in water was achieved using COFTDBA-TTL-coated SPME fiber and gas chromatography-tandem mass spectrometry (GC-MS). The results showed that the extraction enhancement factors (EFs) of pyrethroid insecticides were as high as 2584-7199, and the extraction efficiencies were 3.28-446 times higher than that of commercial fiber, which reflected its high adsorption property. Meanwhile, the limits of detection (LODs) of the COFTDBA-TTL coated fiber were as low as 0.170-1.68 ng/L under the optimal conditions, and the recoveries of 11 pyrethroid insecticides in the actual water samples were 88.5-108 %. In conclusion, the SPME-GC-MS method based on COFTDBA-TTL coated fiber was simple, rapid, and efficient, and should have a promising application in trace detection of pyrethroid insecticides in the environment.

Recent progress in identification of water disinfection byproducts and opportunities for future research.

Numerous disinfection by-products (DBPs) are formed from reactions between disinfectants and organic/inorganic matter during water disinfection. More than seven hundred DBPs that have been identified in disinfected water, only a fraction of which are regulated by drinking water guidelines, including trihalomethanes, haloacetic acids, bromate, and chlorite. Toxicity assessments have demonstrated that the identified DBPs cannot fully explain the overall toxicity of disinfected water; therefore, the identification of unknown DBPs is an important prerequisite to obtain insights for understanding the adverse effects of drinking water disinfection. Herein, we review the progress in identification of unknown DBPs in the recent five years with classifications of halogenated or nonhalogenated, aliphatic or aromatic, followed by specific halogen groups. The concentration and toxicity data of newly identified DBPs are also included. According to the current advances and existing shortcomings, we envisioned future perspectives in this field.

Reactions of neonicotinoids with peroxydisulfate: The generation of neonicotinoid anion radicals and activation pathway to form sulfate radicals.

To activate persulfate to generate reactive species such as sulfate radical (SO4•-) for micropollutants abatement, external energy or chemicals are often needed. In this study, a novel SO4•- formation pathway was reported during the oxidation of neonicotinoids by peroxydisulfate (S2O82-, PDS) without any other chemical additions. Thiamethoxam (TMX) was used as a representative neonicotinoid and SO4•- was the dominant specie contributing to its degradation during PDS oxidation at neutral pH. TMX anion radical (TMX•-) was found to activate PDS to generate SO4•- with the second-order reaction rate constant determined to be (1.44 ± 0.47)× 106 M-1s-1 at pH 7.0 by using laser flash photolysis. TMX•- was generated from the TMX reactions with superoxide radical (O2•-), which was formed from the hydrolysis of PDS. This indirect PDS activation pathway via anion radicals was also applicable to other neonicotinoids. The formation rates of SO4•- were found to negatively linearly correlated with Egap (LUMO-HOMO). The DFT calculations indicated the energy barrier of anion radicals to activate PDS was greatly reduced compared to the parent neonicotinoids. The pathway of anion radicals' activation of PDS to form SO4•- improved the understanding of PDS oxidation chemistry and provided some guidance to enhance oxidation efficiency in field applications.

Aspartame-Sweetened Tap Water: Transformation Products and 2,6-Dichloro-1,4-Benzoquinone Formation.

Aspartame (APM), a dipeptide of aspartic acid (ASP) and phenylalanine (PHE), is a widely used artificial sweetener in beverages. It is unclear whether residual chlorine in tap water can react with APM to form disinfection byproducts (DBPs). Therefore, we investigated the formation of DBPs from the reaction of APM with residual chlorine in authentic tap water. APM and a commercial sweetener (CS) packet containing APM were studied under authentic and simulated tap water conditions. Eight chlorinated products of APM were detected using solid-phase extraction (SPE) and high performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS). These new chloro-products were tentatively identified based on accurate masses, isotopic patterns of 35,37Cl, and MS/MS spectra. Furthermore, we identified APM as a precursor to 2,6-dichloro-1,4-benzoquinone (DCBQ). DCBQ significantly increased to 2.3-12 ng/L with the addition of APM or CS in tap waters collected from different locations compared to 1.4-1.8 ng/L in the same tap water samples without sweetener. DCBQ and two of the chlorinated transformation products were identified in cold prepared tea containing APM. DCBQ formation was eliminated when the residual chlorine in tap water was reduced by ascorbic acid or boiling prior to the addition of APM or CS. This study found that eight new DBPs and DCBQ were produced by the reactions of residual chlorine with APM and CS. These findings show an unintended exposure source of emerging DBPs via APM sweetened beverages.

Trichloramine and Hydroxyl Radical Contributions to Dichloroacetonitrile Formation Following Breakpoint Chlorination.

Breakpoint chlorination is applied to remove ammonia in water treatment. Trichloramine (NCl3) and transient reactive species can be present, but how they affect the formation of nitrogenous disinfection byproducts is unknown. In this study, the dichloroacetonitrile (DCAN) formation mechanisms and pathways involved during breakpoint chlorination (i.e., free chlorine to ammonia molar ratio ≥2.0) were investigated. DCAN formation during breakpoint chlorination of natural organic matter (NOM) isolates was 14.3-20.3 µg/L, which was 2-10 times that in chlorination without ammonia at similar free chlorine residual conditions (2.1-2.9 mg/L as Cl2). The probe tests and electron paramagnetic resonance spectra supported the presence of •OH, •NO, and NCl3 besides free chlorine in breakpoint chlorination. 15N-labeled ammonium-N tests indicated the incorporation of ammonium-N in DCAN formation though ammonia was eliminated during breakpoint chlorination. Aromatic non-nitrogenous moieties, such as phenols (i.e., none DCAN precursors in the free-chlorine-only system), became DCAN precursors during breakpoint chlorination. The reactions involved in reactive nitrogen species, such as •NO/•NO2 and NCl3, led to additional nitrogen sources in DCAN formation, accounting for 36-84% of total nitrogen sources in DCAN formation from NOM isolates and real water samples. Scavenging •OH by tert-butanol reduced DCAN formation by 40-56%, indicating an important role of •OH in transforming DCAN precursors. This study improves the understanding of breakpoint chlorination chemistry.

Integration of solid phase extraction with HILIC-MS/MS for analysis of free amino acids in source water.

Amino acids (AAs) are prevalent in source water, particularly during spring run-off. Monitoring of amino acids in source water is desirable for water treatment plants (WTP) to indicate changes in source water quality. The objective of this study was to establish analytical procedures for reliable monitoring of amino acids in source water. Therefore, we examined two different methods, large volume inject (LVI) and solid phase extraction (SPE), for sample preparation prior to HILIC-MS/MS. The LVI-HILIC-MS/MS method can provide fast and sensitive detection for clean samples, but suffers from matrix effects, resulting in irreproducible separation and shortening column lifetime. We have demonstrated that SPE was necessary prior to HILIC-MS/MS to achieve reproducible and reliable quantification of AAs in source water. A natural heterocyclic amine 1-methyl-1,2,3,4-tetrahydro-ß-carboline-3-carboxylic acid (MTCCA) was also included in the method to indicate changes in other natural nitrogenous compounds in source water. The SPE-HILIC-MS/MS method was able to achieve limits of detection from 2.6-3400 ng/L for the amino acids and MTCCA with RSDs (n=3) of 1.1%-4.8%. As well, retention times (RT) of the analytes were reproducible with variation less than 0.01 min (n=3) through the entire project. We further applied the SPE-HILIC-MS/MS method to determine AAs in authentic source water samples collected from two drinking water treatment plants (WTPs) during the 2021 spring run-off season. The results support that the SPE-HILIC-MS/MS method does not require derivatization and can provide reliable, accurate, and robust analysis of AAs and MTCCA in source water, supporting future monitoring of source water quality.

Synergistic cytotoxicity of binary combinations of inorganic and organic disinfection byproducts assessed by real-time cell analysis.

Chlorine, chlorine dioxide, and ozone are widely used as disinfectants in drinking water treatments. However, the combined use of different disinfectants can result in the formation of various organic and inorganic disinfection byproducts (DBPs). The toxic interactions, including synergism, addition, and antagonism, among the complex DBPs are still unclear. In this study, we established and verified a real-time cell analysis (RTCA) method for cytotoxicity measurement on Chinese hamster ovary (CHO) cell. Using this convenient and accurate method, we assessed the cytotoxicity of a series of binary combinations consisting of one of the 3 inorganic DBPs (chlorite, chlorate, and bromate) and one of the 32 regulated and emerging organic DBPs. The combination index (CI) of each combination was calculated and evaluated by isobolographic analysis to reflect the toxic interactions. The results confirmed the synergistic effect on cytotoxicity in the binary combinations consisting of chlorite and one of the 5 organic DBPs (2 iodinated DBPs (I-DBPs) and 3 brominated DBPs (Br-DBPs)), chlorate and one of the 4 organic DBPs (3 aromatic DBPs and dibromoacetonitrile), and bromate and one of the 3 organic DBPs (2 I-DBPs and dibromoacetic acid). The possible synergism mechanism of organic DBPs on the inorganic ones may be attributed to the influence of organic DBPs on cell membrane and cell antioxidant system. This study revealed the toxic interactions among organic and inorganic DBPs, and emphasized the latent adverse outcomes in the combined use of different disinfectants.

Unique On-Site Spinning Sampling of Highly Water-Soluble Organics Using Functionalized Monolithic Sorbents.

Water utilities encounter unpredictable odor issues that cannot be explained by routine water parameters during spring runoff, even in the summer and fall. Highly water-soluble organics (e.g., amino acids and saccharides) have been reported to form odorous disinfection byproducts during disinfection, but the lack of simple and practical on-site sampling techniques hampers their routine monitoring at trace levels in source water. Therefore, we have created two functionalized nested-in-sponge silica monoliths (NiS-SMs) using a one-pot synthesis method and demonstrated their application for extracting highly soluble organics in water. The NiS-SMs functionalized with the sulfonic group and phenylboronic moiety selectively extracted amino acids and monosaccharides, respectively. We further developed a spinning sampling technique using the composites and evaluated its robust performance under varying water conditions. The spinning sampling coupled to high-performance liquid chromatography tandem mass spectrometry analysis provided limits of detection for amino acids at 0.038-0.092 ng L-1 and monosaccharides at 0.036-0.14 ng L-1. Using the pre-equilibrium sampling-rate calibration, we demonstrated the applicability of the spinning sampling technique for on-site sampling and monitoring of amino acids and monosaccharides in river water. The new composite materials and rapid on-site sampling technique are unique and efficient tools for monitoring highly soluble organics in water sources.

Formation Mechanism of Iodinated Aromatic Disinfection Byproducts: Acid Catalysis with H2OI.

Iodinated aromatic disinfection byproducts (I-DBPs) are a group of nonregulated but highly toxic DBPs. The formation of I-DBPs is attributed mainly to HOI because it is the most abundant reactive iodine species in chloraminated water. In this study, we used computational modeling of thermodynamics to examine the mechanism of iodination of aromatic contaminants, e.g., dipeptides and phenols. Computational prediction of the energy barriers of the formation of iodinated tyrosylglycine (I-Tyr-Gly) (66.9 kcal mol-1) and hydroxylated Tyr-Gly (OH-Tyr-Gly) (46.0 kcal mol-1) via iodination with HOI favors the formation of OH-Tyr-Gly over I-Tyr-Gly. Unexpectedly, mass spectrometry experiments detected I-Tyr-Gly but not OH-Tyr-Gly, suggesting that I-Tyr-Gly formation cannot be attributed to HOI alone. To clarify this result, we examined the thermodynamic role of the most reactive iodine species H2OI+ in the formation of aromatic I-DBPs under chloramination. Computational modeling of thermodynamic results shows that the formation of a loosely bonded complex of aromatic compounds with H2OI+ is the key step to initiate the iodination process. When H2OI+ serves as an acid catalyst and an iodinating agent, with HOI or H2O acting as a proton acceptor, the energy barrier of I-DBP formation was significantly lower (10.8-13.1 kcal mol-1). Therefore, even with its low concentration, H2OI+ can be involved in the formation of I-DBPs. These results provide insight into the mechanisms of aromatic I-DBP formation and important information for guiding research toward controlling I-DBPs in drinking water.

Remediation of preservative ethylparaben in water using natural sphalerite: Kinetics and mechanisms.

As a typical class of emerging organic contaminants (EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes (such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite (NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the ZnS that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.

When vector control and organic farming intersect: Pesticide residues on rice plants from aerial mosquito sprays.

Conflicts often exist between the use of pesticides for public health protection and organic farming. A prominent example is the use of insecticides for mosquito control in rice fields designated for organic farming. Rice fields, with static water and other conducive conditions, are favorable mosquito habitats. Best management practices are urgently needed to ensure the integrity of organic farming while addressing the need for public health protection. In this study, we evaluated aerial ultra-low-volume (ULV) applications of two classes of mosquito adulticides, pyrethrins and organophosphates, and their deposition and residues on rice plants throughout an active growing season in the Sacramento Valley of California. Frequent applications of pyrethrin synergized with piperonyl butoxide (PBO) and rotating applications of synergized pyrethrins and naled, an organophosphate, were carried out on two large blocks of rice fields. Aerial ULV application of either synergized pyrethrins or naled was able to generate uniform droplets above the fields with high efficacy for mosquito control. Rice leaf samples were collected before and after a subset of applications, and rice grains were sampled at harvest. Frequent applications of synergized pyrethrins resulted in some accumulation of the synergist PBO on rice leaves, but pyrethrins and naled dissipated rapidly from the leaves after each application with no noticeable accumulation over repeated applications. At harvest, no detectable residues of the pesticides or PBO were found in the rice grains. The absence of pesticide residues in the rice grains at harvest suggested that the ULV aerial application led to deposition of only very low levels of residues on rice plants during the growing season. When coupled with the short persistence and/or poor mobility of the insecticides, such applications resulted in negligible pesticide residues in rice grains.

Nontargeted identification and predicted toxicity of new byproducts generated from UV treatment of water containing micropollutant 2-mercaptobenzothiazole.

Comprehensive identification of byproducts including intermediate transformation products (TPs) of micropollutants in source water is challenging and paramount for assessment of drinking water quality and treatment technologies. Here, we have developed a nontargeted analysis strategy coupled with computational toxicity assessment to identify indistinguishable TPs including isomers with large differences in toxicity. The new strategy was applied to study the UV treatment of water containing micropollutant 2-mercaptobenzothiazole (2-MBT), and it enabled successful identification of a total of 22 organic TPs. Particularly, the structures of nine new TPs were identified for the first time; in addition, three isomers (P2, P3, and P4) were distinguished from the toxic contaminant 2-hydroxybenzothiazole (2-OH-BT). Computational assessments indicate that estrogenic activity of the three isomers (P2-P4) is higher than that of 2-OH-BT. Mass balance study shows that the 22 organic products accounted for 70% of the 2-MBT degraded, while 30% may degrade to inorganic products. Most TPs are resistant to UV photolysis. Computational toxicity assessment predicted the TPs to increase inhibition of human thyroperoxidase activity although they have lower aquatic toxicity compared to original 2-MBT. This study emphasizes the importance of monitoring the 2-MBT photodegradation products and the overall toxicity of finished water whose production included a UV light-based treatment process.

Nontargeted Identification of an N-Heterocyclic Compound in Source Water and Wastewater as a Precursor of Multiple Nitrosamines.

N-Nitrosamine disinfection byproducts (DBPs) are a health concern because they are probable human carcinogens. Complex organic nitrogenous compounds, nitrosamine precursors, are largely unidentified in source water. Using stable isotopic labeling-enhanced nontargeted analysis, we identified a natural product N-heterocyclic amine 1-methyl-1,2,3,4-tetrahydro-ß-carboline-3-carboxylic acid (MTCCA) in source water. Interestingly, we discovered that chloramination of MTCCA-containing water could produce four nitrosamines: methylethylnitrosamine, N-nitrosopyrrolidine, N-nitrosoanatabine, and N-nitrosoanabasine. Computational modeling and experimental results helped explain potential pathways of nitrosamines generated from chloramination of MTCCA. Further investigations confirmed widespread occurrence of MTCCA in source water and wastewater. Its concentration ranged from high in upstream creeks (23.2-332.2 ng L-1) to low in the river (5.7-37.6 ng L-1) during the 2020 spring runoffs, indicating that sources of MTCCA came from creeks around farms. Analysis of wastewater before and after ultraviolet, as well as microfiltration with subsequent ozonation treatments, showed increased MTCCA after treatments, demonstrating a difficulty to degrade and remove MTCCA in water. This study discovered the extensive presence of MTCCA in source water and wastewater, suggesting that natural N-heterocyclic compounds may serve as a new source of nitrosamine precursors.

Unraveling the behaviors and significances of waste biomass ashes as underlying emission sources of soil polycyclic aromatic hydrocarbons in Tibetan Plateau.

Domestic consumption of biomass fuels has been found as a leading source of polycyclic aromatic hydrocarbons (PAHs) in pristine regions. The biomass ashes would serve as both source and vector for PAHs, which may threaten residents' health. However, research focusing on the behaviors of waste biomass ashes acting as emission resources of PAHs is still lacking. In present study, occurrence and fate of PAHs released from disposal biomass ashes in the Tibetan Plateau were investigated by evaluating their patterns and levels in soils at different distances from the Lhasa landfill. Concentrations of 16 PAHs averaged at 1009 ng/g dry weight and 103 ng/g dry weight in landfill cover soils and surrounding soils, respectively. The spatial distributions of PAHs evidenced the local source of biomass ashes in landfill, while the fractionations of PAHs in soils profiles emphasized the post-deposal leaching. Since PAH compositions altered significantly during their transport and sequestration, the rectification factors were suggested to adjust the source diagnostic ratios. In study area, the emission flux of PAHs from waste biomass ashes to soils was 0.93 ton/year; extended to the Tibetan Plateau, the flux was estimated to be 13.1-32.5 ton/year. This study confirmed that waste biomass ashes would represent significant contributions of PAH emissions in this pristine region, which might remarkably exacerbate the total emissions of PAHs in Tibet by more than 25%.

In vivo monitoring and exposure potency assessment of phase I metabolism of fenthion in vegetables.

In this study, the phase I metabolism of fenthion was monitored in three common vegetables in different chamber situations via an in vivo solid-phase microextraction method. The phase I metabolic pathways of fenthion were evaluated based on the in vivo monitoring results and their comparisons among the chamber situations. Enzyme catalysis was found to play a basic and dominant role, whereas light catalysis could promote subsequent transformations that were difficult for enzyme catalysis. Moreover, according to the concentrations of the metabolites and their toxicity, the total concentrations and total toxicity weighted concentrations were calculated to reveal actual residual levels. The relative total and weighted exposure potency values were calculated to account for the fact that only the parent pesticide was considered in the diet exposure risk assessment. In result, both total and weighted approaches indicated a much higher exposure risk. Present study uncovered the potential pesticide exposure risk associated with phase I metabolism and highlighted the toxicity weighted approach, both of which more realistically reflect the exposure risk than the parent compound concentration does. In general, this study may facilitate further illustrating the phase I metabolism of ubiquitous agricultural pesticides, and provide a more realistically understanding of their exposure risk.

Sheathed in situ heteroepitaxial growth metal-organic framework probe for detection of polycyclic aromatic hydrocarbons in river water and living fish.

Exploring the presence of polycyclic aromatic hydrocarbons (PAHs) in aquatic environment is an important task. Metal-organic frameworks (MOF) are commonly used as sorbents for enriching PAHs but their crystal synthesis, sorbent preparation and robustness remain challenging. In the present study, under mild conditions, a novel sheathed MOF fiber coating was fabricated via in situ heteroepitaxial growth of copper-2,5-diaminoterephthalate (Cu-DAT) crystals and subsequent polyimide (PI) sheath. The copper hydroxide nanotubes were first synthesized on the copper wire to provide a substrate for further in situ heteroepitaxial Cu-DAT growth, and the coating was then sheathed with PI via a simple dip-coating procedure. The well-ranged copper hydroxide nanotubes, the unique adsorption property of Cu-DAT, and the PI sheath, the prepared fiber all contributed to a successful solid-phase microextraction (SPME) device for detecting PAHs. Results demonstrated that the SPME methods using the novel fiber possessed great sensitivity, wide linear range, good reproducibility, and the robustness was significantly improved with PI sheath. The novel SPME material was successfully applied for detection of PAHs in river water samples and in vivo detection of PAHs in fish dorsal muscle. In general, this study explored an effective and convenient method to prepare high-efficient MOF-based SPME fiber for PAHs analysis in complex environmental water samples and living organisms via in situ growth and polymer sheath.

Uptake of pharmaceuticals acts as an abiotic stress and triggers variation of jasmonates in Malabar spinach (Basella alba. L).

In recent years, pharmaceuticals have received increasing attentions because of their potential risks to the environment, but researches focusing on their impacts on defense system of living plants are still lacking. As an important class of phytohormones, jasmonates play crucial roles in plant defense system against environmental stress. In order to investigate the effect of pharmaceuticals uptake on endogenous jasmonates, an in vivo solid phase microextraction (SPME) method was established to simultaneously detect and monitor both pharmaceuticals and jasmonates in living plants. The proposed method exhibited wide linear ranges, high sensitivity (limits of detection ranging 0.0043-0.035 ng g-1 for pharmaceuticals and 0.091-0.22 ng g-1 for jasmonates, respectively), and satisfactory reproducibility (relative standard deviation of intrafiber ranging 4.2%-8.6% and interfiber ranging 5.2%-8.2%, respectively). Subsequently, this method was successfully applied to track the concentrations of each pharmaceutical and corresponding jasmonates in living Malabar spinach plants (Basella alba. L) exposed to three common pharmaceuticals (i.e. gemfibrozil, mefenamic acid and tolfenamic acid) over 15 days. In result, all pharmaceuticals appeared to trigger intensive biosynthesis of jasmonic acid (JA) (3.1-9.4 times of control) while reduced the concentration of methyl jasmonate (MeJA) (18.3%-38.1% of control). We inferred that uptake of pharmaceuticals acted as an abiotic stress and stimulated the plant defense response because of the variation of jasmonates. To the best of our knowledge, this is the first study applying SPME to detect and track both pharmaceuticals and phytohormones in living plants, which not only provided a glimpse to the adverse effect of pharmaceuticals on plants as well as the regulation of endogenous jasmonates, but also set a promising template for future in vivo analysis of xenobiotics and plant endogenous substances.