Site-recognition boosted the sensing performance of terbium-based organic frameworks for UO22+ detection.

A unique fluorescent sensing probe for UO22+ detection was fabricated with terbium-based metal organic frameworks via introducing specific recognition sites (denoted as Tb-TDPAT). The newly formed Tb-TDPAT presented remarkable detection sensitivity and selectivity towards UO22+, surpassing the need for complex post-modification methods.

A review of occurrence, bioaccumulation, and fate of novel brominated flame retardants in aquatic environments: A comparison with legacy brominated flame retardants.

Novel brominated flame retardants (NBFRs) have been developed as replacements for legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). The prevalence of NBFRs in aquatic environments has initiated intense concerns that they resemble to BFRs. To comprehensively elucidate the fate of NBFRs in aquatic environments, this review summarizes the physico-chemical properties, distribution, bioaccumulation, and fates in aquatic environments. 1,2-bis(2,3,4,5,6-pentabromophenyl) ethane (DBDPE) as the major substitute for PBDEs is the primary NBFR. The release from industrial point sources such as e-waste recycling stations is the dominant way for NBFRs to enter the environment, which results in significant differences in the regional distribution of NBFRs. Sediment is the major sink of NBFRs attributed to the high hydrophobicity. Significantly, there is no decreasing trend of NBFRs concentrations, while PBDEs achieved the peak value in 1970-2000 and decreased gradually. The bioaccumulation of NBFRs is reported in both field studies and laboratory studies, which is regulated by the active area, lipid contents, trophic level of aquatic organisms, and the log KOW of NBFRs. The biotransformation of NBFRs showed similar metabolism patterns to that of BFRs, including debromination, hydroxylation, methoxylation, hydrolysis, and glycosylation. In addition, NBFRs show great potential in trophic magnification along the aquatic food chain, which could pose a higher risk to high trophic-level species. The passive uptake by roots dominates the plant uptake of NBFRs, followed by acropetal and basipetal bidirectional transportation between roots and leaves in plants. This review will provide the support to understand the current pollution characteristics of NBFRs and highlight perspectives for future research.

On-Site Ratiometric Analysis of UO22+ with High Selectivity.

Uranyl ions (UO22+) are recognized as important indicators for monitoring sudden nuclear accidents. However, the interferences coexisting in the complicated environmental matrices impart serious constraints on the reliability of current on-site monitoring methods. Herein, a novel ratiometric method for the highly sensitive and selective detection of UO22+ is reported based on a [Eu(diaminoterephthalic acid)] (Eu-DATP) metal-organic framework. Benefiting from the unique chemical structure of Eu-DATP, energy transfer from DATP to UO22+ was enabled, resulting in the up-regulated fluorescence of UO22+ and the simultaneous down-regulated fluorescence of Eu3+. The limit of detection reached as low as 2.7 nM, which was almost 2 orders of magnitude below the restricted limit in drinking water set by the United States Environmental Protection Agency (130 nM). The Eu-DATP probe showed excellent specificity to UO22+ over numerous interfering species, as the intrinsic emissions of UO22+ were triggered. This unprecedentedly high selectivity is especially beneficial for monitoring UO22+ in complicated environmental matrices with no need for tedious sample pretreatment, such as filtration and digestion. Then, by facilely equipping a Eu-DATP-based sampler on a drone, remotely controlled sampling and on-site analysis in real water samples were realized. The concentrations of UO22+ were determined to be from 16.5 to 23.5 nM in the river water of the Guangzhou downtown area, which was consistent with the results determined by the gold-standard inductively coupled plasma mass spectrometry. This study presents a reliable and convenient method for the on-site analysis of UO22+.

Occurrence and Release of Organophosphite Antioxidants and Novel Organophosphate Esters from Plastic Food Packaging.

Organic phosphite antioxidants (OPAs) are widely added in plastic products and can be oxidized to generate oxidized derivatives (OPAs = O), namely organic phosphate esters (OPEs), during production and use processing. Herein, the occurrence of OPEs and OPAs in five plastic food packages was detected by liquid chromatography-tandem mass spectrometry. Three OPEs (TPhP, TCEP, and AO168 = O) and three OPAs (TPhPi, TCEPi, and AO168) were found in the plastic packages, with concentrations of

Application of the NU-1000 coated SPME fiber on analysis of trace organochlorine pesticides in water.

Herein, a novel solid-phase microextraction (SPME) fiber based on the NU-1000 sorbent was developed for direct immersion extraction of organochlorine pesticides (OCPs) in water samples. As a kind of metal-organic framework, the NU-1000 possessed the mesoporous channels which were beneficial for the mass transfer of target analytes. Extraction equilibrium was achieved rapidly with the optimal extraction time of 30 min. The NU-1000 coated fiber with a high specific surface area showed better extraction efficiencies than commercial fibers (65 µm PDMS/DVB or 85 µm PA) towards OCPs, with the enrichment factors of the NU-1000 coated fiber 2-20 times higher than the latter. NU-1000 coated fiber showed higher extraction efficiencies toward polycyclic aromatic hydrocarbons (PAHs) than OCPs and nitrobenzenes. This indicated that π-π interaction and CH-π interaction between pollutants and aromatic groups of the NU-1000 contributed to the high extraction efficiencies. Under the optimal conditions (extraction at 40 °C for 30 min and desorption at 260 °C for 6 min), the NU-1000 coated fiber coupled with gas chromatography-mass spectrometry (GC-MS) exhibited satisfied analytical performance on analysis of OCPs, with a wide linear range (0.1-2000 ng L-1), low limits of detections (LODs, 0.011-0.058 ng L-1), and good reproducibility and repeatability. The established method has been successfully applied to the determination of OCPs in surface water with good sensitivity and recoveries, which proved the great promise of the NU-1000 on the extraction of organic pollutants with conjugated groups.

Superficially capped amino metal-organic framework for efficient solid-phase microextraction of perfluorinated alkyl substances.

Perfluorinated alkyl substances (PFASs) were ubiquitously in the surface and groundwater. It is crucial and urgent to develop a rapid and ultrasensitive analysis method for the quantification of trace-level PFASs. Herein, a highly hydrophobic sorbent by capping phenylsilane groups on the surfaces of NH2-UiO-66(Zr) nanocrystals was used for efficient solid-phase microextraction (SPME) of PFASs in water samples. It was found that the superficially capped nanocrystals (NH2-UiO-66(Zr)-hp) exhibited both faster extraction kinetics and higher enrichment capacity than the non-capped nanocrystals. The extraction of eleven kinds of PFASs by NH2-UiO-66(Zr)-hp fiber reached equilibrium in 20 min. The enrichment factors of the NH2-UiO-66(Zr)-hp fiber ranged from 6.5 to 48, with a preference for long-chain PFASs over short-chain PFASs. It was proposed that superficial capping eliminated competitive moisture adsorption on the surfaces of the non-capped nanocrystals, thus facilitating the adsorption of PFASs through hydrophobic interaction. By using this new sorbent, the limits of detection of the SPME method as low as 0.035 to 0.616 ng·L-1 were achieved for the target PFASs. The recoveries of PFASs in the environmental water samples were 80.9%-120%. This study presents a new strategy for developing an efficient sorbent for PFASs by surface hydrophobic modification.

Efficient solid phase microextraction of organic pollutants based on graphene oxide/chitosan aerogel.

The design and synthesis of novel high-performance solid phase microextraction (SPME) coatings towards organic pollutants with diverse chemical properties is still a challenge in sample preparation. Herein, a stable chitosan cross-linked graphene oxide (GOCS) aerogel was reported as a novel coating for solid phase microextraction. The interpenetrated meso- and macropores ensured the large surface area and high accessibility of the functional groups across the aerogel, resulting in high extraction performance towards target hydrophobic pollutants. The extraction capacities of the GOCS-coated SPME fiber towards analytes (e.g. polycyclic aromatic hydrocarbons, organophosphorus pesticides, organochlorine pesticides, pyrethroids, and polychlorinated biphenyls) were about 0.5-13 times as high as those obtained by the commercial fibers (30 µm polydimethylsiloxane (PDMS), 65 µm polydimethylsiloxane/divinylbenzene (PDMS/DVB)), which was attributed to the hydrophobic, π-π, halogen bond and hydrogen bond interactions between the coating and the analytes. Under the optimized extraction conditions, superior analytical performances for PAHs were achieved with a wide linearity (0.5-1000 ng L-1), high enhancement factors (311-3740), and the low limits of detection (0.03-1.28 ng L-1). Finally, the GOCS-coated SPME fiber was successfully applied to the determination of PAHs in real water samples with good recoveries (91.6%-110%).

Noncovalently Tagged Gas Phase Complex Ions for Screening Unknown Contaminant Metabolites in Plants.

Screening the metabolites of emerging organic contaminants (EOCs) from complicated biological matrices is an important but challenging task. Although stable isotope labeling (SIL) is frequently used to facilitate the identification of contaminant metabolites from redundant interfering components, the isotopically labeled reagents are expensive and difficult to synthesize, which greatly constrains the application of the SIL method. Herein, a new online noncovalent tagging method was developed for screening the metabolites of 1H-benzotriazol (BT) based on the characteristic structural moieties reserved in the metabolites. By selecting ß-cyclodextrin (ß-CD) as a macrocyclic tagging reagent, metabolites with the reserved moiety were expected to exhibit a characteristic shift of the mass-to-charge ratio (Δm/z = 1134.3698) after being noncovalently tagged by ß-CD. Based on the characteristic mass shift, the suspected features were reduced by 1 order of magnitude, as numerous interfering species that could not be effectively tagged by ß-CD were excluded. From these suspected features, two metabolites of BT that have not been reported before were successfully screened out. The significant characteristic mass shift caused by the noncovalent tagging method is easier to identify with more confidence than the previously reported SIL method. Besides, noncovalent tagging reagents can be much more accessible and less expensive than isotopically labeled reagents. Hence, this online noncovalent tagging method can be an intriguing alternative to the conventional SIL method.

Organophosphite Antioxidants in Mulch Films Are Important Sources of Organophosphate Pollutants in Farmlands.

Organophosphite antioxidants (OPAs) are important auxiliary antioxidants used in plastic polymers and can be oxidized to organophosphate esters (OPEs) during production and processing. In this work, the occurrence of OPAs and OPEs in farmlands with or without mulch film applications was investigated. Six OPAs and five OPEs were detected, with the median concentrations of 2.66 ng/g (∑6OPAs) and 100 ng/g (∑5OPEs) in the film-mulching soil and 1.16 ng/g (∑6OPAs) and 47.9 ng/g (∑5OPEs) in the nonfilm-mulching soil, respectively. The oxidative derivative of AO168 (tris (2,4-di-tert-butylphenyl) phosphite), a typical OPA, AO168═O (tris (2,4-di-tert-butylphenyl) phosphate) was frequently detected in farmlands at the concentrations of 0-731 ng/g, which is much higher than that of the commercial OPEs (0-12.1 ng/g). This suggests that the oxidation derivatives of OPAs (OPAs═O) might be important OPE contaminants in soils. Mulch films could be their important source. According to the simulation migration experiment, the emission risk ranges of AO168 and AO168═O from mulch films to soils in China were estimated to be 3.96-87.6 and 10.5-95.3 tons/year, respectively, which were much higher than those of OPEs from sewage sludge applications. Simulation experiments also demonstrated that oxidation was the major pathway for OPAs in soils. OPAs with small substituent groups could be potential sources for organophosphate diesters. For the first time, the serious pollution of OPAs and OPAs═O in soils has been reported, and mulch films have been identified as their potential source.

Development and Application of a Mass Spectrometry Method for Quantifying Nylon Microplastics in Environment.

The quantitative detection methods for many microplastic (MP) polymers in the environment are inadequate. For example, effective detection methods for nylon (polyamide, PA), a widely used plastic, in different environmental samples are still lacking. In the present study, a method based on acid depolymerization-liquid chromatography-tandem mass spectrometry (LC-MS/MS) and without the separation of MPs from samples was developed to quantify nylon MPs. After removing the background monomer compounds, PA6 and PA66 were efficiently depolymerized to 6-aminocaproic acid and adipic acid, respectively, and detected by LC-MS/MS. Accordingly, the quantity of nylon MPs was accurately calculated. By using the proposed method, the recovery of spiked PA6 and PA66 MPs in the environmental samples ranged from 90.8 to 98.8%. The limits of quantification for PA6 and PA66 MPs were 0.680 and 4.62 mg/kg, respectively. PA MPs were widely detected in indoor dust, sludge, marine sediment, freshwater sediment, fishery sediment, and fish guts and gills with concentrations of 0.725-321 mg/kg. Extremely high concentrations of PA66 MPs were detected in indoor dust and fish guts and gills, indicating the unequivocal risk of human exposure through dust ingestion and dietary exposure.

The environment behavior of organophosphate esters (OPEs) and di-esters in wheat (Triticum aestivum L.): Uptake mechanism, in vivo hydrolysis and subcellular distribution.

To reveal the metabolic characteristic of organophosphate esters (OPEs) in plants, uptake efficiency, subcellular distribution and hydrolysis of OPEs and their hydrolysis metabolites in wheat (Triticum aestivum L.) were investigated by hydroponic experiments. Tris(2-chloroethyl) phosphate (TCEP) and bis(2-chloroethyl) phosphate (BCEP) were prone to transporting to shoots by transpiration stream, with the translocation factors of 6.2 and 21 for TCEP and BCEP, respectively, as greater than 40% of TCEP and BECP were distributed in the cell sap due to their hydrophilicity. Hydrophobic OPEs (i.e. tri-n-butyl phosphate [TnBP] and triphenyl phosphate [TPhP]), and their hydrolysis metabolites (di-n-butyl phosphate [DnBP] and diphenyl phosphate [DPhP]) were stored in roots, resulting in low translocation capacity in wheat. As organophosphate diesters with relatively high proportions in cell walls (70-84% of DnBP and 41-43% of DPhP) are difficult to being transmembrane transported due to electrical repulsion of the cytomembrane, it is supposed that cell walls could be a main location for in vivo hydrolysis of OPEs. For DnBP, absorption by roots after in vitro hydrolysis of TnBP in hydroponic media was also an important source in wheat. Inhibition experiments showed that it is usually a non-energy-consuming process for root uptake of OPEs and their hydrolysis metabolites. The uptake of OPEs (i.e. TCEP, TnBP, and TPhP) and DPhP were facilitated diffusion mediated by aquaporins or anion channels, while uptake of BCEP and DnBP were simple diffusion processes. This study illustrated the distribution characteristics and translocation capacity of OPEs and their diester metabolites at the subcellular level.

Screening pesticide residues on fruit peels using portable Raman spectrometer combined with adhesive tape sampling.

In this work, we report a simple and rapid surface-enhanced Raman scattering (SERS) method for the screening of pesticide residues on fruit peels using a portable Raman spectrometer. Adhesive tapes were used as the sampling media; the effectiveness of different tape brands was examined. Collection efficiencies were found to be 60.2 ±â€¯7.6%, 54.3 ±â€¯5.0%, and 52.3 ±â€¯9.0% on glass, aluminum foil, and fruit peels, respectively. SERS was achieved by applying silver nanoparticles (Ag NPs) to the surface of the tape after analyte collection. Preparation of the Ag NPs was optimized for pesticide detection. The limit of detection of triazophos on apple peels was 25 ng/cm2 with the portable Raman spectrometer. Considering the least favorable conditions, the calculated detection limit was 0.0225 mg/kg, which is an order of magnitude less than the maximum residue limit (MRL, 0.2 mg/kg) in China. The method is sufficiently sensitive for use in field analysis.

Widespread Occurrence of Bisphenol A in Daily Clothes and Its High Exposure Risk in Humans.

Bisphenol A (BPA) is an important endocrine disrupting chemical. Although high levels of BPA in some new clothes have been reported, the occurrence of bisphenol chemicals including BPA in daily clothes is still unknown, and the human exposure to BPA in clothes has not been well assessed. In this study, used/washed clothes were collected from residents' wardrobes and the concentrations of BPA and its analogues were detected. BPA was present in all the used clothes at concentrations ranging from <3.30 to 471 ng/g (median: 34.2 ng/g; mean ± SD: 57.5 ± 93.6 ng/g), while bisphenol S was also detected in 29% of the samples. Although higher average concentration (88.4 ± 289 ng/g) and maximum concentration (1823 ng/g) of BPA were found in the new clothes, the median concentration of BPA in the used clothes (34.2 ng/g) was even higher than that in the new clothes (17.7 ng/g). Cross contamination of BPA during laundering was identified by a simulated laundry experiment, which explained the homogenizing tendency of bisphenol contaminants in the used clothes. An estimated dermal exposure dose of 52.1 ng/kg BW/d was obtained for BPA exposure in children from the highly polluted sweaty clothes (with BPA concentration of 199 ng/g). This indicates a relatively high exposure risk in humans. Compared to other exposure routes, the contribution of dermal exposure dose of BPA from the daily clothes should not be neglected.

Effects of benzotriazole on copper accumulation and toxicity in earthworm (Eisenia fetida).

Triazole contaminants in water and soil environments can form complexes with metal ions, and therefore affect the bioavailability and toxicity of some heavy metals. In present study, significant increase of copper (Cu) uptake by earthworm (Eisenia fetida) was observed when combined pollution of benzotriazole (BTR) presented in soil. For instance, Cu accumulation in earthworms increased 55% approximately when BTR presented at the BTR/Cu molar ratio of 1:2.5. While the single Cu exposure (at 32 mg kg-1 in soil) resulted in increased malondialdehyde (MDA) content in earthworms from 0.319 to 0.668 nmol mg protein-1, joint exposure to BTR at BTR/Cu molar ratio of 1:10 significantly decreased the MDA content to 0.405 nmol mg protein-1. This indicates a potential detoxification effect of BTR to Cu induced oxidative damage in earthworms. Varied Cu subcellular distribution can be observed in earthworms of the single and combined exposure treatments. With the combined exposure of BTR, the proportion of Cu associated with granular fraction, the toxically inert fraction in earthworms, increased from 25% to 39%. This phenomenon can be used to explain the protective effects of BTR against oxidative damage.

Effects of single and combined exposures to copper and benzotriazole on Eisenia fetida.

Benzotriazole (BTR), an emerging class of environmental pollutant, is widely used in industrial applications and household dishwashing agents. Despite the reported toxicity of BTR to aquatic organisms, little is known about its effects on terrestrial invertebrates. Copper (Cu) accumulates in agricultural soils receiving urban waste products, fertilizers, fungicides, and urban sewage. In this study, two different types of bioassays (acute toxicity test and behavioral toxicity test) were performed to evaluate the toxicity of Cu and BTR, both singly and together, on the earthworm (Eisenia fetida) in artificial soil. The results of avoidance behaviour tests showed that the EC50,48 h values for Cu and BTR were 1.47 and 0.46 mmol kg-1, respectively. The results of the acute toxicity tests showed that the LC50,7 d and LC50,14 d of Cu in earthworms were 9.19 and 5.28 mmol kg-1, respectively, and the LC50,7 d and LC50,14 d of BTR were 2.43 and 1.76 mmol kg-1, respectively. Toxicity analysis demonstrated that the binary BTR and Cu mixture had predominantly antagonistic effects on the avoidance behaviour and survival of earthworms. The Cu2+ activities and mortality of earthworms decreased significantly with increasing concentrations of BTR, while the solid-liquid distribution coefficient of Cu increased. These results indicated that the presence of BTR can reduce the toxicity as well as the bioavailability of Cu in soil with both BTR and Cu.

Application of an immobilized ionic liquid for the passive sampling of perfluorinated substances in water.

Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10-3-3.6×10-1nmol/L in the influent and from 1.3×10-2-2.2×10-1nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water.