Screening New Persistent and Bioaccumulative Organics in China's Inventory of Industrial Chemicals.

Over a third of the world's annual chemical production and sales occur in China. Thus, knowledge of the properties of the substances produced and emitted there is important from a global perspective. The chemical Inventory of Existing Chemical Substances of China (IECSC) lists over 45 000 chemicals. When compared to the North American and European chemical inventories, 6916 substances were found to be unique to the IECSC. We retrieved structural information for 14 938 organic chemicals in the IECSC and determined their overall environmental persistence , bioaccumulation factor (BAF), and long-range transport potential (transfer efficiency) using in silico approaches with the goal of identifying new chemicals with properties that might lead to global contamination issues. Overall, 10% of the 14 938 chemicals were unique to the IECSC and their environmental persistence and BAF were statistically higher than the values for the rest of the IECSC chemicals. We prioritized 27 neutral organic compounds predicted to have prolonged environmental persistence, and high potential for bioaccumulation and long-range transport when compared with polychlorinated biphenyls as a benchmark. We also identified 69 organofluorine compounds with three or more perfluorinated moieties, unique to the IECSC. Screening approaches and results from this study help to identify and prioritize those to be considered in further environmental modeling and monitoring assessments.

Microplastic Impacts on Microalgae Growth: Effects of Size and Humic Acid.

Research has already demonstrated the toxic effects of microplastics (MPs) on different biota. However, the underlying toxic mechanism of MPs remains to be elucidated, especially the effect of particle size and the presence of dissolved organic matter in water. This study investigated the impact on Scenedesmus obliquus exposed in five types of polystyrene particle suspensions with different sizes and surface charges, in the presence and absence of humic acid (HA). Results indicated that the 50% growth inhibition rate of S. obliquus showed no significant difference between the five types of MPs, but the toxic mechanism varied with particle size. Larger size MPs caused adverse effects by blocking the light transport and affecting photosynthesis, while smaller ones destroyed the cell wall by adsorbing onto the algae surface. Also, the addition of HA significantly alleviated the toxicity of smaller size MPs, but not of the larger ones. Scanning electron microscopy images and the reactive oxygen species assay demonstrated that the HA could form a corona on the surface of MPs, reduce the affinity to microalgae, and minimize the adverse effect. Together, these findings identified important factors in determining the toxicity of MPs, providing valuable data for risk assessment of MPs.

Investigating the toxicities of different functionalized polystyrene nanoplastics on Daphnia magna.

Nanoplastics (NPs) spread widely with water and air current, and they can accumulate in aquatic organisms, even penetrating biofilms, which may cause persistent toxicity and potential hazards. This current study aimed to reveal the toxicological mechanism of different functionalized polystyrene (PS) NPs on Daphnia magna (D. magna) by investigating toxicity endpoints in individual level and biochemical level. In this study, acute toxicity, behavioral parameters and biomarker responses of D. magna was measured in the exposure of different functionalized PS NPs (plain PS, PS-p-NH2, PS-n-NH2 and PS-COOH). The results indicated that when exposed to the plain PS, ROS induction would activate MAPKs, thereby causing lethality and adverse behavior effects on D. magna; while the functionalized PS NPs were less toxic than the plain PS, especially for PS-p-NH2 which was severely flocculated after exposure, thus showing no immobilization at the investigated concentrations. Also, the antioxidant system was mainly stimulated due to the direct interaction with the cell surface receptor, which was different from the plain PS. Consequently, this work suggests significant effects of functional groups on NPs for environmental toxicity studies, and provides a better understanding of the toxicological mechanism on the toxicity of PS NPs toward D. magna.

Improving the Sensitivity of Solid-Phase Microextraction by Reducing the Volume of Off-Line Elution Solvent.

Solid-phase microextraction (SPME) coupled with liquid chromatograph (LC) is widely used to detect polar and ionic organic compounds, including various pharmaceuticals and endogenous bioactive compounds. In this study, a small-sized insert tube for use in the commercial autosampler vial was designed for eluting the extracted analytes from SPME fibers for LC analysis. By using this custom-made insert tube as an alternative to the commercial insert tube, the volume of the elution solvent was reduced by four-fifths. Even though smaller fractions of the analytes were eluted from the fiber coatings, the analyte concentrations in the elution solutions were substantially increased by using the custom-made insert tube. Therefore, larger amounts of the analytes could be injected to LC and higher signal-to-noise ratios could be achieved, even at smaller injection volumes. Since the elution in the custom-made insert tube was nonexhaustive, four strategies were developed to figure out the extracted amounts in the fiber coatings. In combination with the sampling-rate calibration method, these strategies were successfully used to determine the concentrations of fluoxetine in living tilapias. This study provides a simple but effect way for improving the analytical sensitivity when coupling SPME with LC.

Amine-functionalized MIL-53(Al)-coated stainless steel fiber for efficient solid-phase microextraction of synthetic musks and organochlorine pesticides in water samples.

The fiber coating is the key part of the solid-phase microextraction (SPME) technique, and it determines the sensitivity, selectivity, and repeatability of the analytical method. In this work, amine (NH2)-functionalized material of Institute Lavoisier (MIL)-53(Al) nanoparticles were successfully synthesized, characterized, and applied as the SPME fiber coating for efficient sample pretreatment owing to their unique structures and excellent adsorption properties. Under optimized conditions, the NH2-MIL-53(Al)-coated fiber showed good precision, low limits of detection (LODs) [0.025-0.83 ng L-1 for synthetic musks (SMs) and 0.051-0.97 ng L-1 for organochlorine pesticides (OCPs)], and good linearity. Experimental results showed that the NH2-MIL-53(Al) SPME coating was solvent resistant and thermostable. In addition, the extraction efficiencies of the NH2-MIL-53(Al) coating for SMs and OCPs were higher than those of commercially available SPME fiber coatings such as polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, and polyacrylate. The reasons may be that the analytes are adsorbed on NH2-MIL-53(Al) primarily through π-π interactions, electron donor-electron acceptor interactions, and hydrogen bonds between the analytes and organic linkers of the material. Direct immersion (DI) SPME-gas chromatography-mass spectrometry methods based on NH2-MIL-53(Al) were successfully applied for the analysis of tap and river water samples. The recoveries were 80.3-115% for SMs and 77.4-117% for OCPs. These results indicate that the NH2-MIL-53(Al) coating may be a promising alternative to SPME coatings for the enrichment of SMs and OCPs.

Study on the Diffusion-Dominated Solid-Phase Microextraction Kinetics in Semisolid Sample Matrix.

Solid-phase microextraction (SPME) kinetics in semisolid samples should be different from that in aqueous and gaseous samples, as convection is negligible in semisolid samples but dominates mass transfer in bulk phases of aqueous and gaseous samples. This study developed a mathematical model for describing SPME kinetics in semisolid samples by considering the diffusion of analytes in two compartments, i.e., the fiber coating and the ever-increasing diffusion domain in the sample matrix. The mathematical model predicted that SPME and the desorption of preloaded analytes from the fiber would be isotropic in semisolid samples, while SPME in semisolid samples would not follow the first order kinetics as in aqueous and gaseous samples. The predictions were proven true in the experiment of four pharmaceuticals in agarose gel. In return, it was observed in the experiment that SPME kinetics would deviate more significantly from the first order kinetics for the analytes with higher partition coefficients between the fiber and the sample matrix, which was well explained by the mathematical model developed in this study. In addition, SPME kinetics predicted by the model coincided well with the experimental results when the diffusion coefficients were at reasonable levels, which demonstrated that the model could be satisfactory for describing SPME kinetics in semisolid samples. The illustration of the nonfirst order SPME kinetics in semisolid samples can be valuable for evaluating the applicability of the existing pre-equilibrium calibration methods in semisolid samples.

Polyelectrolyte Microcapsules Dispersed in Silicone Rubber for in Vivo Sampling in Fish Brains.

Direct detection of fluoxetine and its metabolite norfluoxetine in living fish brains was realized for the first time by using a novel solid-phase microextraction fiber, which was prepared by mixing the polyelectrolyte in the oligomer of silicone rubber and followed by in-mold heat-curing. The polyelectrolyte was finally encased in microcapsules dispersed in the cured silicone rubber. The fiber exhibited excellent interfiber reproducibility (5.4-7.1%, n = 6), intrafiber reproducibility (3.7-4.6%, n = 6), and matrix effect-resistant capacity. Due to the capacity of simultaneously extracting the neutral and the protonated species of the analytes at physiological pH, the fiber exhibited high extraction efficiencies to fluoxetine and norfluoxetine. Besides, the effect of the salinity on the extraction performance and the competitive sorption between the analytes were also evaluated. Based on the small-sized custom-made fiber, the concentrations of fluoxetine and norfluoxetine in the brains of living fish, which were exposed to waterborne fluoxetine at an environmentally relevant concentration, were determined and found 4.4 to 9.2 and 5.0 to 9.2 times those in the dorsal-epaxial muscle. The fiber can be used to detect various protonated bioactive compounds in living animal tissues.

Bioinspired polydopamine sheathed nanofibers for high-efficient in vivo solid-phase microextraction of pharmaceuticals in fish muscle.

In this study, electrospun nanofibers were used as solid-phase microextraction (SPME) fiber coatings after substituting the water-soluble sheath of the emulsion electrospun polystyrene (PS)@Plurinic F-127 core-sheath nanofibers with biocompatible and water-stable polydopamine (PDA) and subsequently being appropriately cross-linked with glutaraldehyde (GA) to enhance the strength of the electrospun architecture. The novel custom-made PS@PDA-GA coating was wettable in aqueous solutions and thus exhibited much higher extraction efficiency than the nonsheathed PS nanofiber coating and the thicker polydimethylsiloxane (PDMS) coating. The novel coating also possessed excellent stability (relative standard deviations (RSDs) less than 7.3% for six sampling-desorption cycles), interfiber reproducibility (RSDs less than 14.3%), and antibiofouling ability, which were beneficial for in vivo sampling. The PS@PDA-GA fiber was used to monitor pharmaceuticals in dorsal-epaxial muscle of living fish, and satisfactory sensitivities with the limits of detection in the range of 1.1 (mefenamic acid) to 8.9 (fluoxetine) ng·g(-1) and comparable accuracies to liquid extraction were achieved. In general, this study explored a convenient and effective method to sheath nanofibers for high-efficient in vivo SPME of analytes of interest in semisolid tissues.

Preparation of a particle-loaded membrane for trace gas sampling.

A divinylbenzene (DVB) particle-loaded membrane with high extraction capacity was prepared using the bar coating method. The prepared membrane was evaluated in terms of morphology, effect of particle ratio, and membrane size on extraction efficiency, as well as linear calibration curve and limit of detection. The SEM (scanning electron microscope) images showed that the DVB particles were uniformly distributed in the PDMS base, ensuring the repeatability of the membranes. The extraction amount was quantified by gas chromatography-mass spectrometry coupled with a thermal desorption unit. Results showed that the extraction efficiency of the prepared membrane increased about 2 orders of magnitude for benzene sampling as the particle ratio increased from 0% to 30%, and the extraction amount was linearly proportional to the size of the membrane. A comparison with a pure PDMS membrane and DVB/PDMS fiber for outdoor air sampling showed that the extraction efficiency of the DVB/PDMS membrane was significantly enhanced, especially for volatile and polar compounds. The limit of detection was about 0.03 ng/mL for benzene in air, and the linear dynamic range extended to 100 ng/mL. An equilibrium calibration method was proposed for low-level air pollutant sampling using this high capacity membrane, and a displacement effect was not observed. To demonstrate the power of the technique, the developed approach was applied to monitor both spot and time weighted average (TWA) concentrations of benzene in outdoor air. A high spot concentration of benzene was observed in morning and afternoon rush hours, with TWA concentrations of 10.7 ng/L measured over the 11-h monitoring period.

In vivo tracing uptake and elimination of organic pesticides in fish muscle.

Bioconcentration factors (BCFs) measured in the laboratory are important for characterizing the bioaccumulative properties of chemicals entering the environment, especially the potential persistent organic pollutants (POPs), which can pose serious adverse effects on ecosystem and human health. Traditional lethal analysis methods are time-consuming and sacrifice too many experimental animals. In the present study, in vivo solid-phase microextraction (SPME) was introduced to trace the uptake and elimination processes of pesticides in living fish. BCFs and elimination kinetic coefficients of the pesticides were recorded therein. Moreover, the metabolism of fenthion was also traced with in vivo SPME. The method was time-efficient and laborsaving. Much fewer experimental animals were sacrificed during the tracing. In general, this study opened up an opportunity to measure BCFs cheaply in laboratories for the registering of emerging POPs and inspecting of suspected POPs, as well as demonstrated the potential application of in vivo SPME in the study of toxicokinetics of pollutants.

Application of functionalized magnetic nanoparticles in sample preparation.

Functionalized magnetic nanoparticles have attracted much attention in sample preparation because of their excellent performance compared with traditional sample-preparation sorbents. In this review, we describe the application of magnetic nanoparticles functionalized with silica, octadecylsilane, carbon-based material, surfactants, and polymers as adsorbents for separation and preconcentration of analytes from a variety of matrices. Magnetic solid-phase extraction (MSPE) techniques, mainly reported in the last five years, are presented and discussed.

Size-dependent vector effect of microplastics on the bioaccumulation of polychlorinated biphenyls in tilapia: A tissue-specific study.

Microplastics play a significant role in interactions between organisms and hydrophobic organic contaminants (HOCs), leading to a joint toxic effect on aquatic organisms. This study extensively investigated the tissue-specific accumulation of polychlorinated biphenyls (PCBs) resulting from different sized microplastics in tilapia (Oreochromis mossambicus) using a passive dosing device. Based on biological feeding behavior considerations, 1 mm and 2 µm polystyrene (PS) microplastics with concentrations of 2 and 5 mg L-1 were investigated. A physiologically based toxicokinetic (PBTK) model was applied to evaluate the exchange kinetics and fluxes among the tissues. Moreover, an in vitro simulation experiment was conducted to theoretically validate the vector effect. The findings demonstrated that the effects caused by HOCs and microplastics on organisms were influenced by multiple factors such as size and surface properties. The mass transfer kinetics of HOCs in specific tissues were closely related to their adsorption capacity and position microplastics could reach. Specifically, although 2 µm microplastics exhibited high adsorption capacity for PCBs, they were only retained in the intestines and did not significantly contribute to the bioaccumulation of PCBs in gills or muscle. While 1 mm microplastics were ingested but just paused in the mouth and subsequently flew through the gills with oral mucus. Their vector effects increased the desorption of microplastic-bound PCB-118 in the gill mucus microcosm, thereby facilitating the mass transfer and accumulation of PCB-118 in gills and muscle. This study sheds new light on how the size-dependent vector generated by microplastics affects the tissue-specific accumulation of HOCs in aquatic organisms.

Unraveling the distribution characteristic of cyclic volatile methylsiloxanes in various environmental media of a wastewater treatment plant.

Cyclic volatile methylsiloxane (cVMS) is extensively used in consumer products and frequently detected in various environmental media, including water and air. In this study, we developed reliable and convenient methods to sample three cVMS compounds: octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water and air samples collected from different tanks within a wastewater treatment plant (WWTP). The concentrations of D4, D5, and D6 in the water samples ranged from 0.40 to 8.0 µg L-1, 0.35 to 91 µg L-1, and 0.54 to 17 µg L-1, respectively. In the air samples, these concentrations varied from 0.34 to 20 µg m-3, 0.34 to 128 µg m-3, and 0.08 to 12 µg m-3, respectively. It is worth noting that the air-water distribution coefficient (Kaw) for these three cVMS exhibited a strong correlation with their water solubility. Moreover, fugacity fractions indicated a net evaporation process from water to the atmosphere. Furthermore, we investigated the distribution of cVMS between the gaseous and particulate phases. The results revealed a significant fraction, exceeding 72 %, of cVMS resided in the gas phase. D4 and D5 predominate in the gaseous phase, while D5 and D6 are the principal constituents within the particulate phase. The distribution coefficient characterizing the partitioning of cVMS compounds between the gaseous and particulate (Kp) exhibited a strong correlation with their corresponding octanol-air partitioning coefficients (Koa). These findings contribute to a better understanding of the distribution of cVMS in diverse environmental media and the underlying mechanism governing their dispersion.

The effect of microplastics on the depuration of hydrophobic organic contaminants in Daphnia magna: A quantitative model analysis.

Microplastics are emerging pollutants that can absorb large amounts of hydrophobic organic contaminants (HOCs). However, no biodynamic model has yet been proposed to estimate their effects on HOC depuration in aquatic organisms, where the HOC concentrations are time-varying. In this work, a microplastic-inclusive biodynamic model was developed to estimate the depuration of HOCs via ingestion of microplastics. Several key parameters of the model were redefined to determine the dynamic HOC concentrations. Through the parameterized model, the relative contributions of dermal and intestinal pathways can be distinguished. Moreover, the model was verified and the vector effect of microplastics was confirmed by studying the depuration of polychlorinated biphenyl (PCB) in Daphnia magna (D. magna) with different sizes of polystyrene (PS) microplastics. The results showed that microplastics contributed to the elimination kinetics of PCBs because of the fugacity gradient between the ingested microplastics and the biota lipids, especially for the less hydrophobic PCBs. The intestinal elimination pathway via microplastics would promote overall PCB elimination, contributing 37-41 % and 29-35 % to the total flux in the 100 nm and 2 µm polystyrene (PS) microplastic suspensions, respectively. Furthermore, the contribution of microplastic uptake to total HOC elimination increased with decreasing microplastic size in water, suggesting that microplastics may protect organisms from HOC risks. In conclusion, this work demonstrated that the proposed biodynamic model is capable of estimating the dynamic depuration of HOCs for aquatic organisms. The results can shed light on a better understanding of the vector effects of microplastics.

Exploring the release of hazardous volatile organic compounds from face masks and their potential health risk.

Hazardous chemicals released from the petroleum-derived face mask can be inhaled by wearers and cause adverse health effects. Here, we first used headspace solid-phase microextraction coupled with GC-MS to comprehensively analyze the volatile organic compounds (VOCs) released from 26 types of face masks. The results showed that total concentrations and peak numbers ranged from 3.28 to 197 µg/mask and 81 to 162, respectively, for different types of mask. Also, light exposure could affect the chemical composition of VOCs, particularly increasing the concentrations of aldehydes, ketones, organic acids and esters. Of these detected VOCs, 142 substances were matched to a reported database of chemicals associated with plastic packaging; 30 substances were identified by the International Agency for Research on Cancer (IARC) as potential carcinogenic to humans; 6 substances were classified in the European Union as persistent, bioaccumulative, and toxic, or very persistent, very bioaccumulative substance. Reactive carbonyls were ubiquitous in masks, especially after exposure to light. The potential risk of VOCs released from the face masks were then accessed by assuming the extreme scenario that all the VOC residues were released into the breathing air within 3 h. The result showed that the average total concentration of VOCs (17 µg/m3) was below the criterion for hygienic air, but seven substances, 2-ethylhexan-1-ol, benzene, isophorone, heptanal, naphthalene, benzyl chloride, and 1,2-dichloropropane exceeded the non-cancer health guidelines for lifetime exposure. This finding suggested that specific regulations should be adopted to improve the chemical safety of face masks.

Rapid detection and speciation of illicit drugs via a thin-film microextraction approach for wastewater-based epidemiology study.

High detection frequency of illicit drugs in water samples urges the development of rapid detection method for wastewater-based epidemiology (WBE) study. Here, we first developed a fast, convenient, and cost-effective method by combining thin-film microextraction (TFME) with gas chromatography-mass spectrometry (GC-MS) for sensing illicit drugs in wastewater sample. A divinylbenzene particle-loaded membrane was prepared by dip coating on a copper mesh. The sampling conditions of three illicit drugs were optimized and the performance of the proposed method was evaluated. The limit of detection was 5.5 2.0, and 1.1 ng L-1 for methamphetamine (MAMP), ketamine (KET), and methaqualone (MEQA), respectively, with acceptable precision (< 6.1 % for membrane to membrane reproducibility) and recovery from influent water (95 % - 111 %). Then, the proposed method was applied to study the occurrence and distribution of the target compounds in a wastewater treatment plant. The presence of methamphetamine, ketamine, and methaqualone was confirmed and their concentrations in the influent sample were 57 ± 8, 40 ± 4, and 75 ± 2 ng L-1, respectively. The speciation of the target compounds in different ponds was also investigated. Results showed that the content of organic matter and the pH of the sample significantly affected the binding state of the compounds. This work provides an efficient and accurate analytical protocol for WBE investigation of illicit drugs.

New insights into the photo-degraded polystyrene microplastic: Effect on the release of volatile organic compounds.

Excessive use of plastics leads to the ubiquity of plastic waste in the environment. Weathering can cause changes in the properties of plastics and lead to the release of various chemicals especially the volatile organic compounds (VOCs). Possible photodegradation pathway of polystyrene (PS) microplastics (MPs) was proposed and verified by the detection of VOCs. Headspace solid phase microextraction (HS-SPME) was employed to investigate the release behavior of VOCs from PS MPs exposed to simulated ultraviolet (UV). Results indicated that although the physicochemical properties of the PS MPs showed no significantly change after UV-irradiation, a variety of toxic VOCs, such as benzene, toluene, and phenol were detected from the irradiated MPs. UV irradiation progressively enhanced the release amount of VOCs with total concentration up to 66 µg g-1 after 30 d of exposure, about 2.4 times higher than that stored in the darkness (27 µg g-1). Some compounds (e.g., benzene and toluene) showed an upward trend over irradiation time, while others (e.g., styrene and 2-propenylbenzene) reduced over time. Results also found that the size of MPs could affect the release amounts but without consistent pattern for different VOCs detected in the headspace of the vial. In general, current study provided a new insight on the photo-aging process of MPs.

Impact of different modes of adsorption of natural organic matter on the environmental fate of nanoplastics.

Recently, the exposure of nanoplastics (NPs) in the environment has received extensive attention. Research concerning their fate and transport in the aquatic environment is very important and urgent. In this study, the influence of two sources of natural organic matter (NOM) on the behaviour of NPs were investigated in view of the complexity of NOM. Humic acid (HA), Suwannee River humic acid (SRHA) and Upper Mississippi River NOM (MRNOM) were chosen to represent pedogenic NOM, while bovine serum albumin (BSA) was on behalf of aquagenic NOM. The results showed that NOM could reduce the aggregation and sedimentation of NPs, exhibiting excellent stabilization effect. The stability effect was affected by the concentrations and the sources of NOMs. For pedogenic NOMs, the stabilization effect was caused by adsorption modes with different microscopic morphologies through specific functional groups, while it was induced by the mode of steric stabilization in the presence of BSA. Spectroscopic method and micromorphology study further provided a new insight into exploring the possible mechanism of the interaction between NPs and NOMs.

Sample preparation and instrumental methods for illicit drugs in environmental and biological samples: A review.

Detection of illicit drugs in the environmental samples has been challenged as the consumption increases globally. Current review examines the recent developments and applications of sample preparation techniques for illicit drugs in solid, liquid, and gas samples. For solid samples, traditional sample preparation methods such as liquid-phase extraction, solid-phase extraction, and the ones with external energy including microwave-assisted, ultrasonic-assisted, and pressurized liquid extraction were commonly used. The sample preparation methods mainly applied for liquid samples were microextraction techniques including solid-phase microextraction, microextraction by packed sorbent, dispersive solid-phase extraction, dispersive liquid-liquid microextraction, hollow fiber-based liquid-phase microextraction, and so on. Capillary microextraction of volatiles and airborne particulate sampling were primarily utilized to extract illicit drugs from gas samples. Besides, the paper introduced recently developed instrumental techniques applied to detect illicit drugs. Liquid chromatograph mass spectrometry and gas chromatograph mass spectrometry were the most widely used methods for illicit drugs samples. In addition, the development of ambient mass spectrometry techniques, such as desorption electrospray ionization mass spectrometry and paper spray mass spectrometry, created potential for rapid in-situ analysis.