Small extracellular vesicles' enrichment from biological fluids using an acoustic trap.

Small extracellular vesicles (sEVs), a form of extracellular vesicles, are lipid bilayered structures released by all cells. Large-scale studies on sEVs from clinical samples are necessary, but a major obstacle is the lack of rapid, reproducible, efficient, and low-cost methods to enrich sEVs. Acoustic microfluidics have the advantage of being label-free and biocompatible, which have been reported to successfully enrich sEVs. In this paper, we present a highly efficient acoustic microfluidic trap that can offer low and large volume compatible ways of enriching sEVs from biological fluids by flexible structure design. It uses the idea of pre-loading larger seed particles in the acoustic trap to enable sub-micron particle capturing. The microfluidic chip is actuated using a piezoelectric plate transducer attached to a silicon-glass bonding plate with circular cavities. Each cavity works as a resonant unit, excited at the frequency of both the half wave resonance in the main plane and inverted quarter wave resonance in the depth direction, which has the ability to strongly trap seed particles at the center, thereby improving the subsequent nanoparticle capture efficiency. Mean trapping efficiencies of 35.62% and 64.27% were obtained using 60 nm and 100 nm nanobeads, respectively. By the use of this technology, we have successfully enriched sEVs from cell culture conditioned media and blood plasma at a flow rate of 10 µL min-1. The isolated sEV subpopulations are characterized by NTA and TEM, and their protein cargo is determined by WB. This acoustic trapping chip provides a rapid and robust method to enrich sEVs from biofluids with high reproducibility and sufficient quantities. Therefore, it can serve as a new tool for biological and clinical research such as cancer diagnosis and drug delivery.

Bioaccumulation and Trophodynamics of Novel Brominated Flame Retardants (NBFRs) in Marine Food Webs from the Arctic and Antarctic Regions.

The pervasive contamination of novel brominated flame retardants (NBFRs) in remote polar ecosystems has attracted great attention in recent research. However, understanding regarding the trophic transfer behavior of NBFRs in the Arctic and Antarctic marine food webs is limited. In this study, we examined the occurrence and trophodynamics of NBFRs in polar benthic marine sediment and food webs collected from areas around the Chinese Arctic Yellow River Station (n = 57) and Antarctic Great Wall Station (n = 94). ∑7NBFR concentrations were in the range of 1.27-7.47 ng/g lipid weight (lw) and 0.09-1.56 ng/g lw in the Arctic and Antarctic marine biota, respectively, among which decabromodiphenyl ethane (DBDPE) was the predominant compound in all sample types. The biota-sediment bioaccumulation factors (g total organic carbon/g lipid) of NBFRs in the Arctic (0.85-3.40) were 4-fold higher than those in the Antarctica (0.13-0.61). Trophic magnification factors (TMFs) and their 95% confidence interval (95% CI) of individual NBFRs ranged from 0.43 (95% CI: 0.32, 0.60) to 1.32 (0.92, 1.89) and from 0.34 (0.24, 0.49) to 0.92 (0.56, 1.51) in the Arctic and Antarctic marine food webs, respectively. The TMFs of most congeners were significantly lower than 1, indicating a trophic dilution potential. This is one of the very few investigations on the trophic transfer of NBFRs in remote Arctic and Antarctic marine ecosystems, which provides a basis for exploring the ecological risks of NBFRs in polar regions.

Occurrence and Trophic Transfer of Polychlorinated Naphthalenes (PCNs) in the Arctic and Antarctic Benthic Marine Food Webs.

Information about the occurrence and trophic transfer of polychlorinated naphthalenes (PCNs) in polar ecosystems is vital but scarce. In this study, PCNs were analyzed in benthic marine sediment and several biological species, collected around the Chinese polar scientific research stations in Svalbard in the Arctic and South Shetland Island in Antarctica. Total PCNs in biota ranged from 28 to 249 pg/g of lipid weight (lw) and from 11 to 284 pg/g lw in the Arctic and Antarctic regions, respectively. The concentrations and toxic equivalent (TEQ) of PCNs in polar marine matrices remained relatively low, and the compositions were dominated by lower chlorinated homologues (mono- to trichlorinated naphthalenes). Trophic magnification factors (TMFs) were calculated for congeners, homologues, and total PCNs in the polar benthic marine food webs. Opposite PCN transfer patterns were observed in the Arctic and Antarctic regions, i.e., trophic dilution and trophic magnification, respectively. This is the first comprehensive study of PCN trophic transfer behaviors in remote Arctic and Antarctic marine regions, providing support for further investigations of the biological trophodynamics and ecological risks of PCNs.

PM2.5-bound polyhalogenated carbazoles (PHCZs) in urban Beijing, China: Occurrence and the source implication.

Polyhalogenated carbazoles (PHCZs) are recently raising much attention due to their toxicity and ubiquitous environmental distribution. However, little knowledge is known about their ambient occurrences and the potential source. In this study, we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM2.5 from urban Beijing, China. The optimized method provided low method limit of quantifications (MLOQs, 1.45-7.39 fg/m3) and satisfied recoveries (73.4%-109.5%). This method was applied to analyze the PHCZs in the outdoor PM2.5 (n = 46) and fly ash (n = 6) collected from 3 kinds of surrounding incinerator plants (steel plant, medical waste incinerator and domestic waste incinerator). The levels of ∑11PHCZs in PM2.5 ranged from 0.117 to 5.54 pg/m3 (median 1.18 pg/m3). 3-chloro-9H-carbazole (3-CCZ), 3-bromo-9H-carbazole (3-BCZ), and 3,6-dichloro-9H-carbazole (36-CCZ) were the dominant compounds, accounting for 93%. 3-CCZ and 3-BCZ were significantly higher in winter due to the high PM2.5 concentration, while 36-CCZ was higher in spring, which may be related to the resuspending of surface soil. Furthermore, the levels of ∑11PHCZs in fly ash ranged from 338 to 6101 pg/g. 3-CCZ, 3-BCZ and 36-CCZ accounted for 86.0%. The congener profiles of PHCZs between fly ash and PM2.5 were highly similar, indicating that combustion process could be an important source of ambient PHCZs. To the best of our knowledge, this is the first research providing the occurrences of PHCZs in outdoor PM2.5.

Sheathless acoustic based flow cell sorter for enrichment of rare cells.

Cell enrichment is a powerful tool in many kinds of cell research, especially in applications with low abundance cell types. In this work, we developed a microfluidic fluorescence activated cell sorting device that was able to perform on-demand, low loss cell detection, and sorting. The chip utilizes three-dimensional acoustic standing waves to position all cells in the same fluid velocity regime without sheath. When the cells pass through a laser interrogation region, the scattering and fluorescent signals are detected, translated and transported to software. The target cells are then identified by gating on the plots. Short bursts of standing acoustic waves are triggered by order from PC to sort target cells within predefined gating region. For very low abundance and rare labeled lymphocytes mixed with high concentration unlabeled white blood cells (WBCs), (1-100 labeled lymphocytes are diluted in 106 WBCs in 1 ml volume fluid), the device is able to remove more than 98% WBCs and recover labeled lymphocytes with efficiency of 80%. We further demonstrated that this device worked with real clinical samples by successfully isolating fetal nucleated red blood cells (FNRBCs) in the blood samples from pregnant women with male fetus. The obtained cells were sequenced and the expressions of (sex determining region Y) SRY genes were tested to determine fetal cell proportion. In genetic analysis, the proportion of fetal cells in the final picked sample is up to 40.64%. With this ability, the device proposed could be valuable for biomedical applications involving fetal cells, circulating tumor cells, and stem cells.

Modeling of Flame Retardants in Typical Urban Indoor Environments in China during 2010-2030: Influence of Policy and Decoration and Implications for Human Exposure.

Novel flame retardants (FRs) are of increasing concern, given growing evidence of health effects and use to replace polybrominated diphenyl ethers (PBDEs). This study modeled combined effects of use policies and decoration on indoor FRs and human exposure for 18 widely used PBDEs, organophosphate esters (OPEs), and novel brominated flame retardants in typical urban indoor environments in China. The current estimated indoor emission rates and average concentrations in air and dust of the 18 FRs were 102-103 ng/h, 561 ng/m3, and 1.5 × 104 ng/g, respectively, with seven OPEs dominant (>69%). Different use patterns exist between China and the US and Europe. Scenarios modeled over 2010-2030 suggested that decoration would affect indoor concentrations of FRs more than use policies, and use policies were mainly responsible for shifts of FR composition. Additional use of hexabromobenzene and 2,3,4,5,6-pentabromotoluene and removal of BDE-209 would make the total human exposure to the modeled FR mixture increase after the restriction of penta- and octa-BDE but decrease after deca-BDE was banned. Better knowledge of the toxicity of substitutes is needed for a complete understanding of the health implications of such changes. Toddlers may be more affected by use changes than adults. Such studies are supportive to the management of FR use.

The transport and distribution of novel brominated flame retardants (NBFRs) and organophosphate esters (OPEs) in soils and moss along mountain valleys in the Himalayas.

Although the Himalayas act as a natural barrier, studies have demonstrated that certain traditional persistent organic pollutants (POPs) can be transported into the Tibetan Plateau (TP) through the mountain valleys. Herein, we selected five mountain valleys in the Himalayas to investigate novel flame retardants (NFRs), as representative novel POPs, their concentration, distribution, transport behavior, potential sources and ecological risk. The results revealed that total concentrations of 7 novel brominated flame retardants (NBFRs) ranged from 4.89 to 2853 pg/g dry weight (dw) in soil and from not detected (ND) to 4232 pg/g dw in moss. Additionally, total concentrations of 10 organophosphate esters (OPEs) ranged from ND to 84798 pg/g dw in soil. Among the NFRs, decabromodiphenylethane (DBDPE) and tri-phenyl phosphate (TPhP) were the predominant compounds. NBFRs and OPEs concentrations were slightly higher than those in the polar regions. The correlation between different compounds and altitude varies in different areas, indicating that the NFRs distribution in the mountain valleys result from a combination of long-range transport and local sources. The ecological risk assessment using risk quotient (RQs) revealed that TPhP and tris (2-chloroisopropyl) phosphate (TCIPP) exhibited medium or high risks at some sites. This study sheds light on the transport pathways and environmental behaviors of the NFRs in the valleys and highlights the need for increased attention to the ecological risks posed by OPEs in the TP.

Assessment of interactions between elemental carbon and metals in black carbon: Hydroxyl radical generation and glutathione depletion.

Elemental carbon (EC) and metals are two important parts of atmospheric black carbon (BC). However, little information is available regarding the interaction between them and its impacts on the reactive oxygen species (ROS) formation and physiological antioxidants depletion. In this study, we chose six most frequently detected metals (Cu(Ⅱ), Fe(Ⅲ), Mn(Ⅱ), Cr(Ⅲ), Pb(Ⅱ) and Zn(Ⅱ)) in BC and examined their interactions with EC in the ROS generation and glutathione (GSH) oxidation. Results showed that only Cu(Ⅱ) and EC synergically promoted the GSH oxidation and hydroxyl radical (•OH) generation. Other five metals had negligible effects on the GSH oxidation regardless of the presence or absence of EC. The synergistic interaction between Cu(Ⅱ) and EC could be attributed to the superior electrical conductivity of EC. In the process, EC transferred electrons from the adjacent GSH to Cu(Ⅱ) through its graphitic carbon framework to yield Cu(Ⅰ) and GSH radical. Cu(Ⅰ) further reacted with dioxygen to generate •OH, which eventually led to the oxidation of GSH. Our results revealed a new driving force inducing the ROS formation and GSH depletion as well as provided novel insights into the risk assessment of BC.

Hexabromocyclododecanes in soils, plants, and sediments from Svalbard, Arctic: Levels, isomer profiles, chiral signatures, and potential sources.

This study investigated the occurrence, stereoisomeric behavior, and potential sources of hexabromocyclododecanes (HBCDs) in topsoil and terrestrial vegetation from Svalbard and ocean sediment samples from Kongsfjorden, an open fjord on the west coast of Spitsbergen. The mean levels of total concentrations (Σ3HBCDs) were comparable to those in other remote regions and were lower than those in source regions. Elevated proportions of α-HBCD with an average of 41% in the terrestrial samples and 25% in ocean sediments compared to those in commercial products (10-13% for α-HBCD) were observed, implying isomerization from γ- to α-HBCD in the Arctic environment. In addition, the extensive deviations of enantiomeric fractions (EFs) from the racemic values reflected the effect of biotransformation on HBCD accumulation. Linear correlation analysis, redundancy analysis, and back-trajectory were combined to infer possible HBCD sources, and the results showed the important role of global production and long-range environmental transport (LRET) for the entry of HBCDs into the Arctic at an early stage. To the best of our knowledge, this study represents the first report on the diastereoisomer- and enantiomer-specific profiles of HBCDs in the Arctic terrestrial environment and sheds light on the transport pathways and environmental fate for more effective risk management related to HBCDs in remote regions.

A high-precision, effective method for extraction and identification of small-sized microplastics from soil.

A growing evidence showed that the terrestrial ecosystem was a greater sink for microplastics (MPs) compared with ocean. Owing to the limitation of pretreatment methods, there are few reports on the identification of small-sized MPs(<60 µm) in soil currently, which may led to an underestimation of the environmental risk of MPs in soil system. In this study, we established an efficient pretreatment method for MPs in soils by developing a novel device, Plastic Flotation and Separator system (PFSS). The device integrated the suspension, digestion and filtration procedures into one system, reducing the losses of pretreatment process. It was shown that the recovery of MPs with size of 45 µm was 90%, significantly surpassing that of the traditional pretreatment methods in this particle size range. Combined with the SEM-Raman technique, MPs with small size were accurately determined. This work provides an effective method for the extraction and determination of MPs in soils and is of significance for the risk assessment of MPs in soil system.

An evaluation of the impact of traffic on the distribution of PAHs and oxygenated PAHs in the soils and moss of the southeast Tibetan Plateau.

Contaminants in high-altitude mountains such as the Tibetan Plateau (TP) have attracted extensive attention due to their potential impact on fragile ecosystems. Rapid development of the economy and society has promoted pollution caused by local traffic emissions in the TP. Among the pollutants emitted by traffic, polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) are of particular concern due to their high toxicity. The TP provides an environment to explore the degree and range of contribution for traffic-induced PAHs and OPAHs. In this study, soils and moss were collected at different altitudes and distances from the G318 highway in the southeast TP. The total concentrations of PAHs (∑16PAHs) and OPAHs (∑6OPAHs) in soils were in the range of 3.29-119 ng/g dry weight (dw) and 0.54-9.65 ng/g dw, respectively. ∑16PAH and ∑6OPAH concentrations decreased logarithmically with increasing distance from traffic. A significantly positive correlation between ∑16PAHs and altitude was found at sampling points closest to traffic. Dominant PAHs constituents in soil and moss included chrysene (CHR), benzo[g,h,i]perylene (BghiP), and benzo[b]fluoranthene (BbF); prevalent OPAH compounds were 9-fluorenone (9-FO) and 9,10-anthraquinone (ATQ). These compounds were related to characteristics of traffic emissions. The multiple diagnosis ratio and correlation analysis showed that exhaust emissions were the main source of the PAHs and OPAHs in the studied environment. PMF modeling quantification of the relative contribution of traffic emissions to PAHs in roadside soils was 45 % on average. The present study characterized the extent and range of traffic-induced PAH and OPAH emissions, providing valuable information for understanding the environmental behaviors and potential risks of traffic-related contaminants in high-altitude areas.

Insight into the oxidation of glutathione mediated by black carbon from three typical emission sources.

Black carbon (BC) is released into the atmosphere in large quantities from different emission sources each year and poses a serious threat to human health. These BC possessed a variety of characteristics and different mediation abilities for the reactive oxygen species (ROS) generation. In this study, we collected BC (i.e., diesel BC, coal BC and wood BC) from three typica emission sources, and examined their mediation abilities to the oxidation of glutathione (GSH). Results showed that all three BC significantly promoted the GSH oxidation, and the mediation efficiencies were as follows: diesel BC > coal BC > wood BC. In comparison with the water-soluble fraction, the mediation abilities of three BC mainly came from their solid phase fractions. In the coal BC and wood BC systems, the oxidation of GSH was attributed to the catalysis of transition metals in BC. By contrast, the transition metals, phenolic -OH and persistent free radicals in diesel BC were identified as the active sites responsible for the GSH oxidation. In addition, the graphitic surface of diesel BC could synergize with these active sites to accelerate the oxidation of GSH. Under the catalysis of BC, dissolved oxygen was first reduced to ROS (O2•- and H2O2) and then caused the GSH oxidation. These findings not only help to better assess the adverse health effects of different BC, but also deepen the understanding of the reaction mechanisms.

Occurrence, spatial distribution, and sources of PFASs in the water and sediment from lakes in the Tibetan Plateau.

Per-and polyfluoroalkyl substances (PFASs) are omnipresent globally and received increasing attention recently. However, there are limited data on PFASs in the Tibetan Plateau (TP), a remote high-altitude mountain region, which is regard as an important indicator region to study long-range transport behaviors of contaminants. This study investigates the occurrence, distribution, partitioning behavior, and sources of 26 PFASs in water and sediments from the four lakes of TP. The ΣPFAS concentrations ranged from 338 to 9766 pg L-1 in water, and 12.2-414 pg g-1 dry weight in sediments. Perfluorobutanonic acid (PFBA) and perfluorooctane sulfonate (PFOS) were detected in all samples. Qinghai Lake had the highest ΣPFAS concentrations in both water and sediments, while the Ranwu Lake had the lowest. The functional groups and CF2 moiety units were investigated as essential factors influencing the partition behavior. Principal component analysis (PCA) combined back-trajectory was used to infer possible sources of PFASs. The results suggested that the main source of PFASs in Yamdrok Lake, Namco Lake, and Ranwu Lake on southern TP were mainly originated from South Asia via long-range atmospheric transport (LRAT); while for the Qinghai Lake of northern TP, LRAT, local emissions, and tourism activities were the primary sources of PFASs.

Spatial and temporal trends of polychlorinated naphthalenes in the Arctic atmosphere at Ny-Ålesund and London Island, Svalbard.

Polychlorinated naphthalenes (PCNs) are ubiquitous atmospheric pollutants that can even be found in the most remote region of the Arctic. However, temporal trend analysis and reports on mono- to octa-CN in the Arctic air are still scarce. In the present study, 8 years of atmospheric monitoring data of PCNs on Svalbard was investigated using XAD-2 resin passive air samplers (PASs) from 2011-2019. The concentrations of ∑75 PCNs in the Arctic air ranged from 4.56 to 85.2 pg/m3, with a mean of 23.5 pg/m3. The mono-CNs and di-CNs were the dominant homologue groups accounting for 80 % of the total concentrations. The most abundant congeners were PCN-1, PCN-2, PCN-24/14, PCN-5/7, and PCN-3, respectively. A declining time trend of PCN concentration was observed from 2013 to 2019. The reduction in PCN concentrations is likely due to declining global emissions and banned production. However, no significant spatial difference was observed among the sampling sites. The total PCN toxic equivalency (TEQ) concentrations in the Arctic atmosphere ranged from 0.043 to 1.93 fg TEQ/m3 (mean 0.41 fg TEQ/m3). The fraction of combustion-related congeners to ∑PCNs (tri- to octa-CN) analysis results indicated that the sources of PCNs in the Arctic air were contributed mainly from reemissions of historical Halowax mixtures and combustion-related sources. To the best of our knowledge, this is the first research to report all 75 PCN congeners and homologue groups in Arctic air. Therefore, this study provides data on recent temporal trend analysis as well as all the 75 PCN congeners in the Arctic atmosphere.

Single-particle analysis of micro/nanoplastics by SEM-Raman technique.

Micro/nanoplastics (MNPs) have received global concern due to their widespread contamination, ingestion in organisms, and the ability to cross the biological barrier. Although MNPs have been detected in a variety of ecosystems, the identification of single MNPs remains an unsolved challenge. Herein, for the first time, scanning electron microscope (SEM) coupled with surface-enhanced Raman spectroscopy (SERS), which combined the advantages of ultrahigh spatial resolution of SEM and structural fingerprint of Raman spectroscopy, was proposed to identify MNPs at single-particle level. Under the optimum conditions, the polystyrene (PS) MNPs with sizes of 500 nm and 1 µm were identified by the image of SEM and fingerprint peaks of Raman spectroscopy. Additionally, the applicability of the method in different sample matrices and for other types of MNPs such as poly-methyl methacrylate (PMMA) with the sizes of 300 nm, 1 µm were validated. This method is simple, rapid and effective and is likely to provide an essential tool to identify other micro/nanoparticles in addition to MNPs.

First report on hydroxylated and methoxylated polybrominated diphenyl ethers in terrestrial environment from the Arctic and Antarctica.

Terrestrial plants, which account for the world's largest biomass and constitute the basis of most food webs, take up, transform, and accumulate organic chemical contaminants from the ambient environment. In this study, we determined the concentrations and congener profiles of polybrominated diphenyl ethers (PBDEs) and hydroxylated and methoxylated polybrominated diphenyl ethers (OH-PBDEs and MeO-PBDEs) in surface soil and vegetation samples collected from the Arctic (Svalbard) and Antarctica (King George Island) during the Chinese Scientific Research Expeditions. The concentrations of total PBDEs (∑PBDEs) in soil and vegetation samples collected from the Arctic (5.6-270 pg/g dry weight) were higher than those from Antarctica (2.3-33 pg/g dw), whereas the concentrations of ∑MeO-PBDEs and ∑OH-PBDEs were lower in Arctic terrestrial samples (n.d.-0.75 and 0.0008-1.1 ng/g dw, respectively) than in samples from Antarctica (0.007-4.0 and 0.034-25 ng/g dw, respectively). Long-range atmospheric transport and human activities were potential sources of PBDEs in polar regions, whereas the dominance of ortho-substituted MeO-PBDE and OH-PBDE congeners in terrestrial matrices indicated the importance of natural sources. To the best of our knowledge, this study represents the first report on the levels and behaviors of MeO-PBDEs and OH-PBDEs in terrestrial environment of polar regions.

Novel brominated and organophosphate flame retardants in the atmosphere of Fildes Peninsula, West Antarctica: Continuous observations from 2011 to 2020.

Novel brominated flame retardants (NBFRs) and organophosphate esters (OPEs) have been widely detected in various environmental matrices worldwide and raised public concerns in recent years. However, few studies reported their occurrence and temporal trend in Antarctic air. In this study, concentrations, distribution, and temporal trends of NBFRs and OPEs in the air of Fildes Peninsula, West Antarctica, were investigated using XAD resin-based passive air sampling from January 2011 to January 2020. Air concentrations of the total OPEs (Σ7OPEs) were one to two orders of magnitude higher than those of the total NBFRs (Σ6NBFRs). Decabromodiphenyl ethane and tris(2-chloroethyl) phosphate were the most abundant NBFR and OPE congeners, respectively. Significant positive correlations were observed among hexabromobenzene, pentabromoethylbenzene, and pentabromotoluene, indicating that their occurrence in Antarctic air may be affected by similar sources. No spatial differences in any of the NBFR and OPE congeners were observed, implying minor impact from local scientific research stations. Linear regression analysis was used to evaluate the temporal trends of NBFRs and OPEs in Antarctic air, with decreasing trends observed for Σ6NBFRs and Σ7OPEs. This is one of the rare studies providing a comprehensive investigation of the temporal trends in NBFRs and OPEs in Antarctic air and highlights concern regarding the contamination of these chemicals in remote polar regions.

Polychlorinated naphthalenes (PCNs) in soils and plants from Svalbard, Arctic: Levels, distribution, and potential sources.

As persistent organic pollutants (POPs) newly banned by the Stockholm Convention, polychlorinated naphthalenes (PCNs) have been widely detected in various environmental matrices. To date, however, the occurrence of PCNs in soils and plants in the Arctic environment has not been reported. In the current study, the concentrations and distribution of PCNs in Arctic soils and plants from Svalbard were analyzed. Total PCN concentrations ranged from 5.3 to 2550 pg/g dry weight (dw) in soils and 77 to 870 pg/g dw in plants. The higher levels of PCNs near the research stations and Longyearbyen town highlighted the significant influence of local anthropogenic emission sources. The composition of PCNs in Arctic soils and plants was dominated by lower chlorinated homologues, especially mono- to trichlorinated naphthalenes, which accounted for over 80 % of total PCNs in the soil and plant samples. The correlation analysis indicated the potential influences of total organic carbon (TOC) content on PCN concentrations in the soil, and octanol-air partition coefficients (KOA) or octanol-water partition coefficients (KOW) on PCN accumulation from soils to plants. To the best of our knowledge, this is the first study to report on the concentration and distribution of PCNs in Arctic soils and plants.

Cosorption of Zn(II) and chlortetracycline onto montmorillonite: pH effects and molecular investigations.

Ionic antibiotics and metals generally coexist, and their interaction can affect their sorption behaviors onto soil minerals, therefore determining their environmental hazards. This study investigated the sorption and cosorption of Zn(II) and chlortetracycline (CTC) onto montmorillonite at different solution pH (3-10) using batch experiments and extended X-ray absorption fine structure (EXAFS) analysis. The Langmuir model could reproduce well the sorption isotherms of Zn(II) and CTC. The presence of CTC/Zn(II) could promote the maximum sorption capacity (Qm) of Zn(II)/CTC, based on site energy distribution (SED) theory. Generally, Zn(II) sorption increased with pH increasing. Comparatively, CTC sorption decreased as pH increased till approximately pH 5.0, then increased continuously with pH increasing. Both CTC and Zn(II) co-existence enhanced their individual sorption in both acidic and neutral environments. The processes behind CTC and Zn(II) sorption mainly included cation exchange and surface complexation. The EXAFS data evidenced that the presence of CTC could alter the species of Zn(II) on montmorillonite via surface complexation at pH 4.5 and 7.5, with Zn-CTC complexes being the predominant species on montmorillonite at pH 7.5. At pH 9.5, Zn(II) may exist onto montmorillonite in precipitated form similar to Zn-Al hydrotalcite-like compound (HTlc) regardless of CTC presence.

Legacy and novel brominated flame retardants in air of Ny-Ålesund, Arctic from 2011 to 2019.

Concentrations of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in the atmosphere of Ny-Ålesund, Svalbard, were investigated. Passive air samples were collected for eight consecutive one-year periods from August 2011 to August 2019 at seven Arctic sampling sites. High-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC-HRMS) and gas chromatography coupled with election capture negative ionization mass spectrometry (GC-NCI-MS) were employed for PBDE and NBFR analysis, respectively. The median concentrations of Æ©11PBDEs and Æ©6NBFRs were 0.6 pg/m3 and 4.0 pg/m3, respectively. Hexabromobenzene and BDE-47 were the most abundant NBFR and PBDE congeners in the atmosphere, accounting for 31% and 24% of Æ©NBFR and Æ©PBDE concentrations, respectively. Æ©NBFR concentration was approximately six times higher than that of Æ©PBDEs in the same samples. Among NBFRs, the concentrations of 1,2,3,4,5-pentabromobenzene, 2,3,4,5,6-pentabromobenzene, and 2,3-dibromopropyl-2,4,6-tribromophenyl ether showed increasing temporal variations, with estimated doubling times of 3.0, 3.3, and 2.8 years, respectively. The concentrations of almost all PBDE congeners showed a decreasing variation, with halving times ranging from 2.1 to 9.5 years.