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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 Lsup-1/supin water, and 12.2-414 pg gsup-1/supdry 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 CFsub2/submoiety 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.

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 (O

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 Ʃ

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 (Σ

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

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.

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.

Black carbons (BCs) are ubiquitous in the natural environment and can significantly influence the environmental behavior of pollutants. This work examined the mediating effects of graphite, soot, and biochar on 1-naphthylamine (1-NA) oxidation under aerobic conditions. It was shown that the three BCs significantly promoted the oxidation of 1-NA in the dark, and the mediation efficiency of graphite was much greater than that of soot or biochar. The oxidation products were the coupling oligomers (dimers and trimers) and the oxygen-containing oligomers of 1-NA (di-OH-1-NA, OH-azo naphthalene, OH-trimers and amino-naphthoquinone derivatives etc.). The phenolic OH on BCs were identified as the active sites for 1-NA oxidation, which could stimulate O2 to produce reactive oxygen species through successive single electron transfer and then cause 1-NA oxidation. Moreover, the superior catalytic performance of graphite was also related to its high electrical conductivity. The synergies between the sp2-hybridized carbon surface and the active sites (such as phenolic OH and defects) facilitated the oxidation of 1-NA on graphite. Findings in this study not only are helpful for better understanding the reactivity of environmental BCs, but also provide new insights into the risk assessment of 1-NA in the natural environment.

Research on the environmental fate and behavior of novel brominated flame retardants (NBFRs) remains limited, especially in the remote alpine regions. In this study, the concentrations and distributions of NBFRs were investigated in soils and mosses collected from two slopes of Shergyla in the southeast of the Tibetan Plateau (TP), to unravel the environmental behaviors of NBFRs in this background area. The total NBFR concentrations (∑7NBFRs) ranged from 34.2 to 879 pg/g dw in soil and from 72.8 to 2505 pg/g dw in moss. ∑7NBFRs in soil samples collected in 2019 were significantly higher than those in 2012 (p

Metal cations and organic pollutants mostly co-exist in the natural environment. However, their interactions in adsorption processes have yet to be adequately addressed. In the current study, the effect of inorganic cations with different charges (Ag(+), Zn(2+), and Al(3+)) on the adsorption and desorption of 2,4,6-trichlorophenol (TCP) onto and from processed ash derived from wheat (Triticum aestivum L.) straw was investigated. The adsorption and desorption of TCP were both nonlinear; the isotherm and kinetics curves fitted well using the Freundlich equation and a pseudo-second-order model, respectively. The presence of Ag(+) promoted TCP adsorption, while Zn(2+) and Al(3+) reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag(+), Zn(2+), and Al(3+) caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn(2+) and Al(3+) was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al(3+) had a stronger inhibition effect than that of Zn(2+) due to its higher binding capacity and larger hydrated ionic radius than those of Zn(2+). Enhanced adsorption of TCP onto ash by Ag(+) was ascribed to its ability to reduce the competitive adsorption of water molecules on ash surface by replacing the original ions, such as Na(+) and Ca(2+), and compressing the hydrated ionic radius of these metal ions. In addition, Ag(+) was able to bind with the aromatic organic compounds containing π-electrons, which resulted in a further increase of TCP adsorption by ash.

Effect of norfloxacin (Nor) on the sorption of 1,3-dinitrobenzene (1,3-DNB), and PAHs (naphthalene (NAPH), phenanthrene (PHEN) and pyrene (PYR)) to K(+)-montmorillonite was studied. Nor suppressed 1,3-DNB sorption due to their competition for the same sorption sites. 1,3-DNB was sorbed on K(+)-montmorillonite surface via cation-polar interaction and n-π electron donor-acceptor interaction. Nor also was sorbed on these sites through cation exchange, cation bridging and/or surface complexation. Nor increased three PAHs sorption on montmorillonite and the enhanced magnitude was positively correlated with the π-donor strength of three PAHs. The enhanced sorption of PAHs by Nor was primarily attributed to π-π interaction between π-electron-depleted quinoline ring of Nor and π-electron-rich PAHs. Compared with cation (Nor(+)) and anion (Nor(-)), zwitterion (Nor(±)) of Nor increased PHEN and PYR sorption more pronounced due to additional cation-π interaction between the sorbed Nor(±) and PAHs. (1)H NMR spectrum provided direct evidence for π-π and cation-π complexation between PAHs and Nor(+) in solution by ring-current-induced upfield chemical shifts of amino group and methylene group of Nor(+).

The effect of lead on the adsorption of diuron and dichlobenil on multiwalled carbon nanotubes (MWCNTs) was investigated to explore the possible application of MWCNTs for removal of both herbicides from contaminated water. The adsorption of diuron and dichlobenil on MWCNTs at pH 6 was nonlinear and fit the Polanyi-Manes model well. The adsorption of diuron and dichlobenil was closely correlated with specific surface areas and micropore volumes of MWCNTs. An increase in oxygen content of MWCNTs with same diameters and similar surface areas decreased the adsorption of diuron and dichlobenil, while increased the adsorption of lead. Micro-Fourier transform infrared spectroscopic study indicated that hydrogen bonding is a main mechanism responsible for the adsorption of diuron or dichlobenil onto MWCNTs-O. Oxygen containing groups, mainly carboxylic groups, significantly increased the adsorption of lead through the formations of outer-sphere and inner-sphere complexes, which are verified by X-ray absorption spectroscopic measurements. Oxygen containing groups and the presence of lead diminished the adsorption of diuron and dichlobenil. The suppression mechanisms of lead were ascribed to hydration and complexation of lead with carboxylic groups, which may occupy part of surface of MWCNTs-O. The large hydration shell of lead cations may intrude or shield hydrophobic and hydrophilic sites, resulting in a decreased adsorption of diuron and dichlobenil at the lead-complexed moieties. (C) 2011 Elsevier B.V. All rights reserved.

Effects of copper (Cu) and aluminum (Al) on the adsorption of sulfathiazole (STZ) and tylosin (T) to peat and soil were investigated using a batch equilibration method. Results show that Cu suppressed STZ adsorption onto peat and soil at pH 5.0 because of the electrostatic competition, while increased STZ adsorption at pH 5.0 due to the formation of STZ-Cu complexes and/or Cu bridge. In contrast, Al only decreased STZ adsorption at pH 6.0, and exerted slight effect on STZ adsorption at6.0. As for T, both Cu and Al suppressed its adsorption over the entire pH range owing to three reasons: 1) electrostatic competition between Cu/Al and T(+); 2) Cu/Al adsorption made the soil and peat surface less negatively charged, which was unfavorable for T(+) adsorption; 3) the shrunken pore size of peat and soil retarded the diffusion of large-sized T into these pores.

Heavy metals and organic contaminants often coexist in soils. However, very little information is available regarding the effect of metals on the sorption of organic contaminants onto soils and/or of organic contaminants on metal sorption. In the present study, the effect of Cu on the sorption of p-nitrophenol on two Chinese soils was investigated using a batch-equilibration method for three conditions: Copper and p-nitrophenol were sorbed simultaneously, either Cu or p-nitrophenol was sorbed previously, or the soil colloidal phase was removed in part previously. The results suggested that Cu suppressed the sorption of p-nitrophenol on soils, whereas p-nitrophenol had little effect on Cu sorption because of the higher affinity of Cu for soils. Mechanisms of the Cu suppression effect were suggested by the results. First, large hydrated Cu occupy the siloxane surface of soils and prevent nonspecific interaction between p-nitrophenol and soils. Second, the soil colloidal phase is an effective adsorbent of p-nitrophenol; thus, more p-nitrophenol is retained in the aqueous phase. In addition, the aggregation of the colloidal particles may occur, which blocks soil pores, thereby decreasing the sorption of p-nitrophenol on the solid soil phase. Third, x-ray absorption spectroscopy revealed that Cu forms inner-sphere complexes with the carboxyl and hydroxyl functional moieties of the soil particles (clay minerals and organic matter). Fourier-transform infrared spectroscopy study indicated that these groups also react with p-nitrophenol through H-bond formation. These results suggested that Cu and p-nitrophenol have common sorption sites, at least in the soil organic matter domain, which is partially responsible for the observed overall Cu suppression effect.

The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP.

The effect of copper on adsorption of p-nitrophenol on two typical Chinese soils was investigated using a batch-equilibration method. Adsorption experiments were carried out when both copper and p-nitrophenol were adsorbed Simultaneously, and when copper was previously adsorbed oil soils. It was observed that adsorption of p-nitrophenol decreased with increasing copper concentrations thereby indicating a competition between copper and p-nitrophenol for occupying the adsorption sites oil soils. Moisture increased the hydrated sphere and the acidity of Water Surrounding the cation, which further reduced the adsorption of p-nitrophenol. Fourier transform infrared Spectroscopy study provided the direct evidence for the coordination of p-nitrophenol sorbed by soils with metal cation in n-hexane system. It was observed that the perturbations included a red shift of the v(sym) (NO) hand, a concomitant blue-shift of the v(sym) (NO) hand and a blue-shift of C-N hand when compared with the infrared spectra obtained from water solution. (c) 2005 Elsevier Ltd. All rights reserved.

Evidence exists for significant metal enrichment in particulate organic matter (POM) compared to other soil constituents, but the relevant mechanisms are poorly understood. In the present study, adsorption of the heavy metals Pb, Cu, and Cd on a loamy soil and on POM separated from this soil was investigated. The adsorption kinetic data can be well described with a pseudo-second order model, whereas the equilibrium data are well fitted by a Langmuir model. Adsorption isotherms and kinetics data, in addition to the influence of pH on metal adsorption, showed that POM had a much higher adsorption capacity for Pb, Cu, and Cd compared to the whole soil. Ionic strength effects on metal adsorption, Fourier transform infrared spectroscopy, x-ray absorption spectroscopy x-ray absorption spectroscopy including x-ray absorption near-edge structure and extended x-ray absorption fine-structure spectroscopy were employed to elucidate the adsorption mechanisms. The results suggested that Pb and Cu adsorption on POM was mainly through inner-sphere complexes with carboxyl and hydroxyl groups. Cadmium was possibly adsorbed via outer-sphere complexation, indicated by the influence of ionic strength on Cd adsorption.