Comparison of antimony and arsenic behaviour at the river-lake junction in the middle of the Yangtze River Basin

As typical metalloid toxic elements widely distributed in environmental media,the geochemical behaviour of antimony(Sb)and arsenic(As)affects environmental safety.We selected the surface waters and sediments at the river-lake junction of Dongting Lake as the research objects,analysed the concentration and chemical partitioning of Sb and As,assessed its contamination and ecological risk levels,and discussed its sources and potential influencing factors.The concentrations of dissolved Sb and As in surface waters were low(<5.46μg/L),and the concentrations of Sb and As in surface sediments were 2.49-22.65mg/kg and 11.10-136.34 mg/kg,respectively.Antimony and As in sediments were mainly enriched in the fraction of residues,but the proportion of As in bioavailability was significantly higher than that of Sb.Although the contamination level of Sb was higher than that of As,the risk assessment code(RAC)showed that the ecological risk level of As was higher than that of Sb.Rainwater erosion and mining activities(in the midstream of Zijiang River)were the main contaminated sources of Sb,while As was affect mainly by rainwater erosion.The contamination and ecological risk of Sb in the inlet of the Zijiang River should receive considerable attention,while those of As in the inlet of the Xiangjiang River should also be seriously considered.This study highlights the need for multi-index-based assessments of contamination and ecological risk and the importance of further studies on the environmental behaviour of metalloids in specific hydrological conditions,such as river-lake junctions.

Antimony speciation in the environment:Recent advances in understanding the biogeochemical processes and ecological effects

Antimony(Sb) is a toxic metalloid, and its pollution has become a global environmental problem as a result of its extensive use and corresponding Sb-mining activities. The toxicity and mobility of Sb strongly depend on its chemical speciation. In this review, we summarize the current knowledge on the biogeochemical processes(including emission, distribution,speciation, redox, metabolism and toxicity) that trigger the mobilization and transformation of Sb from pollution sources to the surrounding environment. Natural phenomena such as weathering, biological activity and volcanic activity, together with anthropogenic inputs, are responsible for the emission of Sb into the environment. Sb emitted in the environment can adsorb and undergo redox reactions on organic or inorganic environmental media, thus changing its existing form and exerting toxic effects on the ecosystem. This review is based on a careful and systematic collection of the latest papers during 2010–2017 and our research results, and it illustrates the fate and ecological effects of Sb in the environment.

Efect of dissolved organic matter on sorption and desorption of phenanthrene onto black carbon

Sorption and desorption of phenanthrene （PHE） onto black carbon （BC） extracted from sediments were studied in the presence of three types of dissolved organic matter （DOM）, including L-phenylalanine （L-PH）, peptone and citric acid. The nonlinearity of the sorption isotherms increased in the presence of DOM. The presence of L-PH reduced the sorption capacity and desorption hysteresis because of the solubilization of PHE in L-PH solution. Peptone at 50-500 mg/L also led to a decrease in sorption attributed to solubilization, although the sorbed peptone on the BC surface could slightly increase PHE sorption. Unlike L-PH and peptone, citric acid enhanced the sorption capacity and irreversibility of PHE on BC mainly due to the strong sorption of citric acid on the BC surface. Our results may help to understand the different impacts of DOM on the distribution and transport of PAH in the environment.

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed(China)

Black carbon(BC)in ten contaminated sediments from the Song-Liao watershed,NE China,was isolated upon treatments using a combustion method at 375℃,and the isolates’sorption isotherms for phenanthrene(Phen)were determined.All sorption isotherms were nonlinear and fitted well by the Freundlich model.A negative relation was found between Freundlich sorption nonlinearity parameter(n values)and BC/total organic carbon(TOC)content of the original sediments(r^(2)=0.687,p<0.01),indicating the dominance of BC in Phen sorption nonlinearity.The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logKFOC values of 6.02 to 6.42(μg·kg^(–1)·OC^(–1))/(μg·L^(–1))n for Phen.At a given Ce,the BC had higher Koc value than the original sediments,revealing a higher sorption capacity for BC.BC was responsible for 50.0%to 87.3%of the total sorption at Ce=0.05 Sw,clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.

Response of soil microbial activities and ammonia oxidation potential to environmental factors in a typical antimony mining area

Mining,smelting and tailing deposition activities can cause metal(loid)contamination in surrounding soils,threatening ecosystems and human health.Microbial indicators are sensitive to environmental factors and have a crucial role in soil ecological risk assessment.Xikuangshan,the largest active antimony(Sb)mine in the world,was taken as the research area.The soil properties,metal(loid)contents and microbial characteristics were investigated and their internal response relationships were explored by multivariate statistical analysis.The assessment of the single pollution index and Nemerow synthetic pollution index(PN)showed that the soils were mainly polluted by Sb,followed by Cd and As,in which sampling site S1 had a slight metal(loid)pollution and the other sampling sites suffered from severe synthetic metal(loid)pollution.The microbial characteristics were dissimilar among sampling points at different locations from the mining area according to hierarchical cluster analysis.The correlation analysis indicated that fluorescein diacetate hydrolase,acid phosphatase,soil basal respiration andmicrobial biomass carbonwere negatively correlatedwith PN,indicating their sensitivity to combined metal(loid)contamination;that dehydrogenase was positively correlated with pH;and that urease,potential ammonia oxidation and abundance of ammonia-oxidizing bacteria and archaea were correlated with N(nitrogen)contents.However,β-glucosidase activity had no significant correlations with physicochemical properties and metal(loid)contents.Principal components analysis suggested bioavailable Sb and pH were the dominant factors of soil environment in Xikuangshan Sb mining area.Our results can provide a theoretical basis for ecological risk assessment of contaminated soil.

A review of removal technology for antimony in aqueous solution

Antimony(Sb)and its compounds,toxic metalloid,have been classified as high-priority pollutants.Increasing Sb released into the water environment by natural processes and anthropogenic activities,which exposure threatens to human health and ecosystems.Therefore,it is of unquestionable importance to remove Sb from polluted water.Keeping in view the extreme importance of this issue,we summarize the source,chemistry,speciation,distribution,toxicity,and polluted situation of Sb about aqueous solution.Then,we provide the recent and common technology to remove Sb,which are based on adsorption,coagulation/flocculation,electrochemical technology,membrane technology,ion exchange,etc.In this review,we focus in detail on the adsorption method,researchers at present have been investigating to discover more advanced,cost-effective,eco-friendly,reusable adsorbents.However,to date the Sb-containing wastewater treatment technologies are not sufficiently developed and most of research have been tested only in controlled lab conditions.Few reports are available that include field studies and applications.We critically analyzed the salient features and removal mechanisms,evaluating benefits and limitations of these technologies,hoping to provide more references for further research.Finally,we considered the Fe-or Mn-based technologies was the most promising technique to remove Sb for field application.

Insight into removal of dissolved organic matter in post pharmaceutical wastewater by coagulation-UV/H_2O_2

The removal of four dissolved organic matter(DOM) fractions, non-acid hydrophobics,hydrophobic acids, hydrophilics and transphilics, was achieved by coagulation-UV/H_2O_2 oxidation in post-pharmaceutical wastewater(PhW W). Coagulation with Polyferric chloride(PFC), Polymeric ferric sulfate(PFS) and Polymeric aluminum ferric chloride(PAFC) was studied separately to evaluate the effects of the initial pH and coagulant dosage. The coagulation-UV/H_2O_2 oxidation method resulted in much higher reduction rates for dissolved organic carbon(DOC)(by 75%) and UV_(254)(by 92%) than coagulation or UV/H_2O_2 oxidation alone. The proportion of non-acid hydrophobics, hydrophobic acids, transphilics and hydrophilics removed by coagulation was 54%, 49%, 27% and 12 %, while the combined treatment removed 92%, 87%,70% and 39%, respectively. Parallel factor analysis(PARAFAC) of fluorescence measurements revealed that the humic-like fluorescent component C4 showed the highest removal(by 44%)during the coagulation stage. After coagulation-UV/H_2O_2 treatment, the humic-like fluorescent component C3 had the highest removal(by 72%), whereas xenobiotic organic fluorescent components C1 and C4 remained recalcitrant to decomposition. Significant correlations(R2> 0.8)between C1 and the hydrophobic acids and non-acid hydrophobics suggested the possibility of using fluorescence spectroscopy as an effective tool to assess variations in DOM fraction treatment efficacy in coagulation-UV/H_2O_2 systems. After the combined treatment, toxic inhibition of cellular activity by post PhW W decreased from 88% to 47% and biodegradability increased from 0.1 to 0.52.

Comparison of masking agents for antimony speciation analysis using hydride generation atomic fluorescence spectrometry

A sensitive atomic spectrometric method for the redox speciation analysis of Sb in water is described. The proposed method is based on the selective generation of stibine from Sb（III） in a continuous flow system using non-dispersive atomic fluorescence spectrometry for detection. The effects of the HCI concentration on the fluorescence intensities of Sb（III） and Sb（V） were investigated. The results indicated that atomic fluorescence emission due to Sb（V） can constructively interfere with the determination of Sb（III）. For the determination of Sb（III）, four compounds were tested as masking agents to inhibit the generation of stibine from Sb（V）. The effects of the concentrations of the masking agents and of HC1 on the fluorescence signals from Sb（III） and Sb（V） were studied. The results indicated that citric acid and NaF can successfully suppress hydride generation from Sb（V）. To evaluate the developed methodology and the influence of the matrix, the recovery of Sb（III） from natural water that was spiked with different Sb（III） and Sb（V） concentrations was tested.

Antimony smelting process generating solid wastes and dust:Characterization and leaching behaviors

A large amount of solid waste has been produced by the antimony smelting process in the＂World Capital of Antimony＂, Xikuangshan area in China. This study comprehensively investigated the physical and chemical characteristics of the various solid wastes, as well as the leaching behavior of the solid wastes, which included water-quenched slag,arsenic-alkali residue, desulfurized slag and blast furnace dust. These four types of waste were enriched in a variety of heavy metals and metalloids and more specifically with As and Sb levels up to 8.6 × 104 and 3.16 × 105mg/kg, respectively, in arsenic-alkali residue. For desulfurized slag and water-quenched slag, the leaching concentration of Sb significantly exceeded the acceptable limits during the leaching tests using the toxicity characteristic leaching procedure and the synthetic precipitation leaching procedure. In addition, As leaching in arsenic-alkali residue was extraordinarily hazardous, being three orders of magnitude higher than the regulatory level of As. According to the results of the extraction tests, all the tested wastes were classified as hazardous waste.

pH-dependent release characteristics of antimony and arsenic from typical antimony-bearing ores

The pH-dependent leaching of antimony（Sb） and arsenic（As） from three typical Sb-bearing ores（Banxi, Muli and Tongkeng Antimony Mine） in China was assessed using a pH-static leaching experiment. The pH changes of the leached solutions and pH-dependent leaching of Sb and As occurred in different ways. For the Banxi and Muli Sb ores, alkaline conditions were more favorable for the release of Sb compared to neutral and acidic conditions, but the reverse was true for the pH-dependent release of As. For the Tongkeng Sb ore, unlike the previous two Sb-bearing ores, acidic conditions were more favorable for Sb release than neutral and alkaline conditions.The ores with lower Sb and As contents released higher percentages of their Sb and As after 16 day leaching, suggesting that they are the largest potential sources of pollution. This work may provide key information on the geochemistry of Sb and As in the weathering zone.

Organic ligand-induced dissolution kinetics of antimony trioxide

The influence of low-molecular-weight dissolved organic matter （LMWDOM） on the dissolution rate of Sb203 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl, hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid, xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH = 3.7, 6.6 and 8.6 and added to powdered Sb203 in a stirred, thermostatted reactor （25℃）. The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony. In the 10 mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120 rain reaction. There was no effect on the dissolution of Sb203 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb203 was not determined by the stability of the dissolved complex, but by the dissociation constant ofligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms different fractions from two of galaxolide （HHCB） of sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600℃ heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich carbon （DOC） removed, model. The dissolved organic NaOH extracted, and 375℃ heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375~C heating fractions had higher carbon- normalized distribution coefficient （Koc） values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600℃ heating fractions to the overall sorption were the lowest （ 〈 20%）, while the 375℃ heating fractions were the highest （up to 85%）.

Antimony leaching release from brake pads: Effect of pH,temperature and organic acids

Metals from automotive brake pads pollute water, soils and the ambient air. The environmental effect on water of antimony （Sb） contained in brake pads has been largely untested, The content of Sb in one abandoned brake pad reached up to 1.62 × 10^4 mg/kg. Effects of initial pH, temperature and four organic acids （acetic acid, oxalic acid, citric acid and humic acid） on Sb release from brake pads were studied using batch reactors. Approximately 30% （97 mg/L） of the total Sb contained in the brake pads was released in alkaline aqueous solution and at higher temperature after 30 days of leaching. The organic acids tested restrained Sb release, especially acetic acid and oxalic acid. The pH-dependent concentration change of Sb in aqueous solution was best fitted by a logarithmic function. In addition, Sb contained in topsoil from land where brake pads were discarded （average 9 × 10^3 mg/kg） was 3000 times that in uncontaminated soils （2.7 ± 1 mg/kg） in the same areas. Because potentially high amounts of Sb may be released from brake pads, it is important that producers and environmental authorities take precautions.