Chaoyang Wei

Characterizing spatial distribution and sources of heavy metals in the soils from mining-smelting activities in Shuikoushan, Hunan Province, China

The spatial variation of heavy metals in the soils in Shuikoushan mining-smelting area, Hunan Province, China, was investigated using multivariate and geo-statistic analysis. A total of 106 composite soil samples were collected in an area of about 100 km2. Concentrations of total As, Cd, Pb, Zn, Cu and Cr were measured using inductively coupled plasma mass spectrometry (ICP-MS). Arsenic and Pb were found to have a common source, indicating the same sources and spreading processes, such as aerosols and airborne particulates from smelting chimneys. Airborne sources from smelting chimneys contributed greatly to Cd in the area, which demonstrated the same dispersion pattern as As and Pb. However, two hot spots of Cd around smelters were possibly enlarged by wastewaters, demonstrating another important source of Cd in Shuikouhsan. Geo-statistic interpolated mapping demonstrated that hot-spots of Zn were only found proximal to the large smelters, suggesting that Zn primarily came from the chimneys of larger smelters. The major Cu hot-spots appeared closely to the tailing dam, indicating that weathering and leaching of tailings were the major sources of Cu contamination in Shuikoushan. Our findings indicated that airborne volatile particles and aerosols contributed the most to As, Cd, Pb, Zn and Cu contamination, while Cd and Cu may also derive from the discharge of wastewater from smelters and the leaching of tailings, respectively.

Multivariate and spatial analysis of heavy metal sources and variations in a large old antimony mine, China

PurposeContaminations by multiple heavy metals in antimony (Sb) mines produce serious environmental and health problems; however, the spatial variations in various heavy metals relative to the sources and transportation of Sb have rarely been documented. To resolve this problem, we conducted a survey in an old Sb mine in Xikuangshan (XKS), China, to investigate the similarities and differences among the sources and diffusion characteristics of the heavy metals that were present as well as the factors influencing these patterns.Materials and methodsA total of 71 surface soil samples were collected in the central study area, which has a history of intensive mining and smelting activities, as well as in surrounding areas at different distances from the central mine and with different coverage/landscape/land use characteristics; we refer to these areas as the central mining subarea, tailing subarea in the southwest, forestry subarea in the southeast, grass subarea at the northern edge of the study area and vegetation subarea at the southern edge. Multivariate and spatial analyses were performed to explore the correlations and patterns of variation of various heavy metals.Results and discussionHg and Cd were evidently elevated in XKS, whereas the concentrations of As, Pb and Zn were moderate and that of Cr was comparable to the background values. Moderate correlations were found for Sb–As and Hg–Cd, and strong correlations were observed for Pb, Zn, Cd and Cr. The southeast direction was associated with the strongest spatial autocorrelation for Sb, which is consistent with the prevailing wind direction in XKS; the optimal directions for Zn and Cd were similar and indicated the transfer of Zn and Cd contamination from subareas with high levels to those with low levels, significantly affecting the spatial distribution of these metals in XKS.ConclusionsOur results highlight the importance of the effect of wind on the diffusion of Sb in XKS. The co-contamination of Hg and Cd with Sb is widespread in XKS due to the presence of Hg and Cd in Sb-containing ores.

The Accumulation and Subcellular Distribution of Arsenic and Antimony in Four Fern Plants

In the present study, Pteris cretica ‘Albo-Lineata’ (PC), Pteris fauriei (PF), Humata tyermanii Moore (HT), and Pteris ensiformis Burm (PE), were selected to explore additional plant materials for the phytoremediation of As and Sb co-contamination. To some extent, the addition of As and Sb enhanced the growth of HT, PE, and PF. Conversely, the addition of As and Sb negatively affected the growth of PC and was accompanied with the accumulation of high levels of As and Sb in the roots. The highest concentration of Sb was recorded as 6405 mg kg−1 in the roots of PC, and that for As was 337 mg kg−1 in the rhizome of PF. To some degree, As and Sb stimulated the uptake of each other in these ferns. Arsenic was mainly stored in the cytoplasmic supernatant (CS) fraction, followed by the cell wall (CW) fraction. In contrast, Sb was mainly found in the CW fraction and, to a lesser extent, in the CS fraction, suggesting that the cell wall and cytosol play different roles in As and Sb accumulation by fern plants. This study demonstrated that these fern plants show a good application potential in the phytoremediation of As and Sb co-contaminated environments.

Simultaneous Analysis of SbIII, SbV and TMSb by High Performance Liquid Chromatography–Inductively Coupled Plasma–Mass Spectrometry Detection: Application to Antimony Speciation in Soil Samples

This study was conducted to develop a method for the simultaneous separation and detection of antimonite (Sb(III)), antimonate (Sb(V)) and trimethyl antinmony (TMSb) species in soils, using ultrasonic-aided citric acid extraction and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry separation and detection. The extractions were performed using various chemical solutions. The separation was conducted on a PRP-X100 anion exchange column (25 cm × 4.1 mm i.d., 10 µm) using an isocratic elution program. The various factors of the elution procedure, e.g., pH, elution concentration and retention time, were optimized for the best separation of the three Sb species. It was found that two consecutive extractions using 100 mmol/L citric acid at pH 2.03 resulted in the highest extraction efficiency, 53%. The optimal elution procedure was obtained by using 200 mmol/L ammonium tartrate with 4% methanol as the mobile phase at pH 5.0. Under these conditions, the retention times for Sb(III), Sb(V) and TMSb species were 3.8, 2.1 and 6.8 min with detection limits of 0.03, 0.02 and 0.05 µg/L, respectively. Spiked recoveries for Sb(III), Sb(V) and TMSb ranged from 88 to 118%. The proposed method is reliable for antimony speciation in soil samples.

Comparison of mercury speciation and distribution in the water column and sediments between the algal type zone and the macrophytic type zone in a hypereutrophic lake (Dianchi Lake) in Southwestern China

During a heavy algal bloom in 2009, we collected lake water, surface sediment, sediment cores and porewater samples from Dianchi Lake to investigate the effect of eutrophication and different aquatic habitats (algal and macrophytic) on mercury (Hg) distribution and speciation in hypereutrophic lake. The total Hg (THg) concentration in the sediment and lake water was substantially elevated compared to uncontaminated lakes and reservoirs. The spatial distribution of THg pointed to waste water discharged from Kunming City as the dominant source of Hg in Dianchi Lake. Despite the high concentration of THg, the concentration of methyl mercury (MeHg) was relatively low compared to other deep water lakes and reservoirs, and the ratio of MeHg/THg was generally lower than 1% in lake water and sediments, implying the low potential of Hg methylation. No significant relationship was found between the total organic carbon (TOC) and MeHg in either surface sediment or sediment cores. This result is different from previous conclusions that an increase of organic material load in sediment can enhance the potential of Hg methylation in sediments. A significant relationship between the total S and MeHg in the two cores indicated that sulfur played an important role in Hg methylation. However, because of similar concentrations of MeHg and distinct differences in the S concentration in the two cores, the total S should not be a limiting factor for Hg methylation in sediment. The most important limiting factors controlling Hg methylation were high pH and Eh induced by heavy algal blooms and shallow water depth in Dianchi Lake because Hg methylation will be inhibited and the demethylation of MeHg may be accelerated under alkaline and oxic conditions.

Influences of size-fractionated humic acids on arsenite and arsenate complexation and toxicity to Daphnia magna

The intrinsic physicochemical properties of dissolved organic matter (DOM) may affect the mobility and toxicity of arsenic in aquatic environments. In the present study, the humic acid (HA) was ultra-filtered into five fractions according to molecular weight, and their physicochemical properties were characterized. Complexation of HA fractions with arsenite and arsenate was first determined by differential pulse polarography (DPP). The influences of HA fractions on arsenic toxicity were then examined using Daphnia magna as a model organism. As(V) had a higher affinity with HA than As(III), and their complexation was dependent on the total acidity and fluorescence characteristics of DOM. We demonstrated that the acidity and fluorescence also better explained the As toxicity to daphnids than UV absorbance and hydraulic diameter. Arsenic speciation determined by DPP significantly affected the toxicity of arsenite and arsenate. The results extended the free-ion activity model application to the case of arsenic. The present study clearly indicated that DOM with different molecular weights has distinct physicochemical properties, and could influence the speciation and toxicity of As to different extent.

The fluctuation of arsenic levels in Lake Taihu.

This study was conducted to investigate the arsenic levels in the waters of lake Taihu, a huge, shallow, and very important lake which has been suffered with serious eutrophication in China. Unexpected great difference was detected for arsenic levels between the collected water samples of three successive surveys in Taihu in May 2009, Fall 2009, and May 2010, with arsenic levels in May 2009 being more than tenfold of those in Fall 2009 and May 2010. Such difference in arsenic levels do not routinely happen like seasonal changes as reported in many other lakes of the world. Considering arsenic contents as well as some basic aquatic monitoring data of the lake, such great arsenic fluctuations were probably due to the effects of strong hydraulic turbulence in Taihu for its very shallow depth. The spatial distribution of arsenic in Taihu were similar, despite great difference of arsenic levels in the three successive surveys, indicating such differences did not come from arsenic external input around the lake. The sudden increase of arsenic levels in Taihu highlights the importance of stabilization or removing of arsenic in lake sediments so as to keep arsenic lower than the national hygiene standard of China.

Multivariate analysis of elements in Chinese brake fern as determined using neutron activation analysis

Pytoremediaton of arsenic (As) contamination using Chinese brake fern (Pteris vittata L.), an As hyperaccumulator has proven potential because of its cost-effectiveness and environmental harmonies. Aiming to investigate the elemental correlation in Chinese brake fern, 20 elements (As, Br, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, Na, Nd, K, Rb, Se, Sm, Sr, Th, Yb and Zn) were measured in the fronds and roots of the fern by neutron activation analysis. The ferns were sampled from two sites with high geogenic As levels: Zimudang (ZMD) and Lanmuchang (LMC) in Guizhou Province, China. Multivariate statistic analysis was performed to explore the interrelationship between these elements, especially between As and other elements. As was found to be positively related to K, Na, La, and Sm in both the roots and the fronds, suggesting that these four elements might operate as synergies to As during uptake and transportation processes. Se was positively related to most of the other cations measured, except in the fronds of the fern at ZMD, where Br replaced Se as positively related to the other cations. The difference of As and Se in correlation with other cationic elements suggested that the two anionic elements play different roles in elemental uptake processes. Our findings of elemental correlation highlight the importance of the anioncation balance in Chinese brake fern.

Bioaccumulation and oxidative stress in Daphnia magna exposed to arsenite and arsenate

Arsenic pollution and its toxicity to aquatic organisms have attracted worldwide attention. The bioavailability and toxicity of arsenic are highly related to its speciation. The present study investigated the differences in bioaccumulation and oxidative stress responses in an aquatic organism, Daphnia magna, induced by 2 inorganic arsenic species (As(III) and As(V)). The bioaccumulation of arsenic, Na(+) /K(+) -adenosine triphosphatase (ATPase) activity, reactive oxygen species (ROS) content, total superoxide dismutase (SOD) activity, total antioxidative capability, and malondialdehyde content in D. magna were determined after exposure to 500 µg/L of arsenite and arsenate for 48 h. The results showed that the oxidative stress and antioxidative process in D. magna exposed to arsenite and arsenate could be divided into 3 phases, which were antioxidative response, oxidation inhibition, and antioxidative recovery. In addition, differences in bioaccumulation, Na(+) /K(+) -ATPase activity, and total SOD activity were also found in D. magna exposed to As(III) and As(V). These differences might have been the result of the high affinity of As(III) with sulfhydryl groups in enzymes and the structural similarity of As(V) to phosphate. Therefore, arsenate could be taken up by organisms through phosphate transporters, could substitute for phosphate in biochemical reactions, and could lead to a change in the bioaccumulation of arsenic and activity of enzymes. These characteristics were the possible reasons for the different toxicity mechanisms in the oxidative stress process of arsenite and arsenate.

Arsenic characteristics in the terrestrial environment in the vicinity of the Shimen realgar mine, China

In this study, multiple types of samples, including soils, plants, litter and soil invertebrates, were collected from a former arsenic (As) mine in China. The total As concentrations in the soils, earthworms, litter and the aboveground portions of grass from the contaminated area followed the decreasing order of 83-2224 mg/kg, 31-430 mg/kg, 1-62 mg/kg and 2-23 mg/kg, respectively. X-ray absorption near-edge structure (XANES) analysis revealed that the predominant form of As in the soils was arsenate (As(V)), while no arsenite (As(III)) was detected. In the grass and litter of the native plant community, inorganic As species (As(V) and As(III)) were the main species, while minor amounts of DMA, MMA, AsC, and an unknown As species were also detected in the extracts analyzed with high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The As speciation and As concentrations varied with the plant species, and very high As levels (197-584 mg/kg) and proportions of inorganic As (>99%) were found in two As-hyperaccumulating ferns, Pteris vittata and Pteris cretica. The major As species extracted from earthworms were inorganic, with proportions of 51-53% As(III) and 38-48% As(V). AsB was the only organic species present in the earthworm samples, although at low proportions (<8.99%). The internal bioconversion of other As species is hypothesized to contribute greatly to the formation and accumulation of AsB in earthworms, although the direct external absorption of organic As from soils might be another source. This study sheds light on the potential sources of complex organoarsenicals, such as AsB, in terrestrial organisms.