Distribution of dissolved species and suspended particulate copper in an intertidal ecosystem affected by copper mine tailings in Northern Chile

The coastline near Chañaral in Northern Chile is one of the most highly Cu-contaminated zones in the world due to discharges from mining activities for more than 60 years. The speciation of Cu has been studied to determine the importance of organic complexation in highly contaminated areas, and to assess the likely physiological impacts of Cu on marine organisms. Dissolved Cu concentrations of up to 500 nM were measured, completely saturating organic ligands and leading to free Cu²⁺ concentrations in excess of 10^− 8 M. These values are higher than those reported in any other marine environment, and because they occur over an extensive area, provide a unique opportunity to study the effects of Cu on marine ecosystems and to see how Cu behaves when its speciation is predominantly inorganic. We found strong gradients in free Cu²⁺ between Chañaral and adjacent areas with lower Cu, where speciation is dominated by organic complexation. There is also a significant increase in the partitioning of Cu onto suspended particles in the contaminated areas, consistent with previous studies that showed that organic ligands stabilize Cu in the dissolved phase, whilst “excess” Cu is rapidly scavenged. Those high dissolved Cu concentrations persist in spite of solid phase partitioning and advective processes along this open-ocean coastline, suggesting that Cu inputs into the system are still very large. Measurements were made using anodic stripping voltammetry with a thin mercury film coated with Nafion, which previous workers have shown can mitigate ambiguity in the data arising from inadvertent reduction of organic complexes. Our findings suggest that this is a useful methodology for contaminated systems.     

Sample treatment with focused ultrasound and bath sonication as a powerful tool for the evaluation of cadmium pollution in estuarine waters

A new sample treatment was developed for the determination of dissolved cadmium in Tagus estuarine waters, based on focused ultrasound in conjunction with small volumes in the extraction steps for Cd pre-concentration. Cadmium was first pre-concentrated using a classical approach (APDC as the complexing agent and MIBK as the organic phase) and then back-extracted into HNO₃ with the aid of focused ultrasound, which reduced the acid concentration by more than one order of magnitude (from 4 to 0.1 mol L^− 3). This sample treatment was accomplished in less than 5 min, using low sample volume (20 mL), and low-volume, low-concentration reagents. The pre-concentration factor used in this work was 25, but different sample/organic volume ratios may be used in order to increase that value. The limit of detection and the limit of quantification in Tagus water samples were 0.03 nmol L^− 1 and 0.1 nmol L^− 3, respectively. Recoveries from spiked Tagus water were higher than 90%. The procedure was validated using the reference estuarine water NRC-SLEW-3. In the solubilization of Cd particulate, bath ultrasonication was used in conjunction with HNO₃ + HCl, followed by H₂O₂, which took about 2 instead of the usual 12 h (cooling included) when high-pressure microwave digestion is used.     

Geochemistry and environmental effect of cadmium in the super-large Jinding Pb-Zn deposit,Yunnan Province,China

The Jinding Pb-Zn deposit in Yunnan Province is the representative of a Cd-enriched area and mining activities lead to the release of Cd into the hypergenic ecosystem, resulting in Cd pollution. The concentrations of Cd vary greatly from one type to another type of rocks in the mining district. In the host rock, Cd concentrations range from 50×10^-6 to 650×10^-6 with an average of 310×10^-6. In primary ores, Cd concentrations range from 14×10^-6 to 2800×10^-6 with an average of 767×10^-6. However, in oxidized ores, Cd concentrations are highest, varying within the range of 110×10^-6 to 8200×10^-6 , averaging 1661×10^-6. It is shown that the oxidized ores are the main carder and environmental source of Cd. Leaching test showed that Pb/Zn ores are easy to oxidize and thereafter release Cd and other harmful elements. These leached elements in the leachate may be precipitated rapidly in the order of Zn〉Pb〉Cd. As for the concentration distribution of Cd in the Bijiang River, it is estimated to be 15.7 μg/L Cd in water, 49.3 mg/L in suspended substances, and 203.7 mg/L in sediments. The average value of Cd in soil from the polluted area is 83.0 mg/kg. Natural weathering of Cd-rich rocks and minerals imposes a potential environmental risk on the aquatic ecosystem of the Bijiang catchment.     

滇西沘江流域水体中重金属元素的地球化学特征

通过测定流经兰坪金顸铅锌矿区的沘江水体中Pb、Zn、Cd、As的含量和底泥中重金属元素的化学形态的含量,分析了重金属元素的分布和化学形态的变化。结果表明,沘江水遭到了Cd污染,底泥已经成为重金属元素的蓄积库,以国家土壤环境质量标准（Ⅲ级）衡量,Pb、Zn、Cd和舡分别超标3．4倍、15．8倍、106倍和2．6倍。沘江水中重金属元素含量的峰值在矿山附近的下游,而底泥中重金属元素的峰值在矿山下游30-50km的地方,矿业活动、水流变缓、pH等水体环境条件的变化都能影响水和底泥中重金属元素的含量。底泥中的Pb以碳酸盐结合态为主,Zn和Cd以铁锰氧化物结合态为主,而As以残渣态为主。Pb、Cd、Zn三种元素的环境有效态含量比较高,对沘江流域生态环境具有潜在的巨大的危害。     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

Speciation analysis and significance of ecological geochemistry

Different species of one element have different activities, so it has different effects on environment and human health. To analyze qualitatively and quantitatively the speciation of a special element in sample, which is the important basis for appraising the toxicity and studying the rule of transfer and translation of elements. Since the 1970＇s, the scheme of sequential extraction has already been used at many laboratories both at home and abroard, to get the information about heavy metals＇ activity in polluted soils. Because this method has the experimental nature, many schemes of problem has taken place, the absence of consistency of these sequential extraction have been formed. Thus the complexity of the schemes, the lack of selectivity of reagent, the lack of quality control, the result mainly related to the extraction scheme used, and so on. In the face of these problems, the study of experimental methods of sequential extraction on three different soils, sediment in Dongting Lake, soil in Jiangsu Province and loess in Shanxi Province was made. Reference materials of heavy metal speciation following sequential extraction in soil and sediment had been developed. Nowadays two kinds of sequential extraction methods which are widely used are BCR （three steps） and improved Tessier methods （seven steps）. Based on three steps of BCR, water-soluble speciation and the residual speciation were increased in our research. BCR701 was determined eight times at different laboratories using BCR three steps. The results showed that determined data obtained eight times were identical to the standard value, and it is indicated that this method has good reproducibility. The stability and homogeneity experiments indicated that the preparation of three types of candidates accorded with our requirements. Eight laboratories had afforded the determined values of 12 heavy metal elements （Cu, Pb, Zn, Mn, Co, Ni, Cd, Cr, Mo, As, Sb, Hg, Se et al.） using BCR three steps. Also, these three candidates afforded the determined values by seven steps, and 12 laboratories had participated.     

Speciation of sulfate components in size-fractionated aerosol particles using sulfur K-edge X-ray absorption near-edge structure （XANES）

Sulfates are a main constituent of aerosols, which sulfate aerosols, it is necessary to determine what can cause various environmental problems sulfate ions are contained in these aerosols In the evaluation of the influence of In this study, sulfur K-edge XANES was used to determine sulfate species present in size-fractionated aerosol particles based on the post-edge structure after the main absorption peak in the XANES region. Aerosol samples were collected as part of the Japan-China joint project, ＂Asian Dust Experiment on Climate Impact＂ using a low-volume Andersen-type air sampler. XANES was measured at Beamline BL-9A at Photon Factory, Japan. A comparison of the XANES spectra of reference sulfate materials and aerosol samples collected in Tsukuba in Japan clearly showed that （NH4）2SO4 was the main sulfur species in particles with a smaller diameter and gypsum was the main sulfur species in particles with a larger diameter. A simulation of the XANES spectra by reference materials allows us to obtain the quantitative mixing ratios of the different sulfate species present in the aerosol samples. The presence of minor sulfur species other than （NH4）2SO4 and gypsum at the surface of mineral aerosols is suggested in our simulations and by a surface-sensitive conversion electron/He-ion yield XANES. In the absence of a contribution from a large dust event, the mole concentration of gypsum in the mineral aerosol fraction determined by XANES is similar to that of Ca which is determined independently using ion chromatography. This shows that the Ca and sulfate in the mineral aerosols are present only as gypsum. Considering that calcite is the main Ca mineral in the original material arising from an arid and semi-arid area in China, it is strongly suggested that gypsum is formed in aerosol during its long-range transportation by a reaction between calcite and sulfate ions.     

Changes to cadmium associations in canal sediments on drying and oxidation

The mainly 19th Century canal system in the UK, largely managed by British Waterways, has been increasingly brought back into operation over the last few decades, and is now widely used for both leisure, and, increasingly, transport. Both initial and routine dredging of the canal sediment is carried out and these sediments are generally disposed of to land. Because many of the canals were connected with primary industries, their sediments can locally be significantly contaminated with heavy metals, and the behaviour of these metals under differing redox conditions, when introduced into a new environment （i.e., on land） is of importance for environmental risk-assessment purposes. Canal sediments are often rich in sulfidic mineral phases, and we have attempted to quantify the influence of these sulfidic phases on the release and retention of metals in dredged canal sediments, using a combination of traditional chemical techniques （e.g. sequential extraction） and X-ray absorption spectroscopy （XAS）. Sediment samples have been collected from urban fresh-water canals, one in the British Midlands and one in Northern France. It appears from XAS that Cd is largely associated with oxygen in air-dried sediment, and with sulphur in vacuum-dried sediment.     

Distribution of cadmium, chromium, copper, lead and zinc in marine sediments in Hong Kong waters

Partitioning of heavy metals (Cd, Cr, Cu, Pb, Zn) in marine sediments collected from various sites in Hong Kong waters were determined using sequential extraction method. Sediments from Kellette Bank, located in Victoria Harbour, had higher metal concentrations especially Cu and Zn than most other sites. Slightly over 20% of total Cu and Cr existed as readily available forms in Peng Chau and Kellette Bank. At most sampling sites, over 15% of the Cu existed as the exchangeable form indicating that Cu could be readily released into the aqueous phase from sediments. A significantly higher percentage of Pb and Zn was associated with the three non-residual fractions. Hence, there is a greater environmental concern for remobilization of Pb and Zn compared with Cr. The high amount of residual Cd (>50%) and the relatively lower Cd content indicate that little environmental concern is warranted for the remobilization of Cd. Distribution of metals in sediments collected from different depth at Kellette Bank shows that metal concentrations decreased with profile depth. The levels of Pb and Zn associated with the two readily available fractions increased sharply in the surface sediment. These metals represented the pollutants, which were introduced into the area in the mid-eighties through early nineties as a result of rapid economic and industrial development in the territory. As significant portions of these metals were bound to the readily available phases in the surface sediments, metal remobilization could be a concern. An erratum to this article can be found at     

邻苯二酚螯合树脂的合成及水样中铝的测定

合成并表征了新螯合树脂———邻苯二酚螯合树脂(XAD-2-Catechol),研究了XAD-2-Catechol吸附铝的特性和茜素红-铝的显色反应,在pH4.5的HAc-NaAc缓冲介质中,茜素红和铝(Ⅲ)反应生成红色络合物,λm ax=500 nm,铝的含量在0-50μg/25 mL内符合比耳定律。建立了邻苯二酚螯合树脂分离/富集-茜素红分光光度法测定天然水样中铝的新方法,对水样中铝形态进行测定,结果满意。