西南极乔治王岛冰芯研究——冰雪层定年、微粒记录及离子迁移

在分析南极乔治王岛冰帽大冰穹顶部降水和成冰条件的基础上,利用冰芯上部层物理特征参数确定的5个年层及其附近气象站相应的降水记录,结合多年降水资料将大冰穹45m冰芯划分为15个年层.应用此年层剖面,证实了微粒含量的两个异常峰值分别对应于1987年Deception岛和1980年的SealNunataks两次火山喷发.乔治王岛冰帽属于温性冰帽,大、小冰穹冰芯阴阳离子受沉积后融水渗浸淋溶作用的影响.对冰芯阴阳离子的淋溶次序分析显示,大冰穹为SO₄^2->Mg²⁺>Ca²⁺>K⁺>Cl^->Na⁺>NO₃^->Br^-,而小冰穹为Mg²⁺>Ca²⁺>SO₄^2->K⁺>Cl^->Br^->Na⁺.     

Cs+水合结构的密度泛函理论计算研究

基于密度泛函理论在ωB97XD/gen def2-tzvp基组水平上对[Cs(H_2O)n]~+(n=1～15)水合团簇结构的振动光谱进行了研究。研究表明,随着水分子数的增加,在气相和液相中,八配位的Cs~+水合团簇是最稳定的;随着水分子数的增加,Cs-O键长增大,Cs~+上的电荷密度减小。当水分子数大于11时,Cs-O键长和Cs~+上的电荷密度变化很小。O(H_2O)-O(H_2O)距离、∠O(H_2O)-Cs-O(H_2O)°统计结果表明,15个水分子足以形成Cs~+的近似饱和水合层。此外,红外光谱显示[Cs(H_2O)n]~+水合团簇中O-H伸缩振动随着水分子数的增加而发生变化,由此可以作为鉴别水合层位置的一种参考方法。     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.     

Heavy Metal Removal from Soils Using Magnetic Separation: 1. Laboratory Experiments

The removal of Cu, Zn, and Cd from a sandy soil was investigated using iron filings as an adsorbent, and subsequently recovering the iron filings by magnetic separation. The best treatment was obtained by using 5% iron filings and 3 h contact time between iron filings and the soil. The metal removal efficiency from soil extracts was evaluated, using MetPLATE^TM, a toxicity test that is specific for heavy metals, and the 48 h Ceriodaphnia dubia acute toxicity test. The toxicity removal was generally higher than 95% for Cu after a single treatment. With regard to Zn-spiked soil, the toxicity removal was 96.1%, 70.0%, and 49.6% after single treatment at the input concentration of 200 mg/kg, 400 mg/kg, and 800 mg Zn²⁺/kg soil, respectively. After two or three successive treatments, more than 90% of the toxicity was removed for 400 mg/kg and 800 mg/kg Zn-spiked soils. In the case of Cd-spiked soil, a single treatment removed 51.1% of the toxicity from 200 mg/kg Cd-spiked soil extracts while more than 90% of the toxicity was removed after two or three treatments. Chemical analysis and a mass balance study were also carried out to investigate the Cu distribution in the soil fractions. The results indicate that, before treatment, a large portion of Cu was immobilized in the soil matrix. Following magnetic separation, Cu was removed from both the soil matrix and extracts and was indeed adsorbed and concentrated on the iron filings. The retrieval of Cu by iron filings was further examined by energy dispersive X-ray spectroscopy (EDS).     

The Igarapé Weir decelerated transport of contaminated sediment in the Paraopeba River after the failure of the B1 tailings dam (Brumadinho)

The B1 dam of Córrego do Feijão Mine, owned by Vale, S.A. mining company and located on the Ferro-Carvão stream, collapsed and injected 2.8 Mm³ of clayey, silty, and sandy iron- and manganese-rich tailings into the Paraopeba River (Minas Gerais state, Brazil). The accident occurred on 25 January 2019 and the tailings have been co-transported with coarser natural sediment since then, being partly trapped in the Igarapé Weir reservoir located on the Paraopeba River nearly 45 km downstream the injection point. The general purpose of the current study was to model suspended sediment transport in the vicinity of the Igarapé Weir aiming to assess the concomitant barrier effect imposed by this structure. Specifically, the spatial distributions of suspended clay, silt, and very fine-grained sand fractions (CSS) of sediment were mapped around the Igarapé Weir under low-flow (16 m³/s) and high-flow (5 to 10,000 years return period stream discharge; 699–2,699 m³/s) regimes, using RiverFlow2D as the modelling tool. The concentrations of the various grain materials in the upstream and downstream sectors were quantified linking the barrier effect to concentration reductions in the direction of stream flow. It was also a study goal to calculate differences of iron and manganese concentrations in the sediment + tailings mixtures along the Paraopeba River. The study results showed reductions in the CSS between 6.6% and 18%, from upstream to downstream of the Igarapé Weir, related with backwater effects, free and submerged hydraulic jumps, bank sedimentation in periods of high flow, and streambed sedimentation controlled by channel sinuosity and tailings density. These reductions were accompanied by drops in the concentrations of iron and manganese present in the clay and silt fractions, which varied between 6% and 42% under low flows and between 16% and 44% under high flows. Bank sedimentation was viewed as a potential threat to the riparian vegetation in the long-term. Dredging is the potentially most effective mitigation measure to help lead the Paraopeba River to a pre-rupture condition. The retention of sediment + tailings transported in suspension is less effective than the trapping of bedload sediment + tailings behind the Igarapé weir. The efficacy of sediment trapping is expected to be larger for natural sediment because it is much coarser than the tailings. In that context, the simulations revealed for the low-flow period that 33.6% of the sediment deposition comprised suspended transport of natural sediment (thus, was comprised 66.4% of bedload transport), this proportion rose to 86.9% for mixtures of natural sediment + tailings, a result that did not differ much for the high-flow periods.     

Single-crystal electronic absorption spectroscopy of synthetic chromium-, cobalt-, and vanadium-bearing pyropes at different temperatures and pressures

 Single crystals of synthetic vanadium-, chromium- and cobalt-bearing garnets, Pyr:V0.06, Pyr:V0.13, Pyr:Cr0.04, Pyr:Co0.10, and Gt:Co3.00, and a natural vanadium-bearing grossular, Gross:V0.07 (Cr³⁺ < 0.005), were studied by electronic absorption spectroscopy in the wavenumber range 35 000–5000 cm⁻¹ under ambient conditions and at temperatures up to 600 K and pressures up to 8 GPa. The T and P behavior of the absorption band energies and intensities shows the following for the different transition metal-bearing garnets: Cr: The thermal expansion of chromium octahedra are similar to and the Racah parameter the same in synthetic Cr-doped pyrope, α_poly≅ 1.3 × 10⁻⁵ K⁻¹, and in natural pyrope, α_poly≅ 1.5 × 10⁻⁵ K⁻¹, and B=655 cm⁻¹, respectively. Ca^2+[8]-free garnets have a slightly stronger crystal field at the Y^[6] site and, therefore, the energies of the two spin-allowed Cr³⁺ dd bands are ca. 300 cm⁻¹ higher in Mg-pyrope than in natural Ca-bearing pyrope. Co: Increasing temperature causes only a small thermal expansion of the cobalt dodecahedra. Increasing pressure gives rise to appreciable compression, which is similar to that of the Fe²⁺-dodecahedra in almandine, where k=125 ± 25 GPa. T and P dependence of the Co band intensities may be caused by strong spin-orbit coupling. V: Occurs in at least two valence states and structural sites: (1) V³⁺ in octahedral sites gives rise to two spin-allowed bands, at 17 220 cm⁻¹ and 24 600 cm⁻¹, whose temperature dependence is typical for spin-allowed dd transitions in centrosymmetric sites. (2) V⁴⁺, which causes a set of dd absorption bands similar to those observed in the spectrum of V⁴⁺-doped Zr[SiO₄]. The P behavior of the V absorption bands indicates an interaction between V³⁺ and V⁴⁺ species. Received: 27 June 2001 / Accepted: 19 December 2001     

Formation and composition of cemented layers in low-sulphide mine tailings, Laver, northern Sweden

Cemented layers (hardpans) are common in carbonate or sulphide-rich mine tailings and where pyrrhotite is the predominating Fe-sulphide. Laver, northern Sweden, is an abandoned Cu-mine where the tailings have low pyrrhotite content, almost no pyrite and no carbonates. Two cemented layers at different locations in the Laver tailings impoundment were investigated, with the aim to determine their effects on metal mobility. The cementing agents were mainly jarosite and Fe-oxyhydroxides in the layer formed where the tailings have a barren surface, whereas only Fe-oxyhydroxides were identified below grass-covered tailings surface. Arsenic was enriched in both layers which also exhibit high concentrations of Mo, V, Hg and Pb compared to unoxidised tailings. Sequential extraction indicates that these metals and As were mainly retained with crystalline Fe-oxides, and therefore potentially will be remobilised if the oxic conditions become more reducing, for instance as a result of remediation of the tailings impoundment.An erratum to this article can be found at     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。