土壤中钙、镁的形态分析及提取序列的研究

本文采用改进的BCR三步连续提取法对河北某食道癌高发地土壤中钙、镁进行了形态分析及提取序列的研究。实验表明：该地区土壤中镁主要以残渣态形式存在（占总量的83.66％-88.36％）,钙则受提取序列的影响很大,在第一提取序列中,以酸溶态为主（74.11％-83.38％）;第二提取序列中,以有机物结合态为主（78.12％-97.17％）;第三、四提取序列中,以氧化物结合态为主（87.49％-103％）。提取剂的加入顺序明显影响到钙的各个形态的真实含量。     

Reclamation of wastes contaminated by copper,lead, and zinc

Waste materials containing toxic levels of copper, lead, and zinc, such as mine and smelter wastes, present difficult conditions for the establishment of vegetation. This article reviews the many attempts which have been made to reclaim these wastes. Inert wastes from mining and quarrying operations, such as slate quarry waste and certain colliery shales, seem to be good materials for reclaiming wastes contaminated by copper, lead, and zinc. Organic wastes, such as sewage sludge and domestic refuse, may provide only a temporary visual improvement and stabilization of the toxic materials.Nontolerant plant materials may often be planted directly on modern waste materials, which are less toxic than they were in the past. However, tolerant plant materials are needed for revegetating waste materials produced by early and more primitive extraction methods.     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

热脱附对多环芳烃和重金属复合污染土壤的影响

热脱附技术被广泛用于污染场地修复,但其对多环芳烃（PAHs）与重金属复合污染土壤的综合影响仍不清楚。选用PAHs和重金属复合污染模拟土壤,探究热脱附温度（220~400 ℃）和停留时间（5~60 min）对土壤中PAHs的影响,分析空气与氮气气氛下热脱附温度（310、340和370 ℃）对土壤中重金属Cu、Pb、As和Cd形态分布的影响。结果表明：随热脱附温度和停留时间的增加,土壤中PAHs去除率显著增加;低环PAHs占比逐渐减少,而高环PAHs占比逐渐增加。在2种气氛热脱附后,Cu、Pb和As弱酸提取态占比略有增加,而Cd弱酸提取态占比显著降低;可还原态和可氧化态的转化趋势具有差异性。随着热脱附温度的升高,Cu、Pb、As和Cd 4种重金属的残渣态占比均逐渐增加,说明热脱附有利于4种重金属的固定。相较于空气,氮气条件下4种重金属可氧化态和残渣态占比均增加;Cu和Pb可还原态占比显著降低,而As可还原态占比有所降低,Cd可还原态占比变化不大。氮气更有利于Cu、Pb和Cd的稳定;相反,空气更有利于As的稳定。

     

Experimental study and modeling of the transfer of zinc in a low reactive sand column in the presence of acetate

Nowadays, it is necessary to understand and identify the reactions governing the fate of heavy metals introduced into the environment with low complexing organic compounds, particularly when they are transferred through soils in urban areas. In this work the concomitant influence of pH and acetate on the fate of zinc on siliceous sand was studied in batch and non-saturated column experiments. Total zinc concentrations varied between 2 and 20 mg/l, and total acetate concentrations were fixed at 22, 72, 132, and 223 mM to obtain solution pHs of 4, 5, 6 and 7, respectively. Natural sand (diameter, 0.3-2 mm), mainly constituted of silica, was used. In batch adsorption experiments, zinc adsorption is insignificant at pH 4, low and linear at pH 5, and increasingly nonlinear, of the Langmuir type, at pH 6 and 7 indicating near-saturation conditions of surface sites at these high pH values. In column experiments, Zn retardation increases and the maximum outlet concentration of Zn decreases with rising pH and acetate concentrations. Previous column tracer experiments revealed the occurrence of regionalized water transport in the column. Modeling these data was based on a non-electrostatic approach. Batch and column data modeling was based on the PHREEQC code that allows concomitant resolution of chemical speciation and regionalized water transport. The speciation calculation indicates that the ZnAcetate+ species is the dominant Zn species in the solutions used. Batch experimental curves are correctly modeled assuming the formation of the three surface species triple bond SiOZn+, triple bond SiOH-Zn Acetate+ and triple bond SiO-Zn(Acetate)2-. The column data could be adequately modeled assuming a two-region water transport and the formation of the same three species with the same thermodynamic constants determined in the batch experiments. The hypothesis of the modeling leads to a slight overestimation of the quantities of zinc eluted (10%) at pH 6 and 7, mostly in the desorption phase. These results show that the methodology used facilitates the correct modeling of both batch and transport experiments and formulation of the hypothesis on the interactions between the low reactive sand and a complex solution.     

环境中有机锡化合物形态分析方法进展

本文综述了国内外近２０年来环境样品中有机锡化合物的分析技术。对有机锡样品的衍生技术进行了评价：系统介绍了检测有机锡化合物的气相色谱（ＧＣ）联用技术、高效液相色谱（ＨＰＬＣ）联用技术以及超临界流体液相色谱（ＳＦＣ）联用技术。     

Treatment of metal-chloride-enriched wastewater by simulated constructed wetlands

The ability of surface flow and subsurface flow simulated wetlands to remove heavy metals from a NaCI-enriched wastewater was examined, employing bulrush (Scirpus validus) and cattail (Typha angustifolia) plants, and two organically amended substrates (mixtures of mushroom compost and leaf litter,with topsoil) with a limestone liner. A simulated wastewater solution containing Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn as chloride salts was added to the wetlands at a rate of 0.3 l h^–1. During 12 weeks of surface flow, Fe was retained most efficiently (74%), and Mn the least (24%). Most metal retention occurred in residual forms, primarily in the upper 5 cm of the substrate. A subsequent 10 week subsurface flow treatment exhibited greater removal efficiencies for all metals, probably due to increased contact with the highly buffered lower substrate. During both treatments, bioaccumulation occurred in plants, but accounted for a very small portion of the total metal removal. Plant species did not significantly influence wetland performance with respect to metal retention. Substrate type did not affect removal efficiency for most metals, but did influence the forms of the metals retained in the wetland.To whom correspondence should be addressed.     

Biosorption of zinc(II) on rapeseed waste: Equilibrium studies and thermogravimetric investigations

The removal of heavy metals from aqueous effluents so as to avoid their toxic, bioaccumulation and biomagnification effects to humans and environment is usually realized by means of physical, chemical treatment, and biological processes. The aim of this study is to evaluate the potential of rapeseed waste from biodiesel production as a biosorbent for Zn(II) ions.The ability of the rapeseed waste for Zn(II) biosorption exhibited a maximum at pH 4.5–5. The removal efficiency of Zn(II) from solution with an initial concentration of 72 mg L⁻¹ varied from 39% to 89% for an increase of the rapeseed waste dose from 2 to 30 g L⁻¹. The amount of Zn(II) retained on the tested rapeseed increased with increasing metal ion concentration, but the Zn(II) sorption percentage decreased. The equilibrium data are fitted to the Langmuir isotherm better than to the Freundlich isotherm. The kinetics of Zn(II) biosorption process follows a pseudo-second order model. The thermal stability of the rapeseed before and after Zn(II) biosorption was studied by thermogravimetric analysis. It was found that the zinc loaded rapeseed exhibits a better initial thermal stability than the original rapeseed, presumably due to the cross linking generated by the intermolecular complexation of Zn(II) ions. In both cases, the thermal decomposition takes place according to some reassembling kinetic models, in two phases with order n reactions. The results of this study strongly suggest the possibility to use rapeseed as an effective biosorbent for Zn(II) ions removal from aqueous effluents (municipal/industrial wastewaters).     

An Operationally Defined Method to Determine the Speciation of Mercury

This paper presents a modified method of an operationally determined speciation of mercury in soil. The analytical work was mainly concerned to suit properly with inductively coupled plasma-atomic emission spectrometry (ICP-AES). Soil samples analysed in this study were selected from open areas around a crematorium, a waste incinerator, and two power plants. Results show that both topsoil and subsoil samples were dominated by elemental mercury Hg(0) and mercuric sulphide (HgS). The significant correlation between sulphur concentration and HgS was found in topsoil samples.     

A new approach for modelling potential effects in cation adsorption onto binary (hydr) oxides

The current approach for modelling ion adsorption onto binary (hydr)oxides using homogeneous surface complexation models involves the assumption of either an ideal mixture of the two surfaces (i.e. two surface sites on one surface) or a patchwise surface (i.e. two surfaces with one surface site on each surface). As the physical truth should be between these two limiting cases, a model which assumes a patchwise surface constituted of three patches is proposed. Two patches represent the distinct (hydr)oxides, and the third one a mixture of these distinct (hydr)oxides. Using the diffuse layer model, the three approaches are applied to literature data for Cd adsorption onto binary mixtures of alumina-coated silica at total constant Cd concentration and varying amounts of alumina coatings. For Cd adsorption onto these binary (hydr)oxide systems, the new approach explains the observed potential effects. The proposed model, which contains two additional adjustable parameters in terms of site concentrations or one adjustable parameter in terms of specific surface area, is more successful than the two limiting cases. The new model is then validated by predicting Ca and Zn behaviour on the same binary (hydr)oxide system.