湘江水体中重金属的化学形态及分布特征的研究

水体中重金属的生态效应和迁移转化规律与其化学形态密切相关。本文结合湘江重金属水容量与背景值的研究,较系统地研究了铜、铅、镉和锌的化学形态及其在全江段水中的分布特征。应用阳极溶出伏安法,得到湘江水中重金属总量、溶解态含量和悬浮态含量的分配与分布特征,还有溶解态所包含的金属的主要存在形态及与之共存的其它多种形态(包括悬浮态)共十种,该文对其形成、分配和相互转化进行了综合分析。     

聚合铝混凝过程研究:不同形态硅酸的影响作用

研究了不同形态硅酸对聚合铝混凝过程的影响作用 .实验结果表明经预制形成的具有不同形态分布组成的硅酸与聚合铝 ,在投加后相互间发生了十分复杂的物理化学作用 ,并受溶液pH值的影响 ,从而最终决定了混凝效果 .反应过程中所生成的形态产物及其物化特征 ,很大程度上取决于聚合铝碱化度以及所投加的Si Al比 .其中碱化度越高 ,最终产物所带电荷越高 .而不同硅酸所起影响作用分别取决于聚合程度 ,在与聚合铝反应过程中表现出一定的规律性 .单体硅酸与单体铝迅速发生较强的络合作用 ,抑制了多聚水解铝阳离子的形成 .聚合硅酸则倾向于与聚合铝形态相互作用形成一定的胶状化合物 ,从而在溶液中稳定存在 .对于胶体硅酸 ,在聚合铝作用下迅速凝聚形成更大的聚集体 ,在颗粒物间架桥形成粗大的絮体 .所得结果对混凝机理的解释与复合混凝剂的发展提供了一定的参考作用     

Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

污泥在堆肥及油污土壤修复中重金属形态的研究

污泥堆肥工艺是实现污泥减量化,无害化和资源化的重要手段。文章考察了污泥在堆肥前后四类重金属(铜、锌、铅和镉)形态的变化。结果显示,铜、锌、铅和镉在堆肥前后的总量变化不大,Cu、Zn主要以有机结合态和残渣态形式存在,而Pb、Cd主要以残渣态形式存在。堆肥处理过程中可交换态重金属都呈下降趋势,但各种重金属的可交换态变化幅度不同,以Zn和Cd下降幅度最大,Zn的可交换态由堆肥前的10.5%下降到堆肥后的4.8%;Cd的可交换态从堆肥前的3.2%下降到堆肥后的1.8%,下降比例超过和接近50%。随着向土壤中添加污泥及堆肥量的增加,小麦植株地上和地下部分重金属含量也相应增加,且地下部分含量高于地上部分,小麦中重金属含量在地下部与地上部之间的比值恒定,特别是Pd,Cd的地上和地下部分浓度比可分别达到130和15～20,经堆肥处理的污泥可以降低小麦对其中重金属的吸收。将污泥及堆肥腐熟品添加至石油污染土壤中,与对照相比土壤中的石油烃含量有一定幅度的下降,最大下降幅度为19.6%。处理一个月后重金属含量及其形态变化不大,Zn具有向铁锰氧化态转化的趋势。     

硒连续化学提取技术中的若干问题讨论

硒的生物可利用性、毒性、环境行为和生物效应等不仅仅与硒的总量有关,更取决于硒的形态。硒的连续化学提取技术是硒形态研究的一个重要手段。在硒七步连续提取方案的基础上,重点探讨了有机结合态、元素态、硫化物/硒化物结合态硒的提取技术细节,讨论了不同液固比和提取剂对硒提取的影响,并对不同结合态硒提取中存在的问题进行了相应讨论。研究结果表明:在硒的连续化学提取过程中,液固比为20:1到50:1时能够满足不同结合态硒提取的要求;在水浴加热条件下,NaOH浓度0.1～0.5mol/L时能有效提取有机结合态硒;1mol/LNa2SO3溶液是元素硒的较好提取剂;而对于硫化物/硒化物结合态硒,600～700ml/min的载气气流能保证其还原所产生HSe气体的完全吸收。     

垃圾焚烧中氯化物对重金属Cd迁移转化特性的影响

采用管式炉和模拟垃圾对垃圾焚烧中氯化物对重金属Cd迁移转化特性的影响进行了研究,使用ICP-AES(美国EPA消解方法)、SEM、EDS和XRD分析技术对重金属浓度、灰渣表面形貌、成分和灰渣X射线衍射物相等进行了分析.结果表明,氯化物的加入均使得97％以上的Cd分布于飞灰中,且随氯化物含量的增加在飞灰中的分布逐渐增加.有机氯PVC和无机氯NaCl含量的变化对Cd迁移分布的影响没有显著差别.PVC对Cd迁移分布影响受温度影响显著,550℃时Cd在飞灰中分布为80.51%,850℃时Cd在飞灰中的分布上升为97.91%,但在温度超过CdCl₂的熔点568℃后温度的影响较小.NaCl对Cd的迁移分布受温度影响不明显,加入NaCl后550℃时Cd在飞灰中分布为95.02%,1 000℃时在飞灰中的分布为96.58%.氯化物存在下停留时间对Cd迁移分布没有显著影响.底渣和飞灰的SEM/EDS和XRD分析表明,PVC和NaCl对Cd迁移转化作用机理不同.     

砷的发生、形态、污染源及地球化学循环

文章首先总结了砷在地表水、地下水、土壤、沉积物、岩石、大气中的含量和分布;归纳了砷的地球化学循环过程;分析了砷在水和土壤/沉积物固相中的形态;并重点阐述了砷在土壤和沉积物中的迁移转化机理。砷通常与Fe、Al、Mn的氧化物和氢氧化物、粘土矿物、硫化物、磷酸盐和碳酸盐矿物结合,砷的生物可用性和迁移性与其在土壤和沉积物中的形态有密切关系。文章最后定量阐述了砷的污染源,包括金属开采与冶炼,化学燃料的燃烧和含砷化学品使用。     

Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation a ect mercury removal e ciently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor a ecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation e ciency reached 71.0%. Therefore, oxidized mercury removal e ciency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%–96.8% of oxidized mercury was controlled, but only 54.9%–68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal e ciency was 95.9%–98.0%, and there was a big di erence in the total mercury removal e ciencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.     

稀土工业污染土壤对外源钍的吸附行为研究

研究了外源钍在土壤上的吸附行为并评估其对土壤的污染风险.通过静态吸附解吸实验考察土壤样品对不同量外源钍的吸附容量、吸附平衡时间、分配系数和解吸能力.土壤样品对外源钍有很强的吸附能力,在吸附平衡时吸附百分比均大于92%,而解吸率均小于5%;钍在土壤溶液中分配系数最高可达104以上;吸附容量和平衡时间与土壤性质有关.吸附实验结果表明,可用Freundlich吸附等温式和Elovich方程分别描述土壤样品对钍吸附的热力学行为(r≥0.916 7)和动力学过程(R2≥0.898 0).较佳的拟合结果表明,土壤样品对外源钍的吸附是非线性物理化学吸附,吸附反应速率受钍在土壤表面和矿物内层扩散影响.采用形态连续萃取法分析外源钍在土壤上吸附后的赋存形态.由钍形态萃取结果,少量外源钍(10-7~10-6mol.L-1)进入土壤后主要以不稳定非残留态存在,其含量在58%以上;随着外源钍量增加,钍非残留态量增加,同时更多外源钍迁移到稳定残留态.