砷与无定形氧化铝的表面络合反应平衡常数计算

根据不同离子浓度、不同pH值的溶液中As在无定形氧化铝表面的吸附量,利用三种不同的表面络合模型计算As与无定形氧化铝表面络合反应的平衡常数,将计算得到的平衡常数模拟 As(Ⅲ)无定形在氧化铝表面各个络合物种的吸附百分比与 As(Ⅲ)的 X光吸收光谱边缘结构分析结果进行定性比较,表明计算结果与分析结果较为吻合.从而验证了此次计算得到的平衡常数是准确的.     

有机磺酸类化合物的络合萃取研究

本文以三烷基胺为络合剂,正辛醇,煤油,氯仿,四氯化碳等为稀释剂,测定了络合萃取剂对于对甲基苯磺酸,磺基水杨酸稀溶液的相平衡分配系数,讨论了稀释剂,体系ＰＨ值和７３０１络合剂含量对萃取相平衡分配系数Ｄ值的影响,确定了形成的萃合物的组成。     

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.     

络合吸收结合生物转化去除氮氧化物技术

介绍了络合吸收结合生物转化处理NOx 技术的基本原理和目前的研究进展情况 ,并分析了该技术处理氮氧化物存在的问题和未来发展方向     

Ligand exchange rate of metal-nom complexes by EDTA

Metal complexation by natural ligands is important for metal transport and distribution in surface and ground water. The goal of the work was to study the ligand exchange rate for two important metal ions in natural aquatic systems (Al, Fe) was determined using EDTA and natural organic matter (NOM) of humic type as ligands. After adding EDTA to a solution containing metal-NOM complexes, these complexes dissociated and metal-EDTA complexes were formed. Metal-NOM complexes were separated from metal-EDTA complexes with the help of size-exclusion chromatography and detected by on-line inductively coupled plasma-mass spectrometry (ICP-MS). Injecting the samples into the system over time after addition of EDTA allowed us to measure the rate of the exchange of NOM by EDTA. The experiments could be well described with a first-order rate law assuming that the dissociation of the metal-NOM complexes is the rate-determining step. The exchange rate of Fe was found to be faster than that of Al. This corresponds well with the exchange rate of water molecules from the coordination sphere of the metal ions, which is also faster for Fe than for Al. Furthermore, the UV and the fluorescence signal of the chromatograms were measured. The results indicate that no disaggregation of NOM molecules took place, although about 75-85% of the aggregate-forming metal ions exchanged NOM by EDTA in their coordination sphere. This suggests clearly the fundamental role of NOM in colloidal transport of metals and in their bioavailability.     

REST-Rossendorf expert system for surface and sorption thermodynamics

This paper presents a digitized version of a thermodynamic sorption database, implemented as a relational database with MS Access. It is mineral-specific and can therefore be used for additive models of complex solid phases such as rocks or soils. An integrated user interface helps users to access selected mineral and sorption data, to extract internally consistent data sets for sorption modeling, and to export them in formats suitable for other modeling software. Data records comprise mineral properties, specific surface area values, surface binding sites' characteristics, sorption ligand information, and surface complexation reactions. An extensive bibliography is included, providing links not only to the above listed data, but also to background information concerning surface complexation model theories, evidence for surface species, and sorption experimental techniques.     

Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

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.     

污染场地地下水中汞污染反应运移模拟

汞（Hg）是人们持续关注的全球环境污染物之一,其对地下水的污染严重威胁着与地下水相关的生态环境系统.汞在地下水系统中的物理与地球化学反应过程的准确刻画是研究汞迁移转化规律的重点和难点.基于某工业场地汞污染数据,首先采用PHREEQC研究地下水中无机二价汞的存在形态,然后利用PHT3D程序建立汞污染物反应性溶质运移二维剖面模型.该模型考虑了汞污染物在地下水系统中的对流、弥散过程及地球化学反应过程（包括水相络合作用、表面络合吸附作用及受动力学控制的氧化还原作用）.结果表明,无机二价汞的存在形态以HgCl₂和Hg（OH）Cl占主导地位,氧化还原作用是影响地下水中汞污染反应性运移的主要控制因素;另一方面,水合氧化铁HFO对汞迁移的阻滞影响较小,而溶解性有机质对汞较强的络合作用不能忽视.本文研究成果可为预测与评估特定污染场地地下水汞污染的变化趋势及制定相应的修复策略提供科学依据.     

藻菌生物膜胞外聚合物与铅锌尾矿重金属的络合配位作用

矿产资源开采冶炼产生大量尾矿渣,其中富含的可溶性重金属引发的生态环境问题日益突显.铅锌矿是我国重要的矿产资源,尾矿露天堆放使得其富含的可溶性重金属淋溶迁移,对矿区周边地表环境造成严重污染.为探明自然水体环境中的藻菌生物膜与重金属的作用机理,采用三维荧光光谱技术研究干旱区天然湖泊中的藻菌生物膜EPS（胞外聚合物）与铅锌尾矿渣中5种重金属离子的络合配位作用.结果表明:①从藻菌生物膜EPS荧光光谱图中可检测出两个荧光峰,均来源于芳香类蛋白酪氨酸物质;②铅锌尾矿淋滤液中的重金属元素主要包括Pb、Co、Ni、Zn和Cd,且这5种金属离子均能有效淬灭EPS的荧光强度;③荧光淬灭滴定试验得出,Pb2+与EPS的络合能力最强,最大络合常数为4.523 1,最大结合位点数为1.177 5;Cd2+与EPS的络合能力最弱,最大络合常数为1.957 1,最大结合位点数为0.684 8;Co2+、Ni2+和Zn2+与EPS的络合能力相似.研究显示,藻菌生物膜EPS中含有的荧光基团与重金属离子的作用强度与金属离子的类型相关,二者的络合配位作用可能会影响重金属在水环境中的化学形态、迁移、生物有效性和生态毒性.