微生物参与下的水/粒界面吸附反应研究进展

回顾了近年来微生物存在下的水/粒界面吸附反应研究进展,包括微生物对金属阳离子的吸附、矿物微粒对微生物的吸附和微生物参与下的水/粒界面吸附;目前,这些吸附反应的定量化模型研究主要有体积分配关系和表面络合模型两种方法。其中,体积分配关系可从野外直接测得;而表面络合模型是采用不受溶液条件变化影响的准热力学常数来描述表面化学反应,能外推至实验室无法直接模拟的条件。随着人们对微生物在环境中重要性认识的加深,微生物参与下的水/粒界面吸附和可预测吸附程度的定量化模型受到人们越来越多的重视。     

Uranyl Retention on Quartz—New Experimental Data and Blind Prediction Using an Existing Surface Complexation Model

The adsorption behaviour of uranyl onto seven different samples of quartz was studied in batch experiments. Sea-sand (0.1–0.3 mm), Fil-Pro 12/20 (1–2 mm) and five Min-U-Sil samples with smaller particle sizes (5, 10, 15, 30 and 40 μm) were used. The uptake curves show “pH adsorption edges” in the range of pH 4–5. A good agreement of the new data with literature data was found when plotting surface-normalised distribution coefficients versus pH. Differences in the adsorption behaviour for pre-treated and untreated sea-sand samples were detectable resulting in a shift of the pH edge to higher pH values after treatment. A literature surface complexation model was applied for blind predictions of the experimental results. The simulations described the experimental observations quite well for the Min-U-Sil samples. For the two coarser quartz samples, the calculated over-predictions were explained by the larger-than-expected measured specific surface area and measurable amounts of associated minerals, for Fil-Pro 12/20 and sea-sand, respectively. Dissolution of the samples was studied as a function of pH. After 5 days, the measured Si concentrations were all higher than equilibrium quartz solubilities, but lower than those of amorphous silica. With increasing pH, dissolved silica increased. This strongly suggests that formation of dissolved uranyl–silicato complexes have to be considered based on measured silica concentrations.     

Sorption behavior of heavy metal pollutants onto shales and correlation with shale geochemistry

The sorption of lead (II) and cadmium (II) on seven shales belonging to the Proterozoic Vindhyan basin, central India, and a black cotton soil, Mumbai, India, was studied and compared with sorbent geochemistry. The sorption equilibrium studies were conducted under completely mixed conditions in batch reactors (pH=5.0 and ionic strength= 0.01 M) at room temperature. The Freundlich model provided better fits to the experimental data compared to Langmuir model. High cadmium and lead sorption was observed for the calcareous shales with greater than 5% CaCO₃. The Freundlich isotherm parameter relating to sorption capacity, i.e., K_F, yielded a strong correlation with the calcium carbonate and calcium oxide content across the various geosorbents studied. The observed sorption pattern may be attributed to complex formation of CaCO₃ with Pb²⁺ and Cd²⁺ leading to surface precipitation. Moreover, the Ca²⁺ present in the sorbents may also involve in ion exchange reaction with lead and cadmium.     

矿物-水界面的表面离子化和络合反应模式

表面络合模式已广泛应用于研究矿物表面吸附和溶解反应,尤其是(氢)氧化物和层状铝硅酸盐矿物。表面官能团是矿物参与表面络合反应的基本单元,(氢)氧化物矿物只具有表面羟基,而层状铝硅酸盐矿物除表面羟基外还具有离子交换位。矿物的表面电荷由永久结构电荷、配位表面电荷和离解表面电荷组成,各种零表面电荷状态可由不同的零电荷点来表征。恒电容模式、双层模式和三层模式是3种最常用的表面络合模式,它们在双电层结构、表面反应(质子化反应和络合反应)、表面电荷与质量平衡方程及应用范围上存在着一些差异。     

The nature of surface complexation: a continuum approach

Received: 3 March 2000 · Accepted: 9 May 2000     

The effect of cadmium on fulvic acid adsorption to Bacillus subtilis

The effects of Cd on the adsorption of an aquatic fulvic acid (FA) to the surface of Bacillus subtilis were investigated from pH 2.5 to 7.0, at fixed ionic strength (0.1 M NaClO₄) and at ambient temperature (22 °C). Cd (14 mg/l) had no effect on FA adsorption at pH<5 but increased FA adsorption at pH>6. The effects of Cd (0, 14 mg/l) on FA adsorption to B. subtilis were further examined as a function of initial FA concentration (0–45 mg C/l) at pH 6.5. FA adsorption isotherms also were measured at pH 6.5 as a function of dissolved Cd concentration (0–14 mg/l) at three initial FA concentrations (4, 8, 22 mg C/l). At all FA concentrations studied at pH 6.5, FA adsorption increased with increasing initial total Cd concentration.

Under all studied conditions, preferential adsorption of high- to intermediate-molecular-weight FA components to B. subtilis resulted in a fractionation of the FA pool, with lower-molecular-weight components remaining in solution. At pH>6, Cd further enhanced the adsorption of high- to intermediate-molecular-weight FA components but did not significantly enhance the adsorption of lower-molecular-weight components. Hence, the overall process of adsorptive fractionation was not altered significantly by the presence of Cd.

Overall, the results of this study (1) demonstrate that FA adsorption to bacterial surfaces can be altered by the presence of a metal cation, and (2) provide further evidence that microbe–metal–ligand interactions may significantly affect the mobility and fate of natural organic matter in the subsurface.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

四环藻属(Tetracyclus Ralfs) 中的新化石种和变种 (硅藻门 Bacillariophyta)

描述的四环藻属中的3个新种和3个新变种:辐射四环藻Tetracyclus radiatus, 小四环藻T.minutus,近不连结四环藻椭圆形变种 T.subdivisium ellipticus, 岩生四环藻近盾形变种T.rupestris var.subclypeatus, 塞拉托木四环藻T.celatom var. minor constrictus 和短尖头四环藻T.mucronatus.这些新化石种根据形状、初生肋、次生肋和三生肋的数量,中央胸骨的长度及轴区的形态特征加以区别.新化石种的确立有可能是中国中新世硅藻植物群中的特有种.     

不同耕作方式下川芎对土壤中铅、镉含量的富集特征

以彭州川芎种植区的菜园土、稻田翻耕土、稻田免耕土和旱地(未种过川芎和蔬菜)四种土壤为研究对象,探讨了不同耕作方式下川芎对土壤中Cd、Pb的富集特征。结果表明:在四种耕作方式下,菜园土中Cd、Pb含量显著高于其他三种土壤,分别为1.10mg·kg-1和29.78mg·kg-1;土壤Cd综合污染指数和Hacanson系数分别为3.76和133.07,处于重污染和强生态危害状态。稻田翻耕土、稻田免耕土和旱地三种类型土壤在Cd含量上差异显著,依次为稻田免耕土(0.86mg·kg-1)稻田翻耕土(0.59mg·kg-1)旱地(0.37mg·kg--1),在Pb含量上三者差异不显著。川芎植株对Cd的富集在菜园土中显著高于其他土壤,表现为菜园土稻田免耕土旱地稻田翻耕土;川芎植株对Pb的富集以在稻田免耕土中最大,依次为稻田免耕土旱地稻田翻耕土菜园土。在四种土壤中,川芎叶片对Cd、Pb的富集能力均大于根茎,其中川芎叶片对Cd的富集能力是根茎的1.37倍,对Pb的富集能力是根茎的1.42倍,二者对Cd的富集能力在菜园土中差异最大(叶/根为1.56),对Pb的富集能力在稻田免耕土中差异最大(叶/根为1.98)。川芎对Cd、Pb的富集主要受轮作作物种类和耕作措施的影响。     

Evaluation of Experimental Procedures and Discussion of Two Different Modelling Approaches with Respect to Long-term Kinetics of Metal Cation Sorption onto (Hydr)oxide Surfaces

Experimental procedures as well as literature data and modelling of long-term kinetics of metal ion adsorption processes onto thermodynamically stable (hydr)oxide surfaces from aqueous solution are evaluated. It is concluded that when experimental uptake data are obtained by the solution depletion method precise information on experimental procedures is crucial. This is true both for preliminary kinetics studies (which intend to fix an equilibration time used for subsequent thermodynamic studies) and for true kinetic studies. For the usually given adsorption versus time curves the corresponding (possibly changing) values of pH should be added. The use of sorption pH edges measured at different times to obtain kinetics curves at constant pH may not correspond to the actual behaviour of the system but be rather an artificial construct.Concerning the models two basically different mechanisms have been used to account for the slow sorption step, which occurs in long-term studies: intraparticle diffusion of the adsorbing metal cation and slow redistribution of surface species. It is shown that the two mechanisms cannot be distinguished using macroscopic uptake data alone: data, which have been interpreted using one approach, may equally well be interpreted using the other one.     

山东临朐县营子中新世的硅藻植物

山东临胸县中新世山旺组地层中的硅藻土不仅以化石门类丰富保存精美著称于世,而且具有重要的开采经济价值。山旺组在山东省分布十分局限,仅分布临胸县东25公里的山旺村一解家河村一带,是一套由泥岩、页岩、硅藻土及油页岩、煤层间夹玄武岩组成的湖泊沉积。它分布在大片基性火山熔岩发育区,岩性简单,产状平缓,厚度不大。由20-100米不等,地层出露面积不足0.5平方公里,化石极为丰富,尤其是硅藻。