硫化物吸附金属离子的实验研究──Ⅱ．温度与介质条件的影响

合成ＰｂＳ和ＺｎＳ对Ａｇ２＋、Ｃｕ２＋、Ｃｄ２＋、Ｆｅ２＋、Ｍｎ２＋、Ｍｇ２＋、Ｓｂ２＋和Ｂｉ３＋等离子吸附量与温度关系的实验研究表明，其遵从Ｋｅｌｖｉｎ公式：在Ａ类吸附，即抗衡离子交换型吸附中，温度上升，其吸附量升降由反应热决定，本实验中Ａ类吸附多为上升型；而大部分Ｂ和Ｃ类吸附，即朗谬尔型及反朗谬尔型的吸附量则随温度上升呈指数下降。例外的仅有ＰｂＳ对Ｂｉ３＋离子的吸附，其吸附量随温度上升有微弱的上升。这可能与Ｂｉ３＋离子和吸附剂ＰｂＳ之间共晶反应和铅的铋硫盐的形成有关。Ａ类吸附的吸附量受介质条件变化影响很少。但对Ｂ和Ｃ类吸附，吸附量受ｐＨ和离子强度变化影响取决于三个因素：①吸附剂ＰｂＳ、ＺｎＳ表面电荷特性；②溶液介质条件变化时吸附离子在溶液中离子态的分布与变化；③被吸附离子在吸附剂中扩散和形成化合物或共晶的能力。因此，当ｐＨ增加时，Ｐｂｓ和ＺｎＳ对金属离子吸附量的变化表现出多样性：增加的有ＰｂＳ对Ｆｅ２＋离子的吸附；下降的有ＰｂＳ对Ｓｂ３＋离子的吸附和ＺｎＳ对Ｆｅ２＋、Ｍｎ２＋离子的吸附；不变的有ＰｂＳ对Ｂｉ３＋、Ｚｎ２＋离子的吸附和ＺｎＳ对Ｍｇ２＋离子的吸附。当溶液中离子强度增加时，由于溶液中自由态离子     

Suspended sediment and phosphorus in proglacial rivers: bioavailability and potential impacts upon the P status of ice‐marginal receiving waters

This paper adopts standard tests developed in temperate catchment research to determine the total phosphorus (TP) and the algal available (base‐extractable) phosphorus (NaOH–P) content of a wide range of glaciofluvial sediments from the Northern Hemisphere. We find that the TP content of these sediments is broadly similar to the P content of major rock types in Earth's crust (230–670 µgP/g) and so the TP yields of glacier basins may be high owing to the efficacy of suspended sediment evacuation by glacial meltwaters. We show that this is best achieved where subglacial drainage systems are present. The NaOH–P pool of the sediments is found to be low (1–23 µgP/g) relative to the TP pool and also to the NaOH–P pool of suspended sediments in temperate, non‐glacierized catchments. This most probably reflects the restricted duration of intimate contact between dilute meltwaters and glacial suspended sediments during the ablation season. Thus, despite the high surface‐area:volume ratio of glacial suspended sediments, the potential for P adsorption to mineral surfaces following release by dissolution is also low. Further, sorption experiments and sequential extraction tests conducted using glacial suspended sediments from two Svalbard catchments indicate that the generation of reactive secondary minerals (e.g. Fe‐ and other hydroxides) with a strong capacity to scavenge P from solution (and thereby promote the continued dissolution of P) may also be limited by the short residence times. Most P is therefore associated with poorly weathered, calcite/apatite‐rich mineral phases. However, we use examples from the Svalbard glacier basins (Austre Brøggerbreen and Midre Lovénbreen) to show that the high sediment yields of glaciers may result in appreciable NaOH–P loading of ice‐marginal receiving waters. Again, the importance of subglacial drainage is highlighted, as it produces a major, episodic release of NaOH–P at Midre Lovénbreen that results in a yield (8·2 kg NaOH–P/km²/year) more than one order of magnitude greater than that at Austre Brøggerbreen (where subglacial drainage is absent and the yield is 0·48 kg NaOH‐P/km²/year). Therefore, as since both detrimental and beneficial effects of sediment‐bound P loading in ice marginal receiving waters are possible (i.e. either reduced primary productivity owing to increased turbidity or P fertilization following desorption) there is a pressing need to assess the ambient P status of such environments and also the capacity for ice‐marginal ecosystems to adapt to such inputs. Copyright © 2004 John Wiley & Sons, Ltd.     

Kinetics of phosphate adsorption by iron oxyhydroxides in aqueous systems

The rate of uptake of phosphate onto synthetic Fe(III)- and Fe(II)-derived oxyhydroxides has been studied using reaction conditions similar to those encountered in natural waters. Kinetic analyses were carried out on the adsorption profiles and both first-order and second-order conditional rate constants were obtained. The temperature dependence of some of the rate constants was investigated and corresponding apparent activation energies calculated. Similar experiments and analyses were undertaken using Fe from natural sources and in general the conditional rate constants obtained in seawater were in agreement with the synthetic ones. The results of this study are of value when comparing the time scales of adsorption processes in natural waters with the time scales of mixing and advection.     

Adsorption of As on hydroxy-Fe-montmorillonite complexes

DOI: 10.1360/03yd0553 Arsenic, a toxic element, is ubiquitous in the earth’s crust and may lead to health risks for humans. This may come about as a result of oxidative weathering and dissolution of As-containing minerals, use of ar-senical pesticides, excess use of some fertilizers and from mine drainage, smelter wastes and agricultural drainage water from certain arid regions. The dis-solved inorganic arsenic is transported in surface or2156 Science in China Ser. D Earth Sciences groun…     

Surface area, porosity and water adsorption properties of fine volcanic ash particles

Our understanding on how ash particles in volcanic plumes react with coexisting gases and aerosols is still rudimentary, despite the importance of these reactions in influencing the chemistry and dynamics of a plume. In this study, six samples of fine ash (<100 m) from different volcanoes were measured for their specific surface area, a_s, porosity and water adsorption properties with the aim to provide insights into the capacity of silicate ash particles to react with gases, including water vapour. To do so, we performed high-resolution nitrogen and water vapour adsorption/desorption experiments at 77 K and 303 K, respectively. The nitrogen data indicated a_s values in the range 1.1–2.1 m²/g, except in one case where a a_s of 10 m²/g was measured. This high value is attributed to incorporation of hydrothermal phases, such as clay minerals, in the ash surface composition. The data also revealed that the ash samples are essentially non-porous, or have a porosity dominated by macropores with widths >500 Å. All the specimens had similar pore size distributions, with a small peak centered around 50 Å. These findings suggest that fine ash particles have relatively undifferentiated surface textures, irrespective of the chemical composition and eruption type. Adsorption isotherms for water vapour revealed that the capacity of the ash samples for water adsorption is systematically larger than predicted from the nitrogen adsorption a_s values. Enhanced reactivity of the ash surface towards water may result from (i) hydration of bulk ash constituents; (ii) hydration of surface compounds; and/or (iii) hydroxylation of the surface of the ash. The later mechanism may lead to irreversible retention of water. Based on these experiments, we predict that volcanic ash is covered by a complete monolayer of water under ambient atmospheric conditions. In addition, capillary condensation within ash pores should allow for deposition of condensed water on to ash particles before water reaches saturation in the plume. The total mass of water vapour retained by 1 g of fine ash at 0.95 relative water vapour pressure is calculated to be ~10^–2 g. Some volcanic implications of this study are discussed.Editorial responsibility: J. Gilbert     

板桥稀土矿遥感找矿信息提取与矿产预测研究

通过对离子吸附型稀土矿成矿规律的分析,从浙江省板桥地区的遥感地质特征研究入手,在研究区地表范围内进行稀土遥感找矿信息的提取。首先利用SPOT图像和DEM数据构建的坡度数据对与稀土成矿相关的地貌单元进行解译;然后通过光谱特征分析和基于ASTER图像的矿物遥感异常提取,获取与成矿相关的高岭土、绢云母、绿泥石等风化特征矿物的分布信息;最后叠合分析地貌、坡度及异常提取结果,进行稀土遥感找矿预测。与地质调查资料及化探数据的对比分析证实,上述方法对圈定1∶5万的大比例尺离子吸附型稀土矿分布范围是有效的,可为更详细的稀土矿产资源潜力评价提供依据。     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

纳米铁去除饮用水中As(Ⅲ)和As(Ⅴ)

在好氧水体中,As(Ⅲ)比As(Ⅴ)更易迁移,而且在水处理过程中去除效率更低。在实验室合成制得BET比表面积为49.16 m2/g,直径范围为20~40 nm的纳米铁。通过批试验考察纳米铁对As(Ⅲ)和As(Ⅴ)去除能力及其反应动力学情况。结果表明,在pH为7,温度20℃时纳米铁能够快速地去除As(Ⅲ)和As(Ⅴ),在60 m in内,0.25 g纳米铁对起始浓度为968.6μg/L As(Ⅲ)和828.9μg/L As(Ⅴ)的去除率大于99.5%。反应遵循准一级反应动力学方程,标准化后的As(Ⅲ)和As(Ⅴ)比表面积速率常数kSA分别为1.30 mL/(m2.m in)和1.64 mL/(m2.m in)。由实验结果可知,具有高反应活性的纳米铁是用于含砷饮用水处理非常有效的吸附材料。     

桂中坳陷环江凹陷上古生界海相页岩储层孔隙结构和分形特征研究

通过有机地化分析、全岩X衍射矿物分析、甲烷等温吸附及低压氮气吸附实验,本文对桂中坳陷环江凹陷上古生界页岩样品的孔隙结构及分形特征进行了研究.结果表明:研究区页岩总有机碳含量(TOC)平均为2.40%,热成熟度(Ro)平均为2.65%,处于过成熟演化阶段.页岩主要的矿物组成为石英和黏土.页岩的比表面积平均为5.86 m2/g,孔容平均为0.014 9 mL/g,平均孔径为11.2 nm.页岩中发育大量的中孔,主要呈两端开口的圆筒形孔或四边开放的平行板状孔.页岩中TOC含量和石英含量越多,微-中孔越发育、比表面积和孔容越大,而平均孔径则变小.通过Frenkel-Halsey-Hill (FHH)模型和氮气吸附实验数据计算得到孔隙表面分形维数D1(平均为2.428 4)和孔隙结构分形维数D2(平均为2.622 2),对应的相对压力(P/P0)分别是0~ 0.45和0.45 ~ 0.99.分形维数D1、D2随着比表面积、孔容的增加而增加,而平均孔径随着前者的增加而减小.分形维数D1、D2、TOC含量、石英含量和甲烷吸附量之间呈现较好的正相关性,但随着黏土矿物含量的增多而减小.分形维数D1与Langmuir压力存在弱负相关性,分形维数D2随Langmuir压力增大有变大的趋势.桂中坳陷西北部页岩分形维数越大,孔隙结构越复杂,其对天然气的吸附和存储能力越强.     

脱气温度和样品粒径对致密砂岩低温氮气吸附实验结果的影响

基于静态体积法的低温氮气吸附实验已广泛用于分析致密储集层的孔隙结构。本文探索了脱气温度和样品粒径对松辽盆地高台子致密砂岩低温氮气吸附实验结果的影响。结果显示,110℃的脱气条件并不能清除束缚水而使得孔隙体积、比表面积均偏低,300℃的脱气条件容易破坏样品中黏土矿物的结构令孔隙体积、比表面积减小,200℃是比较合适的脱气温度,既能去除束缚水又不破坏黏土矿物结构。样品粒径从5～10目减小至10～30目,氮气探测的孔隙数量增多使比表面积、孔体积增大。从10～30目减小至180～200目,黏土矿物相对含量降低令比表面积、孔体积显著减小;小于200目的样品中减少的黏土矿物主要集中在大于200目的岩样中,因此大于200目岩样的测定结果最高。因此,10～30目是利用低温氮气吸附实验寻求分析致密砂岩储集层特征的最佳粒径范围。