可变电荷土壤和恒电荷土壤与氢离子相互作用机理

研究了可变电荷土壤和恒电荷土壤与H相互作用的机理，并比较了它们之间的差别，研究结果表明，氢离子输入土壤后可以转化为表面正电荷，可溶性铝和可交换性酸，但是由于土壤的组成和性质不同，不同土壤中H＋三种去向的贡献不同。H＋转化为表面正电荷是由于土壤表面Fe-OH,Al-OH的质子化造成的，因此H＋转化为表面正电荷的能力与土壤中氧化铁的含量密切相关，从而可变电荷土壤中H＋转化为表面正电荷的贡献比恒电荷土壤中的大。H＋转化为可溶性铝的能力与土教育部 的矿物组成密切相关，随着H＋输入量的增加，土壤中可溶性铝的含量也增加。可变电荷土壤中可溶性铝增加的顺序为红壤＞赤红壤＞铁质砖红壤，在H＋的加入量小于15mmol/kg时，黄棕壤的可溶性铝介于红壤和赤红壤之间，当H＋的加入量大于约15mmol/kg时，黄棕壤的可溶性铝略小于赤红壤，棕壤的可溶性铝明显小于红壤和赤红壤，但比铁质砖红壤高，恒电荷土壤的可变性酸量明显大于可变电荷土壤，但从总的看来，H＋加入量的变化对可交换性酸量的影响不大。     

茜素红S-微分吸附计时电位法测定土壤中铝形态

报道了茜素红S-微分吸附计时电位法分别在酸性和碱性条件下直接检测土壤浸提液中的无机单核铝[Ali]和总单核铝[Ala]浓度，并用该法测定了酸消化浸提液中的总铝[AlT]，由[Ala]-[Ali]间接得到有机单核铝[Alo]，[AlT]-[Ala]得到酸溶态铝[Alr]，从而实现了土壤浸提液中5种铝形态的电化学测定。应用此方法测定了多个实际土壤样品，与标准Driscoll法进行了对照．结果基本一致。     

偏最小二乘法回归 (PLS)研究酸性森林土壤中铝的释放过程

采集了华南和西南酸性森林小流域中的土壤和土壤水并分析其化学组成,利用偏最小二乘法回归(PLS)研究了土壤中铝的释放过程,以综合评价各种影响因素的相对重要性。连续3年(2000～2002)的现场监测数据表明,尽管土壤水中铝的浓度存在显著差异,但铝的形态分布在各流域之间基本相似。大多数土壤水中单体铝(Ala)主要以无机态(Ali)存在,有机铝(Alo)一般不足10%。在pH3.6～5.6范围内,土壤水中Al3 活度(pAl)与土壤水pH值呈显著正相关关系(P<0.001),上层和下层土壤中pH-pAl拟合直线的斜率分别为1.28和2.00,明显偏离三水铝石(gibbsite)的溶解平衡模式。偏最小二乘法回归分析显示,上层和下层土壤中铝具有不同的来源和主导影响因素。上层土壤中,铝主要来源于有机键合铝(Alorg),土壤水离子强度(I)是造成铝浓度差异的主导因素。与此同时,铝的释放过程明显受到离子交换反应的影响。下层土壤中,铝近乎全部来源于无机键合铝(Alinorg),土壤水H 浓度成为影响铝释放过程的最主要因素。与上层土壤相比,离子交换对土壤铝释放过程影响明显减小。     

珠江三角洲潜在生态风险:土壤重金属活化

珠江三角洲典型土壤模拟酸雨提取实验表明，土壤酸缓冲能力为菜园土大于水稻土大于赤红壤。酸化过程早期，铝铁胶体吸附共沉淀导致重金属溶出量增长不明显甚至下降；进一步酸化时，多数元素溶出量与加入酸量呈显著正相关。计算表明，在pH=4．5的酸雨作用下，溶液中Hg、Mn、Pb、Fe(以Fe2O3表示)浓度已超出Ⅱ级地表水标准，Cu、Zn大大高于渔业用水标准。可见，土壤元素活化溶出对水体生态环境有潜在的危害。     

H+和有机酸对可变电荷土壤铝释放的动力学研究

利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15～40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0～300min内流出液铝的浓度范围约为1～5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20～30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20～75μmol/L,红壤上是70～150μmol/L,随时间延长,流出液中的铝浓度分别为10～20μmol/L和20～30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。     

氟与聚合羟基铝-蒙脱石复合体相互作用机理及土壤环境意义

在一定条件下利用钠基蒙脱石 (Na- Mt)合成了 OH/Al比为 1.6的聚合羟基铝-蒙脱石 (HyAl- Mt)复合体,并研究了弱酸性和强酸化条件下 HyAl- Mt与氟之间的相互作用及土壤环境意义.结果表明, pH在 5.0～ 9.0之间时, HyAl- Mt对氟的吸附受 pH影响小;当 pH < 4.5时,吸附能力随 pH减小迅速增大. pH 6.62时, HyAl- Mt对氟的吸附主要是络合交换机制,而 pH 3.02及高氟浓度条件下是表面吸附、矿物溶解及共沉淀-卷扫等协同作用机制,并使 HyAl- Mt具有异常高的氟去除能力.与蒙脱石粘土相比, HyAl- Mt的氟吸附能力明显提高,土壤中的 HyAl- Mt组分可有效地降低氟污染土壤中氟的迁移性并减少其生物有效性.在酸性氟污染的土壤中,氟与 HyAl- Mt相互作用还可一定程度抑制土壤的酸化.土壤酸度越大,这种抑制作用越明显.施用合成的 HyAl- Mt 可作为酸性氟污染土壤修复并控制土壤酸化的有效途经之一.     

片钠铝石的成因及其对CO2天然气运聚的指示意义

片钠铝石作为胶结物、自生矿物或脉体，不仅分布在海相白云岩、油页岩中，而且还广泛分布在陆源碎屑岩及煤系地层中。大量的实例及人工合成片钠铝石实验表明，片钠铝石的形成需要碳酸溶液或过量的CO2气，片钠铝石的分布往往与CO2天然气藏相伴生。CO2气的来源决定了片钠铝石具有无机和有机两大成因类型，其中，无机成因包括岩浆成因和碳酸盐热解成因。然而，不论源于有机成因CO2气还是无机成因CO2气，片钠铝石均可作为富CO2流体运移或聚集的“示踪矿物”，地质过程中片钠铝石的出现或富集表明该区曾存在大量CO2运移或聚集。     

湖南洞庭湖地区土壤酸化特征及机理研究

湖南省洞庭湖地区是中国酸雨沉降和土壤酸化严重的地区之一,酸雨沉降具有明显的季节性和地域性差异,酸雨沉降与土壤酸化具有较好的空间对应性,但土壤酸化的程度还取决于土壤中盐基离子的含量。在土壤酸化较严重的地区,垂向上,土壤酸化深度已达50cm左右,土壤酸化伴随着大量的可溶性铝的溶出。在土壤pH值与盐基离子、氮和硫含量的关系曲线上,存在着pH值突变的临界点(临界点pH值为8),在碱性范围内,硅酸盐和铝硅酸盐矿物的水解使大量盐基离子溶出,中和了因SO42-和NO3-的输入而造成的土壤酸化,但当pH值下降到小于7·25的中酸性范围时,酸性物质和碱性物质组成的土壤缓冲体系失去缓冲作用,酸性物质略有增加,就会导致土壤迅速酸化。     

高分子铝盐絮凝剂的发展

高分子铝盐广泛应用于水处理中。为提高高分子铝盐絮凝性能，研究者做了大量工作，开发出了多种新型絮凝剂，如聚合硫酸氯化铝、聚合磷酸氯化铝、聚合铁铝、聚合硅酸铝等。就无机－有机高分子絮凝剂联用作了阐述，提出了高分子铝盐絮凝剂在今后水处理领域的发展趋势。     

模拟酸雨对土壤有效磷衰减的影响

采用pH3．0和pH4．5的2种模拟酸雨与对照pH6．0的雨水， 湿润培育加磷后的土壤（2种红壤和1种水稻土）。试验结果表明，土壤中的有效磷的衰减在快反应阶段呈直线下降，而在慢反应阶段缓慢下降。快反应阶段持续时间约3－6h，随模拟降雨的p H值不同而不同，pH值愈低，持续时间愈短。与对照相比，模拟酸雨对有效磷衰减产生较大影响，模拟酸雨pH值愈低，有效磷衰减得愈快，尤其在快反应阶段影响更为明显；在慢反应阶段，随着时间的延续，影响逐渐变小。模拟酸雨对有效磷衰减的影响因土壤类型不同而不同，表现为红壤大于水稻土。酸雨加快土 壤有效磷的衰减，其主要原因是酸雨作用导致活性铝的大量释放，增加了磷的活性吸附点位，从而增加了对磷酸根离子配位吸附。     

Experimental investigation on aluminum release from haplic acrisols in southeastern China

A sequential dissolution technique and a prolonged extraction method were used to investigate aluminium (Al) release from 4 Haplic Acrisols in southeastern China. The results show that the order of acidification of the 4 soils is: Tunxi soil>Yongchun soil>Shengxian soil>Ninghai soil. The amount of exchangeable Al is directly proportional to the extent of soil acidification. Al was released from both organically bound and inorganic Al pools after acid input. During several initial cycles of extraction the release of Al was mainly from the weakly organically bound Al pool. After prolonged extraction, Al release from the inorganic Al pool became more important to the total dissolved Al due to a rapid depletion of the weakly organically bound Al pool. The sizes of readily reactive Al pools in the Ninghai soil and Shengxian soil are larger than in the Yongchun soil and Tunxi soil. Al released from the inorganic Al pool in the Ninghai soil, Shengxian soil and Yongchun soil after 20 cycles of extraction was higher than from the organically bound Al pool, whereas the opposite was the case for the Tunxi soil. A low saturation of Al binding on soil organic matter (SOM) does not necessarily lead to a low Al release as in the case of the Shengxian soil. Also a relatively high saturation does not necessarily ensure a large Al release from the Al pool as in the case of the Tunxi soil and Yongchun soil. Once both organically bound and inorganic Al pools are depleted of readily reactive Al phases due to high soil acidification, Al dissolution would be small even under strong acid input. The high concentration of aqueous Al after rapid Al release from the weakly organically bound Al pool and subsequent depletion of the pool may have significant ecological and environmental effects.     

Selective extraction of organically bound gold in soils, lake sediments and stream sediments

The extraction of organically bound gold from surficial materials is accomplished by using a solution of 5% sodium hypochlorite. A 10-g sample is digested at least twice with 50 mL of hypochlorite solution. The recovery of gold from the organic phase is nearly quantitative for lake sediments and stream sediments high in organic content. For stream sediments and soils low in organics, the recovery of gold is complicated by the sorption of released gold onto inorganic sample components. For these materials, recoveries as low as 70% of the organically bound gold are possible. For a stream sediment sample containing 53.4 ppb gold, the precision of the method is approximately 6% for a 10-g sample and 14% when a 5-g sample of stream sediment is used. The results obtained for all materials tested indicate that a substantial fraction of the gold found in sediments and soils exists as organically bound gold.     

Effect of low-molecular-weight organic acids on the distribution of mobilized Al between soil solution and solid phase

Low-molecular-weight (LMW) organic acids occur widely in soils. Results in pure mineral systems and podzols suggest that LMW organic acids can promote the dissolution of Al from kaolinite, Al oxides and soils, but limited information is available concerning the role of these organic acids on Al mobilization in variable charge soils as yet. This paper deals with the effect of LMW organic acids on Al mobilization and mobilized Al distributed between the solution phase and exchangeable sites in two acidic variable charge soils. The results indicated that LMW organic acids accelerated Al mobilization through proton- and ligand- promoted reactions. The ability of different organic acids to mobilize Al followed the order: citric acid > oxalic acid > malonic acid > malic acid > tartaric acid > salicylic acid > lactic acid > maleic acid. This order was in general agreement with the magnitude of the stability constants of Al–organic acid complexes. The ratio of soluble Al to exchangeable Al also increased as the stability constants increased. These results showed that the organic acids with strong Al-complexation capacity were most effective in Al mobilization, whereas the weak organic acids promoted the retention of mobilized Al by the soil exchangeable sites. Increase in both organic acid concentration and solution pH promoted Al mobilization and also increased the ratio of soluble Al to exchangeable Al due to the increase in the concentration of the effective organic ligands, especially in the strong organic acid systems. These findings may have their practical significance for establishing more effective amelioration procedures for variable charge soils with increased acidity and higher mobility of Al.     

Arsenic mobilization from mine tailings in the presence of a biosurfactant

Batch experiments were conducted to investigate As mobilization from mine tailings in the presence of a biosurfactant (JBR425, mixed rhamnolipids) and to evaluate the feasibility of using biosurfactant in remediating As contaminated mine tailings/soils. Introduction of the biosurfactant increased As mobilization greatly. When the mass ratio was 10 mg biosurfactant/g mine tailings at pH 11, As mobilization by the biosurfactant was greatest after 24 h, with a corresponding concentration ratio (the ratio of As mobilization by the biosurfactant to that by distilled water at same adjusted pH, wt/wt) of 21.6. Selective sequential extraction indicated that As was easily mobilized from the weakly bound and relatively more mobile fractions by washing with the biosurfactant. A mobilization isotherm was developed to predict As mobilization from the mine tailings in the presence of biosurfactant. It was shown that biosurfactant sorption to the mine tailings is essential for As mobilization. Arsenic mobilization was found to be positively correlated with the mobilization of Fe and other metals (i.e., Cu, Pb and Zn), which might further enhance As mobilization by helping incorporate it into soluble complexes or micelles. Capillary electrophoresis analyses indicated that As redox or methylation reactions had insignificant effect on As mobilization. Biosurfactants might be used potentially to remove bulk As from mine tailings or contaminated soils under alkaline conditions.     

Heavy metal and aluminium mobilization in soils from Galicia (NW spain) as a consequence of experimental acidification

In this paper the main results of an experimental acidification of 5 Galician soils are presented. The acid input caused decrease in pH and mobilization of Al and some heavy metals. Owing to the great differences in the soils studied, the type of metal released and its concentrations in solution varied greatly. pH and metal content of the soils were the factors most influencing metal mobilization. The acid input greatly enhanced the mobilization of Al in the most acidic soils, particularly those developed from mica schist or shale. Large increases in Mn were observed in the soils developed from serpentinite and mica schist. The greatest Zn increase took place in soils derived from granulite and shale. Nickel increased only in the soil developed on serpentinite. Mobilization of Cu and Pb did not occur in any soil.     

Mechanism of aluminum release from variable charge soils induced by low-molecular-weight organic acids: Kinetic study

The kinetic curves of aluminum release from two variable charge soils and a kaolinite within 48 h can be divided into three stages: the first stage located within the initial 30 min, at which the release rate of Al was the fastest one and the released Al dominantly originated from exchangeable Al and amorphous Al pools. The Elovich equation fit the kinetics data at this stage fairly well. The moderate and the slow stages occurred within 0.5-2 and 2-48 h, respectively. During these two stages, the released Al was mainly attributed to Al oxides, poorly crystalline kaolinite and easily weathered hydrous mica. The different linear equations also fit the kinetics data at these two stages well. The rate of Al release decreased sharply with time during the fast stage, but the rate remained constant during the moderate and slow stages. In Ultisol, Al oxides were the more important pool for Al release than poorly crystalline kaolinite and easily weathered hydrous mica during the latter two stages. In Oxisol, poorly crystalline kaolinite was the more important Al pool. Compared to the control system, the presence of organic acids increased the rate and quantity of Al release from variable charge soils. The ability of organic acids to accelerate Al release followed the order: oxalic acid > citric acid > malic acid > lactic acid. This is generally in consistent with the magnitude of the stability constants of the Al-organic complexes. The release rate of Al also increased with the rise in concentration of organic acids.     

Dissolved-particulate interactions of aluminium in ocean waters

Two N. Atlantic profiles of dissolved Al are reported, they show an increase in Al concentration with depth as reported previously for the central Arctic Ocean (Moore, 1981) and for the N.W. Atlantic below 1000 m (Hydes, 1979). Laboratory experiments were carried out to investigate the effect of pressure on the equilibrium between dissolved Al and pelagic, red clays. These studies showed an increase in dissolved Al with increasing pressure; e.g. at 1000 atm. the concentration of Al in solution increased by about 30% in two days. It was also observed that when the pressure was released the excess dissolved Al was rapidly removed from solution onto the clays. Calculations of the effect of pressure on the equilibrium concentration of Al in the presence of Gibbsite show that the dissolution should be favoured by a pressure increase. Laboratory leaching experiments using dilute acid were also undertaken to assess the mobility of Al in atmospheric particulates. The results suggest that a significant proportion, up to 20%, of the Al is not strongly bound in mineral lattices: this figure represents the upper limit for the leachable fraction which greatly exceeds earlier estimates.These results improve our understanding of Al marine geochemistry by emphasising the importance of inorganic rather than biological processes in determining its oceanic distribution.     

Concentration and association of minor and trace elements in Mukah coal from Sarawak, Malaysia, with emphasis on the potentially hazardous trace elements

The ash yield and concentrations of twenty-four minor and trace elements, including twelve potentially hazardous trace elements were determined in Mukah coal from Sarawak, Malaysia. Comparisons made to the Clarke values show that Mukah coal is depleted in Ag, Ba, Be, Cd, Co, Mn, Ni, Se, U, and V. On the other hand, it is enriched in As, Cr, Cu, Pb, Sb, Th, and Zn. Among the trace elements studied, V and Ba are associated predominantly with the clay minerals. Manganese, Cr, Cu, Th, and Ni are mostly bound within the aluminosilicate, sulphide and/or carbonate minerals in varying proportions, though a portion of these elements are also organically bound. Arsenic, Pb and Sb are mostly organically bound, though some of these elements are also associated with the sulphide minerals. Zinc is associated with both the organic and inorganic contents of the coal. Among the potentially hazardous trace elements, Be, Cd, Co, Mn, Ni, Se, and U may be of little or no health and environmental concerns, whereas As, Cr, Pb, Sb and Th require further examination for their potential health and environmental concerns. Of particular concern are the elements As, Pb and Sb, which are mostly organically bound and hence cannot be removed by physical cleaning technologies. They escape during coal combustion, either released as vapours to the atmosphere or are adsorbed onto the fine fly ash particles.     

Mineralogy of poorly crystalline aluminium phases in the B horizon of Podzols in southern Sweden

Poorly crystalline Al components of the clay fraction are often neglected in soil mineralogical studies. In this study 7 B horizons from podzolised soils in Sweden were analysed using a combination of infrared (IR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and selective extractions. It was found that most Bhs and Bs horizons contained allophane, imogolite and more or less hydroxy-interlayered vermiculite. Some Bhs and Bs horizons also contained small amounts of kaolinite and/or gibbsite. In one acid Bh horizon organically complexed Al was the only reactive Al fraction of importance. The vertical patterns of vermiculite and allophane/imogolite suggested that both had formed during the podzolisation process, but due to different mechanisms. The pattern of kaolinite and gibbsite occurrences indicated that these minerals were mostly inherited from the parent material. Oxalate and pyrophosphate extractions suggested that allophane and imogolite constituted the most important reactive inorganic Al fraction in the soils. This shows that allophane and imogolite seem to be the typical, rather than the occasional, reactive inorganic Al phases that form in the B horizon as a result of podzolisation.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.