西南表层岩溶带土壤中砷的迁移规律实验与模拟

岩溶地下河是我国西南地区的重要水源,工业生产过程中产生的砷污染物,除通过落水洞等直接进入并污染地下水外,还会在表层岩溶带溶缝、溶隙内吸附、滞留及富集,并在特定条件下再次迁移,成为"稳定次生污染源".以广西某砷污染事件为例,采用窄缝槽物理模型装置进行砷的动态吸附、解吸实验,并结合地球化学模拟研究砷污染物在表层岩溶带土壤中的迁移规律.实验结果显示表层岩溶带对砷的吸附以物理吸附（扩散过程）为主,相比吸附过程而言解吸速率则显得缓慢,而酸溶液相比去离子水可促进砷的解吸过程.地球化学模拟结果表明土壤矿物中以针铁矿对砷的吸附贡献最大,而酸溶液通过溶蚀针铁矿等矿物削弱对砷的吸附能力.因此在西南岩溶地区,表层岩溶带系统一旦纳入砷污染物,则解吸过程缓慢,易形成砷污染物的滞留、富集;而酸雨作用下砷的解吸、迁移过程加快,则会提高地下水系统的污染风险.      

多年冻土区石油污染物迁移过程研究回顾与展望

多年冻土区泄漏石油污染物会引起严重的环境和工程问题．通过对国内外石油污染物迁移过程、迁移机理、迁移模型、影响因素等研究进行回顾,基于国内外冻土区石油污染的研究进展和社会经济发展要求,提出了多年冻土区石油污染物可能引起的环境与工程问题,并对相关的科学问题进行展望,期望对以后研究工作有所指导并逐渐得到解决．     

石油污染地下水取样方式对比试验研究

为了获取取样方式对石油类污染物浓度影响的实证数据,笔者在华北平原一口石油污染的监测井内,开展了不洗井与洗井、不同取样器具采集地下水样品的对比试验研究。试验结果表明：洗井会减小不同取样器具造成的污染物浓度差异程度;采用手动惯性泵和小提桶采集的水样浓度普遍较高,而用低流速气囊泵采集的水样浓度普遍较低,浓度最大可相差40倍,平均为5倍。采用不同取样方式造成污染物浓度差异的主要原因可能是轻质石油物在水中的比重分异,以及取水影响范围内污染物在井管内、砾料层内和含水层内分布不均造成。试验结果提醒我们,在采集石油类污染地下水样品时,洗井是一道必不可少的野外工作程序,采用不同取样器具会对污染物浓度产生较大影响。因此,在进行地下水质量评价、污染风险评价以及地下水污染修复效果评估时,应考虑这种不确定性。     

河口区毒害有机污染物及其生态效应研究进展

河口区的生态环境复杂而脆弱，难降解的毒害性有机污染物会严重影响河口生境的良性发展，并可能通过食物链和其他途径危及人类健康。本简要论述了国内外对河口区毒害有机污染物及其生态效应研究的进展。目前的研究工作主要集中在毒害物质在河口生境中的各种过程、行为方式和分布特征，以及对河口生态平衡、生物机体的危害和毒理方面。这些工作对于了解河口区有机污染的状况及有机污染物在河口环境中的行为方式并有效地控制污染具有重要的意义。     

铬污染土壤复电阻率频散特性

不同含水率、不同铬污染物浓度土壤的复电阻率频散实验,是复电阻率探测方法评价铬渣污染场地的物理基础。实验研究发现,土壤含水率和污染物浓度的不同均会对复电阻率幅值、复电阻率相角、同相电阻率和异相电阻率的测量结果产生影响,但是异相电阻率和相角具有明显的频散特性。研究结果表明,利用基于土壤频散特性发展起来的复电阻率探测技术,可快速有效地对铬渣污染场地进行评价。     

考虑土体固结变形的污染物运移模型

土体的固结压缩变形对污染物的运移具有重要的影响,而目前国内关于污染物在变形多孔介质中运移规律的研究尚处于空白,在国外也是近几年才有人开始这方面的研究工作。在Biot固结理论和污染物运移理论相结合的基础上,提出了污染物在黏土防渗层中迁移转化的一维数学模型,该模型的最大特点是考虑了土体受力变形对污染物运移的影响,在合理简化的基础上给出了模型的解析解,并将计算结果与太湖疏浚污染底泥堆场的实测结果进行了比较分析,模拟计算的结果在一定程度上能够反映实际土层中污染物的运移情况。     

锶、钕、铅同位素样品准备方法介绍

针对同位素样品粉末化过程中易受污染的特点，详细介绍了夏威夷大学同位素实验室所使用的方法，包括样品的选取、切割、粗碎、净化、挑选以及粉末化过程。该方法的优点是尽可能地保证样品在粉碎过程中不受外界物质的污染，并去除一些蚀变及氧化物的影响。     

膨润土负载纳米铁镍同步修复地下水中三氯乙烯和六价铬复合污染

纳米零价铁原位注射修复地下水污染是近年发展的新技术,以往研究多侧重于单一目标污染物的去除效果及作用机理,但是地下水多种污染物共存问题不容忽视。本文针对典型污染物三氯乙烯TCE和六价铬Cr(Ⅵ),运用合成的活性高、稳定性强的膨润土负载纳米铁镍(B-Fe/Ni)开展修复实验,研究B-Fe/Ni对TCE和Cr(Ⅵ)共存复合污染的修复效果及其作用机制。通过一步法合成B-Fe/Ni,对TCE和不同浓度Cr(Ⅵ)混合污染的去除进行试验研究,对反应前后的样品B-Fe/Ni进行表征,并跟踪反应过程中TCE和Cr(Ⅵ)的浓度变化。结果表明:B-Fe/Ni同步去除水中TCE和Cr(Ⅵ)快速高效,50 mg/L Cr(Ⅵ)在2 h内能被B-Fe/Ni (1 g/L)完全去除而不受共存TCE(0. 1 mmol/L)的影响,然而TCE降解速率会随共存Cr(Ⅵ)的浓度(0、10、30、50 mg/L)增大而降低。经透射电镜-电子能谱及X射线光电子能谱表征验证,这是由于B-Fe/Ni与Cr(Ⅵ)快速反应,生成部分Fe-Cr共沉淀会覆盖B-Fe/Ni表面的活性位点,抑制了TCE的降解,但通过分析TCE降解产物可知,B-Fe/Ni同样能对TCE完全脱氯。因此,B-Fe/Ni适用于地下水复合污染修复,实际应用时需考虑多种污染物共存的相互影响,选择适宜试剂用量和注射方式,这对纳米零价铁修复技术的发展具有重要理论意义和应用参考价值。     

识别地下环境的污染源及现存的非氯的表土气体测量

在日本和许多发达国家,地下水被挥发性有机氯污染逐渐成为巨大的环境问题。取自日本全国的地下水样品,超过5％的样品三氯乙烯和乙烯的含量经常超过饮用水的限制。这种被挥发性有氯污染的地下水具有潜伏性,例如,由于许多工业处理所致,描述污染物羽毛状边界地下水等的现有井数,不易鉴定地下环境中污染物来源的形式。     

水中多环芳烃前处理过程中的污染来源及去除方法

实验设备、耗材等物品以及实验室环境中都有可能存在一定浓度的多环芳烃,造成样品在前处理过程中可能受到污染,从而影响多环芳烃测定结果的准确性。文章系统地研究了水样分析中萘、苊、芴、菲、蒽等多环芳烃污染物的引入和去除方法。在排除了数据处理和仪器测试的原因后,确认污染来自于样品前处理过程。对容器污染、试剂干扰、前处理间环境污染和氮吹浓缩系统等因素的排查结果表明,氮吹浓缩系统是主要的污染源。进一步实验证实,氮气、减压阀以及连接管线等均可造成多环芳烃污染。通过采取更换氮气、减压阀和连接管线的措施,并将氮气通过活性炭柱,能够有效地去除这些污染。实验设计了装有活性炭的玻璃柱装置,可以有效去除存在的萘等多环芳烃物质的污染;但专用减压阀避免多环芳烃污染的效果验证、氮气中多环芳烃污染物的来源确认以及多环芳烃污染去除装置的优化改进等问题还有待于进一步研究。     

攀枝花钒钛磁铁矿区土壤重金属地球化学特征及污染评价

为了解攀枝花钒钛磁铁矿区土壤重金属的特征及污染程度,采集了矿区表层土壤样品和两个土壤剖面,用多种分析方法有针对性地分析了Cu、Pb、Zn、Ti、V、Co、Ni、As、Cd、Cr、Hg、Mn十二种元素。在分析分布特征基础上,对重金属进行了污染物负荷指数评价,结果发现:1)攀枝花钒钛磁铁矿矿区表层土壤大部分属于中等污染,少数属于强污染,个别达到了极强污染;2)Co、V、Cu、Cd、Ti几种元素的最高污染系数大,Zn、Mn、Ni、Cr四种元素的最高污染系数次之,Hg、Pb两种元素的最高污染系数较小,As的最高污染系数最小;3)从各区域的污染物负荷指数来看,排土场周围和朱矿采矿场下游附近污染程度较大,远离矿区以及矿区上游污染较小。     

地球化学调查数据在地质背景、成矿条件分析中的应用:以中国西北干旱荒漠区为例

1:5万矿产地质调查中通常会优先部署地球化学调查工作,采样密度一般大于8点/km2,并分析多达38项地球化学指标,其主要目的是发现"矿致异常",指导矿产勘查工作.而研究表明,区域地球化学数据是地表物质化学组成的直接反映,所以不仅包含了与成矿有关的异常信息,更包含了丰富的地质信息.在本次工作中应用中国西北干旱荒漠景观区1:5万地球化学调查数据成功识别了工作区地质体单元的分布.相比1:20万地质底图,通过clr-PCA分析提取出的1:5万地球化学数据信息展现了更多的细节:（1）地质体单元可以更为细致地划分为多个次级单元;（2）侵入体单元可以进行期次或岩相划分;（3）可为地质体单元的归属提供依据.本项研究结果成功指导了后续开展的1:5万地质调查工作,并对最终的1:5万地质图进行了验证,此外还提供了多处有利找矿线索.      

The Moon

Recent geochemical and geophysical data from the Moon enable a revision of earlier interpretations regarding lunar origin, structure and bulk composition. Earth and Moon show many similarities among their isotopic compositions, but they have evolved in totally dissimilar ways, probably related to the deficiency of water and volatile elements in the Moon as well as the vast differences in size and internal pressure. Some global geochemical differences from the Earth such as volatile depletion based on K/U ratios have been established. However, all current lunar samples come from differentiated regions, making the establishment of a bulk composition more reliant on bulk geophysical properties or isotopic similarities; it remains unclear how the latter arose or relate to whole Moon composition. The lack of fractionation effects among the refractory and super-refractory elements indicates that the proto-lunar material seems unlikely to have been vaporized while the presence of volatile elements may place lower limits on proto-lunar temperatures. The apparent lack of geochemical evidence of an impacting body enables other possible impactors, such as comets, to be considered. Although the origin of the Moon remains currently unknown, it is generally believed that the Moon originated as the result of a giant impact on the Earth.     

The effects of phase fractionation on the composition of oils, condensates and gases

The effects of phase fractionation on the composition of oils, condensates and gases have been studied in the laboratory by a differential evaporation experiment. The experiment was designed to simulate the behaviour of a single-charge petroleum during (upward) migration or in a reservoir undergoing uplift, scenarios thought to be typical for the Norwegian continental shelf. After each pressure reduction step, samples from all phases (oil, condensate, free and associated gas) were collected and analysed. The results show that, in general, small molecules are preferentially enriched in the gas phase, both at elevated pressure and temperature and under standard conditions (15°C, 1 bar). The solvent power of the gas phase for large molecules is drastically reduced at lower pressures (here below approx. 300 bar). Carbon isotope ratios of individual compound are not affected, while variations in isotope ratios of fractions can be explained by changes in the fraction compositions. Individual geochemical parameters behave as can be expected based on the molecular size and structure of the compounds involved. However, a generally valid, quantitative prediction of how geochemical parameters vary as a result of phase fractionation is very difficult, as this will depend not only on the pressure and temperature of fractionation, but also on the composition and amounts of the oil and gas that are involved. The observations from this study confirm the importance of phase fractionation as an important process to consider when interpreting geochemical data for both condensates and oils.     

藏东南措美大火成岩省中OIB型镁铁质岩的全岩地球化学和锆石Hf同位素

西藏南东部新识别出来的措美大火成岩省的地幔柱头部物质成分尚未得到很好的约束。为探讨此问题,在全岩地球化学数据基础上,本文首次报道了藏东南措美大火成岩省中机布淌、打隆、措美和哲古错OIB型镁铁质岩的锆石Hf同位素和微量元素数据。本文报道的OIB型镁铁质岩包括碱性(组Ⅰ)和亚碱性(组Ⅱ)系列的辉长岩和辉绿岩,以岩墙或岩床的形式产出。这些镁铁质岩具有高的TiO₂(2.61%～4.07%)和P₂O₅(0.32%～0.51%)含量,富集轻稀土元素和高场强元素,地球化学特征类似于OIB。全岩微量元素地球化学指标显示组Ⅰ样品没有或很少受到地壳混染,组Ⅱ样品经历了较高程度的地壳混染。组Ⅰ中一件样品(JBT03-1)具有变化范围大的锆石ε_Hf(t)值(-4.8～+5.3),可能暗示其受到了地壳和/或岩石圈地幔物质的混染。本文结果表明锆石Hf同位素比全岩地球化学数据能够更为有效地识别基性岩浆是否受到地壳和/或岩石圈地幔物质混染。措美大火成岩省中的OIB型镁铁质岩样品(组Ⅰ和组Ⅱ),具有不同于俯冲带镁铁质岩和洋壳镁铁质岩的锆石稀土元素配分型式和锆石Ti温度,这可能是岩浆源区温度和成分不同的结果。综合考虑全岩地球化学和锆石Hf同位素指标,本文提出未受到地壳或岩石圈地幔混染的打隆镇辉长岩体(以组I中的DL01样品为代表)很可能代表了措美大火成岩省纯的地幔柱头部物质成分[⁸⁷Sr/⁸⁶Sr_(t)=0.7047,ε_Nd(t=+1.5,ε_Hf(t=+2.1～+5.7]。这些成分与代表白垩纪Kerguelen地幔柱头部物质的Site 1138和Bunbury Casuarina玄武岩非常相似,可能指示措美大火成岩省中的OIB型镁铁质岩本身就是Kerguelen地幔柱头部物质发生减压熔融的产物。     

Metallogenic provinces,geochemical provinces and regional geology — what causes large-scale patterns in low density geochemical maps of the C-horizon of podzols in Arctic Europe?

The <2 mm fraction of 605 samples of the C-horizon of podzols collected from an area of 188,000 km² in the European Arctic was analysed for more than 40 chemical elements. The results were used to construct geochemical maps which showed clear regional distribution patterns, notwithstanding the very low sample density of 1 site per 300 km². Some of these patterns fit established lithological boundaries. Others fit lineament structures in the area and underline the relative importance of certain tectonic directions some of which have not yet been delineated on existing geological maps. Some mark large-scale hydrothermal events and related alteration. Finally, some are connected with prominent, known ore deposits occurring in the area. However, several large deposits and even famous metallogenic provinces (Fe, Ni/Cu) are hardly, or not at all, reflected in the regional geochemical maps. In their present definitions geochemical provinces and metallogenic provinces are thus not necessarily related. Special geochemical features can occur at very different scales. The term geochemical province is so imprecise in terms of processes leading to regional-scale geochemical features that it should be avoided. Low-density geochemistry can be used to aid the interpretation of the geological evolution of large regions. It can also be used to find prospective areas within such regions.     

Geochemical tracing and hydrogeochemical modelling of water–rock interactions during salinization of alluvial groundwater (Upper Rhine Valley,France)

In the southern Upper Rhine Valley, groundwater has undergone intensive saline pollution caused by the infiltration of mining brines, a consequence of potash extraction carried out during the 20th century. Major and trace elements along with Sr and U isotopic ratios show that groundwater geochemical characteristics along the saline plumes cannot reflect conservative mixing between saline waters resulting from the dissolution of waste heaps and one or more unpolluted end-members. The results imply the occurrence of interactions between host rocks and polluted waters, and they suggest that cationic exchange mechanisms are the primary controlling process. A coupled hydrogeochemical model has been developed with the numerical code KIRMAT, which demonstrates that cationic exchange between alkalis from polluted waters and alkaline-earth elements from montmorillonite present in the host rock of the aquifer is the primary process controlling the geochemical evolution of the groundwater. The model requires only a small amount of montmorillonite (between 0.75% and 2.25%), which is in agreement with the observed mineralogical composition of the aquifer. The model also proves that a small contribution of calcite precipitation/dissolution takes places whereas other secondary mineral precipitation or host rock mineral dissolution do not play a significant role in the geochemical signature of the studied groundwater samples. Application of the model demonstrates that it is necessary to consider the pollution history to explain the important Cl, Na and Ca concentration modifications in groundwater samples taken over 2 km downstream of waste heaps. Additionally, the model shows that the rapidity of the cationic exchange reactions insures a reversibility of the cation fixation on clays in the aquifer.     

硒、钼、钒污染环境的生态地球化学修复物种筛选与展望

在对以往硒、钼、钒富集植物及其生态环境地球化学研究成果综述基础上,提出了植物生态地球化学富集类型和金属矿化植物划分的新方案,探讨了硒、钼、钒在植物中传输规律,初步筛选出硒、钼、钒污染环境的生态地球化学修复物种,提出了固体矿山污染环境的生态地球化学修复治理的研究和发展方向的建议,以期促进该研究方向的深入发展。     

The role of arsenic-bearing rocks in groundwater pollution at Zimapán Valley, México

 Interaction of groundwater with As-bearing rocks has been proposed as one of three main sources of arsenic at Zimapán valley, México. The complexity of the geology and hydrogeology of the valley make it difficult to identify the natural causes of arsenic poisoning. Samples from the different rock outcrops and water from wells tapping various rock formations were analyzed. The rocks from mineralized areas contained higher concentrations of arsenic with respect to the same formations in non-mineralized areas. The arsenic minerals arsenopyrite, scorodite, and tennantite were identified in some rock samples. Higher temperature and lower Eh values were found for those wells containing more arsenic. The physicochemical characteristics of these naturally polluted well waters could be produced by arsenopyrite oxidation. The geochemical model PHREEQCI was used to perform the inverse modeling of two wells located along the same fault. Arsenopyrite oxidation and scorodite dissolution appear to be the geochemical processes producing the natural pollution according to the model. The release and transport of arsenic mainly occur through fractures within the cretaceous limestones where the most productive wells are drilled. The presence of arsenic should be expected also in other formations near mineralized zones in the Zimapán Valley. Field determinations of Eh and T could be used to detect potentially polluted wells. Received: 29 April 1999 / Accepted: 18 July 2000     

山西阳泉三矿煤层粘土岩夹矸地球化学特征

采用化学法和中子活化(INAA)法对采自山西阳泉三矿山西组3号煤层和太原组12号煤层的3件煤层夹矸粘土岩样品的8种常量元素(氧化物)和33种微量元素含量进行了测定。通过对具有示踪意义的元素及其比值的对比分析,3个样品总体上均不具有典型的沉积岩特征,应该是由酸性或酸性偏碱性火山物质(降落的或陆源搬运的)在地表覆水较浅的弱氧化条件下经原地淋滤、蚀变形成的。原岩蚀变程度较高,不稳定或较不稳定的元素大量流失,甚至一些较稳定的元素(如高岭岩中的铁、锰)也明显流失。强烈的化学蚀变以及岩石中矿物成分的变化是造成粘土岩间以及粘土岩与原岩间元素(尤其是REE)含量及REE配分模式差异的主要原因。