Clay-Microbe Interactions and Implication for Remediation of Inorganic Contaminants

Mineral–microbe interactions indirectly affect the geochemical fluxes and biogeochemical cycling of a large number of elements. Among them are toxic heavy metals (e.g. chromium), radionuclides (uranium and technetium), and nitrogen. Heavy metals and radionuclides enter the environment from various sources such as mining activity, nuclear weapons production, metallurgical and chemical industries. Other metals, such as lead, arsenic, antimony, and cadmium, are enriched in certain environments by either natural or anthropogenic processes. Because many of these metals and radionuclides are carcinogens, their release into the environment and their fate cause intense scientific and public concern and are the subject of substantial research. Nitrate enters the environment largely through agricultural activity. Human health risks from nitrate uptake from drinking water supplies run the gamut from increased cancer risk to birth defects.     

地下水中稳定铬同位素的生物地球化学作用

铬是地下水中常见的一种变价重金属污染物,在自然界中广泛分布且应用广泛。将Cr(Ⅵ)还原为Cr(Ⅲ)是地下水铬污染防治中的主要策略。在Cr(Ⅵ)的非生物还原过程中存在铬同位素分馏现象,通过地下水中铬同位素组成的变化情况可以定量地指示Cr(Ⅵ)的还原程度和速率。这被认为是一个重要发现,在地下水铬污染防治中有着广阔的应用前景。文中对铬与铬的来源、地下水中铬同位素的测定方法、铬同位素的生物地球化学作用、铬同位素在地下水污染防治中的应用等进行了系统综述。研究认为：微生物广泛参与地下水中铬的氧化与还原作用,并有可能产生显著的铬同位素分馏。地下水中被还原的Cr(Ⅵ)在微生物作用下有可能被活化,用非生物还原条件下的铬同位素分馏规律指示地下水中Cr(Ⅵ)还原程度可能会产生较大的误差。开展地下水中铬同位素的生物地球化学作用研究,特别是生物氧化Cr(Ⅲ)过程中的铬同位素分馏规律研究,对于更全面地认识铬同位素的指示作用具有重要意义。     

Biogeochemical indication of pollution with metals and radionuclides in oil-producing regions

The results of investigation of the biogeochemical indication of pollution with metals and radio-nuclides in the oil-producing regions of Western Siberia are presented. It was ascertained that eight years after the oil spill, biota components (lichens, mosses, small mammals, etc.) on technogenic territories contain higher elemental concentrations as compared to the background sites, which allows us to use them to assess the anthropogenic load. Original data pertaining to radionuclide content in mosses and woody plants in Western Siberia are presented; they prove the fact that both oil production and trans-regional transportation contribute to the total pollution of Western Siberia with radionuclides.     

地下河出口河流水化学昼夜动态变化——生物地球化学过程的控制

昼夜动态变化的研究有助于揭示水体中相对快速的生物地球化学过程,同时也有助于判别影响水化学变化的主导因子。本文选择由地下水补给且富含水生植物的典型河流,开展高分辨率水文地球化学监测和高频率水样取样工作,分析了水化学的昼夜动态变化特征并对比其沿流程的变化,探讨了水化学昼夜循环产生的生物地球化学控制机理。结果表明,河流水化学离子成分多呈现出昼夜动态变化的特点,Ca2+、DIC白天下降幅度达22.4%,昼夜循环主要受水生植物光合作用控制,但不同成分沿流程具有不同的变化规律,存在Ca2+、DIC和营养元素成分的流失。研究河段硝酸盐含量较高(农业活动产生的面源氮补给),沿流程有减小趋势,受生物同化作用控制,白天小幅升高夜间回落的昼夜动态变化,主要受硝化作用过程控制。DOC与TOC含量小时数据呈现快速波动特点,白天上升夜间下降,受生物代谢活动控制,DOC的日变化幅度可相差1倍。岩溶区地表河流水化学昼夜动态变化规律与生物地球化学过程研究,不仅能揭示水化学无机组分昼夜循环的控制因素,也有助于更好理解岩溶作用过程中无机碳与有机碳的快速转换特性,对提高岩溶碳汇的估算精度有重要意义。     

陆地硅的生物地球化学循环研究进展

地球表层硅(Si)的生物地球化学循环与大气CO2浓度变化、大洋生物泵作用以及海岸带富营养化等过程密切相关,因此成为全球环境变化研究的核心问题之一。在地质时间尺度上,硅酸盐矿物的化学风化是地球表层所有次生Si的来源。陆地生态系统各次生Si库具有不同的形成机制和驱动因子,这导致各Si库的贮存量和循环周期存在明显差异。土壤Si库中的黏土矿物Si、溶解硅(DSi)和淀积在其他矿物表面的无定形Si都源自硅酸盐矿物的化学风化过程;植物生长过程中吸收土壤中的DSi形成生物Si,然后经微生物分解过程返还给土壤;地表径流将流域陆源Si以悬移质Si和DSi的形式输入河流、海洋。迄今,陆地不同形态Si库的大小及其对全球Si循环的贡献仍不确定。因此,在研究陆地Si的生物地球化学循环过程中,综合考虑各种地表过程及其耦合作用是非常必要的。     

Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province,Cambodia

Natural arsenic(As)contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue,particularly in South and Southeast Asia.A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region,however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry.The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn(hydr)oxides is an important control in As mobilization.Here,selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province,Cambodia,were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes(Fe,Mn and P)between groundwater and the associated solid aquifer matrix.In general,groundwater As is strongly affected by both pH and Eh throughout the study area.However,contrasting sorption behaviour is observed in two distinct sand-dominated(T-Sand)and clay dominated(T-Clay)transects,and plausibly attributed to differing dominant lithologies,biogeochemical and/or hydrogeological conditions.Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects,but to varying extents and in different ways.In T-Sand,which is typically highly reducing,correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter;in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur.Multiple linear regression analysis was conducted with groups categorised by transect and by Eh,and the output correlations support the contrasting sorption behaviours encountered in this study area.Irrespective of transect,however,the key biogeochemical processes which initially control As mobilization in such aquifers,may be "masked" by the re-setting of As concentrations through in-aquifer sorption/desorption processes.     

放射性核素在地下介质中迁移机理与模型研究

介绍了铀尾矿库的物理、化学概念模型和其中重金属、放射性核素迁移的一般过程 ;论述了沉淀作用、络合作用和胶体作用对放射性核素迁移的影响 ;重点讨论了描述吸附作用的离子交换模型和表面络合模型的建模机理 ;对定量模拟放射性核素迁移行为的 Kd模型、表面络合模型及“反应 -运移模型”的应用进行了评述。     

Biogeochemical Modelling of a Seasonally Anoxic Lake: Calibration of Successive and Competitive Pathways and Processes in Lake Aydat,France

A reactive transport model was developed to describe seasonal variations of biogeochemical and physical processes in Lake Aydat. The model includes physical processes such as vertical mixing, sedimentation and advection related to inflows into the lake and biogeochemical conversion processes in the water column and in the sediment surface layer. The reactions described in the model include primary redox reactions such as primary production, aerobic and anaerobic respiration, methanogenesis and secondary reactions established between oxidants and reducers produced by the primary reactions. After adjusting various kinetic constants, the model reasonably reproduced the main features of seasonal variations of dissolved oxygen and nitrate depth profiles and pH. The reactive transport model was also used to quantify the relative importance of different biogeochemical pathways. For instance, ferrous denitrification seems to play an important role when stratification is increasing.     

海洋生物地球化学模式研究进展

海洋生物地球化学模式是定量认识物质的海洋生物地球化学循环、理解其控制机制以及预测体系变动的重要手段。20世纪90年代以来,该研究领域的进展主要体现在海洋生物地球化学循环的物理输送和生态动力学过程以及年际、年代际变动的模拟3个方面。物理过程模拟方面的进展,集中在寡营养海区上层海水营养盐的供应机制问题上,在经典的上升流、垂直扩散之外,提出涡旋可能构成一种重要的物理输入过程。而生态动力学过程的模拟方面,90年代前期考虑食物网基本结构,由浮游植物、浮游动物和细菌三大类群构成生物状态变量,氮和磷营养盐以及颗粒碎屑构成其他状态变量;90年代后期,开始引入铁和硅的限制问题,考虑不同浮游植物和浮游动物群落结构的影响,特别是浮游植物粒级结构变化的预测可能是未来该领域力图解决的一个技术问题。年际变化的模拟,多围绕ENSO事件对初级生产的影响及其机制问题展开;年代际和地质年代尺度的体系变动问题仍存在争论,相对缺乏有效的数值模拟研究。该研究领域未来应加强生物—化学过程的函数表达、物理模式、中尺度过程、边界交换以及资料获取技术等方面的研究,以应对目前面临的诸多问题与挑战。     

生态系统营养离子循环及水化学演经的锶同位素示踪

综述了Ｓｒ同位素示踪生态系统离子循环水化学演化的基本原理、主要内容和最新进展。着重介绍了Ｓｒ同位素在矿物风化速率研究、流域营养离子来源识别及其循环通量计算、地下水体化学尬发演化机制的示踪应用;最后展望了Ｓｒ同位素在生物地球化学过程示踪上的潜在价值。     

Progress in the Study of Marine Stable Nitrogen Isotopic Changes and Its Geological Records

Marine stable nitrogen isotope containing much key biogeochemical information, is an important way in identifying marine nitrogen sources and understanding the marine nitrogen cycles. These isotopic signals can be preserved in marine sediments and used to trace the marine biogeochemical cycles and environment changes during geological history. Studies in recent decades have illustrated the key role of nitrogen fixation and denitrification. Because of the spatiotemporal variability and the complexity of ocean processes and nitrogen sources in the marine environment, we need to combine the modern observations with geological records, integrate oceanography, biology, and geology, and consider the hydrological environment, geological processes and climate changes, to understand the coupling between the ocean nitrogen cycle, climate and environmental changes.     

陆地生态系统与气候相互作用的研究进展

陆地生态系统与气候系统通过地面与大气之间能量平衡、水汽交换和生物地球化学循环相互作用,影响大气中温室气体浓度和气溶胶,继而影响气候变化。较系统分析总结了当代国际上陆地生态系统与气候相互作用的最新研究进展。首先介绍了陆地生态系统与气候相互作用的机制与过程,总结了陆地生态系统与气候相互作用研究的三个发展阶段,以及当代相互作用的过程模拟研究中三类主要的全球生态系统模型,即生物物理模型、生物地理模型和生物地球化学模型。并介绍了气候对生态系统变化的响应,即两种主要的反馈机制。最后,对未来的研究方向和重点作了分析。     

生态系统营养离子循环及水化学演化的锶同位素示踪

综述了Ｓｒ同位素示踪生态系统离子循环和水化学演化的基本原理、主要内容和最新进展。着重介绍了Ｓｒ同位素在矿物风化速率研究、流域营养离子来源识别及其循环通量计算、地下水体化学成分演化机制的研究中的示踪应用;最后展望了Ｓｒ同位素在生物地球化学过程示踪上的潜在价值。     

台湾国姓地区中新世海相菱铁矿的成因

菱铁矿很好地记录了过去地质流体的信息,能够用于示踪生物地球化学反应相关的成岩作用带。台湾国姓地区中新世海相泥页岩中发育自生的菱铁矿结核,其成因尚未厘清。野外观察发现菱铁矿以不连续透镜体平行散布于泥页岩中,主要由自生碳酸盐菱铁矿（78.63%）等矿物组成。菱铁矿的稀土元素配分模式为轻稀土亏损、中稀土富集,无Ce异常,指示菱铁矿形成于弱氧化的沉积环境,弱氧化的环境促进了菱铁矿在次氧化带的沉淀。菱铁矿的δ13C_VPDB和δ18O_VPDB值分别为-3.69‰~+0.08‰和-1.09‰~+0.25‰,指示菱铁矿形成于次氧化带,碳源很可能是海水和有机质降解混合产生。研究表明自生菱铁矿能够被用于识别沉积物中的生物地球化学过程和指示成岩作用带。     

Evidence for Non-Conservative Behaviour of Chlorine in Humid Tropical Environments

The knowledge of the biogeochemical cycle of chlorine (Cl)is important since this element is used as a tracer of geochemical and hydrological processes in oceanic or continental environments. More specifically, Cl can be used to correct surface water composition from atmospheric contribution in order to calculate precise chemical weathering rates in watersheds. Beyond the problem of potential Cl sources in a given watershed, which is directly related to the lithology, vegetation, and industrial activities, the Cl normalization is based on the assumption that this element behaves conservatively during surface processes (e.g., chemical weathering, adsorption/desorption processes).The purpose of the present study is to forecast the geochemical behavior of Cl in a forested ecosystem located under humid tropical environment.For this reason, we have analyzed the Cl (and also Ca and Na) concentrations ofsurface waters (rainwater, groundwater, river water) over a two-year period in the Nsimi–Zoetele watershed (Cameroon).The Cl mass balance for the watershed appears to be equilibrated over the studied period (1995–1996) but Cl behavior in Mengong River draining the watershed suggests a non-conservative behavior. Indeed, Cl concentrationsin the Mengong River are low during dry seasons and high during wet seasons, which is the reverse tendency to what is usually observed taking into account dilution and evaporation processes. As Cl concentrations in the Mengong River are lower than those measured in all the feeding reservoirs, Cl should be adsorbed onto the soils of the watershed. However, as the Cl mass balance is equilibrated over the whole-year, Cl should be adsorbed and releasedat a seasonal scale. The results we obtained for this small watershed were not generalized for a larger studied basin (i.e., Nyong River basin). Even if these results should be followed by further investigations, this study suggests that Cl normalization should be used with caution to avoid under- or over-estimation of chemical weathering rates.     

Natural analogues

Natural analogues, which are occurrences of materials or processes which are analogous to expected materials or processes in a waste repository, are used to clarify the ability of the geologic environment and engineered system to contain the waste. It is hoped that natural analogues can provide data and insight on processes which generally occur on temporal or geometric scales which are too large to be studied in laboratory or field experiments. Natural analogues have been described for the study of transport and migration of radionuclides through the backfill and host rock, and the stability of backfill, shaft seals, waste forms, and waste containers. Natural analogues have also been suggested as an aid in predicting overall repository performance.     

Review of interactions between phosphorus and arsenic in soils from four case studies

Arsenic is a non-essential element that poses risks in many environments, including soil, groundwater, and surface water. Insights into the environmental biogeochemistry of As can be gained by comparing As and P reaction processes. Arsenic and P are chemical analogues, and it is proposed that they have similar chemical behaviors in environmental systems. However some chemical properties of As and P are distinct, such as redox reactions, causing the biogeochemical behavior of the two elements to differ. In the environment, As occurs as either As(V) or As(III) oxyanions (e.g., AsO₄^3? or AsO₃^3?). In contrast, P occurs predominantly as oxidation state five plus; most commonly as the orthophosphate ion (PO₄^3?). In this paper, data from four published case studies are presented with a focus on P and As distribution and speciation in soil. The goal is show how analyzing P chemistry in soils can provide greater insights into As reaction processes in soils. The case studies discussed include: (1) soil developed from shale parent material, (2) mine-waste impacted wetland soils, (3) phosphate-amended contaminated soil, and (4) plants grown in biochar-amended, mine-contaminated soil. Data show that while P and As have competitive reactions in soils, in most natural systems they have distinct biogeochemical processes that create differing mobility and bioavailability. These processes include redox reactions and rhizosphere processes that affect As bioavailability. Results from these case studies are used as examples to illustrate how studying P and As together allows for enhanced interpretation of As biogeochemical processes in soils.     

Some geochemical and environmental aspects of the Chernobyl nuclear accident

The Chernobyl nuclear accident took place on 1986-04-26, and resulted in radionuclide pollution of vast regions of Byelorussia. This has raised several geochemical problems: (1) investigation of the distribution and behaviour of radionuclides in the natural and technogenic landscapes (which were examined as a result of a 5-a study); (2) modes of occurence of radioactive elements in the environment; and (3) preliminary estimation of radionuclide migration in the future. As background information, geochemical studies carried out within Byelorussia, as well as landscape investigations in the period 1953–1987 made under the guidance of K.I. Lukashev were very important for solving the above questions. According to the results of these investigations, the lithogeochemical and hydrogeochemical zoning of Byelorussia is understood and the radioactive background of the republic was studied in the 1960s, as well as the distribution and peculiarities of clay minerals, carbonates, FeMn oxides, organic matter, pH-Eh, and the contents of many elements in the surficial deposits of Byelorussia. All these factors are of great importance for understanding the behaviour of radionuclides.Radionuclide fallout on Byelorussia in the first days after the accident was mainly dependent on the mass movement of air and rain. In cities, fallout was confined to regions with intensive industrial dust emissions, as well as to river valleys, where degassing of deep-seated zones through faults occurred side by side with evaporation. Radionuclide washout from upland territories can be related to secondary processes.After 5 a, the radioactive emission near the surface of the Earth decreased due to the decay of short-lived isotopes and penetration of radionuclides deeper into the soil, although the major part still occurs at a depth of 1–5 cm. Bogs, peat-bog soils, aquifers with fluctuating groundwater levels, variable pH-Eh conditions and a igh biological activity are all factors contributing to radionuclide migration in the Byelorussian landscape. A part of the radionuclides is gradually removed from eluvial landscape and accumulated in subareal landscape (e.g. lakes, oxbow-lakes, water-storage basins).The Chernobyl debris are represented by the following substances: “hot” particles, pseudocolloids, aerosols and gaseous compounds. Study of the modes of occurrence of radionuclides by different methods (e.g. extracts, sorbents) made it possible to estimate the migration capacity of some radionuclides (Cs, Sr, Ce, Ru), and to distinguish two zones around the reactor—the nearest and remote ones—differing in the ratio of “hot” particles and condensate fallout, which causes a different migration capcity of radionuclides.A very important part is assigned to biological processes and organic matter, which cause the destruction of “hot” paricles, the formation of organomethallic complexes, and water migration of nuclides.In the future (within 300 and more years), the redistribution of radionuclides in the landscape involves processes of weathering, erosion and sedimentation which will strongly depend on climatic conditions, Side by side with a gradual decay of Cs and Sr, an appreciable accumulation of²⁴¹Am, which is very mobile in landscape, should be expected due to decaying²⁴¹Pu.A considerable development of scientific and applied exploration should also be expected in the future and this will help in solving problems of radioactive pollution of landscapes.     

Chernobyl fallout and radionuclide activity in bottom sediments at the River Adige estuary (northern Adriatic Sea, Italy)

The artificial radionuclides ¹³⁷Cs, ¹³⁴Cs and ¹⁰⁶Ru have been determined up to 16 cm deep in two sediment cores collected in March 1988 at the River Adige estuary in the northern Adriatic Sea. Interdependent relations between the properties of the sediment levels and the activity of radionuclides have been investigated using multivariate statistical analysis. The interactions between radiocontaminants and the particulate matter or water phase are discussed during their transfer processes from the river to the estuary and the marine environment. Diffusion phenomena within the sedimentary column have also been considered. The vertical distribution of the artificial radionuclides due to Chemobyl fallout in sediment cores from the River Adige mouth, compared to those from similar estuarine environments in the Adriatic Sea, point out a general rapid accumulation of river-borne solid material in coastal zones of the North Adriatic Sea.