运用STOMP数值模拟器进行多空介质中尿素水解以及方解石沉淀数值模拟

遍布于美国能源部所辖野外场地的地下放射性核素和痕量金属污染对美国能源部的长期监管职能提出了最严峻的挑战。目前较有前景的一个原地固化污染物方法是利用尿素酶催化尿素水解,进而推动方解石沉淀及与之共同沉淀。运用STOMP数值模拟器实施一系列反应性溶质数值模拟来研究系统中水流、运移、反应与反应导致的介质性质变化之间的紧密的非线性耦合,并在研究中系统性增加反应系统的复杂度和物理-化学的非均质性以考察模拟效果。通过调整反应速率表达式中尿素酶浓度和沉淀反应常数,对尿素水解和方解石沉淀速率进行了敏感度分析。结果显示:尿素水解速率是矿物沉淀总量的决定性因素,沉淀物的空间分布既取决于水解速率也取决于沉淀速率;在一维水流柱6个空隙体积的时间段模拟中,观察到了5%的最大空隙度减少;当二维模拟中考虑一个低渗透性包裹体时,被改变的流场重新对生成的沉淀组成物进行了分布,形成了扭曲的反应锋面。模拟结果也显示沉淀在低渗透性区域边界上形成,这说明位于这个区域里面的污染物可能被囊裹而从流线中被隔离起来。     

Self-organization of recent rhythmic iron-manganese precipitations in underground mines in the Harz mountains

A recent early diagenetic banded iron-manganese mud has been forming underground in a closed lead-zinc mine for approximately 40 years. The processes leading to the banded structure of the precipitate were studied during a period of 2 years. Therefore, 19 physical and chemical parameters were measured regularly in short intervals. The resulting time series were analysed with respect to the data sets of the monthly chemical analyses of the descendent mine water, the daily rainfall and the mineral content. The results reveal that the precipitated material undergoes internal self-organization due to interaction of redox, colloid-chemical, microbial, electrical and ripening processes, and not exclusively produced by seasonal fluctuations of material input. Thus, the primary banding of the material, caused by externally forced fluctuations of the redox conditions within the mine water, is reorganized after a short time. The finally observed bands are controlled by non-linear coupling of reaction and transport processes within the mud. A genetic model for the banded mineralization was developed and verified by numerical simulation.     

The effect of metamorphic fluid flow on the nucleation and growth of garnets from Troms, North Norway

A spatial association is observed between the size distribution of garnet porphyroblasts and the size distribution of quartz veins in greenschist facies metapelites from Troms, North Norway. The size distribution of quartz veins reflects the flow regime of metamorphic fluids. The hypothesis that the flow regime of metamorphic fluids is also responsible for the size distribution of garnet crystals was tested by ascribing empirical acceleration parameters to the nucleation and growth rates of garnet crystals.
In regions where fluid flow was interpreted as pervasive', acceleration parameters for nucleation were high, whereas in regions where fluid flow was interpreted as channelled', acceleration parameters for growth were high. Accelerated crystal growth is further implied from the chemical zoning and crystal morphologies of garnets collected near discrete veins.
This spatial association may imply that fluid flow can be instrumental in controlling garnet crystallization. Fluid flow could affect garnet crystallization kinetics by facilitating thermal advection and/or mass transfer. In the study area, rhodochrosite (MnCO₃) veins provide evidence for mass transfer of Mn by fluid flow. An influx of Mn would expand the stability field of garnet to lower temperatures. The resulting thermal overstep could accelerate nucleation and/or growth of garnets.
The corollary of this study is that size distributions and chemical zoning of garnets, or other porphyroblast phases, can be used to study metamorphic fluid flow.     

Iron Reduction Along an Inundation Gradient in a Tidal Sedge (<Emphasis Type="Italic">Cyperus malaccensis</Emphasis>) Marsh: the Rates,Pathways, and Contributions to Anaerobic Organic Matter Mineralization

Incubation experiments were adopted to characterize the rates and pathways of iron reduction and the contributions to anaerobic organic matter mineralization in the upper 0–5 cm of sediments along a landscape-scale inundation gradient in tidal marsh sediments in the Min River Estuary, Southeast China. Similar sediment characteristics, single-species vegetation, varied biomass and bioturbation, distinct porewater pH, redox potential, and electrical conductivity values have resulted in a unique ecogeochemical zonation along the inundation gradient. Decreases in solid-phase Fe(III) and increases in nonsulfidic Fe(II) and iron sulfide were observed in a seaward direction. Porewater Fe²⁺ was only detected in the upland area. High rates of iron reduction were observed in incubation jars, with significant accumulations of nonsulfidic Fe(II), moderate accumulations of iron sulfides, and negligible accumulations of porewater Fe²⁺. Most of the iron reduction was microbially mediated rather than coupled to reduced sulfides. Microbial iron reduction accounted for 20–89 % of the anaerobic organic matter mineralization along the inundation gradient. The rate and dominance of microbial iron reduction generally decreased in a seaward direction. The contributions of microbial iron reduction to anaerobic organic matter mineralization depended on the concentrations of bioavailable Fe(III), the spatial distribution of which was significantly related to tidal inundation. Our results clearly showed that microbial iron reduction in the upper sediments along the gradient is highly dependent on spatial scales controlled primarily by tidal inundation.     

Surface reaction versus diffusion control of mineral dissolution and growth rates in geochemical processes

The kinetics of chemical reactions at mineral surfaces and the rates of diffusion of species in an aqueous phase are coupled in many geochemical systems. Analytical solutions to equations describing coupled mineral dissolution/growth and solute transport in both transient and steady-state systems are used to delimit regimes of pure reaction control, pure transport control and mixed kinetic control of mass-transfer rates. The relative significance of the two processes depends on the magnitudes of the diffusion coefficients and rate constants as functions of temperature, and the degree of disequilibrium in the system. In addition, the system geometry, the ratio of mineral surface area to diffusion cross-section, and the porosity and tortuosity of the medium through which aqueous species diffuse affect reaction vs. diffusion control. In general, diffusion control increases with increasing temperature and increasing distance over which diffusion occurs. Calculations for the mixed kinetic regime in transient systems demonstrate that the relative significance of diffusion and surface reaction varies with reaction progress, and approaches a limiting value as equilibrium is approached. This limiting value may be appropriate to natural water-rock interactions that occur at conditions that are close to equilibrium. This result permits extension of simple models for irreversible mass transfer in homogeneous systems to systems in which mass-transfer kinetics are controlled by coupled surface reactions and mass transport. Criteria are established for time and length scales and fluid velocity limits on the validity of the continuum hypothesis and the local equilibrium assumption in mass-transport modeling.     

Geochemistry of sterols in sediments from Black Sea and the southwest African shelf and slope

Surface sediment samples from the shelf and continental slope off southwest Africa and sediment cores from the deepest part of the Black Sea were analyzed for sterols. Because the organic matter in these anoxic sediments is relatively well-preserved, the input from source organisms in the water column is important in controlling sterol distribution patterns. The sterol distribution on the Namibian shelf is complex, probably because of the great spatial and temporal variability of biological productivity caused by seasonal upwelling and changes in oxygen concentration. The Black Sea, perhaps because of greater physical stability of the water column, has sterol distributions which can be explained by microbial activity or chemical processes acting on a constant input of organic carbon from surface production.     

塔里木盆地西北缘下寒武统黑色岩系差异性成岩演化及其影响因素

尽管泥页岩在埋藏过程中经历的复杂成岩改造会显著影响页岩油气储层发育潜力,但对其成岩作用,特别是泥页岩中成岩矿物的类型、成岩演化及其影响因素、成岩矿物元素在低孔低渗孔隙系统中的迁移等问题的认识仍很薄弱,因而制约了对泥页岩储层的深入认识。为此,本文以塔里木盆地西北缘下寒武统玉尔吐斯组发育的两套黑色岩系为例,在沉积环境认识的基础上,通过矿物组分、黏土矿物组合、有机碳含量及有机质成熟度等测定分析,着重研究了黑色岩系自生矿物的分布及在成岩演化阶段的变化特征,阐述了成岩变化的时空分布及其影响因素。研究结果表明：（1）在浅水缓坡台地环境下,玉尔吐斯组受两个较为完整的海进-海退沉积旋回控制而形成的两套黑色岩系主要经历了早成岩阶段和中成岩阶段;（2）受沉积环境和热液作用的影响,这两套黑色岩系在石英、重晶石、碳酸盐胶结物和黏土矿物等自生矿物的组合、分布及形成顺序上存在显著的差异,呈现出差异性成岩演化的特点;（3）伊利石、伊蒙混层、绿泥石、白云石、石英胶结等中成岩阶段成岩产物的广泛分布,反映出在成岩过程中特别是中成岩阶段低孔低渗的泥页岩仍存在一定程度的内部和外部来源的矿物元素迁移。本次研究对深入认识塔里木西北缘下寒武统黑色岩系成岩机制,以及分析页岩储层发育特征提供了重要的依据。     

塔北埃迪卡拉系奇格布拉克组多类型共生鲕粒特征及其成因探讨*

碳酸盐岩中的鲕粒是古沉积环境重建的重要载体之一。塔里木盆地北部露头剖面、星火1井区埃迪卡拉系奇格布拉克组潟湖相及浅滩相沉积中发现了多种类型鲕粒及其共生现象。文中通过剖面详勘、岩心观察以及薄铸片、阴极发光、环境扫描电镜等研究方法,阐明了不同类型鲕粒的基本特征及分布,探讨了鲕粒成核、生长的特殊沉积环境和成岩改造等过程。按显微结构、特殊形态、组合以及成岩改造,依次将研究区奇格布拉克组鲕粒划分出12种类型,其中大气淡水、快速拟晶白云岩化、重结晶、交代白云岩化等成岩作用主要发现于中等水动力条件形成的同心(圈)鲕、同心—放射状鲕等。近源风暴引起的底流和涡流产生的撕裂、磨损及搬运作用为泥晶(大)鲕、薄皮鲕、放射状泥晶(正常或大)鲕、脑状鲕以及部分球(或细菌)鲕、复鲕的成核和微生物作用提供了基本条件,而文石—白云石海中低能环境下的黏性软底质中广泛发育的文石—高镁方解石胶结促进鲕粒的形成; 前者发育于潮道或浅滩环境,后者发育于潮坪—潟湖环境,短暂风暴潮或底流是两者共生的可能原因。 微生物参与泥晶成核、一定水动力条件下台阶状生长、差异性成岩改造是前寒武纪多种类型鲕粒发育的主控因素。鲕模孔、粒间(内)溶孔、晶间孔、有机微孔等孔隙具有一定储集意义。对奇格布拉克组鲕粒的研究,有助于深化对前寒武纪古海洋和大气组分、黏性软底质中成核与生长中的水动力及微生物作用、早期成岩改造及孔隙形成与保存机理等的认识。     

Modelling Microbial Degradation Coupled to Reactive Transport in Groundwater: A Benchmark Analysis

Microbes are ubiquitous in groundwater systems, and they play an important role in the redox state of groundwater and especially on the fate of organic contaminants. In this context, numerical simulations that couple microbial processes to reactive transport models are becoming more popular. In the present work, we revisit the mathematical ground of microbial redox reactions and perform a benchmark analysis of the simulation of aerobic benzene degradation in a shallow and oxidizing aquifer. Numerical results indicate that the two codes tested (one using the finite elements approach and the other using the finite differences approach) lead to very similar results. In addition, the coupling of heterogeneous geochemical reactions to the benchmarked example problem provides a solid basis for the understanding of the redox reactions and the changes on the carbon system triggered by the aerobic degradation of benzene.     

High-resolution monitoring of biogeochemical gradients in a tar oil-contaminated aquifer

The detailed understanding of in situ biodegradation of petroleum hydrocarbons in porous aquifers requires knowledge on biogeochemical gradients, the distribution of individual redox species and microorganisms. The generally limited spatial resolution of conventional monitoring wells, however, hampers appropriate characterization of small-scale gradients and thus localization of the relevant processes. Groundwater sampling across a BTEX plume in a sandy aquifer by means of a novel high-resolution multi-level well (HR-MLW) is presented here. The presence of distinct and steep biogeochemical gradients is demonstrated in the centimeter and decimeter scale, which could not be resolved with a conventional multi-level well. The thin BTEX plume with a vertical extension of only 80 cm exhibited a decline of contaminant concentrations by two orders of magnitude within a few centimeters in the upper and lower fringe zone. The small-scale distribution of sulfate, sulfide and Fe(II) in relation to the contaminants and elevated δ³⁴S and δ¹⁸O values of groundwater sulfate strongly indicated sulfate and iron reduction to be the dominant redox processes involved in biodegradation. High microbial activities and biomass especially at the plume fringes and the slope of chemical gradients supported the concept that the latter are regulated by microbial processes and transverse dispersion, i.e. vertical mixing of electron donors and acceptors. Transverse dispersion therefore was suggested to be a driving factor controlling biodegradation in porous aquifers, but not exclusively limiting natural attenuation processes at this site. Broad overlapping zones of electron donors and electron acceptors point towards additional factors limiting anaerobic biodegradation in situ. The identification of small-scale gradients substantially contributed to a better understanding of biodegradation processes and hence is a prerequisite for the development of reliable predictive mathematical models and future remediation strategies.     

Barite in the ocean – occurrence,geochemistry and palaeoceanographic applications

The mineral barite (BaSO₄) can precipitate in a variety of oceanic settings: in the water column, on the sea floor and within marine sediments. The geological setting where barite forms ultimately determines the geochemistry of the precipitated mineral and its usefulness for various applications. Specifically, the isotopic and elemental composition of major and trace elements in barite carry information about the solution(s) from which it precipitated. Barite precipitated in the water column (marine or pelagic barite) can be used as a recorder of changes in sea water chemistry through time. Barite formed within sediments or at the sea floor from pore water fluids (diagenetic or cold seeps barite) can aid in understanding fluid flow and sedimentary redox processes, and barite formed in association with hydrothermal activity (hydrothermal barite) provides information about conditions of crust alteration around hydrothermal vents. The accumulation rate of marine barite in oxic‐pelagic sediments can also be used to reconstruct past changes in ocean productivity. Some key areas for future work on the occurrence and origin of barite include: fully characterizing the mechanisms of precipitation of marine barite in the water column; understanding the role and potential significance of bacteria in barite precipitation; quantifying parameters controlling barite preservation in sediments; determining the influence of diagenesis on barite geochemistry; and investigating the utility of additional trace components in barite.     

A concept for estimating depth of the redox interface for catchment-scale nitrate modelling in a till area in Denmark

A concept was developed for distributing the depth of the redox interface at catchment scale in tills for use in nitrate modelling. The hypothesis was that the redox interface has been developing since the beginning of the Holocene due to oxidation of inherent reduced compounds in the sediment by oxygen in recharging water. Key to the concept is estimation of the spatial pattern of the redox interface, inferred from variability in groundwater recharge and the amount of reduced compounds in the sediments. The concept was tested for the 101-km² Norsminde fjord catchment in Denmark using a catchment-scale nitrate model, where two parameters controlling the estimated redox interface were calibrated based on the observed amount of nitrate transported to the fjord. Estimated depths of the redox interface across the catchment enabled reproduction of the cumulative distribution of measured depths across the catchment, but they did not fit well with the observations at individual wells. It is therefore concluded that the concept may be useful for simulation of nitrate transport and reduction in the saturated zone at catchment scale, but it is not able to correctly predict nitrate reduction at point scale.     

Diagenetic cycling of trace elements in the bottom sediments of the Swan River Estuary,Western Australia

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.     

Urban Soil Microbial Features and Their Environmental Significance as Exemplified by Aberdeen City,UK

Urban soil research has invoked great interest in recent years.Previous studies were mainly focused on urban soil physics and chemistry,and soil geography to constrain the source,distribution,transport and deposition of pollutants such as heavy metals and health-hazardous organic matter,bu t litte has been done on soil microbiology.In this paper,the authors reported the variation of microbial features in urban soils compared with those from adjacent rual areas.The results show great changes in basal respiration rates microbial biomass and ecophysiological parameters have taken place in urban environment because of the anthropogenic stress, thus activating the microorganisms.As a result,much more energy,carbon is consumed at a low utilization efficiency.So microbial biosensors can be used to indicate urban environmental pollution effectively.     

Modelling of rock alteration due to coupled heat and mass transport

 A three-dimensional computer model is presented for studying the interaction of heat and mass transport regarding the temporal and spatial evolution of sandstones. The model simulates coupled heat and reactive mass transport in porous rocks. In general, mineral solubilities in water are low. Therefore, large fluid volumes are required to flow through the rock to explain observed mineral cements in sandstones. Besides mass transport, pore fluids transport heat which modifies rock temperatures. Very high flow rates result in strong temperature modifications and, therefore, enhance diagenesis. Low flow rates often cannot account for observed cementation. The model results show the effect of advective, convective and conductive heat transport on temperature and diagenetic evolution of sandstones for two different flow systems in a simple geological environment. Received: 6 August 1996/Accepted: 18 December 1996     

苏格兰阿伯丁城市土壤的微生物特性研究

在重金属的胁迫下,阿伯丁城市土壤中微生物特征发生了显著的变化,与农村土相比,微生物基底呼吸作用明显增强,但微生物生物量却显著降低,微生物生理参数Ｃｍｉｎ／Ｃｏｒｇ、ｑＣＯ２值明显升高,Ｂｉｏｌｏｇ数据显示城市土壤对能源碳的消耗量和速度显著升高,而且对能源碳的利用方式发生了改变,但利用效率却明显降低,反映出微生物特性可作为城市土壤环境质量变异的有效指标。     

二叠纪—三叠纪之交凝块石（微生物岩）的沉积成岩过程——以华南广西百色地区作登剖面为例

二叠纪末大灭绝之后,在我国华南地区广泛发育了一套钙质微生物岩,这套微生物岩以凝块石为主,代表了大灭绝事件后特殊环境下的生物沉积建造。早期对凝块石的分布以及沉积特征有详细研究。通过镜下显微观察,阴极发光照相,背散射成像以及探针元素分析,对凝块石的显微特征进行了详细研究。通过对凝块石中化石的分布,矿物组成以及元素分布规律观察,对比现代凝块石沉积成岩过程总结了二叠纪末凝块石的沉积成岩过程,即早期生长阶段,沉积阶段,早期成岩阶段和后期成岩阶段。清晰的凝块石的沉积成岩过程为解析该时期微生物沉积建造打下基础。     

滇中砂岩铜矿成矿过程中水－岩反应的证据与机理

从野外地质产状、岩石化学、有机岩石学、元素地球化学、有机地球化学等方面详细分析了滇中砂岩铜矿成矿过程中的水－岩反应证据，阐明了成矿过程中水－岩反应的机理，其中包括渗滤作用、扩散作用、混染作用、交代作用、交代溶蚀作用、氧化还原作用和沸腾作用     

A model for coupled sulfate reduction and methane oxidation in the sediments of Saanich Inlet

A methane-sulfate coupled reaction diffusion model has been developed to describe the inverse relationship commonly observed between methane and sulfate concentrations in the pore waters of anoxic marine sediments. The sediment column was divided into two zones; an upper zone where diagenetic reaction rates are limited by the concentration of oxidizable organic matter and a lower zone in which reaction rates are limited by the concentration of oxidizing agent—sulfate. For each zone differential equations describing the distribution of methane and sulfate were derived. The boundary conditions used to solve these equations resulted in a set of four coupled equations. When fit to data from Saanich Inlet (B.C., Canada) and Skan Bay (Alaska) the model not only reproduces the observed methane and sulfate pore water concentration profiles but also accurately predicts the methane oxidation and sulfate reduction rates. Maximum methane oxidation rates occur at the transition boundary from the upper to the lower layer. In Saanich Inlet sediments from 23 to 40% of the downward sulfate flux is consumed in methane oxidation while in Skan Bay this value is only about 12%.     

Stress response model for the tropical seagrass<Emphasis Type="Italic">Thalassia testudinum</Emphasis>: The interactions of light,temperature, sedimentation,and geochemistry

Our modeling objective was to better define the relationship between subtropical seagrass and potential water column and sediment stressors (light, organic and particle sedimentation, sediment nutrients, and the porewater sulfide system). The model was developed and optimized for sediments inThalassia testudinum seagrass beds of Lower Laguna Madre, Texas, U.S., and is composed of a plant submodel and a sediment diagenetic submodel. Simulations were developed for a natural stressor (harmful algal bloom,Aureoumbra lagunensis) and an anthropogenic, stressor (dredging event). The observed harmful algal bloom (HAB) was of limited duration and the simulations of that bloom showed no effect of the algal bloom on biomass trends but did suggest that sediment sulfides could inhibit growth if the bloom duration and intensity were greater. To examine this hypothesis we ran a simulation using data collected during a sustained 4-yr bloom in Upper Laguna Madre. Simulations suggested that light attenuation by the HAB could cause a small reduction inT. testudinum biomass, while input of organic matter from the bloom could promote development of a sediment geochemical environment toxic toT. testudinum leading to a major reduction in biomass. A 3-wk dredging event resulted in sedimentation of a layer of rich organic material and reduction of canopy light for a period of months. The simulations suggested that the seagrass could have recovered from the effects of temporary light reduction but residual effects of high sulfides in the sediments would make the region inhospitable for seagrasses for up to 2.5 yr. These modeling exercises illustrate that both natural and anthropogenic stressors can result in seagrass losses by radically altering the sedimentary geochemical environment.