Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl₂·4H₂O, FeCl₂·6H₂O, FeSO₄·H₂O, FeSO₄·7H₂O, FeCO₃, and Fe(OH)₃] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO₄, Fe-HCO₃, H-Fe-Cl, and H-Fe-SO₄.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO₃), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO₃ dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO₄-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O₂(g)], but later caused oxidation of iron [high O₂(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.     

Reaction time scales for sulphate reduction in sediments of acidic pit lakes and its relation to in-lake acidity neutralisation

Sulphate reduction is a key reaction to remove acidity from water bodies affected by acid mine drainage. In this study, ³⁵SSO₄²⁻ reduction rates determined in sediments from a variety of acidic lignite pit lakes have been compiled. The rates decreased with pH and are strongly dependent on carbon substrate. The rates were fitted to a Monod model adapted to the specific conditions of acidic pit lakes (APL) sediments: i) sulphate reduction rate is independent from sulphate concentration due to the high concentration typically observed in APL systems (10–30 mM), ii) the observed pH dependency of sulphate reduction was accounted for by an inhibition function F_inihibt which considers the occurrence of low cell numbers of sulphate reducing bacteria at pH values < 4.75. Simulated steady-state sulphate reduction rates are predicting measured rates at carbon substrate concentrations of <10 μM. Estimated steady-state reaction time scales range between 2.4 h at pH 7 and 41 h at pH 3 at a carbon half-saturation constant of K_C−S = 100 μM and are increasing with increasing K_C−S values. Time scales at low pH are too long to allow for significant generation of alkalinity during the time of residence of groundwater passing through the top and hence most reactive zone of APL sediments which has important implications for the remediation of acidic pit lakes.     

The acidic mine pit lakes of the Iberian Pyrite Belt: An approach to their physical limnology and hydrogeochemistry

This study examines some relevant limnological and hydrogeochemical characteristics of 22 mine pit lakes of the Iberian Pyrite Belt (IPB). The studied pit lakes include some of the largest and historically most important mines of the IPB (including Corta Atalaya and Cerro Colorado in Riotinto, Filón Norte, Filón Centro and Filón Sur in Tharsis, Aznalcóllar, or San Telmo) and many other of minor size. As a whole, these lakes constitute, at present, a large volume of highly acidic and metal-polluted water. Some of these pit lakes are very recent (e.g., Corta Atalaya, 2.5 a; Los Frailes, 6 a) and present a continuous hydrological and geochemical evolution, although many others were abandoned decades ago and show nearly constant water volume. Depth profiles obtained in several pit lakes (e.g., San Telmo, Confesionarios, Cueva de la Mora, Concepción) indicate that many of them have developed meromixis and show, at present, a permanent thermal and chemical stratification with a well defined chemocline separating an anoxic, Fe(II)-rich monimolimnion, and a well mixed, oxygenated and Fe(III)-rich mixolimnion. In the upper layer, the bacterial oxidation of Fe(II) competes with photoreductive processes which take place in the surface water, thus provoking diel cycles of Fe(II) concentration. The observed water chemistry reflects the oxidation and dissolution of pyrite and other sulphides and gangue aluminosilicates from the country rock. The pit lakes of the IPB cover a wide range of water compositions, from circumneutral and relatively low-metal (e.g., Los Frailes, pH 7.2, 0.07 mg/L Fe, 3.8 mg/L Mn, 30 mg/L Zn), to extremely acidic and metal(loid)-rich (e.g., Corta Atalaya, pH 1.2, 36.7 g/L Fe, 6.7 g/L Zn, 1.3 g/L Cu, 159 mg/L As). Most pit lakes, however, are comprised within the pH range of 2.2–3.6 and appear to be strongly buffered by the hydrolysis and precipitation of Fe(III) in the form of schwertmannite, which forms colloids that can sorb trace elements from the aqueous phase.     

The composition and evolution of primordial solutions on Mars, with application to other planetary bodies

We examine a model for Mars involving bulk primordial solutions (oceans and lakes) that were relatively Mg-rich and SO₄/(SO₄ + Cl)-rich. Such solutions could be produced when (1) volatiles leached a planet (or portions of a planet) with an ultramafic-mafic composition in a process called “planetary leaching”; and/or by (2) “impactor leaching” where meteoritic and/or cometary impactor fragments were leached. When Mg-SO₄/(SO₄ + Cl)-rich solutions are concentrated, we predict that the following sequence of salts precipitates: phosphates; carbonates; gypsum; epsomite; bloedite; halite; hexahydrite; and, finally bischofite. This sequence is modified slightly if appreciable Fe-, Mg- or Na-carbonates, Fe-sulfates, Mg-phosphate, or other halide salts crystallized before the Mg-Na-sulfate salts, or if HCO₃+CO₃ concentrations vary due to other effects (e.g., atmosphere CO₂ levels change).On Mars, the initial primordial solutions would have been relatively salt-rich and water-poor; therefore, the surface solutions formed Mg-Na-SO₄-Cl salts (cements, veneers, and dust) and subsurface solutions or ice (solid H₂O). This model is supported by the compositions of cements in the regolith on Mars (high Mg, Na, S, and Cl) and geochemical and petrographic evidence that the salts precipitated in the predicted sequence. We suggest that the partial pressure of oxygen was above the hematite-magnetite buffer where Fe³⁺-(hydrous)-oxides are stable and SO₄^2- or HSO₄^- are solutes in any solution. Such a partial pressure of oxygen may have been attained via H₂-loss.In contrast, on the Galilean satellites (Europa, Ganymede, and Callisto) surface solutions were relatively water-rich and formed ice, Mg-SO₄-rich salts, and solutions, thereby producing surface features dependent on the initial water content and the crystallization path. Unlike the Na-Cl-rich oceans on Earth, the solutions of these planetary bodies likely did not change greatly from their bulk primordial Mg-rich, SO₄/(SO₄ + Cl)-rich compositions; hence they did not attain compositions similar to modern seawater.     

Evidence for a simple pathway to maghemite in Earth and Mars soils

Soil magnetism is greatly influenced by maghemite (γ-Fe₂O₃), the presence of which is usually attributed to the following: (1) heating of goethite in the presence of organic matter; (2) oxidation of magnetite (Fe₃O₄); or (3) dehydroxylation of lepidocrocite (γ-FeOOH). Formation of the latter two minerals in turn requires the presence of Fe(II) in the system. No laboratory experiment or soil study to date has shown whether maghemite can form from ferrihydrite, a poorly crystalline Fe(III) oxide [∼Fe_4.5(O,OH,H₂O)_13.5], below 250°C. However, ferrihydrite is the usual precursor of goethite (α-FeOOH) and hematite (α-Fe₂O₃), the most frequently occurring crystalline Fe(III) oxides in soils. Here is presented in vitro evidence that ferryhidrite can partly transform into maghemite at 150°C. This transformation occurs upon aging of ferrihydrite precipitated in the presence of phosphate or other ligands capable of ligand exchange with Fe-OH surface groups. This maghemite coexists with hematite and is a transient phase in the transformation of ferrihydrite to hematite, which is apparently stabilized by the adsorbed ligands. Its particle size is small (10 to 30 nm), and its X-ray diffraction pattern exhibits superstructure reflections. The possible formation of maghemite in Mars and in different Earth soils can partly be explained in the light of this pathway with minimal ad hoc assumptions.     

Study of two alteration systems as natural analogues for radionuclide release and migration

U-deposit hosted in hydrothermally altered tuffs in Mexico, together with weathering profiles from Cameroon were studied as natural analogues of radionuclide release and migration. Using petrological and spectroscopic methods (infrared and electron paramagnetic resonance), we have distinguished successive secondary mineral parageneses and the behaviour of radionuclides.

In the U-deposit, the mineral parageneses show that uranium migration is mainly controlled by the redox potential and silica activity of the altering solutions. The high silica content of the solutions is caused by the intense alteration of volcanic rocks. Two types of secondary clay mineral parageneses are evidenced: a kaolinization, intense where uranium is accumulated in the welded tuffs, and a smectitization mainly developed in the underlying weakly welded tuffs.

Several types of kaolinite have been defined according to their genesis (fillings in fissures and feldspar pseudomorphs), their location relative to a breccia pipe where uranium has accumulated (core and rim of the pipe; surrounding rhyolitic tuffs), and particle morphology, structural order and substitutional Fecontent. It is shown that the variations of the concentration of paramagnetic defect centres, always more than ten times as important than those measured in weathering kaolinites, are only correlated to the location of the kaolinites. The highest values correspond to the breccia pipe kaolinites, e.g. kaolinites located in the uranium accumulation zones. Moreover, one or two main defects centres are detected depending on the intimate association of kaolinites with uranium-bearing minerals. Besides, in weathering kaolinites from U-depleted laterites, defect centre concentrations are correlated to the total Fe203 content in bulk samples. This means that the defect centre acts as a memory of the travel of uranium when this element was sorbed onto iron gels in the first stage of weathering.

It is concluded that paramagnetic defect centres in kaolinites might allow an efficient fingerprint of successive irradiations in the natural analogues under study and could be an useful tool to control radionuclides migration through kaolinite-containing clayey materials such as those used for waste repository.

A better understanding of radiation efficiency as well as accurate dose-ratekaolinite-containing clayey materials such as those used for waste reposit estimation are needed for a quantitative tracing of the migration ofA better understanding of radiation efficiency as well as accurate dose-ratekaolin radionuclide elements. With this aim, a simulation has been undertaken withestimation are needed for a quantitative tracing of the migration of various radiations sources. We have determined for each irradiation the parameters of the paramagnetic centres created in order to understand the way they are forming. The knowledge of the parameters governing the formation and the stability of the radiation centres in kaolinites allow to use this mineral as a natural dosimeter.     

A lacustrine GDGT-temperature calibration from the Scandinavian Arctic to Antarctic: Renewed potential for the application of GDGT-paleothermometry in lakes

Quantitative climate reconstructions are fundamental to understand long-term trends in natural climate variability and to test climate models used to predict future climate change. Recent advances in molecular geochemistry have led to calibrations using glycerol dialkyl glycerol tetraethers (GDGTs), a group of temperature-sensitive membrane lipids found in Archaea and bacteria. GDGTs have been used to construct temperature indices for oceans (TEX₈₆ index) and soils (MBT/CBT index). The aim of this study is to examine GDGT-temperature relationships and assess the potential of constructing a GDGT-based palaeo-thermometer for lakes. We examine GDGT-temperature relationships using core top sediments from 90 lakes across a north-south transect from the Scandinavian Arctic to Antarctica including sites from Finland, Sweden, Siberia, the UK, Austria, Turkey, Ethiopia, Uganda, Chile, South Georgia and the Antarctic Peninsula. We examine a suite of 15 GDGTs, including compounds used in the TEX₈₆ and MBT/CBT indices and reflecting the broad range of GDGT inputs to small lake systems.GDGTs are present in varying proportions in all lakes examined. The TEX₈₆ index is not applicable to our sites because of the large relative proportions of soil derived and methanogenic components. Similarly, the MBT/CBT index is also not applicable and predicts temperatures considerably lower than those measured. We examine relationships between individual GDGT compounds and temperature, pH, conductivity and water depth. Temperature accounts for a large and statistically independent fraction of variation in branched GDGT composition. We propose a GDGT-temperature regression model with high accuracy and precision (R² = 0.88; RMSE = 2.0 °C; RMSEP = 2.1 °C) for use in lakes based on a subset of branched GDGT compounds and highlight the potential of this new method for reconstructing past temperatures using lake sediments.     

ANN技术在地下水含水量预测建模中的研究与应用

将人工神经网络(ANN)技术引入到地下水含水量预测工作,以华北平原和河套平原为试验场,以若干已知钻孔为验证,采用激电和电阻率测深等地面物探方法获取视电阻率ρS、视极化率ηS、半衰时Th、衰减度D和偏离度σ等参数为输入神经元对单孔单位涌水量建立人工神经网络预测模型。同时,为消除不同地区矿化度的影响,通过实验对比引入综合参数T",改良了输入神经元的配比。最终建立以半衰时Th、衰减度D、偏离度σ和综合参数T"为输入神经元的含水量预测模型,进一步提高了预测精度。通过检验,发现所建立的模型对平原地区进行含水量的定量预测有着较好的效果,为含水量预测工作研究与发展带来了新理念、打开了新思路。     

三维空间下的证据权建模方法与资源预测应用

为了探索证据权法在三维空间下成矿预测的实际应用,在传统证据权的基础上,探讨了适用于三维空间下成矿预测的证据权建模思路和方法。并以Visual Studio 2010为开发平台,在Access 2003中建立多元地学空间数据库,开发可进行证据因子选择、因子权重计算及后验概率计算的证据权软件WofE3DSys,其输出结果可在Voxler中进行三维可视化呈现。经分析,WofE3DSys计算结果与Arc WofE输出结果在异常圈定方面基本一致,验证了WofE3DSys的准确性。最后,以招平断裂带大尹格庄金矿为实例,选取成矿信息作为证据图层,进行成矿预测。该研究是对三维空间下证据权法的一次探索,为将来该证据权法在其他矿区的成矿预测提供了现实依据     

城市供水系统多水源联合调度模型及应用

从城市供水系统的关键元素出发,通过系统网络拓扑分析,构建了"水源—水厂—分区用户"三层供水系统网络拓扑结构;基于此拓扑结构和兼顾整个供水系统的社会效益和供水成本两个调度目标,建立城市供水系统的多水源联合供水优化调度模型;利用NSGA-II(Non-dominated Sorting Genetic Algorithm II)算法进行模型求解,并给出最佳均衡解的选择规则;将该模型应用于南水北调中线一期工程通水后的天津市供水系统.实例研究结果表明,该模型实现了天津市不同来水丰枯组合情景下多种水源的合理分配,能够为决策者提供均衡社会效益与供水成本的详细供水方案,还可以在一定程度上反映出供水系统存在的工程问题,可为保障城市供水安全提供技术支撑.如最不利典型年来水情景下,总可供水量(14.73亿m3)大于天津市总需水量(13.77亿m3),但由于供水工程能力限制,特定供水规则下推荐的社会效益与供水成本折中方案的缺水量为2.44亿m3、总供水成本为32.6亿元.     

Neutral monosaccharides as biomarker proxies for bog-forming plants for application to palaeovegetation reconstruction in ombrotrophic peat deposits

The application of molecular approaches to palaeovegetation reconstruction in peat is still relatively rare, with molecular level studies of carbohydrate organic geochemistry being generally uncommon. In this report, neutral monosaccharides derived via acid hydrolysis were investigated in modern bog-forming plants in order to assess their potential application as biomarkers in peat palaeovegetation reconstruction. The concentrations of major neutral monosaccharides, i.e. glucose (Glu), xylose (Xyl), arabinose (Ara), galactose (Gal), mannose (Man), rhamnose (Rha) and fucose (Fuc), were determined using gas chromatography (GC) for 7 lichens, 10 Sphagnum species and 7 vascular plants collected from three ombrotrophic mires across northern Europe. Based on factor analysis of the modern plant monosaccharide compositions, two carbohydrate proxies: [(Man + Gal):(Ara + Xyl)] and % contributions of Rha and Fuc in total Glu-free monosaccharides [%(Rha + Fuc)], were selected as biomarkers for bog-forming plants. The three plant groups could be separated by [(Man + Gal):(Ara + Xyl)], which showed decreasing values following the order: lichens > Sphagna > vascular plants. The high [%(Rha + Fuc)] in Sphagna allowed their separation from lichens and vascular plants. These two factors were applied as plant group-specific indices to investigate vegetation change in a peat core from Kontolanrahka Bog, Finland. Our findings show strong correspondence with fossil plant abundances from the same core, thereby confirming the potential of carbohydrate compositional parameters as proxies for palaeovegetation reconstruction in peat bogs.     

200 ka以来澳大利亚西北岸外沉积物源区风化的Mg同位素记录及其对澳洲古季风的响应

本文通过对IODP 363航次于澳大利亚西北岸外陆架上钻取的U1483站岩芯进行沉积物粒度、镁同位素以及主量元素成分等分析,重建200 ka以来帝汶海西南部沉积物输入演化及其指示的源区风化和侵蚀历史,探讨海洋沉积物中细粒硅质碎屑组分镁同位素的古环境指示意义。U1483站陆源碎屑组分主要由黏土质粉砂组成,其δ²⁶Mg变化范围超过0.25‰。通过计算化学蚀变指数(chemical index of alteration, CIA)和两种物理侵蚀指标(包括陆源物质堆积速率和Ti/Ca比值),结果显示200 ka以来δ²⁶Mg指标与CIA具有非常一致的曲线形态。本文推测陆源碎屑组分的Mg同位素组成主要反映物源区大陆硅酸盐风化强度的变化,而受矿物学分选、岩性和早期成岩作用的影响较小。结合区域古气候记录,我们发现本研究中的风化和侵蚀记录与同一个站位已发表的澳洲夏季风降水和表层海水温度变化具有较好的耦合关系,而与赤道太平洋海平面变化的相关程度较低,反映了轨道时间尺度上沉积物所记录的物源区风化和侵蚀演化主要受控于澳洲古季风系统,表现为气候驱动型风化模式。本研...     

铀矿床作为高放废物处置库天然类似物的国内外研究进展

铀矿床具有目前国际上开发的高放废物深地质处置概念的相似特征，对其开展天然类比研究，是认识核素在地质环境中迁移行为的一种有效方法。本文阐述了高放废物深地质处置库天然类似物的一般概念及天然类比研究拟解决的科学问题。重点介绍了30年来国内外在天然类比研究中取得的主要成果、认识以及国内外研究进展。     

Potential for irradiation of methane to form complex organic molecules in impact craters: Implications for Mars, Titan and Europa

The release of methane from crater sites following meteorite impact is a possible consequence of the thermal alteration of organic matter, or tapping of reservoired gas of biogenic or abiogenic origin. At least the latter is feasible on Mars. Methane and higher hydrocarbons are susceptible to polymerization and precipitation by radioactive minerals. Where such minerals are present in impact target rocks, the craters can be a preferred site for carbon concentration, and the formation of complex organic molecules. On icy bodies, such as Titan and Europa, methane released by impact could be a fuel for prebiotic chemistry involving other forms of irradiation.     

Simulations of the Viking Gas Exchange Experiment using palagonite and Fe-rich montmorillonite as terrestrial analogs: implications for the surface composition of Mars

Simulations of the Gas Exchange Experiment (GEX), one of the Viking Lander Biology Experiments, were run using palagonite and Fe-rich montmorillonite as terrestrial analogs of the Martian soil. These terrestrial analogs were exposed to a nutrient solution of the same composition as that of the Viking Landers under humid (no contact with nutrient) and wet (intimate contact) conditions. The headspace gases in the GEX sample cell were sampled and then analyzed by gas chromatography under both humid and wet conditions. Five gases were monitored: CO2, N2, O2, Ar, and Kr. It was determined that in order to simulate the CO2 gas changes of the Viking GEX experiment, the mixture of soil analog mineral plus nutrient medium must be slightly (pH = 7.4) to moderately basic (pH = 8.7). This conclusion suggests constraints upon the composition of terrestrial analogs to the Mars soil; acidic components may be present, but the overall mixture must be basic in order to simulate the Viking GEX results.     

The distribution and abundance of chironomids in high-latitude Eurasian lakes with respect to temperature and continentality: development and application of new chironomid-based climate-inference models in northern Russia

The large landmass of northern Russia has the potential to influence global climate through amplification of climate change. Reconstructing climate in this region over millennial timescales is crucial for understanding the processes that affect the global climate system. Chironomids, preserved in lake sediments, have the potential to produce high resolution, low error, quantitative summer air temperature reconstructions. Canonical correspondence analysis of modern surface sediments from high-latitude lakes, located in northern European Russia and central Siberia, suggests that mean July air temperature is the most significant variable explaining chironomid distribution and abundance. This strong relationship enabled the development of a chironomid-based mean July air temperature-inference model based on 81 lakes and 89 taxa which has a r_jack² = 0.92 and RMSEP = 0.89 °C. Comparison of taxon responses to July temperature between this Russian and existing Norwegian data-sets shows that the temperature optima of individual taxa were between 1 and 3 °C higher in the Russian data regardless of modelling technique. Reconstructions based on fossil assemblages from a Russian tundra lake core (VORK5) using a Norwegian chironomid-based inference model provide mean July air temperature estimates that are 1.0–2.7 °C colder than from the 81-lake Russian model and are also lower than the instrumental record from a nearby meteorological station. The Norwegian model also did not reconstruct decadal-scale fluctuations in temperature seen in the instrumental record. These observations suggest that chironomid-based inference models should only be applied to sediment cores which have similar climate regimes to the geographic area of the training set. In addition a 149 lake, 120 taxa chironomid-based continentality inference model was also developed from the modern Norwegian and Russian training sets. A 2-component WA-PLS model was the minimal adequate model with r_jack² = 0.73 and RMSEP = 9.9 using the Gorczynski continentality index. Comparison of reconstructed continentality indices from the tundra lake, VORK5, show close agreement with local instrumental records over the past 70 years and suggest that the model is reliable. Recent warming in the Arctic has been spatially and seasonally heterogeneous; in many areas warming is more pronounced in the spring and autumn leading to a lengthening of the summer, while summer temperatures have remained relatively stable. A continentality inference model has the potential to detect these seasonal changes in climate.     

A kinetic model for distribution coefficients and application to Mg-calcites

A review of experimental and natural Mg-calcite occurrences indicates that no simple relation exists between $\text{mMg}\text{mCa}$ in solution and $\text{X}{}^{\mathrm{Mg}}\text{X}{}^{\mathrm{ca}}$ in growing calcite crystals. The great variability of the data suggests a strong influence of precipitation kinetics on the distribution of Mg⁺² between solution and crystal. We have derived a kinetic formulation for the distribution coefficient (λ^Mg = X^Mg/X_Ca/ mMg/mCa) based upon the existence, at steady state conditions, of a constant mass surface phase. The resulting formulation is consistent with both experimental and natural Mg-calcite compositions. The primary factors which influence the value of λ^Mg are temperature and the ratio of K_sp^MCO3 to the activity product ([M⁺²][CO₃^?2]/[MCO₃]) for magnesite and calcite. The results suggest that Mg-calcite composition (X^Mg/X^Ca) is at best a crude measure of the mMg/mCa ratio in paleosolutions.     

Geomorphological,pedological, and hydrological characteristics of karst lakes at Conversano (Apulia,southern Italy) as a basis for environmental protection

The land around Conversano (Apulia, southern Italy) is part of the Murge karst, interesting limestones and dolomitic limestones of Upper Cretaceous age, in a flat environment with sub-horizontal setting. Dolines and karst depressions are the most typical landforms in the area. Filling of these landforms with eluvial deposits locally created the possibility of water stagnancy at the surface. The Conversano territory presents ten karst lakes that represented, until some decades ago, the only water resource available for the local people, who built the typical bell-shaped wells to collect water volumes satisfying local needs during the dry season. Currently, these lakes have no great importance as water supplies, but represent habitats of great naturalistic value that are still able to support the ecological functionality and the wet environments with self-vegetation. Hydrological and hydrogeological studies have been carried out with the aim to fully estimate the related environmental problems. For this purpose, the hydrogeologic data of historical time series have been collected and compared to those of the last 5 years; successively, according to the Thornthwaite method, a hydrological monthly balance has been evaluated to quantify the distribution of water volumes interacting annually between the surface water bodies and the underlying carbonate groundwater. This evaluation has highlighted the need to carefully consider all the parameters concurring to a right definition of water balance for a karst environment, where pedological features, climatic conditions and anthropogenic modifications to the environment represent the elements of a very delicate system. Particularly, on the basis of recent soil map and field surveys, a re-evaluation of the available water capacity, estimated in some 40 mm, has been carried out. The studies have highlighted the need to extend the environmental protection rules to larger areas around the lakes, e.g. at the catchment scale, with definition of buffer zones; in this manner, it will be possible to constantly monitor the protected land and the local anthropogenic activities, that represent real polluting sources for both the surface water resources and the underlying carbonate groundwaters.     

克里金参数估值法及其在参数估计分析中的应用

为考虑岩土介质参数的空间分布的结构性和随机性等不确定因素,引入了克里金参数估值法。采用变异函数描述参数在空间结构上的变化,建立其空间变异规律的数学模型,从而实现对岩土参数的估值。通过实例分析揭示了克里金估值法具有反映“过滤效应”和“集团效应”的优点,对不同位置的数据赋予不同的权重系数,能够有效地反映参数空间变异结构,有利于对参数的合理化分析     

蒙皂石转化伊利石的数值模拟——溶解沉淀模型与化学动力学模型

提出了改进的溶解沉淀数学模型，在塔里木盆地塔中4井应用获得成功。该井石炭系的实例表明:该模型在粘土矿物内的模拟结果，与K Ar定年分析吻合，并接近于粘土矿物分析数据。实例指出:在较早提出的化学动力学模型、新近提出的溶解沉淀模型中，最敏感的参数都是活化能；将粘土矿物分析数据作为约束条件来校准活化能，是获得正确的蒙皂石史和伊利石史之关键。采用最佳活化能计算，可获得最佳模拟结果:①算出的伊利石开始生长的年代与K Ar定年分析吻合；②模拟结果与粘土矿物分析数据接近。通过实例还发现:溶解沉淀模型仅适用于粘土矿物内的转化问题，而化学动力学模型仅适用于伊/蒙间层内的转化问题。