Evolution of groundwater chemical composition under human activity in an oilfield

 Analysis and hydrogeochemical modeling of hydrocarbonate groundwater, including its buffering geochemical properties, have demonstrated that this water has undergone a geochemical transformation almost throughout the whole of one industrial region. It is known that hydrocarbonate groundwater possesses a high protective natural geochemical potential, supporting neutralization of acid atmospheric precipitation. Natural hydrocarbonate water undergoes three stages of anthropogenic transformation caused by acid atmospheric precipitation over more than 50 years. The first stage is transformation of neutral hydrocarbonate water into alkaline water, accompanied by calcite precipitation and sodium carbonate dissolution from the unsaturated zone. The second stage is transformation of alkaline water into neutral hydrocarbonate water; the hydrocarbonate content, being less than the lower limit for background concentrations, showed reduced water buffering properties or protective potential relative to acid precipitation. The third stage is transformation of neutral hydrocarbonate water into acidic water, with a complete loss of protective geochemical potential. This unfavorable ecological situation with natural geochemically hydrocarbonate groundwater shows that natural groundwater less protected from the impact of acid atmospheric precipitation is in a worse ecological condition, which is confirmed by observations in northern and Western Europe and other regions of the world. Received: 30 October 1997 · Accepted: 23 March 1998     

Coal as a source rock for oil: a review

The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and ¹³C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO₂ and CH₄ could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.     

Measured and computed neutralization potentials from static tests of diverse rock types

Static tests typically are used in the initial stage of environmental assessments to predict the potential for acid mine drainage, and also are used to monitor waste disposal at active mining operations. The neutralization potential (NP) of 19 sedimentary, metamorphic, and igneous extrusive rocks was measured by the Sobek method to compare the results with those computed by using the quantitative mineralogy of the rocks and the NP values that were deemed to be appropriate for the individual minerals. Most of the computed NP values of the rocks are lower than the measured values, but a close relationship is evident. If the contents of carbonate minerals are low, the NP in non-ultramafic igneous rocks typically is controlled by the amount of Ca substitution in plagioclase, whereas in ultramafic rocks the NP contribution is dominated by the amount of olivine and serpentine. Compositional and NP analyses of plagioclase concentrates indicate that the NP systematically varies from <1 for the Na end-member to about 14 for compositions near that of the Ca end-member. Among several variables that can affect the Sobek NP values, the volume and normality of the acid added to the sample are well-known to influence the results; however, the temperature and duration of the acidification stage can also have a pronounced effect on the measured NP of some rocks, depending on their mineralogy. Fizz tests to estimate the carbonate content and the consequent acid addition are highly subjective, and the ‘no fizz’ rating is not to be taken literally. The NP results themselves provide a clear indication of whether a sample has been over-acidified or under-acidified in the test procedure.     

Modelling natural attenuation of heavy-metal groundwater contamination in the Selebi-Phikwe mining area,Botswana

Seepage from a tailings dam is the major source of groundwater pollution in the Selebi-Phikwe area, where mining of sulphidic nickel–copper–cobalt ore started in 1973 and will continue until 2014. The seepage water has a pH in the range of 1.7–2.8 and is strongly enriched in SO₄ ²⁻ (5,680 g/L) and heavy metals (6,230 μg/L Ni, 1,860 μg/L Cu and 410 μg/L Co). The fracture aquifer affected by pollution from the dam exhibits a remarkable capacity of heavy-metal sorption. Most of the Ni, Cu and Co is scavenged at less than 500 m distance downgradient from the polluting source, whereas SO₄ ²⁻ is not immobilized significantly. The heavy-metal sorption process is assumed to be due to surface complexation, which is supported by a relatively high groundwater pH (in the range of 6.2–7.8 at >200 m distance from the tailings dam). The objective of this study is to demonstrate that the sorption process can be incorporated into a realistic three-dimensional reactive-transport groundwater model that is implicitly charge-balanced. The simulations are performed with the PHAST1.2 program, which is based on the HST3D flow and transport code and the hydrochemical PHREEQC2.12 code.     

The Geochemical Effects of Microbial Humic Substances Reduction

As part of a study on microbial redox alteration of humic substances we investigated the potential effect of this metabolism on the fate of heavy metals and hydrocarbons as a result of conformational alteration of the humic molecular structure due to microbial reduction. Our studies indicate that the microbial reduction of humic acids (HA) results in significant morphological and geochemical alterations. X‐ray microscopy analysis indicate that the conformational structure of the humic colloids is altered as a result of the redox change. In the reduced state, the HA appeared as small dense particles, on reoxidation, large loose aggregates were formed. In addition, spectrofluorometric studies indicated that the binding capacity of the HA for naphthalene was decreased by 10% when the HA was reduced. Similarly, the reduced HA yielded higher surface tension values at all concentrations tested which is indicative of a more hydrophilic and less hydrophobic solute. On reoxidation, the surface tension values reverted back to values similar to those obtained for the untreated oxidized HA. These data indicate that the hydrophobicity of the HA is altered on biological reduction of the HA and that this alteration is reversible. In contrast the reduced HA demonstrated a 15% higher affinity for heavy metals such as divalent cobalt than the oxidized HA. In addition to increasing the binding capacity of HA for heavy metals, the reduction of the HA also decreased the bioavailability and toxicity of bound heavy metals such as chromium. When incubated in the presence of Cr(III) and HA, cells of Escherichia coli grew much more rapidly in the presence of the reduced HA suggesting that the higher metal binding capacity of the reduced humic substances resulted in a removal of the Cr(III) from solution and hence reduced its bioavailability and toxicity. These studies demonstrate that HA redox state and reduction of humic acids by microorganisms can have a significant effect on the molecular morphology and binding constants of HA for heavy metals and hydrocarbons and also directly affects the bioavailability of these compounds in the environment.     

基于二苯乙醇酸体系快速测定区域地质矿产调查样品中的钨钼

本文建立了一种快速分析区域地质矿产调查样品中钨钼的方法。试样经高温焙烧、碱熔分解,钨、钼与其它杂质元素所形成的氢氧化物沉淀分离;在二苯乙醇酸体系(0.25mol/L硫酸-0.04g/L二苯乙醇酸-0.10g/L二苯胍-20g/L氯酸钠)中,钼、钨分别于约-0.25V、-0.85V产生灵敏的平行催化波,根据极限扩散电流的大小同时测定这两种元素。该方法的测定下限(X0+3S)<0.10×10-6;准确度(|Δlog|)≤0.05;精密度(RSD)≤7.72%。国家标准物质测定值与标准值相符;实际样品测定值优于电感耦合等离子体发射质谱法。方法扩大了催化极谱法的适应性,提高了实际应用价值。     

海水腐植质的基本化学组成研究

于１９９２－１９９３年用＾１Ｈ－ＮＭＲ，＾１３Ｃ－ＮＭＲ和ＩＲ等分析技术对甲基化前后的海水腐植质（１９９２年从青岛近岸海水中吸附提取）的基本化学组成和结构特征进行研究，并与风化煤和海洋沉积物中的腐植质作比较。结果表明，ＩＲ和＾１Ｈ－ＮＭＲ谱图显示，海水腐植质主要由脂肪链化合物组成，含有一定量的肽类和多糖，芳香结构较少。采用ＮＮＥ技术的＾１３Ｃ－ＮＭＲ谱图中各类碳的相对含量为：脂肪族碳，３３．２％；     

湖北西部城市酸雨特征及其与气象条件的关系

根据对湖北省西部宜昌、襄樊、巴东、十堰等城市自然降水pH值的检测结果,对降水pH值变化、时空分布,降水的化学成分、酸雨出现时的风与气象条件、酸雨与降水云类的关系进行了详细的分析。分析结果表明:酸雨形成与当地的地理条件和气象因子有关。稳定的大气环境对酸雨形成有利,较强的逆温和静风频率,可以为当地降水的二次酸化提供有利条件。各地酸性降水化学成分中阴阳离子SO42-/NO2-比值表明,西部城市酸雨具有典型的硫酸型特征。巴东监测的时间较短,但酸雨年出现频率有上升的趋势,并且酸雾出现的几率比较大。襄樊、十堰酸雨出现频率较低与雨水中有较高浓度的阳离子有关。