The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Deformation-induced garnet zoning

Compositional zoning patterns in garnet porphyroblasts from kyanite-bearing samples of the Devonian Littleton Formation, north-central Massachusetts, reveal complex patterns of growth that are related to multiple deformation and metamorphic events. Garnet porphyroblasts exhibit asymmetrical and irregular zoning patterns in X_Mn, X_Ca and Fe/(Fe + Mg). Zoning reversals in Mn and Fe/(Fe + Mg) and patch distribution in Ca appear to occur around the boundaries of the textural zones. Also, the compositions of the garnet at the textural boundaries are variable for all traverses. These observations suggest that the garnet zoning was not only modified from diffusion processes, but was also influenced by pre-existing microfabrics through the effects of preferential dissolution and resorption in partial disequilibrium. Relationships between chemical and textural truncations indicate that the zoning patterns of garnet were strongly modified from preferential dissolution and precipitation during the development of successive foliations that occurred in zones of high strain/stress (cleavage seams) and zones of low strain/stress, respectively.     

Preliminary evaluation of hydrochemistry of the Kalambaina Formation, Sokoto Basin, Nigeria

Hydrochemical investigations in the Kalambaina Formation have been initiated to determine potability and suitability of the shallow groundwater for domestic and agricultural uses. This limestone formation is an extensive aquifer supplying water to livestock and domestic wells in its outcrop areas. The aquifer is recharged by rainfall and discharges mainly into the Sokoto–Rima River system and lakes at Kware, Gwadabawa and Kalmalo in Nigeria. Because recharge to the aquifer is mainly from rainfall, the quality of the groundwater is controlled essentially by chemical processes in the vadose zone and locally by human activities. Water samples were taken at 11 sites comprising boreholes, dug wells and a spring and were chemically analysed for their major ion components. Hydrochemical results show water of fairly good quality. It is, however, hard and generally of moderate dissolved solids content. Concentration of the total dissolved solids is between 130 and 2,340 mg/l. Concentrations of ions vary widely but a high concentration of K⁺ is found in places. NO₃⁻ is on the higher side of the World Health Organization (WHO) permissible limits, indicating pollution in such areas. Groundwater chemistry is predominantly of two facies, namely the calcium–magnesium–bicarbonate and calcium–magnesium–sulphate–chloride facies. These facies probably evolved primarily as a result of dissolution of calcium and magnesium carbonates as well as some human/land-use activities.     

塔里木盆地阿克库勒地区石炭系卡拉沙依组成岩作用

阿克库勒地区卡拉沙依组碎屑岩储层的成分成熟度和结构成熟度均较低．储层的次生溶蚀孔隙所占比例远高了：原生孔隙，次生孔隙是储层的主要储集空间．样品数据统计显示，卡拉沙依组储层属于低孔、低渗储层类型．根据岩石薄片、铸体薄片观察及储层样品的扫描电镜和阴极发光分析结果，本区石炭系储层主要经历的成岩作用有压实（压溶）作用、胶结作用、溶蚀作用和交代作用，其中碳酸盐矿物的沉淀和溶蚀作用是本区卡拉沙依组储层所经历的最重要的成岩作用．成岩作用已达到晚成岩B期，早期方解石交代石英颗粒并发生大量溶蚀，生成大量次生孔隙，晚期方解石没有发生溶蚀．     

一种新的储层孔隙成因类型--石英溶解型次生孔隙

石英作为碎屑岩储层中的一种难溶组分,普遍认为它和次生孔隙的形成关系不十分密切。研究认为泌阳凹陷核桃园组储层中的碎屑石英颗粒存在明显的溶解现象,并形成以石英直接溶解型孔隙为主的储集空间特征。石英颗粒被溶解的部分在薄片中所占的范围为 2 %～ 7%者常见,高者达 8%以上,在总孔隙中所占的相对含量也多数在10 %～ 35 %之间,早成岩B期是其最主要形成期。石英溶解型次生孔隙的大量存在为碎屑岩储层中SiO₂ 胶结物及次生孔隙成因等问题的解释以及储层预测和评价提供了新的可能性。     

25～75℃酸性NaCl溶液中方铅矿的溶解动力学

在25～75℃、pH=0.43～2.45的1mol/LNaCl溶液中进行了方铅矿的溶解动力学实验。发现在远平衡条件下,方铅矿的溶解速率r与氢离子活度犤H+犦呈线性关系,溶解速率方程(速率定律)为:r=k犤H+犦,即对H+而言,溶解反应为一级。其中速率常数k为2.344×10-7mol/m2·s(25℃)、1.380×10-6mol/m2·s(50℃)、7.079×10-6mol/m2·s(75℃)。溶解反应的活化能为43.54kJ/mol,方铅矿的溶解机理为表面化学反应,速率决定步骤为表面配合物的离解。     

Variation in element release rate from different mineral size fractions from the B horizon of a granitic podzol

Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10⁻¹⁴ mol/m²/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10⁻¹⁴ mol/m²/s) and sheet silicates (100×10⁻¹⁴ mol/m²/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10⁻¹⁴ mol/m²/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions.     

Sulfur Content and Isotopic Ratio of Cambro-Ordovician Carbonate Rocks from South Korea: A Possible Source for Mesozoic Magmatic-hydrothermal Ore Sulfur

Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ³⁴S values. The δ³⁴S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ³⁴S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ³⁴S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ³⁴S value of +12.8 permil (n=24). The estimated δ³⁴S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ³⁴S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ³⁴S values of the Korean ore deposits might be caused to some extent by ³⁴S enrichment from the host carbonates, resulting in the low SSS contents observed.     

四川江油地区上泥盆统-下石炭统灰岩的岩石磁学研究

四川江油地区上泥盆统三分量样品和下石炭统样品的岩石磁学研究表明：上泥盆统样品的主要载磁矿物为磁铁矿，且以假单畴、多畴和少量单状态存在，下石炭统样品的载磁矿物则主要是假单畴和多畴磁铁矿的混合物，从样品中分离出的中温分量由假单畴磁铁矿携带，上泥盆统样品的高温分量则由记录了岩石原生剩磁的单畴磁铁矿携带。