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.     

The origin of the Pedra Furada sandstone tubular structures (South of Lisbon, Portugal)

The Pedra Furada is a 12 m wide, 18 m high outcrop feature showing hundreds of ferruginised sandy tubes and looking in part like a giant organ. In this paper the origin of the tubes is explained on the basis of geochemical, petrographic and microscopic (optical and electronic) analytical data. The tubes are considered to represent vertical escape channels for overpressured water, exhibiting inward decreasing grain size due to water velocity gradients inside the escape channels. The ferruginisation is due to iron oxides associated with colloidal/clayey fine sediments and to goethite formed from solution. The overpressure of water may be due to seismically fluidised beds below the Pedra Furada outcrop or to artesian water ascent. In both cases, fault rupturing may have played a major role in the focussing of the ascending flow.     

Bearing capacity of rock over mined cavities in Nottingham

A significant geohazard is created in Nottingham, UK, by hundreds of man-made caves cut in the weak sandstone beneath the city centre. Stability of the caves has been assessed by a single full-scale loading test, by numerical modelling with FLAC and by physical modelling in plaster. For typical caves 4 m wide, bearing capacity of the rock roof rises from 2 MPa where it is 1 m thick to 8 MPa where 3 m thick. Stability decreases over wider caves and where the loading pad edge is over the edge of the cave. Numerical modelling of a very wide cave revealed the failure mechanisms and also showed that an internal support wall increased roof bearing capacity by 50%. Local building regulations that require 3-5 m of rock cover over the sandstone caves appear to be conservative. In stronger rocks, including karstic limestone, a guideline that cover thickness exceeds 70% of the cave width appears to be appropriate.     

中国海相油气田勘探实例之十三 塔里木盆地东河塘海相砂岩油田勘探与发现

东河塘油田位于新疆库车县,构造上隶属于塔里木盆地塔北隆起轮台凸起东河塘断裂构造带,是我国发现的第一个高产高丰度海相砂岩油田,它的发现是中国海相砂岩油气勘探理论和实践的一次重大突破。油田发现于1990年7月,至1994年探明石油地质储量3323.13×104t,天然气地质储量15.5×108m3,至2009年底累计产原油825.75×104t。石炭系东河砂岩油藏是东河塘油田的主体,其储层东河砂岩段是一套滨岸相砂体,具有厚度巨大、埋深大、储集性能好的特点;其油藏类型为块状底水背斜油藏,产能高,储量丰度高。论述了东河塘油田勘探与发现的历程,剖析了取得勘探成功的实践认识与意义。     

A methodology for locating the original quarries used for constructing historical buildings: application to Málaga Cathedral, Spain

It is often necessary to locate the original quarry which supplied the stone for a particular historical building. This stones could be used for future restoration work and for testing in the laboratory (artificial aging tests, physical properties determination, control of the efficacy of conservation treatments, etc.). Generally, reviewing historical documentation gives information about the geographical setting of quarries and location of the stones in the monument, but this information needs to be proved by field and laboratory studies. The comparative study of stone from quarries and monuments should basically include the following: (1) mineralogical and petrographical studies; (2) the chemical analysis of major, minor and trace elements; (3)stable isotopes determinations; (4) physical properties of quarry materials and unweathered building stone (water absorption, ultrasound transmission velocity, porosity and porous system, density, bulk density, compressive strength, etc.). This methodology was applied to Málaga Cathedral stones represented in the main façade, towers, and the western zone of the terrace, which, according to historical literature, came from Almayate (Miocene–Pliocene limestones) and Cerro Coronado (Permotriassic sandstone) in Málaga. The conclusion of the comparative study carried out on quarries and building stones was consistent with the information available from the historical documentation.     

鄂尔多斯盆地北部砂岩型铀矿铀矿物地质地球化学特征及其成因意义

鄂尔多斯盆地北部已发现系列砂岩型铀矿,由东往西依次有东胜铀矿、杭锦旗(纳岭沟)铀矿、大营铀矿等大型、特大型矿床,成为我国目前砂岩型铀矿发现规模最大、最具远景的地区。研究表明,它们具有相似的矿床地质特征和形成环境。在矿床成矿作用研究中,铀的存在形式及铀矿物特征对砂岩铀矿来说是一项重要的内容,其认识对铀的地浸开采可提供重要依据,也是了解砂岩型铀矿形成机制或矿床形成环境及成因的重要信息。本文主要从三个方面对鄂尔多斯盆地北部大营铀矿、纳岭沟铀矿等主要砂岩型铀矿中铀矿物地质地球化学特征和成因进行了研究和探讨。通过电子探针测试,高分辨率扫描电镜观察等手段,认为盆地北部铀矿的铀矿物类型主要为铀石,含少量的沥青铀矿、钛铀矿、水硅铀石、钍铀石等;铀矿物常与黄铁矿、有机质(煤屑)及方解石相伴生。采用逐级化学提取等方法定量地分析了铀矿物占矿石中铀配分的比例关系,认为其中铀矿物和吸附态约各占铀存在形式的50%。首次对砂岩型铀矿的铀矿物进行微区原位LA-ICP-MS稀土元素分析,认为ΣREE在铀矿物铀石中高度富集,是矿石中稀土元素的主要载体;稀土元素是铀矿石中可综合利用的有益组份,其标准化曲线表现为明显的右倾型,轻稀土富集,轻重稀土分馏强烈,δEu和δCe具较弱的负异常,说明总体上铀矿化形成于外生后成环境。从上述铀矿物特征,初步探讨了铀矿化形成的环境与成因,认为铀矿化形成经历了至少为低温流体作用的环境;铀矿化形成于浅部地壳即外生后成环境而与深源作用无关。     

承德避暑山庄砂岩文物的基本性质和风化机理

世界文化遗产地承德避暑山庄内有大量的砂岩文物。在长期风化作用下,很多砂岩文物发生了严重的风化病害,亟须保护。通过现场调查,发现避暑山庄砂岩文物的风化病害主要为开裂、剥落、粉化、生物寄生等。通过室内测试,得出了该砂岩的矿物学、岩石学性质和物理、力学性质。在此基础上,分析了该砂岩的风化机理,认为钙质胶结物的溶解、干湿交替和盐分结晶膨胀是造成该砂岩粉化、剥落风化的主要原因。相关研究为该砂岩文物的修复保护提供科学支撑。     

多重孔岩石微分等效介质模型及其干燥情形下的解析近似式

经典的微分等效介质(DEM)理论可用于确定多孔介质的弹性性质,但由于缺乏多重孔DEM方程,其估计的多重孔岩石的等效弹性模量依赖于包裹体(即不同孔隙纵横比的孔或缝)的添加顺序.本文首先从Kuster-Toksöz理论出发建立了Zimmermann和Norris两种形式的多重孔DEM方程.Norris形式的多重孔DEM方程预测的等效弹性模量总是位于Hashin-Shtrikman上下限内,而Zimmermann形式的多重孔DEM方程有时会越界.然后,通过使用干燥岩石模量比的解析近似式,对两个相互耦合的Norris形式DEM方程进行解耦得到干燥多重孔岩石的体积和剪切模量解析式.用全DEM方程的数值解对解析近似式的有效性进行了测试,解析公式的计算结果在整个孔隙度分布区间与数值解吻合良好.对实验室测量数据在假设岩石含有双重孔隙的情形下用双重孔DEM解析公式对岩石的弹性模量进行了预测,结果表明,解析式准确地预测了弹性模量随孔隙度的变化.双重孔(即软、硬孔)DEM解析模型可用来反演各孔隙类型的孔隙体积比,它可以通过实验室测量与理论预测之间的平方误差最小反演得到.砂岩样品的反演结果揭示,软孔的孔隙体积百分比与粘土含量没有明显的相关性.     

Stress‐dependent elastic wave velocity of microfractured sandstone

A model for the stress‐dependent elastic wave velocity response of fractured rock mass is proposed based on experimental evidence of stress‐dependent fracture normal and shear stiffness. Previously proposed models and previous experimental studies on stress‐dependent fracture stiffness have been reviewed to provide a basis for the new model. Most of the existing stress‐dependent elastic wave velocity models are empirical, with model parameters that do not have clear physical meanings. To propose the new model, the rock mass is assumed to have randomly oriented microscopic fractures. In addition, the characteristic length of microfractures is assumed to be sufficiently short compared to the rock mass dimensions. The macroscopic stress‐dependent elastic wave velocity response is assumed to be attributed to the stress dependency of fracture stiffness. The stress‐dependent fracture normal stiffness is defined as a generalized power law function of effective normal stress, which is a modification of the Goodman's model. On the other hand, the stress dependency of fracture shear stiffness is modeled as a linear function of normal stress based on experimental data. Ultrasonic wave velocity responses of a dry core sample of Berea sandstone were tested at effective stresses ranging from 2 to 55 MPa. Visual observation of thin sections obtained from the Berea sandstone confirms that the assumptions made for microstructure of rock mass model are appropriate. It is shown that the model can describe the stress‐dependent ultrasonic wave velocity responses of dry Berea sandstone with a set of reasonable material parameter values. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Diagenesis and origin of calcite cement in the Flemish Pass Basin sandstone reservoir (Upper Jurassic): Implications for porosity development

The Flemish Pass Basin is a deep-water basin located offshore on the continental passive margin of the Grand Banks, eastern Newfoundland, which is currently a hydrocarbon exploration target. The current study investigates the petrographic characteristics and origin of carbonate cements in the Ti-3 Member, a primary clastic reservoir interval of the Bodhrán Formation (Upper Jurassic) in the Flemish Pass Basin.The Ti-3 sandstones with average Q_86.0F_3.1R_10.9 contain various diagenetic minerals, including calcite, pyrite, quartz overgrowth, dolomite and siderite. Based on the volume of calcite cement, the investigated sandstones can be classified into (1) calcite-cemented intervals (>20% calcite), and (2) poorly calcite-cemented intervals (porous). Petrographic analysis shows that the dominant cement is intergranular poikilotopic (300–500 μm) calcite, which stared to form extensively at early diagenesis. The precipitation of calcite occured after feldspar leaching and was followed by corrosion of quartz grains. Intergranular calcite cement hosts all-liquid inclusions mainly in the crystal core, but rare primary two-phase (liquid and vapor) fluid inclusions in the rims ((with mean homogenization temperature (T_h) of 70.2 ± 4.9 °C and salinity estimates of 8.8 ± 1.2 eq. wt.% NaCl). The mean δ¹⁸O and δ¹³C isotopic compositions of the intergranular calcite are −8.3 ± 1.2‰, VPDB and −3.0 ± 1.3‰, VPDB, respectively; whereas, fracture-filling calcite has more depleted δ¹⁸O but similar δ¹³C values. The shale normalized rare earth element (REE_SN) patterns of calcite are generally parallel and exhibit slightly negative Ce anomalies and positive Eu anomalies. Fluid-inclusion gas ratios (CO₂/CH₄ and N₂/Ar) of calcite cement further confirms that diagenetic fluids originated from modified seawater. Combined evidence from petrographic, microthermometric and geochemical analyses suggest that (1) the intergranular calcite cement precipitated from diagenetic fluids of mixed marine and meteoric (riverine) waters in suboxic conditions; (2)the cement was sourced from the oxidation of organic matters and the dissolution of biogenic marine carbonates within sandstone beds or adjacent silty mudstones; and (3) the late phases of the intergranular and fracture-filling calcite cements were deposited from hot circulated basinal fluids.Calcite cementation acts as a main controlling factor on the reservoir quality in the Flemish Pass reservoir sandstones. Over 75% of initial porosity was lost due to the early calcite cementation. The development of secondary porosity (mostly enlarged, moldic pores) and throats by later calcite dissolution due to maturation of organic matters (e.g., hydrocarbon and coals), was the key process in improving the reservoir quality.