Estimation of covariance matrix from geochemical data with observations below detection limits

Multivariate statistical analyses have been extensively applied to geochemical measurements to analyze and aid interpretation of the data. Estimation of the covariance matrix of multivariate observations is the first task in multivariate analysis. However, geochemical data for the rare elements, especially Ag, Au, and platinum-group elements, usually contain observations the below detection limits. In particular, Instrumental Neutron Activation Analysis (INAA) for the rare elements produces multilevel and possibly extremely high detection limits depending on the sample weight. Traditionally, in applying multivariate analysis to such incomplete data, the observations below detection limits are first substituted, for example, each observation below the detection limit is replaced by a certain percentage of that limit, and then the standard statistical computer packages or techniques are used to obtain the analysis of the data. If a number of samples with observations below detection limits is small, or the detection limits are relatively near zero, the results may be reasonable and most geological interpretations or conclusions are probably valid. In this paper, a new method is proposed to estimate the covariance matrix from a dataset containing observations below multilevel detection limits by using the marginal maximum likelihood estimation (MMLE) method. For each pair of variables, sayY andZ whose observations containing below detection limits, the proposed method consists of three steps: (i) for each variable separately obtaining the marginal MLE for the means and the variances, , , , and forY andZ: (ii) defining new variables by and and lettingA=C+D andB=C–D, and obtaining MLE for variances, and forA andB; (iii) estimating the correlation coefficient _YZ by and the covariance _YZ by . The procedure is illustrated by using a precious metal geochemical data set from the Fox River Sill, Manitoba, Canada.     

The history and impact of air pollution at Čertovo Lake,southwestern Czech Republic

This multi-disciplinary investigation documents the longterm effects of atmospheric pollution of metals and acids on a geologically sensitive catchment in the umava Mountains, southwestern Czech Republic, a region with a long history of human disturbance. A 30 cm long sediment core (I) from ertovo Lake was analyzed for natural and artifical radionuclides, metals, diatoms, chrysophytes, and pollen in sediments accumulated during the last 200 years. A second core (II), extending to 95 cm, included sediment judged to be free of atmospheric deposition of pollutants associated with the Industrial Revolution. Chronostratigraphic markers include several changes in the pollen assemblages corresponding to well-documented changes in land-use, and distinct distributions of ¹³⁷Cs, ¹³⁴Cs and ²⁴¹Am from weapons testing and the 1986 nuclear accident at Chernobyl, Russia. These markers corroborate the ²¹⁰Pb dating and, together, produce a reliable chronology extending back nearly to 1800 A.D.Stratigraphic profiles of Cu, Pb, and Zn in Core I are unlike any previously reported in the literature. Concentrations of Cu, Pb, and Zn remain generally above 100, 400, and 200 g g^-1, respectively, for the 200 years represented by Core I. These values are unusually high for sediments from a watershed with no known heavy-metal ore bodies. Accumulation rates for Cu, Pb, and Zn, which include both atmospheric and watershed contributions, are also high (ca 1, > 1 and > 1 g cm^-2 yr^-1, respectively) for the same period, although the anthropogenic contribution of Zn rose from nearly zero at 1800 A.D. The Cu and Pb accumulation rates rose dramatically about 1640 A.D.Accumulation rates of anthropogenically-derived Be, a relatively abundant element in the soft coals of the region, are also elevated by about 0.01 g cm^-2 yr^-1 in sediments of this period. Vanadium accumulation rates increased only since 1980 A.D., presumably along with increased consumption of oil.Diatom assemblages illustrate that the lake was acidic (pH between 4.5 and 5) through at least the past 200 years. The pH declined significantly (from ca 5 to 4) between 1960 and 1985 with a slight increase to 4.5 in the last few years. Recent diatom and chrysophyte assemblages suggest high trace metal concentrations, consistent with the present lake-water chemistry.     

寒武系古流体地球化学特征及其对页岩气保存的指示意义 ——以中扬子地区寒武系页岩气发现井宜地2井为例

保存条件是中扬子地区页岩气富集的关键因素之一，宜地2井是中扬子寒武系页岩气发现井，通过对该井全井段岩芯裂缝古流体的地球化学分析，探讨了寒武系古流体成因和对水井沱组页岩气保存条件的指示意义。结果认为：① 覃家庙组膏岩层之上方解石脉缺少Fe2+、Mn2+，且δ13C和δ18O值较围岩偏负，指示其形成于氧化的环境，石牌组方解石脉δ13C偏负，黄铁矿脉δ34S值与膏盐相似，表明其成因与TSR密切相关；水井沱组脉体δ13C和δ18O与围岩相似，形成于封闭的环境。② 方解石脉包裹体群SO42-、Ca2+、Mg2+含量整体上由覃家庙组向上向下分别递减，钠氯系数以水井沱组最低，整体上向上升高，表明覃家庙组是高盐度卤水的主要来源，水井沱组受外来流体影响弱；包裹体水溶液δD和δ18O也指示娄山关组、石牌组方解石脉成因分别与大气水、TSR相关。③ 古流体地球化学研究表明宜昌地区页岩气保存条件整体较好，页岩气散失的主要通道是垂直裂缝，页岩气保存条件好与膏盐盖层发育、后期构造破坏弱、脉体对裂缝的及时封闭以及白垩系盖层等因素密切相关。     

珠江口盆地西江主洼油气差异分布机制

西江主洼是珠江口盆地一个低勘探程度洼陷，油气差异聚集特征明显，但其机理不清。本文在断陷盆地油气成藏理论指导下，利用研究区地质、地球物理和地球化学等资料，开展了烃源岩、断盖组合、储集体系和运聚模式等方面的研究。结果表明，裂陷期沉降、沉积中心有序迁移，造成主力烃源岩自东向西由文四段迁移至文三段、文一+二段，控制东、西部油气差异分布。恩平组区域性泥岩发育且晚期断裂缺乏，导致油气纵向上更易聚集于下构造层；区域泥岩减薄尖灭或晚期断裂切开盖层的区域，上构造层有一定油气分布。"源-汇"类型从宏观上控制储层优劣，影响下构造层油气富集程度；"仓储"运移是控制上构造层油气规模聚集的主要模式。下构造层古近系应作为重点部署方向，东部围绕文四段、西部围绕文三段、文一+二段烃源岩构成的含油气系统展开；上构造层勘探需关注珠海组，在隆起周边寻找具备"仓储"运移模式的有利区带。     

Global climatic change – the latest scientific understanding

IPCCs statement in its 1995 report (IPCC 1996) that a human influence was discernible in global climate has been widely quoted but often misunderstood. The character of the evidence underpinning this detection statement is explained so that its strengths and weaknesses can be better understood and the subtleties of its message better appreciated. To demonstrate the close linkage between the government-approved summary and the underlying chapters of the IPCC report the detailed evolution of the detection statement from first draft through to the form finally approved by the IPCC is described.     

“煤特征指数”与矿井瓦斯危险类型的关系

矿井瓦斯危险程度与煤层中瓦斯赋存状况及其泄出方式有关,并取决于多种地质条件和采掘工艺。其中,煤特征条件特别重要。本文分析了湖南省的5种矿井瓦斯危险类型以及相应的煤特征条件,提出了“煤特征指数(I_c)”这一概念。I_c是一项评价矿井瓦斯危险程度的综合指标。研究表明,矿井瓦斯危险愈严重,则其I_c值愈高。应用该项成果预测了16对矿井的瓦斯危险类型,取得了满意的效果。     

综合利用地震多参数预测油气藏

以吉林省境内红星构造带(已发现油田)和杨柳青构造带(未发现油田)为试验区,首先利用地震地层学方法,研究间接参数特征,确定有利相带和有效圈闭,并在有效圈闭上选择了39个2×2cm时窗。在时窗内提取与地震波动力学有关的信息,即频率、振幅、频谱能量等,然后对这种信息进行统计计算,获得振幅方差等九个参数并对其进行综合分析,从已知油气藏出发,对未知圈闭油气状况进行了三级预测,指出了最有利的勘探靶区。     

Environmental aspects of selected trace metals in soils and waters surrounding Singaran Nala, Raniganj Coalfield

The Raniganj Coalfield is the oldest coalfield in India that has been continuously and extensively mined since the late eighteenth century. The present study reports a geochemical investigation and environmental quality assessment using soil and water in the area surrounding a stream, locally known as Singaran Nala （Nala means storm water drains in Bengali）, in the Raniganj Coalfield. Soil （top soil, mud, silty clay and laterite） and rock samples （sandstone and shale） were collected from the study area and were analyzed for trace metals （Cr, Cu, Fe, Mn, Ni and Zn）. Surface waters from the stream and the Damodar River as well as ground waters from hand pumps and underground mine pits were collected. Water samples were analyzed for major ions （Na^＋, Ca^2＋, Mg^2＋, Cl^-, HNO3^- and SO4^2-） and trace metals （Cu, Fe, Mn, Ni, and Zn）. Trace metal concentrations in soil samples are found higher than the average world soil composition. Nevertheless, trace metal （Cr, Cu, Ni and Zn） concentrations in soils exceed or reach the maximum allowable concentrations （MAC） proposed by the European Commission for agricultural soils. In particular, Ni concentrations exceed the typical value for cultivated soils. Chromium, Cu and Ni concentrations in laterite and Cr concentration in topsoil exceed the ecotoxicological limit.     

The ＂CO2-rich gas vents＂ of Mt. Amiata volcano （Tuscany, Central Italy）： Geochemistry,genetic mechanism and hazard evaluation

Mt. Amiata （Southern Tuscany, Central Italy） is an extinct Quaternary volcano located in an area still marked by high heat-flow that is caused by deep seated （6-10 km） hot masses related to Pliocene magmatic activity. The anomalous geothermal gradient gives rise, within the Mesozoic limestone formation （Tuscan series）, to geothermal systems that fed the Ca-SO4 thermal springs characterizing this area. Besides of thermal fluids, several cold, dry CO2-rich gas emissions seep out on the NE flank of the volcano. These gas vents mostly consist of large sub-circular craters at variable depth and diameter （5-15 m and 10-50 m, respectively）, and represent a serious hazard for the local population, as testified by the several asphyxia casualties that have been repeatedly occurred within these morphological depressions. In this work, the chemical and isotopic compositions of the Mt. Amiata ＂CO2-rich gas vents＂ and the estimation of both the CO2 flux from the soil and the CO2 distribution in air of their surroundings, has been carried out in order to： （1） assess the origin of gases, （2） recognize the mechanism of formation for these gas emissions and their relationship with local tectonics, and （3） to evaluate the CO2 hazard in the high flux emanations. The chemical composition of the gases is largely dominated by CO2 （up to 98 % by vol） and shows relatively high concentrations of N2, CH4 and H2S （up to 1.1%, 0.9% and 3.9 % by vol, respectively）. These features, coupled with the carbon and nitrogen isotopic signatures, suggest that the origin of the main gas compounds may be related to the contribution of deep （i.e., thermometamorphic processes on carbonate formations for CO2） and shallow （i.e. thermal decomposition of organic material for CH4, N2 and H2S） sources.     

Continuous air rate measurement in flotation cells: Some fundamental considerations

A robust and reliable sensor to measure gas (air) superficial velocity (J_g) continuously in flotation systems is introduced. It is based on the sampling of bubbles by buoyancy with the accumulating air allowed to exit through an orifice. At steady state, pressure drop is measured and related to the J_g by prior calibration. The continuous device is readily automated and extended to a multi-unit set-up. The sensor and data collections are described. The governing gas flow equation and models of the dynamic response to air flow rate set point change and fluctuations in froth depth are derived. Model predictions are confirmed against plant data. By taking a moving average, the J_g remains valid in the face of typical plant disturbances.