Chemical and isotopic examination of produced waters from the BP-Wolf lake in situ combustion pilot

The chemical and isotopic compositions of co-produced waters can be used to monitor the processes that take place during in situ combustion. Anticipated processes include mixing of waters, production of CO₂, production of high concentrations of dissolved sulphate and variations in water chemistry associated with heated zones. Water sources include pore waters in oil-bearing strata, waters in overlying or underlying aquifers, water condensed from previously injected steam, and waters associated with combustion. Waters from all sources may mix during production and interpretation of the combustion process can be refined by an understanding of water sources. Produced fluids from the BP-Wolf Lake pilot site in Alberta have been examined to evaluate the effectiveness of the chemical composition of water and the isotopic compositions of aqueous species for monitoring in situ combustion.Produced waters do not show simple conservative mixing behaviour. This suggests that multiple sources of water and other processes, including water-rock reactions, act to modify water compositions. At least three sources of produced waters can be recognized and these are interpreted to be formation water, injected steam and waters that have low Cl and high HCO₃ due to combustion. It is not possible to distinguish waters in the oil-bearing formation from regional waters present in aquifers that underlie the stimulated intervals. Dissolved aqueous species, such as SiO₂, Na, K (as Na/K) and Cl can be used to monitor the approach of the combustion front. Sulphate has been suggested as an indicator of approaching combustion and, although sulphate concentrations rise as combustion approaches a producing well, this indicator is not reliable in all cases. The use of all the above chemical parameters is recommended for detection of combustion zones during operation.The isotope composition of produced waters confirms that there has been significant water-rock interaction during combustion. Carbon isotope compositions of HCO₃ that range from −8 to −25% δ¹³C show that oil oxidation is a major contributor of CO₂ at high temperatures, but CO₂ produced by carbonate mineral dissolution becomes more significant as temperature decreases. Sulphate concentrations in waters produced during combustion can be an order of magnitude higher than those observed during steam stimulation. Both the oil (bitumen) and pyrite (FeS₂) are significant sulphur sources. Typically, the sulphur in both phases is in a reduced state and is available through oxidation associated with combustion. The δ³⁴S of dissolved sulphate in produced waters does not unequivocally identify either of the two major sources of sulphur. However, the relatively depleted δ³⁴ values for SO₄ suggest that the high sulphate concentrations generally associated with the approach of the combustion front result from the oxidation of pyrite.     

Origin of sulfur species in acid sulfate-chloride thermal waters,northeastern Japan

Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ³⁴S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ³⁴S_ys value of +2.5 to +31. The δ³⁴S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO₄ to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ³⁴S, with ground water at 200°C, and/or the removal of sulfide phase depleted in ³⁴S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations.     

Metals in the river waters of Primorye

New data are presented on the contents of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in dissolved and particulate modes of occurrence in unpolluted or anthropogenically contaminated major rivers of Primorye. The background contents of dissolved metals are as follows: 0.1–0.5 μg/l for Zn and Ni, 0.3–0.7 μg/l for Cu, 0.01–0.04 μg/l for Pb and Cd, and 2–20 μg/l for Fe and Mn. Common anthropogenic loading (communal wastewaters) notably increases the dissolved Fe and Mn concentrations Industrial wastes lead to a local increase in the contents of dissolved metals in river waters by one to three orders of magnitude. The effect of hydrological regime is expressed most clearly in the areas of anthropogenic impact. The metal contents in the particulate matter are controlled mainly by its granulometric composition. Original Russian Text ? V.M. Shulkin, N.N. Bogdanov, V.I. Kiselev, 2007, published in Geokhimiya, 2007, No. 1, pp. 79–88.     

Geochemistry of lake waters of Pulicat,India

Pulicat Lake, which is a shallow depression bordering the E Coast of India, represents the coastal waters having transitional characters between terrestrial and deep sea waters. The geochemical characterisation of major elements in Pulicat lake is discussed. It has been observed that the concentrations of different constituents (physical and chemical) in Pulicat lake waters are much higher during dry season and lower in monsson season than the normal sea waters.     

Trace element geochemistry in the waters of Pulicat lake,South India

The distribution of trace elements like Cu, Zn, Ni, Co and Mn in the waters of Pulicat lake has been studied in four aqueous environments — northern, central, southern and channel parts. It is observed that the concentration of the trace elements increase with increase of pH, chlorides and sodium in both monsoon and dry seasons. The concentration and the behaviour of the trace elements are controlled by adsorption, supplemented by organic reactions and by precipitation in sulphide-rich environments.     

Oxidation products of Mn(II) in lake waters

Oxygenation of Mn(II)-rich water samples taken from two English lakes (Esthwaite Water, Cumbria, and Rostherne Mere, Cheshire) during the summer months caused the precipitation of Mn-oxide, the process being catalysed by particulate matter. The Mnoxide formed resembles vernadite (δ-MnO₂) with regard to: (1) Mn oxidation state (> 3.6 in all but one case); and (2) its fine morphology (crumpled thin sheets) as determined by electron microscopy. The precipitates are, however, rather amorphous to X-rays, giving only very weak reflections which cannot be assigned unequivocally. Electron probe microanalysis shows the presence of a number of other elements in the Mn-containing phase. The most abundant is Ca (Ca/Mn weight ratio $\text{? 0.1}$), others are Mg, Si, P, S, Cl, K, Ba and Fe. The precipitates contain much organic matter (20–30 wt.%) but little appears to be associated directly with the Mn phase. Only small amounts (～ 1 wt.%) of humic substances are present. Some but not all of the specimens examined had the gross morphology of Metallogenium, a Mn-depositing bacterium.Naturally occurring Mn-oxides present in Esthwaite Water during the summer resemble, the products of oxygenation in their fine morphology and contents of other elements. Mn-oxides present during the winter are somewhat different morphologically. In one summer sample of particulate matter from Esthwaite Water no Mn-oxide could be found by electron microscopic examination, but Mn was found concentrated in bacteria. This observation, the rapid rates of oxidation and the high Mn oxidation states, suggest that bacteria might play a rôle in catalysing the oxidation of Mn(II).     

Chemical equilibria in the thermal spring waters of Virginia

The composition of waters from 10 thermal springs located in western Virginia near the 38th parallel lineament have been analysed for major dissolved components and for Sr, Fe, Cu, Zn and Cd; from these analyses, free ion activities have been calculated. The temperatures of the springs range from 17° to 39°C, the heat apparently being derived simply from deep circulation along synclinal, Middle Ordovician limestones. More than 95 per cent of the dissolved solids consist of Ca²⁺, Mg²⁺ HCO₃^?, and SO₄^2?. The concentrations of these components, as well as the spring temperatures, have not changed appreciably in 140 yr in some springs. The waters that have temperatures below 25° are all undersaturated with respect to calcite and dolomite, possibly because they have been contaminated by shallow ground waters. The waters with temperatures above 25° are in equilibrium with calcite and dolomite. Furthermore, in this latter group, the calcium-sulfate activity product and the sulfate-carbonate activity ratio are nearly constant, even though the waters are under saturated with respect to gypsum, anhydrite, celestite and strontianite. This can be explained if CaSO⁴ is coprecipitated in a mineral such as aragonite. The waters have absorbed some dissolved oxygen near the surface, but at depth they may be anoxic with Eh controlled by the oxidation of pyrite to goethite. The extremely low chloride concentrations of these waters clearly distinguish them from the brines which deposited Mississippi Valley and Appalachian type epithermal ore deposits.     

Deglaciation and glacial lake development in the Kaamasjoki river basin, Finnish Lapland

The glacial hydrology of the meltwaters of the ice sheet during deglaciation in a large river basin has been reconstructed on the basis of heights of thresholds and saddles of bedrock topography, glaciofluvial accumulation forms (eskers, deltas and plains of sorted material) and erosional landforms (drainage channels and shorelines) as well as a few terminal moraines. The water level of glacial lake dropped in several stages. The lake existed and deglaciation took place before 9740±280 years B.P. The deglaciation took place at a much faster rate in the studied region than later in western Lapland.     

长江中下游河湖水量交换过程

长江中下游的河湖水交换关系典型且复杂,为描述河湖水量相互交换过程,提出了河湖水量交换系数的概念,即某一时段内由支流汇入湖泊的径流量与湖泊泄入干流径流量的比值,表示河湖水量交换的激烈程度。根据水量平衡原理推导出河湖水量交换系数计算的经验公式,并把河湖水量交换过程分为3种状态:“湖分洪”、“稳定”和“湖补河”。近60多年来河湖水交换系数年际变化趋势表明:洞庭湖与长江干流的水交换状态从“湖分洪”到“稳定”,再到“湖补河”状态发展;鄱阳湖与长江干流的水交换系数在稳定状态附近波动,河湖水交换状态无明显趋势性变化,河湖系统演化稳定。河湖水交换系数与长江干流径流量相关性良好,而与湖泊支流径流量相关性较差,表明长江干流径流量的大小是河湖水量交换过程的主控因素。     

四川什邡青牛沱崩塌群特征及其形成的堰塞坝体稳定性评价

2008-5.12地震中,由于当时强烈的地震作用,使得地震灾区地表变形巨大,生态环境严重破坏。地震诱发的地质灾害威胁着灾区人民群众的生命财产安全,震中地区出现的主要灾害形式为边坡的崩滑及崩滑堆积体堵江(河、路)。本文通过对青牛沱崩塌群及崩滑堵江形成堰塞湖的基本特征的论述,分析了其形成机制和产生的危害特征,最后因地制宜地提出了防治对策。为在恶劣环境下的地质灾害评价和防治提供了一套完整的技术思路,也为以后相似情况下的其他地区的灾害评价、防治提供参考。     

青藏高原北部不同地区河流和湖岸阶地的演化特征

把青藏高原北部空白区已完成的1：25万区调成果报告中有关河流和湖岸地貌的剖面、实测数据提炼出来．将其位置点绘于同一张水系分布图上,然后根据不同位置、不同的剖面、不同的测试数据进行区域性对比研究,结果表明：①青藏高原北部昆仑山中部和东部地区,河谷、湖岸地貌都具有100kaBP、10kaBP、5-6 kaBP的阶地,这3个时期东西部河谷、湖岸地貌的形成具有同步性;②昆仑山中部地区具有70kaBP的阶地,昆仑山东部地区具有50kaBP的阶地,这2个时期昆仑山东西部河流、湖岸地貌的形成不具有同步性。对该地区河流、湖岸地貌成因分析后认为,除气候作用外,河流阶地、湖岸阶地对高原北部的隆升具有一定的指示作用,表现为从西向东抬升速率逐渐减小,总体上同一地方从老到新抬升速率逐渐增加。     

Chemical composition of bottled mineral waters in Estonia

Five commercially available in Estonia brands of bottled water have been analysed for 59 chemical elements by ICP-QMS and ICP-AES techniques to assess the quality of domestic mineral waters in scope of the European Groundwater Geochemistry Project initiated by the Geochemistry Expert Group of EuroGeoSurveys. Contents of 9 cations and anions, pH and electrical conductivity (EC) were measured in the bottled mineral waters by IC, titration and photometric methods. The data showed a significant difference between natural undiluted mineral water (Värska Originaal) characterised by the highest values of pH, EC and majority of trace elements studied, and other domestic waters sold in Estonia.     

Oxygen and hydrogen isotopic ratios in groundwaters and river waters from India

A comprehensive set of measurements of oxygen and hydrogen isotopic ratios in groundwaters as well as waters from rivers, lakes, hot springs etc. taken from a variety of locations in India has been carried out for the first time. Isotopically the most depleted samples occur in the high altitude precipitations in the Himalayas e.g. in the lakes of Bhutan and the source water of the Ganga. The shallow groundwater data display a continental effect where the heavy isotope content decreases with distance from the coast (about 4 to 6 per mil decrease in δ¹⁸O per 1000 km). The δ D and δ¹⁸O of these fresh waters are linearly related and an analysis of this relation vis-a-vis the meteoric water line shows the unambiguous effect of enrichment due to evaporation from soils.     

德兴铜矿大坞河流域环境特征

文章主要研究德兴铜矿大坞河流域水、土壤、植物的重金属污染情况，分析重金属在水、土壤、植物体内的迁移和转化。发现大坞河流域水体、底泥和土壤中Cu元素含量严重超过国家标准，其他元素的污染较轻。而植物体内Cu没有超标，而Cd、Pb元素在植物体内得到富集。通过对土壤元素形态的研究发现Cd、Pb元素存在的形态容易被植物吸收，Cu元素存在形态较稳定，导致植物体内中Cd、Pb的富集。     

Mobilization of gold into lake sediments from acid and alkaline mineralized environments in the southern Canadian Shield: Gold in lake sediments and natural waters

To be an effective indicator of mineralization in lake sediment surveys within the Canadian Shield, it is desirable that an element migrate in solution or adsorbed on suspensates. Given the low relief and disorganized drainage patterns of this region, dispersal in clastic form in drainage systems is limited and gives rise to erratic distributions. The purpose of this study was to discover whether Au shows significant hydromorphic mobility, which would justify the increasing use that is being made of this element in lake sediments as an indicator for gold mineralization.Waters and lake sediments were collected from Napier Lake, Ontario; PAP Lake, Saskatchewan; and Foster Lake, Manitoba, all of which contain Au-quartz vein mineralization and lie within the glaciated boreal forest zone of the Canadian Shield. In all three areas, profundal lake sediments down-drainage of mineralization contain Au concentrations higher than regional mean concentrations. Significant dissolution and transport of Au was found under oxidizing conditions associated with waters with pH that varied from acid to alkaline. Waters from drill holes penetrating mineralization contain up to 401 ng L⁻¹ Au (note; 1 ng L⁻¹ is equivalent to 1 part per trillion, 10⁻¹²). Surface waters overlying or near mineralization collected from bogs, seeps, ponds and streams contain up to 13 ng L⁻¹. The content of Au in lake waters is lower, with a maximum of 1.1 ng L⁻¹. There is also a detectable quantity of Au present in suspensates. Two samples of particulates (> 1 μm) filtered from lake water have Au equivalent to 0.17 ng L⁻¹ and 0.039 ng L⁻¹. While the contents of Au present in solution or as suspensates in lake and stream water are relatively small, they are sufficient, if precipitated, to generate anomalies in lake sediments. Thus for Reservoir Lake, in the Foster Lake area, water from the principal stream entering the lake carries 0.3 ng L⁻¹ Au. This provides an annual flux which far exceeds that required to generate the 7.3 ppb Au contained in profundal sediments of this lake; a content that is anomalous relative to the regional median content of < 1 ppb Au for lake sediments.Hydrogeochemical prospecting involving analysis for Au is one method for tracing the source of anomalous Au in lake sediments. Collection of 1 L samples without field treatment, followed by extraction of Au into MIBK, then analysis by graphite-furnace atomic absorption spectrophotometry, permits detection levels for Au of 0.5 ng L⁻¹. This is below the contents of Au found in some waters from mineralized areas. A detection limit of 0.3 ng L⁻¹ was obtained using larger water samples.     

Early diagenesis in anaerobic lake sediments: chemical equilibria in interstitial waters

As part of a study of early diagenesis in anaerobic lake sediments the major ions and P, Fe, Mn, pS, p? and pH were measured in interstitial waters of cores from eutrophic Greifensee in north-central Switzerland. A guide for the interpretation of such data is thermodynamic equilibrium between the dissolved species and mineral phases. The results show that CaCO₃, which precipitates from the lake water, dissolves rapidly in the CO₂-rich interstitial waters resulting in equilibrium with calcite in the top few centimeters of sediment. Siderite, on the other hand, is nearly ten-fold supersaturated 20–30 cm below the surface. Iron monosulfides are metastable in the surface 10–20 cm of sediment and pS and p? results indicate equilibrium between polysulfides and orthorhombic sulfur. Vivianite appears to be limiting the solubility of phosphate below a few centimeters of sediment.The above processes are highly interactive, especially in the case of ferrous iron, with one result being a two order of magnitude decrease in dissolved phosphate in a depth interval of 20cm in the interstitial waters.     

Chemical composition of river particulates in eastern China

A total of 42 aquatic particulate sample:, (suspended matter and < 63 m surficial sediments) was collected from 11 large rivers in eastern China. Contents of both major elements (Al, Si, Ca, Mg, K, Na, Ti, Fe, Mn) and trace elements (Cu, Pb, Zn, Cd, Cr, Co, Ni, V) in the particulate samples were analyzed. The geographic variations of river particulate compositions were studied. The results showed that the Yellow River particulates contained a notably high content of Ca and a low content of Al. Except for the Yellow River, A1 contents in particulates increased from the northern rivers to the southern rivers, while K and Na decreased. Trace elements were relatively enriched in the southern river particulates. The geographic variations seemed to be related to the weathering types and geological background within the river basins. The average composition of river particulates in China was then estimated. Based on the Chinese river data from this paper, as well as on the literature data for other main world rivers, a new estimation of the global average particulate composition was reported. Since the earlier estimations in the literature were not concerned with or at best concerned only with few of the Chinese rivers which contribute a major proportion to the global load of river particulates, this new estimation may be more reasonable.     

The behaviour of the rare earth elements during mixing of river and sea waters

Rare earth element concentrations have been measured in organic-rich Luce river water and coastal sea water. Concentrations (e.g. ～350?1850 pmol/kg Nd in the Water of Luce and ～45?350 pmol/ kg Nd in Luce Bay) are related to the presence of particles, with 30–60% of the REE associated with >0.4?0.7 μm particles, and to riverine Fe concentrations. REE fractionation occurs in the river water the submicrometre river water is heavy REE enriched whereas the coarser fraction has a more shale-like REE pattern.Laboratory experiments show that the REE in organic-rich river waters are chiefly associated with Feorganic matter colloids which flocculate during estuarine mixing. Preferential removal of heavy REE (～95%) relative to light REE (～60%) occurs, but no Ce anomaly is developed. In contrast, no REE removal occurs during estuarine mixing with organic-poor river water.     

青藏高原北部不同地区河流和湖岸阶地的演化特征

把青藏高原北部空白区已完成的1∶25万区调成果报告中有关河流和湖岸地貌的剖面、实测数据提炼出来,将其位置点绘于同一张水系分布图上,然后根据不同位置、不同的剖面、不同的测试数据进行区域性对比研究,结果表明:①青藏高原北部昆仑山中部和东部地区,河谷、湖岸地貌都具有100kaBP、10kaBP、5～6kaBP的阶地,这3个时期东西部河谷、湖岸地貌的形成具有同步性;②昆仑山中部地区具有70kaBP的阶地,昆仑山东部地区具有50kaBP的阶地,这2个时期昆仑山东西部河流、湖岸地貌的形成不具有同步性。对该地区河流、湖岸地貌成因分析后认为,除气候作用外,河流阶地、湖岸阶地对高原北部的隆升具有一定的指示作用,表现为从西向东抬升速率逐渐减小,总体上同一地方从老到新抬升速率逐渐增加。