Geochemical evaluation of flowback brine from Marcellus gas wells in Pennsylvania,USA

Large quantities of highly saline brine flow from gas wells in the Marcellus Formation after hydraulic stimulation (“fracking”). This study assesses the composition of these flowback waters from the Marcellus shale in Pennsylvania, USA. Concentrations of most inorganic components of flowback water (Cl, Br, Na, K, Ca, Mg, Sr, Ba, Ra, Fe, Mn, total dissolved solids, and others) increase with time from a well after hydraulic stimulation. Based on results in several datasets reported here, the greatest concentration of Cl⁻ in flowback water is 151,000 mg/L. For total Ra (combined ²²⁶Ra and ²²⁸Ra) in flowback, the highest level reported is 6540 pCi/L. Flowback waters from hydraulic fracturing of Marcellus wells resemble brines produced from conventional gas wells that tap into other Paleozoic formations in the region. The Br/Cl ratio and other parameters indicate that both types of brine formed by the evaporation of seawater followed by dolomitization, sulfate reduction and subsurface mixing with seawater and/or freshwater. Trends and relationships in brine composition indicate that (1) increased salt concentration in flowback is not mainly caused by dissolution of salt or other minerals in rock units, (2) the flowback waters represent a mixture of injection waters with highly concentrated in situ brines similar to those in the other formations, and (3) these waters contain concentrations of Ra and Ba that are commonly hundreds of times the US drinking water standards.     

Trace metal distribution and mobility in drill cuttings and produced waters from Marcellus Shale gas extraction: Uranium,arsenic, barium

Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg⁻¹, respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L⁻¹) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals.Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates.     

http://www.sciencedirect.com/science/article/pii/S1674987114001649

Hydrocarbon production from shale has attracted much attention in the recent years. When applied to this prolific and hydrocarbon rich resource plays, our understanding of the complexities of the flow mechanism(sorption process and flow behavior in complex fracture systems- induced or natural) leaves much to be desired. In this paper, we present and discuss a novel approach to modeling, history matching of hydrocarbon production from a Marcellus shale asset in southwestern Pennsylvania using advanced data mining, pattern recognition and machine learning technologies. In this new approach instead of imposing our understanding of the flow mechanism, the impact of multi-stage hydraulic fractures, and the production process on the reservoir model, we allow the production history, well log, completion and hydraulic fracturing data to guide our model and determine its behavior. The uniqueness of this technology is that it incorporates the so-called "hard data" directly into the reservoir model, so that the model can be used to optimize the hydraulic fracture process. The "hard data" refers to field measurements during the hydraulic fracturing process such as fluid and proppant type and amount, injection pressure and rate as well as proppant concentration. This novel approach contrasts with the current industry focus on the use of "soft data"(non-measured, interpretive data such as frac length, width,height and conductivity) in the reservoir models. The study focuses on a Marcellus shale asset that includes 135 wells with multiple pads, different landing targets, well length and reservoir properties. The full field history matching process was successfully completed using this data driven approach thus capturing the production behavior with acceptable accuracy for individual wells and for the entire asset.     

不同水力加载条件下非均质储层缝网扩展规律研究

水力压裂可显著提高页岩气等致密储层岩体的渗透性以增加油气产量,然而受多因素影响,水力压裂形成缝网结构的机理和压裂优化设计一直是研究的焦点和难点。本研究基于渗流-应力-破坏耦合计算模拟方法,对不同水力加载条件下的非均质储层水力压裂过程进行了模拟和对比研究。研究结果表明:水力压裂过程中起始注水压力和增量大小对水力压裂缝网扩展和改造区域形态有着显著的影响。当起始注水压力小于等于模型材料体抗拉强度,并缓慢增压致裂时,压裂过程可近似视为稳态应力-破坏-渗流耦合作用过程的不同阶段,这种情况下仅在压裂井孔周围形成两组对称式的伞状水力裂缝带。当对模型体施加高于模型材料体破裂压力的注水压力时,相当于对压裂孔快速施加高动水压力,水力裂缝沿压裂孔全方位迅速萌生并快速扩展,当注水压力值高于破裂压力一定幅值时,压裂改造可形成围绕压裂井全方位的放射状裂缝网络,使压裂储层得以最大范围改造。在拟静力和拟动力两种加载条件下,不同水岩相互作用机理是造成不同水力加载条件出现不同缝网结构的力学机制,而对于实际的页岩气储层改造,压裂产生围绕压裂井全方位放射状的缝网结构则是一种最优的体积压裂改造。     

An experimental investigation of barite formation in seawater

We report results from time-series decay and sequential leaching experiments of laboratory cultured and coastal plankton to elucidate the mechanisms controlling barite formation in seawater. Batch-cultured diatoms (Stephanopyxis palmerina) and coccolithophorids (Emiliania huxleyi) were let to decay in the dark for 8-10 weeks, suspended in aerated seawater. The development of barite crystals was monitored by Scanning Electron Microscopy (SEM). A similar experiment was conducted with plankton collected during the spring-bloom in Vineyard Sound (MA). In addition to SEM, suspended particles were sequentially leached for Ba (distilled water rinse; 10% (v/v) HNO₃ rinse at room temperature; 30% (v/v) HCl at 80°C overnight; 50% (v/v) HNO₃ at 80°C overnight) immediately after collection, and after 10-week decay in seawater, in seawater poisoned with HgCl₂, and in seawater spiked with ¹³⁵Ba.Both experiments showed an increase in the number of barite crystals during decay. The spring-bloom plankton had initially a large pool of labile Ba, soluble in distilled water and cold dilute HNO₃ that was lost from the plankton after 10-week decay in both axenic and nonaxenic conditions. In contrast, Ba in the decayed plankton samples was predominantly in forms extracted by hot HCl and hot HNO₃ acids, which were attributed to presence of barite Ba and refractory organic Ba respectively. The increase in barite crystal counts under a Scanning Electron Microscope (SEM), the increase in HCl extractable Ba relative to organic carbon, and the loss of a large fraction of Ba during plankton decay suggest that living plankton consists of a relatively large pool of labile Ba, which is rapidly released during plankton decomposition and acts as the main source of Ba for barite formation in supersaturated microenvironments. Since mass balance indicates that only a small proportion (2 to 4%) of the labile-Ba pool is converted to barite, the availability of microenvironments that could locally concentrate Ba released by plankton decay seems to be the main limiting factor in barite precipitation.     

Fingerprinting Marcellus Shale waste products from Pb isotope and trace metal perspectives

Drill cuttings generated during unconventional natural gas extraction from the Marcellus Shale, Appalachian Basin, U.S.A., generally contain a very large component of organic-rich black shale because of extensive lateral drilling into this target unit. In this study, element concentrations and Pb isotope ratios obtained from leached drill cuttings spanning 600 m of stratigraphic section were used to assess the potential for short and long term environmental impacts from Marcellus Shale waste materials, in comparison with material from surrounding formations. Leachates of the units above, below and within the Marcellus Shale yielded Cl/Br ratios of 100–150, similar to produced water values. Leachates from oxidized and unoxidized drill cuttings from the Marcellus Shale contain distinct suites of elevated trace metal concentrations, including Cd, Cu, Mo, Ni, Sb, U, V and Zn. The most elevated Mo, Ni, Sb, U, and V concentrations are found in leachates from the lower portion of the Marcellus Shale, the section typically exploited for natural gas production. In addition, lower ²⁰⁷Pb/²⁰⁶Pb ratios within the lower Marcellus Shale (0.661–0.733) provide a distinctive fingerprint from formations above (0.822–0.846) and below (0.796–0.810), reflecting ²⁰⁶Pb produced as a result of in situ ²³⁸U decay within this organic rich black shale. Trace metal concentrations from the Marcellus Shale leachates are similar to total metal concentrations from other black shales. These metal concentrations can exceed screening levels recommended by the EPA, and thus have the potential to impact soil and water quality depending on cuttings disposal methods.     

Analytical investigation of hydraulic fracture-induced seismicity and fault activation

More recent public discourse has taken place regarding the potential correlation between seismic activity and hydraulic fracturing in shale gas reservoirs. Public fears about the risk of seismicity stem mainly from past earthquakes induced by conventional deep injections because the two types of projects share similar mechanisms of rock failure and fault activation. Although previous earthquake risks associated with fluid injection were not serious, the situation would be far more problematic if hydraulic fracturing in a shale gas reservoir triggered a similar-sized earthquake due to potential environmental issues. In fact, almost all documented injection-induced earthquakes have been associated with long-duration and high-volume injection rather than short-term (hours) pressurization (e.g., hydraulic fracturing). In general, hydraulic fracturing operations mostly induce microseismic events through rock failure and activation of small fractures. Although shale reservoirs in tectonically active zones pose a high risk of inducing large-magnitude seismic activities, the internal geological conditions and external stimulation conditions are impossible to be satisfied simultaneously to trigger activation of an entire fault and to result in a destructive earthquake during hydraulic fracturing operations.     

贵州热液型重晶石矿集区地质特征及成矿规律

贵州热液型重晶石矿分布主要在黔东北、黔南及黔东南地区,矿床具有成群、成带和集中分布特点。按照构造分区、矿床式及矿床边界等原则,将贵州热液型重晶石矿床划分为务川-湄潭重晶石矿集区和施秉-都匀重晶石矿集区,按矿床产出构造部位不同分为丰水岭式和顶罐坡式。前者产于黔北隆起区,矿床以萤石、重晶石共生为特征;后者产于黔南坳陷区,矿床以单一重晶石为特征。矿床主要受地层、岩相、构造和Si/Ca界面的控制。建立"矿源层-容矿层-盖层"的找矿模式,区内下寒武系牛蹄塘组(留茶坡组)黑色岩系为主矿源层;当大气降水下渗地下,受地热增温作用发生水-岩反应形成热卤水,热卤水与Ba元素混合形成含矿流体;当成矿流体通过深大断裂运移上升至Si/Ca界面附近发生侧向分异,导致矿液在容矿层(碳酸盐岩)断裂构造带内充填-交代成矿。     

页岩储层-超临界CO2-模拟压裂液相互作用实验研究及其环境意义

近年来,页岩气作为一种重要的非常规天然气来源,逐渐成为国内外关注的热点。当前的研究工作总体侧重于页岩气开采技术的改进与环境监测,对页岩气开采过程中水岩相互作用还少有报道。本文采用模拟实验,选取储层页岩样品,在温度90 ℃、压力10 MPa环境下,开展了CO2压裂液页岩相互作用实验研究。主要探讨页岩气开采过程中,由于常规水力压裂液以及后期超临界CO2的增注,造成的储层岩石矿物的变化以及返排液成分的变化。实验结果显示：压裂液能使岩石矿物发生溶蚀,超临界CO2的存在会进一步加剧溶蚀反应的进行,促使孔隙变大并产生更多的微孔隙,为页岩气提供更多的运移通道,有利于油气的运移。但是,存在的环境威胁不容忽视：一方面,岩石中会溶解出大量的Ca、Mg、Si元素和少量Fe、Mn等金属元素,超临界CO2、富有机质页岩以及压裂液中表面活性剂等物质在高温高压酸性环境条件下,容易生成挥发性有机物残留在地层中,极有可能沿着岩石破碎的孔隙、断裂发生迁移或泄露,从而对地下含水层造成污染;另一方面,多种成分进入高矿化度溶液体系经返排回到地表,也会增大处理返排液的难度。本文取得的实验数据和成果有助于理解页岩气储层在开采过程中可能发生的水岩相互作用过程及其潜在的环境风险。     

断层影响下的页岩气储层水力压裂模拟研究

断层对页岩气储层压裂改造有重要影响,甚至诱发深部地震事件和近地表环境问题.本文采用多物理场耦合方法,基于渗流和应力耦合理论,研究储层水力压裂过程中断层以及封闭顶板中水力破坏区域的产生与演化机理,并分析讨论流体沿高渗通道运移扩散机理,研究结果表明:(1)断层改变储层水力破坏区域形态并且扩展了水力压裂破坏空间.较高注水压力...     

The relationship between methane migration and shale-gas well operations near Dimock,Pennsylvania, USA

Migration of stray methane gas near the town of Dimock, Pennsylvania, has been at the center of the debate on the safety of shale gas drilling and hydraulic fracturing in the United States. The presented study relates temporal variations in molecular concentrations and stable isotope compositions of methane and ethane to shale-gas well activity (i.e., vertical/horizontal drilling, hydraulic fracturing and remedial actions). This was accomplished by analyzing data collected, between 2008 and 2012, by state and federal agencies and the gas well operator. In some cases, methane migration started prior to hydraulic fracturing. Methane levels of contaminated water wells sampled were one to several orders of magnitude greater than the concentrations due to natural variation in water wells of the local area. Isotope analyses indicate that all samples had a thermogenic origin at varying maturity levels, but from formations above the hydraulically fractured Marcellus Shale. The results from the initial water well samples were similar to annular gas values, but not those of production gases. This indicates that leakage by casing cement seals most likely caused the impacts, not breaks in the production casing walls. Remediation by squeeze cementing was partially effective in mitigating impacts of gas migration. In several cases where remediation caused a substantial reduction in methane levels, there were also substantial changes in the isotope values, providing evidence of two sources, one natural and the other man-induced. Sampling water wells while venting gas wells appears to be a cost-effective method for determining if methane migration has occurred.

     

Experimental Investigation on the Basic Law of Hydraulic Fracturing After Water Pressure Control Blasting

Because of the advantages of integrating water pressure blasting and hydraulic fracturing, the use of hydraulic fracturing after water pressure control blasting is a method that is used to fully transform the structure of a coal-rock mass by increasing the number and range of hydraulic cracks. An experiment to study hydraulic fracturing after water pressure blasting on cement mortar samples (300 × 300 × 300 mm³) was conducted using a large-sized true triaxial hydraulic fracturing experimental system. A traditional hydraulic fracturing experiment was also performed for comparison. The experimental results show that water pressure blasting produces many blasting cracks, and follow-up hydraulic fracturing forces blasting cracks to propagate further and to form numerous multidirectional hydraulic cracks. Four macroscopic main hydraulic cracks in total were noted along the borehole axial and radial directions on the sample surfaces. Axial and radial main failure planes induced by macroscopic main hydraulic cracks split the sample into three big parts. Meanwhile, numerous local hydraulic cracks were formed on the main failure planes, in different directions and of different types. Local hydraulic cracks are mainly of three types: local hydraulic crack bands, local branched hydraulic cracks, and axial layered cracks. Because local hydraulic cracks produce multiple local layered failure planes and lamellar ruptures inside the sample, the integrity of the sample decreases greatly. The formation and propagation process of many multidirectional hydraulic cracks is affected by a combination of water pressure blasting, water pressure of fracturing, and the stress field of the surrounding rock. To a certain degree, the stress field of surrounding rock guides the formation and propagation process of the blasting crack and the follow-up hydraulic crack. Following hydraulic fracturing that has been conducted after water pressure blasting, the integrity of the sample is found to be far lower than after traditional hydraulic fracturing; moreover, both the water injection volume and water injection pressure for hydraulic fracturing after water pressure blasting are much higher than they are for traditional hydraulic fracturing.     

Hydrogeochemical exploration for barite, Ouachita Mountains, U.S.A.

Approximately 100 springs were sampled as part of a general geochemical survey in a 130 by 140 km multi-mineralized area of the Ouachita Mountains. The study area was subdivided into Area I and Area II based on differences in lithology and mineralization. Area I is composed primarily of the Paleozoic Stanley Shale and the Arkansas Novaculite Formation, and has considerable manganese (often present as psilomelane) and barite mineralization. The barite occurs primarily as replacement deposits in shale in Area I. Area II is composed of Paleozoic and Cretaceous sedimentary rocks, and Quaternary alluvium. Mercury, antimony, strontium and barite mineralization is present. The barite mineralization occurs as cement in the Cretaceous sandstone and gravel in this area.The widely prevalent barite cement in Area II is reflected by higher median and upper range values of barium concentration and also higher median and threshold % BaSO₄ saturation values. The presence of barite as cement in the sediments of Area II tends to mask the detection of the barite deposits in this area. Approximately 83% of the sites within 1.7 km of known barite mineralization in Area I were characterized by anomalous barium concentration, and 67% within 3.4 km. Anomalous % BaSO₄ saturation values and Ba/Sr ratios produced success rates generally similar to those of anomalous barium concentrations. Anomalous strontium concentrations did not prove effective in detecting barite mineralization.     

The role of pore pressure during hydraulic fracturing and implications for groundwater outbursts in mining and tunnelling

Water outbursts from the floor during underground mining, and those from the surrounding rock mass of tunnels, involve the basic principle of hydraulic fracturing. Based on the hydraulic-fracturing mechanism, considered to be dependent on the coupling between seepage and damage, it is deemed that the variation of the pore-fluid pressure coefficient must be taken into account during this coupled process, in order to correctly establish the crack propagation mechanism during hydraulic fracturing. The coupled seepage-damage model is validated using numerical simulations of hydraulic fracturing around one hole and three holes; the model may also enable scientific and reasonable explanation of the dominance of hydraulic gradient on the crack propagation path in permeable rock. Finally, the water outburst from the floor at a coal mining site in Hebei Province, China, is numerically simulated, and the coupled seepage and damage mechanism during the mining-induced rock failure is clarified. The numerical simulation implies that the seepage-damage is the main mechanism for controlling the water outburst. Therefore this mechanism should be considered in the numerical simulation to understand the essence of water outburst induced in mines.     

Rapid barium removal in the Delaware estuary

Six profiles of dissolved barium covering the entire salinity range of the Delaware River and Bay estuary from March through September 1996 were collected and analyzed. The profiles are similar to one another in both shape and magnitude except for one attribute. A sudden (≤24 days), nearly complete (>90%) removal of dissolved Ba in midestuary occurs in mid-May followed by an 80% recovery in early June. This removal appears to be temporally and spatially coupled to the end of the spring bloom. Based on such episodic behavior, and on recent work with flocculation of diatom exudates, we conclude that the Ba depletion is caused by barite precipitation in the estuary during the late stages of the bloom. This would imply that lower estuary and inner coastal margin sediments associated with eutrophic estuaries receive a seasonal pulse of barite. The suddenness of this event also implies that sedimentary barite is strongly influenced by high productivity events.Comparison of the riverine Ba concentration with the effective riverine end member after desorptive barium release yields an estimated 30–40 nM Ba available from the suspended sediments as they enter the estuary. This estimate is supported by excess barium in unfiltered samples over filtered samples taken from the river and also by calculations done elsewhere.     

Linking groundwater quality to residence times and regional geology in the St. Lawrence Lowlands,southern Quebec,Canada

The assessment of groundwater quality in shallow aquifers is of high societal relevance given that large populations depend directly on these water resources. The purpose of this study was to establish links between groundwater quality, groundwater residence times, and regional geology in the St. Lawrence Lowlands fractured bedrock aquifer. The study focuses on a 4500 km² watershed located in the St. Lawrence Lowlands of the province of Quebec in eastern Canada. A total of 150 wells were sampled for major, minor, and trace ions. Tritium (³H) and its daughter element, ³He, as well as radiocarbon activity (A¹⁴C) were measured in a subset of wells to estimate groundwater residence times. Results show that groundwater evolves from a Ca–HCO₃ water type in recharge zones (i.e., the Appalachian piedmont) to a Na–HCO₃ water type downgradient, toward the St. Lawrence River. Locally, barium (Ba), fluoride (F), iron (Fe), and manganese (Mn) concentrations reach 90, 2, 18, and 5.9 mg/L respectively, all exceeding their respective Canadian drinking water limits of 1, 1.5, 0.3, and 0.05 mg/L. Release of these elements into groundwater is mainly controlled by the groundwater redox state and pH conditions, as well as by the geology and the duration of rock–water interactions. This evolution is accompanied by increasing ³H/³He ages, from 4.78 ± 0.44 years upgradient to more than 60 years downgradient. Discrepancies between calculated ³H/³He and ¹⁴C water ages (the latter ranging from 280 ± 56 to 17,050 ± 3410 years) suggest mixing between modern water and paleo-groundwater infiltrated through subglacial recharge when the Laurentide Ice Sheet covered the study area, and during the following deglaciation period. A linear relationship between ³H activity and corrected ¹⁴C versus Mg/Ca and Ba support a direct link between water residence time and the chemical evolution of these waters. The Ba, F, Fe, and Mn concentrations in groundwater originate from Paleozoic rocks from both the St. Lawrence Platform and the Appalachian Mountains. These elements have been brought to the surface by rising hydrothermal fluids along regional faults, and trapped in sediment during their deposition and diagenesis due to reactions with highly sulfurous and organic matter-rich water. Large-scale flow of meltwater during subglacial recharge and during the subsequent retreat of the Laurentide Ice Sheet might have contributed to the leaching of these deposits and their enrichment in the present aquifers. This study brings a new and original understanding of the St. Lawrence Lowlands groundwater system within the context of its geological evolution.     

页岩气开发水力压裂技术综述

世界页岩气资源丰富,但由于页岩地层渗透率很低,目前还没有广泛开发。水力压裂技术是页岩气开发的核心技术之一,广泛用于页岩储层的改造。介绍了水力压裂作业的压裂设计、裂缝监测、压裂液配制和添加剂选择,以及常用的压裂技术,包括多级压裂、清水压裂、同步压裂、水力喷射压裂和重复压裂。结合国外页岩气开发的实例和国内压裂技术的应用情况,分析了各种压裂技术的适用性。研究认为,清水压裂是现阶段中国页岩气开发储层改造的适用技术,开采长度(厚度)大的页岩气井,可以使用多级分段清水压裂技术。同步压裂技术是规模化的页岩气开发的客观需要。     

水劈裂过程中岩体渗透性规律及机理分析

岩体的结构及其透水性直接关系到建筑物围岩的稳定及安全。通过水力劈裂试验,可以真实地反映高水压作用下岩体的结构和渗透性的变化规律。以某水电站工程坝址区岩体所作的水力劈裂试验资料为基础,分析了在水力劈裂过程中,岩体的结构和渗透性发生的变化及其规律以及在该过程中岩体裂隙形成的机理。     

Petrography and textural development of inorganic and biogenic lithotypes in a relict barite tufa deposit at Flybye Springs, NT, Canada

A relict mound of Holocene barite (BaSO₄) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca²⁺ and ≤0·77 wt% Sr²⁺. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.     

Ra/Ra and Ra/Ba ratios in the Western Mediterranean Sea: Barite formation and transport in the water column

²²⁶Ra, ²²⁸Ra and Ba distributions as well as ²²⁸Ra/²²⁶Ra and ²²⁶Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the ²²⁸Ra_ex/²²⁶Ra_ex ratios (Ra_ex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Ba_ex (Ba_ex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high ²²⁸Ra/²²⁶Ra ratio) and formed in the mesopelagic layer (with a low ²²⁸Ra/²²⁶Ra ratio). ²²⁸Ra_ex/²²⁶Ra_ex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High ²²⁶Ra_ex/Ba_ex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in ²²⁶Ra may thus contribute to the decrease in the dissolved ²²⁶Ra activity and ²²⁶Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.