Food consumption expenditure pattern of urban households in Bangladesh

Summary The technically recoverable hydrocarbon reserves of the North Sea are currently estimated at 23 × 10⁹ bbls of oil, condensate and NGL and 90 × 10¹² scf of gas.The North Sea underwent a complex geological evolution. The oil and gas occurrences in the central and northern North Sea are tied to Mesozoic and Tertiary sediments; the gas fields of the southern North Sea are mainly contained in Permian series.The proven hydrocarbon provinces cover at best one third of the total area of the North Sea.It is estimated that in the early 1980's the oil production from the North Sea will meet 22% of the oil demand of Western Europe.

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Zusammenfassung Die technisch ausbeutbaren Kohlenwasserstoffreserven der Nordsee werden gegenwärtig auf 23 × 10⁹ bbls Öl, Kondensat und NGL 90 × 10¹² scf Gas geschätzt.Das Nordseegebiet durchlief eine komplexe geologische Entwicklungsgeschichte. Die Öl- und Gasfelder der zentralen und nördlichen Nordsee sind hauptsächlich and mesozoische und tertiäre Sedimente gebunden. Die Gasfelder der südlichen Nordsee sind hauptsächlich in permischen Serien enthalten.Die nachgewiesenen Kohlenwasserstoffprovinzen bedecken höchstens ein Drittel der Gesamtoberfläche der Nordsee.Es wird angenommen, da die Ölproduktion der Nordsee während der ersten Hälfte der 1980er Jahre 22 % des Ölbedarfs von West-Europa decken wird.

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Résumé Les réserves exploitables de la mer du Nord sont actuellement estimées 23 × 10⁹ bbl de pétrole, condensat et NGL et 90 × 10¹² scf de gaz.L'évolution géologique du bassin de la mer du Nord est très complèxe. Les champs de pétrole et de gaz des parties centrales et septentrionales de la mer du Nord se trouvent surtout dans des séries mésozoiques et tertiaires, tandis que la majorité des champs de gaz des régions méridionales sont situés dans des réservoirs permiens.Les provincespetrolfières connues couvrent moins d'un tiers de la surface totale de la mer du Nord.La production de pétrole de la mer du Nord est estimée correspondre pour les premirès années de 1980 à 22 % de la demande en pétrole de l'Europe occidentale.

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Abbreviations scf standard cubic feet (atmospheric conditions at 15° C) - TCF 10¹² scf - bbls barrels - NGL Natural Gas Liquids     

Long-term growth of the oil industry in the United States

A number of growth models have been developed and used in an attempt to project the historical pattern of oil activities to some estimate of their upper limit. Techniques are outlined for the estimation of parameters of the logistic and Gompertz curves. Factor analysis indicated a close relationship between production and demand, whereas annual discoveries and discoveries classified by year of discovery tended to comprise unique factors which were indifferent to changes in time. The growth models projected relatively high values for ultimate demand and production in comparison to the figures for ultimate reserves. Inasmuch as these trends seemed to be occurring independently, some reconciliation of the results was necessary. Using the highest projections of estimates for reserves suggests that over 420 billion barrels of oil in place will eventually be discovered in the United States, with perhaps 200 billion barrels of this eventually to be proved in the form of reserves. Projections for production were higher, corresponding to a trend indicating high levels in demand for crude oil. The only credible long-term estimate of demand was given by a bounded exponential growth model, in which ultimate cumulative demand for crude oil would reach about 416 billion barrels. These figures imply that over 150 billion barrels of oil would be imported into the United States from 1970 to 2070. Provided the time pattern for one of the variables has been determined, then estimates of the other variables probably would be facilitated because of the high interrelationship between variables. Models are suggested in which accurate pivotal forecasting in the short term might be possible—assuming the particular future trend in some of the independent variables has been predetermined.Research Council of Alberta Contribution No. 596.     

冰上丝绸之路与北极油气资源

油气是重要的战略资源。其中天然气作为清洁能源,它曾经是,现在是,在可预期的未来——全球碳减排、中国碳达峰情景下,仍然是最重要的能源资源。能源进口渠道的多元化一直是中国缓解能源紧张的有效措施之一。北极地区油气资源丰富且以天然气为主,已发现的油气资源中绝大多数在俄罗斯,尤其是天然气。但是俄罗斯天然气生产的油气田80%以上已经进入北极圈。2012年,中俄合作开发北极亚马尔液化天然气项目正式启动,标志着中国参与北极油气资源开发利用取得重要进展,也事实上开启了中国主导的"丝绸之路经济带建设"和俄罗斯主导的"欧亚经济联盟建设"对接合作的进程。北极地区已发现的油气资源共计3289.4亿桶油当量,其中石油605.4亿桶（84.1亿吨）油当量,仅为全球已发现石油资源的2.5%;天然气41.4万亿立方米（约合2683亿桶,372.6亿吨油当量）,占全球已发现天然气资源的15.5%。北极地区已发现的油气总资源中绝大多数在俄罗斯,俄罗斯已发现的北极油气资源合计2905亿桶油当量（403.5亿吨）,占88.3%;其中天然气约39.47万亿立方米,约合2557.9亿桶（355.3亿吨）油当量,占北极地区已发现天然气总资源的95%以上。北极待发现的油气资源量也非常可观,约占世界待发现常规石油资源的15%;天然气占世界待发现常规天然气资源的30%,其分布也主要在俄罗斯。随着全球气候变暖和能源战略博弈,俄罗斯为确保其天然气出口及财政来源,必然要加大北极油气、特别是天然气的开采和开发,并通过北极航道运到中国和其他消费国。本文在概括分析北极油气资源分布特点、俄罗斯油气资源与北极战略及北方海航道通行能力的基础上,回顾了北极亚马尔液化天然气项目诞生、发展演变及其国际博弈的背景;概括介绍了中国成功介入北极油气资源项目这一标志性事件过程,并进一步提出了中国对北极油气资源利用战略举措的建议。      

Polygenic formation model of the planet’s bituminous belts

In recent years, much attention has been paid to nontraditional hydrocarbon sources. Today the portion of nontraditional gas in the world extraction is 15% or 450 billion cubic meters, which hat makes up the volume of total gas exports from Russia. As is known, the easy-prospecting oil has been already found. The innovative technologies in geophysics, drilling, and excavation and the increased extraction coefficient expect further development and industrial compliance with these requirements. Based on calculations, the world oil reserves are now one trillion of stock tank barrels and one trillion barrels have been already extracted. The evergrowing demand for energy gives rise to the necessity of searching for and extracting more oil resources, and both these aspects are unique problems. The search for profitable petroleum deposits has become more and more difficult even in the leading companies. The increment of the world resources is a key vital question; therefore, the elaboration of criteria for the discovery of nontraditional deposits take on special significance in the economic respect. The authors are working out a conception that will be a guideline for future finding of the richest oil deposits in active geodynamic zones. For the first time, we suggest the polygenic formation model of the planet’s bituminous belts.     

Contribution to study of evolution of the folding process within the tectonic cycle

Afghanistan consists largely of a series of continental fragments that, moving northward, docked and accreted to the southern proto-Asia continent. The tectonization of the accreted terranes is generally severe and petroleum prospects are limited essentially to the 48,000 mi² (124,000 km²) North Afghanistan basin. This basin represents the Afghan portion of the Turanian platform, plus the orogenic belt around its southern and eastern perimeter. Exploration to date is judged to be preliminary in character, with some 5 trillion cubic feet (TCF) of gas and 80 million barrels of oil being discovered by 1980. There are two types of traps: Mesozoic low-amplitude drapes or tilted fault blocks, and Neogene highamplitude folds. Appreciable reservoirs are limited to three horizons—Upper Jurassic, Lower Cretaceous, and Paleogene—of which the Lower Cretaceous is considered to be the best. Source rock is confined largely to the Lower and Middle Jurassic shales. Upper Jurassic evaporites form a barrier between the Jurassic source shales and the Lower Cretaceous reservoirs and Neogene folds. There appear to be five principal plays, and estimated total recoverable petroleum in them is 300 million barrels of oil, 9.6 TCF of gas, and 145 million barrels of condensate.     

Origin and quantitative source assessment of deep oils in the Tazhong Uplift,Tarim Basin

A large amount of deep oil has been discovered in the Tazhong Uplift, Tarim Basin whereas the oil source is still controversial. An integrated geochemical approach was utilized to unravel the characteristics, origin and alteration of the deep oils. This study showed that the Lower Cambrian oil from well ZS1C (

_1x) was featured by small or trace amounts of biomarkers, unusually high concentration of dibenzothiophenes (DBTs), high δ³⁴S of DBTs and high δ¹³C value of n-alkanes. These suggest a close genetic relationship with the Cambrian source rocks and TSR alteration. On the contrary, the Middle Cambrian oils from well ZS1 (

_2a) were characterized by low δ¹³C of n-alkanes and relatively high δ³⁴S of individual sulfur compounds and a general “V” shape of steranes, indicating a good genetic affinity with the Middle–Upper Ordovician source rocks. The middle Cambrian salt rock separating the oils was suggested to be one of the factors responsible for the differentiation. It was suggested that most of the deep oils in the Tazhong Uplift were mixed source based on biomarkers and carbon isotope, which contain TSR altered oil in varied degree. The percentage of the oils contributed by the Cambrian–Lower Ordovician was in the range of 19–100% (average 57%) controlled by several geological and geochemical events. Significant variations in the δ³⁴S values for individual compounds in the oils were observed suggesting a combination of different extent of TSR and thermal maturation alterations. The unusually high DBTs concentrations in the Tazhong-4 oilfield suggested as a result of mixing with the ZS1C oil (

_1x) and Lower Ordovician oils based on δ³⁴S values of DBT. This study will enhance our understanding of both deep and shallow oil sources in the Tazhong Uplift and clarify the formation mechanisms of the unusually high DBTs oils in the region.     

Estimating long-term soil respiration rates from carbon isotopes occluded in gibbsite

Carbon occluded in the soil gibbsite crystal structure at the Panola Mountain Research Watershed, Georgia, U.S. is presumed to be in isotopic equilibrium with the CO₂ respired from soil organics by microbes and plant roots. Fitting of the stable carbon isotopic data to a Fickian diffusion-based depth function results in an estimate of 47 gC m⁻² y⁻¹ for the long-term soil respiration rate. A numerical model that includes depth-dependent production and diffusion terms results in estimates of 28-12 gC m⁻² y⁻¹. These values range from 15 to 50 times less than the average of modern values for mixed deciduous forests in wet temperate climates. This disparity has several implications for our understanding of the geologic record of climate change, which include: (1) evidence for a cooler and seasonally drier climate during the mid-Holocene in the southeastern U.S., or (2) fluxes of carbon from the soil pool as recorded by soil mineral proxies (i.e., long-term soil respiration rates) under estimate atmosphere annual carbon flux measurements (i.e., short-term measures), and (3) the need to refine soil respiration models used to relate paleosol stable carbon isotopic measurements to paleo-atmospheric estimates.     

Arsenic, iron and sulfur co-diagenesis in lake sediments

Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (ΣS^−II), total zero-valent sulfur (ΣS⁰), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (). The model defines depth intervals where As is either released to (positive ) or removed from (negative ) the porewaters.At two of the sites, whose bottom water were oxygenated at sampling time, a production zone ( = 12 × 10⁻¹⁸ mol cm⁻³ s⁻¹-71 × 10⁻¹⁸ mol cm⁻³ s⁻¹) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption ( = −5 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −53 × 10⁻¹⁸ mol cm⁻³ s⁻¹), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant of 0.12 ± 0.03 cm³ mol⁻¹ s⁻¹ is estimated for this adsorption reaction.Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., ΣS^−II ? 0.1 μM), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of As^V oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As ( = −1 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −23 × 10⁻¹⁸ mol cm⁻³ s⁻¹) consistently occurred when saturation, with respect to FeS_(s), was reached and when As^V oxythioanions were predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments.     

Oxidation of Sb(III) to Sb(V) by O2 and H2O2 in aqueous solutions

The rates of Sb(III) oxidation by O₂ and H₂O₂ were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O₂ was first order with respect to the Sb(III) concentration and inversely proportional to the H⁺ concentrations at a constant O₂ content of 0.22 × 10⁻³ M. Pseudo-first-order rate coefficients, k_obs, ranged from 3.5 × 10⁻⁸ s⁻¹ to 2.5 × 10⁻⁶ s⁻¹ at pH values between 10.9 and 12.9. The relationship between k_obs and pH was:

     

Grain boundary partitioning of Ar and He

An experimental procedure has been developed that permits measurement of the partitioning of Ar and He between crystal interiors and the intergranular medium (ITM) that surrounds them in synthetic melt-free polycrystalline diopside aggregates. ³⁷Ar and ⁴He are introduced into the samples via neutron irradiation. As samples are crystallized under sub-solidus conditions from a pure diopside glass in a piston cylinder apparatus, noble gases diffusively equilibrate between the evolving crystal and intergranular reservoirs. After equilibration, ITM Ar and He is distinguished from that incorporated within the crystals by means of step heating analysis. An apparent equilibrium state (i.e., constant partitioning) is reached after about 20 h in the 1450 °C experiments. Data for longer durations show a systematic trend of decreasing ITM Ar (and He) with decreasing grain boundary (GB) interfacial area as would be predicted for partitioning controlled by the network of planar grain boundaries (as opposed to ITM gases distributed in discrete micro-bubbles or melt). These data yield values of GB-area-normalized partitioning, , with units of (Ar/m³ of solid)/(Ar/m² of GB) of 6.8 × 10³-2.4 × 10⁴ m⁻¹. Combined petrographic microscope, SEM, and limited TEM observation showed no evidence that a residual glass phase or grain boundary micro-bubbles dominated the ITM, though they may represent minor components. If a nominal GB thickness (δ) is assumed, and if the density of crystals and the grain boundaries are assumed equal, then a true grain boundary partition coefficient , may be determined. For reasonable values of δ, is at least an order of magnitude lower than the Ar partition coefficient between diopside and melt. Helium partitioning data provide a less robust constraint with between 4 × 10³ and 4 × 10⁴ cm⁻¹, similar to the Ar partitioning data. These data suggest that an ITM consisting of nominally melt free, bubble free, tight grain boundaries can constitute a significant but not infinite reservoir, and therefore bulk transport pathway, for noble gases in fine grained portions of the crust and mantle where aqueous or melt fluids are non-wetting and of very low abundance (i.e., <0.1% fluid). Heterogeneities in grain size within dry equilibrated systems will correspond to significant differences in bulk rock noble gas content.     

Geochemical features and origin of natural gas in heavy oil area of the Western Slope,Songliao Basin,China

The Western Slope of the Songliao Basin is rich in heavy oil resources (>70 × 10⁸ bbl), around which there are shallow gas reservoirs (∼1.0 × 10¹² m³). The gas is dominated by methane with a dryness over 0.99, and the non-hydrocarbon component being overwelmingly nitrogen. Carbon isotope composition of methane and its homologs is depleted in ¹³C, with δ¹³C₁ values being in the range of −55‰ to −75‰, δ¹³C₂ being in the range of −40‰ to −53‰ and δ¹³C₃ being in the range of −30‰ to −42‰, respectively. These values differ significantly from those solution gases source in the Daqing oilfield. This study concludes that heavy oils along the Western Slope were derived from mature source rocks in the Qijia-Gulong Depression, that were biodegraded. The low reservoir temperature (30–50 °C) and low salinity of formation water with neutral to alkaline pH (NaHCO₃) appeared ideal for microbial activity and thus biodegradation. Natural gas along the Western Slope appears mainly to have originated from biodegradation and the formation of heavy oil. This origin is suggested by the heavy δ¹³C of CO₂ (−18.78‰ to 0.95‰) which suggests that the methane was produced via fermentation as the terminal decomposition stage of the oil.     

阿拉斯加北坡区域地质演化及油气资源

在收集国内外资料的基础上, 分析研究阿拉斯加北坡地区的构造演化过程, 地层序列及演化阶段, 并对本区石油勘探历史, 地质特征和油气资源进行了总结。确定了4个主要地层序列, 分别为富兰克林层序(密西西比系之下), 埃尔斯米尔层序(密西西比系-三叠系), 波弗特层序(侏罗系-下白垩统)和布鲁克斯层序(下白垩统-第四系)。阿拉斯加北坡地区经历了比较复杂的演化过程, 北坡盆地即位于此。盆地主要经历了3个演化阶段, 分别为埃尔斯米尔造山阶段、同裂谷阶段和前陆阶段。本区具有石油远景的岩石大多在密西西比纪及之后的地层中, 它们记录了整个被动大陆边缘、裂谷和前陆盆地构造阶段地层序列和地质方面的演化。本区油气潜力巨大, 勘探历史悠久。石油和天然气的未探明储量分别为244.9×108桶和2.905×1012 m3, 页岩油约9.4×108桶, 页岩气约1.19×1012 m3。      

Calcium and magnesium isotope systematics in rivers draining the Himalaya-Tibetan-Plateau region: Lithological or fractionation control?

In rivers draining the Himalaya-Tibetan-Plateau region, the ²⁶Mg/²⁴Mg ratio has a range of 2‰ and the ⁴⁴Ca/⁴²Ca ratio has a range of 0.6‰. The average δ²⁶Mg values of tributaries from each of the main lithotectonic units (Tethyan Sedimentary Series (TSS), High Himalayan Crystalline Series (HHCS) and Lesser Himalayan Series (LHS)) are within 2 standard deviation analytical uncertainty (0.14‰). The consistency of average riverine δ²⁶Mg values is in contrast to the main rock types (limestone, dolostone and silicate) which range in their average δ²⁶Mg values by more than 2‰. Tributaries draining the dolostones of the LHS differ in their values compared to tributaries from the TSS and HHCS. The chemistry of these river waters is strongly influenced by dolostone (solute Mg/Ca close to unity) and both δ²⁶Mg (−1.31‰) and (0.64‰) values are within analytical uncertainty of the LHS dolostone. These are the most elevated values in rivers and rock reported so far demonstrating that both riverine and bedrock values may show greater variability than previously thought.Although rivers draining TSS limestone have the lowest values at −1.41 and 0.42‰, respectively, both are offset to higher values compared to bedrock TSS limestone. The average δ²⁶Mg value of rivers draining mainly silicate rock of the HHCS is −1.25‰, lower by 0.63‰ than the average silicate rock. These differences are consistent with a fractionation of δ²⁶Mg values during silicate weathering. Given that the proportion of Mg exported from the Himalaya as solute Mg is small, the difference in ²⁶Mg/²⁴Mg ratios between silicate rock and solute Mg reflects the ²⁶Mg/²⁴Mg isotopic fractionation factor () between silicate and dissolved Mg during incongruent silicate weathering. The value of of 0.99937 implies that in the TSS, solute Mg is primarily derived from silicate weathering, whereas the source of Ca is overwhelmingly derived from carbonate weathering. The average value in HHCS rivers is within uncertainty of silicate rock at 0.39‰. The widespread hot springs of the High Himalaya have an average δ²⁶Mg value of −0.46‰ and an average value of 0.5‰, distinct from riverine values for δ²⁶Mg but similar to riverine values. Although rivers draining each major rock type have and δ²⁶Mg values in part inherited from bedrock, there is no correlation with proxies for carbonate or silicate lithology such as Na/Ca ratios, suggesting that Ca and Mg are in part recycled. However, in spite of the vast contrast in vegetation density between the arid Tibetan Plateau and the tropical Lesser Himalaya, the isotopic fractionation factor for Ca and Mg between solute and rocks are not systematically different suggesting that vegetation may only recycle a small amount of Ca and Mg in these catchments.The discrepancy between solute and solid Ca and Mg isotope ratios in these rivers from diverse weathering environments highlight our lack of understanding concerning the origin and subsequent path of Ca and Mg, bound as minerals in rock, and released as cations in rivers. The fractionation of Ca and Mg isotope ratios may prove useful for tracing mechanisms of chemical alteration. Ca isotope ratios of solute riverine Ca show a greater variability than previously acknowledged. The variability of Ca isotope ratios in modern rivers will need to be better quantified and accounted for in future models of global Ca cycling, if past variations in oceanic Ca isotope ratios are to be of use in constraining the past carbon cycle.     

Solubility of NaCl in CO2 at high pressure and temperature: First experimental measurements

NaCl solubility in gaseous carbon dioxide has been measured in the pressure range from 30 to 70 MPa at 623 and 673 K. Our originally-designed high pressure apparatus allows in situ sampling of a portion of the fluid phase for chemical analysis. The results indicate that the solubility of NaCl increases with both temperature and pressure, and is about 4-5 orders of magnitude higher than saturated NaCl pressure values at the same temperature conditions (6.02 × 10⁻¹² at 623 K and 1.51 × 10⁻¹⁰ at 673 K). It is also 1-2 orders of magnitude greater than predictions according to the Equation of State of the ternary H₂O-CO₂-NaCl system by Duan, Moeller and Weare [Duan, Z., Moller, N., and Weare, J. H. (1995) Equation of state for the NaCl-H₂O-CO₂ system: prediction of phase equilibria and volumetric properties. Geochim. Cosmochim. Acta59, 2869] and has the opposite pressure dependence. The activity values of NaCl in the vapor phase, calculated from the experiments (with pure molten NaCl as a standard state in the vapor), have been fitted to the Darken Quadratic Formalism: , where, x_NaCl,v is mole the fraction of NaCl in the vapor phase, , , where P is the pressure in MPa and T the absolute temperature. Caution should be exerted while extrapolating this empirical equation far beyond the experimental P-T-compositional range.     

Re-assessing the surface cycling of molybdenum and rhenium

We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg⁻¹ (Mo), and 16.5 pmol kg⁻¹ (Re, natural + anthropogenic). The linear relationship of dissolved Re and in global rivers (R² = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg⁻¹. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03-5.9 pmol kg⁻¹), and the nmol kg⁻¹ level Re concentrations of mine waters. The linear Mo- relationship (R² = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10⁵ yr (τ_Mo) and 1.3 × 10⁵ yr (τ_Re, pre-anthropogenic).     

Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in ¹⁸O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in ¹⁸O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens’ δ¹³C values are mainly controlled by seasonal variations in δ¹³C_DIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope ‘vital effects’ in ostracods. Two mechanisms that might enrich the ¹⁸O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.     

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H⁺ and Al³⁺ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10⁻⁶ molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F⁻, and major complexes (, AlF²⁺, and ) account for more than 95% of total fluoride. Occasionally, some complex species like , FeF²⁺, , MgF⁺ and may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.     

Gold and copper partitioning in magmatic-hydrothermal systems at 800 °C and 100 MPa

Porphyry-type ore deposits sometimes contain fluid inclusion compositions consistent with the partitioning of copper and gold into vapor relative to coexisting brine at the depositional stage. However, this has not been reproduced experimentally at magmatic conditions. In an attempt to determine the conditions under which copper and gold may partition preferentially into vapor relative to brine at temperatures above the solidus of granitic magmas, we performed experiments at 800 °C, 100 MPa, oxygen fugacity () buffered by Ni-NiO, and fixed at either 3.5 × 10⁻² by using intermediate solid solution-pyrrhotite, or 1.2 × 10⁻⁴ by using intermediate solid solution-pyrrhotite-bornite. The coexisting vapor (∼3 wt.% NaCl eq.) and brine (∼68 wt.% NaCl eq.) were composed initially of NaCl + KCl + HCl + H₂O, with starting HCl set to <1000 μg/g in the aqueous mixture. Synthetic vapor and brine fluid inclusions were trapped at run conditions and subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Our experiments demonstrate that copper and gold partitioned strongly into the magmatic volatile phase(s) (MVP) (i.e., vapor or brine) relative to a silicate melt over the entire imposed range of . Nernst style partition coefficients between coexisting brine (b) and melt (m), D^b/m (±1σ), range from 3.6(±2.2) × 10¹ to 4(±2) × 10² for copper and from 1.2(±0.6) × 10² to 2.4(±2.4) × 10³ for gold. Partition coefficients between coexisting vapor (v) and melt, D^v/m range from 2.1 ± 0.7 to 18 ± 5 and 7(±3) × 10¹ to 1.6(±1.6) × 10² for copper and gold, respectively. Partition coefficients for all experiments between coexisting brine and vapor, D^b/v (±1σ), range from 7(±2) to 1.0(±0.4) × 10² and 1.7(±0.2) to 15(±2) for copper and gold, respectively. Observed average D^b/v at an of 1.2 × 10⁻⁴ were elevated, 95(±5) and 15 ± 1 for copper and gold, respectively, relative to those at the higher of 3.5 × 10⁻² where D^b/v were 10(±5) for copper and 7(±6) for gold. Thus, there is an inverse relationship between the and the D^b/v for both copper and gold with increasing resulting in a decrease in the D^b/v signifying increased importance of the vapor phase for copper and gold transport. This suggests that copper and gold may complex with volatile S-species as well as Cl-species at magmatic conditions, however, none of the experiments of our study at 800 °C and 100 MPa had a D^b/v ? 1. We did not directly determine speciation, but infer the existence of some metal-sulfur complexes based on the reported data. We suggest that copper and gold partition preferentially into the brine in most instances at or above the wet solidus. However, in most systems, the mass of vapor is greater than the mass of brine, and vapor transport of copper and gold may become more important in the magmatic environment at higher , lower , or near the critical point in a salt-water system. A D^b/v ? 1 at subsolidus hydrothermal conditions may also occur in response to changes in temperature, , , and/or acidity.Additionally, both copper and gold were observed to partition into intermediate solid solution and bornite much more strongly than into vapor, brine or silicate melt. This suggests that, although vapor and brine are both efficient at removing copper and gold from a silicate melt, the presence of Cu-Fe sulfides can sequester a substantial portion of the copper and gold contained within a silicate melt if the Cu-Fe sulfides are abundant.