Hydrogeology of the Krafla geothermal system,northeast Iceland

The Krafla geothermal system is located in Iceland's northeastern neovolcanic zone, within the Krafla central volcanic complex. Geothermal fluids are superheated steam closest to the magma heat source, two‐phase at higher depths, and sub‐boiling at the shallowest depths. Hydrogen isotope ratios of geothermal fluids range from ?87‰, equivalent to local meteoric water, to ?94‰. These fluids are enriched in ¹⁸O relative to the global meteoric line by +0.5–3.2‰. Calculated vapor fractions of the fluids are 0.0–0.5 wt% (~0–16% by volume) in the northwestern portion of the geothermal system and increase towards the southeast, up to 5.4 wt% (~57% by volume). Hydrothermal epidote sampled from 900 to 2500 m depth has δD values from ?127 to ?108‰, and δ¹⁸O from ?13.0 to ?9.6‰. Fluids in equilibrium with epidote have isotope compositions similar to those calculated for the vapor phase of two‐phase aquifer fluids. We interpret the large range in δD_EPIDOTE and δ¹⁸O_EPIDOTE across the system and within individual wells (up to 7‰ and 3.3‰, respectively) to result from variable mixing of shallow sub‐boiling groundwater with condensates of vapor rising from a deeper two‐phase reservoir. The data suggest that meteoric waters derived from a single source in the northwest are separated into the shallow sub‐boiling reservoir, and deeper two‐phase reservoir. Interaction between these reservoirs occurs by channelized vertical flow of vapor along fractures, and input of magmatic volatiles further alters fluid chemistry in some wells. Isotopic compositions of hydrothermal epidote reflect local equilibrium with fluids formed by mixtures of shallow water, deep vapor condensates, and magmatic volatiles, whose ionic strength is subsequently derived from dissolution of basalt host rock. This study illustrates the benefits of combining phase segregation effects in two‐phase systems during analysis of wellhead fluid data with stable isotope values of hydrous alteration minerals when evaluating the complex hydrogeology of volcano‐hosted geothermal systems.     

The sources and formation processes of brines from the Lunnan Ordovician paleokarst reservoir,Tarim Basin,northwest China

The most important petroleum exploration target in the Tarim Basin, northwest China, is the paleokarst reservoir. To understand the source and evolution of brine in this type of reservoir, a total of 37 formation‐water samples were collected from the Middle‐Lower Ordovician paleokarst reservoir in the Lunnan oilfield. The δD‐δ¹⁸O correlation and Cl/Br ratios reflect the mixture of two fluids: meteoric water and evaporated seawater. The different degree of mixture divided samples into two groups. Group 1 samples, from deep strata (5150–6667 m.b.s.l.) in the east of the field, with elevated δD (?53.5 to ?38.0‰), δ¹⁸O values (0.66–5.99‰), and lower Cl/Br ratios (336–478 for Cl/Br, except LN634‐1 and LN631‐1) were formed by evaporation of seawater plus a small contribution from meteoric water. Group 2 samples, from shallow strata (5038–6067 m.b.s.l.), in the west of the field, have contrasting features (?59.6 to ?48.5‰ for δD, ?0.47 to 2.17‰ for δ¹⁸O, and 501 to 871 for Cl/Br), which reflect a mixture of evaporated seawater with a high proportion of meteoric water. Both of the fluid types exchanged oxygen isotope with minerals. The investigation into cation composition reveals that, before entering into the current reservoir, waters suffered albitization of plagioclase; moreover, meteoric water dissolved evaporites and seawater experienced dolomitization. A mixing trend showed by strontium isotopes (0.709801–0.711628) gave further evidence for the mixture of two fluid types. Based on the correlation of geological history with our data, two infiltration models of meteoric waters can be constructed. According to the chemical and isotopic compositions of the waters, an east fluid regime (Group 1) and a west fluid regime (Group 2) have thus been defined. Better understanding of the subsurface fluid movement patterns may be helpful for the local exploration.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.     

Temperature‐dependent Li isotope ratios in Appalachian Plateau and Gulf Coast Sedimentary Basin saline water

Lithium (Li) concentrations of produced water from unconventional (horizontally drilled and hydraulically fractured shale) and conventional gas wells in Devonian reservoirs in the Appalachian Plateau region of western Pennsylvania range from 0.6 to 17 mmol kg^?1, and Li isotope ratios, expressed as in δ⁷Li, range from +8.2 to +15‰. Li concentrations are as high as 40 mmol kg^?1 in produced waters from Plio‐Pleistocene through Jurassic‐aged reservoirs in the Gulf Coast Sedimentary Basin analyzed for this study, and δ⁷Li values range from about +4.2 to +16.6‰. Because of charge‐balance constraints and rock buffering, Li concentrations in saline waters from sedimentary basins throughout the world (including this study) are generally positively correlated with chloride (Cl), the dominant anion in these fluids. Li concentrations also vary with depth, although the extent of depth dependence differs among sedimentary basins. In general, Li concentrations are higher than expected from seawater or evaporation of seawater and therefore require water–mineral reactions that remove lithium from the minerals. Li isotope ratios in these produced waters vary inversely with temperature. However, calculations of temperature‐dependent fractionation of δ⁷Li between average shale δ⁷Li (?0.7‰) and water result in δ⁷Li_water that is more positive than that of most produced waters. This suggests that aqueous δ⁷Li may reflect transport of water from depth and/or reaction with rocks having δ⁷Li lighter than average shale.     

Boron isotope geochemistry of Na‐bicarbonate,Na‐chloride,and Ca‐chloride waters from the Northern Apennine Foredeep basin: other pieces of the sedimentary basin puzzle

The boron stable isotope ratio δ¹¹B of 12 water samples representative of three chemical facies (fresh Na‐bicarbonate, brackish Na‐chloride, saline, and brine Ca‐chloride) has been analyzed. Interpretation of the δ¹¹B data, along with the chemical compositions, reveals that Na‐carbonate waters from the Northern Apennine are of meteoric origin, with boron contributions from clay desorption and mixing with seawater‐derived fluids of Na‐chloride or Ca‐chloride compositions. The comparison of our new results with the literature data on other sedimentary basins of Mediterranean, and worldwide, confirms the contribution of Na‐bicarbonate waters to the genesis of mud volcano fluids. The Na‐chloride sample of Salvarola (SAL), which may represent the end‐member of the mud volcanoes, and the Ca‐chloride brine water from Salsomaggiore (SM) indicate boron release from clays compatible with the diagenetic process. The empirical equation: relating boron concentration and the stable isotope composition of the fluids observed in this study and the literature is proposed to trace the effect of diagenesis in sedimentary basins. A geothermometer associated to the diagenetic equation is also proposed: The application of this equation to obtain reservoir temperatures from δ¹¹B compositions of waters should be carefully evaluated against the results obtained from other chemical and isotopic geothermometers from other basins around the world.     

Fracture-fill calcite as a record of microbial methanogenesis and fluid migration: a case study from the Devonian Antrim Shale, Michigan Basin

The Devonian Antrim Shale is an organic‐rich, naturally fractured black shale in the Michigan Basin that serves as both a source and reservoir for natural gas. A well‐developed network of major, through‐going vertical fractures controls reservoir‐scale permeability in the Antrim Shale. Many fractures are open, but some are partially sealed by calcite cements that retain isotopic evidence of widespread microbial methanogenesis. Fracture filling calcite displays an unusually broad spectrum of δ¹³C values (+34 to ?41‰ PDB), suggesting that both aerobic and anaerobic bacterial processes were active in the reservoir. Calcites with high δ¹³C values (>+15‰) record cementation of fractures from dissolved inorganic carbon (DIC) generated during bacterial methanogenesis. Calcites with low δ¹³C values (13C values between ?10 and ?30‰ can be attributed to variable organic matter oxidation pathways, methane oxidation, and carbonate rock buffering. Identification of ¹³C‐rich calcite provides unambiguous evidence of biogenic methane generation and may be used to identify gas deposits in other sedimentary basins. It is likely that repeated glacial advances and retreats exposed the Antrim Shale at the basin margin, enhanced meteoric recharge into the shallow part of the fractured reservoir, and initiated multiple episodes of bacterial methanogenesis and methanotrophic activity that were recorded in fracture‐fill cements. The δ¹⁸O values in both formation waters and calcite cements increase with depth in the basin (?12 to ?4‰ SMOW, and +21 to +27‰ PDB, respectively). Most fracture‐fill cements from outcrop samples have δ¹³C values between ?41 and ?15‰ PDB. In contrast, most cement in cores have δ¹³C values between +15 and +34‰ PDB. Radiocarbon and ²³⁰Th dating of fracture‐fill calcite indicates that the calcite formed between 33 and 390 ka, well within the Pleistocene Epoch.     

Changes in fluid pathways in a calcite vein mesh (Natih Formation,Oman Mountains): insights from stable isotopes

We present a structural, microstructural, and stable isotope study of a calcite vein mesh within the Cretaceous Natih Formation in the Oman Mountains to explore changes in fluid pathways during vein formation. Stage 1 veins form a mesh of steeply dipping crack‐seal extension veins confined to a 3.5‐m‐thick stratigraphic interval. Different strike orientations of Stage 1 veins show mutually crosscutting relationships. Stage 2 veins occur in the dilatant parts of a younger normal fault interpreted to penetrate the stratigraphy below. The δ¹⁸O composition of the host rock ranges from 21.8‰ to 23.7‰. The δ¹³C composition ranges from 1.5‰ to 2.3‰. This range is consistent with regionally developed diagenetic alteration at top of the Natih Formation. The δ¹⁸O composition of vein calcite varies from 22.5‰ to 26.2‰, whereas δ¹³C composition ranges from ?0.8‰ to 2.1‰. A first trend observed in Stage 1 veins involves a decrease of δ¹³C to compositions nearly 1.3‰ lower than the host rock, whereas δ¹⁸O remains constant. A second trend observed in Stage 2 calcite has δ¹⁸O values up to 3.3‰ higher than the host rock, whereas the δ¹³C composition is similar. Stable isotope data and microstructures indicate an episodic flow regime for both stages. During Stage 1, formation of a stratabound vein mesh involved bedding‐parallel flow, under near‐lithostatic fluid pressures. The ¹⁸O fluid composition was host rock‐buffered, whereas ¹³C composition was relatively depleted. This may reflect reaction of low ¹³C CO₂ derived by fluid interaction with organic matter in the limestones. Stage 2 vein formation is associated with fault‐controlled fluid flow accessing fluids in equilibrium with limestones about 50 m beneath. We highlight how evolution of effective stress states and the growth of faults influence the hydraulic connectivity in fracture networks and we demonstrate the value of stable isotopes in tracking changes in fluid pathways.     

Precipitation of fracture fillings and cements in the Buntsandstein (NW Germany)

The relationship between fracturing and fracture filling in opening‐mode fractures in the Triassic Buntsandstein in the Lower Saxony Basin (LSB; NW Germany) has been studied by an integration of petrographic and structural analysis of core samples, strontium isotope analysis and microthermometry on fluid inclusions. This revealed the relationship between the timing of the fracturing and the precipitation of different mineral phases in the fractures by constraining the precipitation conditions and considering the possible fluid transport mechanisms. The core was studied from four different boreholes, located in different structural settings across the LSB. In the core samples from the four boreholes, fractures filled with calcite, quartz and anhydrite were found, in addition to pore‐filling calcite cementation. In boreholes 2 and 3, calcite‐filled fractures have a fibrous microstructure whereas in borehole 1, fractures are filled with elongate‐blocky calcite crystals. Anhydrite‐filled fractures have, in all samples, a blocky to elongate‐blocky microstructure. Fractures that are filled with quartz are observed in borehole 2 only where the quartz crystals are ‘stretched’ with an elongated habit. Fluid inclusion microthermometry of fracturing‐filling quartz crystals showed that quartz precipitation took place at temperatures of at least 140°C, from a fluid with NaCl–CaCl₂–H₂O composition. Melting phases are meta‐stable and suggest growth from high salinity formation water. Strontium isotopes, measured in leached host rock, indicate that, in boreholes 2 and 3, the fluid which precipitated the calcite cements and calcite‐filled fractures is most likely locally derived whereas in borehole 1, the ⁸⁷Sr/⁸⁶Sr ratios from the pore‐filling cements and in the elongate‐blocky calcite‐filled fracture can only be explained by mixing with externally derived fluids. The elongate‐blocky anhydrite‐filled fractures, present in boreholes 1, 3 and 4, precipitated from a mixture of locally derived pore fluids and a significant quantity of fluid with a lower, less radiogenic, ⁸⁷Sr/⁸⁶Sr ratio. Taking into account the structural evolution of the basin and accompanying salt tectonics, it is likely that the underlying Zechstein is a source for the less radiogenic fluids. Based on the samples in the LSB, it is probable that fibrous fracture fillings in sedimentary rocks most likely developed from locally derived pore fluids whereas elongate‐blocky fracture fillings with smooth walls developed from externally derived pore fluids.     

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.     

From deep to shallow fluid reservoirs: evolution of fluid sources during exhumation of the Sierra Almagrera,Betic Cordillera,Spain

The combination of structural, geochemical and palaeotopographic data proves to be an efficient tool to understand fluid transfers in the crust. This study discriminates shallow and deep fluid reservoirs on both sides of the brittle–ductile transition under an extensional regime and points out the role of major transcurrent fault activity in this palaeohydrogeological setting. Palaeofluids trapped in quartz and siderite–barite veins record the transfer of fluids and metal solute species during the Neogene exhumation of the Sierra Almagrera metamorphic belt. Ductile then brittle–ductile extensional quartz veins formed from a deep fluid reservoir, trapping metamorphic secondary brines containing low‐density volatile phases derived from the dissolution of Triassic evaporites. During exhumation, low‐salinity fluids percolated within the brittle domain, as shown by transgranular fluid inclusion planes affecting previous veins. These observations indicate the opening of the system during Serravalian to early Tortonian times and provide evidence for the penetration of surficial fluids of meteoric or basinal origin into the upper part of the brittle–ductile transition. During exhumation, synsedimentary transcurrent tectonic processes occurred from late Tortonian times onwards, while marine conditions prevailed at the Earth's surface. At depth in the brittle domain, quartz veins associated with haematite record a return to high‐salinity fluid circulation suggesting an upward transfer fed from a lower reservoir. During the Messinian, ongoing activity of the trans‐Alboran tectono‐volcanic trend led to the formation of ore deposits. Reducing fluids caused the formation of siderite and pyrite ores. The subsequent formation of galena and barite may be related to an increase of temperature. The high salinity and Cl/Br ratio of the fluids suggest another source of secondary brine derived from dissolved Messinian evaporites, as corroborated by the δ³⁴S signature of barite. These evaporites preceded the main sea‐level drop related to the peak of the salinity crisis (5.60–5.46 Ma).     

Stable Carbon and Oxygen Isotope Spacing Between Bone and Tooth Collagen and Hydroxyapatite in Human Archaeological Remains

Spacing between stable isotope values in bones and teeth is a valuable tool for examining dietary influences and diagenesis. This study examines carbon and oxygen isotope values from collagen and hydroxyapatite (structural carbonate and phosphate) in archaeological human bones and teeth to derive species‐specific correlation equations and isotope spacing values. The δ¹³C_collagen and δ¹³C_{structural carbonate} in bone and dentin collagen show a strong correlation (R = 0.87, 0.90, respectively) with an average Δ¹³C_carb‐coll spacing of 5.4‰. The consistency of this isotope spacing with other large mammals and in humans with both low and high protein intake (as indicated by enriched δ¹⁵N values) suggests a similar allocation of protein‐derived carbon and whole diet‐derived carbon to collagen and structural carbonates, respectively, as other terrestrial mammals regardless of absolute meat intake. The δ¹⁸O_{structural carbonate} and δ¹⁸O_phosphate show the strongest correlation in enamel (R = 0.65), weaker correlations in dentin (R = 0.59) and bone (R = 0.35), with an average Δ¹⁸O_carb‐phos of 7.8‰. This isotope spacing is slightly lower than previously reported for large mammals and limited available data for humans. The results potentially indicate species‐specific fractionations and differing access to body water and blood‐dissolved inorganic carbonates in the presence of collagen formation. The use of correlation between δ¹⁸O_{structural carbonate} and δ¹⁸O_phosphate to determine diagenetic state is not recommended. The strength of this correlation observed in bones and teeth is variable and alternate indicators of diagenetic state (i.e. C:N ratios of collagen) provide more robust and independent evidence of isotope preservation despite presence/absence of a strong isotope correlation. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.     

Fluid environment for preservation of pore spaces in a deep dolomite reservoir

Well TS1 reveals many uncemented pores and vugs at depths of more than 8000 m in a deep Cambrian dolomite reservoir in the Tarim Basin, northwestern China. The fluid environment and mechanism required for the preservation of reservoir spaces have yet not been well constrained. Carbon, oxygen, and strontium isotope compositions and fluid inclusion data suggest two types of fluids, meteoric water and hydrothermal fluid, affecting the Lower Paleozoic carbonate reservoirs in the Tarim Basin. Based on simulation using a thermodynamic model for H₂O‐CO₂‐NaCl‐CaCO₃ system, meteoric water has the ability to continuously dissolve carbonate minerals during downward migration from the surface to deep strata until it reaches a transition depth, below which it will begin to precipitate carbonate minerals to fill preexisting pore spaces. In contrast, hydrothermal fluid has the ability to dissolve carbonate in deep strata and precipitate carbonate in shallow strata during upward migration. Based on the dissolution–precipitation characteristics of the two types of fluids, the ideal fluid environment for the preservation of preexisting reservoir spaces occurs when carbonate reservoir is neither in the CaCO₃ precipitation domain of meteoric water nor in the CaCO₃ precipitation domain of hydrothermal fluid. Taking the Lower Paleozoic carbonate reservoirs in the north uplift area as an example, the spaces in the deep Cambrian dolomite reservoir near well TS1 were seldom filled because thick Ordovician deposits blocked meteoric water from migrating downward into the Cambrian dolomite reservoir and because the Cambrian dolomite reservoir has been in the domain of hydrothermal dissolution since the Permian. The deep carbonate layers in basins elsewhere with a similar fluid environment may have high uncemented porosity and consequently have good hydrocarbon exploration potential.     

Anthropogenic saltpetre: dual (oxygen and nitrogen) isotopic constraints to the biogeochemical processes

Saltpetre constitutes one of the major ingredients of gunpowder, which was a driving force during the political changes in late medieval to early modern times in Japan. Two types of model saltpetre mineralization are studied. One represents efflorescent saltpetre formed as the byproduct of indigo dye manufacture, whereas the second is anthropogenic, derived from relict nitre‐beds. Here, oxygen and nitrogen isotopic analysis, as expressed by δ¹⁸O and δ¹⁵N notations, is applied. The calculated δ¹⁸O values for ambient water, responsible for the microbial‐mediated oxidation of ammonium into oxygen in nitrates, tended to have higher ranges than average local meteoric waters of the relevant regions. An overall trend could be seen, showing the apparent positive nitrogen isotopic fractionation during the microbial transformation from initial organic nitrogen into nitrate product. Dual isotopic analysis for industrial nitrates provides a useful tool for investigation of the provenance of historic gunpowder. Present anthropogenic saltpetre involves positive control over temperature–moisture regimes and oxygen fugacity during formation, the process being distinctive from those prevailed in British India and other European countries.     

Origin of palaeofluids in a normal fault setting in the Aegean region

The province of Burdur (SW Turkey) is seismically an active region. A structural, geochronological, petrographical, geochemical and fluid inclusion study of extension veins and fault‐related calcite precipitates has been undertaken to reconstruct the palaeofluid flow pattern in this normal fault setting in the Aegean region. A palaeostress analysis and U/Th dating of the precipitates reveals the neotectonic significance of the sampled calcites. Fluid inclusion microthermometry of calcites‐filling extension veins shows final melting temperatures (T_m ice) of 0°C. This indicates pure water, most likely of meteoric origin. The oxygen isotope values (?9.8‰ to ?6.5‰ VPDB) and the carbon isotopic composition (?10.4‰ to ?2.9‰ VPDB) of these calcites also show a near‐surface meteoric origin of the fluid responsible for precipitation. The microstructural characteristics of fault‐related calcites indicate that calcite precipitation was linked with fault activity. Final melting temperature of fault‐related calcites ranges between 0 and ?1.9°C. The oxygen isotope values show a broad range between ?15.0‰ and ?2.2‰ VPDB. Several of these calcites have a δ¹⁸O composition that is higher or lower than the oxygen isotopic composition of meteoric calcites in the area (i.e. between ?10‰ and ?6‰ VPDB). The δ¹³C composition largely falls within the range of the host limestones and reflects a rock‐buffered system. Microthermometry and stable isotopic study indicate a meteoric origin of the fluids with some degree of water–rock interaction or mixing with another fluid. Temperatures deduced from microthermometry and stable isotope analyses indicate precipitation temperatures around 50°C. These higher temperatures and the evidence for water–rock interaction indicate a flow path long enough to equilibrate with the host–rock limestone and to increase the temperature. The combined study of extension vein‐ and fault‐related calcite precipitates enables determining the origin of the fluids responsible for precipitation in a normal fault setting. Meteoric water infiltrated in the limestones to a depth of at least 1 km and underwent water–rock interaction or mixing with a residual fluid. This fluid was, moreover, tapped during fault activity. The extension veins, on the contrary, were passively filled with calcites precipitating from the downwards‐migrating meteoric water.     

Thermochemical and bacterial sulfate reduction in the Cambrian and Lower Ordovician carbonates in the Tazhong Area,Tarim Basin,NW China: evidence from fluid inclusions,C, S,and Sr isotopic data

Petrographic features, C, O, S, and Sr isotopes were determined, and fluid inclusions (FI) were analyzed on various stages of vug‐ and fracture‐fillings from the Cambrian and Lower Ordovician reservoirs in the Tazhong area, Tarim basin, NW China. The aim was to assess the origin of pyrite and anhydrite and the processes affecting sulfur during diagenesis of the carbonates. Pyrite from seven wells has δ³⁴S values from ?22‰ to +31‰. The pyrites with low δ³⁴S values from ?21.8‰ to ?12.3‰ were found close to fracture‐filling calcites with vapor‐liquid double‐phase aqueous fluid inclusions homogenization temperatures (FI‐Th) from 55.7 to 73.2°C, salinities from 1.4wt% to 6.59wt% NaCl equiv and δ¹³C values from ?2.3‰ to ?14.2‰, indicating an origin from bacterial sulfate reduction by organic matter. Other sulfides with heavier δ³⁴S values may have formed by thermochemical sulfate reduction (TSR) during two episodes. The earlier TSR in the Middle and Lower Cambrian resulted in pyrites and H₂S having δ³⁴S values from 30 to 33‰, close to those of bedded anhydrite and oilfield water (approximately 34‰). The later TSR is represented by calcites with δ¹³C values as light as ?17.7‰ and FI‐Th of about 120–145°C, and pyrite and H₂S with δ³⁴S values close to those of the Upper Cambrian burial‐diagenetic anhydrite (between +14.8‰ and +22.6‰). The values of the anhydrite are significantly lighter than contemporary seawater sulfates. This together with ⁸⁷Sr/⁸⁶Sr values of anhydrite and TSR calcites from 0.7091 to 0.7125 suggests a source from the underlying Ediacaran seawater sulfate and detrital Sr contribution.     

Residence times and source ages of deep crustal fluids: interpretation of 129I and 36Cl results from the KTB‐VB drill site,Germany

We present here ¹²⁹I/I and ³⁶Cl/Cl ratios, together with halogen concentrations in crustal fluids from the continental deep drill site (KTB‐VB) in Germany, where fluids were collected from 4000 m depth during a pump test carried out in 2002 and 2003. Compared with seawater, the fluids are enriched by factors of 2, 8 and 40 for Cl^?, Br and I, respectively, and show little variation over the test period. The ¹²⁹I/I ratios are between 1700 and 4100 × 10^?15; the ³⁶Cl/Cl ratios are below 10 × 10^?15. Co‐variation between ¹²⁹I and ³⁶Cl concentrations in the fluids indicates that anthropogenic components are absent and that the ratios reflect an addition from crustal sources. The results suggest residence times of 10 Ma or more for the fluids in formations with uranium concentrations of 1 ppm. A minimum age of 30 Ma for the iodine source was derived from the correlation between ¹²⁹I and ³⁶Cl concentrations in the fluids. The results demonstrate that the halogen characteristics of the KTB fluids are very similar to those of other deep crustal fluids and that the combination of ¹²⁹I and ³⁶Cl systematics allows determination of residence times and source ages of such fluids.     

Stable Isotope Record of Human and Sheep Enamel Carbonate from the Ancient Middle Euphrates Valley (Syria)

Stable isotope analyses of human tooth enamel have allowed us to reconstruct the isotope composition of dietary carbon, changes in the oxygen isotope composition of drinking water and the possible migration of humans in ancient Terqa and Tell Masaikh (SE Syria). δ¹⁸O_carbonate values of human tooth enamel from the interval comprising the Neo‐Assyrian to the modern Islamic periods (from 900 BC to AD 1949) generally mirror the isotope composition of Euphrates water, which is believed to have been a major drinking water source. Lower δ¹⁸O_carbonate values of human Bronze Age apatite are linked to a different hydrologic system that was present in the Middle Euphrates valley at that time (2650–1700 BC). Higher δ¹⁸O_carbonate values of some individuals in the Neo‐Assyrian (900–700 BC) and Islamic periods (AD 600–1200) may indicate human migration from the interior of the Near East. Low δ¹³C_carbonate values (−11.3 to −12.4‰) of human tooth enamel from the interval comprising the Early Bronze to the Islamic periods (from 2650 BC to AD 1200) indicate C₃ plants as a predominant source of dietary carbon. Changes in human dietary customs in SE Syria (with inferred usage of C₄ plants) occurred in the modern Islamic period only (AD 1850–1949). Oxygen and carbon isotope data of sheep enamel show the usage of water bodies characterised by an enhanced evaporation rate during the Neo‐Assyrian time (900–700 BC) and grazing sheep herds on drier areas during the Islamic and the modern Islamic periods (after AD 600). Copyright © 2015 John Wiley & Sons, Ltd.     

Human Response to Climate Change during the Umm an‐Nar/Wadi Suq Transition in the United Arab Emirates

Stable oxygen isotope ratios in archaeological human dental enamel represent an under‐utilised tool in the examination of changing climatic patterns in the ancient world. In the Oman Peninsula at the end of the third millennium bc , rapid aridification was accompanied by a breakdown in interregional trade relations; however, the human response to these changes is poorly understood. At the Bronze Age necropolis at Shimal in the United Arab Emirates, dental enamel from individuals interred in both Umm an‐Nar (ca 2700–2000 bc ) and Wadi Suq (ca 2000–1300 bc ) tombs underwent oxygen, strontium and carbon isotope analyses to examine how local inhabitants of southeastern Arabia responded to both environmental and socioeconomic change. While individuals from Shimal exhibit a clear shift in mean δ¹⁸O_c(VPDB) values from the Umm an‐Nar (−3.5 ± 0.6‰, 1σ) to the Wadi Suq (−2.4 ± 0.9‰, 1σ), corresponding ⁸⁷Sr/⁸⁶Sr and δ¹³C_ap signatures display homogeneity indicative of continuity in Bronze Age lifeways. Together, these data highlight the ability of local communities to successfully adapt to their changing environs (in lieu of societal collapse or a shift to a more mobile lifestyle) in an effort to maintain their way of life. Copyright © 2014 John Wiley & Sons, Ltd.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.