Formation of pockmarks and submarine canyons associated with dissociation of gas hydrates on the Joetsu Knoll,eastern margin of the Sea of Japan

This study, based on 3.5 kHz SBP, 3D seismic data and long piston cores obtained during MD179 cruise, elucidated the timing and causes of pockmark and submarine canyon formation on the Joetsu Knoll in the eastern margin of the Sea of Japan. Gas hydrate mounds and pockmarks aligned parallel to the axis on the top of the Joetsu Knoll are associated with gas chimneys, pull-up structures, faults, and multiple bottom-simulating reflectors (BSRs), suggesting that thermogenic gas migrated upward through gas chimneys and faults from deep hydrocarbon sources and reservoirs. Seismic and core data suggest that submarine canyons on the western slope of the Joetsu Knoll were formed by turbidity currents generated by sand and mud ejection from pockmarks on the knoll. The pockmark and canyon formation probably commenced during the sea-level fall, lasting until transgression stages. Subsequently, hydropressure release during the sea level lowering might have instigated dissociation of the gas hydrate around the base of the gas hydrate, leading to generation and migration of large volumes of methane gas to the seafloor. Accumulation of hydrate caps below mounds eventually caused the collapse of the mounds and the formation of large depressions (pockmarks) along with ejection of sand and mud out of the pockmarks, thereby generating turbidity currents. Prolonged pockmark and submarine canyon activities might have persisted until the transgression stage because of time lags from gas hydrate dissociation around the base of the gas hydrate until upward migration to the seafloor. This study revealed the possibility that submarine canyons were formed by pockmark activities. If that process occurred, it would present important implications for reconstructing the long-term history of shallow gas hydrate activity based on submarine canyon development.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Submarine landslide identified in MD179 cores,off-Joetsu area,eastern margin of the Sea of Japan

Gas hydrate is exposed on the sea floor and is buried in shallow sediments in the off-Joetsu area at the eastern margin of the Sea of Japan. Sediment cores recovered from topographic highs of the Joetsu Knoll and Umitaka Spur show pockmarks and mounds formed by gas hydrate dissociation, but those from the Un-named ridge have no such topographic features. All topographic highs and pockmarks mainly comprise bioturbated layers interbedded with thinly laminated (TL) layers, which are common Sea of Japan sediments. Recovered sediments are, however, mostly disturbed by submarine landslides, showing tilted horizons, faults, slump folds, and breccia, except that from the Un-named ridge. The timing of events is well constrained by identification of the number of TL layers in some sediment cores. Landslides occurred both during the cold glacial period of the late MIS3 to the last glacial maximum (LGM) and during the warm interglacial period of the post-LGM. All were caused by the explosive rise of gas hydrate formed at very shallow depths of the sea bottom by the supply of gas from the depth of the gas hydrate stability zone through gas chimney passages developed under the pockmarks. Seismic activity demands consideration as a factor because the off-Joetsu area is tectonically active.     

Origin,distribution and hydrogeochemical controls on methane occurrences in shallow aquifers,southwestern Ontario,Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ¹³C of CH₄, C₂, C₃, and CO₂, and δD of CH₄. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH₄ (29.7–98.6 mol% of total gas volume), N₂ (0.8–66.2 mol%), Ar + O₂ (0.2–3.4 mol%), and CO₂ (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH₄. The relatively low δ¹³C values of CH₄ (−89.9‰ to −57.3‰), covariance of δD values of CH₄ and H₂O, positive correlation between δ¹³C values of CH₄ and CO₂, and lack of higher chain hydrocarbons (C₃₊) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO₃, SO₄), in addition to organic substrates, controls the occurrence of microbial CH₄ in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH₄ (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H₂O).     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Regional evaluation of the coalbed-methane potential of the Foothills/Mountains of Alberta,Canada

Coal is present in the Alberta Foothills/Mountains in five zones: the Kootenay, Gething, Gates, Brazeau and Coalspur coal zones. For coalbed-methane (CBM) evaluation purposes, they can be divided into shallow (less than 1000 m depth) and deep (greater than 1000 m depth) coal zones. The potential gas content of all shallow coal zones totals about 878 × 10⁹ m³ (31 Tcf) of CBM, which is considered an inferred, initial, in-place, coalbed-methane resource estimate based on limited data. The limited amount of data on formation testing and measured gas content indicate that the inferred resource is bordering on the speculative category.The gas content of all deep coal zones (deeper than 1000 m) totals 2.8 × 10¹² m³ (about 99 Tcf) of in-place coalbed-methane gas. Consequently, the total ultimate coalbed-methane resource could be 3.7 × 10¹² m³ (130 Tcf). However, coalbed-methane recovery from deep coals is generally not attempted because of the high cost of drilling and the low permeability that results from high overburden load and stress.The only (limited) Foothills coalbed-methane production has been from the southern Alberta Kootenay Coal Zone, which is very prospective for coalbed-methane production. The shallow Gates Coal Zone in the central and northern Foothills is also prospective, but needs to be better tested. The best potential for coalbed methane in the Coalspur Coal Zone is in the Edson area (Entrance Syncline and Triangle Zone). The Kootenay and Gates coal zones are not well defined in the northern part of the Calgary (NTS 82O) map sheet.     

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S,Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H₂S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (?²H_H2O = 7.6–8.7‰) and of oxygen (?¹⁸O_H2O = 2.2–2.4‰).The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (?²H_H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR.The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ?²H_H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5.The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.     

An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in ¹³C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C₁ in C_1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C₂/C₃) vs. δ¹³C₂–δ¹³C₃ and δ¹³C₁ vs. δ¹³C₂–δ¹³C₃, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C_1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C_1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C_1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C_1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of ¹³C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.     

Helium–carbon relationships in geothermal fluids of western Anatolia,Turkey

We investigate the helium, carbon and oxygen–hydrogen isotopic systematics and CO₂/³He ratios of 8 water and 6 gas samples collected from 12 geothermal fields in western Anatolia (Turkey). ³He/⁴He ratios of the samples (R) normalized to the atmospheric ³He/⁴He ratio (R_A = 1.39 × 10^? 6) range from 0.27 to 1.67 and are significantly higher than the crustal production value of 0.05. Fluids with relatively high R / R_A values are generally found in areas of significant heat potential (K?z?ldere and Tuzla fields). CO₂/³He ratios of the samples, ranging from 1.6 × 10⁹ to 2.3 × 10¹⁴, display significant variation and are mostly higher than values typical of an upper mantle source (2 × 10⁹). The δ¹³C (CO₂) and δ¹³C (CH₄) values of all fluids vary from ? 8.04 to + 0.35‰ and ? 25.80 to ? 23.92‰ (vs. PDB), respectively. Stable isotope values (δ¹⁸O–δD) of the geothermal waters are conformable with the Mediterranean Meteoric Water Line and indicate a meteoric origin. The temperatures calculated by gas geothermometry are significantly higher than estimates from chemical geothermometers, implying that either equilibrium has not been attained for the isotope exchange reaction or that isotopic equilibration was disturbed due to gas additions en route to the surface.Evaluation of He–CO₂ abundances indicates that hydrothermal degassing and calcite precipitation (controlled probably by adiabatic cooling due to degassing) significantly fractionate the elemental ratio (CO₂/³He) in geothermal waters. Such processes do not affect gas phase samples to anywhere near the same extent. For the gas samples, mixing between mantle and various crustal sources appears to be the main control on the observed He–C systematics: however, crustal inputs dominate the CO₂ inventory. Considering that limestone is the main source of carbon (～ 70 to 97% of the total carbon inventory), the carbon flux from the crust is found to be at least 20 times that from the mantle. As to the He-inventory, the mantle-derived component is found to vary up to 21% of the total He content and is probably transferred to the crust by fluids degassed from deep mantle melts generated in association with the elevated geotherm and adiabatic melting accompanying current extension. The range of ³He/enthalpy ratios (0.000032 to 0.19 × 10^? 12 cm³ STP/J) of fluids in western Anatolia is consistent with the release of both helium and heat from contemporary additions of mantle-derived magmas to the crust. The deep faults appear to have facilitated the deep circulation of the fluids and the transport of mantle volatiles and heat to the surface.     

Origin of a barite-sulfide ore deposit in the Mykonos intrusion,cyclades: Trace element,isotopic, fluid inclusion and raman spectroscopy evidence

The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H₂S and SO₂.Calculated δ¹⁸O_H2O and δD_H2O, initial ⁸⁷Sr/⁸⁶Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ³⁴S_SO4^− 2 and δ³⁴S_H2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO₄^− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logf_S2 = − 13.8 to − 12.5, logf_O2 = − 31.9 to − 30.9, logf_H2S(g) = − 1.9 to − 1.7, logf_Te2 = − 7.9 and logα(SO₄^− 2_(aq)/H₂S_(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO₄^− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.     

Iodine as a tracer of organic material: I results from gas hydrate systems and fore arc fluids

The strong association of iodine with organic material and the presence of the cosmogenic radioisotope ¹²⁹I make the iodine isotopic system useful in tracing and dating organic materials and their derivatives. We present here results from two new applications of this system, investigations of gas hydrates from the Peru Margin (ODP Leg 201, Site 1230) and of fluids collected from the fore arc region of the North Island, New Zealand. Pore fluids from Site 1230 are strongly enriched in iodine and show a distinct decrease in ¹²⁹I/I ratios from 920 × 10^− 15 close to the surface to 140 × 10^− 15 at a depth of 200 mbsf, suggesting the presence of a shallow, young source and deep, old source of fluids. The fore arc fluids from New Zealand are also enriched in iodine and show a similar range in ¹²⁹I/I ratios. In both cases minimum ages are calculated to be between 40 and 60 Ma for these fluids. The results are in good agreement with earlier investigations of gas hydrate systems at Blake Ridge and Nankai Trough and of fore arc fluids from Central America and Japan, but are not compatible with derivation from subducting sediments in active margins. The results indicate that continental margins contain large amounts of old iodine, reflecting the presence of large quantities of organic material stored in these regions. Results for gas hydrate systems and fore arc fluids show similar characteristics, but differ strongly from those obtained for fluids collected from the main zones of volcanic activity associated with active margins.     

Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

The origins of the Mengye potash deposit in the Lanping–Simao Basin,Yunnan Province,Western China

The Lanping–Simao Basin (LSB) is a Mesozoic–Cenozoic continental margin rift basin in Western China. It formed during the opening and closing of the Tethys Ocean. This basin is also known as a “metal belt” as it hosts several metal deposits, besides, the Mengye potash deposit. However, the exact dates of the formation either in the Paleocene or the Cretaceous, and thus the origins of the marine, continental or mixed origins of the Mengye deposits, remain disputed. Based on the basin's evolution, materials of marine origin and/or remnant seawater should be present, but instead the salt layers of the Mengye potash deposit present typically continental lithological features. This study examines and reviews evaporative minerals, Br/Cl and I/Cl molar ratios, and isotopes of S, B, and Sr·I and I/Cl data for this area has not been previously reported. The basin's evaporative minerals are dominated by halite and sylvite. The amounts of anhydrite, chlorocalcite, langbeinite, glaserite, tachyhydrite and glauberite are small. All of these form in both marine and continental environments. The values of I and the I/Cl molar ratios of halite and sylvite are from 0.07 to 0.27 ppm, and from 0.03 to 0.11 × 10^− 6, respectively, dependent on organic substances. Br and molar Br/Cl values are from 89.08 to 555.45 ppm and from 0.06 × 10^− 3 to 0.38 × 10^− 3, respectively. All of the Br/Cl molar ratios are lower than those of seawater, and most of them are < 0.1, suggesting continental or mixed origin. Previously published δ³⁴S, δ¹¹B and ⁸⁷Sr/⁸⁶Sr values for evaporative minerals indicate a continental origin for the Mengye potash deposit. However, materials of hydrothermal origin are widely distributed in the basin and may have played an active role for the formation of the potash deposit. Thus the Mengye potash deposit could be of continental origin, with a remnant seawater trace.     

Geochemical assessment of hydrocarbon migration phenomena: Case studies from the south-western margin of the Dead Sea Basin

Calcite veins with fluid and solid bitumen inclusions have been discovered in the south-western shoulder of the Dead Sea rift within the Masada-Zohar block, where hydrocarbons exist in small commercial gas fields and non-commercial fields of heavy and light oils. The gas–liquid inclusions in calcite are dominated either by methane or CO₂, and aqueous inclusions sometimes bear minor dissolved hydrocarbons. The enclosed flake-like solid bitumen matter is a residue of degraded oil, which may be interpreted as “dead carbon”. About 2/3 of this matter is soot-like amorphous carbon and 1/3 consists of n-C₈C₁₈ carboxylic acids and traces of n-alkanes, light dicarboxylic acids, and higher molecular weight (>C₂₀) branched and/or cyclic carboxylic acids. Both bitumen and the host calcites show genetic relationship with mature Maastrichtian chalky source rocks (MCSRs) evident in isotopic compositions (δ¹³C, δ³⁴S, and δ¹⁸O) and in REE + Y patterns. The bitumen precursor may have been heavy sulfur-rich oil which was generated during the burial compaction of the MCSR strata within the subsided blocks of the Dead Sea graben. The δ¹⁸O and δ¹³C values and REE + Y signatures in calcites indicate mixing of deep buried fluids equilibrated with post-mature sediments and meteoric waters. The temperatures of fluid generation according to Mg–Li-geothermometer data range from 55 °С to 90 °С corresponding to the 2.5–4.0 km depths, and largely overlap with the oil window range (60–90 °С) in the Dead Sea rift (Hunt, 1996; Gvirtzman and Stanislavsky, 2000; Buryakovsky et al., 2005). The bitumen-rich vein calcites originated in the course of Late Cenozoic rifting and related deformation, when tectonic stress triggers damaged small hydrocarbon reservoirs in the area, produced pathways, and caused hydrocarbon-bearing fluids to rise to the subsurface; the fluids filled open fractures and crystallized to calcite with entrapped bitumen. The reported results are in good agreement with the existing views of maturation, migration, and accumulation of hydrocarbons, as well as basin fluid transport processes in the Dead Sea area.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Geology,fluid inclusions,and geochemistry of the Zhazixi Sb–W deposit,Hunan, South China

The Zhazixi Sb–W deposit in the Xuefeng uplift, South China, exhibits a unique metal association of W and Sb, where the W orebodies are hosted by interlayer fractures and the Sb orebodies are contained within NW-trending faults. This study proposes that the W and Sb mineralization took place in two separate periods. The mineral paragenesis of the W mineralization reveals a mass of quartz, scheelite and minor calcite. The mineral assemblage of the Sb mineralization developed after W mineralization and consists of predominantly quartz and stibnite, and small amounts of native Sb, berthierite, chalcostibnite, pyrite, and chalcopyrite. Fluid inclusions in quartz and coexisting scheelite are dominated by two-phase, liquid-rich, aqueous inclusions at room temperature. Microthermometric studies suggest that ore-forming fluids for W mineralization are characterized by moderate temperatures (170–270 °C), low salinity (3–7 wt% NaCl equiv.), low density (0.75–0.95 g/cm³), and moderate to high pressure (57.2–99.7 MPa) and these fluids experienced a cooling and dilution evolution during W mineralization. Ore-forming fluids for Sb mineralization are epithermal types with low temperatures (150–230 °C), low salinity (4–6 wt% NaCl equiv.), moderate density (0.82–0.94 g/cm³), and high pressure (42.2–122.5 MPa) and these fluids display an evident decline in homogenization temperature during Sb mineralization. Laser Raman analyses of the vapor phase indicate that the ore-forming fluids for both W and Sb mineralization contain a small amount of CO₂.The ore-forming fluids for Sb mineralization are identified as predominantly originating from the continental crust, as suggested by the low ³He values (0.009 × 10⁻¹² cc.STP/g) and ³He/⁴He ratios (0.002–0.056 Ra) as well as high ³⁶Ar values (1.93 × 10⁻⁹ cc.STP/g) and ⁴⁰Ar/³⁶Ar ratios (909.5–2279.7). The source of S is identified to be the Neoproterozoic Wuqiangxi Formation, as traced by the δ³⁴S_V-CDT values of stibnite (3.1–9.4‰). The ²⁰⁸Pb/²⁰⁴Pb (37.643–40.222), ²⁰⁷Pb/²⁰⁴Pb (15.456–15.681), and ²⁰⁶Pb/²⁰⁴Pb (17.093–20.042) ratios suggest a mixture of lower crustal and supracrustal Pb sources.It is thus concluded that the ore genesis of the Zhazixi Sb–W deposit is related to the intracontinental orogeny during the early Mesozoic. Fluid mixing is considered to be the critical mechanism involved in W mineralization, whereas a fluid cooling process is responsible for Sb mineralization. Furthermore, the absence of Au is attributed to the low Σa_s content in Sb-mineralizing fluids.     

Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 °C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 °C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% R_r, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. δ¹³C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the δ¹³C of the original kerogen, with ¹³C enriched kerogen generating more ¹³C enriched hydrocarbon gases than kerogen less enriched in ¹³C. The typically assumed linear trend for δ¹³C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called “dogleg” trend, exemplified by relatively ¹³C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar “dogleg” trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the Δδ¹³C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13–84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115–1568 Nm³/t) compared with those determined from the experiments (65–302 Nm³/t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations.     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Ore genesis and hydrothermal evolution of the Huanggang skarn iron–tin polymetallic deposit,southern Great Xing'an Range: Evidence from fluid inclusions and isotope analyses

The southern Great Xing'an Range is one of the most important metallogenic belts in northern China, and contains numerous Pb–Zn–Ag–Cu–Sn–Fe–Mo deposits. The Huanggang iron–tin polymetallic skarn deposit is located in the Sn-polymetallic metallogenic sub-belt. Skarns and iron orebodies occur as lenses along the contact between granite plutons and the Lower Permian Huanggangliang Formation marble or Dashizhai Formation andesite. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity, i.e., skarn, oxide and sulfide stages, all contributed to the formation of the Huanggang deposit.The skarn stage is characterized by the formation of garnet and pyroxene, and high-temperature, hypersaline hydrothermal fluids with isotopic compositions that are similar to those of typical magmatic fluids. These fluids most likely were generated by the separation of brine from a silicate melt instead of being a product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by amphibole, chlorite, quartz and magnetite. The hydrothermal fluids of this stage are represented by L-type fluid inclusions that coexist with V-type inclusions with anomalously low δD values (approximately − 100 to − 116‰). The decrease in ore fluid δ¹⁸O_H2O values with time coincides with marked decreases in the fluid salinity and temperature. Based on the fluid inclusion and stable isotopic data, the ore fluid evolved by boiling of the magmatic brine. The sulfide stage is characterized by the development of sphalerite, chalcopyrite, fluorite, and calcite veins, and these veins cut across the skarns and orebodies. The fluids during this stage are represented by inclusions with a variable but continuous sequence of salinities, mainly low-salinity inclusions. These fluids yield the lowest δ¹⁸O_H2O values and moderate δD values ( − 1.6 to − 2.8‰ and − 101 to − 104‰, respectively). The data indicate that the sulfide stage fluids originated from the mixing of residual oxide-stage fluids with various amounts of meteoric water. Boiling occurred during this stage at low temperatures.The sulfur isotope (δ³⁴S) values of the sulfides are in a narrow range of − 6.70 to 4.50‰ (mean = − 1.01‰), and the oxygen isotope (δ¹⁸O) values of the magnetite are in a narrow range of 0.1 to 3.4‰. Both of these sets of values suggest that the ore-forming fluid is of magmatic origin. The lead isotope compositions of the ore (²⁰⁶Pb/²⁰⁴Pb = 18.252–18.345, ²⁰⁷Pb/²⁰⁴Pb = 15.511–15.607, and ²⁰⁸Pb/²⁰⁴Pb = 38.071–38.388) are consistent with those of K-feldspar granites (²⁰⁶Pb/²⁰⁴Pb = 18.183–18.495, ²⁰⁷Pb/²⁰⁴Pb = 15.448–15.602, ²⁰⁸Pb/²⁰⁴Pb = 37.877–38.325), but significantly differ from those of Permian marble (²⁰⁶Pb/²⁰⁴Pb = 18.367–18.449, ²⁰⁷Pb/²⁰⁴Pb = 15.676–15.695, ²⁰⁸Pb/²⁰⁴Pb = 38.469–38.465), which also suggests that the ore-forming fluid is of magmatic origin.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.