Volcanic degassing,hydrothermal circulation and the flourishing of early life on Earth: A review of the evidence from c. 3490-3240 Ma rocks of the Pilbara Supergroup,Pilbara Craton,Western Australia

New data gathered during mapping of c. 3490–3240 Ma rocks of the Pilbara Supergroup in the Pilbara Craton show that most bedded chert units originated as epiclastic and evaporative sedimentary rocks that were silicified by repeated pulses of hydrothermal fluids that circulated through the footwall basalts during hiatuses in volcanism. For most cherts, fossil hydrothermal fluid pathways are preserved as silica ± barite ± Fe-bearing veins that cut through the footwall and up to the level of individual bedded chert units, but not above, indicating the contemporaneity of hydrothermal silica veining and bedded chert deposition at the end of volcanic eruptive events. Silica ± barite ± Fe-bearing vein swarms are accompanied by extensive hydrothermal alteration of the footwall to the bedded chert units, and occurred under alternating high-sulphidation and low-sulphidation conditions. These veins provided pathways to the surface for elements leached from the footwall (e.g., Si, Ba, Fe) and volcanogenic emissions from underlying felsic magma chambers (e.g., CO₂, H₂S/HS⁻, SO₂).Stratigraphic evidence of shallowing upward and subsequent deepening associated with the deposition of Warrawoona Group cherts is interpreted to relate to the emplacement of subvolcanic laccoliths and subsequent eruption and/or degassing of these magmas. Heat from these intrusions drove episodes of hydrothermal circulation. Listric normal faulting during caldera collapse produced basins with restricted circulation of seawater. Eruption of volcanogenic emissions into these restricted basins formed brine pools with concentration of the volcanogenic components, thereby providing habitats suitable for early life forms.Fossil stromatolites from two distinct stratigraphic units in the North Pole Dome grew in shallow water conditions, but in two very different geological settings with different morphologies. Stratiform and domical stromatolites in the stratigraphically lower, c. 3490 Ma, Dresser Formation of the Warrawoona Group are intimately associated with barite and chert precipitates from hydrothermal vents, suggesting that component microbes may have been chemoautotrophic hyperthermophiles. Evidence of shallow water to periodically exposed conditions, active growth faulting and soft sediment deformation indicates that the volcanogenic emissions were erupted into a shallow water, tectonically active caldera and concentrated therein to produce an extreme habitat for early life.Widespread conical and pseudocolumnar stromatolites in the c. 3400 Ma, Strelley Pool Chert at the base of the unconformably overlying Kelly Group occur in shallow marine platform carbonates. Silicification was the result of later hydrothermal circulation driven by heat from the overlying, newly erupted Euro Basalt. The markedly different morphology and geological setting of these only slightly younger stromatolites, compared with the Dresser Formation, suggests a diversity of microbial life on early Earth.The biogenicity of putative microfossils from this and younger hydrothermal silica veins in the Warrawoona Group remains controversial and requires further detailed study.     

Greenhouse gas emissions from soils—A review

Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO₂e m⁻² h⁻¹ (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO₂e (CO₂e = CO₂ equivalents = total effect of all GHG normalized to CO₂). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO₂ are being emitted annually by fossil fuel combustion and the cement industry.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Fluid evolution of the Yuchiling porphyry Mo deposit,East Qinling,China

The Yuchiling Mo deposit, East Qinling, China, belongs to a typical porphyry Mo system associated with high-K calc-alkaline intrusions. The pure CO₂ (PC), CO₂-bearing (C), aqueous H₂O-NaCl (W), and daughter mineral-bearing (S) fluid inclusions were observed in the hydrothermal quartz. Based on field investigations, petrographic, microthermometric and LA-ICP-MS studies of fluid inclusions, we develop a five-stage fluid evolution model to understand the ore-forming processes of the Yuchiling deposit. The earliest barren quartz ± potassic feldspar veins, developed in intensively potassic alteration, were crystallized from carbonic-dominant fluids at high temperature (> 416 °C) and high pressure (> 133 MPa). Following the barren quartz ± potassic feldspar veins are quartz-pyrite veins occasionally containing minor K-feldspar and molybdenite, which were formed by immiscible fluids at pressures of 47–159 MPa and temperatures of 360–400 °C. The fluids were characterized by high CO₂ contents (approximately 8 mol%) and variable salinities, as well as the highest Mo contents that resulted in the development of quartz-molybdenite veins. The quartz-molybdenite veins, accounting for > 90% Mo in the orebody, were also formed by immiscible fluids with lower salinity and lower CO₂ content of 7 mol%, at temperatures of 340–380 °C and pressures of 39–137 MPa, as constrained by fluid inclusion assemblages. After the main Mo-mineralization, the uneconomic Cu-Pb-Zn mineralization occurred, as represented by quartz-polymetallic sulfides veins consisting of pyrite, molybdenite, chalcopyrite, digenite, galena, sphalerite and quartz. The quartz-polymetallic sulfide veins were formed by fluids containing 5 mol% CO₂, with minimum pressures of 32–110 MPa and temperatures of 260–300 °C. Finally, the fluids became dilute (5 wt.% NaCl equiv) and CO₂-poor, which caused the formation of late barren quartz ± carbonate ± fluorite veins at 140–180 °C and 18–82 MPa.It is clear that the fluids became more dilute, CO₂-poor, and less fertile, with decreasing temperature and pressure from quartz-pyrite to late barren veins. Molybdenite and other sulfides can only be observed in the middle three stages, i.e., quartz-pyrite, quartz-molybdenite and quartz-polymetallic sulfide veins. These three kinds of veins are generally hosted in potassic altered rocks with remarkable K-feldspathization, but always partly overprinted by phyllic alteration. The traditional porphyry-style potassic–phyllic–propylitic alteration zoning is not conspicuous at Yuchiling, which may be related to, and characteristic of, the CO₂-rich fluids derived from the magmas generated in intercontinental collision orogens.Among the fluid inclusions at Yuchiling, only the C-type contains maximum detectable Mo that gradationally decreases from 73 ppm in quartz-pyrite veins, through 19 ppm in quartz-molybdenite veins, and to 13 ppm in quartz-polymetallic sulfide veins, coinciding well with the decreasing CO₂ contents from 8 mol%, through 7 mol%, to 5 mol%, respectively. Hence it is suggested that decreasing CO₂ possibly results in decreasing Mo concentration in the fluids, as well as the precipitation of molybdenite from the fluids. This direct relationship might be a common characteristic for other porphyry Mo systems in the world.The Yuchiling Mo deposit represents a new type Mo mineralization, with features of collision-related setting, high-K calc-alkaline intrusion, CO₂-rich fluid, and unique wall-rock alterations characterized by strong K-feldspathization and fluoritization.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Metallogenic age and hydrothermal evolution of the Jidetun Mo deposit in central Jilin Province,northeast China: Evidence from fluid inclusions,isotope systematics,and geochronology

The Jidetun deposit is a large porphyry Mo deposit that is located in central Jilin Province, northeast China. The Mo mineralization occurs mainly at the edge of porphyritic granodiorite, as well as the adjacent monzogranite. Field investigations, cross-cutting relationships, and mineral paragenetic associations indicate four stages of hydrothermal activity. To determine the relationships between mineralization and associated magmatism, and better understand the metallogenic processes in ore district, we have undertaken a series of studies incluiding molybdenite Re–Os and zircon U–Pb geochronology, fluid inclusions microthermometry, and C–H–O–S–Pb isotope compositions. The molybdenite Re–Os dating yielded a well-defined isochron age of 168.9 ± 1.9 Ma (MSWD = 0.34) that is similar to the weighted mean ²⁰⁶Pb/²³⁸U age of 173.5 ± 1.5 Ma (MSWD = 1.8) obtained from zircons from the porphyritic granodiorite. The results lead to the conclusion that Mo mineralization, occurred in the Middle Jurassic (168.9 ± 1.9 Ma), was spatially, temporally, and genetically related to the porphyritic granodiorite (173.5 ± 1.5 Ma) rather than the older monzogranite (180.1 ± 0.6 Ma). Fluid inclusion and stable (C–H–O) isotope data indicate that the initial H₂O–NaCl fluids of mineralization stage I were of high-temperature and high-salinity affinity and exsolved from the granodiorite magma as a result of cooling and fractional crystallization. The fluids then evolved during mineralization stage II into immiscible H₂O–CO₂–NaCl fluids that facilitated the transport of metals (Mo, Cu, and Fe) and their separation from the ore-bearing magmas due to the influx of abundant external CO₂ and heated meteoric water. Subsequently, during mineralization stage III and IV, increase of pH in residual ore-forming fluids on account of CO₂ escape, and continuous decrease of ore-forming temperatures caused by the large accession of the meteoric water into the fluid system, reduced solubility and stability of metal clathrates, thus facilitating the deposition of polymetallic sulfides.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

A rapid method for preparing low volume CH4 and CO2 gas samples for 14C AMS analysis

¹⁴C measurements of CH₄ in environmental samples (e.g. soil gas, lake water, gas hydrates) can advance understanding of C cycling in terrestrial and marine systems. The measurements are particularly useful for detecting the release of old C from climate sensitive environments such as peatlands and hydrate fields. However, because ¹⁴C CH₄ measurements tend to be complex and time consuming, they are uncommon. Here, we describe a novel vacuum line system for the preparation of CH₄ and CO₂ from environmental samples for ¹⁴C analysis using accelerator mass spectrometry (AMS). The vacuum line is a flow-through system that allows rapid preparation of samples (1 h for CH₄ and CO₂, 30 min for CH₄ alone), complete separation of CH₄ and CO₂ and is an easy addition to multipurpose CO₂ vacuum lines already in use. We evaluated the line using CH₄ and CO₂ standards with different ¹⁴C content. For CH₄ and CO₂, respectively, the total line blank was 0.4 ± 0.2 and 1.4 ± 0.6 μg C, the ¹⁴C background 51.1 ± 1.2 and 48.4 ± 1.5 kyr and the precision (based on pooled standard deviation) 0.9‰ and 1.3‰. The line was designed for sample volumes of ca. 180 ml containing 0.5–1% CH₄ and CO₂, but can be adjusted to handle lower concentration and larger volume samples. This rapid and convenient method for the preparation of CH₄ and CO₂ in environmental samples for ¹⁴C AMS analysis should provide more opportunities for the use of ¹⁴C CH₄ measurements in C cycle studies.     

Isotope and fluid inclusion geochemistry and genesis of the Qiangma gold deposit,Xiaoqinling gold field,Qinling Orogen,China

The Qiangma gold deposit is hosted in the > 1.9 Ga Taihua Supergroup metamorphic rocks in the Xiaoqinling terrane, Qinling Orogen, on the southern margin of the North China Craton. The mineralization can be divided as follows: quartz-pyrite veins early, quartz-polymetallic sulfide veinlets middle, and carbonate-quartz veinlets late stages, with gold being mainly introduced in the middle stage. Three types of fluid inclusions were identified based on petrography and laser Raman spectroscopy, i.e., pure carbonic, carbonic-aqueous (CO₂–H₂O) and aqueous inclusions.The early-stage quartz contains pure carbonic and CO₂–H₂O inclusions with salinities up to 12.7 wt.% NaCl equiv., bulk densities of 0.67 to 0.86 g/cm³, and homogenization temperatures of 280−365 °C. The early-stage is related to H₂O–CO₂ ± N₂ ± CH₄ fluids with isotopic signatures consistent with a metamorphic origin (δ¹⁸O_water = 3.1 to 5.2‰, δD = − 37 to − 73‰). The middle-stage quartz contains all three types of fluid inclusions, of which the CO₂–H₂O and aqueous inclusions yield homogenization temperatures of 249−346 °C and 230−345 °C, respectively. The CO₂–H₂O inclusions have salinities up to 10.9 wt.% NaCl equiv. and bulk densities of 0.70 to 0.98 g/cm³, with vapor bubbles composed of CO₂ and N₂. The isotopic ratios (δ¹⁸O_water = 2.2 to 3.6‰, δD = − 47 to − 79‰) suggest that the middle-stage fluids were mixed by metamorphic and meteoric fluids. In the late-stage quartz only the aqueous inclusions are observed, which have low salinities (0.9−9.9 wt.% NaCl equiv.) and low homogenization temperatures (145−223 °C). The isotopic composition (δ¹⁸O_water = − 1.9 to 0.5‰, δD = − 55 to − 66‰) indicates the late-stage fluids were mainly meteoric water.Trapping pressures estimated from CO₂–H₂O inclusions are 100−285 MPa for the middle stage, suggesting that gold mineralization mainly occurred at depths of 10 km. Fluid boiling and mixing caused rapid precipitation of sulfides and native Au. Through boiling and inflow of meteoric water, the ore-forming fluid system evolved from CO₂-rich to CO₂-poor in composition, and from metamorphic to meteoric, as indicated by decreasing δ¹⁸O_water values from early to late. The carbon, sulfur and lead isotope compositions suggest the hostrocks within the Taihua Supergroup to be a significant source of ore metals. Integrating the data obtained from the studies including regional geology, ore geology, and fluid inclusion and C–H–O–S–Pb isotope geochemistry, we conclude that the Qiangma gold deposit was an orogenic-type system formed in the tectonic transition from compression to extension during the Jurassic−Early Cretaceous continental collision between the North China and Yangtze cratons.     

Geochemistry,radiocarbon ages,and paleorecharge conditions along a transect in the central High Plains aquifer,southwestern Kansas,USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N₂, Ar, O₂, CH₄) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O₂ reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka (¹⁴C) B.P. near the water table to 12.8 ± 0.9 ka (¹⁴C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO₃ in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO₃ in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N₂ derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10⁻³ μmol N L⁻¹ a⁻¹), indicating this process would require >10 ka to reduce the average NO₃ concentration in recent recharge to the Holocene background concentration.     

Tectonics and thermal structure of western Satpura,India

Increased seismicity and occurrences of hot springs having surface temperature of 36–58 °C are observed in the central part of India (74–81° E, 20–25° N), where the NE trending Middle Proterozoic Aravalli Mobile Belt meets the ENE trending Satpura Mobile Belt. Earlier Deep Seismic Sounding (DSS) studies along Thuadara-Sendhwa-Sindad profile in the area has showed Mesozoic Sediments up to around 4 km depth covered by Deccan Trap and the Moho depth with a boundary velocity (P_n) of 8.2 km/s. In the present study, surface heat flow of 48 ± 4 mW m^?2 has been estimated based on P_n velocity, which agrees with the value of heat flow of 52 ± 4 mW m^?2 based on Curie point isotherms estimates. The calculated temperature-depth profile shows temperature of 80–120 °C at the basement, which is equivalent to oil window temperature in Mesozoic sediments and around 570–635 °C at Moho depth of 38–43 km and the thermal lithosphere is about 110 km thick, which is comparatively higher than those of adjoining regions. The present study reveals the brittle–ductile transition zone at 14–41 km depth (temperature around 250–600 °C) where earthquake nucleation takes place.     

Deep carbon cycle and geodynamics: the role of the core and carbonatite melts in the lower mantle

Carbon, though being abundant in the Solar system, barely exceeds 0.01 wt.% in the silicate mantle, whereas it is ~ 3.6 wt.% in primitive chondritic meteorites that most likely formed our planet. This deficit may be due to redistribution of carbon in the liquid metal phase and then in the core at the stage of magma ocean fractionation, because carbon is much more soluble in Fe–Ni ± S melt than in silicate melts. The terrestrial heat and mass transfer are controlled mainly by layered convection and periodic peaks of plume activity as fast mantle jets that rise from the core. Plumes carry significant amounts of CO₂, H₂O, and K₂O (most probably in the form of carbonatite or hydrous carbonatite melts) released by the degassing core on its interaction with oxidized silicate material. There are two mechanisms that may maintain fast plume ascent: (1) local melting at the plume front as a result of doping with volatiles (H₂O, CO₂) as in a gas burner (rise rate 60–110 cm/yr) or (2) flow controlled by diffusion transport of silicate components in carbonatite melt (rise rate ~ 100 cm/yr).     

Geology and fluid characteristics of the Ulu Sokor gold deposit,Kelantan, Malaysia: Implications for ore genesis and classification of the deposit

The Ulu Sokor gold deposit is one of the most famous and largest gold deposits in Malaysia and is located in the Central Gold Belt. This deposit consists of three major orebodies that are related to NS- and NE-striking fractures within fault zones in Permian-Triassic meta-sedimentary and volcanic rocks of the East Malaya Block. The faulting events represent different episodes that are related to each orebody and are correlated well with the mineralogy and paragenesis. The gold mineralization consists of quartz-dominant vein systems with sulfides and carbonates. The hydrothermal alteration and mineralization occurred during three stages that were characterized by (I) silicification and brecciation; (II) carbonatization, sericitization, and chloritization; and (III) quartz–carbonate veins.Fluid inclusions in the hydrothermal quartz and calcite of the three stages were studied. The primary CO₂–CH₄–H₂O–NaCl fluid inclusions in stage I are mostly related to gold mineralization and display homogenization temperatures of 269–389 °C, salinities of 2.77–11.89 wt.% NaCl equivalent, variable CO₂ contents (typically 5–29 mol%), and up to 15 mol% CH₄. In stage II, gold was deposited at 235–398 °C from a CO₂ ± CH₄–H₂O–NaCl fluid with a salinity of 0.83–9.28 wt.% NaCl equivalent, variable CO₂ contents (typically 5–63 mol%), and up to 4 mol% CH₄. The δ¹⁸O_H2O and δD values of the ore-forming fluids from the stage II quartz veins are 4.5 to 4.8‰ and − 44 to − 42‰, respectively, and indicate a metamorphic–hydrothermal origin. Oxygen fugacities calculated for the entire range of T-P-X_CO2 conditions yielded log f_O2 values between − 28.95 and − 36.73 for stage I and between − 28.32 and − 39.18 for stage II. These values indicate reduced conditions for these fluids, which are consistent with the mineral paragenesis, fluid inclusion compositions, and isotope values.The presence of daughter mineral-bearing aqueous inclusions is interpreted to be a magmatic signature of stage IIIa. Combined with the oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 6.8 to 11.9‰, δD = − 77 to − 62‰), these inclusions indicate that the initial fluid was likely derived from a magmatic source. In stage IIIb, the gold was deposited at 263° to 347 °C from a CO₂–CH₄–H₂O–NaCl fluid with a salinity of 5.33 to 11.05 wt.% NaCl equivalent, variable CO₂ contents (typically 9–15 mol%), and little CH₄. The oxygen and hydrogen isotopic compositions of this fluid (δ¹⁸O_H2O = 8.1 to 8.8‰, δD = − 44 to − 32‰) indicate that it was mainly derived from a metamorphic–hydrothermal source. The CO₂–H₂O ± CH₄–NaCl fluids that were responsible for gold deposition in the stage IIIc veins had a wide range of temperatures (214–483 °C), salinities of 1.02 to 21.34 wt.% NaCl equivalent, variable CO₂ contents (typically 4–53 mol%), and up to 7 mol% CH₄. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 8.5 to 9.8‰, δD = − 70 to − 58‰) were probably acquired at the site of deposition by mixing of the metamorphic–hydrothermal fluid with deep-seated magmatic water and then evolved by degassing at the site of deposition during mineralization. The log f_O2 values from − 28.26 to − 35.51 also indicate reduced conditions for this fluid in stage IIIc. Moreover, this fluid had a near-neutral pH and δ³⁴S values of H₂S of − 2.32 to 0.83‰, which may reflect the derivation of sulfur from the subducted oceanic lithospheric materials.The three orebodies represent different gold transportation and precipitation models, and the conditions of ore formation are related to distinct events of hydrothermal alteration and gold mineralization. The gold mineralization of the Ulu Sokor deposit occurred in response to complex and concurrent processes involving fluid immiscibility, fluid–rock reactions, and fluid mixing. However, fluid immiscibility was the most important mechanism for gold deposition and occurred in these orebodies, which have corresponding fluid properties, structural controls, geologic characteristics, tectonic settings, and origins of the ore-forming matter. These characteristics of the Ulu Sokor deposit are consistent with its classification as an orogenic gold deposit, while some of the veins are genetically related to intrusions.     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

New insights into the origin of the Evate apatite-iron oxide-carbonate deposit,Northeastern Mozambique,constrained by mineralogy,textures, thermochronometry,and fluid inclusions

The Evate deposit represents the largest resource of apatite in south-east Africa (155 Mt. ore grading 9.3 wt.% P₂O₅) accumulated in up to 100 m thick magnetite-carbonate-apatite horizons conformable to the granulitic gneiss of the Monapo Klippe. Baddeleyite and zircon from early iron-oxide (magnetite, geikielite, spinel), apatite- and forsterite-bearing rocks have been dated to 590 ± 6 Ma using the LA-ICPMS U-Pb method, whereas monazites from anhydrite-apatite-carbonate rocks show a concordant U-Pb-Th age corresponding to 449 ± 2 Ma. Temperatures inferred from calcite-dolomite solvus data and graphite structural ordering span the interval from ≥ 815 to 276 °C. Primary and secondary fluid inclusions in apatite document calciocarbonatite melts associated with early apatite, and CO₂-bearing sulfate-chloride brines progressively diluted with low-salinity, probably metoric waters, towards ultimate stages of the deposit formation. The calciocarbonatite melts have initially coexisted with liquid nitrogen and later with sulfate-chloride brines mixed with N₂ ± CO₂ gas.Crystallization of spinel around baddeleyite by the mechanism of Ostwald ripening, nucleation of graphite spherules along pyrrhotite-carbonate boundaries, the occurrence of molybdenite, baddeleyite-to-zircon transformation, and high crystallization temperatures inferred from graphite structural ordering and calcite-dolomite thermometry suggest a magmatic origin of the early mineral assemblages. In contrast, microthermometric characteristics of primary aqueous inclusions in the late apatite and the presence of zeolites (thomsonite-Ca, mezolite) is diagnostic of a low-temperature hydrothermal crystallization.Formation of the early magnetite-apatite-forsterite assemblage is thought to be coeval with mafic alkalic intrusions of the Mazerapane Suite superimposed on the granulite facies metamorphism of the Monapo Klippe. The low-temperature, anhydrite-bearing mineralization was associated with the massive circulation of sulfate-rich brines along fractures activated during the Late Cambrian-Ordovician extension. Origin of the sulfate-rich brines may be genetically related either with the magmatic-hydrothermal differentiation, or with the remobilization of crustal evaporites.     

One-year spatial and temporal monitoring of concentration and carbon isotopic composition of atmospheric CO2 in a Wrocław (SW Poland) city area

The main aim of this study was to assess the natural and anthropogenic contributions of CO₂ in the urban atmosphere of Wrocław City (SW Poland) using combined quantitative (CO₂ concentrations) and qualitative analysis (δ¹³C of CO₂). Between 21 January 2011 and 22 December 2011, 17 sampling campaigns were performed at 3-week intervals and in total 255 samples were collected. The mean CO₂ concentration was 469 ± 71 ppm and the mean δ¹³C(CO₂) was −10.8 ± 1‰.The measured δ¹³C(CO₂) values of major end-members for two winter heating seasons (−25.7‰ in January–March of 2011 and −27.6 ‰ in October–December of 2011) and for one vegetative season (−20.4‰ in April–September of 2011) suggest soil respiration as a main source of atmospheric CO₂ during the vegetative season, and a very significant impact of fossil fuel combustion during the winter heating seasons. There were significant increases of CO₂ concentrations at many sampling locations after the opening of a new motorway on 31 August 2011. The authors hypothesise that the new motorway contributes to the increase of CO₂ across the city.     

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.     

Neoproterozoic arc magmatism in the southern Madurai Block,India: Subduction,relamination, continental outbuilding,and the growth of Gondwana

The Madurai Block in southern India is a composite collage of at least three sub-blocks, with Neoarchean–Paleoproterozoic segments in the north and central domains, and a Neoproterozoic segment in the south. Here we investigate a suite of rocks with magmatic protoliths that constitute the basement in the southern margin of the Madurai Block including alkali granites, charnockites, enderbites and gabbros. The alkali granites are dominantly composed of perthitic K-feldspar, minor plagioclase and quartz, with hornblende as the main mafic mineral suggesting a calc-alkaline nature. The enderbites and charnockites have a broadly similar mineralogical constitution except for the variation in the modal content of plagioclase, K-feldspar and quartz, as well as the additional presence of clinopyroxene in some of the enderbites. The high modal content of hornblende in the gabbros suggests crystallization from hydrous basaltic melts. The geochemical features of this suite are identical to those of arc magmatic rocks, with distinct Nb, Ta, and Ti depletion suggesting magmatism in a subduction-related environment. We envisage that the underplating of basaltic magmas within a convergent margin setting provided the heat input for lower crustal melting generating the charnockitic suite of rocks. The intrusion of the underplated mafic melts as gabbroic dykes and sills into the crystallizing felsic magmas resulted in magma mixing and mingling generating the widespread enclaves of gabbroic rocks. The alkali granites were derived from the differentiation of lower crustal melts. Zircon U–Pb data from the alkali granites yield weighted mean ²⁰⁶Pb/²³⁸U ages of 786 ± 10 to 772 ± 11 Ma for the oldest and the most dominant group of magmatic grains, with a 662 ± 20 Ma subordinate group. The oldest group of magmatic zircons in the charnockite samples shows ages of 938 ± 27 Ma, 896 ± 12 Ma, and 786 ± 9 Ma, suggesting multiple magmatic pulses during early and mid-Neoproterozoic. A subordinate population of magmatic zircons with ages of 661 ± 9 Ma and 632 ± 7 Ma is also present. In the enderbites, the magmatic zircon population yields weighted mean ages of 926 ± 22 Ma, 923 ± 36 Ma, 889 ± 13 Ma, 803 ± 10 Ma, 787 ± 23 Ma, 786 ± 10 Ma, 748 ± 27 Ma, 742 ± 11 Ma, 717 ± 8 Ma and 692 ± 10 Ma suggesting continuous and multiple pulses of magmas emplaced throughout early to mid-Neoproterozoic. Magmatic zircons from the gabbros show weighted mean ²⁰⁶Pb/²³⁸U ages of 903 ± 13 Ma, 777 ± 10 Ma, 729 ± 10 Ma and 639 ± 27 Ma. Metamorphic zircons from all the rock types show latest Neoproterozoic-Cambrian ages in the range of 567 ± 19 Ma to 510 ± 8 Ma suggesting prolonged heating. Zircon Lu–Hf data show that the alkali granite-charnockite-enderbite suite has depleted mantle ages (T_DM) in the range of 1164–2172 Ma and crustal residence ages (T_DM^C) of 1227–3023 Ma. These spots show both negative εHf(t) and positive εHf(t) values (− 22.1 to 10.6), suggesting magma derivation from mixed juvenile mid- to late-Mesoproterozoic components and reworked Mesoarchean to mid-Mesoproterozoic components. Zircon grains from the gabbroic rocks show depleted mantle ages and (T_DM) in the range of 1112–2046 Ma, crustal residence ages (T_DM^C) of 1306–2816 Ma, and both negative and positive εHf(t) values (− 17.8 to 7.9), suggesting that the magmas were dominantly derived from juvenile mid-Mesoproterozoic to Neoproterozoic components as well as reworked Mesoarchean to mid-Mesoproterozoic sources.Our data clearly reveal multiple arc magmatism along the southern Madurai Block during distinct pulses throughout early to late Neoproterozoic, suggesting an active convergent margin along this zone at this time. Crustal thickening occurred through relamination by mafic magmas associated with slab melting. Continental outbuilding and southward growth of the Madurai Block were associated with the lateral accretion of the vast sedimentary belt of Trivandrum Block, culminating in collisional metamorphism during latest Neoproterozoic–Cambrian associated with Gondwana assembly.     

Evolution of the Mo-rich scheelite skarn mineralization at Kozbudaklar,Western Anatolia,Turkey: Evidence from mineral chemistry and fluid inclusions

The Kozbudaklar scheelite skarn deposit in the Tavşanlı Zone, located approximately 22 km southeast of Bursa, is hosted by the Triassic calcic İnönü Marble and Eocene Topuk Pluton. At least four stages have been recognized through skarn evolution. Scheelite skarn distributed close to the Topuk Pluton occurred during the early (stage 1) and late (stage 2) prograde substages. The early prograde endo and exoskarn are composed of hedenbergite (Hd₉₆Joh₄)–plagioclase (An_55–64) and hedenbergite (Hd_61–94Joh_4–7), accompanied by calcic garnet (Grs_38–94Sps_1–5Alm₀) and scheelite (Pow_1–6). The second stage represents a relatively oxidized mineralogy dominated by diopside (Hd_16–48Joh_0–9), subcalcic garnet (Grs_24–92Sps_0–11Alm_0–31) and scheelite (Pow_7–32). The stage 3 and 4 mineral assemblages are characterized by few hydrous minerals in the retrograde stage and intense fracturing.Fluid inclusions from skarn rocks are indicative of multiple fluid events: (1) low-moderate salinity (5–16 wt.%NaCl equiv.) inclusions homogenized dominantly by a high-temperature (308 °C to > 600 °C) liquid phase in stage 1. Fluid inclusions in an early garnet homogenized over a similar temperature range (440 °C and 459 °C) into both liquid and vapor phases. Eutectic temperatures ranging from − 61.7 °C to − 35.0 °C that indicate the presence of H₂O–NaCl–(± MgCl₂ ± CaCl₂)–CO₂ solutions; (2) coexisting daughter mineral-bearing high salinity (29.5 ≥ 70 wt.%NaCl equiv.) and vapor-rich moderate salinity (11.5–16.7 wt.%NaCl equiv.) inclusions that homogenized in the liquid phase by the disappearance of the vapor phase at a similar temperature range (308 °C to > 600 °C) in stage 2. Eutectic temperatures range from − 67.9°C to − 51.8°C that shows the presence of H₂O–NaCl–CO₂–(± CH₄/N₂) solutions; (3) low-moderate salinity (12.5–7.6 wt.%NaCl equiv.) and temperature (320 °C to 215 °C) inclusions homogenized by the liquid phase in stage 3. Eutectic temperatures range from − 59.5 °C to − 44.2 °C indicating the presence of H₂O–NaCl–(± MgCl₂ ± CaCl₂)–CO₂ solutions; (4) inclusions of low salinity (9.9–0.9 wt.%NaCl equiv.) and homogenization temperature (183 °C to 101 °C) in stage 4.These data show that the Kozbudaklar skarn deposit was formed in a magmatic–hydrothermal system. In this model, carbonaceous fluids may have been exsolved from the plutonic rock during its emplacement and crystallization. Fluid inclusion data indicate that fluid boiling and immiscibility occurred at temperatures between 440 °C and 459 °C and pressures ranging from 50 MPa to 60 MPa based on hydrostatic considerations. Early scheelite was precipitated with relatively reduced mineral compositions. As a result of depressurization, Mo-rich scheelite with oxidized minerals formed via high salinity and vapor-rich inclusions. The second scheelite mineralization occurred in a normal hydrothermal system by an infiltration mechanism at pressures between approximately 40 and 1.5 MPa. At shallow depths (< 1.5 MPa) with increasing permeability, sulfide and oxide minerals were deposited in the retrograde stage, greatly assisted by meteoric water. Finally, as a result of the diminishing of ore-forming fluids, post-depositional barren quartz and calcite veins were formed.