Mantle Volatiles Research Articles

Mantle Volatiles and Heat Contributions to the Cu-Pb-Zn Mineralization in the Baoshan Deposit, South China: Constraints from He and Ar Isotopes

The Baoshan deposit is one of the important Cu-Pb-Zn deposits associated with granitic rocks in the Nanling Range, South China. Here, we present He and Ar isotope data for the Baoshan deposit to decipher the contributions of mantle-derived volatiles and heat to its Cu-Pb-Zn mineralization. The ore-forming fluids in sphalerite and pyrite exhibited 3He/4He ratios up to 1.51 Ra. A linear correlation between He and Ar isotopes suggests that the ore-forming fluids were a mixture of a predominantly mantle-derived fluid with a high 3He/4He ratio and a shallow crustal fluid, characterized by a low 3He/4He ratio. The δ34S values of sulfides in the Baoshan deposit ranged from +2.30 to +5.21‰, consistent with the magma-derived sulfur. The calculated 3He/Q ratios for the ore-forming fluid exceeded those of mid-oceanic ridge hydrothermal solutions by 10 to 50 times, indicating that the ore-forming fluids acquired both heat and volatiles in a convective hydrothermal regime rather than a conductive one. Therefore, there is a significant contribution of mantle-derived volatiles, heat, and possibly metals, to the Cu-Pb-Zn mineralization in the Baoshan deposit, and the continuous influx of mantle-derived fluids/melts probably plays a crucial role during the Cu-Pb-Zn mineralization related to granitic rocks.

The low primordial heavy noble gas and 244Pu-derived Xe contents of Earth's convecting mantle

Clues to unraveling the origin and history of terrestrial volatiles lie in the noble gas record of Earth's mantle. However, the low abundance of heavy noble gases (Ar-Kr-Xe) in mantle-derived rocks presents a major analytical challenge that limits our understanding of mantle volatile evolution. Here, we employ a new technique of ultrahigh precision dynamic mass spectrometry to measure Ar-Kr-Xe isotopes in mantle-derived gas collected from Mt. Etna (Italy) and Eifel (Germany), which both tap depleted convecting mantle reservoirs. We find that the fractions of primordial Kr-Xe from accretionary sources (≤ 7 % of non-radiogenic, non-fissiogenic isotopes) and 244Pu-derived 136Xe (≤ 9.8 ± 9.3 % of total fissiogenic Xe) are both markedly lower than previously estimated. For Mt. Etna, we find an apparent lack of detectable primordial Xe, which could reflect an additional contribution from recycled atmospheric volatiles from nearby subduction. In addition, slight excesses of 238U-derived fissiogenic Xe relative to the upper mantle composition may reflect the contribution of a crustal component related to the occurrence of a HIMU (“high μ” where μ = 238U/204Pb)-type source in Mt. Etna volcanic products. The low primordial heavy noble gas and 244Pu-derived Xe contents of Earth's convecting mantle, as derived from these new data, requires extensive volatile loss during terrestrial accretion, followed by long-term degassing and pervasive overprinting of primordial heavy noble gases by subduction recycling. In addition, we suggest that quantitative incompatible element (including Pu, U) extraction to the Hadean crust and subsequent reintroduction of U via subduction could have contributed to lowering the ultimate fraction of 244Pu-derived 136Xe in the upper mantle. The differences observed between this study and other upper mantle Xe studies may reflect mantle source heterogeneities (e.g. due to the heterogeneous overprinting of mantle volatiles by subduction) but could also result from analytical inconsistencies and/or subsurface isotope fractionation in natural systems. Future studies are crucial to gain insight into the origin of these different results.

Crustal carbonate build-up as a driver for Earth’s oxygenation

Oxygenation of Earth’s atmosphere and oceans played a pivotal role in the evolution of the surface environment and life. It is thought that the rise in oxygen over Earth’s history was driven by an increasing availability of the photosynthetic limiting nutrient phosphate combined with declining oxygen-consuming inputs from the mantle and crust. However, it has been difficult to assess whether these processes alone can explain Earth’s oxygenation history. Here we develop a theoretical framework for the long-term global oxygen, phosphorus and carbon cycles, incorporating potential trajectories for the emergence of continents, the degassing of mantle volatiles and the resulting increase in the size of the crustal carbonate reservoir. We find that we can adequately simulate the Earth’s oxygenation trajectory in both the atmosphere and oceans, alongside reasonable reconstructions of planetary temperature, atmospheric carbon dioxide concentration, phosphorus burial records and carbon isotope ratios. Importantly, this is only possible when we include the accumulation of carbonates in the crust, which permits ever-increasing carbon recycling rates through weathering and degassing. This carbonate build-up is a missing factor in models of Earth’s coupled climate, nutrient and oxygen evolution and is important for reconstructing Earth’s history and potential exoplanet biogeochemistry.

Roadblocks and speed limits: Mantle-to-surface volatile flux through the lithospheric-scale Denali fault, Alaska

Abstract Helium and carbon isotopic data from 12 springs along a ~400 km segment of the Denali fault system (Alaska, USA), inform mantle-to-surface connections of this enigmatic structure. Warm springs on the main strand, west of the 2002 M7.9 Denali fault earthquake rupture, have 3He/4He as high as 2.4 RC/RA (air-corrected 3He/4He relative to air ratio) indicating ~30% mantle He. Corresponding δ13C values are −9.1‰ to −7.8‰ (relative to Vienna Peedee belemnite), suggesting that the CO2 at these western springs is partially mantle derived. At the eastern end of the 2002 rupture, Totschunda fault springs have 3He/4He of 0.65–0.99 RC/RA (~8%–12% mantle He), with δ13C values (~0‰) from carbonates. Results confirm the Denali fault system is a lithosphericscale feature tapping mantle volatiles. Springs along the 2002 rupture yield air-like 3He/4He of 1 R/RA and δ13C values from −9.2‰ to −3.4‰, interpreted as representing shallow groundwater circulation through shales and carbonates without mantle contributions. A thrust splay parallel to the rupture zone has air-like 3He/4He, whereas an along-strike high-angle normal splay yields 3He/4He of 1.3 RC/RA (~16% mantle He), implying that flow paths along the ruptured strand are disrupted in the upper 10 km of the fault zone. Because the Denali fault is a lithospheric-scale, transcurrent structure separating North America from independently moving southern Alaska, we suggest that it has characteristics of a transform boundary. The similarity of our results to helium isotope values at analogous tectonic settings suggest that without magmatism influence, there is a maximum mantle fluid flux through continental strike-slip faults.

Genesis of the world-class Dachang gold deposit, northern Qinghai-Tibet Plateau: A multiproxy approach

Dachang is a world-class gold deposit that occurs in the Bayan Har Terrane, northern Qinghai-Tibet Plateau, with Au resources of 121 t at an average grade of 3.0 g/t. Although this deposit was investigated in some previous studies, its genesis remains debated. The deposit is controlled by the Gande-Maduo anticlinorium and thrust fault zone, and the orebodies occur in subsidiary interlayer faults or fractures in thin-bedded, stratatoid, lenticular and vein forms. The host strata belong to the Lower Triassic Bayan Har Shan Group consisting of metasandstone, metasiltstone, slate, and carbonaceous slate interlayered with phyllite. The mineralization of Dachang can be divided into the following four stages. Stage 1 gold-sulfide-quartz veins, stage 2 gold-sulfide-carbonate-quartz veins, stage 3 stibnite-quartz veins and stage 4 quartz-carbonate veins. There are two types of ores: altered rocks and quartz veins. The main ore minerals are pyrite, arsenopyrite, stibnite and native gold, with trace amounts of tetrahedrite, chalcopyrite, galena and sphalerite. The wallrock alteration comprises mainly sulfidation, silicification, carbonatization, and sericitization. The element association is As, Sb, Au, Te, Bi, Ag, W and Pb in order of enrichment factors, whereas Cu, Mo, and Sn are depleted relative to their crustal abundances.In this study, we identified three types of primary fluid inclusions in quartz from veins of the four mineralization stages as follows: type 1 liquid-dominated two-phase aqueous inclusions; type 2 aqueous-carbonic inclusions, including aqueous-dominated (type 2a) and carbonic-dominated inclusions (type 2b); and type 3 two-phase hydrocarbon inclusions. Microthermometric measurements of fluid inclusion assemblages (FIAs) and bulk fluid inclusion analyses show that the ore-forming fluids had similar low-salinity compositions (1.7 to 6.9 wt% NaCl equiv.) in the H2O-CO2-N2 system with trace amounts of hydrocarbons. The mineralization temperatures range from 150 to 200 °C, and estimated depths are approximately 5 to 6.5 km. Fluid/wallrock reactions and immiscibility or boiling during mineralization in response to pressure fluctuations in a brittle faults were the main triggers for gold precipitation at Dachang.The hydrogen, oxygen, carbon and He-Ar isotopic compositions indicate that the ore-forming fluids originated from metamorphic devolatilization of immediate- and deep-level country rocks and no meteoric water or mantle volatiles were involved. The organic carbon proportions account for 42 to 53% of the total carbon in ore-forming fluid, and carbon fractions from sedimentary carbonates range from 47 to 58%. The gold mineralization followed immediately after the regional metamorphism (240–225 Ma) and occurred when the host rocks had exhumated into a brittle environment. The Dachang deposit is an epizonal orogenic gold deposit.

Deep magma degassing and volatile fluxes through volcanic hydrothermal systems: Insights from the Askja and Kverkfjöll volcanoes, Iceland

Mantle volatiles are transported to Earth's crust and surface by basaltic volcanism. During subaerial eruptions, vast amounts of carbon, sulfur and halogens can be released to the atmosphere during a short time-interval, with impacts ranging in scale from the local environment to the global climate. By contrast, passive volatile release at the surface originating from magmatic intrusions is characterized by much lower flux, yet may outsize eruptive volatile quantities over long timescales. Volcanic hydrothermal systems (VHSs) act as conduits for such volatile release from degassing intrusions and can be used to gauge the contribution of intrusive magmatism to global volatile cycles. Here, we present new compositional and isotopic (δD and δ18O-H2O, 3He/4He, δ13C-CO2, Δ33S-δ34S-H2S and SO4) data for thermal waters and fumarole gases from the Askja and Kverkfjöll volcanoes in central Iceland. We use the data together with magma degassing modelling and mass balance calculations to constrain the sources of volatiles in VHSs and to assess the role of intrusive magmatism to the volcanic volatile emission budgets in Iceland.The CO2/ΣS (10−30), 3He/4He (8.3–10.5 RA; 3He/4He relative to air), δ13C-CO2 (−4.1 to −0.2 ‰) and Δ33S-δ34S-H2S (−0.031 to 0.003 ‰ and −1.5 to +3.6‰) values in high-gas flux fumaroles (CO2 > 10 mmol/mol) are consistent with an intrusive magmatic origin for CO2 and S at Askja and Kverkfjöll. We demonstrate that deep (0.5–5 kbar, equivalent to ∼2–18 km crustal depth) decompression degassing of basaltic intrusions in Iceland results in CO2 and S fluxes of 330–5060 and 6–210 kt/yr, respectively, which is sufficient to account for the estimated CO2 flux of Icelandic VHSs (3365–6730 kt/yr), but not the VHS S flux (220–440 kt/yr). Secondary, crystallization-driven degassing from maturing intrusions and leaching of crustal rocks are suggested as additional sources of S. Only a minor proportion of the mantle flux of Cl is channeled via VHSs whereas the H2O flux remains poorly constrained, because magmatic signals in Icelandic VHSs are masked by a dominant shallow groundwater component of meteoric water origin. These results suggest that the bulk of the mantle CO2 and S flux to the atmosphere in Iceland is supplied by intrusive, not eruptive magmatism, and is largely vented via hydrothermal fields.

Meteoritic noble gas constraints on the origin of terrestrial volatiles

The elemental and isotopic compositions of noble gases trapped in primitive meteorites have the potential to yield stringent constraints on the origin of matter in the solar system. The isotopic compositions of key elements like O, Ti, Ru, Mo suggest that the Earth accreted from material having similarities with two classes of meteorites, carbonaceous chondrites (CC) and non‑carbonaceous chondrites (NC), in particular enstatite chondrites (EC). In this contribution, I examine published noble gas (neon and argon) data for CI-CM as representative of CCs, and ECs as representative of NC terrestrial building blocks. Data were corrected for contributions of cosmic ray-produced isotopes in order to identify the trapped component compositions. For both CCs and ECs, corrected noble gas data indicate that high temperature objects such as chondrules were evolving in a dusty environment. The dust consisted of refractory phases including nanodiamonds, impacts-related debris, medium to low temperature phases mainly made of organics and, in the case of CC, hydrated minerals and icy grains. Remnants of such a dust are found as rims around chondrules and as a matrix between high temperature assemblages. The dust was probably the main source of volatiles on Earth.In terrestrial reservoirs, covariations of 20Ne/22Ne ratios with 36Ar/22Ne ratios are consistent with mixing between a solar-like neon component trapped in the mantle and a chondritic Ne–Ar component mainly present in the atmosphere and hydrosphere. The chondritic end-member is clearly of the CC type and excludes EC-like material as the source of atmospheric volatiles. In addition to CC-like material, the isotopic composition of heavy noble gases (Kr and Xe) in the atmosphere points to a ~ 20% contribution of cometary material akin of the composition of comet 67P/Churyumov-Gerasimenko. In contrast, comets might have contributed less than 1% terrestrial water, C and N. Solar-like neon in the terrestrial mantle might have originated from solar irradiation of free-floating dust before parent body compaction, but this would require a cleared, dust-free environment. Trapping of nebular gas into forming solids during the gas epoch of the nascent solar system appears a more promising possibility. For other mantle volatiles, the stable isotopes of H, N, Ar, Kr and Xe point to a chondritic origin. The hydrogen and nitrogen isotopic signatures of mantle rocks and minerals are consistent with an EC-like contribution whereas those of heavy noble gases are still too imprecise to conclude. Further progress in the field will require high precision analysis of noble gases (in particular, Kr and Xe) trapped in the terrestrial (and martian) mantle(s), as well as documenting the composition of the Venusian atmosphere.

Mantle-Derived Helium Distribution and Tectonic Implications in the Sichuan-Yunnan Block, China.

The geochemical characteristics of mantle degassing observed on the surface of the earth can indicate the origin and migration path of mantle fluids. Compared with the plate boundary tectonic environment, the intraplate tectonic environment does not have a large number of active volcanoes and active faults, and the observation of mantle volatiles in hot spring gas is relatively limited. We selected the Sichuan–Yunnan block to discuss mantle degassing based on the carbon and noble gas isotopes of the spring gases and previous studies on the fault slip rate and geophysical research. A total of five hot spring gas samples (including two free gases and three dissolved gases) were collected from the Sichuan–Yunnan block. Chemical and isotopic compositions were analyzed in N2-dominant hot spring gases. The 3He/4He ratio (0.068–0.541 Ra) indicates the occurrence of mantle-derived helium throughout the Sichuan–Yunnan block, which has been diluted by a crustal radiogenic 4He component. The occurrence of mantle-derived helium in the study areas ranges from 0.74 to 5.67%. The lower proportion of mantle-derived helium in YNWQ and HGWQ than that in other spring gases near the Jinghe-Qinghe fault may be caused by the smaller scale of fault around YNWQ and HGWQ than the Jinghe-Qinghe fault. The correlation between 4He, 20Ne, and N2 concentrations implies a common trapping mechanism for 4He, 20Ne, and N2 in hot spring gases. The 40Ar/36Ar ratios and N2/Ar ratios indicate that N2 and Ar are mostly meteoric, and YNWQ and HGWQ have more crustal-derived Ar contribution (40.56 and 51.49%, respectively). The δ13C(CO2)o values calculated by Rayleigh fractionation and CO2 concentration suggest that CO2 has inorganic and organic origins. The plot of Rc/Ra versus δ13C(CO2) indicates that the spring gas CO2 origin in the Sichuan–Yunnan block is mainly derived from mixing of limestone and organic sediments with minor mantle CO2. The δ13C(CH4) versus CH4/3He values indicate that the origin of methane is thermogenic and microbial oxidation. The low mantle-derived helium distribution pattern is most likely controlled by the weak fault activity rate, the small fault scale, and not obvious magmatic activity in the Sichuan–Yunnan block.

Low volcanic outgassing rates for a stagnant lid Archean earth with graphite-saturated magmas

Volcanic gases supplied a large part of Earth's early atmosphere, but constraints on the value of this flux are scarce. Here we model how C-O-H outgassing could have evolved through the late Hadean and early Archean, under the conditions that global plate tectonics had not yet initiated, all outgassing was subaerial, and graphite was the stable carbon phase in the melt source regions. The model fully couples numerical mantle convection, partitioning of volatiles into the melt, and chemical speciation in the gas phase. The mantle oxidation state (which may not have reached late Archean values in the Hadean) is the dominant control on individual species' outgassing rates because it affects both the carbon content of basaltic magmas and the speciation of degassed volatiles. Volcanic gas from mantles more reduced than the iron-wüstite mineral redox buffer would contain virtually no CO2 because (i) carbonate ions dissolve in magmas only in very limited amounts, and (ii) almost all degassed carbon takes the form of CO instead of CO2. For oxidised mantles near the quartz-fayalite-magnetite buffer, we predict median CO2 outgassing rates of less than approximately 5 Tmol yr−1, still lower than the outgassing rates used in many Archean climate studies. Relatively weak outgassing is due in part to the redox-limited CO2 contents of graphite-saturated melts, and also to a stagnant lid regime's inefficient replenishment of upper mantle volatiles. Our results point to certain chemical and geodynamic prerequisites for sustaining a clement climate with a volcanic greenhouse under the Faint Young Sun.

Deciphering a mantle degassing transect related with India-Asia continental convergence from the perspective of volatile origin and outgassing

Mantle degassing transect across different tectonic units within a plate convergent setting has been well documented for oceanic convergent margins by systematic changes in geochemistry (e.g., 3He/4He, δ13C, and CO2/3He) of hydrothermal gases. However, little is known about spatial variations in volatile geochemistry across a continental convergent margin. In this study, we identify a mantle degassing transect in the southeastern Tibetan Plateau using He-CO2 systematics of hydrothermal gases, which extends from India-Asia continental convergent margin to intra-continent extensional region. δ13C-CO2 (−11.8‰ to −3.1‰) and CO2/3He (1.7 × 108 to 7.1 × 1011) values of hydrothermal gases show large variations that are consistent with modification by secondary physico-chemical processes, such as multi-component mixing, hydrothermal degassing, and calcite precipitation. Three levels of He degassing can be recognized based on 3He/4He dataset (0.01–5.87 RA) of the hydrothermal gas samples and their distances to volcanic centers. A magmatic level He degassing (35–74% mantle He) is found near active and/or Quaternary volcanoes fed by mantle-derived magmas. With increasing distance to volcanic centers, the outgassed magmatic volatiles are gradually diluted by crustal components (e.g., radiogenic 4He), defining a transitional level He degassing (13–33% mantle He). The 3He/4He values (8.16–8.48 RA) of olivine phenocrysts indicate a MORB (mid-ocean ridge basalts)-type mantle source for the magmatic and transitional levels of He degassing that are localized in Quaternary volcanic fields. In contrast, a background level He degassing (<12% mantle He) dominates the entire study area, and can be attributed to (i) degassing of sub-continental lithospheric mantle, and/or (ii) higher degrees of crustal contamination than those of the transitional level He degassing near volcanic centers. Combined with olivine 3He/4He data reported in this study and whole-rock 87Sr/86Sr data of host basalts from literature, source components of the mantle-derived magmas are suggested to include the MORB-type convective mantle, subducted Indian slab materials, and less degassed mantle materials, which can account for the possible decoupling between He and Sr isotope systematics. These findings delineate the origin and outgassing of mantle volatiles controlled by the India-Asia continental convergence, and would contribute to a better understanding of the deeply-sourced volatile emissions in these tectonic settings.

Hydrochemical, isotopic, and dissolved gas characterization of groundwater in Gariz aquifer, Southwest of Yazd Province, central Iran

Here we discussed the results of the first geochemical investigation of the fluids (groundwater and the associated gases) emerging in the southwest of Yazd Province. We carried out two surveys, one in July 2019 and the second in September 2019s, in the region of the Gariz aquifer (central Iran). We focused our attention to 1) the chemistry of the water (major and minor constituents coupled to the stable isotopes of oxygen and hydrogen), 2) the chemical composition of dissolved gases in water together with 3) the isotopic composition of Helium (3He/4He) and 4) the dissolved carbon in water (δ13CTDIC). Hydrogen and oxygen isotope values of groundwater display a fairly narrow range and indicate that the waters are of meteoric origin. On the base of the major ions chemistry, the bulk of the water samples are classified as Ca-HCO3, CaCl and NaCl types. The groundwater chemistry is mainly influenced by the interaction with CO2-rich fluids, leakage of chlorinated saline water into the alluvial aquifer, and silicate dissolution. High dissolved carbon contents, mainly as bicarbonate ion, reflect the noticeable interaction of the groundwater with CO2-rich fluids. CO2 is the dominant gaseous component in most samples and its amount is always greater with respect to a water in equilibrium with the atmosphere (Air Saturated Water, ASW). Such excess of CO2 contents (more than 730 cc/l STP) dissolved in groundwater also supports the presence of a deep source of CO2-rich gas. The computed δ13C(CO2) in equilibrium with the groundwater highlight a mixing in different proportion between an inorganic deep sourced CO2 (13C-enriched) and organic CO2 (13C-depleted). We also used the helium isotopes as a tools to figure out the origin of helium in the aquifer (air vs. mantle, and crust). The collected samples show a contribution of mantle-derived He in the Gariz aquifer up to (~45%) and the crust suggesting that at regional scale the tectonic discontinuities had a connection with the mantle or magmatic intrusions migrated through the crust transporting mantle volatiles to shallow crustal layers. However, we cannot infer the timing of this possible magmatism at depth in the complex tectonic evolution of the area.

A secretive mechanical exchange between mantle and crustal volatiles revealed by helium isotopes in 13C-depleted diamonds

Fluid inclusions trapped in fast-growing diamonds provide a unique opportunity to examine the origin of diamonds, and the conditions under which they formed. Eclogitic to websteritic diamondites from southern Africa show 13C-depletion and 15N-enrichment relative to mantle values (δ13C = -4.3 to -22.2 ‰ and δ15N = -4.9 to +23.2 ‰). In contrast the 3He/4He of the trapped fluids have a strong mantle signature, one sample has the highest value so far recorded for African diamonds (8.5 ± 0.4 Ra). We find no evidence for deep mantle He in these diamondites, or indeed in any diamonds from southern Africa. A correlation between 3He/4He ratios and 3He concentration suggests that the low 3He/4He are largely the result of ingrowth of radiogenic 4He in the trapped fluids since diamond formation. The He-C-N isotope systematics can be best described by mixing between fluid released from subducted altered oceanic crust and mantle volatiles. The high 3He/4He of low δ13C diamondites reflects the high 3He concentration in the mantle fluids relative to the slab-derived fluids. The presence of post-crystallisation 4He in the fluids means that all 3He/4He are minima, which in turn implies that the slab-derived carbon has a sedimentary organic origin. In short, although carbon and nitrogen stable isotope data show strong evidence for crustal sources for diamond-formation, helium isotopes reveal an unambiguous mantle component hidden within a strongly 13C-depleted system.

Nebular atmosphere to magma ocean: A model for volatile capture during Earth accretion

The origin and abundance of mantle volatiles present major questions for Earth's evolution. Here we quantify volatile capture from an atmosphere derived from the solar nebula during accretion, using a boundary layer model of magma ocean dynamics coupled to a nebular atmosphere model adapted to Earth formation. Key elements include (i) nebular atmosphere winds based on scaling laws for deep rotating fluids; (ii) water production at the magma surface; and (iii) gas transfer between magma and atmosphere based on the systematics of air-sea gas exchange by wind and diffusion. Provided the Earth accreted to 30% or more of its final mass in the presence of the solar nebula, the mantle is expected to have ingassed several ocean mass equivalents of water plus hydrogen, along with hundreds of petagrams of helium-3 and other light noble gases. In contrast to light gases, nebular ingassing does not provide the mantle with enough heavy noble gases to account for their present-day atmosphere abundances. Our model also predicts that thermal insulation by the nebular atmosphere led to very hot conditions in Earth's interior during accretion, with peak temperatures above 6000 K at the core-mantle boundary and possible dynamo conditions in the Early Hadean.

Outgassing of Mantle Volatiles in Compressional Tectonic Regime Away From Volcanism: The Role of Continental Delamination

AbstractIn this study we discuss the occurrence of mantle‐derived heat and volatiles (i.e., helium and CO2) feeding hydrothermal systems in a seismically active margin between two convergent plates (African and European) without any signals of volcanism. The helium (He) isotopes clearly indicate a mantle‐derived component in the outgassing volatiles. The estimated mantle‐derived He fluxes are up to two to three orders of magnitude greater than those in a stable continental area. Such high He fluxes cannot be provided by a long‐lasting diffusion, thereby implying a more efficient transport (i.e., advective transport through faults). He data coupled to heat‐He relationship suggest the occurrence of active degassing of magmatic intrusions in this area of continental collisional. Geophysical data indicate the presence of a hot mantle wedge below the outgassing of mantle volatiles and a system of faults cutting the continental crust down to the hot mantle wedge. Here we discuss the hot mantle wedge and possible associated magmatic intrusions as the source of the mantle‐derived volatiles outgassing in the region. We also assessed the output of mantle‐derived CO2 from the investigated hydrothermal basins. The possible occurrence of magma at depth as well as the geometry of the thick‐skinned deformed wedge unambiguously indicates delamination processes that are related to continental subduction. Hence, we show that delamination processes can really produce magma at depth without evidences of volcanism at the surface. Finally, we have also provided the fault systems that work as a network of pathways and actively sustain the advective transfer of the mantle fluids toward the surface.

Origin and evolution of the thermal waters from the Pamukkale Geothermal Field (Denizli Basin, SW Anatolia, Turkey): Insights from hydrogeochemistry and geothermometry

The Pamukkale Geothermal Field (PGF) of the Denizli Basin (SW Turkey) is one of the most distinguished active geothermal fields known in the World. The thermal waters from the PGF are subdivided into two groups (Group 1A: Ca-HCO3 and Group 1B: Ca-SO4 types). The cold waters are also classified into two groups (Group 2A: Ca-HCO3 and Group 2B: Mg-HCO3 types). The hydrogeochemical properties of the PGF thermal waters suggest interactions with the basal metamorphic rocks of the Menderes Massif, tectonically overriding by the carbonate rocks of the Lycian Nappes and sedimentary rocks of the Neogene formations. The bedrock units are stratigraphically overlain by the Neogene sedimentary units of the Denizli Group. The thermal springs of the PGF are affected by several hydrothermal processes including mixing, water-rock interaction and input of mantle volatiles.The thermal water plots of the PGF deviate from the full equilibrium line indicating a low water maturity and/or mixing processes. Mixing models and Na-K-Mg ternary diagram suggest mixing between meteoric and thermal waters during the uprising of the deep-originated fluids. The water-rock interaction leads saturation of calcite and induces travertine precipitation in the discharge area.Low tritium (<1 TU) values of the PGF thermal waters confirm a deep circulation. The δ18O (−9.23 to −8.32‰) and δD (−61.00 to −57.00‰) isotopic values of the PGF indicate that the meteoric waters serve as the source of the thermal waters. Based on the δ18O and δD data, the PGF thermal waters are produced from precipitation in the southern side of Yenice Horst with elevation of 850–880 m.a.s.l. The δ13CDIC values (+6.26 to +8.07‰) of the PGF thermal waters indicate that CO2 in thermal waters is mainly of a metamorphic origin. In order to identify the reservoir temperature of the PGF, various geothermometric methods have been applied. Accordingly, theoretical reservoir temperature ranges from 60 to 125 °C. The total hydrothermal CO2 flux in the PGF is calculated to be approximately 1.4 × 108 mol/year (excluding free CO2 flux) as similar to those of other geothermal fields in the World (e.g., central-southern Italy).This study proposes a conceptual hydrogeological-hydrogeochemical-tectonic model for the PGF: the thermal waters are derived from the infiltration of rainwater through fractures and faults in high recharge areas to the deep hot reservoir. Heating produced by the high geothermal gradient is interpreted in relation with the regional crustal thinning. Thermal waters upwell along WNW-ESE-trending deep faults and fractures (the Pamukkale Fault System) that act as hydrothermal pathways favouring migration of a huge amount of CO2-rich gas from deep geothermal reservoir. The geochemical and isotopic data of the thermal waters and gas indicate that the degassing of both metamorphic CO2 and mantle derived CO2 occurs in the PGF. Helium isotope data indicate that mantle volatiles produce possibly an upwelling into asthenosphere and ascent along these tectonic discontinuities. In this context, the PGF is one of the best example of geothermal fields as an interaction of active magmatism in the actively extending crustal setting.

A noble gas and 87Sr/86Sr study in fluids of the Los Azufres geothermal field, Mexico – Assessing impact of exploitation and constraining heat sources

Thirty geothermal wells and two hot springs were sampled for volume fraction and isotopic measurements of noble gases (He, Ne, Ar, Kr, Xe) and strontium in the Los Azufres Geothermal Field (LAGF), Mexico. The aim of this study was to understand the evolution of fluid circulation following three decades of exploitation and re-injection of used brines and to identify the heat source. The LAGF, divided into the Southern Production Zone (SPZ) and the Northern Production Zone (NPZ), is hosted in a Miocene to Pliocene andesitic volcanic complex covered by Quaternary rhyolitic-dacitic units. Air component corrected 3He/4He ratios (Rc) normalized to the atmospheric ratio (Ra = 1.384 × 10−6), range from 4.21 to 7.93 for most samples pointing to the occurrence of a MORB-type mantle helium component, with contributions of crustal helium up to 53% and 18% in NPZ and SPZ, respectively. Observations based on Rc/Ra and 87Sr/86Sr ratios point to mixing of three magmatic sources supplying mantle helium to the LAGF: (1) a pure mantle He (Rc/Ra = 8) and Sr (87Sr/86Sr = 0.7035) source related to mafic magmas; (2) a pure mantle helium component (Rc/Ra = 7) with some radiogenic Sr (87Sr/86Sr = 0.7049) source, possibly related to Quaternary rhyolitic magmas; and (3) a fossil mantle He component (Rc/Ra = 4.0) with some radiogenic Sr (87Sr/86Sr = 0.7038), corresponding possibly to Miocene andesitic magmas. Parental magmas related to sources (1) and (2) emplaced <50 kyrs ago are likely responsible for the addition of mantle volatiles and heat (Q) to the hydrothermal system of Los Azufres. An observed 4He/36Ar vs. 3He/Q correlation suggests that heat is transferred by conduction and convection in both NPZ and SPZ. Atmospheric noble gas elemental ratios suggest that geothermal wells located closer to the western re-injection zone are dominated by re-injection of used brines (injectate). The area affected by boiling in LAGF has extended further to the north and west since the last noble gas sampling campaign in 2007–2009 (Pinti et al., 2013).

Mantle volatiles and heat contributions in high sulfidation epithermal deposit from the Zijinshan Cu-Au-Mo-Ag orefield, Fujian Province, China: Evidence from He and Ar isotopes

The source of metal and sulphur in porphyry and related epithermal deposits is a long debated issue. The role of mantle-derived magmas in providing the metals has proved particularly problematic. Here we report new He and Ar isotope determinations from ore fluids from the Zijinshan high sulfidation-epithermal Cu-Au deposit and Wuziqilong transitional Cu deposit from the giant Zijinshan porphyry-epithermal Cu-Au-Mo-Ag ore system (from 105 to 91 Ma), to decipher the contribution of mantle-derived volatiles and heat. Hydrothermal fluids in pyrite and digenite have 3He/4He up to 5.7 Ra, among the highest measured in ancient ore-forming fluids. A linear correlation between He and Ar isotopes indicate that the ore fluids were, to a first order, a mixture between a shallow crustal fluid, with low 3He/4He, and a dominantly mantle-derived fluid with high 3He/4He. The mantle 3He/4He is close to values typical of the upper mantle indicating the initial magmas that provided the heat for hydrothermal systems did not assimilate large volumes of continental crust. The ore-forming fluids have 3He/heat ratios that are 10 to 80 times higher than that of mid-oceanic ridge hydrothermal fluids, indicating that the metal-bearing fluids acquired heat and volatiles in a convective, rather than conductive, hydrothermal regime. It appears that mantle-derived volatiles, heat and probably metals have made a major contribution to the Cu-Au-Mo-Ag mineralization in the Zijinshan orefield.

Origin, evolution and geothermometry of the thermal waters in the Gölemezli Geothermal Field, Denizli Basin (SW Anatolia, Turkey)

The Gölemezli Geothermal Field (GGF) is one of the best known geothermal fields in western Anatolia (Turkey). The exploited fluids are of meteoric origin, mixed with deep magmatic fluids, which interacted with the metamorphic rocks of the Menderes Massif. The geothermal fluids are channeled along Quaternary faults belonging to the main normal faults system delimiting the northern side of the Denizli Basin and their associated transfer zones. In this study, hydrochemical and isotopic analyses of the thermal and cold waters allow us to determine water-rock interactions, fluid paths and mixing processes.Two groups of thermal waters have been distinguished: (i) Group 1A, comprising Na-SO4 type and Ca-SO4 type and (ii) Group 1B, only consisting Ca-HCO3 type waters. Differently, two groups were recognized in the cold waters: (i) Group 2A, corresponding to Ca-HCO3 type and (ii) Group 2B, including Mg-HCO3 type. Their geochemical characteristics indicate interactions with the Paleozoic metamorphic rocks of the Menderes Massif and with the Neogene lacustrine sedimentary rocks. Dissolution of host rock and ion-exchange reactions modify thermal water composition in the reservoir of the GGF. High correlation in some ionic ratios and high concentrations of some minor elements suggest an enhanced water-rock interaction. None of the thermal waters has been reached a complete chemical re-equilibrium, possibly as a result of mixing with cold water during their pathways. Geothermal reservoir temperatures are calculated in the range of 130-210°C for the Gölemezli field.Very negative δ18O and δ2H isotopic ratios are respectively between −8.37 and −8.13‰ and −61.09 and −59.34‰ for the SO4-rich thermal waters, and ca. −8.40 and −8.32‰ and −57.80 and −57.41‰ for the HCO3-rich thermal waters. Low tritium (<1 TU) and low oxygen isotope values reflect a deep circuit and fluids of meteoric origin. Positive δ13CDIC ratios (+5.11 to +7.54‰) of all thermal waters imply a contribution of metamorphic origin. Heating is guaranteed by a deep circuit within an overheated continental crust, mainly affected by damaged rock volumes. Volatile ascent from deep magmatic sources through crustal structures can explain the occurrence of mantle volatiles at shallow depth in the Denizli Basin. The NW- and NE-trending fault systems, associated with their related fractures, played as hydraulic conduits underlining the strict link existing between fractures and fluid convection in the extensional settings. In this view, the GGF is a very good example of geothermal field associated to active tectonic setting and magmatism, as it is the case of the other geothermal fields occurring in the Denizli Basin.

Noble gas data from Goldfield and Tonopah epithermal Au-Ag deposits, ancestral Cascades Arc, USA: Evidence for a primitive mantle volatile source

The He, Ne, and Ar isotopic composition of fluid inclusions in ore and gangue minerals were analyzed to determine the source of volatiles in the high-grade Goldfield and Tonopah epithermal Au-Ag deposits in southwestern Nevada, USA. Ar and Ne are mainly atmospheric, whereas He has only a minor atmospheric component. Corrected 3He/4He ratios (with atmospheric He removed) range widely from 0.05 to 35.8 times the air 3He/4He ratio (RA), with a median of 1.43 RA. Forty-one percent of measured 3He/4He ratios are ≥4 RA, corresponding to ≥50% mantle He assuming a mantle ratio of 8 RA. These results suggest that mafic magmas were part of the magmatic-hydrothermal system underlying Goldfield and Tonopah, and that associated mantle-sourced volatiles may have played a role in ore formation. The three highest corrected 3He/4He ratios of 17.0, 23.7, and 35.8 RA indicate a primitive mantle He source and are the highest yet reported for any epithermal-porphyry system and for the Cascades arc region. Compiled 3He/4He measurements from epithermal-porphyry systems in subduction-related magmatic arcs around the world (n=209) display a statistically significant correlation between 3He/4He and Au-Ag grade. The correlation suggests that conditions which promote higher fluid inclusion 3He/4He ratios (abundance of mantle volatiles and focused upward volatile transport) have some relation to conditions that promote higher Au-Ag grades (focused flow of metal-bearing fluids and efficient chemical traps). Results of this and previous investigations of He isotopes in epithermal-porphyry systems are consistent with the hypothesis posed in recent studies that mafic magmas serve an important function in the formation of these deposits.

Recycled noble gases preserved in podiform chromitites from Luobusa, Tibet

We report noble gas (He, Ne, Ar) signatures of chromite and olivine separates from the Luobusa chromitites in Tibet to better understand the volatile compositions trapped in the minerals, and further to trace the origin of melts responsible for formation of the chromite deposits. The studied samples can be divided into two groups based on petrography and distinct noble gas signatures. Group I samples are free of carbonates and have 3He/4He ratios from 0.81 to 2.36 Ra (where Ra is the 3He/4He ratio of air=1.4×10−6) and air-like Ne and Ar isotopic compositions irrespective of chromitite structure types. Most 3He/4He ratios of Group I samples are higher than air, suggesting apparent presence of mantle volatiles. Given the 4He/20Ne and 3He/36Ar several orders of magnitude higher than air, negligible contributions are from the atmospheric helium. The observed He isotope compositions thus can be regarded as a two-component mixture of mantle-derived and radiogenic He. A broadly positive correlation between 3He and 36Ar in nodular chromitite samples indicates a source mixing between mantle and recycled noble gases but not due to shallow air contamination. In addition, the wide distribution range of 20Ne/36Ar also supports a subduction-related origin of neon and argon. Combined with major element data, the most appropriate tectonic setting to generate such noble gas signatures in Group I samples is subduction zone (probably forearc) where favorable conditions are present for the formation of the chromitites. In contrast, Group II samples containing carbonates have much more radiogenic 3He/4He ratios of 0.03 to 0.3 Ra but much less radiogenic 40Ar/36Ar ratios of 344 to 420. In combination with the occurrence of carbonate veins it is suggested that Group II samples are predominated by supracrustal components that may be imparted during or after the emplacement stage. A comparison of these two group samples indicates that the primary noble gas signatures reflecting the characteristics of ore-forming melts can be preserved in chromite and olivine grains (Group I samples) and thus used to trace the origin of podiform chromitites.