Aqueous magmatic fluids are essential to the transport of hydrogen (H), carbon (C), and nitrogen (N) from the mantle to the surface, during which changes in pressure, temperature, and redox conditions affect the chemical speciation and intermolecular isotopic fractionations of H, C, and N. Here, we performed a series of hydrothermal diamond-anvil cell experiments to evaluate the role of pressure, temperature, and redox conditions on the speciation and intermolecular fractionations of H and N during the decompression and cooling of aqueous fluids from 780 MPa to 800°C to 150 MPa and 200°C. We used Raman spectroscopy to investigate the distribution and exchange reactions of H and N isotopologues between water, methane, ammonia, and di-nitrogen molecules under changing physicochemical conditions. Our experiments show that upon decompression, a C- and N-bearing fluid will preferentially degas D-rich methane and 15 N-rich N 2 , depleting the residual aqueous fluid in those isotopes. If this fluid precipitates N-rich (i.e., NH 4 + -bearing) minerals, the observed N isotopic fractionation is opposite to that during N 2 degassing, enriching the aqueous fluid in 15 N. Because these fractionations result from changes in H, C, and N speciation in the aqueous fluid, their magnitudes depend on redox conditions as well as pressure and temperature. Our new in-situ experimental results are consistent with the large H and N isotopic fractionations observed between water, methane, and ammonia species in aqueous fluids at high pressures and temperatures, although the magnitude of the fractionations in our experiments cannot be quantified. Nonetheless, our results suggest that statistical thermodynamic models likely underestimate isotopic fractionation effects for isotopic molecules under these conditions, and should account for solubility and isotopic effects of the solvent associated with the solvation of water, methane, and ammonia isotopologues in aqueous fluids.This work has significant implications for interpreting isotopic measurements of natural samples from hydrothermal systems because it offers insights into isotopic fractionations in multicomponent and multiphase systems under hydrothermal temperatures and pressures.
Abstract Accurate reconstruction of diagenetic P‐T conditions in petroleum reservoirs from fluid inclusion data relies on valid measurements of methane concentration in aqueous inclusions. Techniques have been developed (Raman spectrometry) to provide sufficiently accurate data, assuming measured methane concentration has not been modified after aqueous inclusion entrapment. This study investigates the likelihood that organic acids derived from petroleum fluids and dissolved in formation water might suffer decarboxylation upon postentrapment heating within the fluid inclusion chamber, thereby generating excess CH 4 in the inclusions. Four different experiments were conducted in fused silica capillary capsules (FSCCs), mimicking fluid inclusions. The capsules were loaded with acetic (CH 3 COOH) or formic (HCOOH) acid solution and were heated to 250°C for short durations (<72 h) in closed‐system conditions, with or without applying a fixed P H2 . Reaction products were characterized by Raman and FT ‐ IR spectrometry. Results indicate that decarboxylation reactions did take place, at variable degrees of progress, and that measurable excess CH 4 was produced in one experiment using acetic acid. This suggests that methane may be produced from dissolved organic acids in natural aqueous inclusions in specific situations, possibly inducing errors in the thermodynamic interpretation.
The Latala base and precious metals deposit is hosted by quartz veins, associated with a porphyry pluton intruded into a Cenozoic volcanic sequence. Euhedral quartz with sulfide mineralization such as pyrite, chalcopyrite, galena and sphalerite, with minor sulfosalts occurs in these veins as open space fillings and minor replacement bodies. Progressive growth of quartz crystals is evidenced by their texture revealed by cathodoluminescence imaging. The analysis of fluid inclusions indicate a decreasing homogenization temperature from 350°C in the core to 135°C along the edge of the quartz crystals with overgrowths. The presence of CO2 vapor suggested by the thermometric analysis is confirmed by Raman spectrometry. The solid phases in fluid inclusions identified as phyllosilicates, presumably muscovite and illite, chlorite, quartz and carbonate-mineral such as (Natrocarbonate, Dawsonite) by petrography and Raman spectrometry. Solid phase of halite were identified in two fluid inclusions. The homogenization temperature and salinity varies between 131 to 380 °C and 0.17 to 7.7 wt.% NaCl eq respectively. The properties of fluid inclusions corresponds to a magmatic hydrothermal fluid circulating from depth to shallower environments. The sulfur isotopic composition for galena, sphalerite, chalcopyrite and pyrite varies between -9.8 and -1‰, which correspond to values of magmatic sulfur. The δ34S values from +1.8 to -9.2‰ are in the range of hydrothermal fluids. Fluid inclusions features show a magmatic hydrothermal source which transported magmatic fluid and vapor from the depth through fractures to shallow environment. It suggests that magmatic water mixing with meteoric water was responsible for transportation of metals in Latala. Epithermal mineral precipitation during boiling, mixing and water-rock interaction formed hydrothermal quartz and sulfide mineralization. The available evidence suggests that the hydrothermal fluids changed from magmatic to epithermal in the region.
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