Chlorine stable isotope ratios as tracer for pore‐water advection rates in a submarine gas‐hydrate field: implication for hydrate concentration

At Ocean Drilling Program Site 997 in Blake Ridge gas‐hydrate field in West Atlantic, pore‐water studies revealed a pronounced downward depletion of the heavy chlorine isotope to nearly ?4‰δ³⁷Cl at approximately 750 m below sea floor (mbsf) associated with a 10% downward chlorinity decrease. This is one of the stronger ³⁷Cl depletions hitherto reported for marine pore waters. Chlorinity reductions in hydrate‐bearing sediments commonly result from fresh‐water release by hydrate melting. However, in situ measurements at Site 997 suggest that >50% of the chlorinity reduction occurred prior to hydrate dissociation. Modeling the chlorinity profile shows that advection of a strongly ³⁷Cl‐depleted, low‐chlorinity water (506 mm ) from below the drilled sequence can explain the reduction prior to sampling. Fitting the model to the δ³⁷Cl curve yielded an advection rate of 0.18 mm year^?1. Diffusive mixing with near‐0‰‐δ³⁷Cl paleo‐seawater with maximum chlorinity at shallow subsurface depths (561 mm at approximately 20 mbsf) produced the smooth, steady trend. Separating that part of the freshening caused by advection and diffusion from that due to hydrate dissociation allowed estimation of average hydrate concentrations of 3.8% of the pore space (up to 24.5% in hydrate‐rich layers; near‐100% in rare massive hydrate layers). The deep‐seated source of the ³⁷Cl‐depleted, low‐chlorinity water remains unknown and might be located below the sedimentary section in the oceanic basement.     

The geochemical evolution of very dilute CO2‐rich water in Chungcheong Province,Korea: processes and pathways

A geochemical study was carried out on the CO₂‐rich water occurring in granite areas of Chungcheong Province, Korea. In this area, very dilute and acidic CO₂‐rich waters [62–242 mg l^?1 in total dissolved solid (TDS), 4.0–5.3 in pH; group I) occur together with normal CO₂‐rich waters (317–988 mg l^?1 in TDS, 5.5–6.0 in pH; group II). The concentration levels and ages of group I water are similar to those of recently recharged and low‐mineralized groundwater (group III). Calculation of reaction pathways suggests that group I waters are produced by direct influx of CO₂ gas into group III type waters. When the groundwater is injected with CO₂, it develops the capacity to accept dissolved solids and it can evolve into water with very high solute concentrations. Whether the water is open or closed to the CO₂ gases becomes less important in controlling the reaction pathway of the CO₂‐rich groundwater when the initial pco ₂ is high. Our data show that most of the solutes are dissolved in the CO₂‐rich groundwater at pH > 5 where the weathering rates of silicates are very slow or independent of pH. Thus, groundwater age is likely more important in developing high solute concentrations in the CO₂‐rich groundwaters than accelerated weathering kinetics because of acidic pH caused by high pco ₂.