The effect of extraction techniques on calcium concentrations and isotope ratios of marine pore water

Comparing two different techniques applied for the extraction of marine pore water samples from sediments, the well-established whole round (WR) method and the more recent Rhizon method, in terms of their effects on stable calcium isotope ratios in extracted pore waters, we recognize a systematic offset between the two sampling methods. Higher δ44/40Ca values are associated with lower Ca concentrations for the Rhizon sampling technique and lower δ44/40Ca values are associated with higher Ca concentrations for the corresponding WR-derived pore water samples. Models involving Rayleigh fractionation and mixing calculation suggest that the observed offset is most likely caused by a combined process of CaCO3 precipitation and ion exchange taking place during Rhizon sampling-induced CO2 degassing. Changing pressure, extraction time or extraction yield during WR pressing does not lead to a variation in δ44/40Ca, indicating that no Ca isotope fractionation takes place during the sampling of pore water. On the basis of analytical and modelling results, WR samples appear to provide δ44/40Ca values that are more representative of the ‘true’ pore water isotopic composition. While the difference between the sampling techniques is close to the present-day analytical precision of Ca isotope analysis, it may become more relevant with increasing analytical precision in the future

Formation of carbonate chimneys in the Mediterranean Sea linked to deep-water oxygen depletion

Marine sediments at ocean margins vent substantial amounts of methane1, 2. Microbial oxidation of the methane released can trigger the precipitation of carbonate within sediments and support a broad diversity of seafloor ecosystems3, 4. The factors controlling microbial activity and carbonate precipitation associated with the seepage of submarine fluid over geological time remain poorly constrained. Here, we characterize the petrology and geochemistry of rocks sampled from metre-size build-ups of methane-derived carbonate chimneys located at the Amon mud volcano on the Nile deep-sea fan. We find that these carbonates comprise porous structures composed of aggregated spherules of aragonite, and closely resemble microbial carbonate reefs forming at present in the anoxic bottom waters of the Black Sea5. Using U-series dating, we show that the Amon carbonate build-ups formed between 12 and 7 thousand years ago, contemporaneous with the deposition of organic-rich sediments in the eastern Mediterranean, the so-called sapropel layer S1. We propose that the onset of deep-water suboxic or anoxic conditions associated with sapropel formation resulted in the development of intense anaerobic microbial activity at the sea floor, and thus the formation of carbonate chimneys

Sidescan sonar imagery of widespread fossil and active cold seeps along the central Chilean continental margin

The central Chilean subduction zone between 35°S and 37°S was investigated in order to identify, document and possibly understand fluid flow and fluid venting within the forearc region. Several areas were mapped using multibeam bathymetry and backscatter, high-resolution sidescan sonar, chirp subbottom profiling and reflection seismic data. On a subsequent cruise ground-truthing observations were made using a video sled. In general, this dataset shows surprisingly little evidence of fluid venting along the mid-slope region, in contrast to other subduction zones such as Central America and New Zealand. There were abundant indications of active and predominantly fossil fluid venting along the upper slope between 36.5°S and 36.8°S at the seaward margin of an intraslope basin. Here, backscatter anomalies suggest widespread authigenic carbonate deposits, likely the result of methane-rich fluid expulsion. There is unpublished evidence that these fluids are of biogenic origin and generated within the slope sediments, similar to other accretionary margins but in contrast to the erosional margin off Central America, where fluids have geochemical signals indicating an origin from the subducting plate