Abstract
The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reduction as dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE (∑REE) concentrations is evident immediately below the sediment–water interface, which can be related to early diagenetic release of REEs into pore water resulting from the re-mineralization of particulate organic matter. The highest pore water ∑REE concentrations were measured close to the sediment–water interface at ~2 cm depth. Distinct shale-normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shale-normalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in ∑REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.
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Acknowledgements
We are grateful to the master and the crew for the support at sea, and appreciate the skilful and experienced work of the ALVIN team during R/V Atlantis cruise AT3-35b. Andy Ungerer (Oregon State University) is acknowledged for analytical guidance. Thanks go to two anonymous referees for constructive comments, and to Burg W. Flemming and Monique T. Delafontaine for editorial remarks that improved the quality of the paper. Valuable comments provided by Wolfgang Bach, Germain Bayon, Gerald Dickens and Alan Shiller on earlier versions of this manuscript are acknowledged. Funding was provided through the DFG-Research Center/Excellence Cluster ‘The Ocean in the Earth Systems’.
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Himmler, T., Haley, B.A., Torres, M.E. et al. Rare earth element geochemistry in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean. Geo-Mar Lett 33, 369–379 (2013). https://doi.org/10.1007/s00367-013-0334-2
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DOI: https://doi.org/10.1007/s00367-013-0334-2