Dolomite-rich coralline algae in reefs resist dissolution in acidified conditions

Coral reef ecosystems develop best in high-flow environments but their fragile frameworks are also vulnerable to high wave energy. Wave-resistant algal rims, predominantly made up of the crustose coralline algae (CCA) Porolithon onkodes and P. pachydermum, are therefore critical structural elements for the survival of many shallow coral reefs. Concerns are growing about the susceptibility of CCA to ocean acidification because CCA Mg-calcite skeletons are more susceptible to dissolution under low pH conditions than coral aragonite skeletons. However, the recent discovery of dolomite (Mg0.5Ca0.5(CO3)), a stable carbonate, in P. onkodes cells necessitates a reappraisal of the impacts of ocean acidification on these CCA. Here we show, using a dissolution experiment, that dried dolomite-rich CCA have 6-10 times lower rates of dissolution than predominantly Mg-calcite CCA in both high-CO2 (~ 700 ppm) and control (~ 380 ppm) environments, respectively. We reveal this stabilizing mechanism to be a combination of reduced porosity due to dolomite infilling and selective dissolution of other carbonate minerals. Physical break-up proceeds by dissolution of Mg-calcite walls until the dolomitized cell eventually drops out intact. Dolomite-rich CCA frameworks are common in shallow coral reefs globally and our results suggest that it is likely that they will continue to provide protection and stability for coral reef frameworks as CO2 rises.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Whole rock and Cr-rich spinel geochemistry of ODP Legs 152 and 163 and DSDP Hole 38-338 samples

Coring during Ocean Drilling Program and Deep Sea Drilling Project Legs 163, 152, 104, 81, and 38 recovered sequences of altered basalt from North Atlantic seaward-dipping reflector sequences (SDRS) erupted during the initial rifting of Greenland from northern Europe and likely associated with excessive mantle temperatures caused by an impacting mantle plume head. Cr-rich spinel is found abundantly as inclusions and groundmass crystals within the olivine-rich lavas of Hole 917A (Leg 152) cored into the Southeast Greenland SDRS, but only rarely as inclusions within plagioclase in the lavas of the Vøring Plateau SDRS, and it is absent from other cored SDRS lavas from the Rockall Plateau and Southeast Greenland. Eruptive melt compositions determined from inferred, thermodynamically-defined, spinel-melt exchange equilibria indicate that the most primitive melts represented by Hole 917A basalts have Mg/(Mg + Fe2+) at least as high as 0.70 and approach near-primary mantle melt compositions. In contrast, Cr-rich spinels from Hole 338 (Leg 38) lavas on the Vøring Plateau SDRS give evidence for melt with Mg/(Mg + Fe2+) only as high as 0.64. This study underlines that primitive melts similar to those from Hole 917A comprise only a small fraction of the eruptive North Atlantic SDRS melts, and that most SDRS basalts were, in fact, too evolved to have precipitated Cr-rich spinel, with true melt Mg/(Mg + Fe2+) likely below 0.60. The evolved nature of the SDRS basalts implies large amounts of fractionation at the base of the crust or deep within it, consistent with seismic results that indicate an abnormally thick Layer 3 underlying the SDRS.

Database of Ice-Rich Yedoma Permafrost (IRYP)

Vast portions of Arctic and sub-Arctic Siberia, Alaska and the Yukon Territory are covered by ice-rich silty to sandy deposits that are containing large ice wedges, resulting from syngenetic sedimentation and freezing. Accompanied by wedge-ice growth in polygonal landscapes, the sedimentation process was driven by cold continental climatic and environmental conditions in unglaciated regions during the late Pleistocene, inducing the accumulation of the unique Yedoma deposits up to >50 meters thick. Because of fast incorporation of organic material into syngenetic permafrost during its formation, Yedoma deposits include well-preserved organic matter. Ice-rich deposits like Yedoma are especially prone to degradation triggered by climate changes or human activity. When Yedoma deposits degrade, large amounts of sequestered organic carbon as well as other nutrients are released and become part of active biogeochemical cycling. This could be of global significance for future climate warming as increased permafrost thaw is likely to lead to a positive feedback through enhanced greenhouse gas fluxes. Therefore, a detailed assessment of the current Yedoma deposit coverage and its volume is of importance to estimate its potential response to future climate changes. We synthesized the map of the coverage and thickness estimation, which will provide critical data needed for further research. In particular, this preliminary Yedoma map is a great step forward to understand the spatial heterogeneity of Yedoma deposits and its regional coverage. There will be further applications in the context of reconstructing paleo-environmental dynamics and past ecosystems like the mammoth-steppe-tundra, or ground ice distribution including future thermokarst vulnerability. Moreover, the map will be a crucial improvement of the data basis needed to refine the present-day Yedoma permafrost organic carbon inventory, which is assumed to be between 83±12 (Strauss et al., 2013, doi:10.1002/2013GL058088) and 129±30 (Walter Anthony et al., 2014, doi:10.1038/nature13560) gigatonnes (Gt) of organic carbon in perennially-frozen archives. Hence, here we synthesize data on the circum-Arctic and sub-Arctic distribution and thickness of Yedoma for compiling a preliminary circum-polar Yedoma map. For compiling this map, we used (1) maps of the previous Yedoma coverage estimates, (2) included the digitized areas from Grosse et al. (2013) as well as extracted areas of potential Yedoma distribution from additional surface geological and Quaternary geological maps (1.: 1:500,000: Q-51-V,G; P-51-A,B; P-52-A,B; Q-52-V,G; P-52-V,G; Q-51-A,B; R-51-V,G; R-52-V,G; R-52-A,B; 2.: 1:1,000,000: P-50-51; P-52-53; P-58-59; Q-42-43; Q-44-45; Q-50-51; Q-52-53; Q-54-55; Q-56-57; Q-58-59; Q-60-1; R-(40)-42; R-43-(45); R-(45)-47; R-48-(50); R-51; R-53-(55); R-(55)-57; R-58-(60); S-44-46; S-47-49; S-50-52; S-53-55; 3.: 1:2,500,000: Quaternary map of the territory of Russian Federation, 4.: Alaska Permafrost Map). The digitalization was done using GIS techniques (ArcGIS) and vectorization of raster Images (Adobe Photoshop and Illustrator). Data on Yedoma thickness are obtained from boreholes and exposures reported in the scientific literature. The map and database are still preliminary and will have to undergo a technical and scientific vetting and review process. In their current form, we included a range of attributes for Yedoma area polygons based on lithological and stratigraphical information from the original source maps as well as a confidence level for our classification of an area as Yedoma (3 stages: confirmed, likely, or uncertain). In its current version, our database includes more than 365 boreholes and exposures and more than 2000 digitized Yedoma areas. We expect that the database will continue to grow. In this preliminary stage, we estimate the Northern Hemisphere Yedoma deposit area to cover approximately 625,000 km². We estimate that 53% of the total Yedoma area today is located in the tundra zone, 47% in the taiga zone. Separated from west to east, 29% of the Yedoma area is found in North America and 71 % in North Asia. The latter include 9% in West Siberia, 11% in Central Siberia, 44% in East Siberia and 7% in Far East Russia. Adding the recent maximum Yedoma region (including all Yedoma uplands, thermokarst lakes and basins, and river valleys) of 1.4 million km² (Strauss et al., 2013, doi:10.1002/2013GL058088) and postulating that Yedoma occupied up to 80% of the adjacent formerly exposed and now flooded Beringia shelves (1.9 million km², down to 125 m below modern sea level, between 105°E - 128°W and >68°N), we assume that the Last Glacial Maximum Yedoma region likely covered more than 3 million km² of Beringia. Acknowledgements: This project is part of the Action Group "The Yedoma Region: A Synthesis of Circum-Arctic Distribution and Thickness" (funded by the International Permafrost Association (IPA) to J. Strauss) and is embedded into the Permafrost Carbon Network (working group Yedoma Carbon Stocks). We acknowledge the support by the European Research Council (Starting Grant #338335), the German Federal Ministry of Education and Research (Grant 01DM12011 and "CarboPerm" (03G0836A)), the Initiative and Networking Fund of the Helmholtz Association (#ERC-0013) and the German Federal Environment Agency (UBA, project UFOPLAN FKZ 3712 41 106).