Iron species determination to investigate early diagenetic reactivity in marine sediments

Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative

Environmental considerations for subseabed geological storage of CO2: a review

Many countries are now using or investigating offshore geological storage of CO2 as a means to reduce atmospheric CO2 emissions. Although associated research often focuses on deep-basin geology (e.g. seismic, geomagnetics), environmental data on the seabed and shallow subseabed is also crucial to (1) detect and characterise potential indicators of fluid seeps and their potential connectivity to targeted storage reserves, (2) obtain baseline environmental data for use in future monitoring, and (3) acquire information to facilitate an improved understanding of ecosystem processes for use in impact prediction. This study reviews the environmental considerations, including potential ecological impacts, associated with subseabed geological storage of CO2. Due to natural variations in CO2 levels in seafloor sediments, baseline CO2 measurements and knowledge of physical–chemical processes affecting the regional distribution of CO2 and pH are critical for the design of appropriate monitoring strategies to assess potential impacts of CO2 seepage from subseabed storage reservoirs. Surficial geological and geophysical information, such as that acquired from multibeam sonar and sub-bottom profiling, can be used to investigate the connectivity between the deep reservoirs and the surface, which is essential in establishing the reservoir containment properties. CO2 leakage can have a pronounced effect on sediments and rocks which in turn can have carryover effects to biogeochemical cycles. The effects of elevated CO2 on marine organisms are variable and species-specific but can also have cascading effects on communities and ecosystems, with marine benthic communities at some natural analogue sites (e.g. volcanic vents) showing decreased diversity, biomass, and trophic complexity. Despite their potential applications, environmental surveys and data are still not a standard and integral part of subseabed CO2 storage projects. However, the habitat mapping and seabed characterisation methodology that underpins such surveys is well developed and has a strong record of providing information to industry and decision makers. This review provides recommendations for an integrated and interdisciplinary approach to offshore geological storage of CO2, which will benefit national programs and industry and will be valuable to researchers in a broad range of disciplines

Life in cold seeps. A synthesis of biogeochemical and ecological data from Kazan mud volcano, eastern Mediterranean sea

Recent field observations have identified the widespread occurrence of fluid seepage through the eastern Mediterranean Sea floor in association with mud volcanism or along deep faults. Gas hydrates and methane seeps are frequently found in cold seep areas and were anticipated targets of the MEDINAUT/MEDINETH initiatives. The study presented herein has utilized a multi-disciplinary approach incorporating observations and sampling of visually selected sites by the manned submersible Nautile and by ship-based sediment coring and geophysical surveys. The study focuses on the biogeochemical and ecological processes and conditions related to methane seepage, especially the anaerobic oxidation of methane (AOM), associated with ascending fluids on Kazan mud volcano in the eastern Mediterranean. Sampling of adjacent box cores for studies on the microbiology, biomarkers, pore water and solid phase geochemistry allowed us to integrate different biogeochemical data within a spatially highly heterogeneous system. Geophysical results clearly indicate the spatial heterogeneity of mud volcano environments. Results from pore water geochemistry and modeling efforts indicate that the rate of AOM is ~6 mol m−2 year−1, which is lower than at active seep sites associated with conditions of focused flow, but greater than diffusion-dominated sites. Furthermore, under the non-focused flow conditions at Kazan mud volcano advective flow velocities are of the order of a few centimeters per year and gas hydrate formation is predicted to occur at a sediment depth of about 2 m and below. The methane flux through these sediments supports a large and diverse community of micro- and macrobiota, as demonstrated by carbon isotopic measurements on bulk organic matter, authigenic carbonates, specific biomarker compounds, and macrofaunal tissues. Because the AOM community appears to be able to completely oxidize methane at the rate it is seeping through the sediments, ultimate sinks for methane in this environment are authigenic carbonates and biomass. Significant differences in organic geochemical data between this site and those of other cold seep environments, even within the eastern Mediterranean mud volcanoes, indicate that the microbiological communities carrying out AOM varies depending on specific conditions such as methane flux and salinity

Thermal treatment of simulant plutonium contaminated materials from the Sellafield site by vitrification in a blast-furnace slag

Four waste simulants, representative of Plutonium Contaminated Materials (PCMs) at the Sellafield site, were vitrified through additions of Ground Granulated Blast-furnace Slag (GGBS). Ce (as a Pu surrogate) was effectively partitioned into the slag product, enriched in an amorphous CaO–Fe2O3–Al2O3–SiO2 phase when other crystalline phases were also present. Ce L3 edge XANES data demonstrated Ce to be present as trivalent species in the slag fraction, irrespective of the waste type. Estimated volume reductions of ca. 80–95% were demonstrated, against a baseline of uncompacted 200 L PCM waste drums. The dissolution behaviour of PCM slag wasteforms was investigated at 50 �C in saturated Ca(OH)2 solution under N2 atmosphere, to simulate the hyperalkaline anoxic environment of a cementitious UK Geological Disposal Facility for Intermediate Level Waste (ILW). These experiments demonstrated the performance of the slag wasteforms to be comparable to that of other vitrified ILW materials considered potentially suitable for geological disposa