Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Chemistry of Jurassic/Cretaceous black shales

Black shale samples of Jurassic to Cretaceous age recovered during the 'Norwegian Shelf Drilling Program' between 1987 and 1991 from Sites 7430/10-U-01 (Barents Sea), 6814/04-U-02 (Norwegian Shelf near the Lofoten) and 6307/07-U-02 (Norwegian Shelf near Trondheim) were analyzed for major and trace elements. These laminated black shales are characterized by high total organic carbon (TOC) and total sulfur (TS) contents as well as by significant enrichments in several redox-sensitive and/or sulfide-forming trace metals (Ag, Bi, Cd, Co, Cr, Cu, Mo, Ni, Re, Sb, Tl, U, V, and Zn). Enrichment factors relative to 'average shale' are comparable to those found in Cenomanian-Turonian boundary event (CTBE) black shales and Mediterranean sapropels. The Re content is high in the studied black shales, with maximum values up to 1221 ng/g. Re/Mo ratios averaging 2.3*10**-3 are close to the seawater value. High trace metal enrichments and Re/Mo ratios close to the seawater value point to a dominantly anoxic and sulfidic water column during black shale formation. Interbeds with higher Re/Mo ratios, especially in high-resolution sampled core sections, point to brief periods of suboxic conditions. Additionally, enhanced Zn concentrations in the black shales from the Barents Sea support the assumption that hydrothermal activity was also high during black shale deposition. Trace metal signatures of black shales at different drill sites on a transect along the Norwegian Shelf are not only influenced by water depth but also by their location in the boreal realm. Metal enrichments are higher in the northern compared to the southern sites. Volgian (=Tithonian 151-144 Ma BP) black shales exhibit elevated trace metal contents in comparison to their Berriasian (144-137 Ma BP) counterparts. This probably reflects a change in the circulation pattern during periods of black shale formation. Therefore different paleoceanographic conditions, probably controlled by climatic change linked to the transgression of the paleo-sealevel and the North Atlantic opening, may have developed from the Volgian to the Berriasian.

Estudio a escala laboratorio y planta piloto, de la adsorción de NO y SO2, sobre CR2O3/AL2O3 a altas temperaturas, provenientes de fuentes fijas

Resumen: Se planificaron las experiencias con el objeto de analizar el comportamiento del catalizador en la columna metálica de mayor diámetro. Se modificaron las masas usadas para verificar la eficiencia de retención respecto de la masa. Se realizaron ciclos de adsorción, desorción y readsorción sobre una misma muestra para determinar variaciones en la eficiencia del catalizador. En otra fase, en colaboración con el Dr. V. A. Ranea y el Prof. E. E. Mola (INIFTA, UNLP), se desarrolló el estudio teórico de la adsorción de moléculas de SO2, CH4, CO2, O2 y CO sobre Cr2O3(0001) mediante Teoría del Funcional Densidad (programa VASP, Vienna Ab-initio Simulation Package), y el estudio de la cinética de la reacción entre CH4, SO2 y el O2 junto con la presencia de especies sulfito y sulfato. Este estudio permitió hallar los sitios preferenciales de adsorción de Sº y la posible competencia con SO2 experimentalmente y por cálculos teóricos. Dentro del marco de la presente línea de investigación, la Ing. Sabrina Hernández Guiance continúa realizando experiencias en el marco del proyecto conjunto con el INIFTA, las cuales forman parte del desarrollo de su tesis doctoral. Experimentalmente, se observa que la eficiencia de adsorción del catalizador respecto al SO2 es cercana al 100%. Se observa un pico de termodesorción a 1120 K. Luego, se estudió la oxidación de CH4 con SO2. Se observa que hay producción de CO2 desde temperatura inicial, seguida de un aumento significativo en la formación de CO2 hasta 330-340 K. Luego, la producción de CO2 se mantiene aproximadamente constante. Mediante el empleo de la ecuación de Arrhenius y resultados experimentales, se obtuvo la energía de activación de la reacción global, de 7 Kcal/mol. Mediante estudios teóricos, se determinó que la energía de quimisorción del SO2 sobre el Cr2O3 es de -3.09 eV para la configuración más estable, una energía de adsorción de O2 en estado disociativo de -1.567 eV, una energía para CH4 sobre O2 adsorbido previamente de -0.335 eV, y - 0.812 eV para la configuración más estable de CO2 sobre el sustrato.