Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Age and structure of the southern Rockall Trough new evidence

The Rockall Trough separates the Rockall Plateau microcontinent from the shelf and slope west of the British Isles. The structure and age of the trough has been the source of considerable discussion. Although widely considered to be of oceanic origin, postulated ages for the spreading range from Permian to Cretaceous. New seismic profiles linked to the IPOD sites in the Bay of Biscay and to oceanic anomalies of known age are used to present a new assessment of the age and structure of the southern Rockall Trough. It is concluded that about 120 km of ocean crust is present in the trough and that spreading took place in the Albian-Maastrichtian interval.     

Permian volcanism in the Central Western Carpathians (Slovakia): Basin-and-Range type rifting in the southern Laurussian margin

The 1,500- to 2,000-m-thick Permian volcano-sedimentary Malu?iná Formation of the uppermost nappe of the Central Western Carpathians (a segment of the Alpine-Carpathian orogenic belt) occurs in several fault blocks distributed across Slovakia. This unit is a part of a post-Variscan overstep suite that followed accretion of the Gothic terranes to Laurussia. It consists of three upward-fining megacycles of semi-arid/arid, fluvial-lacustrine clastic redbeds and local dolomites and evaporites. Abundant intercalated volcanic rocks are predominantly mafic lava flows; volcaniclastic rocks and dykes are subordinate. Felsic rocks are represented by rare volcaniclastics and dykes. Compositionally, the mafic rocks are rift-related continental tholeiites with enriched light REE patterns having (La/Yb)_n ratios between 2 and 5.5 and with mantle-normalized patterns characterized by negative Nb-Ta anomalies. The rocks were derived from subcontinental lithospheric mantle and were affected by crustal contamination. It is inferred that the volcanism of the Malu?iná Formation formed in a Basin and Range tectonic setting in which rifting followed collision of the Palaeo-Tethys ridge with the trench bordering southern Laurussia. This model can be applied to other Permian volcanic suites of rift basins in the Eastern Alps and Carpathians over a strike-length of about 1,000 km, which indicates the width of the slab window.     

Co-diagenesis of iron and phosphorus in hydrothermal sediments from the southern East Pacific Rise: Implications for the evaluation of paleoseawater phosphate concentrations

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ∼19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ∼12 m. Molar P/Fe ratios are then relatively constant to a depth of ∼35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.     

Possible forerunners of droughts in agricultural areas of Russia

Considered is the regional index of anticyclonic circulation IpH taking account of the percentage of the area occupied by the significant positive anomalies of the geopotential at the level of 500 hPa for the main agricultural areas of Russia. Analyzed are the variations of the index in the 20th and 21st centuries using the NCEP/NCAR reanalysis data and the outputs of model experiments with the ECHAM5 climate model (Germany). Discussed is the possibility of revealing the drought forerunners using the combination of indices of anticyclonic circulation, quasi-biennial cyclicity in the wintertime equatorial stratosphere, and teleconnections.     

Application of the Genetic Algorithm to the Problem of Reconstruction of Missing Data

We study the problem of reconstruction (interpolation and extrapolation) of the vertical profiles of hydrochemical and hydrobiological elements according to incomplete sets of data with simultaneous filtration of short-period components based on expansions in empirical orthogonal functions. The genetic algorithm is used to compute the coefficients of expansion of profiles with missing data. We present the results of processing the data arrays on oxygen, chlorophyll A, and biogenic elements collected in the Black Sea in 1982–1993. The mean error of reconstruction of the profiles enables us to conclude that the proposed method has considerable advantages over the conventional approaches.     

Hamilton Harbour, Ontario: 8300 years of limnological and environmental change inferred from microfossil and isotopic analyses

Limnological changes in Hamilton Harbour, Lake Ontario, over the Holocene were investigated by using proxy evidence from diatoms and other siliceous microfossils in a radiometrically dated sediment core (HH26comp), together with environmental data derived from sediment pollen and oxygen and carbon isotope analyses. The evidence demonstrates that the site of Hamilton Harbour has changed over the past 8300 y from a shallow, separate waterbody, to a deep embayment of Lake Ontario. The earliest evidence, from 8300 BP to 7000 BP, is of a mesotrophic pond of moderate alkalinity, warmer than present, and probably with an extensive marginal wetland. An initial transitory connection with the rising water level of Lake Ontario was established at c. 7000 BP, possibly via a deep outlet channel. This connection is 2000 y earlier then previously estimated. Permanent confluence with Lake Ontario was established at c. 6200 BP, causing a decline in inferred trophic level and water temperatures. Microfossils reach a minimum at 4400 BP coincident with the Nipissing Flood. Decreased mixing of Lake Ontario water from about 4000 BP following the Nipissing Flood highstand is evidenced in isotopic and diatom data. Three isolated shifts in the diatom spectrum at c. 4900 BP, 4500 BP, and 3500 BP may be associated with extreme turbidity or storm deposit events. Between 3200 BP and 280 BP, Hamilton Harbour was evidently a moderately alkaline embayment of Lake Ontario, oligotrophic to mesotrophic, and relatively cooler than present. The final 280 y sedimentary record reveals the magnitude of anthropogenically induced changes to the harbour, including eutrophication and organic pollution.