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.     

Cesstibtantite—a geologic introduction to the inverse pyrochlores

Summary The crystal structure of cesstibtantite has been solved from diffractometer data collected on samples from Leshaia, Russia and the Tanco pegmatite, Manitoba. Cesstibtantite from the Leshaia pegmatite (type locality) hasa 10.515(2) Å, space groupFd3m, composition Cs_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_O.91(Ta_1.88Nb_0.12)₂(O_5.69[OH, F]_0.31)₆(OH, F)_0.69, Z 8; its structure was refined toR 3.8,wR 4.3% using 96 observed (F > 3[F]) reflections (MoK). Cesstibtantite from the Tanco pegmatite hasa 10.496(1) Å, space groupFd3m, composition (Cs_0.22K_0.01)_0.23(Na_0.45Sb_0.39Pb_0.14· Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78[OH,F]_0.22)₆(OH,F)_0.55,Z 8; its structure was refined toR 3.9w R 3.7% using 104 observed reflections. Cesstibtantite differs from the normal pyrochlores in that it contains significant amounts of very large cations such as Cs. As these cations are too large (^VIII[r] > 1.60 Å) for the conventional [8]-coordinated A site, they occupy the [18]-coordinated site, which normally contains monovalent anions. Natural cesstibtantite samples are non-ideal in that both Cs and monovalent anions occur at the site; thus cesstibtantite is intermediate to thenormal pyrochlores (with only monovalent anions at the site) and theinverse pyrochlores (with only large cations at the site).

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Cesstibtantit—eine geologische Einfiihrung in die inversen Pyrochlore

Zusammenfassung Die Kristallstruktur von Cesstibtantit wurde auf der Basis von Diffraktometerdaten von Proben von Leshaia, Russland and dem Tanco Pegmatit, Manitoba, gelöst. Cesstibtantit aus dem Leshaia Pegmatit (Typlokalität) hat a 10.515(2) Å, RaumgruppeFd3m, die Zusammensetzung CS_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_0.91(Ta_1.88Nb_0.12)₂· (O_5.69OH, F_0.31)₆(OH, F)_0.69 Z 8; die Struktur wurde aufR 3.8,wR 4.3% verfeinert unter Benützung von 96 beobachteten Reflexen. Cesstibtantit vom Tanco Pegmatit hat a 10.496(1) Å, RaumgruppeFd3m, die Zusammensetzung (Cs_0.22K_0.01)_0.23(Na_0.45· Sb_0.39Pb_0.14Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78OH,F_0.22)₆(OH,F)_0.55,Z 8; seine Struktur wurde aufR 3.9wR 3.7% auf der Basis von 104 beobachteten Rettexen verfeinert. Cesstibtantit unterscheidet sich von normalen Pyrochloren insofern, als er signifikante Mengen von sehr großen Kationen, wie z.B. Cs enthält. Da these Kationen zu groß sind (^VIII r 1.60 Å) für eine konventionelle [8]-koordinierteA Stelle, nehmen she die [18]-koordinierten Positionen ein, welche normalerweise monovalente Anionen enthalten. Natürliche Cesstibtantitproben sind nicht ideal insofern als sowohl Cs als auch monovalente Anionen in der Position vorkommen. Somit ist Cesstibtantit intermediär zu den normalen Pyrochloren (mit nur monovalenten Anionen auf der Position) and den inversen Pyrochloren (mit ausschließlichen großen Kationen an der Position).

     

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.     

An ephemeral turbidity maximum generated by resuspension of organic-rich matter in a macrotidal estuary, S.W. Wales

An ephemeral estuarine turbidity maximum (ETM) occurs at high water in the macrotidal Taf estuary (SW Wales, United Kingdom). A new mechanism of ETM formation, due to resuspension and advection of material by flood tidal currents, is observed that differs from classical mechanisms of gravitational circulation and tidal pumping. The flood tide advances across intertidal sand flats in the main body of the estuary, progressively entraining material from the rippled sands. Resuspension creates, a turbid front that has suspended sediment concentrations (SSC) of about 4,000 mg I⁻¹ by the time it reaches its landward limit which is also the landward limit of salt penetration. This turbid body constitutes the ETM. Deposition occurs at high slack water but the ETM retains SSC values up to 800 mg I⁻¹, 1–2 orders of magnitude greater than ambient SSC values in the river and estuarine waters on either side. The ETM retreats down the estuary during the ebb; some material is deposited thinly across emergent intertidal flats and some is flushed out of the estuary. A new ETM is generated by the next flood tide. Both location and SSC of the ETM scale on Q/R³ where Q is tidal range and R is river discharge. The greatest expression of the ETM occurs when a spring tide coincides with low river discharge. It does not form during high river discharge conditions and is poorly developed on neap tides. Particles in the ETM have effective densities (120–160 kg m⁻³) that are 3–4 times less than those in the main part of the estuary at high water. High chlorophyll concentrations in the ETM suggest that flocs probably originate from biological production in the estuary, including production on the intertidal sand flats.     

Using a Thermal Proxy to Examine Sediment–Water Exchange in Mid-Continental Shelf Sandy Sediments

Fluid exchange across the sediment–water interface in a sandy open continental shelf setting was studied using heat as a tracer. Summertime tidal oscillation of cross-shelf thermal fronts on the South Atlantic Bight provided a sufficient signal at the sediment–water interface to trace the advective and conductive transport of heat into and out of the seabed, indicating rapid flushing of ocean water through the upper 10–40 cm of the sandy seafloor. A newly developed transport model was applied to the in situ temperature data set to estimate the extent to which heat was transported by advection rather than conduction. Heat transported by shallow 3-D porewater flow processes was accounted for in the model by using a dispersion term, the depth and intensity of which reflected the depth and intensity of shallow flushing. Similar to the results of past studies in shallower and more energetic nearshore settings, transport of heat was greater when higher near-bed velocities and shear stresses occurred over a rippled bed. However, boundary layer processes by themselves were insufficient to promote non-conductive heat transport. Advective heat transport only occurred when both larger boundary layer stresses and thermal instabilities within the porespace were present. The latter process is dependent on shelf-scale heating and cooling of bottom water associated with upwelling events that are not coupled to local-scale boundary layer processes.