Ground- and surface water mass balances to ensure protection of St Lawrence River ecostystems

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Ruthenium/Iridium Ratios in the Cretaceous-tertiary Boundary Clay: Implications for Global Dispersal and Fractionation Within the Ejecta Cloud

Ruthenium (Ru) and iridium (Ir) are the least mobile platinum group elements (PGE's) within the Cretaceous-Tertiary (K-T) boundary clay (BC). The Ru/Ir ratio is, therefore, the most useful PGE interelement ratio for distinguishing terrestrial and extraterrestrial contributions to the BC. The Ru/Ir ratio of marine K-T sections (1.77 +/- 0.53) is statistically different from that of the continental sections (0.93 +/- 0.28). The marine Ru/Ir ratios are chondritic (C1 = 1.48 +/- 0.09), but the continental ratios are not. We discovered an inverse correlation of shocked quartz size (or distance from the impact site) and Ru/Ir ratio. This correlation may arise from the difference in Ru and Ir vaporization temperature and/or fractionation during condensation from the ejecta cloud. Postsedimentary alteration, remobilization, or terrestrial PGE input may be responsible for the Ru/Ir ratio variations within the groups of marine and continental sites studied. The marine ratios could also be attained if approximately 15 percent of the boundary metals were contributed by Deccan Trap emissions. However, volcanic emissions could not have been the principal source of the PGE's in the BC because mantle PGE ratios and abundances are inconsistent with those measured in the clay. The Ru/Ir values for pristine Tertiary mantle xenoliths (2.6 +/- 0.48), picrites (4.1 +/- 1.8), and Deccan Trap basalt (3.42 +/- 1.96) are all statistically distinct from those measured in the K-T BC

The SPICE carbon isotope excursion in Siberia: a combined study of the upper Middle Cambrian-lowermost Ordovician Kulyumbe River section, northwestern Siberian Platform

An integrated, high-resolution chemostratigraphic (C, O and Sr isotopes) and magnetostratigraphic study through the upper Middle Cambrian–lowermost Ordovician shallowmarine carbonates of the northwestern margin of the Siberian Platform is reported. The interval was analysed at the Kulyumbe section, which is exposed along the Kulyumbe River, an eastern tributary of the Enisej River. It comprises the upper Ust’-Brus, Labaz, Orakta, Kulyumbe, Ujgur and lower Iltyk formations and includes the Steptoean positive carbon isotopic excursion (SPICE) studied here in detail from upper Cambrian carbonates of the Siberian Platform for the first time. The peak of the excursion, showing δ13C positive values as high as+4.6‰and least-altered 87Sr/86Sr ratios of 0.70909, is reported herein from the Yurakhian Horizon of the Kulyumbe Formation. The stratigraphic position of the SPICE excursion does not support traditional correlation of the boundary between theOrakta and Labaz formations at the Kulyumbe River with its supposedly equivalent level in Australia, Laurentia, South China and Kazakhstan, where the Glyptagnostus stolidotus and G. reticulatus biozones are known to immediately precede the SPICE excursion and span the Middle–Upper Cambrian boundary. The Cambrian–Ordovician boundary is probably situated in the middle Nyajan Horizon of the Iltyk Formation, in which carbon isotope values show a local maximum below a decrease in the upper part of the Nyajan Horizon, attributed herein to the Tremadocian Stage. A refined magnetic polarity sequence confirms that the geomagnetic reversal frequency was very high during Middle Cambrian times at 7–10 reversals per Ma, assuming a total duration of about 10 Ma and up to 100 magnetic intervals in the Middle Cambrian. By contrast, the sequence attributed herein to the Upper Cambrian on chemostratigraphic grounds contains only 10–11 magnetic intervals

A Cenozoic-style scenario for the end-Ordovician glaciation

The end-Ordovician was an enigmatic interval in the Phanerozoic, known for massive glaciation potentially at elevated CO2 levels, biogeochemical cycle disruptions recorded as large isotope anomalies and a devastating extinction event. Ice-sheet volumes claimed to be twice those of the Last Glacial Maximum paradoxically coincided with oceans as warm as today. Here we argue that some of these remarkable claims arise from undersampling of incomplete geological sections that led to apparent temporal correlations within the relatively coarse resolution capability of Palaeozoic biochronostratigraphy. We examine exceptionally complete sedimentary records from two, low and high, palaeolatitude settings. Their correlation framework reveals a Cenozoic-style scenario including three main glacial cycles and higher-order phenomena. This necessitates revision of mechanisms for the end-Ordovician events, as the first extinction is tied to an early phase of melting, not to initial cooling, and the largest δ13C excursion occurs during final deglaciation, not at the glacial apex

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1- to 15-m-thick beds within the approximate to2.0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680-m-thick formation is composed of a stromatolite-dolomite-'red bed' sequence formed in a complex combination of shallow-marine and non-marine, evaporitic environments. Dolomite-collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by delta C-13 values from +7.1 parts per thousand to +11.6 parts per thousand (V-PDB) and delta O-18 ranging from 17.4 parts per thousand to 26.3 parts per thousand (V-SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high delta C-13 values ranging from +9.0 parts per thousand to +11.6 parts per thousand and delta O-18 values of 20.0-25.7 parts per thousand. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water-derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high delta C-13 values reflect a combined contribution from both global and local carbon reservoirs. A C- 13-rich global carbon reservoir (delta C-13 at around +5 parts per thousand) is related to the perturbation of the carbon cycle at 2.0 Ga, whereas the local enhancement in C-13 (up to +12 parts per thousand) is associated with evaporative and restricted environments with high bioproductivity

Applications of stable water and carbon isotopes in watershed research: Weathering, carbon cycling, and water balances

Research on rivers has traditionally involved concentration and flux measurements to better understand weathering, transport and cycling of materials from land to ocean. As a relatively new tool, stable isotope measurements complement this type of research by providing an extra label to characterize origin of the transportedmaterial, its transfer mechanisms, and natural versus anthropogenic influences. These new stable isotope techniques are scalable across a wide range of geographic and temporal scales. This review focuses on three aspects of hydrological and geochemical river research that are of prime importance to the policy issues of climate change and include utilization of stable water and carbon isotopes: (i) silicate and carbonate weathering in river basins, (ii) the riverine carbon and oxygen cycles, and (iii) water balances at the catchment scale. Most studies at watershed scales currently focus on water and carbon balances but future applications hold promise to integrate sediment fluxes and turnover, ground and surface water interactions, as well as the understanding of contaminant sources and their effects in river systems

Discriminating cool-water from warm-water carbonates and their diagenetic environments using element geochemistry: the Oligocene Tikorangi Formation (Taranaki Basin) and the dolomite effect

Fields portrayed within bivariate element plots have been used to distinguish between carbonates formed in warm- (tropical) water and cool- (temperate) water depositional settings. Here, element concentrations (Ca, Mg, Sr, Na, Fe, and Mn) have been determined for the carbonate fraction of bulk samples from the late Oligocene Tikorangi Formation, a subsurface, mixed dolomite-calcite, cool-water limestone sequence in Taranaki Basin, New Zealand. While the occurrence of dolomite is rare in New Zealand Cenozoic carbonates, and in cool-water carbonates more generally, the dolomite in the Tikorangi carbonates is shown to have a dramatic effect on the "traditional" positioning of cool-water limestone fields within bivariate element plots. Rare undolomitised, wholly calcitic carbonate samples in the Tikorangi Formation have the following average composition: Mg 2800 ppm; Ca 319 100 ppm; Na 800 ppm; Fe 6300 ppm; Sr 2400 ppm; and Mn 300 ppm. Tikorangi Formation dolomite-rich samples (>15% dolomite) have average values of: Mg 53 400 ppm; Ca 290 400 ppm; Na 4700 ppm; Fe 28 100 ppm; Sr 5400 ppm; and Mn 500 ppm. Element-element plots for dolomite-bearing samples show elevated Mg, Na, and Sr values compared with most other low-Mg calcite New Zealand Cenozoic limestones. The increased trace element contents are directly attributable to the trace element-enriched nature of the burial-derived dolomites, termed here the "dolomite effect". Fe levels in the Tikorangi Formation carbonates far exceed both modern and ancient cool-water and warm-water analogues, while Sr values are also higher than those in modern Tasmanian cool-water carbonates, and approach modern Bahaman warm-water carbonate values. Trace element data used in conjunction with more traditional petrographic data have aided in the diagenetic interpretation of the carbonate-dominated Tikorangi sequence. The geochemical results have been particularly useful for providing more definitive evidence for deep burial dolomitisation of the deposits under the influence of marine-modified pore fluids

Chemostratigraphy of Neoproterozoic carbonates: implications for 'blind dating'

The delta C-13(carb) and Sr-87/Sr-86 secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local delta C-13(carb) fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative delta C-13(carb) excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590-544 Myr interval, and two age-groups at 660-610 and 740-690 Myr can be resolved