Formation water oxygen isotope fractionation

The water sequestered in the hydrate lattice is preferentially enriched in 0 and deuterium (D), thus the isotopic composition of the water in the pore spaces collected from gas hydrate bearing sediment can provide additional information on the abundance and the characteristics of these deposits. Pore fluid samples that had been modified by hydrate decomposition upon core recovery during ODP Legs 146 (Kastner et al. 1998), and 164 (Matsumoto and Borowski 2000) provided the first field data to derive the oxygen isotope fractionation factor for in situ hydrate formation. A more comprehensive sampling... 

Calcium carbonate is also the main constituent of the shells of sea animals, which make their shells from elements acquired from the surrounding waters. Now, the degree of fractionation of the oxygen isotopes as well as the formation of mineral carbonates and of animal shells in sea waters are determined on the basis of the temperature-dependent fractionation of the isotopes of oxygen the oxygen isotope composition of these materials reflects, therefore, the temperature at the time of their formation. Thus determining the isotope ratio between the stable isotopes of oxygen... 

Any isotope fractionation occurring in such a way that the products are isolated from the reactants immediately after formation will show a characteristic trend in isotopic composition. As condensation or distiUation proceeds, the residual vapour or liquid will become progressively depleted or enriched with respect to the heavy isotope. A natural example is the fractionation between oxygen isotopes in the water vapour of a cloud and the raindrops released from the cloud. The resulting decrease of the iso/i o ratio in the residual vapour and the instantaneous isotopic composition of the raindrops released from the cloud are shown in Fig. 1.4 as a function of the fraction of vapour remaining in the cloud. 

To summarize, the most probable explanation of the C isotope spread in the shallow-water facies of the Manjeri Formation (Spring Valley and Shavi sediments and Rupemba (Spring Valley) stromatolites), and in the Cheshire Formation stromatohtes and black shales is thus that carbon isotope fractionation records a diverse ecology that existed based primarily on oxygenic photosynthesis, but with associated organisms... 

Table 4. Bulk-rock carbon and oxygen isotope results for dolomite cement in the Angel Formation, Angel Field. Precipitation temperatures for dolomite cement were calculated using the fractionation factor of Northrop Clayton (1966) and assuming a marine composition for the original 8 0 pore water (6 0 = 0%o). When integrating the calculated dolomite precipitation temperatures (93-97 °C) with the geohistory plot for Angel-2 (Fig. 4) an Eocene to Late Miocene age for the dolomite cement is suggested, closely matching the seismic evidence (Fig. 22c)...

For water masses deeper than 2000 m, Zahn and Mix (1991) obtained a slope as high as 1.53. This gradient is explained with the formation of sea-ice in the source areas especially for southern component water masses. Since the freezing of polar snrface waters raises the salinity, but does not fractionate oxygen isotopes, southern source deep water masses, like the Antarctic Bottom Water, exhibit relatively low 5 0 values, and so do other water masses, which are derived from the admixtnre of sonth polar water masses (Macken-sen2001). 

The carbonate horizons of the Cheshire and Manjeri Formations contain extensive well-preserved stromatolites. These were formed in shallow or intertidal waters, as demonstrated by interbedded ripple-marked and mud-cracked silts. Texturally, the limestones show many indications of organic activity and gas release structures (Martin et al. 1980). The simplest uni-formitarian explanation is that the structures were built by cyanobacteria. Isotopically, carbon from kerogen in the stromatolites typically has 6 C = -25 to -30%o. This implies but does not prove fractionation by rubisco of carbon captured from the atmosphere-ocean system. Carbonate in Cheshire limestones is typically close to 0%o, suggesting that carbon in the atmosphere-ocean system was modulated by rubisco and dominated by oxygenic photosynthesis on a planetary scale (Fig. 1) at least by this date. It should be noted that the c. 3 Ga Steep Rock stromatolites are similar (work by Abell, Grassineau and Nisbet). 

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