Isotopic data

Meteorites show a very large difference in ratio between carbonate and 

Although fractionations of 60-80%o are theoretically possible under equilibrium conditions at very low temperatures ( 0 °C), they are not observed on Earth. Urey (1967) therefore proposed that the two types of carbon came from two unrelated reservoirs, whereas Arrhenius and Alfven (1971) suggested fractionation during carbonate growth from the gas phase, involving multiple desorption or metastable molecules. 

It turns out, however, that the Fischer-Tropsch reaction gives an isotopic fractionation of just the right sign and magnitude, owing to a kinetic isotopic effect (Lancet and Anders, 1970 Lancet, 1972). The temperature dependence of the fractionation between 375 and 500 K suggests that the observed fractionations in Cl and C2 chondrites correspond to about 360 to 400 K (Fig. 11). These values agree rather well with the formation temperatures of carbonates and silicates, based on ratios, 360 K for Cl s and 380 K for C2 s (Onuma et al., 1972, 

The Miller-Urey reaction gives a fractionation of only —0.4 + 0.2%o (Lancet, 1972). 

This interpretation has been questioned by Chang and Mack (1978), who found that water-soluble organics, especially amino acid extracts from the Murchison meteorite, were almost as heavy as carbonate C [8C (PDB) = -1-23 to -l-44%o vs. +44.4%o], in contrast to the much lighter insoluble polymer (—15.3 to —16.8%o) or benzene-methanol extracts ( + 5.0%o)- They suggested that these various forms of carbon represent several stages of carbon condensation in the solar nebula, in different environments separated in space and possibly in time . 

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Once the model was complete, it was adjusted to a steady state condition and tested using historic carbon isotope data from the atmosphere, oceans and polar ice. Several important parameters were calculated and chosen at this stage. Sensitivity analysis indicated that results dispersal of the missing carbon - were significantly influenced by the size of the vegetation carbon pool, its assimilation rate, the concentration of preindustrial atmospheric carbon used, and the CO2 fertilization factor. The model was also sensitive to several factors related to fluxes between ocean reservoirs. 

The interpretation of the factors mentioned above in the context of palaeodietary research is not straightforward a lack of nitrogen isotope data in relevant plant species makes the situation even more complicated. The observed variability in plants, even within ecosystems, is so extensive and so unpredictable that modelling of the behaviour of natural nitrogen abundances in plants is fraught with difficulties because there are no simple, universal laws governing the site-specific details of the N cycle, there will be no simple, universal laws of 8 N (in plants) (Handley and Raven 1992 Handley and Scrimgeour 1996). 

Below we will describe some individual cases where we think that may be possible to pinpoint the cause for isotopic variations, and will try to give a general idea of human variations that can be found in Europe. The characterization will not be comprehensive, given the fact that we have only recently started analyzing and comparing isotopic data across Europe, but we hope that a start can be made with matching actually observed variations and the causes behind them. 

Two possibilities for the observed enriched values for many of the grazers, and the often concomitant but slight enrichment of browsers (Fig. 5.6), present themselves. Either these shifts represent atmospheric CO2 enrichment shifts at particular periods during the last -lOOKa represented (the Late Pleistocene), or a hitherto unknown or unrecognized fractionation process has taken place during burial and fossilization. The former hypothesis could be tested by comparison of observations from a larger sample set from the site, with CO2 concentration and carbon isotope data from Antarctic ice-core records or high resolution marine isotope records. 

Figure 5.6. 5 C data for browsers and grazers from Border cave, plotted against age (vertical scale). The shaded areas represent the 5 C values of modem grazers and browsers. Filled squares and circles are tooth enamel the open square is bone. The chronology obtained from ESR measurements of faunal enamel has been used hence the sequence appears somewhat younger than outlined previously (Grun et al. 1990 Beaumont et al. 1978). The sequence is in fact longer, but no isotopic data are available beyond Stratum IGBS.LRA ( 80Ka).

In the million year range, however, there is clearer evidence for isotopic alteration which also apparently increases with age. Unfortunately, at present there are few reliable browser and grazer data beyond the Late Pleistocene, i.e., in the Middle Pleistocene, which would allow determination of the periods during which bone apatite and enamel begin to deviate. The indications are that the timing should be different. Material from the site of Florisbad falls within the late Middle Pleistocene ( 125-200 Ka), but at present carbon isotope data are only available for three species of uncertain and/or opportunistic diets (Brink and Lee-Thorp 1992), so that extent or direction of isotopic alteration is impossible to separate from dietary vagaries. 

Two alternate methods have recently been developed and both are used in the present study. A laser probe analytical method provided the majority of the oxygen isotope data (see Kohn et al. 1996 for details on testing and developing the method). Laser probes were originally developed for the stable isotope analysis of silicates, oxides, and sulfides in ciystalline rocks (Crowe... 

Ambrose, S.H. and Norr, L. 1992 On stable isotopic data and prehistoric subsistence in the Soconusco region. Current Anthropology 33 401 04. 

Modeling Protein Diagenesis in Ancient Bone Towards a Validation of Stable Isotope Data... 

Table 9.4. C N molar ratios (calculated and measured), total C and N content and stable carbon and nitrogen isotope data from bacteria, their growth medium (nutrient broth), and from collagen (infected and non-infected marten bone). The bacteria for inoculation were raised on nutrient broth (nb), with/without additives.

Abe Y, D Hunkeler (2006) Does the Raleigh equation apply to evaluate field isotope data in contaminant hydrogeology Environ Sci Technol 40 1588-1596. 

Sulfur isotopic data of separated pyrite as the commonest sulfide mineral (Kajiwara, 1971 Kajiwara and Date, 1971) show different values for the three sub-types of Horikoshi and Shikazono (1978). The values of pyrite in the C sub-type deposits are higher than the values of pyrite from the Y and B sub-types. The values of pyrite from the Y sub-type seem to be slightly higher than those from the B sub-type. Kajiwara and Date (1971) are of a different opinion the values from the Kosaka district are higher than those in the Hanaoka district, because all sulfur isotopic data from the C sub-type were obtained in the Kosaka district. The sulfur isotopic data on the obtained Uwamuki deposits of the B sub-type in the Hanaoka district indicate systematic decrease in 8 S passing from the yellow ore (4-7%o) to the black siliceous ore (4-5%c) (Bryndzia et al., 1983). Kajiwara and Date s data (1971) include three values of pyrite in the Doyashiki deposit of C sub-type in the Hanaoka district. The main Doyashiki... 

Lead isotopic data on Kuroko deposits, vein-type deposits in Honshu and volcanic rocks are summarized and plotted in Fig. 1.44 (Fehn et al., 1983). 

Lead isotopic data support this interpretation namely, these data clearly indicate leaching of lead from the rocks (Pehn et al., 1983). 

Wolery (1978) and Reed (1982, 1983) have indicated based on a computer calculation of the change in chemistry of aqueous solution and mineralogy during seawater-rock interactions that epidote is formed under the low water/rock ratio less than ca. 50 by mass. Humphris and Thompson (1978), Stakes and O Nell (1982) and Mottl (1983) have also suggested on the basis of their chemical and oxygen isotopic data of the altered ridge basalts that epidote is formed by seawater-basalt interaction at elevated temperatures (ca. 200-350°C) under the rock-dominated conditions. If epidote can be formed preferentially under such low water/rock ratio, the composition of epidote should be influenced by compositions of the original fresh rocks. 

Lead isotopic data on the epithermal deposits together with Kuroko deposits are plotted in Fig. 1.116 (Sato and Sasaki, 1973 Sato et al., 1973, 1981 Sato, 1975 Sasaki et al., 1982 Sasaki, 1987 Fehn et al., 1983). It is evident that lead isotopic compositions of epithermal vein ores are more scattered than Kuroko ores, although averaged values are similar to the Kuroko ores. This variation seems to be due to the difference in crustal materials underlying the ore deposits Lead isotopic compositions of different ore deposits which formed at different ages in the same district show the same values (Sasaki, 1974). 

This mechanism as a main cause for epithermal-type Au deposition is supported by sulfur isotopic data on sulfides. Shikazono and Shimazaki (1985) determined sulfur isotopic compositions of sulfide minerals from the Zn-Pb and Au-Ag veins of the Yatani deposits which occur in the Green tuff region. The values for Zn-Pb veins and Au-Ag veins are ca. +0.5%o to -f4.5%o and ca. -l-3%o to - -6%c, respectively (Fig. 1.126). This difference in of Zn-Pb veins and Au-Ag veins is difficult to explain by the equilibrium isotopic fractionation between aqueous reduced sulfur species and oxidized sulfur species at the site of ore deposition. The non-equilibrium rapid mixing of H2S-rich fluid (deep fluid) with SO -rich acid fluid (shallow fluid) is the most likely process for the cause of this difference (Fig. 1.127). This fluids mixing can also explain the higher oxidation state of Au-Ag ore fluid and lower oxidation state of Zn-Pb ore fluid. Deposition of gold occurs by this mechanism but not by oxidation of H2S-rich fluid. 

Figure 1.151. Sulfur isotopic compositions of sulfides in the vein-type and Kuroko deposits. Solid box represents sulfur isotopic data from the ore deposits occurring in basement rocks (Shikazono and Shimizu, 1993).

The sulfur isotopic data are consistent with geologic environments of Hg and Sb deposits Sedimentary rocks are dominant and marine rocks are not present in Sb-Hg mineralization districts. However, a few samples of stibnite and cinnabar from the deposits in Green tuff region display high S S values. In contrast of this interpretation on the origin of sulfur, Ishihara and Sasaki (1994) thought that sulfur came from ilmenite-series granific rocks. However, these rocks are not found in the north Hokkaido. 

Sasaki, A. (1974) Isotopic data of Kuroko deposits. Mining Geology Special Issue, 6, 389-398. 

Halbach et al. (1997) reported lead isotope data on volcanic rocks, sediments and ores from the hydrothermal JADE field in the Okinawa Trough and pointed out that lead isotopic compositions of Okinawa JADE ores are very similar to Kuroko ores (Fig. 2.31) and both sediments and volcanic rocks contributed comparable amounts of lead to the deposit. 

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