Hydrogen isotope compositions of terrestrial plant-wax n-alkanes analysed on a transect of marine surface sediment samples from 1°N to 28°S off southwest Africa

A transect of marine surface sediment samples from 1° N to 28° S off southwest Africa was analysed to verify the application of hydrogen isotope compositions of terrestrial plant-wax n-alkanes preserved in ocean sediments as a proxy for continental hydrological conditions. Conditions on the adjacent continent range from humid evergreen forests to deciduous forests, wood- and shrub land and further to arid grasslands and deserts. The hydrogen isotope values for the dominant n-alkane homologues (C29, C31 and C33) vary from -123 per mil to -141 per mil VSMOW and correlate with the modelled hydrogen isotope composition of mean annual and growing season precipitation of postulated continental source areas (r up to 0.8, p < 0.01). The apparent hydrogen isotope fractionation between alkanes and mean annual precipitation is remarkably uniform (-109 per mil on average, Sigma <= 5 per mil, n = 27). Potentially, effects of aridity on the apparent hydrogen isotope fractionation are concealed by the contribution of different plants (C3 dicotyledons vs C4 grasses). Thus, isotope ratios of leaf wax n-alkanes preserved in ocean margin sediments in these and similar tropical regions may be directly converted to dD ratios of ancient precipitation by employing a constant hydrogen isotope fractionation.

Stable hydrogen and carbon isotope records and concentration data for four long chain n-alkanes from core GIK16160-3 derived from the Zambezi delta in the Mozambique Channel during the last 37,000 years

Hydrogen isotope values (dD) of sedimentary terrestrial leaf wax such as n-alkanes or n-acids have been used to map and understand past changes in rainfall amount in the tropics because dD of precipitation is commonly assumed as the first order controlling factor of leaf wax dD. Plant functional types and their photosynthetic pathways can also affect leaf wax dD but these biological effects are rarely taken into account in paleo studies relying on this rainfall proxy. To investigate how biological effects may influence dD values we here present a 37,000-year old record of dD and stable carbon isotopes (d13C) measured on four n-alkanes (n-C27, n-C29, n-C31, n-C33) from a marine sediment core collected off the Zambezi River mouth. Our paleo d13C records suggest that each individual n-alkanes had different C3/C4 proportional contributions. n-C29 was mostly derived from a C3 dicots (trees, shrubs and forbs) dominant vegetation throughout the entire record. In contrast, the longer chain n-C33 and n-C31 were mostly contributed by C4 grasses during the Glacial period but shifted to a mixture of C4 grasses and C3 dicots during the Holocene. Strong correlations between dD and d13C values of n-C33 (correlation coefficient R2 = 0.75, n = 58) and n-C31 (R2 = 0.48, n = 58) suggest that their dD values were strongly influenced by changes in the relative contributions of C3/C4 plant types in contrast to n-C29 (R2 = 0.07, n = 58). Within regions with variable C3/C4 input, we conclude that dD values of n-C29 are the most reliable and unbiased indicator for past changes in rainfall, and that dD and d13C values of n-C31 and n-C33 are sensitive to C3/C4 vegetation changes. Our results demonstrate that a robust interpretation of palaeohydrological data using n-alkane dD requires additional knowledge of regional vegetation changes from which nalkanes are synthesized, and that the combination of dD and d13C values of multiple n-alkanes can help to differentiate biological effects from those related to the hydrological cycle.

Multiscale study on hydrogen mobility in metallic fusion divertor material

For achieving efficient fusion energy production, the plasma-facing wall materials of the fusion reactor should ensure long time operation. In the next step fusion device, ITER, the first wall region facing the highest heat and particle load, i.e. the divertor area, will mainly consist of tiles based on tungsten. During the reactor operation, the tungsten material is slowly but inevitably saturated with tritium. Tritium is the relatively short-lived hydrogen isotope used in the fusion reaction. The amount of tritium retained in the wall materials should be minimized and its recycling back to the plasma must be unrestrained, otherwise it cannot be used for fueling the plasma. A very expensive and thus economically not viable solution is to replace the first walls quite often. A better solution is to heat the walls to temperatures where tritium is released. Unfortunately, the exact mechanisms of hydrogen release in tungsten are not known. In this thesis both experimental and computational methods have been used for studying the release and retention of hydrogen in tungsten. The experimental work consists of hydrogen implantations into pure polycrystalline tungsten, the determination of the hydrogen concentrations using ion beam analyses (IBA) and monitoring the out-diffused hydrogen gas with thermodesorption spectrometry (TDS) as the tungsten samples are heated at elevated temperatures. Combining IBA methods with TDS, the retained amount of hydrogen is obtained as well as the temperatures needed for the hydrogen release. With computational methods the hydrogen-defect interactions and implantation-induced irradiation damage can be examined at the atomic level. The method of multiscale modelling combines the results obtained from computational methodologies applicable at different length and time scales. Electron density functional theory calculations were used for determining the energetics of the elementary processes of hydrogen in tungsten, such as diffusivity and trapping to vacancies and surfaces. Results from the energetics of pure tungsten defects were used in the development of an classical bond-order potential for describing the tungsten defects to be used in molecular dynamics simulations. The developed potential was utilized in determination of the defect clustering and annihilation properties. These results were further employed in binary collision and rate theory calculations to determine the evolution of large defect clusters that trap hydrogen in the course of implantation. The computational results for the defect and trapped hydrogen concentrations were successfully compared with the experimental results. With the aforedescribed multiscale analysis the experimental results within this thesis and found in the literature were explained both quantitatively and qualitatively.

The variations and climatic significance of D/H ratios in the carbon-bound hydrogen of cellulose in trees

The σD values of nitrated cellulose from a variety of trees covering a wide geographic range have been measured. These measurements have been used to ascertain which factors are likely to cause σD variations in cellulose C-H hydrogen.

It is found that a primary source of tree σD variation is the σD variation of the environmental precipitation. Superimposed on this are isotopic variations caused by the transpiration of the leaf water incorporated by the tree. The magnitude of this transpiration effect appears to be related to relative humidity.

Within a single tree, it is found that the hydrogen isotope variations which occur for a ring sequence in one radial direction may not be exactly the same as those which occur in a different direction. Such heterogeneities appear most likely to occur in trees with asymmetric ring patterns that contain reaction wood. In the absence of reaction wood such heterogeneities do not seem to occur. Thus, hydrogen isotope analyses of tree ring sequences should be performed on trees which do not contain reaction wood.

Comparisons of tree σD variations with variations in local climate are performed on two levels: spatial and temporal. It is found that the σD values of 20 North American trees from a wide geographic range are reasonably well-correlated with the corresponding average annual temperature. The correlation is similar to that observed for a comparison of the σD values of annual precipitation of 11 North American sites with annual temperature. However, it appears that this correlation is significantly disrupted by trees which grew on poorly drained sites such as those in stagnant marshes. Therefore, site selection may be important in choosing trees for climatic interpretation of σD values, although proper sites do not seem to be uncommon.

The measurement of σD values in 5-year samples from the tree ring sequences of 13 trees from 11 North American sites reveals a variety of relationships with local climate. As it was for the spatial σD vs climate comparison, site selection is also apparently important for temporal tree σD vs climate comparisons. Again, it seems that poorly-drained sites are to be avoided. For nine trees from different "well-behaved" sites, it was found that the local climatic variable best related to the σD variations was not the same for all sites.

Two of these trees showed a strong negative correlation with the amount of local summer precipitation. Consideration of factors likely to influence the isotopic composition of summer rain suggests that rainfall intensity may be important. The higher the intensity, the lower the σD value. Such an effect might explain the negative correlation of σD vs summer precipitation amount for these two trees. A third tree also exhibited a strong correlation with summer climate, but in this instance it was a positive correlation of σD with summer temperature.

The remaining six trees exhibited the best correlation between σD values and local annual climate. However, in none of these six cases was it annual temperature that was the most important variable. In fact annual temperature commonly showed no relationship at all with tree σD values. Instead, it was found that a simple mass balance model incorporating two basic assumptions yielded parameters which produced the best relationships with tree σD values. First, it was assumed that the σD values of these six trees reflected the σD values of annual precipitation incorporated by these trees. Second, it was assumed that the σD value of the annual precipitation was a weighted average of two seasonal isotopic components: summer and winter. Mass balance equations derived from these assumptions yielded combinations of variables that commonly showed a relationship with tree σD values where none had previously been discerned.

It was found for these "well-behaved" trees that not all sample intervals in a σD vs local climate plot fell along a well-defined trend. These departures from the local σD VS climate norm were defined as "anomalous". Some of these anomalous intervals were common to trees from different locales. When such widespread commonalty of an anomalous interval occurred, it was observed that the interval corresponded to an interval in which drought had existed in the North American Great Plains.

Consequently, there appears to be a combination of both local and large scale climatic information in the σD variations of tree cellulose C-H hydrogen.

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondonia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondonia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Barbara deposit (Rondonia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sri (+/-W, +/-Ta, +/-Nb), and base-metal suite (Zn-Cu-Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0-19 wt.% NaCl eq.) CO2-bearing aqueous fluids homogenizing at 245-450 degreesC, and (2) aqueous solutions with low CO2, low to moderate salinity (0-14 wt.% NaCl eq.), which homogenize between 100 and 340 T. In the Santa Barbara deposit, the early inclusions are represented by (1) low-salinity (5-12 wt.% NaCl eq.) aqueous fluids with variable CO2 contents, homogenizing at 340 to 390 T, and (2) low-salinity (0-3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320380 degreesC. Cassiterite, wolframite, columbite-tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0-6 wt.% NaCl eq.) CO2-free aqueous solution, which homogenizes at (100-260 degreesC) and characterizes the sulfide fluorite-sericite association in the Correas deposit. The late fluid in the Santa Barbara deposit has lower salinity (0-3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240-450 degreesC, and 1,0-2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (delta(18)O quartz from 9.9parts per thousand to 10.9parts per thousand, deltaDH(2)O from 4.13parts per thousand to 6.95parts per thousand) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 degreesC. In the Santa Barbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 degreesC, respectively), and that for the cassiterite-quartz-veins is 415 degreesC. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (delta(18)O(qtz-H2O)=5.5-6.1parts per thousand) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (delta(18)O(mica-H2O)=33-9.8parts per thousand) suggest mixing with meteoric water. Late muscovite veins (delta(18)O(qtz-H2O)=-6.4parts per thousand) and late quartz (delta(18)O(mica-H2O)=-3.8parts per thousand) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor coluChange in the redox conditions related to mixing-of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit. (C) 2004 Elsevier B.V. All rights reserved.