Geothermometry of calcite spar at 10-50 °C.

Carbonate geothermometry is a fundamental tool for quantitative assessment of the geothermal and geochemical evolution of diagenetic and hydrothermal systems, but it remains difficult to obtain accurate and precise formation temperatures of low-temperature calcite samples (below ~ 40 to 60 °C). Here, we apply three geothermometry methods (∆47-thermometry, nucleation-assisted fluid inclusion microthermometry-hereafter NA-FIM-and oxygen isotope thermometry) to slow-growing subaqueous calcite spar samples to cross-validate these methods down to 10 °C. Temperatures derived by NA-FIM and Δ47-thermometry agree within the 95% confidence interval, except for one sample. Regression analyses suggest that the real uncertainty of ∆47-thermometry exceeds the 1 SE analytical uncertainty and is around ± 6.6 °C for calcite spar that formed at 10-50 °C. The application of δ18O thermometry was limited to a few samples that contained sufficient primary fluid inclusions. It yielded broadly consistent results for two samples with two other geothermometers, and showed higher temperature for the third spar. We also found that calcite with steep rhombohedral morphologies is characteristic of low temperatures (11-13 °C), whereas blunt rhombohedra prevail in the 10-29 °C domain, and the scalenohedral habit dominates > 30 °C. This suggests that the calcite crystal morphology can be used to qualitatively distinguish between low- and higher-temperature calcite.

Combined use of conventional and clumped carbonate stable isotopes to identify hydrothermal isotopic alteration in cave walls.

Alteration of conventional carbonate stable isotopes (δ18O, δ13C) in cave walls has been shown to be a useful tool to identify cave formation driven by deep-seated processes, i.e., hypogene karstification. If combined with a prior information on the paleowater stable isotope composition, further insights can be obtained on the temperature and the source of the paleowater. Clumped isotope composition (Δ47) of carbonates is an independent measurement of temperature, and if combined with the conventional stable isotopes, can provide information on the paleowater stable isotope composition. On the example of Provalata Cave (N. Macedonia), we apply for the first time, both conventional and clumped stable isotope analysis, and identify two different isotope alteration trends, reflecting two distinct hydrothermal events: an older, hotter one, where isotope alteration was likely related to isotope diffusion, lowering the δ18O values of the carbonate; and a younger one, related to the cave formation by low-temperature CO2-rich thermal waters, with dissolution-reprecipitation as the alteration mechanism, causing decrease in δ18O values, and unexpected increase in δ13C values. The findings are further corroborated by additional insight from optical petrography and cathodoluminescence microscopy, as well as fluid inclusion analysis of secondary calcite crystals related to the cave forming phase.

Bacterial and abiogenic carbonates formed in caves-no vital effect on clumped isotope compositions.

Speleothems (dominated by cave-hosted carbonate deposits) are valuable archives of paleoclimate conditions. As such, they are potential targets of clumped isotope analyses that may yield quantified data about past temperature variations. Clumped isotope analyses of stalagmites, however, seldom provide useful temperature values due to various isotope fractionation processes. This study focuses on the determination of the microbially induced vital effect, i.e., the isotope fractionation processes related to bacterial carbonate production. A cave site with biologically mediated amorphous calcium carbonate precitation was selected as a natural laboratory. Calcite deposits were farmed under a UV lamp to prevent bacterial activity, as well as under control conditions. Microbiological analyses and morphological investigations using scanning electron microscopy showed that the UV lamp treatment effectively reduced the number of bacterial cells, and that bacterial carbonate production strongly influenced the carbonate's morphology. Stable oxygen isotope analyses of calcite and drip waters, as well as clumped isotope measurements revealed that, although most of the studied carbonates formed close to oxygen isotope equilibrium, clumped isotope Δ47 values varied widely from equilibrium to strongly fractionated data. Site-specific kinetic fractionations played a dominant role in the distribution of Δ47 values, whereas bacterial carbonate production did not result in a detectable clumped isotope effect.

Modulation of Cosmogenic Tritium in Meteoric Precipitation by the 11-year Cycle of Solar Magnetic Field Activity.

The relationship between the atmospheric concentration of cosmogenic isotopes, the change of solar activity and hence secondary neutron flux has already been proven. The temporal atmospheric variation of the most studied cosmogenic isotopes shows a significant anti-correlation with solar cycles. However, since artificial tritium input to the atmosphere due to nuclear-weapon tests masked the expected variations of tritium production rate by three orders of magnitude, the natural variation of tritium in meteoric precipitation has not previously been detected. For the first time, we provide clear evidence of the positive correlation between the tritium concentration of meteoric precipitation and neutron flux modulated by solar magnetic activity. We found trends in tritium time series for numerous locations worldwide which are similar to the variation of secondary neutron flux and sun spot numbers. This variability appears to have similar periodicities to that of solar cycle. Frequency analysis, cross correlation analysis, continuous and cross wavelet analysis provide mathematical evidence that the correlation between solar cycle and meteoric tritium does exist. Our results demonstrate that the response of tritium variation in precipitation to the solar cycle can be used to help us understand its role in the water cycle.

A mass spectrometric line for tritium analysis of water and noble gas measurements from different water amounts in the range of microlitres and millilitres.

This paper describes the procedure followed for noble gas measurements for litres, millilitres and microlitres of water samples in our laboratory, including sample preparation, mass spectrometric measurement procedure, and the complete calibrations. The preparation line extracts dissolved gases from water samples of volumes of 0.2 µ l to 3 l and it separates them as noble and other chemically active gases. Our compact system handles the following measurements: (i) determination of tritium concentration of environmental water samples by the (3)He ingrowth method; (ii) noble gas measurements from surface water and groundwater; and (iii) noble gas measurements from fluid inclusions of solid geological archives (e.g. speleothems). As a result, the tritium measurements have a detection limit of 0.012 TU, and the expectation value (between 1 and 20 TU) is within 0.2 % of the real concentrations with a standard deviation of 2.4 %. The reproducibility of noble gas measurements for water samples of 20-40 ml allows us to determine solubility temperatures by an uncertainty better than 0.5 °C. Moreover, noble gas measurements for tiny water amounts (in the microlitre range) show that the results of the performed calibration measurements for most noble gas isotopes occur with a deviation of less than 2 %. Theoretically, these precisions for noble gas concentrations obtained from measurements of waters samples of a few microlitres allow us to determine noble gas temperatures by an uncertainty of less than 1 °C. Here, we present the first noble gas measurements of tiny amounts of artificial water samples prepared under laboratory conditions.

Modulation of the free energy of the primary quinone acceptor (QA) in reaction centers from Rhodobacter sphaeroides: contributions from the protein and protein-lipid(cardiolipin) interactions.

The redox midpoint potential (E(m)) of Q(A), the primary quinone of bacterial reaction centers, is substantially modulated by the protein environment. Quite subtle mutations in the Q(A) binding site, e.g., at residues M218, M252 and M265, cause significant increases in the equilibrium constant for electron transfer to Q(B), which indicate relative lowering of the E(m) of Q(A). However, reports of functional linkage between the Q(A) and Q(B) sites make it difficult to partition such effects between Q(A) and Q(B) from purely relative changes. We report here measurements on the yield of delayed fluorescence emission from the primary donor (P) accompanying the thermally activated charge recombination of P(+)Q(A)(-) to form the excited singlet state of the primary donor, P*. The results show that for mutations of the Q(A) site residues, Met(M218) and Ile(M265), essentially all the substantial thermodynamic effect is localized at Q(A), with no evidence for a significant effect of these residues on the properties of Q(B) or the mutual influence (linkage) of Q(A) and Q(B). We also report a significant lowering of the E(m) of Q(A) by the native lipid, cardiolipin, which brings the E(m) in isolated reaction centers more in line with that seen in native membrane vesicles (chromatophores). Possible origins of this effect are discussed in the context of the Q(A) binding site structure.

A mathematical model for quinone-herbicide competition in the reaction centres of Rhodobacter sphaeroides.

A quantitative model describing the amplitude of semiquinone absorption in photosynthetic reaction centres after successive flashes in the presence of increasing inhibitor concentration is presented. By using relatively simple algebra, the semiquinone signals can be calculated and fitted to the oscillation pattern by optimizing only two parameters; the electron and quinone equilibrium constants, Ke and Kq, respectively. In this work we expand our earlier model [Tandori et al. (1991) Photosynthetica 25, 159-166] by introducing the inhibitor equilibrium constant, Ki, describing the best fit of the model to the measured oscillation pattern. We found that there are characteristic parameters of the measured and normalized signal, and of those calculated from the mathematical model, which fit well with competitive Michaelis-Menten kinetics.