Ultrafast solvation dynamics in water: Isotope effects and comparison with experimental results

A detailed theoretical study of solvation dynamics in water is presented. The motivation of the present study comes from the recent experimental observation that the dynamics of solvation of an ion in water is ultrafast and the solvation time correlation function decays with a time constant of about 55 fs. The slower decay in the long time can be described by a sum of two exponentials with time constants equal to 126 and 880 fs. The molecular theory (developed earlier) predicts a time constant equal to 52 fs for the initial Gaussian decay and time constants equal to 134 and 886 fs for the two exponential components at the long time. This nearly perfect agreement is obtained by using the most detailed dynamical information available in the literature. The present study emphasizes the importance of the intermolecular vibrational band originating from the O...O stretching mode of the O�H...O units in the initial dynamics and raises several interesting questions regarding the nature of the decay of this mode. We have also studied the effects of isotope substitution on solvation dynamics. It is predicted that a significant isotope effect may be observed in the long time. The experimental results have also been compared with the prediction of the dynamic mean spherical approximation (DMSA); the agreement is not satisfactory at the long time. It is further found that the molecular theory and the DMSA lead to virtually identical results if the translational modes of the solvent molecules are neglected in the former. DMSA has also been used to investigate the dynamics of solvation of a dipolar solute in water. It is found that the dynamics of dipolar solvation exhibit features rather different from those of ion solvation. © 1995 American Institute of Physics.

Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects

Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

Tracing the source of bottled water using stable isotope techniques

The Indian Summer Monsoon (ISM) precipitation recharges ground water aquifers in a large portion of the Indian subcontinent. Monsoonal precipitation over the Indian region brings moisture from the Arabian Sea and the Bay of Bengal (BoB). A large difference in the salinity of these two reservoirs, owing to the large amount of freshwater discharge from the continental rivers in the case of the BoB and dominating evaporation processes over the Arabian Sea region, allows us to distinguish the isotopic signatures in water originating in these two water bodies. Most bottled water manufacturers exploit the natural resources of groundwater, replenished by the monsoonal precipitation, for bottling purposes. The work presented here relates the isotopic ratios of bottled water to latitude, moisture source and seasonality in precipitation isotope ratios. We investigated the impact of the above factors on the isotopic composition of bottled water. The result shows a strong relationship between isotope ratios in precipitation (obtained from the GNIP data base)/bottled water with latitude. The approach can be used to predict the latitude at which the bottled water was manufactured. The paper provides two alternative approaches to address the site prediction. The limitations of this approach in identifying source locations and the uncertainty in latitude estimations are discussed. Furthermore, the method provided here can also be used as an important forensic tool for exploring the source location of bottled water from other regions. Copyright (C) 2011 John Wiley & Sons, Ltd.

Si isotope variability in Proterozoic cherts

We report Si-isotopic compositions of 75 sedimentologically and petrographically characterized chert samples with ages ranging from similar to 2600 to 750 Ma using multi-collector inductively coupled plasma mass spectrometry. delta Si-30 values of the cherts analyzed in this study show a similar to 7 parts per thousand range, from -4.29 to +2.85. This variability can be explained in part by (1) simple mixing of silica derived from continental (higher delta Si-30) and hydrothermal (lower delta Si-30) sources, (2) multiple mechanisms of silica precipitation and (3) Rayleigh-type fractionations within pore waters of individual basins. We observe similar to 3 parts per thousand variation in peritidal cherts from a single Neoproterozoic sedimentary basin (Spitsbergen). This variation can be explained by Rayleigh-type fractionation during precipitation from silica-saturated porewaters. In some samples, post-dissolution and reprecipitation of silica could have added to this effect. Our data also indicate that peritidal cherts are enriched in the heavier isotopes of Si whereas basinal cherts associated with banded iron formations (BIF) show lower delta Si-30. This difference could partly be due to Si being derived from hydrothermal sources in BIFs. We postulate that the difference in delta Si-30 between non-BIF and BIF cherts is consistent with the contrasting genesis of these deposits. Low delta Si-30 in BIF is consistent with laboratory experiments showing that silica adsorbed onto Fe-hydroxide particles preferentially incorporates lighter Si isotopes. Despite large intrabasinal variation and environmental differences, the data show a clear pattern of secular variation. Low delta Si-30 in Archean cherts is consistent with a dominantly hydrothermal source of silica to the oceans at that time. The monotonically increasing delta Si-30 from 3.8 to 1.5 Ga appears to reflect a general increase in continental versus hydrothermal sources of Si in seawater, as well as the preferential removal of lighter Si isotopes during silica precipitation in iron-associated cherts from silica-saturated seawater. The highest delta Si-30 values are observed in 1.5 Ga peritidal cherts; in part, these enriched values could reflect increasing sequestration of light silica during soil-forming processes, thus, delivering relatively heavy dissolved silica to the oceans from continental sources. The causes behind the reversal in trend towards lower delta Si-30 in cherts younger than 1.5 Ga old are less clear. Cherts deposited 1800-1900 Ma are especially low delta Si-30, a possible indication of transiently strong hydrothermal input at this time. (C) 2012 Elsevier Ltd. All rights reserved.

Precision and long-term stability of clumped-isotope analysis of CO2 using a small-sector isotope ratio mass spectrometer

RATIONALE The ratio of the measured abundance of 13C18O bonding CO2 to its stochastic abundance, prescribed by the delta 13C and delta 18O values from a carbonate mineral, is sensitive to its growth temperature. Recently, clumped-isotope thermometry, which uses this ratio, has been adopted as a new tool to elucidate paleotemperatures quantitatively. METHODS Clumped isotopes in CO2 were measured with a small-sector isotope ratio mass spectrometer. CO2 samples digested from several kinds of calcium carbonates by phosphoric acid at 25 degrees C were purified using both cryogenic and gas-chromatographic separations, and their isotopic composition (delta 13C, delta 18O, Delta 47, Delta 48 and Delta 49 values) were then determined using a dual-inlet Delta XP mass spectrometer. RESULTS The internal precisions of the single gas Delta 47 measurements were 0.005 and 0.02 parts per thousand (1 SE) for the optimum and the routine analytical conditions, respectively, which are comparable with those obtained using a MAT 253 mass spectrometer. The long-term variations in the Delta 47 values for the in-house working standard and the heated CO2 gases since 2007 were close to the routine, single gas uncertainty while showing seasonal-like periodicities with a decreasing trend. Unlike the MAT 253, the Delta XP did not show any significant relationship between the Delta 47 and delta 47 values. CONCLUSIONS The Delta XP gave results that were approximately as precise as those of the MAT 253 for clumped-isotope analysis. The temporal stability of the Delta XP seemed to be lower, although an advantage of the Delta XP was that no dependency of delta 47 on Delta 47 was found. Copyright (c) 2012 John Wiley & Sons, Ltd.

High precision Mg isotope measurements of meteoritic samples by secondary ion mass spectrometry

The possibility of establishing an accurate relative chronology of the early solar system events based on the decay of short-lived Al-26 to Mg-26 (half-life of 0.72 Myr) depends on the level of homogeneity (or heterogeneity) of Al-26 and Mg isotopes. However, this level is difficult. to constrain precisely because of the very high precision needed for the determination of isotopic ratios, typically of +/- 5 ppm. In this study, we report for the first time a detailed analytical protocol developed for high precision in situ Mg isotopic measurements ((25)mg/(24)mg and (26)mg/Mg-24 ratios, as well as Mg-26 excess) by MC-SIMS. As the data reduction process is critical for both accuracy and precision of the final isotopic results, factors such as the Faraday cup (FC) background drift and matrix effects on instrumental fractionation have been investigated. Indeed these instrumental effects impacting the measured Mg-isotope ratios can be as large or larger than the variations we are looking for to constrain the initial distribution of Al-26 and Mg isotopes in the early solar system. Our results show that they definitely are limiting factors regarding the precision of Mg isotopic compositions, and that an under- or over-correction of both FC background instabilities and instrumental isotopic fractionation leads to important bias on delta Mg-25, delta(26)mg and Delta Mg-26 values (for example, olivines not corrected for FC background drifts display Delta Mg-26 values that can differ by as much as 10 ppm from the truly corrected value). The new data reduction process described here can then be applied to meteoritic samples (components of chondritic meteorites for instance) to accurately establish their relative chronology of formation.

Chromium isotope variations (delta Cr-53/52) in mantle-derived sources and their weathering products: Implications for environmental studies and the evolution of delta Cr-53/52 in the Earth's mantle over geologic time

Here we report chromium isotope compositions, expressed as delta Cr-53/ 52 in per mil (&) relative to NIST 979, measured in selected Cr-rich minerals and rocks formed by the primary magmatic as well as the secondary metamorphic and weathering processes. The main objectives of this study were: (i) to further constrain the isotope composition of the Earth's mantle Cr inventory and its possible variation during geological history, based on the analysis of globally distributed and stratigraphically constrained mantle-derived chromites; and (ii) to investigate the magnitude and systematics of Cr isotope fractionation during oxidative weathering and secondary alteration (i. e., hydration, serpentinization) of the magmatic Cr sources. Specifically, we analyzed delta Cr-53/ 52 in a set of globally distributed mantle-derived chromites (FeMgCr2O4, n = 30) collected from various locations in Europe, Asia, Africa and South America, and our results confirm that a chromite-hosted Earth's mantle Cr inventory is uniform at - 0.079 +/- 0.129& (2SD), which we named here as a ` canonical' mantle d 53/ 52 Cr signature. Furthermore our dataset of stratigraphically constrained chromites, whose crystallization ages cover most of the Earth's geological history, indicate that the bulk Cr isotope composition of the chromite-hosted mantle inventory has remained uniform, within about +/- 0.100&, since at least the Early Archean times (similar to 3500 million years ago, Ma). To investigate the systematics of Cr isotope fractionation associated with alteration processes we analyzed a number of secondary Cr-rich minerals and variably altered ultramafic rocks (i. e., serpentinized harzburgites, lherzolites) that revealed large positive delta Cr-53/ 52 anomalies that are systematically shifted to higher values with an increasing degree of alteration and serpentinization. The degree of aqueous alteration and serpentinization was quantified by the abundances of fluid-mobile (Rb, K) elements, and by the Loss On Ignition (LOI) parameter, which determines the amount of structurally bound water (OH/ H2O) present in secondary hydrated minerals like serpentine. Overall, we observed that altered ultramafic rocks that yielded the highest LOI values, and the lowest amounts of fluid mobile elements, also yielded the heaviest delta Cr-53/ 52 signatures. Therefore, we conclude that secondary alteration (i.e., hydration, serpentinization) of ultramafic rocks in near-surface oxidative environments tend to shift the bulk Cr isotope composition of the weathered products to isotopically heavier values, pointing to a dynamic redox cycling of Cr in the Earth's crustal and near-surface environments. Hence, if validated by future

Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.

A Short Review on Lu-Hf Isotope System in Zircon: Implications for Crustal Evolution

Zircon has been recognized as the unaltered part of the Earth's history which preserves nearly 4 billion year record of earth's evolution. Zircon preserves igneous and metamorphic processes during its formation and remains unaffected by sedimentary processes and crustal recycling. U-Pb and Lu-Hf in zircon work as geochronometer and geochemical tracer respectively. Zircon provide valuable information about the source composition of the rocks and the intrinsic details of an unseen crust-mantle processes. The world wide data of U-Pb and Lu-Hf isotope systems in zircon reveal crustal evolution through geological history. Moreover, the U-Pb age pattern of zircons show distinct peaks attributed to preservation of crustal rocks or mountain building during supercontinent assembly. The histogram of continental crust preservation shows that nearly one-third of continental crust was formed during the Archean, almost 20% was formed during Paleoproterozoic and 14% in last 400 Ma.

Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean

Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45 degrees E and 80 degrees E and 10 degrees N to 53 degrees S) were analysed and compared with the equilibrium delta O-18 and delta C-13 values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within similar to 0.25% for the region between 10 degrees N and 40 degrees S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40 degrees S to 55 degrees S), however, the measured delta O-18 and delta C-13 values are higher than the expected values by similar to 2% and similar to 1% respectively. These enrichments can be attributed to either a `vital effect' or a higher calcification rate. An interesting pattern of increase in the delta C-13(DIC) value of the surface water with latitude is observed between 35 degrees S and similar to 60 degrees S, with a peak at similar to 42 degrees S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the delta C-13(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.