Relative contributions of sulfate- and iron(III) reduction to organic matter mineralization and process controls in contrasting habitats of the Georgia saltmarsh

The objectives of this study were to partition out the predominant anaerobic respiration pathways coupled to C oxidation and to further elucidate the controls of anaerobic C respiration in three major saltmarsh habitats at Skidaway Island, GA; the short form of Spartina alterniflora (SS), the tall form of S. alterniflora (TS), and unvegetated, bioturbated creekbank (CB). Geochemical analysis of pore water and solid phase constituents revealed that the SS site experienced highly reducing conditions with two orders of magnitude higher pore water sulfide inventories (1.884 mmol m⁻²) than TS (0.003 mmol m⁻²) and CB (0.005 mmol m⁻²), respectively. Conversely, reactive Fe(III) inventories at TS (2208 mmol m⁻²) and CB (2881 mmol m⁻²) were up to 7–9 times higher than at SS (338 mmol m⁻²). Incubations and intact core experiments indicated that reduction accounted for 95% (SS), 37% (TS) and 66% (CB) of total anaerobic respiration. There was no detectable Fe(III) reduction at SS, while Fe(III) reduction accounted for up to 70% of C oxidation in the 3–6 cm depth interval at TS and 0–3 cm depth of CB, and on average, approximately 55% of C oxidation over two-thirds of marsh surface area. Laboratory manipulations provided further evidence for the importance of Fe(III) reduction as the accumulation rates of fermentation products were high when Fe(III) reduction was inhibited by removing the Fe(III) minerals from highly bioturbated CB sediments with higher Fe(III) mineral contents. Anaerobic C oxidation, - and Fe(III)-reduction rates appeared to be highest at the TS site during active plant growth in summer. Overall results suggest that bioturbation by macrofauna is the overriding factor in modulating the pathway of C mineralization in the saltmarsh, whereas availability of organic substrates from plants is a key factor in controlling the C oxidation rate.     

Calcite dissolution kinetics in saline waters

The effect of ionic strength (I), pCO₂, and temperature on the dissolution rate of calcite was investigated in magnesium-free, phosphate-free, low calcium (m_Ca2+ ≈ 0.01 m) simple KCl and NaCl solutions over the undersaturation range of 0.4 ≤ Ω_calcite ≤ 0.8. First-order kinetics were found sufficient to describe the rate data where the rate constant (k) is dependent on the solution composition. Rates decreased with increasing I and were faster in KCl than NaCl solutions at the same I indicating that Na⁺ interacts more strongly with the calcite surface than K⁺ or that water is less available in NaCl solutions. Rates increased with increasing pCO₂ and temperature, and their influences diminished at high I. Arrhenius plots yielded a relatively high activation energy (E_a ≈ 20 ± 2 kJ mol^− 1) which indicated that dissolution was dominated by surface-controlled processes. The multiple regression model (MR) of Gledhill and Morse (2006a) was found to adequately describe the results at high I in NaCl solutions, but caution must be used when extrapolating to low I or pCO₂ values. These results are consistent with the hypothesis that the mole fraction of “free” solvent (X_{“free”H2O}) plays a significant role in the dissolution kinetics of calcite with a minimum value of  45–55% required for dissolution to proceed in undersaturated solutions at 25–55 °C and pCO₂ = 0.1–1 atm. This hypothesis has been incorporated into a modified version of the MR model of Gledhill and Morse (2006a) where X_{“free”H2O} has replaced I and the Ca²⁺ and Mg²⁺ terms have been dropped:

     

Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

Diffusion coefficients (D) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO₂ as an internal standard. FSC capsules (3.25 × 10⁻⁴ m OD, 9.9 × 10⁻⁵ m ID, and 0.01 m long) containing CO₂ and H₂ were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H₂ (near 587 cm⁻¹) and CO₂ (near 1387 cm⁻¹). The sample capsules were then heated at a fixed temperature (T) at one atmosphere to let H₂ diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m² s⁻¹) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by:

where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol.The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.     

Clinopyroxene dissolution in basaltic melt

The history of magmatic systems may be inferred from reactions between mantle xenoliths and host basalt if the thermodynamics and kinetics of the reactions are quantified. To study diffusive and convective clinopyroxene dissolution in silicate melts, diffusive clinopyroxene dissolution experiments were conducted at 0.47–1.90 GPa and 1509–1790 K in a piston-cylinder apparatus. Clinopyroxene saturation is found to be roughly determined by MgO and CaO content. The effective binary diffusivities, D_MgO and D_CaO, and the interface melt saturation condition, , are extracted from the experiments. D_MgO and D_CaO show Arrhenian dependence on temperature. The pressure dependence is small and not resolved within 0.47–1.90 GPa. in the interface melt increases with increasing temperature, but decreases with increasing pressure. Convective clinopyroxene dissolution, where the convection is driven by the density difference between the crystal and melt, is modeled using the diffusivities and interface melt saturation condition. Previous studies showed that the convective dissolution rate depends on the thermodynamics, kinetics and fluid dynamics of the system. Comparing our results for clinopyroxene dissolution to results from a previous study on convective olivine dissolution shows that the kinetic and fluid dynamic aspects of the two minerals are quite similar. However, the thermodynamics of clinopyroxene dissolution depends more strongly on the degree of superheating and composition of the host melt than that of olivine dissolution. The models for clinopyroxene and olivine dissolution are tested against literature experiments on mineral–melt interaction. They are then applied to previously proposed reactions between Hawaii basalts and mantle minerals, mid-ocean ridge basalts and mantle minerals, and xenoliths digestion in a basalt at Kuandian, Northeast China.     

Solubility of Pt in sulphide mattes: Implications for the genesis of PGE-rich horizons in layered intrusions

The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS₂ and fO₂ at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS₂ and decreases weakly with increasing fO₂. The increase in Pt solubility with increasing fS₂ is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO₂ to the diluting effect of increasing O in the melt at high fO₂. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 10⁷ and 10¹¹, depending on fO₂ and fS₂, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 10⁷ and for the Stillwater Pt-rich horizon 10⁸. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions.     

Gradients controlling natural attenuation of ammonium

Oxidation of reduced pollutants such as in groundwater often takes place at steep redox gradients where oxygenated water is being mixed into polluted water such as landfill leachate. In order to identify controlling parameters and quantify the influence of environmental factors for degradation, sensitivity analysis was performed by means of scenario specific numerical modelling. Geometrical factors such as aquifer thickness have been shown to be very influential on the capability of natural attenuation of pollutants in groundwater. The scenarios investigated here include biodegradation at redox gradients in groundwater, so called fringe processes, for (i) a partly contaminated aquifer with two reaction fronts, (ii) and a spatially variable aquifer thickness. In addition, (iii) the influence of groundwater recharge and (iv) restricted supply of O₂ to contaminated water by slow dispersion and diffusion across the capillary fringe are investigated. Contaminated aquifer thickness, zones of enhanced mixing due to flow focussing and diffusion/dispersion coefficients in the capillary fringe are identified qualitatively as controlling factors for natural attenuation under complex conditions, whereas predictive functions will require further research.     

Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

NanoSIMS analysis and Auger electron spectroscopy of silicate and oxide stardust from the carbonaceous chondrite Acfer 094

We have detected 138 presolar silicate, 20 presolar oxide and three presolar complex grains within the carbonaceous chondrite Acfer 094 by NanoSIMS oxygen isotope mapping. These grains were further investigated by scanning electron microscopy (SEM) and Auger electron spectroscopy for morphological and chemical details and their distribution within the meteorite matrix. The three complex grains consist of Al-rich oxides (grossite and hibonite) attached to non-stoichiometric Si-rich silicates. Refractory Al-rich oxides therefore serve as seed nuclei for silicates to condense onto, which is proposed by condensation theory and astronomical observations. However, in the majority of presolar silicates we did not find any indications for large subgrains. Most of the grains (80%) belong to O isotope Group I (¹⁷O-enriched) and come from 1 to 2.5 M asymptotic giant branch (AGB) stars of close-to-solar or slightly lower-than-solar metallicity. About 60% of these grains are irregular in shape; 40% display elliptical morphologies together with smooth, platy surfaces. Three grains with large ¹⁷O enrichments (¹⁷O/¹⁶O > 3 × 10⁻³) have highly irregular shapes and are very small (<250 nm); these grains may have formed in binary star systems or around higher mass () AGB stars. About 10% of the presolar silicates in this study can be assigned to the O isotope Group IV, which most likely originate from type II supernovae (SNeII). These grains are also generally smaller than 300 nm and are often irregular in shape (88%), consistent with the SNII origin scenario. The presolar grains are generally evenly distributed within the matrix on an mm scale, although in one case a statistically significant clustering of five grains in one 10 × 10 μm² sized field is observed. This could be an important hint that the distribution of presolar material in the parental molecular cloud was heterogeneous on a very fine scale. The matrix-normalized abundance of silicate stardust in Acfer 094 is 163 ± 14 ppm, which is among the highest abundance of O-rich stardust in primitive meteorites. Oxide stardust comprises 26 ± 6 ppm of the matrix. Auger Nanoprobe measurements of 69 presolar silicates and oxides (30 on a quantitative, 39 on a qualitative basis) indicate that most of the grains are Fe-rich (Mg/(Mg + Fe) of 0.82 and lower), which is either due to non-equilibrium condensation, secondary alteration, or both. (Mg + Fe)/Si ratios of the silicates are mostly non-stoichiometric and scatter around pyroxene-like rather than olivine-like compositions, which is consistent with recent Auger and transmission electron microscopy observations and astrophysical predictions. Mg-rich grains (Mg/(Mg + Fe) > 0.5) more likely exhibit elliptical, smooth surfaces (14 out of 18 grains), which is an indication that these grains have not been strongly altered since their circumstellar condensation. We identified only one grain similar to the “glass with embedded metal and sulfides” (GEMS) with a statistically significant sulfur content (>2–3 at.%). It remains unclear why the typical high-sulfur GEMS grains are only found in interplanetary dust particles, but have not yet been unequivocally identified in primitive meteorites.     

Chemical controls on the solubility, speciation and mobility of lanthanum at near surface conditions: A geochemical modeling study

Recent experimental determinations of the solubility products of common rare earth minerals such as monazite and xenotime and stability constants for chloride, sulfate, carbonate and hydroxide complexes provide a basis to model quantitatively the solubility, and therefore the mobility, of rare earth elements (REE) at near surface conditions. Data on the mobility of REE and stabilities of REE complexes at near-neutral conditions are of importance to safe nuclear waste disposal, and environmental monitoring. The aim of this study is to understand REE speciation and solubility of a given REE in natural environments. In this study, a series of formation constants for La aqueous complexes are recommended by using the specific interaction theory (SIT) for extrapolation to infinite dilution. Then, a thermodynamic model has been employed for calculation of the solubility and speciation of La in soil solutions reacted with the La end-member of mineral monazite (LaPO₄), and other La-bearing solid phases including amorphous lanthanum hydroxide (La(OH)₃, am) and different La carbonates, as a function of various inorganic and organic ligand concentrations. Calculations were carried out at near-neutral pH (pH 5.5–8.5) and 25 °C at atmospheric CO₂ partial pressure. The model takes account of the species: La³⁺, LaCl²⁺, , , , , , , , , La(OH)²⁺, LaOx⁺, , LaAc²⁺ and (where Ox²⁻ = oxalate and Ac⁻ = acetate).The calculations indicate that the La species that dominate at pH 5.5–8.5 in the baseline model soil solution (BMSS) include La³⁺, LaOx⁺, , and in order of increasing importance as pH rises. The solubility of monazite in the BMSS remains less than 3 × 10⁻⁹ M, exhibiting a minimum of 2 × 10⁻¹² M at pH 7.5. The calculations quantitatively demonstrate that the concentrations of La controlled by the solubility of other La-bearing solid phases are many orders of magnitude higher than those controlled by monazite in the pH range from 5.5 to 8.5, suggesting that monazite is likely to be the solubility-controlling phase at this pH range. The calculations also suggest that significant mobility of La (and other REE) is unlikely because high water–rock ratios on the order of at least 10⁴ (mass ratio) are required to move 50% of the La from a soil. An increase in concentration of oxalate by one order of magnitude from that of the baseline model solution results in the dominance of LaOx⁺ at pH 5.5–7.5. Similarly, the increase in concentration of by one order of magnitude makes the dominant species at pH 5.5–7.5. Above pH 7.5, carbonate complexes are important. The increase in oxalate or concentrations by one order of magnitude can enhance the solubility of monazite by a factor of up to about 6 below neutral pH, in comparison with that in the baseline model soil solution. From pH 7.0 to 8.5, the solubility of monazite in the soil solutions with higher concentrations of oxalate or is similar, or almost identical, to that in the BMSS.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.     

Surface and groundwater quality in the northeastern region of Buenos Aires Province, Argentina

This work studies the water quality of the Pergamino–Arrecifes River zone in the Rolling Pampa, northeast Buenos Aires Province, Argentina. Temperature, pH, specific conductivity, Na, K, Mg, Ca, , Cl⁻, , , Si, Ag, Al, As, B, Ba, Be, Br, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, P, Pb, Se, Tl, U, V, Zn, and the environmental stable δ¹⁸O and δ²H isotope ratios were determined in 18 sampling stations. Natural and anthropogenic features influence surface and groundwater quality. Point pollution sources (septic wells and other domestic and farming effluents) increase the nitrate concentration. The values of pH, , Al, As, B, Fe, and Mn exceed the respective Argentine reference thresholds in different sampling stations for human drinking water; B, Mo, U, and V for irrigation; and V and Zn for cattle consumption.     

Energetics of potential heterotrophic metabolisms in the marine hydrothermal system of Vulcano Island, Italy

Values of overall Gibbs free energy of 144 organic oxidation (respiration) and disproportionation (fermentation) reactions are calculated at the temperatures and chemical compositions that exist in nine submarine vents, sediment seeps and geothermal wells in the hydrothermal system of Vulcano Island, Italy. The organic compounds considered here include four carboxylic acids (formic, acetic, propanoic and lactic), two C₅ aldoses (arabinose and xylose), three C₆ aldoses (galactose, glucose and mannose), and 15 protein-forming amino acids (Ala, Arg, Asp, Glu, Gly, His, Ile, Leu, Lys, Met, Phe, Ser, Thr, Tyr, and Val). Oxidation of these compounds is coupled to five redox pairs: O₂/H₂O, , S⁰/H₂S, and Fe₃O₄/Fe²⁺. Energy yields from potential respiration reactions range from 6 to 118 kJ/mol of electrons transferred and show systematic behavior with respect to the terminal electron acceptor. Overall, respiration with O₂ yields the most energy (98–118 kJ/mol e⁻), followed by reactions with (53– 86 kJ/mol e⁻), magnetite (29–91 kJ/mol e⁻), S⁰ (11–33 kJ/mol e⁻) and (6–34 kJ/mol e⁻). Energy yields show little correlation with organic compound family, but are correlated with fluid pH. Variability in energy yields across the nine sites is greatest for Fe(III) reduction and is primarily influenced by pH and the activity of Fe²⁺. In addition to the potential respiration reactions, the energetics of 24 potential fermentation reactions are also calculated. As expected, fermentation reactions generally yield much less energy than respiration. Normalized to the number of moles of carbon transferred, fermentation yields−8 to 71 kJ/mol C, compared with 16 to 531 kJ/mol C for respiration reactions. All respiration and fermentation reactions, except for methionine (Met) fermentation, are exergonic under the in situ hydrothermal conditions and represent a plethora of potential metabolisms for Vulcano’s diverse thermophilic heterotrophs.     

Environmental isotopes (N, S, C, O, D) to determine natural attenuation processes in nitrate contaminated waters: Example of Osona (NE Spain)

Nitrate-contaminated groundwater from an aquifer in the Osona region (NE Spain) was chemically and isotopically (δ¹⁵N_NO3,δ¹⁸O_NO3,δ³⁴S_SO4,δ¹⁸O_SO4, δD, δ¹⁸O_H2O and δ¹³C_DIC) characterized. Diffuse- contamination reached values of 366 mg/L. Nearly 75% of the 37 sampled sites had higher concentrations than the 50 mg/L in limit for drinking water. To identify the source of pollution δ¹⁵N_NO3 and δ¹⁸O_NO3 were used with results, for most samples, in the range of pig manure . Nitrification processes were evaluated by means of the δ¹⁸O of and water. Isotopic data suggested that natural attenuation of was taking place. This process was confirmed using the δ¹⁸O_NO3 coupled with the ratio, avoiding the influence of continuous inputs. A further insight on denitrification processes was obtained by analyzing the ions involved in denitrification reactions. Although the role of organic matter oxidation could neither be confirmed nor discarded, this approach showed a link between denitrification and pyrite oxidation. Therefore, in areas with no adequate infrastructure (e.g. multipiezometers), such as the one studied, this approach could be useful for implementing better water management.     

Diffusion of helium in zircon and apatite

Diffusion of helium has been characterized in natural zircon and apatite. Polished slabs of zircon and apatite, oriented either normal or parallel to c were implanted with 100 keV ³He at a dose of 5 × 10^{15 3} He/cm². Diffusion experiments on implanted zircon and apatite were run in Pt capsules in 1-atm furnaces. ³He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction ³He(d,p)⁴He. For diffusion in zircon we obtain the following Arrhenius relations:

Although activation energies for diffusion normal and parallel to c are comparable, there is marked diffusional anisotropy, with diffusion parallel to c nearly 2 orders of magnitude faster than transport normal to c. These diffusivities bracket the range of values determined for He diffusion in zircon in bulk-release experiments, although the role of anisotropy could not be directly evaluated in those measurements.In apatite, the following Arrhenius relation was obtained over the temperature range of 148–449 °C for diffusion normal to c:

In contrast to zircon, apatite shows little evidence of anisotropy. He diffusivities obtained in this study fall about an order of magnitude lower than diffusivities measured through bulk release of He through step-heating, and within an order of magnitude of determinations where ion implantation was used to introduce helium and He distributions measured with elastic recoil detection.Since the diffusion of He in zircon exhibits such pronounced anisotropy, helium diffusional loss and closure cannot be modeled with simple spherical geometries and the assumption of isotropic diffusion. A finite-element code (CYLMOD) has recently been created to simulate diffusion in cylindrical geometry with differing radial and axial diffusion coefficients. We present some applications of the code in evaluating helium lost from zircon grains as a function of grain size and length to diameter ratios, and consider the effects of “shape anisotropy”, where diffusion is isotropic (as in the case of apatite) but shapes of crystal grains or fragments may depart significantly from spherical geometry.     

Hydration in solution is critical for stable oxygen isotope fractionation between carbonate ion and water

Various isotope studies require accurate fractionation factors (α’s) between different chemical compounds in thermodynamic equilibrium. Although numerous isotope systems involve aqueous solutions, the conventional theory is formulated for the gas-phase and predicts incorrect α’s for many compounds dissolved in water. Here I show that quantum-chemistry calculations, which take into account solute–water interactions, accurately predict, for instance, oxygen isotope fractionation between dissolved and H₂O (hereafter ). Simple force field and quantum-chemistry calculations for the ‘gas-phase’ ion predict (15‰) at 25 °C. However, based on -clusters with up to 22 H₂O molecules, I calculate a value of 25‰, which agrees with the experimental value of 24.5 ± 0.5‰. Effects of geometry and anharmonicity on the calculated α were also examined. The calculations reveal the critical role of hydration in solution, which is ignored in the gas-phase theory. The approach presented provides an adequate framework for calculating fractionation factors involving dissolved compounds; it may also be used to predict α’s that cannot (or have not yet been) determined experimentally.     

Spatial and seasonal variation of major ions in Himalayan snow and ice: A source consideration

The spatial and temporal variation of major ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, , , and Cl⁻) in Himalayan snow and ice is investigated by using two snow pits from the East Rongbuk glacier (28°01′N, 86°58′E, 6500 m a.s.l.), one snow pit from the Nangpai Gosum glacier (28°03′N, 86°39′E, 5700 m a.s.l.), one snow pit from the Gyabrag glacier (28°11′N, 86°38′E, 6303 m a.s.l.), and three ice cores from the Sentik (35°59′N, 75°58′E, 4908 m a.s.l.), Dasuopu (28°33′N, 85°44′E, 7000 m a.s.l.), and East Rongbuk (27°59′N, 86°55′E, 6450 m a.s.l.) glaciers, respectively. In general, the major ions show a significant seasonal variation, with high concentrations during the non-monsoon (pre-monsoon and post-monsoon) season and relatively low concentrations during the monsoon season. Monsoon precipitation with high local/regional dust loading related to summer circulation is possibly responsible for the high concentrations occurring sporadically during the monsoon season. The crest of the Himalayas is an effective barrier to the spatial distribution of Na⁺, Cl⁻ and concentrations, but not to the major ions associated with dust influx (e.g. Ca²⁺ and Mg²⁺). Atmospheric backward trajectories from the HYSPLIT_4 model used in identifying chemical species sourcing suggest that the major ions in the Himalayan snow and ice come mainly from the Thar Desert located in the North India, as well as West Asia, or even the distant Sahara Desert in the North Africa during the winter and spring seasons. This is different from the conventionally assumed arid and semi-arid regions of the central Asia. Factors, such as different vapor sources due to atmospheric circulation patterns and geographical features (e.g. altitude, topography), may contribute to the differences in major ionic concentrations between the western and eastern Himalayas.     

Structural and geochronological constraints on the tectono-thermal evolution of the Danba domal terrane, eastern margin of the Tibetan plateau

The Songpan-Ganze terrane of the Tibetan plateau is underlain by Neoproterozoic crystalline basement rocks of the Yangtze block. These basement rocks are exposed as a series of extensional tectonic domes that form a nearly north–south trending extensional belt more than 1000 km long in the eastern margin of the Tibetan plateau. In the Danba area, detachment faults separate the basement core complexes (e.g., the Gezong and Gongcai complexes) from the Paleozoic strata which have been thinned or removed completely. The cover sequences have undergone upper greenschist to lower amphibolite facies metamorphism to form the Danba schist and are overlain by the Triassic Xikang Group, a thick flysch sequence. Both the basement rocks and the Paleozoic rocks have undergone multiple stages of deformation and thus provide an excellent opportunity to study the tectono-thermal evolution of the eastern margin of the Tibetan plateau. Two stages of deformation, corresponding to three generations of foliation (S₁, , and ), have been recognized on the basis of structural and microscopic observations. We selected amphibole and biotite separates associated with distinct generations of foliation for ⁴⁰Ar/³⁹Ar dating using laser microprobe incremental heating technique to place numerical constraints on the major tectono-thermal events within the Danba area. The geochronogical results reveal an earliest metamorphic event at 258.6 ± 0.5 Ma (S₁ biotite) and 263.6 ± 0.8 Ma (S₁ amphibole), coinciding temporally with the mantle plume that produced the voluminous Emeishan flood basalts. The second event was a progressive extensional deformation first occurred at 159–166 Ma ( amphibole) responsible for the earlier tectonic doming of the crystalline basement, and then the final tectono-thermal overprint recorded by foliation and metamorphism locally in the core complexes at 47–58 Ma for the Gezong complex and 64–81 Ma for the Gongcai complex. This major post-orogenic extensional event is believed to be a consequence of collision between the North China and South China blocks. The apparent discrepancy of the ⁴⁰Ar/³⁹Ar ages observed between localities suggests a slow cooling process associated with progressive uplift.     

Isotopic composition of nitrate in five German rivers discharging into the North Sea

We determined concentrations and isotopic composition of nitrate in five German rivers (Rhine, Elbe, Weser, Ems, and Eider) that discharge into the North Sea. Samples were obtained on a biweekly to monthly basis and chemical and isotopic analyses were conducted for the period January 2006 to March 2007 at sampling stations situated before estuarine mixing with North Sea water. We observed maximum nitrate loads in winter and fall, when both discharge and concentration of nitrate are highest. Mean annual isotope values in nitrate ranged from 8.2‰ to 11.3‰ for and 0.4‰ to 2.2‰ for . The ranges of isotope values suggest that nitrate in these rivers derives from soil nitrification, sewage, and/or manure. These and published data on other rivers in northern Europe and northern America reveal a correlation between agricultural land use (>60% in the catchment areas of rivers examined) and values. The rivers Rhine, Elbe, Weser and Ems show similar seasonal patterns of the isotopic fractionation of nitrate with increasing values and simultaneously decreasing concentrations during summer months, indicating that assimilation of nitrate is the main fractionation process of riverine nitrate. Isotopic signals in winter are more depleted than the mean summer isotope values, attributed to less microbial activity and assimilative processes. Load weighted nitrate δ¹⁵N of the riverine input to the German Bight Coastal Water mass before estuarine mixing and processing is between 8‰ and 12‰. The high δ¹⁵N value of river nitrate is matched by high δ¹⁵N of nitrate in surface sediments in the German Bight.     

H2O diffusion models in rhyolitic melt with new high pressure data

Water diffusion in silicate melts is important for understanding bubble growth in magma, magma degassing and eruption dynamics of volcanos. Previous studies have made significant progress on water diffusion in silicate melts, especially rhyolitic melt. However, the pressure dependence of H₂O diffusion is not constrained satisfactorily. We investigated H₂O diffusion in rhyolitic melt at 0.95–1.9 GPa and 407–1629 °C, and 0.2–5.2 wt.% total water (H₂O_t) content with the diffusion-couple method in a piston-cylinder apparatus. Compared to previous data at 0.1–500 MPa, H₂O diffusivity is smaller at higher pressures, indicating a negative pressure effect. This pressure effect is more pronounced at low temperatures. Assuming H₂O diffusion in rhyolitic melt is controlled by the mobility of molecular H₂O (H₂O_m), the diffusivity of H₂O_m (D_H2Om) at H₂O_t ≤ 7.7 wt.%, 403–1629 °C, and ≤ 1.9 GPa is given by

D_H2Om=D₀exp(aX),