Chemical weathering of a marine terrace chronosequence, Santa Cruz, California I: Interpreting rates and controls based on soil concentration-depth profiles

The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America.Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile b_s is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux q_h, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (q_h = 0.025-0.17 m yr⁻¹).During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined as

     

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar

Here we report on an experimental investigation of the relation between the dissolution rate of albite feldspar and the Gibbs free energy of reaction, ΔG_r. The experiments were carried out in a continuously stirred flow-through reactor at 150 °C and pH_(150 °C) 9.2. The dissolution rates R are based on steady-state Si and Al concentrations and sample mass loss. The overall relation between ΔG_r and R was determined over a free energy range of −150 < ΔG_r < −15.6 kJ mol⁻¹. The data define a continuous and highly non-linear, sigmoidal relation between R and ΔG_r that is characterized by three distinct free energy regions. The region furthest from equilibrium, delimited by −150 < ΔG_r < −70 kJ mol⁻¹, represents an extensive dissolution rate plateau with an average rate . In this free energy range the rates of dissolution are constant and independent of ΔG_r, as well as [Si] and [Al]. The free energy range delimited by −70 ? ΔG_r ? −25 kJ mol⁻¹, referred to as the ‘transition equilibrium’ region, is characterized by a sharp decrease in dissolution rates with increasing ΔG_r, indicating a very strong inverse dependence of the rates on free energy. Dissolution nearest equilibrium, defined by ΔG_r > −25 kJ mol⁻¹, represents the ‘near equilibrium’ region where the rates decrease as chemical equilibrium is approached, but with a much weaker dependence on ΔG_r. The lowest rate measured in this study, R = 6.2 × 10⁻¹¹ mol m⁻² s⁻¹ at ΔG_r = −16.3 kJ mol⁻¹, is more than two orders of magnitude slower than the plateau rate. The data have been fitted to a rate equation (adapted from Burch et al. [Burch, T. E., Nagy, K. L., Lasaga, A. C., 1993. Free energy dependence of albite dissolution kinetics at 80 °C and pH 8.8. Chem. Geol.105, 137-162]) that represents the sum of two parallel reactions

R=k₁[1-exp(-ng^m₁)]+k₂[1-exp(-g)]^m₂,     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and ⁸⁷Sr/⁸⁶Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q_h), based on Cl mass balances, vary from 0.06 to 0.22 m yr⁻¹, resulting in fluid residence times in the terraces of 10-24 yrs.As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO₃ > HCO₃ > SO₄ reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute ⁸⁷Sr/⁸⁶Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and ⁸⁷Sr/⁸⁶Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate.Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R_solute are estimated from linear Na and Si pore weathering gradients b_solute such that

     

Quantifying inorganic sources of geochemical energy in hydrothermal ecosystems, Yellowstone National Park, USA

Combining analytical data from hot spring samples with thermodynamic calculations permits a quantitative assessment of the availability and ranking of various potential sources of inorganic chemical energy that may support microbial life in hydrothermal ecosystems. Yellowstone hot springs of diverse geochemical composition, ranging in pH from <2 to >9 were chosen for this study, and dozens of samples were collected during three field seasons. Field measurements of dissolved oxygen, nitrate, nitrite, total ammonia, total sulfide, alkalinity, and ferrous iron were combined with laboratory analyses of sulfate and other major ions from water samples, and carbon dioxide, hydrogen, methane, and carbon monoxide in gas samples to evaluate activity products for ∼300 coupled oxidation-reduction reactions. Comparison of activity products and independently calculated equilibrium constants leads to values of the chemical affinity for each of the reactions, which quantifies how far each reaction is from equilibrium. Affinities, in turn, show systematic behavior that is independent of temperature but can be correlated with pH of the hot springs as a proxy for the full spectrum of geochemical variability. Many affinities are slightly to somewhat dependent on pH, while others are dramatically influenced by changes in chemical composition. All reactions involving dissolved oxygen as the electron acceptor are potential energy sources in all hot spring samples collected, but the ranking of dominant electron donors changes from ferrous iron, and sulfur at high pH to carbon monoxide, hydrogen, and magnetite as pH decreases. There is a general trend of decreasing energy yields depending on electron acceptors that follows the sequence: O₂(aq) > NO₃⁻ ≈ NO₂⁻ ≈ S > pyrite ≈ SO₄⁻² ≈ CO(g) ≈ CO₂(g) at high pH, and O₂(aq) ≈ magnetite > hematite ≈ goethite > NO₃⁻ ≈ NO₂⁻ ≈ S ≈ pyrite ≈ SO₄⁻² at low pH. Many reactions that are favorable sources of chemical energy at one set of geochemical conditions fail to provide energy at other conditions, and vice versa. This results in energy profiles supplied by geochemical processes that provide fundamentally different foundations for chemotrophic microbial communities as composition changes.     

The dissolution rates of gibbsite in the presence of chloride, nitrate, silica, sulfate, and citrate in open and closed systems at 20°C

The dissolution of well crystallized gibbsite far at from equilibrium was studied in batch and mixed flow through reactors. The dissolution experiments were carried out between pH 2 and 6 in the presence of 10 mmol L⁻¹ citrate, at pH 2 and 3 in the presence of 10 mmol L⁻¹ chloride, nitrate, and sulfate, and at pH 2 and 3 in the presence of 1.5 mmol L⁻¹ silica at 20°C. The dissolution rate of gibbsite, R_Al (mol m⁻² s⁻¹), increases in the order of chloride ≈ nitrate < silica < sulfate ≈ citrate. In presence of silica, sulphate, and citrate dissolution is catalysed by the formation of aluminium complexes at the gibbsite surface (pH 2 and 3). From pH 2 to 3 no effect of R_Al on hydrogen activity is predicted as singly coordinated surface sites at the edges of the platy gibbsite crystals, [≡AlOH₂^+0.5] ≈ [≡AlOH], are almost saturated with protons. However at pH >3 dissolution is slowed by a decrease of [≡AlOH₂^+0.5].Gibbsite dissolution rates measured in closed and open systems were identical within the experimental and analytical uncertainty. This observation indicates that gibbsite dissolution is a surface controlled process. If dissolution of gibbsite occurs close to equilibrium R_Al values may be predicted by an approximately linear function of ΔG_r.     

The role of sulfur in chemical weathering and atmospheric CO2 fluxes: Evidence from major ions, δCDIC, and δSSO4 in rivers of the Canadian Cordillera

Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO₃⁻, SO₄²⁻, Cl⁻, Ca²⁺, Mg²⁺, K⁺, Na⁺), δ¹³C of dissolved inorganic carbon (δ¹³C_DIC), and δ³⁴S of dissolved sulfate (δ³⁴S_SO4) to quantify chemical weathering rates and exchanges of CO₂ between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ³⁴S_SO4 (−8.9 to 14.1‰_CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ¹³C_DIC values (−9.8 to −3.7‰ _VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ³⁴S_SO4 is negatively correlated with δ¹³C_DIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ¹³C_DIC of rivers. The negative correlation between δ³⁴S_SO4 and δ¹³C_DIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 10³ mol C · km⁻² · yr⁻¹) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 10³ mol C · km⁻² · yr⁻¹). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO₂ to carbonate rocks, sulfide-carbonate weathering can liberate CO₂ from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO₂ drawdown by silicate weathering in the region.     

The weathering of stones due to dissolution

We hypothesize that the weathering of building stones can be attributed to surface dissolution processes. We assume that chemical interactions occur on grain boundaries and/or microcracks and that diffusion is the controlling process. A dissolution layer (rind) develops adjacent to the weathering surface. We quantify the extent of dissolution by introducing a damage variable f; f=0 for pristine rock, and when f=1 the rock disintegrates. We assume that the variations of the damage variable are given by the diffusion equation. We solve two problems. The first is for the structure of the transient dissolution boundary layer prior to surface disintegration. We find an incubation time t_i, before active weathering (disintegration) begins. The second is the solution for steady-state weathering with a constant weathering velocity v_w. Our results are entirely consistent with weathering studies on Carrara marble gravestones in the United Kingdom. Typical incubation times are t_i=20–30 years, and typical steady-state weathering velocities are v_w=5–50 m year^–1.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Solubilities of corundum, wollastonite and quartz in H2O-NaCl solutions at 800 °C and 10 kbar: Interaction of simple minerals with brines at high pressure and temperature

Solubilities of corundum (Al₂O₃) and wollastonite (CaSiO₃) were measured in H₂O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H₂O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al₂O₃ molality (m_Al2O3) of 0.0013(1) (1σ error) in pure H₂O and then leveling off to a maximum of ∼0.015 at halite saturation (X_NaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H₂O, , passes through a maximum at X_NaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H₂O at this P and T(m_CaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H₂O at X_NaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H₂O-NaCl-SiO₂, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from m_SiO2=1.248 in pure H₂O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H₂O reproduces the data and indicates that hydrogen bonding of molecular H₂O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na⁺ and/or Cl⁻ species produced by molar ratios of reactant H₂O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.     

Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy

The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H₂O (H₂O_m), OH species (OH) and total water (H₂O_t) were determined. The diffusion profile of H₂O_m in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H₂O_m in the hydrated region is much higher than that of OH species. Thus, the reaction from H₂O_m to OH appears to be little and H₂O_m is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H₂O_m(D_H2Om) and H₂O_t(D_H2Ot) were determined to be 2.8 × 10⁻¹⁰ and 3.4 × 10⁻¹⁰ μm² s⁻¹ for Ohsawa lava, and 5.2 × 10⁻¹¹ and 4.1 × 10⁻¹¹ μm² s⁻¹ for Awanomikoto lava, respectively. The obtained D_H2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.     

Connections between surface complexation and geometric models of mineral dissolution investigated for rhodochrosite

Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO₃H regulates dissolution for pH < 7 while the surface concentration of >MnOH₂⁺ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ_1/2(k_co + k_ca)[>CO₃H] + χ_1/2(k_mo + k_ma)[>MnOH₂⁺ ], where R is the dissolution rate (mol m⁻² s⁻¹), 2χ_1/2 is the fraction of surface sites located at steps, [>CO₃H] and [>MnOH₂⁺ ] are surface concentrations (mol m⁻²), and k_co, k_ca, k_mo, and k_ma are the respective dissolution rate coefficients (s⁻¹) for the >CO₃H and the >MnOH₂⁺ surface species on obtuse and acute steps. We find k_co = 2.7 s⁻¹, k_ca = 2.1 × 10⁻¹ s⁻¹, k_mo = 4.1 × 10⁻² s⁻¹, k_ma = 3.7 × 10⁻² s⁻¹, and χ_1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface step processes, including double-kink initiation and single-kink propagation. We propose that the SSCM model may have general applicability for dissolution far from equilibrium of flat mineral surfaces of ionic crystals, at least those that dissolve by step retreat.     

Fe(CO3)OH in goethite from a mid-latitude North American Oxisol: estimate of atmospheric CO2 concentration in the Early Eocene “climatic optimum”

Measured mole fractions (X) and δ¹³C values of the Fe(CO₃)OH component in pedogenic goethite from a mid-latitude Oxisol of Early Eocene age (≈52 Ma B.P.) range from 0.0014 to 0.0064 and −20.1 to −15.4‰, respectively. These values of X imply that concentrations of CO₂ gas in the paleosol were ≈7400 to ≈34,000 ppm. δ¹³C and 1/X are correlated and define a linear, soil-CO₂ diffusive mixing line with a positive slope. Such positive slopes are characteristic of mixing of two isotopically distinct CO₂ endmembers (atmospheric CO₂ and CO₂ from oxidation of soil organic matter). From the intercept of the mixing line, it is calculated that the δ ¹³C value of organic matter in the ancient soil was ≈−28.0‰. The magnitude of the slope implies an Early Eocene atmospheric CO₂ concentration of ≈2700 ppm.A simple model for forest soils suggests that a “canopy effect” may cause atmospheric CO₂ concentrations deduced from pedogenic minerals to underestimate the actual concentrations of atmospheric CO₂. If a significant forest canopy were present at the time of formation of pedogenic goethite in the Ione Fm, the concentration of 2700 ppm calculated for atmospheric CO₂ could be slightly low, but the underestimate is expected to be < ≈300 ppm (i.e., less than the analytical uncertainty). The relatively high concentration of 2700 ppm inferred for atmospheric CO₂ at ≈52 Ma B.P. would have been coincident with the Early Eocene climatic optimum. This result seems to support the case for an important role for variations of atmospheric CO₂ in the modification of global paleoclimate.     

Copper Adsorption by Chernozem Soils and Parent Rocks in Southern Russia

Laboratory data in Cu²⁺ adsorption by chernozems and parent rocks in Rostov region show that adsorption isotherms can be approximated by the Langmuir equation, whose parameters (K_l and C_∞) were calculated for all of the samples. The values of C_∞ show a strong negative correlation with the values of cationexchange capacity (CEC) (r =–0.88 at Р = 0.95), and K_l is correlated with the content of physical clay (particles <0.01 mm) (r = 0.78) and with clay (particles <0.001 mm) content in ordinary chernozem and southern chernozems of various particle size distribution (r = 0.80). Even stronger correlations were detected between these parameters in southern chernozems (r = 0.89 for the physical clay (PC) and r = 0.91 for the silt). However, none of the samples displays a significant correlation of C_∞ and K_l with the contents of physical clay and silt. This led us to conclude that the composition of the samples, for example, their organic matter, can affect Cu²⁺ adsorption by the soils and parent rocks. Acidification mechanisms of the equilibrium solutions during the Cu²⁺ adsorption by soils are discussed, as also are the reasons for the absence of balance between Cu²⁺ adsorbed by soils and exchangeable cations transferred into solution. Analysis of the fine structures of the XANES and EXAFS spectra suggests that Cu²⁺ can form coordinated chelate complex compounds with humic acids (HA) of soils and can substitute Al³⁺ at octahedral sites when interacting with clay minerals in soils.     

The origin of Zn isotope fractionation in sulfides

Isotope fractionation of Zn between aqueous sulfide, chloride, and carbonate species (Zn²⁺, Zn(HS)₂, , , ZnS(HS)⁻, ZnCl⁺, ZnCl₂, , and ZnCO₃) was investigated using ab initio methods. Only little fractionation is found between the sulfide species, whereas carbonates are up to 1‰ heavier than the parent solution. At pH > 3 and under atmospheric-like CO₂ pressures, isotope fractionation of Zn sulfides precipitated from sulfidic solutions is affected by aqueous sulfide species and the δ⁶⁶Zn of sulfides reflect these in the parent solutions. Under high P_CO2 conditions, carbonate species become abundant. In high P_CO2 conditions of hydrothermal solutions, Zn precipitated as sulfides is isotopically nearly unfractionated with respect to a low-pH parent fluid. In contrast, negative δ⁶⁶Zn down to at least −0.6‰ can be expected in sulfides precipitated from solutions with pH > 9. Zinc isotopes in sulfides and rocks therefore represent a potential indicator of mid to high pH in ancient hydrothermal fluids.     

Compositional zoning in garnet and kinetics of metamorphic crystallization

The kinetics of zoned garnet porphyroblast growth is exemplified in a sample of garnet-staurolite-biotite schist from the northern Ladoga region. The diffusion-controlled porphyroblast growth was accompanied by a decrease in the kinetic coefficient during phase reactions. Even at insignificant (1–2°C) thermal overstepping, the leading role of diffusion as a factor that controls kinetics of porphyroblast growth in medium-grade metapelites is consistent with the parameters of metamorphic crystallization: T = 500–650°C, t = 1 Ma; D _A1 ^app = 10^?14 cm²/s, L = 0.2–0.6 cm, r = 1–3 mm, ΔC _Al = 1.5 × 10^?4–1.5 × 10^?3 mol/cm³.     

The distribution of nitrate N/N in marine sediments and the impact of benthic nitrogen loss on the isotopic composition of oceanic nitrate

We report ¹⁵N/¹⁴N ratios of porewater nitrate in sediments from the Bering Sea basin, where microbial nitrate reduction has been identified as a significant sink for fixed nitrogen (N). Strong ¹⁵N enrichment in porewater nitrate is observed as one goes deeper in the sediments and nitrate concentration decreases (δ¹⁵N generally reaches 25-35‰). Analysis of profiles with a one-dimensional diffusion-reaction model yields organism-scale isotope effects for dissimilatory nitrate reduction (ε_cell) of 11‰ to 30‰, in the same range as measured in previous studies of cultures and the marine and lacustrine water column. Estimates of ε_cell, while uncertain, show a negative correlation with bottom water [O₂]; we propose that this relates to the at the depth of denitrification. The N isotope effect at the scale of nitrate sediment-water exchange (ε_app) is ∼0‰ in two unreactive deep sites and is typically <3‰ at more reactive sites at various depths. ε_app is much lower than ε_cell because nitrate consumption is nearly complete at the sediment depth of denitrification, minimizing the escape of ¹⁵N-enriched nitrate from the sediments. In reactive sediments, this is due to rapid denitrification, while in less reactive sediments, it is due to greater diffusive distances for nitrate to the depth of denitrification. The data suggest that low bottom water [O₂] tends to yield more complete expression of ε_cell at the sediment-water scale, due to higher at the depth of denitrification. While porewater ammonium-N isotopes were not measured, our porewater model suggests that, in sediments with high organic matter supply and/or low-[O₂] bottom waters, the efflux and subsequent oxidation of ammonium enriched in ¹⁵N by incomplete nitrification can significantly enhance the total net isotope effect of sedimentary N loss (ε_sed, equivalent to ε_app but including ammonium fluxes). Model analysis of representative sedimentary environments suggests a global mean ε_sed of ∼4‰ (∼2‰ if restricted to seafloor below 1 km depth).     

Hydrochemical characteristics of groundwater in the plains of Phalgu River in Gaya, Bihar, India

Assessment of groundwater quality is essential to ensure sustainable use of it for drinking, agricultural, and industrial purposes. The chemical quality of groundwater of Gaya region has been studied in detail in this work to delineate the potable groundwater zones. A total of 30 groundwater samples and 2 surface water samples were collected in and around Gaya district of Bihar. The major cations follow the trend: Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺. The domination of calcium ions in the groundwater is due to weathering of rocks. The K⁺ ranged between 0.2 and 47.95 ppm, suggesting its abundance the below desired limit; but some samples were found to be above permissible limit. K⁺ weathering of potash silicate and the use of potash fertilizer could be the source. The major anions abundance followed the order HCO ₃ ^? ?>?Cl^??>?SO ₄ ^2? ?>?NO ₃ ^? ?>?PO ₄ ^3? . Dissolution of carbonates and reaction of silicates with carbonic acid accounts for the addition of HCO ₃ ^? to the groundwater and oxidation of sulphite may be the source of SO ₄ ^2? . Principal component analysis was utilized to reflect those chemical data with the greatest correlation and seven major principal components (PCs) representing >80 % of cumulative variance were able to interpret the most information contained in the data. PC1, PC2 and PC3 reflect the hydrogeochemical processes like mineral dissolution, weathering and anthropogenic sources. PC4, PC5, PC6 and PC7 show monotonic, random and independent relationships.