Variation in element release rate from different mineral size fractions from the B horizon of a granitic podzol

Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10⁻¹⁴ mol/m²/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10⁻¹⁴ mol/m²/s) and sheet silicates (100×10⁻¹⁴ mol/m²/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10⁻¹⁴ mol/m²/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions.     

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

High-resolution methane profiles across anoxic brine–seawater boundaries in the Atlantis-II, Discovery, and Kebrit Deeps (Red Sea)

A decrease in temperature (ΔT up to 45.5 °C) and chloride concentration (ΔCl up to 4.65 mol/l) characterises the brine–seawater boundary in the Atlantis-II, Discovery, and Kebrit Deeps of the Red Sea, where redox conditions change from anoxic to oxic over a boundary layer several meters thick. High-resolution (100 cm) profiles of the methane concentration, stable carbon isotope ratio of methane, and redox-sensitive tracers (O₂, Mn⁴⁺/Mn²⁺, Fe³⁺/Fe²⁺, and SO₄²⁻) were measured across the brine–seawater boundary layer to investigate methane fluxes and secondary methane oxidation processes.

Substantial amounts of thermogenic hydrocarbons are found in the deep brines (mostly methane, with a maximum concentration up to 4.8×10⁵ nmol/l), and steep methane concentration gradients mainly controlled by diffusive flow characterize the brine–seawater boundary (maximum of 2×10⁵ nmol/l/m in Kebrit Deep). However, locally the actual methane concentration profiles deviate from theoretical diffusion-controlled concentration profiles and extremely positive δ¹³C–CH₄ values can be found (up to +49‰ PDB in the Discovery Deep). Both, the actual CH₄ concentration profiles and the carbon-13 enrichment in the residual CH₄ of the Atlantis-II and Discovery Deeps indicate consumption (oxidation) of ¹²C-rich CH₄ under suboxic conditions (probably utilizing readily available—up to 2000 μmol/l—Mn(IV)-oxihydroxides as electron acceptor). Thus, a combined diffusion–oxidation model was used to calculate methane fluxes of 0.3–393 kg/year across the brine–seawater boundary layer. Assuming steady-state conditions, this slow loss of methane from the brines into the Red Sea bottom water reflects a low thermogenic hydrocarbon input into the deep brines.     

Geochemical mass balance and weathering rates of ultramafic schists in Amazonia

The hydrochemical balance of the Yaou catchment in French Guiana was determined over a period of 1 year, combined with a detailed characterization of the primary minerals and their weathering products, in order to estimate ultramafic rock weathering rates in a rainforest environment. The time required to develop the main horizons of the laterite profile was obtained from estimations of the weathering rates and dissolution kinetics of some major parent minerals (chlorite, serpentine, biotite, calcite).

The specific transport of solute matter in the catchment is 205 kg/ha/a. The Cl and NO₃ net outputs shows that the system is in dynamic equilibrium, notably with respect to the biomass reservoir. The output flux of Mg in solution is mainly supplied from the weathering of primary minerals, whereas that of Ca comes both from atmospheric contributions and from the dissolution of carbonates. The fluxes of K and, more particularly, Na derive essentially from the atmosphere. Knowing the weathering rate of primary minerals, the total CO₂ consumption rate by silicate weathering is estimated at 1430 mol/ha/a.

The weathering rates of chlorite, serpentine and biotite range from 18 to 65 mol/ha/a, and those of talc and calcite are, respectively 51 and 153 mol/ha/a. Weathering rates normalized to mineral modal proportions give a decreasing order of stability resistance to weathering (calcitebiotitechlorite>serpentine>talc) that agrees with their vertical distribution in the weathering profile. The dissolution kinetics of chlorite, biotite and serpentine, expressed in relation to the Si release rate, were calculated using estimations of the mineral exchange surface by (a) optical microscope image processing of crystal outlines, and (b) BET specific surface measurements. The release rate of Si, computed for biotite, chlorite and serpentine, ranges around 10⁻¹³ and 10⁻¹⁴ mol/m²/s using microscope images on particle sizes. The estimated dissolution kinetics is two orders of magnitude lower when using the BET measured exchange surface, which is 100 times larger.

The saprolitization rate, calculated from the weathering rates of calcite, chlorite and biotite, is on average 7.5 m/Ma. The rate of latosol development, calculated from the weathering rate of serpentine at the saprolite–latosol interface, is estimated at 4.5 m/Ma. That means that the profile is chemically thickening at a rate of 3 m/Ma.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

四川盆地北部早白垩世剑门关组泥质岩地球化学特征及其地质意义

早白垩世剑门关组是研究四川盆地北部沉积环境演化的良好地层,对该地层开展系统的地球化学研究,对探讨四川盆地北部早白垩世剑门关组物源区性质、构造背景、古风化作用及古环境具有重要意义。系统分析了剑门关组泥质岩主量、微量和稀土元素地球化学特征,发现早白垩世剑门关组泥质岩富CaO、MgO,贫Al_2O_3、Fe_2O_3、K_2O、Na_2O、TiO_2、P_2O_5、MnO,富Cr、Cs、V,贫Sr、Nb、U、Hf,稀土元素总量为(164.96～234.35)×10^-6,轻、重稀土元素比值为11.77～15.87,轻、重稀土元素分馏程度高,轻稀土元素相对富集,具弱的正Eu异常。综合分析认为:剑门关组为同一物源的近物源再旋回沉积岩;源岩为沉积岩,可能富含斜长石、重晶石等富Eu矿物;源岩在沉积前经历了中等程度的化学风化作用,并发生了钾交代作用;剑门关组沉积期为温暖、湿润的气候,物源区具有由活动大陆边缘向大陆岛弧转化的特征。     

河西走廊疏勒河流域出山径流变化规律及趋势预测

依据甘肃省河西走廊疏勒河流域1956-2013年水文站实测及水文调查资料, 对流域出山径流的年内、年际变化进行统计分析, 并用坎德尔秩次相关法等检验流域径流变化趋势. 结果表明: 1956-2013年多年平均出山径流量为11.6679×10⁸ m³; 汛期集中在6-9月, 各河流来水量占年来水量的35.9%~78.7%; 地下水补给平均占径流量的40.46%; 出山径流年际变化相对稳定, 趋势表现为持续性上升的特点. 未来2014-2018年疏勒河干流出山径流为偏丰, 年平均径流量预计为13.01×10⁸ m³.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Constraints on paleowater dissolved loads and on catchment weathering over the past 16 ka from Sr/Sr ratios and Ca/Mg/Sr chemistry of freshwater ostracode tests in sediments of Lake Constance, Central Europe

Sr isotope and Ca/Mg/Sr chemical compositions of freshwater ostracode tests separated from a sediment core represent the last 16 ka of sedimentation in Lake Constance, Central Europe. The chemical evolution of the paleowater's dissolved load of Lake Constance was estimated by correcting the ostracode data for Ca/Mg/Sr fractionation due to biogenic calcification. Since the Late Pleistocene deglaciation, the Ca/Sr molar ratios of paleowaters increased systematically from about 100 (a near marine signature) to about 200. Ca/Mg molar ratios varied in the range of 1–25. The ⁸⁷Sr/⁸⁶Sr ratios indicate Late Pleistocene paleowater compositions of 0.7086–0.7091, significantly more radiogenic than present day waters (0.7085). Sr isotopes and Ca/Mg/Sr chemical data together show that weathering of Mesozoic evaporites consistently dominated the dissolved Sr load (80–90%). Carbonate and silicate weathering were less important (1–10%). Trends of Sr dissolved loads were therefore not related to Mg which was mainly mobilized by carbonate weathering. Biotite weathering was an important source of radiogenic Sr in the paleowaters. The short-term release (duration about 600–800 years) of radiogenic Sr during glacier retreat started 15.2 ka ago and was due to enhanced biotite weathering at the glacier base. Long-term release of radiogenic Sr was due to biotite weathering in glacial soils and silicate rocks, and has gradually declined since the Late Pleistocene/Holocene transition.     

Weathering of Valle Ricca stiff and jointed clay

The study proposes a weathering model of Pliocene–Pleistocene stiff and jointed blue-grey clay transforming into yellow clay. Physical, mineralogical, chemical and textural changes, as well as the weathering profile were investigated in a quarry of central Italy. Based on geological records and inferences, these changes are likely to have occurred within a time-span of about 50,000 years BP, upon overburden stress unloading and in a stress regime that is locally controlled by suction. Weathering propagated into the clay at a rate of about 0.3 mm/year and was enhanced by the enlargement of the pre-existing tectonic discontinuities and by the formation of new joints. A mass loss of about 22–25 wt.% was calculated. Considering Fe and P as immobile elements, the individual oxides contribute to mass loss in the following order: SiO₂ > CaO = CO₂ > Al₂O₃ > MgO > K₂O > S > Na₂O > TiO₂ > MnO. The Fe₂O₃ / (Fe₂O₃ + FeO) ratio varies from 9–29% in the blue-grey clay to 75–82% in the yellow one. Oxidation and/or dissolution of 7 Å-Fe²⁺-bearing clay minerals, mica-like minerals and calcite and parallel increase of smectite and Fe-hydroxides play a critical role in the chemical changes and explain the higher plasticity of the yellow clay with respect to the blue-grey one. The role of water during the weathering process was inferred to occur in cyclical steps: 1) seepage of meteoric water; 2) dissemination of highly oxidizing meteoric water; 3) triggering of oxidation and dissolution of minerals; 4) water evaporation; 5) partial migration of the elements contained in the aqueous solution and consequent deposition of minerals in the joints.     

Terrestrial Kr-Kr ages of Antarctic meteorites

The production rate of ³⁸Ar in meteorites—P(38)—has been determined, as a function of the sample's chemical composition, from ⁸¹Kr-Kr exposure ages of four eucrite falls. The cosmogenic ⁷⁸Kr/⁸³Kr ratio is used to estimate the shielding dependence of P(38).

From the “true” ³⁸Ar exposure ages and the apparent ⁸¹Kr-Kr exposure ages of nine Antarctic eucrite finds, terrestrial ages are calculated. They range from about 3 × 10⁵ a (Pecora Escarpment 82502) to very recent falls (Thiel Mountains 82502). Polymict eucrites from the Allan Hills (A78132, A79017 and A81009) have within the limits of error the same exposure age (15.2 × 10⁶ a) and the same terrestrial age (1.1 × 10⁵ a). This is taken as strong evidence that these meteorites are fragments of the same fall. A similar case are the Elephant Moraine polymict eucrites A79005, A79006 and 82600 with an exposure age of 26 × 10⁶ a and a terrestrial age of 1.8 × 10⁵ a. EETA79004 may be different from this group because its exposure age and terrestrial age are 21 × 10⁶ a and 2.5 × 10⁵ a, respectively.

The distribution of terrestrial ages of Allan Hills meteorites is discussed. Meteorites from this blue ice field have two sources: Directly deposited falls and meteorites transported to the Allan Hills inside the moving Antarctic ice sheet. During the surface residence time meteorites decompose due to weathering processes. The weathering “half-life” is about 1.6 × 10⁵ a. From the different age distributions of Allan Hills and Yamato meteorites, it is concluded that meteorite concentrations of different Antarctic ice fields need different explanations.     

南伊沟水体水化学及氢氧同位素特征分析

南伊沟是林芝地区重要水源涵养区,研究南伊沟水体水化学和氢氧同位素特征,揭示“三水转化”规律,对提高林芝地区水体水文地球化学研究程度,支撑当地林水关系研究,服务高原地区水生态保护具有重要意义。运用水化学和氢氧同位素分析方法,分析了地区水化学特征、水岩作用情况和水循环特征。结果表明：南伊沟水体为极低矿化度淡水,地表水水化学类型为HCO₃-Ca·Mg型和SO₄·HCO₃-Ca·Mg型,地下水水化学类型为HCO₃-Ca·Na型;地表水和地下水的水化学离子成分主要受岩石风化控制,离子来源主要受碳酸盐岩溶解和硅酸盐岩风化影响,地表水中Na⁺、K⁺、Cl^-主要来源于盐岩溶解,同时还受降雨影响,地表水和地下水中Ca²⁺、Mg²⁺主要来源于碳酸盐岩矿物溶解;地下水和地表水水岩作用较弱,对比上游雅鲁藏布江和拉萨河地表水,大部分δ¹⁸O、δD值具有明显的高度效应和大陆效应;南伊沟枯水年内强烈...     

A soil acidification study using the PROFILE model on two contrasting regions in Switzerland

The steady-state soil chemistry model PROFILE was used to calculate the chemical status of forest soils under present deposition loads for two areas with dissimilar ecosystem properties. Two regions in Switzerland, with contrasting bedrock geology were selected to be investigated in detail: 88 locations in the Jura Mountains, representative for carbonate bedrock and 91 locations in the Ticino Area dominated by metamorphic crystalline host rocks. Weathering rates calculated for the key regions cover the tremendous range between 0.013 and 25 keq ha⁻¹ yr⁻¹. In the Ticino Area, the effect of increased abundance of relatively fast weathering silicates (epidote, hornblende and plagioclase) on the weathering rate is apparently masked by the total effects of the physical conditions applied and by the variation in the deposition load. In the Jura Mountains, generally high weathering rates occur with about 50% of the sites yielding rates above 1 keq ha⁻¹ yr⁻¹. In many of the sites investigated, however, carbonates have already been dissolved completely in the soil horizons of interest resulting in very low weathering rates. The critical load of actual acidity was calculated according to: CL_Acidity=R_Weathering−ANC_Leaching, where alkalinity leaching is estimated by keeping the base cation to aluminum molar ratio at the critical limit of 1 at steady-state. The minimum critical load calculated was 0.2 keq ha⁻¹ yr⁻¹ and the maximum was 6.2 keq ha⁻¹ yr⁻¹. Comparing the cumulative frequency distributions of critical loads of actual acidity for forest soils in the individual areas it can be seen that the differences between the key regions are less substantial than with the weathering rates. Critical loads of acidity for the Ticino Area range from 1 to 3.9 keq ha⁻¹ yr⁻¹. Sites yielding the lowest critical loads of acidity are observed in the Jura Mountains. Among these apparent sensitive soils are soils with intermediate or high weathering rates, although it has depleted topsoil layers. Within the context of this model application, it becomes apparent that the sensitivity of these soils with respect to acidification is also governed by the alkalinity leaching term and not only by the susceptibility of its minerals to weathering.     

长江干流水化学成因与风化过程CO2消耗通量解析

长江流域面积巨大,岩性多变,加之三峡大坝等重大水利工程的影响,干流河水的水化学成因存在较大争议。此外,以往研究中流域矿物风化过程的碳汇通量估算一般基于阳离子来源分析,但该算法通常涉及多种矿物端元的参数选取,结果具有不确定性。本次研究对长江干流水化学的时空演变进行了整体分析,并基于上游河水样品HCO₃~-含量的校正与计算,提出了一种计算矿物风化过程碳汇通量的新方法。研究结果表明,蒸发盐溶解、循环盐作用、矿物风化及硫酸盐溶解是控制长江干流河水离子组成的主要水文地球化学作用,而人类活动主要影响了离海距离3 000 km以内河水NO₃~-含量;长江上游干流硅酸盐风化消耗CO₂速率为1.16×10~5 mol/(km~2·a),碳酸盐风化消耗CO₂速率为4.75×10~5 mol/(km~2·a)。本研究有助于加深对长江干流主要水文地球化学作用的认识,丰富和完善碳循环研究理论。     

Dissolved load of the Loire River: chemical and isotopic characterization

The Loire River, with one of the largest watersheds in France, has been monitored just outside the city of Orleans since 1994. Physico-chemical parameters and major and trace elements were measured between 2-day and 1-week intervals according to the river flow. The sampling site represents 34% of the total Loire watershed with 76% silicate rocks and 24% carbonate rocks.

Elements are transported mainly in the dissolved phase with the ratio of total dissolved salts (TDS) to suspended matter (SM) ranging between 1.6 and 17.4. Chemical weathering of rocks and soils are thus the dominant mechanisms in the Loire waters composition. The highest TDS/SM ratios are due to dissolved anthropogenic inputs. The database shows no link between NO₃⁻ content and river flow. The Na⁺, K⁺, Mg²⁺, SO₄²⁻, and Cl⁻ concentrations are seen to decrease with increasing discharge, in agreement with a mixing process involving at least two components: the first component (during low flow) is concentrated and may be related with input from the groundwater and sewage station water, the second component (during high flow) is more dilute and is in agreement with bedrock weathering and rainwater inputs. A geochemical behaviour pattern is also observed for HCO₃⁻ and Ca²⁺ species, their concentrations increase with increasing discharge up to 300 m³/s, after which, they decrease with increasing discharge. The Sr isotopic composition of the dissolved load is controlled by at least five components — a series of natural components represented by (a) waters draining the silicate and carbonate bedrock, (b) groundwater, and (c) rainwaters, and two kinds of anthropogenic components.

The aim of this study is to describe the mixing model in order to estimate the contribution of each component. Finally, specific export rates in the upper Loire watershed were evaluated close to 12 t year⁻¹ km⁻² for the silicate rate and 47 t year⁻¹ km⁻² for the carbonate rate.     

Weathering processes in the Indus River Basin: implications from riverine carbon, sulfur, oxygen, and strontium isotopes

This study deals with the major ions and isotope systematics for C, O, S, and Sr in the Indus River Basin (IRB). Major ion chemistry of the Indus, and most of its headwater tributaries, follow the order Ca²⁺>Mg²⁺>(Na⁺+K⁺) and HCO₃⁻>(SO₄²⁻+Cl⁻)>Si. In the lowland tributaries and in some of the Punjab rivers, however, (Na⁺+K⁺) and (SO₄²⁻+Cl⁻) predominate. Cyclic salts, important locally for Na⁺ in dilute headwater tributaries, constitute about 5% of the annual solutes transported by the Indus. Weathering of two lithologies, sedimentary carbonates and crystalline rocks, controls the dissolved inorganic carbon (DIC) concentrations and its carbon isotope systematics throughout the Indus, but turbulent flow and lower temperatures in the headwaters, and storage in reservoirs in the middle and lower Indus promote some equlibration with atmospheric carbon dioxide. Combined evidence from sulfur and oxygen isotopic composition of sulfates refutes the proposition that dissolution of these minerals plays a significant role in the IRB hydrochemistry and suggests that any dissolved sulfates were derived by oxidation of sulfide minerals.

In the upper Indus, silicate weathering contributes as much as 75% (or even higher in some tributaries) of the total Na⁺ and K⁺, declining to less than 40% as the Indus exits the orogen. In contrast, about two-thirds of Ca²⁺ and Mg²⁺ in the upper Indus (over 70% in some tributaries) and three-fourth in the lower Indus, are derived from sedimentary carbonates. The ⁸⁷Sr/⁸⁶Sr ratios tend to rise with increasing proportions of silicate derived cations in the headwater tributaries and in the upper and middle Indus, but are out of phase or reversed in the lower Indus. Finally, close to the river mouth, the discharge weighted average contribution of silicate derived Ca²⁺+Mg²⁺ and silicate derived Na⁺+K⁺ are, respectively, about one-fourth and two-thirds of their total concentrations.     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.