Climatic and tectonic controls on chemical weathering in the New Zealand Southern Alps

Climatic and tectonic controls on the relative abundance of solutes in streams draining the New Zealand Southern Alps were investigated by analyzing the elemental and Sr isotope geochemistry of stream waters, bedload sediment, and hydrothermal calcite veins. The average relative molar abundance of major cations and Si in all stream waters follows the order Ca²⁺ (50%) > Si (22%) > Na⁺ (17%) > Mg²⁺ (6%) > K⁺ (5%). For major anions, the relative molar abundance is HCO₃⁻ (89%) > SO₄²⁻ (7%) > Cl⁻ (4%). Weathering reactions involving plagioclase and volumetrically small amounts of hydrothermal calcite define the ionic chemistry of stream waters, but nearly all streams have a carbonate-dominated Ca²⁺ and HCO₃⁻ mass-balance. Stream water Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios vary from 0.173 to 0.439 μmol/nmol and from 0.7078 to 0.7114, respectively. Consistent with the ionic budget, these ratios lie solely within the range of values measured for bedload carbonate (Ca/Sr = 0.178 to 0.886 μmol/nmol; ⁸⁷Sr/⁸⁶Sr = 0.7081 to 0.7118) and hydrothermal calcite veins (Ca/Sr = 0.491 to 3.33 μmol/nmol; ⁸⁷Sr/⁸⁶Sr = 0.7076 to 0.7097).Streams draining regions in the Southern Alps with high rates of physical erosion induced by rapid tectonic uplift and an extremely wet climate contain ∼10% more Ca²⁺ and ∼30% more Sr²⁺ from carbonate weathering compared to streams draining regions in drier, more stable landscapes. Similarly, streams draining glaciated watersheds contain ∼25% more Sr²⁺ from carbonate weathering compared to streams draining non-glaciated watersheds. The highest abundance of carbonate-derived solutes in the most physically active regions of the Southern Alps is attributed to the tectonic exhumation and mechanical denudation of metamorphic bedrock, which contains trace amounts of calcite estimated to weather ∼350 times faster than plagioclase in this environment. In contrast, regions in the Southern Alps experiencing lower rates of uplift and erosion have a greater abundance of silicate- versus carbonate-derived cations. These findings highlight a strong coupling between physical controls on landscape development and sources of solutes to stream waters. Using the Southern Alps as a model for assessing the role of active tectonics in geochemical cycles, this study suggests that rapid mountain uplift results in an enhanced influence of carbonate weathering on the dissolved ion composition delivered to seawater.     

Silicate and carbonate weathering in the drainage basins of the Ganga-Ghaghara-Indus head waters: Contributions to major ion and Sr isotope geochemistry

The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the⁸⁷Sr/⁸⁶Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between⁸⁷Sr/⁸⁶Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low⁸⁷Sr/⁸⁶Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and⁸⁷Sr/⁸⁶Sr in the headwaters on a basin-wide scale, however, the high⁸⁷Sr/⁸⁶Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of⁸⁷Sr/⁸⁶Sr and Ca/Sr data of the source waters show that they diverge from a low⁸⁷Sr/⁸⁶Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO₂ consumption rates and their global significance.     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

Relative contributions of silicate and carbonate rocks to riverine Sr fluxes in the headwaters of the Ganges

Exhumation of the Himalayan-Tibetan orogen is implicated in the marked rise in seawater ⁸⁷Sr/⁸⁶Sr ratios since 40 Ma. However both silicate and carbonate rocks in the Himalaya have elevated ⁸⁷Sr/⁸⁶Sr ratios and there is disagreement as to how much of the ⁸⁷Sr flux is derived from silicate weathering. Most previous studies have used element ratios from bedrock to constrain the proportions of silicate- and carbonate-derived Sr in river waters. Here we use arrays of water compositions sampled from the head waters of the Ganges in the Indian and Nepalese Himalaya to constrain the end-member element ratios. The compositions of tributaries draining catchments restricted to a limited range of geological units can be described by two-component mixing of silicate and carbonate-derived components and lie on a plane in multicomponent composition space. Key elemental ratios of the carbonate and silicate components are determined by the intersection of the tributary mixing plane with the planes Na = 0 for carbonate and constant Ca/Na for silicate. The fractions of Sr derived from silicate and carbonate sources are then calculated by mass-balance in Sr-Ca-Mg-Na composition space. Comparison of end-member compositions with bedrock implies that secondary calcite deposition may be important in some catchments and that dissolution of low-Mg trace calcite in silicate rocks may explain discrepancies in Sr-Ca-Na-Mg covariation. Alternatively, composition-dependent precipitation or incongruent dissolution reactions may rotate mixing trends on cation-ratio diagrams. However the calculations are not sensitive to transformations of the compositions by incongruent dissolution or precipitation processes provided that the transformed silicate and carbonate component vectors are constrained. Silicates are calculated to provide ∼50% of the dissolved Sr flux from the head waters of the Ganges assuming that discrepancies between Ca-Mg-Na covariation and the silicate rock compositions arise from addition of trace calcite. If the Ca-Mg-Na mixing plane is rotated by composition-dependent secondary calcite deposition, this estimate would be increased. Moreover, when ⁸⁷Sr/⁸⁶Sr ratios of the Sr inputs are considered, silicate Sr is responsible for 70 ± 16% (1σ) of the ⁸⁷Sr flux forcing changes in seawater Sr-isotopic composition. Since earlier studies predict that silicate weathering generates as little as 20% of the total Sr flux in Himalayan river systems, this study demonstrates that the significance of silicate weathering can be greatly underestimated if the processes that decouple the water cation ratios from those of the source rocks are not properly evaluated.     

Chemical weathering in the Upper Huang He (Yellow River) draining the eastern Qinghai-Tibet Plateau

We examined the fluvial geochemistry of the Huang He (Yellow River) in its headwaters to determine natural chemical weathering rates on the northeastern Qinghai-Tibet Plateau, where anthropogenic impact is considered small. Qualitative treatment of the major element composition demonstrates the dominance of carbonate and evaporite dissolution. Most samples are supersaturated with respect to calcite, dolomite, and atmospheric CO₂ with moderate (0.710-0.715) ⁸⁷Sr/⁸⁶Sr ratios, while six out of 21 total samples have especially high concentrations of Na, Ca, Mg, Cl, and SO₄ from weathering of evaporites. We used inversion model calculations to apportion the total dissolved cations to rain-, evaporite-, carbonate-, and silicate-origin. The samples are either carbonate- or evaporite-dominated, but the relative contributions of the four sources vary widely among samples. Net CO₂ consumption rates by silicate weathering (6-120 × 10³ mol/km²/yr) are low and have a relative uncertainty of ∼40%. We extended the inversion model calculation to literature data for rivers draining orogenic zones worldwide. The Ganges-Brahmaputra draining the Himalayan front has higher CO₂ consumption rates (110-570 × 10³ mol/km²/yr) and more radiogenic ⁸⁷Sr/⁸⁶Sr (0.715-1.24) than the Upper Huang He, but the rivers at higher latitudes are similar to or lower than the Upper Huang He in CO₂ uptake by silicate weathering. In these orogenic zones, silicate weathering rates are only weakly coupled with temperature and become independent of runoff above ∼800 mm/yr.     

Sr and Sr/Sr in the Yamuna River System in the Himalaya: sources, fluxes, and controls on sr isotope composition

Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Yamuna river headwaters and many of its tributaries (YRS) in the Himalaya. These results, with those available for major ions in YRS rivers and in various lithologies of their basin, have been used to determine their contributions to riverine Sr and its isotopic budget. Sr in the YRS ranges from 120 to 13,400 nM, and ⁸⁷Sr/⁸⁶Sr from 0.7142 to 0.7932. Streams in the upper reaches, draining predominantly silicates, have low Sr and high ⁸⁷Sr/⁸⁶Sr whereas those draining the lower reaches exhibit the opposite resulting from differences in drainage lithology. ⁸⁷Sr/⁸⁶Sr shows significant co-variation with SiO₂/TDS and (Na^* + K)/TZ⁺ (indices of silicate weathering) in YRS waters, suggesting the dominant role of silicate weathering in contributing to high radiogenic Sr. This is also consistent with the observation that streams draining largely silicate terrains have the highest ⁸⁷Sr/⁸⁶Sr, analogous to that reported for the Ganga headwaters. Evaluation of the significance of other sources such as calc-silicates and trace calcites in regulating Sr budget of these rivers and their high ⁸⁷Sr/⁸⁶Sr needs detailed work on their Sr and ⁸⁷Sr/⁸⁶Sr. Preliminary calculations, however, indicate that they can be a significant source to some of the rivers.It is estimated that on an average, ∼25% of Sr in the YRS is derived from silicate weathering. In the lower reaches, the streams receive ∼15% of their Sr from carbonate weathering whereas in the upper reaches, calc-silicates can contribute significantly (∼50%) to the Sr budget of rivers. These calculations reveal the need for additional sources for rivers in the lower reaches to balance their Sr budget. Evaporites and phosphorites are potential candidates as judged from their occurrence in the drainage basin. In general, Precambrian carbonates, evaporites, and phosphorites “dilute” the high ⁸⁷Sr/⁸⁶Sr supplied by silicates, thus making Sr isotope distribution in YRS an overall two end member mixing. Major constraints in quantifying contributions of Sr and ⁸⁷Sr/⁸⁶Sr from different sources to YRS rivers are the wide range in Sr and ⁸⁷Sr/⁸⁶Sr of major lithologies, limited data on Sr and ⁸⁷Sr/⁸⁶Sr in minor phases and on the behavior of Sr, Na, and Ca during weathering and transport.The Ganga and the Yamuna together transport ∼0.1% of the global Sr flux at the foothills of the Himalaya which is in the same proportion as their contribution to global water discharge. Dissolved Sr flux from the Yamuna and its mobilization rate in the YRS basin is higher than those in the Ganga basin in the Himalaya, a result consistent with higher physical and chemical erosion rates in the YRS.     

Strontium isotope composition of runoff from a glaciated carbonate terrain

The relationship between subglacial chemical weathering processes and the Sr isotope composition of runoff from Robertson Glacier, Alberta, Canada, is investigated. This glacier rests on predominantly carbonate bedrock of Upper Devonian age, but silicate minerals are also present. The provenance of solute in meltwaters is found to vary systematically with solute concentration and, by inference, subglacial water residence time. In dilute waters, the principal process of solute acquisition is calcite dissolution fueled by protons derived from the dissolution of CO₂ and subsequent dissociation of carbonic acid. At higher solute concentrations, dolomite dissolution coupled to sulfide oxidation is more important. Sr concentration is found to increase with total solute concentration in two separate meltwater streams draining from the glacier, but ⁸⁷Sr/⁸⁶Sr only increases in the eastern melt stream. Carbonate and K-feldspar sources are shown to dominate the Sr content of the western stream, irrespective of concentration. They also dominate the Sr content of the eastern stream at low and intermediate concentrations, but at higher concentrations, muscovite (with high ⁸⁷Sr/⁸⁶Sr) is also an important Sr source. This reflects the outcrop of muscovite-bearing lithologies in the catchment of the eastern stream and an increase in the rate of weathering of K-silicates relative to that of carbonates as more concentrated solutions approach saturation with respect to carbonates. Nonstoichiometric release of ⁸⁷Sr/⁸⁶Sr and preferential release of Sr over K from freshly ground K-silicate surfaces may also occur. This may help to explain the radiogenic nature of runoff from distributed subglacial drainage systems, which are characterized by long water:rock contact times and water flow through environments in which crushing and grinding of bedrock are active processes.Although the exchangeable Sr in tills has higher ⁸⁷Sr/⁸⁶Sr than local carbonate bedrock, only the more concentrated meltwaters from the eastern stream display similarly high values. The most dilute waters, which probably transport the bulk of the dissolved Sr flux from the glacier, have ⁸⁷Sr/⁸⁶Sr characteristic of local carbonate bedrock. Thus, the results suggest that although enhanced weathering of silicate minerals containing radiogenic Sr (such as muscovite) does occur in glaciated carbonate terrains, it is unlikely to contribute to any enhanced flux of radiogenic Sr from glaciated continental surfaces to the oceans.     

Hydrologic controls on radiogenic Sr in meltwater from an alpine glacier system: Athabasca Glacier,Canada

Filtered subglacial meltwater samples were collected daily during the onset of melt (May) and peak melt (July) over the 2011 melt season at the Athabasca Glacier (Alberta, Canada) and analyzed for strontium-87/strontium-86 (⁸⁷Sr/⁸⁶Sr) isotopic composition to infer the evolution of subglacial weathering processes. Both the underlying bedrock composition and subglacial water–rock interaction time are the primary influences on meltwater ⁸⁷Sr/⁸⁶Sr. The Athabasca Glacier is situated atop Middle Cambrian carbonate bedrock that also contains silicate minerals. The length of time that subglacial meltwater interacts with the underlying bedrock and substrate is a predominant determining factor in solute concentration. Over the course of the melt season, increasing trends in Ca/K and Ca/Mg correspond to overall decreasing trends in ⁸⁷Sr/⁸⁶Sr, which indicate a shift in weathering processes from the presence of silicate weathering to primarily carbonate weathering.Early in the melt season, rates of carbonate dissolution slow as meltwater approaches saturation with respect to calcite and dolomite, corresponding to an increase in silicate weathering that includes Sr-rich silicate minerals, and an increase in meltwater ⁸⁷Sr/⁸⁶Sr. However, carbonate minerals are preferentially weathered in unsaturated waters. During the warmest part of a melt season the discharged meltwater is under saturated, causing an increase in carbonate weathering and a decrease in the radiogenic Sr signal. Likewise, larger fraction contributions of meltwater from glacial ice corresponds to lower ⁸⁷Sr/⁸⁶Sr values, as the meltwater has lower water–rock interaction times in the subglacial system. These results indicate that although weathering of Sr-containing silicate minerals occurs in carbonate dominated glaciated terrains, the continual contribution of new meltwater permits the carbonate weathering signal to dominate.     

Dolomite Versus Calcite Weathering in Hydrogeochemically Diverse Watersheds Established on Bedded Carbonates (Sava and So?a Rivers, Slovenia)

The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg²⁺/Ca²⁺ ratios to the local bedrock lithology and the HCO₃ ^? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg²⁺/Ca²⁺ ratio of the main channel of the Sava River indicates that the HCO₃ ^? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg²⁺/Ca²⁺ mole ratio of 0.33). The HCO₃ ^? concentration and pCO₂ values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO₃ ^? from the alpine to the dinaric karst regions. Streams in general do not change in HCO₃ ^?, Mg²⁺/Ca²⁺, or Mg²⁺/HCO₃ ^? concentrations down course, but warming and degassing of CO₂ produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km²-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO₃ ^?, Ca²⁺, and Mg²⁺ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

Interpreting the Ca isotope record of marine biogenic carbonates

An 18 million year record of the Ca isotopic composition (δ^44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ^44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ^44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ^44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ^44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (Δ_sed) results in unrealistically large variations in the total mass of Ca²⁺ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ^44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ^44/42Ca_w and Δ_sed have been established, modeling the Ca²⁺ content of seawater from Ca isotope curves should be approached cautiously.     

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg⁻¹ (mean = 2.52 g kg⁻¹). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and ⁸⁷Sr/⁸⁶Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO₂ in DI water for 75 d at 25°C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and ⁸⁷Sr/⁸⁶Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and ⁸⁷Sr/⁸⁶Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO₂ fugacities, calcite is a stable phase at temperatures of 400 to 700°C.     

Dissolved rhenium in the Yamuna river system and the Ganga in the Himalaya: role of black shale weathering on the budgets of Re, Os, and U in rivers and CO2 in the atmosphere

Extensive measurements of dissolved Re and major ion abundances in the Yamuna River System (YRS), a major tributary of the Ganga, have been performed along its entire stretch in the Himalaya, from its source near the Yamunotri Glacier to its outflow at the foothills of the Himalaya at Saharanpur. In addition, Re analysis has been made in granites and Precambrian carbonates, some of the major lithologies of the drainage basin. These data, coupled with those available for black shales in the Lesser Himalaya, allow an assessment of these lithologies’ contributions to the Re budget of the YRS.The Re concentrations in the YRS range from 0.5 to 35.7 pM with a mean of 9.4 pM, a factor of ∼4 higher than that reported for its global average concentration in rivers. Dissolved Re and ΣCations∗ (= Na∗+K+Ca+Mg) are strongly correlated in the YRS, indicating that they are released to these waters in roughly the same proportion throughout their course. The Re/ΣCations∗ in most of these rivers are one to two orders of magnitude higher than the (Re/Na+K+Mg+Ca) measured in granites of the Yamuna basin. This leads to the conclusion that, on average, granites/crystallines make only minor contributions to the dissolved Re budget of the YRS on a basin-wide scale, though they may be important for rivers with low dissolved Re. Similarly, Precambrian carbonates of the Lesser Himalaya do not seem to be a major contributor to dissolved Re in these rivers, as their Re/(Ca+Mg) is much less than those in the rivers. The observation that Re concentrations in rivers flowing through black shales and in groundwaters percolating through phosphorite-black shale-carbonate layers in phosphorite mines are high, and that Re and SO₄ are significantly correlated in YRS, seems to suggest that the bulk of the dissolved Re is derived from black shale/carbonaceous sediments. Material balance considerations, based on average Re of 30 ng g⁻¹ in black shales from the Lesser Himalaya, require that its abundance in the drainage basin of the YRS needs to be a few percent to yield average Re of 9.4 pM. Furthermore, the positive correlation between Re and ΣCations∗ would require that these Re-rich sediments (e.g., black shales) and Re-poor lithologies (e.g., crystallines, Precambrian carbonates) contribute Re and cations in roughly the same proportion throughout the drainage basin. The available data on the abundance and distribution of black shales in the basin are not adequate to test if these requirements can be met.The annual fluxes of dissolved Re at the base of the Himalaya from the Yamuna are ∼150 mol at Batamandi and ∼100 mol at Saharanpur, compared to ∼120 mol from the Ganga at Rishikesh. The total flux from the Yamuna and the Ganga account for ∼0.4% of the global riverine Re flux, much higher than their contribution to global water discharge. This is also borne out from the mobilization rate of Re: ∼1 to 3 g km⁻² y⁻¹ in the Ganga and Yamuna basins in the Himalaya, compared to the global average of ∼0.1 g km⁻² y⁻¹.Black shale weathering can also significantly influence the budgets of Os and U in rivers and CO₂ in rivers and the atmosphere. Using dissolved Re in rivers as a proxy, it is estimated that ∼(6-9) × 10⁸ kg y⁻¹ of black shales are being weathered in the Ganga and Yamuna basins in the Himalaya. Weathering of such amounts of black shales can account for the reported concentrations of Os and U in these rivers. Furthermore, if the weathering results in the conversion of organic carbon in the black shales to CO₂, it would release ∼2 × 10⁵ mol of CO₂ km⁻² y⁻¹ in the Yamuna and Ganga basins in the Himalaya, comparable to the CO₂ consumption from silicate weathering.     

Processes controlling Sr in surface and ground waters of Tertiary tholeiitic flood basalts in Northern Iceland

Strontium concentrations of 253 natural water samples from Skagafjördur, a Tertiary tholeiitic flood basalt region in northern Iceland range between 0.10 and 28 ppb. Surface environments (rivers, lakes, and peat soil waters) include the whole range of observed Sr concentrations whereas the Sr concentrations of ground waters are, in most cases, <3.5 ppb. Concentrations of Sr derived from basalt dissolution (i.e., rock-derived Sr) in waters of rivers and lakes exhibit a near linear correlation with the concentration of rock-derived Ca with a median molar Ca/Sr ratio of 1350. This systematic correlation suggests that Ca and Sr concentrations are controlled by weathering processes, i.e., the extent of dissolution of the basalt. The relative mobility of Sr during weathering in Skagafjördur is approximately half that of Ca, which is consistent with observed relative mobilities of these elements elsewhere in Iceland and in other basaltic regions. Peat soil waters commonly have lower concentrations of Sr and higher Ca concentrations than rivers and lakes, and molar ratios of rock-derived Ca to Sr in peat soil waters exhibit no systematic pattern. In several cases calculated concentrations of rock-derived Sr in peat soil waters yield negative values, suggesting a mineralogic sink for Sr in these waters.The low Sr concentrations in cold and thermal ground waters (<3.5 ppb) suggest mineralogic control over Sr in the ground water systems. Precipitation of secondary Sr minerals such as strontianite and celestite is ruled out as the ground waters are understaturated with respect to these minerals. Ground waters are characterized by high Ca/Sr molar ratios (∼5000 compared to bedrock Ca/Sr ratio of 730) suggesting that Sr is being preferentially incorporated (relative to Ca) into secondary minerals. The secondary minerals present in the bedrock in Skagafjördur that can preferentially incorporate Sr include zeolites, such as heulandite, chabazite, and thomsonite, and smectite. Ion-exchange calculations demonstrate that activities of Sr²⁺ and Ca²⁺ in ground water solutions in Skagafjördur are consistent with ion-exchange equilibria between these waters and heulandite from other Tertiary basalts in Iceland suggesting that this mineral may play an important role in controlling the concentration of Sr in the Skagafjördur ground waters. Incorporation of Sr into calcite cannot explain the observed high Ca/Sr ratios of the Skagafjördur ground waters because calcite, when precipitating, only admits limited amounts of Sr. Aragonite is not considered a likely candidate either because it has only very slight preference for Sr over Ca and ground waters above 40 °C are undersaturated with respect to this phase. However, predicted Sr content of calcite in equilibrium with the Skagafjördur ground waters (0.5-83 ppm Sr) is in good agreement with measured Sr content of this mineral in Tertiary basalts elsewhere in Iceland (<0.1-63 ppm), suggesting that the Skagafjördur ground waters can be used as analogues for Tertiary crustal solutions involved in the zeolite facies metamorphism of the Icelandic crust.     

Major ion chemistry of the Yarlung Tsangpo-Brahmaputra river: Chemical weathering, erosion, and CO2 consumption in the southern Tibetan plateau and eastern syntaxis of the Himalaya

The Yarlung Tsangpo-Brahmaputra river drains a large portion of the Himalaya and southern Tibetan plateau, including the eastern Himalayan syntaxis, one of the most tectonically active regions on the globe. We measured the solute chemistry of 161 streams and major tributaries of the Tsangpo-Brahmaputra to examine the effect of tectonic, climatic, and geologic factors on chemical weathering rates. Specifically, we quantify chemical weathering fluxes and CO₂ consumption by silicate weathering in southern Tibet and the eastern syntaxis of the Himalaya, examine the major chemical weathering reactions in the tributaries of the Tsangpo-Brahmaputra, and determine the total weathering flux from carbonate and silicate weathering processes in this region. We show that high precipitation, rapid tectonic uplift, steep channel slopes, and high stream power generate high rates of chemical weathering in the eastern syntaxis. The total dissolved solids (TDS) flux from the this area is greater than 520 tons km⁻² yr⁻¹ and the silicate cation flux more than 34 tons km⁻² yr⁻¹. In total, chemical weathering in this area consumes 15.2 × 10⁵ mol CO₂ km⁻² yr⁻¹, which is twice the Brahmaputra average. These data show that 15-20% of the total CO₂ consumption by silicate weathering in the Brahmaputra catchment is derived from only 4% of the total land area of the basin. Hot springs and evaporite weathering provide significant contributions to dissolved Na⁺ and Cl⁻ fluxes throughout southern Tibet, comprising more than 50% of all Na⁺ in some stream systems. Carbonate weathering generates 80-90% of all dissolved Ca²⁺ and Mg²⁺ cations in much of the Yarlung Tsangpo catchment.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment,southwestern India

River water composition (major ion and ⁸⁷Sr/⁸⁶Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L⁻¹) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L⁻¹), with radiogenic ⁸⁷Sr/⁸⁶Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and ⁸⁷Sr/⁸⁶Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO₂/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO₂/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin.     

The CO2 system in rivers of the Australian Victorian Alps: CO2 evasion in relation to system metabolism and rock weathering on multi-annual time scales

The patterns of dissolved inorganic C (DIC) and aqueous CO₂ in rivers and estuaries sampled during summer and winter in the Australian Victorian Alps were examined. Together with historical (1978–1990) geochemical data, this study provides, for the first time, a multi-annual coverage of the linkage between CO₂ release via wetland evasion and CO₂ consumption via combined carbonate and aluminosilicate weathering. δ¹³C values imply that carbonate weathering contributes ∼36% of the DIC in the rivers although carbonates comprise less than 5% of the study area. Baseflow/interflow flushing of respired C3 plant detritus accounts for ∼50% and atmospheric precipitation accounts for ∼14% of the DIC. The influence of in river respiration and photosynthesis on the DIC concentrations is negligible. River waters are supersaturated with CO₂ and evade ∼27.7 × 10⁶ mol/km²/a to ∼70.9 × 10⁶ mol/km²/a CO₂ to the atmosphere with the highest values in the low runoff rivers. This is slightly higher than the global average reflecting higher gas transfer velocities due to high wind speeds. Evaded CO₂ is not balanced by CO₂ consumption via combined carbonate and aluminosilicate weathering which implies that chemical weathering does not significantly neutralize respiration derived H₂CO₃. The results of this study have implications for global assessments of chemical weathering yields in river systems draining passive margin terrains as high respiration derived DIC concentrations are not directly connected to high carbonate and aluminosilicate weathering rates.