Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

Influence of landscape position and vegetation on long-term weathering rates at the Hubbard Brook Experimental Forest, New Hampshire, USA

The spatial variability of long-term chemical weathering in a small watershed was examined to determine the effect of landscape position and vegetation. We sampled soils from forty-five soil pits within an 11.8-hectare watershed at the Hubbard Brook Experimental Forest, New Hampshire. The soil parent material is a relatively homogeneous glacial till deposited ∼14,000 years ago and is derived predominantly from granodiorite and pelitic schist. Conifers are abundant in the upper third of the watershed while the remaining portion is dominated by hardwoods. The average long-term chemical weathering rate in the watershed, calculated by the loss of base cations integrated over the soil profile, is 35 meq m⁻² yr⁻¹—similar to rates in other ∼10 to 15 ka old soils developed on granitic till in temperate climates. The present-day loss of base cations from the watershed, calculated by watershed mass balance, exceeds the long-term weathering rate, suggesting that the pool of exchangeable base cations in the soil is being diminished. Despite the homogeneity of the soil parent material in the watershed, long-term weathering rates decrease by a factor of two over a 260 m decrease in elevation. Estimated weathering rates of plagioclase, potassium feldspar and apatite are greater in the upper part of the watershed where conifers are abundant and glacial till is thin. The intra-watershed variability across this small area demonstrates the need for extensive sampling to obtain accurate watershed-wide estimates of long-term weathering rates.     

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg⁻¹, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO₂, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57–98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering.The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.     

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.     

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.     

Characterization of elemental release during microbe-granite interactions at T = 28 °C

This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species (Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH₄ or NO₃ as N sources, and either dissolved PO₄ or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ∼7 to 4 in NH₄-bearing reactors, whereas pH remained near-neutral in NO₃-bearing reactors. Measurements of dissolved CO₂ and gluconate together with mass-balances for cell growth suggest that pH lowering in NH₄-bearing reactors resulted from gluconic acid release and H⁺ extrusion during NH₄ uptake. In NO₃-bearing reactors, B. fungormum likely produced gluconic acid and consumed H⁺ simultaneously during NO₃ utilization.Over the entire 35-day period, NH₄-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al-F and Fe-F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH₄ only moderately elevate silicate weathering reactions that consume atmospheric CO₂. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.     

Geochemical mass balances of major chemical constituents in the watershed of the Changhuajian River in China

Based on the geological background, R-mode factor statistics, and the analysis of the stability diagram for the corresponding system, five weathering reactions controlling the surface-water chemical composition in the watershed of the Changhuajiang River are deduced. In the mass balance model, the precipitation accounts for some solute input, since the rainwater is dilute without pollution. Most of the Ca²⁺ and HCO ₃ ^– ions are from the dissolution of calcite, K⁺, Na⁺, H₄SiO₄ and some of the Mg²⁺ and HCO ₃ ^– come from albite and biotite weathering to kaolinite. The dissolution of dolomite and gypsum controls the mass balances of Mg²⁺ and SO ₄ ^2– . The dissolution of calcite is the dominant chemical weathering reaction in the watershed because of its reactivity and high concentration. In the watershed in 1986, the chemical weathering rate was 0.073 (kg/m² a), and the mechanical denudation rate is 0.093 (kg/m² a). The chemical weathering mass output proportion of carbonate rocks to silicate rocks was about three to one.     

Strontium isotopic and chemical variations of the granitic rocks in the Tsukuba district,Japan

Initial ⁸⁷Sr/⁸⁶Sr ratios, major and trace element compositions have been determined for the Paleogene granitic rocks in the Tsukuba district, Japan. Isotopic ages strongly suggest that the granitic rocks (seven units) were continuously emplaced and solidified during a short time interval. Initial ⁸⁷Sr/⁸⁶Sr ratios for seven granitic units vary from 0.7082 to 0.7132, while sedimentary and metasedimentary country rocks have ratios at the time of granitic magma emplacement ranging from 0.7149 to 0.7298. Continuous linear arrays for the granitic rocks in the diagrams of initial ⁸⁷Sr/⁸⁶Sr ratios versus some chemical parameters can be explained by either of following two processes. One is the assimilation — fractional crystallization (AFC) process between the parental magma (SiO₂ of 68% and initial ratio of 0.7078) and sedimentary country rocks, and the other is magma mixing process between above parental magma and sediment derived acidic magma (melt) (SiO₂ of 75%). The high initial ratios (0.7078–0.7098) for basic rocks such as gabbro or diorite in the Tsukuba district and the similar characteristics observed in the rocks of Ryoke belt (SW Japan) suggest that the parental magma had the same source region as the basic rocks, probably the lower crustal source.     

Linking lithology and land use to sources of dissolved and particulate organic matter in headwaters of a temperate, passive-margin river system

A number of rivers have been found to transport highly aged organic matter [OM]; however, the sources of this aged material remain a matter of debate. One potential source may be erosion and weathering of headwater lithologies rich in ancient sedimentary OM. In this study, waters, suspended particulates, streambed sediments, rocks and soils from fourteen small headwater watersheds of a mid-size, temperate, passive margin river were sampled and characterized by Δ¹⁴C, δ¹³C, and POC/TPN ratios to identify sources of particulate and dissolved OM delivered to the river mainstem. These headwater sites encompass a range in lithology (OM-rich shales, OM-lean carbonate/mudstone facies, and OM-free crystalline rocks) and land use types (forested and agricultural), and allow investigation of the influence of agriculture and bedrock types on stream OM characteristics. Streams draining large areas of both agricultural land use and OM-rich lithology contain particulate OM [POM] that is more ¹⁴C-depleted than streams draining forested, shale-free watersheds. However, this is not sufficient to account for the significantly lower Δ¹⁴C-POC measured in the river mainstem. Dissolved OM [DOM] Δ¹⁴C are in all cases enriched compared to POM from the same stream, but are otherwise highly variable and unrelated to either land use or lithology. POC/TPN ratios were likewise highly variable. POC and DOC δ¹³C signatures were similar across all watersheds. Based on isotope mass balance, ¹⁴C-free fossil OM sources contribute 0-12% of total stream POM. Although these results do not unequivocally separate the influences of land use and lithology, watershed coverage by shale and agriculture are both important controls on stream Δ¹⁴C-POC. Thus export of aged, particle-associated OM may be a feature of river systems along both passive and active continental margins.     

Elevated stream trace and minor element concentrations in the foreland of receding tropical glaciers

Globally, the ongoing retreat of mountain glaciers will ultimately diminish fresh water supplies. This has already begun in watersheds with greatly reduced glacial coverage. Still unknown are the affects of glacial retreat on downstream water quality, including the threats to human and ecosystem health. In the Cordillera Blanca, retreating glaciers have exposed sulfide-rich rock outcrops, negatively affecting the quality of the glacial meltwater. This study has evaluated glacial melt stream hydrogeochemistry in the sulfide-bearing Rio Quilcay watershed (∼9°27′S, ∼77°22′W) during the 2008 dry season. Surface water samples were collected from the upper 12 km of the watershed during the 2008 dry season. Dissolved (0.4 μm) and unfiltered acidified (pH < 2) Al, Co, Cu, Fe, Ni, Mn, Pb, Zn and dissolved major ions and organic C (DOC) concentrations were quantified and pH and temperature were measured in the field. Twenty of 22 stream samples had pH values below 4, generating significantly (p < 0.01, α = 0.05) greater cation denudation normalized to discharge than other worldwide glacier-fed streams. Additionally, dissolved trace and minor element concentrations were comparable to acid mine drainage. Non-conservative dissolved element behaviors resulted from adsorption/desorption reactions in tributary mixing zones. At low pH values, hydrous Fe oxides acted as the dominant sorption surfaces. The poor water quality observed in Cordillera Blanca headwaters coupled with the likely exposure of additional sulfide-rich outcrops from ongoing glacial retreat may pose water quality challenges.     

The fluvial geochemistry, contributions of silicate, carbonate and saline-alkaline components to chemical weathering flux and controlling parameters: Narmada River (Deccan Traps), India

The Narmada River in India is the largest west-flowing river into the Arabian Sea, draining through the Deccan Traps, one of the largest flood basalt provinces in the world. The fluvial geochemical characteristics and chemical weathering rates (CWR) for the mainstream and its major tributaries were determined using a composite dataset, which includes four phases of seasonal field (spot) samples (during 2003 and 2004) and a decade-long (1990-2000) fortnight time series (multiannual) data. Here, we demonstrate the influence of minor lithologies (carbonates and saline-alkaline soils) on basaltic signature, as reflected in sudden increases of Ca²⁺-Mg²⁺ and Na⁺ contents at many locations along the mainstream and in tributaries. Both spot and multiannual data corrected for non-geological contributions were used to calculate the CWR. The CWR for spot samples (CWR_spot) vary between 25 and 63 ton km⁻² year⁻¹, showing a reasonable correspondence with the CWR estimated for multiannual data (CWR_multi) at most study locations. The weathering rates of silicate (SilWR), carbonate (CarbWR) and evaporite (Sal-AlkWR) have contributed ∼38-58, 28-45 and 8-23%, respectively to the CWR_spot at different locations. The estimated SilWR (11-36 ton km⁻² year⁻¹) for the Narmada basin indicates that the previous studies on the North Deccan Rivers (Narmada-Tapti-Godavari) overestimated the silicate weathering rates and associated CO₂ consumption rates. The average annual CO₂ drawdown via silicate weathering calculated for the Narmada basin is ∼0.032 × 10¹² moles year⁻¹, suggesting that chemical weathering of the entire Deccan Trap basalts consumes approximately 2% (∼0.24 × 10¹² moles) of the annual global CO₂ drawdown. The present study also evaluates the influence of meteorological parameters (runoff and temperature) and physical weathering rates (PWR) in controlling the CWR at annual scale across the basin. The CWR and the SilWR show significant correlation with runoff and PWR. On the basis of observed wide temporal variations in the CWR and their close association with runoff, temperature and physical erosion, we propose that the CWR in the Narmada basin strongly depend on meteorological variability. At most locations, the total denudation rates (TDR) are dominated by physical erosion, whereas chemical weathering constitutes only a small part (<10%). Thus, the CWR to PWR ratio for the Narmada basin can be compared with high relief small river watersheds of Taiwan and New Zealand (1-5%) and large Himalayan Rivers such as the Brahmaputra and the Ganges (8-9%).     

Rates of Biotite Weathering,and Clay Mineral Transformation and Neoformation,Determined from Watershed Geochemical Mass-Balance Methods for the Coweeta Hydrologic Laboratory,Southern Blue Ridge Mountains,North Carolina,USA

Biotite is a common constituent of silicate bedrock. Its weathering releases plant nutrients and consumes atmospheric CO₂. Because of its stoichiometric relationship with its transformational weathering product and sensitivity to botanical activity, calculating biotite weathering rates using watershed mass-balance methods has proven challenging. At Coweeta Hydrologic Laboratory the coupling of biotite to its transformational weathering product is only valid if the stoichiometric relationship for the two phases is known; this relationship is unlikely layer-for-layer. Rates of biotite weathering and transformation of its secondary weathering product at the Coweeta Hydrological Laboratory are comparable with other Appalachian watersheds. The magnitude and sign of the difference between field- and laboratory-determined biotite weathering rates are similar to those of other silicate minerals. The influence of major-cation proportions in biomass on the rates of biotite weathering and transformational weathering product is greatest for watersheds with high biomass aggradation rates. The watershed with the lowest bedrock reactivity and highest flushing rate yielded the highest gibbsite formation rate of ~500 mol ha^?1 year^?1 and lowest kaolin-group mineral formation rates of 4–78 mol ha^?1 year^?1. The kaolin-group mineral formation rate increases as bedrock reactivity increases and flushing rate decreases to a maximum of ~300 mol ha^?1 year^?1, with a similar minimum gibbsite formation rate. The relative differences in bedrock reactivity and flux of water through Coweeta Hydrological Laboratory watersheds studied appear to be invariant over geologic timescales.     

Geochemical fluxes and weathering of volcanic terrains on high standing islands: Taranaki and Manawatu-Wanganui regions of New Zealand

Sediment fluxes from high standing oceanic islands (HSIs) such as New Zealand are some of the highest known [Milliman J. D. and Syvitski J. P. M. (1992) Geomorphic/tectonic control of sediment discharge to the ocean: the importance of small mountainous rivers. J. Geol.100, 525-544]. Recent geochemical work has suggested that along with their extremely high physical weathering yields, many New Zealand watersheds also have very high chemical weathering yields. In New Zealand, the magnitude of both the physical and chemical weathering yields is related to the lithology of the watershed. Most of the previous work on this topic has been undertaken in Southern Alps watersheds of schist and greywacke and in East Cape watersheds of semi-consolidated marine sediments and greywacke. We recently sampled North Island watersheds in the Taranaki and Manawatu-Wanganui regions which have been subjected to volcanism since the Miocene. We sampled watersheds that contain both volcanic and sedimentary rocks. A series of water and sediment samples was collected and analyzed for major, minor and trace elements. This was done to quantify the weathering intensities in the watersheds and to establish the relationship between physical and chemical weathering yields in volcanic lithologies. Our results reveal distinct chemical signatures for the different regions. Waters draining the Taranaki region volcanics are significantly enriched in K⁺, and depleted in Ca²⁺ and Sr²⁺ compared to waters draining the Manawatu-Wanganui region volcanics, which also traverse expanses of sedimentary siltstones and mudstones. The Ca²⁺ and Sr²⁺ depletions may reflect the relative absence of CaCO₃ in the Taranaki region watersheds. In addition, sediment samples from the Taranaki region show significant enrichment in Ti, Al, Ca, Fe, Mn, Mg, Ca, and P and depletion in Si and Rb compared to those of the Manawatu-Wanganui region. From total dissolved solids concentrations and mean annual water discharge, we calculate chemical weathering yields of 60-240 tons km⁻² a⁻¹. These weathering yields fall within the middle to upper range of those previously documented for the Southern Alps (93-480 tons km⁻² a⁻¹) and East Cape (62-400 tons km⁻² a⁻¹). Calculated silicate weathering yields of 12-33.6 tons km⁻² a⁻¹ and CO₂ consumption of 852-2390 × 10³ mol km⁻² a⁻¹ for the rivers draining the Taranaki volcanic region are higher than those previously reported for watersheds hosted in sedimentary and metamorphosed rock terrains on HSIs. CO₂ consumption is found to be within the range previously measured for the basaltic terrains of the Deccan Traps (580-2450 × 10³ mol km⁻² a⁻¹) and Réunion Island(1300-4400 × 10³ mol km⁻² a⁻¹). Our calculated chemical weathering yields demonstrate the importance of HSIs, particularly those with volcanic terrains, when considering global geochemical fluxes.     

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.     

Geochemistry of mineralization with exchangeable REY in the weathering crusts of granitic rocks in South China

Mineralization with exchangeable rare earth element (REE) and yttrium (MEX-REY) has been recognized in the weathering profiles in South China since the early 1970's. This type of REY mineralization occurs in weathering profiles of parent rocks ranging in composition from granite to acidic volcanic rocks and lamprophyre. The majority of the known resources occurring in the weathering profiles of granitic rocks. Total resources of this type of REY amount to millions tons of rare earth oxides, and therefore represent one of the most important types of rare earth resources in China, particularly for heavy rare earth elements (HREE) and yttrium.Accumulation of REY in the weathering profiles of granitic rocks is strongly controlled by the resistance to weathering of the principal REY-bearing accessory minerals in the parent rocks; only a limited proportion of total REY (< 30%) is incorporated in the rock-forming minerals. MEX-REY more commonly occur in weathering profiles developed on granitic rocks within which most of the REY are incorporated in accessory minerals weakly resistant to weathering (doverite, parisite, etc.). For the well-developed weathering profiles, three horizons can be distinguished from surface downwards: the lateritic horizon (A), the weathered horizon (B), and the weathering front (C). Continuous leaching, coupled with low rate of denudation, results in the accumulation of REY in the subsurface horizons (the B and C horizons), and thus results in REE differentiation within the well-developed, layered, and mature weathering profiles. Exchangeable REY, which can be replaced by cations like NH⁴⁺ and Na⁺ etc. in electrolyte solutions and can be removed by complexing agents such as EDTA, are commonly the major form of REE occurrence in the B horizon. Cerium is enriched in the top layer (A horizon) and depleted in the subsurface horizons of the weathering profiles, most likely due to the oxidation of Ce(III) to Ce(IV) followed by cerianite formation or absorption onto clays and/or Fe and Al oxyhydroxides.     

Experimental silicate mineral/melt partition coefficients for beryllium and the crustal Be cycle from migmatite to pegmatite

Partition coefficients (D_Be^mineral/melt) for beryllium between hydrous granitic melt and alkali feldspars, plagioclase feldspars, quartz, dark mica, and white mica were determined by experiment at 200 MPa H₂O as a function of temperature (650-900°C), activity of Be in melt (trace levels to beryl saturation), bulk composition, and thermal run direction. At trace levels, Be is compatible in plagioclase of An₃₁ (1.84 at 700°C) and muscovite (1.35 at 700°C) but incompatible in biotite (0.39-0.54 from 650-800°C), alkali feldspar (0.38-0.19 from 680-850°C), quartz (0.24 at 800°C), and albite (0.10 at 750°C). The partition coefficients are different at saturation of the melt in beryl: lower in the case of plagioclase of An₃₁ (0.89 at 700°C), muscovite (0.87 at 700°C), biotite (0.18-0.08 from 675-800°C), alkali feldspar (0.18-0.14 from 680-700°C), and quartz (0.17-0.08 from 750-800°C), but higher in the case of albite (0.37 at 750°C).With other data sources, these new partition coefficients were utilized to track, first, the distribution of Be between aluminous quartzofeldspathic source rocks and their anatectic melts, and second, the dispersion or concentration of Be in melt through igneous crystal fractionation of different magma types (e.g., S-type, I-type) up to beryl-saturated granitic pegmatites and, finally, into their hydrothermal aureoles. Among the rock-forming minerals, cordierite, calcic oligoclase, and muscovite (in this order) control the fate of Be because of the compatibility of Be in these phases. In general, beryl-bearing pegmatites can arise only after extended crystal fractionation of large magma batches (to F, fraction of melt remaining, ≤0.05); granitic magmas that originate from cordierite-bearing protoliths or that contain large modal quantities of calcic oligoclase will not achieve beryl saturation at any point in their evolution.     

Formation of the Neoarchean Bad Vermilion Lake Anorthosite Complex and spatially associated granitic rocks at a convergent plate margin,Superior Province,Western Ontario,Canada

The Bad Vermilion Lake Anorthosite Complex (henceforth, the BVLA Complex) in western Ontario is one of the well-exposed, anorthosite-bearing, Archean layered intrusions in the Superior Province, Canada. This study presents new whole-rock major and trace element data for the various units of the Complex, oxygen isotope data for the anorthosite, and major and trace element data for the spatially associated granitic rocks intruding the BVLA Complex to constrain their petrogenetic and geodynamic origin. Zircons from granitic rocks have yielded a ²⁰⁷Pb/²⁰⁶Pb age of 2716 ± 18 Ma, constraining the minimum intrusion age of the Complex.Despite deformation and greenschist facies metamorphism, primary igneous textures are locally well preserved in the BVLA Complex. Its whole-rock major and trace elemental compositions and the oxygen isotopic systematics appear not to have been substantially modified by deformation and metamorphism. Mantle-like oxygen isotope signatures and major and trace element compositions are inconsistent with significant crustal contamination of the BVLA Complex during its emplacement. The existence of primary calcic igneous plagioclase, coherent negative Nb anomalies (Nb/Nb* = 0.08–0.88), and geochemical similarities between gabbros from the BVLA Complex and gabbros from Cenozoic arcs collectively suggest an intra-oceanic subduction zone geodynamic setting for the Complex. Near-flat REE patterns in the various units of the BVLA Complex suggest that they were derived from melting of a shallow source beneath a subarc mantle wedge. Trends in immobile major (e.g., MgO) and trace (e.g., Zr) element data indicate that the mineralogical composition of the Complex can be explained by fractional crystallization and accumulation of olivine, orthopyroxene, clinopyroxene, plagioclase and possibly amphibole.Compositionally, the bordering granitic rocks are A₂-type and strongly enriched in Th and REE (> 100 times chondrite) and depleted of Ba, Sr, Eu and Ti. We suggest that they formed in a post-collisional, extensional, tectonic regime following emplacement of the BVLA Complex in an oceanic arc.     

Impact of trace mineral phases on the total solute flux from andesitic volcanics

Recent work on the weathering of high standing islands (HSI’s) of New Zealand (Goldsmith et al., 2008), Dominica (Goldsmith et al., 2010) Martinique and Guadeloupe (Rad et al., 2006) and portions of the Philippines (Schopka et al., 2011) shows weathering rates based on stream water chemistry for areas draining andesitic terrains are comparable to weathering rates determined for basaltic terrains, indicating that andesite weathering might be much more important in drawing down atmospheric CO₂ than previously recognized. While an easily erodible parent material has been largely attributed to sustaining rates at these locations, little is known to known regarding its associated reaction kinetics. We conducted a series of batch dissolution experiments on andesitic material collected from ∼10,000 year old tephra deposits from Dominica to determine the dissolution rate of major and trace mineral phases to better understand geochemical processes controlling weathering flux from these areas. Dissolution experiments were conducted over a range of pH (4 and 7) on bulk samples and mineral separates.The dissolution rates based on Si release from the Dominica tephra bulk samples were similar, and ranged from 0.04 to 0.13 μmole Si/g-day in water, and ∼0.14 to 0.27 μmole Si/g-day in dilute acid (initial pH ∼4). Although the bulk of the ash is predominately composed of vesicular felsic (Na–Al–Si) volcanic glass, reaction rates and stoichiometry indicate ash dissolution is dominated by the reactivity of trace Mg or Ca-bearing silicate phases (olivine, pyroxene or amphiboles) and Ca–phosphate phases (apatite), especially under slightly acidic conditions. Analysis of reacted phases by SEM shows little evidence of alteration of glassy material, whereas surfaces of Ca–Mg inosilicates, olivine and apatite show etched features indicative of dissolution. Results of the dissolution experiments suggest that, although these phases are relatively minor components of the ash, they contribute disproportionately to the overall weathering flux, and their reactivity may be particularly important in areas where physical weathering and erosion are constantly exposing new fresh surfaces available for chemical reaction.     

Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed,Jamieson Creek,British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO₂, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.