The release of Pb and REE from granitoids by the dissolution of accessory phases

The release of Pb and rare earth elements (REE) during granitoid weathering was investigated through dissolution experiments of fresh granite and soil samples. Two aliquots of a granite sample from the El-Capitan Granite, Sierra Nevada, California, were leached several times using a dilute acid at pH = 1. The results of the experiment were compared with Pb and REE data from soils developed on the same rock. During the early stages of granitoid dissolution, Pb and REE were preferentially released from some of the accessory phases (i.e., allanite, sphene, and apatite). This caused higher ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb values and different REE patterns in solution compared with the rock values. Based on Pb isotopes and REE patterns, three stages of rock dissolution can be identified. In the first stage the dissolution of allanite dominates the release of Pb and REE from accessory phases, as ²⁰⁸Pb/²⁰⁷Pb, Ce/Pb, and chondrite-normalized Ce/Yb ratios in solution increase and approach the values of allanite. In the second stage, the dissolution of apatite and sphene become more significant. In the third stage, the isotopic ratios of Pb and the normalized-REE patterns reflect the depletion of accessory phases and the increase in the rate of feldspar dissolution. According to our estimate (based on Si release from the rock) all three stages account for the first 500 kyr of granitoid weathering.Using the isotopic ratios of Pb, major elemental compositions, and REE concentrations both in the experimental solutions and in the soil we were able to establish the following order of the weathering rates of accessory phases: allanite > apatite > sphene. In addition, we have demonstrated that biotite is significantly less resistant to weathering than hornblende under acidic conditions, and is probably dissolved completely after approximately 500 kyr of rock weathering. We also suggest that within 500 kyr of granitoid weathering K-feldspar accounts for 15% of the released K.     

Ein Beitrag zur Geochemie und Entstehung der Oberpfälzischen Kaolin-Feldspat-Lagerstätten

The plagioclase of the kaolinised granite of Tirschenreuth is decomposed quantitatively and the biotite almost quantitatively, on the contrary potassium feldspar and mucovite of the parent rock remained unaffected by kaolinisation. The quantity of produced kaolinite is equivalent to the quantity of decomposed plagioclase and biotite. The rare elements Pb, Cu, Cr, Ni, P, and Ti from the kaolinised minerals are adsorbed quantitatively by the kaolin. All other elements are diminished, no element has been added to the kaolin from other sources than from parent rock material. The selective decomposition of plagioclase and biotite in the kaolin-feldspar deposit of Tirschenreuth and the association of rare elements in the kaolin are explainable by weathering processes only. Kaolins from Hirschau-Sehnaittenbach are characterised by extremely high concentrations of the rare elements Ba, Sr, Pb, Cu, and P. The association of rare elements of the kaolin has been originated from the decomposed potassium feldspar of the kaolinised arcoses. The rare elements Pb, Cu, Cr, and P are adsorbed quantitatively by the kaolin. The other elements are diminished, Ba and Sr inclusive and in spite of their high absolute concentrations. The composition of the arcoses of Hirschau-Schnaittenbach prior to kaolinisation is calculated to 56% of quartz and 44% of potassium feldspar by means of the quantities of the elements Pb and Cu analysed in the feldspar and in the kaolin. The kaolin of Hirschau-Schnaittenbach has originated by weathering of the potassium feldspar of the Triassic arcoses. The kaolinisation is of Triassic age because kaolins of the Hirschau-Schnaittenbach type were redeposited near Ehenfeld in the Cenomanian. Kaolin deposits of hydrothermal origin are characterised by a zonal structure and are associated by ores. They are different in geological behaviour and mineral association from kaolin deposits which originated by weathering of feldspathic rocks like the deposits of Tirschenreuth and Hirschau-Schnaittenbach (Upper Palatinate, Bavaria).     

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.     

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.     

Ge/Si and Sr/Sr tracers of weathering reactions and hydrologic pathways in a tropical granitoid system

Ge/Si and ⁸⁷Sr/⁸⁶Sr data from primary and secondary minerals, soil waters, and stream waters in a tropical granitoid catchment quantitatively reflect mineral alteration reactions that occur at different levels within the bedrock–saprolite–soil zone. Near the bedrock–saprolite interface, plagioclase to kaolinite reaction yields low Ge/Si and 87Sr/86Sr. Higher in the regolith column, biotite weathering and kaolinite dissolution drive Ge/Si and 87Sr/86Sr to high values. Data from streams at base flow sample the bedrock–saprolite interface zone, while at high discharge solutes are derived from upper saprolite–soil zone. Coupled Ge/Si and 87Sr/86Sr can be effective tools for quantifying the importance of specific weathering reactions, and for geochemical hydrograph separation.     

The impact of dolomite and plagioclase weathering on the chemistry of shallow groundwaters circulating in a granodiorite-dominated catchment of the Sila Massif (Calabria,Southern Italy)

This work is aimed at investigating the weathering processes of the granodiorites cropping out in a small catchment of the Sila Massif. The mineral constituents in this granodiorite are plagioclase, often zoned with a Ca-rich core and a Na-rich rim, quartz, chlorite, K-feldspar, white mica and epidote. During this study, dolomite was discovered in local stream sediments, as separate monomineralic grains, probably resulting from erosion of veins cutting the crystalline rocks. Prevailing dissolution of foreign dolomite and a Ca-rich plagioclase is suggested by the Ca–Mg–HCO₃ chemical composition of local groundwaters and stream waters, which is rather unexpected for waters interacting with granitoid rocks. These qualitative observations are quantitatively confirmed by reaction path modelling of the weathering processes occurring in the study area, which was carried out using the EQ3/6 software package, version 8.0, and the Double Solid Reactant Method. Indeed, it was possible to ascertain that the release of both major dissolved constituents and several trace elements (Ba, Co, Cr, Fe, Mn, Ni, Pb, Sr, V and Zn), from rocks to waters, is chiefly controlled by the dissolution of foreign dolomite and the Ca-rich core of zoned plagioclases.     

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.     

Evidence for mass-dependent isotopic fractionation of strontium in a glaciated granitic watershed

The stable isotope composition of strontium (expressed as δ^88/86Sr) may provide important constraints on the global exogenic strontium cycle. Here, we present δ^88/86Sr values and ⁸⁷Sr/⁸⁶Sr ratios for granitoid rocks, a 150 yr soil chronosequence formed from these rocks, surface waters and plants in a small glaciated watershed in the central Swiss Alps. Incipient chemical weathering in this young system, whether of inorganic or biological origin, has no resolvable effect on the ⁸⁷Sr/⁸⁶Sr ratios and δ^88/86Sr values of bulk soils, which remain indistinguishable from bedrock in terms of Sr isotopic composition. Although due in part to the chemical heterogeneity of the forefield, the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of Sr; a low degree of chemical weathering is also implied by bulk soil chemistry. The isotopic composition of Sr in streamwater is more radiogenic than median soil, reflecting the preferential weathering of biotite in the catchment; streamwater δ^88/86Sr values, however, are indistinguishable from bulk soil δ^88/86Sr values, implying that no resolvable fractionation of Sr isotopes takes place during release to the weathering flux in the Damma forefield. Analyses of plant tissue reveal that plants (Rhododendron and Vaccinium) preferentially assimilate the lighter isotopes of Sr such that their δ^88/86Sr values are significantly lower than those of the soils in which they grow. Additionally, δ^88/86Sr values of foliar and floral tissues are lower than those of roots, contrary to observations for Ca, for which Sr is often used as an analogue in weathering studies. We suggest that processes that discriminate against Sr in favour of Ca, due to the different nutritional requirement of plants for these two elements, are responsible for the observed contrast.     

小兴安岭霍吉河钼矿区含矿花岗岩类特征及成矿年龄

黑龙江霍吉河钼矿区内含矿花岗岩类岩石组合为黑云母二长花岗岩、二长花岗岩和花岗细晶岩,属高钾钙碱性岩-钾玄岩系列准铝质-过铝质岩石,具有轻稀土富集、重稀土亏损分馏模式;富集不相容元素(Cs、Th)并表现为Ta和Nb负异常以及Pb、Sr正异常,显示俯冲带地球化学特征.含矿岩浆岩明显富集Mo、Cu、Pb、Zn、W、Cr等金属元素.岩石全岩铅同位素来源比较复杂,具有混合成因铅特征.辉钼矿Re-Os模式年龄为180.7±2.5Ma和181.3±2.6Ma,钼矿成矿时代为早侏罗世.霍吉河钼矿是在蒙古-鄂霍茨克洋和古太平洋相向联合俯冲作用下,导致霍吉河地区发生地壳增生和壳幔相互作用以及后来的拆沉作用,形成了该区花岗质岩石和钼矿床.高度演化的花岗岩体(脉)可以作为今后本区钼矿床的找矿方向.     

吉林东部花岗岩风化的地球化学

描述了吉林东部花岗岩风化壳的特征。研究了花岗岩风化过程中主要造岩矿物的变化特点;建立了主要造岩矿物的风化序列。研究了主量元素、微量元素及稀土元素的地球化学行为;探讨了影响风化过程中元素行为的主要因素。计算了风化速率。     

Chemical and isotopic compositions of Absaroka granitoids,Southwestern Montana

Contents of major and most trace elements of granitoids in three intrusions associated with the Cretaceous Independence volcanic complex, Montana, correlate well with SiO₂. Major-element contents in granitoids in each intrusion are accurately modeled as mixtures of minimum melts and phenocryst assemblages (presumably restite). Restite assemblages are hypersthene+augite+plagioclase, hornblende+plagioclase, and biotite+plagioclase+quartz. Residues of melting are granulite or amphibolite. Melts in two of the bodies were LREE-enriched but unfractionated in MREE and HREE. REE patterns are consistent with residues dominated by pyroxene or amphibole and feldspar. Initial ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb of granitoids define a line interpreted as a secondary isochron established during crustal homogenization 3.3 Ga ago. The relatively low of source rocks (8.25) suggests that they did not spend long in U-rich environments. Source regions had variable trace element patterns; Th/Pb and U/Pb were correlated, Rb/Sr and Sm/Nd moderately well correlated, but Rb/Sr and U/Pb were decoupled. This is consistent with poor correlation of Rb, Sr and Ba with SiO₂ in some granitoids and may suggest that minor phases that concentrate these elements were inhomogeneously distributed in source regions. The source probably consisted of LREE-rich, Rb-poor metamorphic rocks. Archean amphibolites, exposed in the Beartooth Mountains, are similar to the postulated source materials. They contain plagioclase, hornblende, minor quartz, biotite, and muscovite, and have low Rb/Sr and high LREE/HREE. Certain trace-element characteristics of the granitoids indicate that the deep crust in this part of Montana may be dominated by metamorphosed mafic-intermediate lavas that formed on the sea-floor. Metapelites, intercalated with amphibolites at the surface, were rare in granitoid source regions. This buried supracrustal pile was isotopically homogenized 3.3 Ga ago. Although some material melted 2.7 Ga ago to form granites that dominate the exposed basement, enough remained fertile that heating by mantle-derived magmas 85–90 Ma ago produced the granitic rocks at Independence.     

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.     

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio ⁸⁷Sr/⁸⁶Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

Mineralogical and geochemical constraints on environmental impacts from waste rock at Taojiang Mn-ore deposit,central Hunan,China

The mineralogy and geochemistry of the waste rocks distributed at Taojiang Mn-ore deposit, central Hunan province, China, were studied using X-ray powder diffraction (XRD), electron microprobe analysis (EMPA) fitted with energy dispersive spectrometer (EDS) and inductively coupled plasma mass spectrum (atomic emission spectra) ICP-MS (AES), with the aim of predicting the environmental impacts of weathering of the waste rocks. The mineralogical results from microscope observation and XRD and EMPA studies show that the waste rock is composed of black shale and minor Mn carbonates. The oxidation of sulfide minerals such as galena, pyrite and chalcopyrite is accompanied by decomposition of Mn carbonates and K-feldspar during exposure to atmospheric O₂. The geochemical characteristics of major, rare earth elements (REE) and trace elements of the waste rocks also show that the waste rock can be divided into black shale and Mn carbonate, and both of them are currently under chemical weathering. The major alkalies and alkaline elements (Ca, Mg, Na, K, Rb, Sr and Cs) and major elements (Fe, S and P) and heavy metals (Sc, V, Cr, Th, U, Sn, Co, Ni, Cu, Zn, Pb, Mo, Cd, Sb, an Tl) are being released during weathering. The mobility of alkalis and alkaline elements Ca, Mg, Na, K, Rb, Sr and Cs is controlled by decomposition of Mn carbonates. The dispersion of Cr, Sc and Th (U) might be related to weathering of K-feldspar, and the release of the heavy metals Co, Ni, Cu, Zn, Pb, Mo, Cd Sb and Tl is dominated by the breaking of sulfide minerals. The REE of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks, the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area. This is predicted by the mass-balance calculation by using Zr as an immobile element. Therefore, it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection.     

The influence of mineralogy on weathering rates and processes in an acid-sensitive granitic catchment

Weathering in an upland catchment on granitic parent material has been studied by chemical and mineralogical analyses of soils. Long-term weathering rates for base cations, calculated from chemical analyses of the mineral horizons from soil profiles using Zr as an internal, immobile, index element, are among the smallest recorded for Scottish soils (1.7–3.1 meq m⁻² a⁻¹), indicating that these soils are susceptible to acid deposition. Sodium is the base cation lost to the greatest extent from the soils, due to weathering of plagioclase feldspar, mainly in the coarse size-fractions. Calcium is lost not only from plagioclase feldspar, but also from hornblende, grains of which show dissolution etch pits and denticulate surface features when examined by scanning electron microscopy. Weathering of hornblende, present in basic inclusions in the granite, is a significant weathering process in these soils. A range of values for ⁸⁷Sr/⁸⁶Sr ratios in stream-waters confirms the spatial variability of the material supplying Ca to the streams. The current weathering rate, calculated from input–output budgets to be 28.9 meq m⁻² a⁻¹, is much greater than the long-term weathering rate, but small compared to other catchments on similar parent material.     

Rare Earth Element Behaviour During Evolution and Alteration of the Dartmoor Granite, SW England

The distribution of rare earth elements (REE) within the compositionallyzoned Dartmoor pluton is used to constrain models of graniteevolution and to assess the effects of pervasive hydrothermalalteration on REE mobility. The main process of magma evolutionwas crystal fractionation of early plagioclase, biotite, andaccessory minerals (apatite, monazite, zircon, and xenotime).Concentrations of REE (particularly LREE and Eu) and other elements(Fe₂O₃t, MgO, CaO, TiO₂, Zr, Ba, and Sr) decrease strongly withevolution of the pluton from 71 to 74% SiO2. These trends, andthe inward zoning of the pluton, are compatible with differentiationby crystal fractionation at the level of emplacement, a processthat gave rise to a marginal cumulate granite (CGM) modifiedby country rock assimilation, a body of inner granite (PM),and a late-stage evolved granite (FG) that intruded the earliertypes. REE modelling of the Dartmoor granite types by fractionalcrystallization of REE-enriched accessory minerals from a parentPM-granite shows that the FG-granite cannot have formed froma residual liquid left by crystallization of the CGM-granite.Two discrete stages of crystallization occurred; side-wall cumulateCGM-granite crystallization dominated by LREE-en-riched monazitefractionation followed by a late-stage mobile residual FG-granitein which fractionation was dominated by HREE-enriched apatiteand zircon. Modelling supports the idea that large-scale assimilationof country rock was not the dominant process during Dartmoorgranite evolution. Pervasive hydrothermal alteration locally affected all Dartmoorgranite types, altering primary plagioclase, biotite, apatite,monazite, and, to a lesser extent, zircon and xenotime. Duringpervasive sericitization, chloritization, and tourmalinization,REE were mobilized over distances of centimetres only and redistributedinto the secondary alteration products seridte, chlorite, tourmaline,allanite, and sphene. Whole-rock REE abundances were not affected     

The dissolution kinetics of a granite and its minerals—Implications for comparison between laboratory and field dissolution rates

The present study compares the dissolution rates of plagioclase, microcline and biotite/chlorite from a bulk granite to the dissolution rates of the same minerals in mineral-rich fractions that were separated from the granite sample. The dissolution rate of plagioclase is enhanced with time as a result of exposure of its surface sites due to the removal of an iron oxide coating. Removal of the iron coating was slower in the experiment with the bulk granite than in the mineral-rich fractions due to a higher Fe concentration from biotite dissolution. As a result, the increase in plagioclase dissolution rate was initially slower in the experiment with the bulk granite. The measured steady state dissolution rates of both plagioclase (6.2 ± 1.2 × 10⁻¹¹ mol g⁻¹ s⁻¹) and microcline (1.6 ± 0.3 × 10⁻¹¹ mol g⁻¹ s⁻¹) were the same in experiments conducted with the plagioclase-rich fraction, the alkali feldspar-rich fraction and the bulk granite.Based on the observed release rates of the major elements, we suggest that the biotite/chlorite-rich fraction dissolved non-congruently under near-equilibrium conditions. In contrast, the biotite and chlorite within the bulk granite sample dissolved congruently under far from equilibrium conditions. These differences result from variations in the degree of saturation of the solutions with respect to both the dissolving biotite/chlorite and to nontronite, which probably was precipitating during dissolution of the biotite and chlorite-rich fraction. Following drying of the bulk granite, the dissolution rate of biotite was significantly enhanced, whereas the dissolution rate of plagioclase decreased.The presence of coatings, wetting and drying cycles and near equilibrium conditions all significantly affect mineral dissolution rates in the field in comparison to the dissolution rate of fully wetted clean minerals under far from equilibrium laboratory conditions. To bridge the gap between the field and the laboratory mineral dissolution rates, these effects on dissolution rate should be further studied.     

Water–granite interaction: Clues from strontium,neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the ⁸⁷Sr/⁸⁶Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed ⁸⁷Sr/⁸⁶Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.     

Age and isotopic evidence for the origin of the Archæan granitoid intrusives of the Johannesburg Dome,South Africa

Results of RbSr, PbPb and SmNd whole rock, Rbr biotite and PbPb zircon evaporation analyses are presented for certain granitoid rocks from the Johannesburg Dome. These data indicate that the granodiorite, granite and leucosome from migmatite were emplaced ∼ 3090 Ma ago, were genetically related and were derived primarily from a source between ∼ 3300 and ∼ 3500 Ma old. A portion of the granodiorite and granite might have been derived from a source between ∼ 4000 and ∼ 4300 Ma old. The tonalite was emplaced ∼ 3170 Ma ago and was derived from a source between 3.3 and 3.5 Ga old. RbSr biotite-whole rock ages, ranging between about ∼ 2614 and ∼ 2080 Ma, probably reflect complete resetting during differential uplift, erosion and cooling of the granitoid rocks in the Neoarchæan and Palæoproterozoic. If so, they apparently were not influenced by the emplacement of the ∼ 2060 Ma Bushveld Igneous Complex or the ∼ 2000 Ma Vredefort event. The granodiorite, granite and leucosome were emplaced coeval with and may be genetically related to compositionally similar plutonic and volcanic rocks in the Barberton area, Vredefort structure and Dominion Group.