Roles of sorting and chemical weathering in the geochemistry and magnetic susceptibility of Xiashu loess, East China

Uncertainties in paleoenvironmental interpretations for traditional chemical analysis of bulk samples result from different grain-size sub-populations of sediments containing variable distributions of elements and minerals. Therefore, it is important to understand the elemental and mineral distribution in different grain sizes in determining the quantitative relationship between chemical weathering and climatic change. We sieved a series of Xiashu loess samples into three sub-populations of different grain sizes (<2, 2–45 and >45 μm, respectively), and then analyzed each population for rubidium (Rb), strontium (Sr), rare earth elements and magnetic susceptibility. In comparison with elemental concentrations of bulk samples, clay mineralogy and illitic crystallinity, our results show that distinct elemental distributions and magnetic susceptibilities for different grain-size sub-populations are controlled by sorting and/or chemical weathering, although we also suggest that the Xiashu loess may have the same provenance as the Central Chinese Loess. Maximum concentrations of Rb and fine-grained magnetic minerals in the less than 2 μm sub-population, coupled with our finding of maximum Sr in the larger than 45 μm fraction, indicate that Sr was lost during chemical weathering. Grain-size sub-population analysis is, therefore, an effective method for extracting paleoenvironmental information, because individual sub-populations show minimal variations in initial Rb/Sr ratios compared to bulk analysis of all sizes together. Furthermore, a negative correlation between Rb/Sr ratios and Sr concentrations for the <2 μm fraction (R² = 0.97) may indicate that clay is a sensitive indicator of intensity of chemical weathering and is an ideal sub-population for determining Rb/Sr ratios, but not for magnetic susceptibility.     

Major element geochemistry of purple soils/rocks in the red Sichuan Basin, China: implications of their diagenesis and pedogenesis

Major element compositions and chemical weathering features of the purple soils and their corresponding rocks in the Red Sichuan Basin, China were studied in this paper to infer the diagenetic features of the purple rocks and the pedogenetic features of the purple soils. The results showed that all of the rock and soil samples, except those from Yibin, have strongly similar major element compositions and the distribution patterns of their major element compositions are similar to those of the upper continental crust. Chemical index of alteration, chemical index of weathering and Na₂O/K₂O indicate that the purple soils and rocks have similar chemical weathering intensities, whereas the Al₂O₃–CaO* + Na₂O–K₂O (A–CN–K) relationship, suggests that chemical weathering was strong during diagenesis of the purple rocks, but weak during pedogenesis of the purple soils. Variations in major element compositions of the purplish rock samples, except that from Yibin, do not primarily reflect differences in compositions of the sediment source, sediment recycling and potassium metasomatism, and therefore the effects of chemical weathering on the major element compositions were mainly dependent on climate condition and the residence time of material exposed to chemical weathering. Chemical weathering of the purple rocks reached only moderate degrees under the general influence of warm and humid climate during Jurassic and Cretaceous. Warmer and more humid climate conditions partly resulted in stronger chemical weathering of rocks in the southern region of the basin than in the central and western region, whereas shorter residence time of material in upslope position partly resulted in weaker chemical weathering of rocks in the eastern region than in the central and western region. The same climate and stable tectonic setting led to comparable chemical weathering intensities of rocks in the Ziliujing and Jiaguan Formations. Gradually colder and dryer climate from Early Jurassic to Middle Jurassic then to Late Jurassic and shorter residence time in tectonically active setting of Middle Jurassic and late Late Jurassic resulted in the following order of chemical weathering intensity of the purple Jurassic rocks: Ziliujing Formation ? Shaximiao Formation ≈ Suining Formation > Penglaizhen Formation.     

Climatic and lithologic controls on the temporal and spatial variability of CO2 consumption via chemical weathering: An example from the Australian Victorian Alps

A detailed geochemical study on river waters of the Australian Victorian Alps was carried out to determine: (i) the relative significance of silicate, carbonate, evaporite and sulfide weathering in controlling the major ion composition and; (ii) the factors regulating seasonal and spatial variations of CO₂ consumption via silicate weathering in the catchments. Major ion chemistry implies that solutes are largely derived from evaporation of precipitation and chemical weathering of carbonate and silicate lithologies. The input of solutes from rock weathering was determined by calculating the contribution of halite dissolution and atmospheric inputs using local rain and snow samples. Despite the lack of carbonate outcrops in the study area and waters being undersaturated with respect to calcite, the dissolution of vein calcite accounts for up to 67% of the total dissolved cations, generating up to 90% of dissolved Ca and 97% of Mg. Dissolved sulfate has δ³⁴S values of 16 to 20‰_CDT, indicating that it is derived predominantly from atmospheric deposition and minor gypsum weathering and not from bacterial reduction of FeS₂. This militates against sulphuric acid weathering in Victorian rivers. Ratios of Si vs. the atmospheric corrected Na and K concentrations range from ~ 1.1 to ~ 4.3, suggesting incongruent weathering from plagioclase to smectite, kaolinite and gibbsite.Estimated long-term average CO₂ fluxes from silicate weathering range from ~ 0.012 × 10⁶ to 0.039 × 10⁶ mol/km²/yr with the highest values in rivers draining the basement outcrops rather than sedimentary rocks. This is about one order of magnitude below the global average which is due to low relief, and the arid climate in that region. Time series measurements show that exposure to lithology, high physical erosion and long water–rock contact times dominate CO₂ consumption fluxes via silicate weathering, while variations in water temperature are not overriding parameters controlling chemical weathering. Because the atmospheric corrected concentrations of Na, K and Mg act non-conservative in Victorian rivers the parameterizations of weathering processes, and net CO₂ consumption rates in particular, based on major ion abundances, should be treated with skepticism.     

Major and trace element geochemistry in upper Ganga river in the Himalayas, India

Chemical weathering and resulting water compositions in the upper Ganga river in the Himalayas were studied. For the first time, temporal and spatial sampling for a 1 year period (monthly intervals) was carried out and analyzed for dissolved major elements, trace elements, Rare Earth Elements (REE), and strontium isotopic compositions. Amounts of physical and chemical loads show large seasonal variations and the overall physical load dominates over chemical load by a factor of more than three. The dominant physical weathering is also reflected in high quartz and illite/mica contents in suspended sediments. Large seasonal variations also occur in major elemental concentrations. The water type is categorized as HCO₃^––SO₄^2––Ca²⁺ dominant, which constitute >60% of the total water composition. On an average, only about 5–12% of HCO₃^– is derived from silicate lithology, indicating the predominance of carbonate lithology in water chemistry in the head waters of the Ganga river. More than 80% Na⁺ and K⁺ are derived from silicate lithology. The silicate lithology is responsible for the release of low Sr with extremely radiogenic Sr (⁸⁷Sr/⁸⁶ Sr>0.75) in Bhagirathi at Devprayag. However, there is evidence for other end-member lithologies for Sr other than carbonate and silicate lithology. Trace elements concentrations do not indicate any pollution, although presence of arsenic could be a cause for concern. High uranium mobilization from silicate rocks is also observed. The REE is much less compared to other major world rivers such as the Amazon, perhaps because in the present study, only samples filtered through <0.2 m were analysed. Negative Eu anomalies in suspended sediments is due to the excess carbonate rock weathering in the source area.     

Lithium isotopic composition and concentration of the upper continental crust

The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ⁷Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ⁷Li and the clay content of shales (as measured by Al₂O₃/SiO₂), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ⁷Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ⁷Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ⁷Li of −5‰ to + 5‰), with an average (δ⁷Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ⁷Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al₂O₃, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.     

River dissolved and solid loads in the Lesser Antilles: New insight into basalt weathering processes

We present here the first available estimations of chemical weathering and associated atmospheric CO₂ consumption rates as well as mechanical erosion rate for the Lesser Antilles. The chemical weathering (100–120 t/km²/year) and CO₂ consumption (1.1–1.4 × 10⁶ mol/km²/year) rates are calculated after subtraction of the atmospheric and hydrothermal inputs in the chemical composition of the river dissolved loads. These rates thus reflect only the low-temperature basalt weathering. Mechanical erosion rates (approx. 800–4000 t/km²/year) are estimated by a geochemical mass balance between the dissolved and solid loads and mean unaltered rock. The calculated chemical weathering rates and associated atmospheric CO₂ consumption rates are among the highest values worldwide but are still lower than those of other tropical volcanic islands and do not fit with the HCO₃⁻ concentration vs. 1/T correlation proposed by Dessert et al. (2001). The thick soils and explosive volcanism context of the Lesser Antilles are the two possible keys to this different weathering behaviour; the development of thick soils limits the chemical weathering and the presence of very porous pyroclastic flows allows an important water infiltration and thus subsurface weathering mechanisms, which are less effective for atmospheric CO₂ consumption.     

Zr-rich accessory minerals (titanite, perrierite, zirconolite, baddeleyite) record strong oxidation associated with magma mixing in the south Peruvian potassic province

The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K₂O/Na₂O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite [up to 5.3 wt.% ZrO₂ and 5.2 wt.% (Y₂O₃ + REE₂O₃)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO₂ and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe₂O₃, 3.2 wt.% TiO₂, 1.5 wt.% HfO₂, 1.2 wt.% Nb₂O₅, 0.25 wt.% CeO₂) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe³⁺ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.     

Petrogenesis of the early Cretaceous Valle Chico igneous complex (SE Uruguay): Relationships with Paraná–Etendeka magmatism

The early Cretaceous (130 Ma) igneous complex of Valle Chico (SE Uruguay) is made up of felsic plutonic and subordinate volcanic rocks and dykes cropping out over an area of about 250 km². This complex is strictly linked with the formation of the Paraná–Etendeka Igneous Province and the first stages of the South Atlantic Ocean rifting. The plutonic rocks range from quartz-monzonite to syenite, quartz-syenite and granite. The volcanic rocks and the dykes range from quartz-latite to trachyte and rhyolite; no substantial differences in term of chemical composition have been found between plutonic and volcanic rocks. Only a sample of basaltic composition (with tholeiitic affinity) has been sampled associated with the felsic rocks. The Agpaitic Index of the Valle Chico felsic rocks range from 0.72 to 1.34, with the peralkaline terms confined in the most evolved samples (SiO₂>65 wt.%). Initial ⁸⁷Sr/⁸⁶Sr₍₁₃₀₎ of the felsic rocks range from 0.7046 to 0.7201, but the range of ⁸⁷Sr/⁸⁶Sr of low-Rb/Sr samples cluster at 0.7083; ¹⁴³Nd/¹⁴⁴Nd₍₁₃₀₎ ratios range from 0.5121 (syenite) to 0.5117 (granite). The tholeiitic basalt show more depleted isotopic compositions (⁸⁷Sr/⁸⁶Sr₍₁₃₀₎=0.7061; ¹⁴³Nd/¹⁴⁴Nd₍₁₃₀₎=0.5122), and plots in the field of other early Cretaceous low-Ti basaltic rocks of SE Uruguay. The radiogenic Sr and unradiogenic Nd of the Valle Chico felsic rocks require involvement of lower crustal material in their genesis either as melt contaminant or as protolith (crustal anatexis). In particular, most of the Valle Chico (VC) felsic rocks define a near-vertical array in Sr–Nd isotopic spaces, pointing toward classical EMI-type composition; this feature is considered to reflect a lower crust involvement as observed for other mafic and felsic rocks of the Paraná–Etendeka Igneous Province. Decompression melting of the lower crust related to Gondwana continental rifting before the opening of the South Atlantic Ocean or the presence of thermal anomalies related to the Tristan plume may have induced the lower crust to partially melt. Alternative hypothesis considers contamination of upper mantle by a mafic/ultramafic keel composed of lower crust and uppermost mantle after delamination and detachment processes. This interaction may have occurred after the continent–continent collision during the last stages of the Panafrican Orogeny. This “lower crust” model does not exclude active involvement of upper crust as contaminant, necessary to explain the strongly radiogenic ⁸⁷Sr/⁸⁶Sr₍₁₃₀₎ isotopic composition of some VC SiO₂-rich rocks. Mineralogical (sporadic presence of pigeonite, Ca–Na and Na clinopyroxene, calcic- and calco-sodic amphibole) and geochemical evidences (major and trace element as well as Sr–Nd isotopic similarities with the felsic early Cretaceous volcanic rocks of the Arequita Formation in SE Uruguay) allow us to propose for the VC rocks a transitional rock series (the most abundant rock types are of syenitic/trachytic composition) preferentially evolving towards SiO₂-oversaturated compositions (granite/rhyolite) also with a strong upper crustal contribution as melt contaminant. This conclusion is in contrast with previous studies according which the VC complex had clear alkaline affinity. Many similarities between VC and the coeval Paresis granitoids (Etendeka, Namibia) are evidenced in this paper. The genetic similarities between VC and the rhyolites (s.l.) of SE Uruguay may find counterparts with the genetic link existing between the early Cretaceous tholeiitic-alkaline Messum complex and the quartz latites (s.l.) of the Awahab Formation (Etendeka region, Namibia).     

Voluminous granitic magmas from common basaltic sources

Granitic—rhyolitic liquids were produced experimentally from moderately hydrous (1.7–2.3 wt% H₂O) medium-to-high K basaltic compositions at 700 MPa and fO₂ controlled from Ni-NiO –1.3 to +4. Amount and composition of evolved liquids and coexisting mineral assemblages vary with fO₂ and temperature, with melt being more evolved at higher fO₂s, where coexisting mineral assemblages are more plagioclase- and Fe–Ti oxide-rich and amphibole-poor. At fO₂ of Ni–NiO +1, typical for many silicic magmas, the samples produce 12–25 wt% granitic–rhyolitic liquid, amounts varying with bulk composition. Medium-to-high K basalts are common in subduction-related magmatic arcs, and near-solidus true granite or rhyolite liquids can form widely, and in geologically significant quantities, by advanced crystallization–differentiation or by low-degree partial remelting of mantle-derived basaltic sources. Previously differentiated or weathered materials may be involved in generating specific felsic magmas, but are not required for such magmas to be voluminous or to have the K-rich granitic compositions typical of the upper continental crust.     

Solid inclusions of magmatic halite and sylvite in felsic granitoids, Sierra Norte, Córdoba, Argentina

This study provides evidence for the existence of halite and sylvite solid inclusions in igneous quartz and feldspars, the first to be reported in intrusive rocks, and to partially constrain the physicochemical environment that lets halides crystallize under magmatic conditions.Halite and sylvite solid inclusions were found included in quartz and feldspars from a micrographic–granophyric assemblage in a miarolitic aplite and, rarer, in alkali-feldspar from a miarolitic monzogranite. Monzogranite and aplite represent I-type, K-enriched postcollisional rocks of the Late Cambrian–Early Ordovician Sierra Norte–Ambargasta batholith in the Eastern Sierras Pampeanas. Both granitoids fall among the most evolved felsic rocks of the batholith, with aplite approaching haplogranitic compositions. Halite is far more common than sylvite and the presence and distribution of one or both halides are erratic within the felsic intrusive bodies. Halides occur as small skeletal grains, commonly in cross-shaped aggregates of less than 50 μm. No K or Na was found at the detection limits of EDS in either halite or sylvite respectively. Textural relationships suggest that the alkali-chlorides separated from the melt near the minima along the quartz–feldspar cotectics of P_H2O > 160 < 200 MPa in a silica-, and potassium-rich magmatic system at approximately 750–700 °C, prior to the H₂O-vapor saturated miarole-forming stage.Computed ratios for the magmatic volatile phase (MVP) coexisting with melt at the early stage of aplite crystallization are: NaCl/HCl = 0.11–0.97 and KCl/HCl = 0.24–1.62, being the highest range of values (0.79–0.97 and 1.45–1.62, respectively) found in those alkali-chloride-bearing samples. Maximum HCl/ΣCl_(MVP) (0.28 to 0.31) indicates higher total Cl concentration in the MVP of alkali-chloride-bearing aplites, which is much higher in the halite-free aplite samples (HCl/ΣCl_(MVP) = 0.59 to 0.74). One miarolitic monzogranite sample, where halite solid inclusions are present, also yielded the highest ratios for NaCl/HCl_(MVP) (0.91) and KCl/HCl_(MVP) (1.46), and the HCl/ΣCl_(MVP) is 0.30. A high HCl concentration in the fluid phase is suggested by the log f(HF)/f(H₂O) = − 4.75 to − 4.95, log f(HCl)/f(H₂O) = − 3.73 to − 3.86, and log f(HF)/f(HCl) = − 0.88 to − 1.22, computed at 750 °C after biotite composition. The Cl concentrations at 800 °C, computed with a D^v/l_Cl = 0.84 + 26.6P (P at 200 MPa), yielded values within the range of  70 to 700 ppm Cl in the melt and  4000 to 40 000 ppm Cl in the coexisting MVP. The preferential partitioning of Cl in the vapor phase is controlled by the D^v/l_Cl; however, the low concentration of Cl in the melt suggests that high concentrations of Cl are not necessary to saturate the melt in NaCl or KCl.Cl-saturation of the melt and coexisting MVP might have been produced by a drop in Cl solubility due to the near-haplogranitic composition of the granitoids after extreme fractionation, probably enhanced by fluctuating reductions of the emplacement pressure in the brittle monzogranite host. Liquid immiscibility, based in the differential viscosity and density among alkali-chloride saturated hydrosaline melt, aluminosilicate felsic melt, and H₂O-rich volatiles is likely to have crystallized halite and sylvite from exsolved hydrosaline melt. High degrees of undercooling might have been important at the time of alkali-chloride exsolution. The effectiveness of alkali-chloride separation from the melt at magmatic temperatures is in line with the interpretation of “halite subtraction” as a necessary process to understand the origin of the “halite trend” in highly saline fluid inclusions from porphyry copper and other hydrothermal mineralizations, despite the absence of the latter in the Cerro Baritina aplites, where this process preceded the exsolution of halite-undersaturated fluids.Pervasive alteration of the monzogranite country rock as alkali-metasomatic mineral assemblages, the mineral chemistry of some species, and the association of weak molybdenite mineralization are compatible with the activity of alkaline hypersaline fluids, most likely exsolved during the earliest stages of aplite consolidation.     

Lithogenic concentrations of trace metals in soils and saprolites over crystalline basement rocks: A case study from SW Nigeria

In this study, an assessment of the lithogenic concentrations of trace metals in soils and saprolite over basement rock units in Ibadan, SW-Nigeria is presented in respect of bedrock types and geochemical controls on the weathering-associated release of trace metals. Consequently, soil, weathered and fresh rock samples from the Precambrian Basement of SW Nigeria were collected from three different bedrock units within Ibadan metropolis and subjected to mineralogical and geochemical analyses. The analytical results revealed major proportions of oxides in the range of 18–20% Al₂O₃, 2–6% Na₂O and 1–6% K₂O for weathered profiles over granite-gneiss and pegmatite units, compared to 2–3% Al₂O₃, <0.5% Na₂O and <1.0% K₂O over schist-quartzite. For the trace elements, weathered profiles on granite-gneiss and schist-quartzite settings exhibit similar enrichment trends (enrichment factor, EF l) for most of the trace elements, unlike the pegmatite bedrock. However, enrichments are relatively greater in the top soil unit compared to the intermediate saprolite unit, especially for Pb, Ni, Zn, Cr, Co, Rb, Sr and Ba, a situation attributed to leaching and redistribution within the weathered profiles through pedogenetic process and percolating groundwater.Furthermore, the estimated weathering indices using Ruxton Ratio (RR = {SiO₂/Al₂O₃}) and Chemical Index of Alteration (CIA = 100{Al₂O₃/[Al₂O₃ + CaO + Na₂O + K₂O]}) revealed RR of 2.9–3.7 and CIA of 54–73% for granite-gneiss and pegmatite units, implying medium levels of weathering, compared to RR of 30.8–35.5 and CIA of >60% for schist-quartzite units, which suggest weak chemical weathering. Also, the estimated high percentage loss, especially for Pb, Rb, Sr, Ba relative to the bedrocks, shows that the trace elements can be mobilized within the weathering profiles even at a low degree of chemical weathering. Such weathering-induced release of trace metals is of environmental significance as natural lithogenic input sources and as background reference for future monitoring of possible human/anthropogenic impacts.     

Ages,rare-earth element enrichment,and petrogenesis of tholeiitic and alkalic basalts from Kahoolawe Island,Hawaii

Kahoolawe Island, Hawaii (18×11 km), is a basaltic shield volcano with caldera-filling lavas, seven identified postshield vents, and at least two occurrences of apparent rejuvenated-stage eruptive. We examined 42 samples that represent all stages of Kahoolawe volcano stratigraphy for their petrography, whole-rock major-and trace-element contents, mineral compositions, and K–Ar ages. The two oldest shield samples have an average age of 1.34±0.08 Ma, and four postshield samples (3 are alkalic) average 1.15±0.03 Ma; ages of 1.08 and 0.99 Ma for two additional tholeiitic samples probably are minimum ages. Whole-rock major- and trace-element and mineral compositions of Kahoolawe shield and caldera-fill laves are generally similar to the lavas forming Kilauea and Mauna Loa tholeiitic shields, but in detail, Kahoolawe shield lavas have distinctive compositions. An unusual aspect of many postshield Ka-hoolawe lavas is anomalously high REE and Y abundances (up to 200 ppm La and 175 ppm Y) and negative Ce anomalies. These enrichments reflect surficial processes, where weathering and soil development promoted REE-Y transport at the weathering front. Major element abundances (MgO, 10–6 wt.%) for shield and caldera-fill basalts are consistent with fractionation of ol+px+pl in frequently replenished magma reservoirs. In general, tholeiitic basalts erupted from late vents are higher in SiO₂ than the shield lavas, and temporal differences in parental magma compositions are the likely explanation. Alkalic basalts that erupted from vents are comparable in composition to those at other Hawaiian volcanoes. Trace-element abundance ratios indicate that alkalic basalts represent either relatively lower degrees of melting of the shield source or a distinct source. Apparent rejuvenated-stage basalts (i.e., emplaced after substantial Kahoolawe erosion) are tholeiitic, unlike the rejuvenated-stages at other Hawaiian volcanoes (alkalic). Kahoolawe, like several other Hawaiian volcanoes, has intercalated tholeiitic and alkalic basalts in the postshield stage, but it is the only volcano that appears to have produced tholeiitic rejuvenated-stage lavas.     

Modelling Compositional Change: The Example of Chemical Weathering of Granitoid Rocks

Perturbation on the simplex is an operation which can be used to numerically describe changes in the composition of, for example, soils, sediments, or rocks. The combination of perturbation and power transformation provides a strong tool for analyzing compositional linear processes in the simplex. When the process is constrained in the sense of a well-known starting (or final) composition, noncentred principal component analysis can be used to estimate the leading perturbation vector of the process. Applying these mathematical tools to chemical major element data from a weathering profile developed on granitoid rocks allows us to model the compositional changes associated with the process of chemical weathering. The comparison of these results with the compositional linear trend defined by erosional products of several of the world's major drainage systems yields close similarities. The latter observation allows for a mathematical formulation of a global mean weathering trend within the system Al₂O₃–CaO– Na₂O– K₂O. We further demonstrate the usefulness of the approach for validating processes behind individual trends and for combining the effects of different processes which modify the composition of soils, sediments, and rocks. Alternatives to the Chemical Index of Alteration (CIA) are discussed to obtain a translation-invariant scale for the process of chemical weathering.     

Heterogeneous magnesium isotopic composition of the upper continental crust

High-precision Mg isotopic data are reported for ∼100 well-characterized samples (granites, loess, shales and upper crustal composites) that were previously used to estimate the upper continental crust composition. Magnesium isotopic compositions display limited variation in eight I-type granites from southeastern Australia (δ²⁶Mg = −0.25 to −0.15) and in 15 granitoid composites from eastern China (δ²⁶Mg = −0.35 to −0.16) and do not correlate with SiO₂ contents, indicating the absence of significant Mg isotope fractionation during differentiation of granitic magma. Similarly, the two S-type granites, which represent the two end-members of the S-type granite spectrum from southeastern Australia, have Mg isotopic composition (δ²⁶Mg = −0.23 and −0.14) within the range of their potential source rocks (δ²⁶Mg = −0.20 and +0.15) and I-type granites, suggesting that Mg isotope fractionation during crustal anatexis is also insignificant. By contrast, δ²⁶Mg varies significantly in 19 A-type granites from northeastern China (−0.28 to +0.34) and may reflect source heterogeneity.Compared to I-type and S-type granites, sedimentary rocks have highly heterogeneous and, in most cases, heavier Mg isotopic compositions, with δ²⁶Mg ranging from −0.32 to +0.05 in nine loess from New Zealand and the USA, from −0.27 to +0.49 in 20 post-Archean Australian shales (PAAS), and from −0.52 to +0.92 in 20 sedimentary composites from eastern China. With increasing chemical weathering, as measured by the chemical index of alternation (CIA), δ²⁶Mg values show a larger dispersion in shales than loess. Furthermore, δ²⁶Mg correlates negatively with δ⁷Li in loess. These characteristics suggest that chemical weathering significantly fractionates Mg isotopes and plays an important role in producing the highly variable Mg isotopic composition of sedimentary rocks.Based on the estimated proportions of major rock units within the upper continental crust and their average MgO contents, a weighted average δ²⁶Mg value of −0.22 is derived for the average upper continental crust. Our studies indicate that Mg isotopic composition of the upper crust is, on average, mantle-like but highly heterogeneous, with δ²⁶Mg ranging from −0.52 to +0.92. Such large isotopic variation mainly results from chemical weathering, during which light Mg isotopes are lost to the hydrosphere, leaving weathered products (e.g., sedimentary rocks) with heavy Mg isotopes.     

Petrography and geochemistry of the Upper Cretaceous Nubia sandstones,Eastern Desert,Egypt: implications for provenance,paleoweathering, and tectonic setting

The provenance of the Upper Cretaceous Nubia sandstones from four vertical sections along Qena-Safaga and Qena-Quseir roads in central Eastern Desert of Egypt was investigated based on their modal composition and geochemical data. The Nubia sandstone samples are abundant in quartz content with low feldspar and lithic fragments. Their average modal composition (Q_94.2F_1.3R_4.5) classifies them as quartz arenites with subordinate quartz wackes which is consistent with geochemistry data. The average CIA, CIW, PIA, and Th/U ratio values revealed that the intensity of weathering in the studied areas was similar, varying from moderate to intensive weathering, and may reflect low-relief and warm humid climatic conditions in the source area. The ICV (<?1) and SiO₂/Al₂O₃ ratio (>?5) indicate that the Nubia sandstones are texturally and mineralogically mature. The petrographical and geochemical analyses suggest that the Nubia sandstones were mainly derived from felsic (granitic) and/or recycled sand sources. The major element-based multidimensional tectonic discrimination diagrams suggested the Nubia sandstones were deposited in a passive continental margin of a syn-rift basin. This result agreed with the general geology of central Eastern Desert of Egypt during the Upper Cretaceous.     

Rare-earth and trace elements and hydrogen and oxygen isotopic compositions of Cretaceous kaolinitic sediments from the Lower Benue Trough,Nigeria: provenance and paleoclimatic significance

This study evaluated the Cretaceous (Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma–mass spectrometry and isotope ratio mass spectrometry was used to investigate trace and rare-earth element geochemistry and hydrogen and oxygen isotopic compositions. These data were then used to infer the sediments’ provenance and paleoclimatic conditions during their deposition. The sediments contained low concentrations of most trace elements, with the exceptions of Zr (651–1352 ppm), Ba (56–157 ppm), V (38–90 ppm), and Sr (15.1–59.6 ppm). Average values of Co and Ni were 1.5 and 0.7 ppm, respectively. Trace and rare earth element values were lower than corresponding values for upper continental crust and Post-Archean Australian Shale, with the exception of Zr. The samples showed only slight light rare-earth enrichment and nearly flat heavy rare-earth depletion patterns, with negative Eu and Tm anomalies, typical of felsic sources. Geochemical parameters such as La/Sc, Th/Sc, and Th/Co ratios support that the kaolinitic sediments were derived from a felsic rock source, likely deposited in an oxic environment. ¹⁸O values ranged from + 15.4 to + 21.2‰ for the investigated samples, consistent with a residual material derived from chemical weathering of felsic rock and redeposited in a sedimentary basin (typical values of + 19 to + 21.2‰). While in the basin, the sediments experienced extended interactions with meteoric water enriched in δD and δ¹⁶O. However, the variation in δD and δ¹⁶O values for the investigated samples is attributed to the high temperature of formation (54–91 °C). The δD and δ¹⁸O values suggest that the sediments, although obtained from different localities within the Lower Benue Trough, formed under similar hot, tropical climatic conditions.

     

Al_2O_3/Ti:风化与蚀变过程中的原岩示踪

Al_2O_3和Ti在风化和热液蚀变等地球化学过程中通常被认为是不活动元素,两者的比值Al_2O_3/Ti常被用来指示地球化学作用过程。通过对中国157件火成岩样品元素含量平均值的统计发现,火成岩样品中Al_2O_3/Ti与SiO_2含量值之间存在着较好的幂函数关系:ln(Al_2O_3/Ti)=0.073×SiO_2-0.89,式中Al_2O_3和SiO_2和Ti含量单位均为%。本文基于得到的经验方程和TAS图解构建了一个新的判别岩石类型的图解——Al_2O_3-Ti图解。该图解可以区分酸性岩、中酸性岩、中性岩、中基性岩-基性岩四类岩性。通过对三个火成岩风化剖面的研究发现,花岗岩风化剖面从新鲜基岩到风化形成的土壤在Al_2O_3-Ti图解中均落在酸性岩区,花岗闪长岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中酸性岩区,玄武质安山岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中基性岩-基性岩区。不同风化程度的风化产物与其母岩在Al_2O_3-Ti图解中所在的区域一致,即Al_2O_3-Ti图解可以用来追溯火成岩风化产物的母岩岩性。通过对胶东焦家金矿和豫西牛头沟金矿两个矿区岩石的研究发现,黑云母花岗岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在酸性岩区。玄武质安山岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在中基性岩-基性岩区。即不同蚀变程度的蚀变产物与其原岩在Al_2O_3-Ti图解中所在的区域一致,这表明新构建的Al_2O_3-Ti图解可以用来示踪蚀变岩的原岩性质。     

The role of supergene sulphuric acid during weathering in small river catchments in low mountain ranges of Central Europe: Implications for calculating the atmospheric CO2 budget

The geochemistry of dissolved and suspended loads in river catchments of two low mountain ranges in Central Europe allows comparison of pertinent chemical weathering rates. Distinct differences in lithology, i.e. granites prevailing in the Black Forest compared to Palaeozoic sediments in the Rhenish Massif, provide the possibility to examine the influence of lithology on weathering. Here we determine the origin of river water using the stable isotope ratio δ¹⁸O_H2O and we quantify the geogenic proportions of sulphate from stable isotope ratios δ³⁴S_SO4 and δ¹⁸O_SO4. Particularly in catchments with abundant pyrite, determination of the geogenic amount of sulphate is important, since oxidation of pyrite leads to acidity, which increases weathering. Our results show that spatially averaged silicate weathering rates are higher for the river catchments Acher and Gutach in the Black Forest (10–12 t/km²/yr) compared to the river catchments of the Möhne dam and the Aabach dam in the Rhenish Massif (2–6 t/km²/yr). Correspondingly, the CO₂ consumption by silicate weathering in the Black Forest (334–395 × 10³ mol/km²/yr) is more than twice as high as in the Rhenish Massif (28–151 × 10³ mol/km²/yr). These higher rates for watersheds of the Black Forest are likely due to steeper slopes leading to higher mechanical erosion with respective higher amounts of fresh unweathered rock particulates and due to the fact that the sediments in the Rhenish Massif have already passed through at least one erosion cycle. Carbonate weathering rates vary between 12 and 38 t/km²/yr in the catchments of the Rhenish Massif. The contribution of sulphuric acid to the silicate weathering is higher in the catchments of the Rhenish Massif (9–16%) than in the catchments of the Black Forest (5–7%) due to abundant pyrite in the sediments of the Rhenish Massif. Three times higher long-term erosion rates derived from cosmogenic nuclides compared to short-term erosion rates derived from river loads in Central Europe point to three times higher CO₂ consumption during the past 10³ to 10⁴ years.     

Geochemistry of organic-rich river waters in Amazonia: Insights on weathering processes of intertropical cratonic terrain

In this study, eight organic-rich rivers that flow through the Brazilian craton in the southwestern Amazon rainforest are investigated. This investigation is the first of its type in this area and focuses on the effects of lithology, long-term weathering, thick soils, forest cover and hydrological period on the dissolved load compositions in rivers draining cratonic terrain. The major dissolved ion concentrations, alkalinity (TAlk), SiO₂, trace element concentrations, and Sr isotope contents in the water were determined between April 2009 and January 2010. In addition, the isotopic values of oxygen and hydrogen were determined between 2011 and 2013. Overall, the river water is highly dilute and dominated by the major dissolved elements TAlk, SiO₂ and K⁺ and the major dissolved trace elements Al, Fe, Ba, Mn, P, Zn and Sr, which exhibit large temporal and spatial variability and are closely correlated with the silicatic bedrock and hydrology. Additionally, rainwater and recycled water vapor and the size of the basin contribute to the geochemistry of the waters. The total weathering flux estimated from our results is 2–4 t km⁻².yr⁻¹, which is one of the lowest fluxes in the world. The CO₂ consumption rate is approximately 21–61 10³ mol km⁻² yr⁻¹, which is higher than expected given the stability of the felsic to basic igneous and metamorphic to siliciclastic basement rocks and the thick tropical soil cover. Thus, weathering of the cratonic terrain under intertropical humid conditions is still an important consumer of CO₂.     

Petrography and geochemistry of Cretaceous to quaternary siliciclastic rocks in the Tarfaya basin,SW Morocco: implications for tectonic setting,weathering, and provenance

The petrography, heavy mineral analysis, major element geochemical compositions and mineral chemistry of Early Cretaceous to Miocene–Pliocene rocks, and recent sediments of the Tarfaya basin, SW Morocco, have been studied to reveal their depositional tectonic setting, weathering history, and provenance. Bulk sediment compositional and mineral chemical data suggest that these rocks were derived from heterogeneous sources in the Reguibat Shield (West African Craton) including the Mauritanides and the western Anti-Atlas, which likely form the basement in this area. The Early Cretaceous sandstones are subarkosic in composition, while the Miocene–Pliocene sandstones and the recent sediments from Wadis are generally carbonate-rich feldspathic or lithic arenites, which is also reflected in their major element geochemical compositions. The studied samples are characterized by moderate SiO₂ contents and variable abundances of Al₂O₃, K₂O, Na₂O, and ferromagnesian elements. Binary tectonic discrimination diagrams demonstrate that most samples can be characterized as passive continental marginal deposits. Al₂O₃/Na₂O ratios indicate more intense chemical weathering during the Early Cretaceous and a variable intensity of weathering during the Late Cretaceous, Early Eocene, Oligocene–Early Miocene, Miocene–Pliocene and recent times. Moreover, weathered marls of the Late Cretaceous and Miocene–Pliocene horizons also exhibit relatively low but variable intensity of chemical weathering. Our results indicate that siliciclastics of the Early Cretaceous were primarily derived from the Reguibat Shield and the Mauritanides, in the SW of the basin, whereas those of the Miocene–Pliocene had varying sources that probably included western Anti-Atlas (NE part of the basin) in addition to the Reguibat Shield and the Mauritanides.