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.     

水对硅酸盐岩体系部分熔融行为的影响：第二临界端点的重要意义

水对硅酸盐岩体系的许多物理-化学行为有着非常重大的影响.具体对部分熔融过程来说,水可以显著地降低熔融温度、改变熔体性质、影响微量元素在固-液相之间的分配.近年来,科学家们就大量水对硅酸盐岩体系的部分熔融过程的影响进行了许多的高压实验,他们主要关注第二临界端点对熔融过程的重要作用:第二临界端点的出现极大地改变着部分熔融过程中的基本相关系.本文主要针对这些高压实验研究做一总结,并对未来研究方向做一初步探讨.     

Density of peridotite melts at high pressure

Densities of ultramafic melts were determined up to 22 GPa by relative buoyancy experiments. Olivine and diamond were used as buoyancy markers. We confirmed that the density crossover of PHN 1611 melt and its equilibrium olivine (Fo94) occurs at around 13.5 GPa and 2030 °C and that olivine floats from deeper regions in the magma ocean of the primordial terrestrial mantle. The comparison of the compression curves of basic and ultrabasic melts implies that the basic melt is more compressible. This can be explained by the difference in the amount of compressible linkage of SiO_n and AlO_n polyhedra. The interstitial melt trapped by the density crossover can be the cause of the impedance anomaly of the seismic wave in the deep upper mantle.     

Water chemistry and control of weathering of Pichola Lake,Udaipur District,Rajasthan, India

The water chemistry of Pichola lake revealed that it is dominated by Na and HCO₃. The lake water chemistry strongly reflects the dominance of continental weathering aided by anthropogenic activity, such as tourist influx, developmental activities in the catchment area, and disposal of untreated municipal and domestic sewage into the lake basin. The supply of major ions is mainly through weathering of the silicate rock exposed in the drainage basin and the contribution from saline and alkaline soils/groundwater because of the semiarid conditions of the region. The increase in phosphate loading and consequent depletion of silica suggests biological consumption of the latter. The observed chemical data of Pichola lake was used to predict the mineral assemblages in the carbonate and aluminosilicate system. It demonstrates that calcite and dolomite are the possible minerals that are in equilibrium with the lake water system and that the lake water chemistry is in the range of stability of kaolinite.     

Viscosity of albite melt at high pressure and high temperature

 The viscosity of albite (NaAlSi₃O₈) melt was measured at high pressure by the in situ falling-sphere method using a high-resolution X-ray CCD camera and a large-volume multianvil apparatus installed at SPring-8. This system enabled us to conduct in situ viscosity measurements more accurately than that using the conventional technique at pressures of up to several gigapascals and viscosity in the order of 10⁰ Pa s. The viscosity of albite melt is 5.8 Pa s at 2.6 GPa and 2.2 Pa s at 5.3 GPa and 1973 K. Experiments at 1873 and 1973 K show that the decrease in viscosity continues to 5.3 GPa. The activation energy for viscosity is estimated to be 316(8) kJ mol⁻¹ at 3.3 GPa. Molecular dynamics simulations suggest that a gradual decrease in viscosity of albite melt at high pressure may be explained by structural changes such as an increase in the coordination number of aluminum in the melt. Received: 6 January 2001 / Accepted: 27 August 2001     

Emplacement age and isotope geochemistry of Sung Valley alkaline–carbonatite complex, Shillong Plateau, northeastern India: implications for primary carbonate melt and genesis of the associated silicate rocks

The early Cretaceous (Albian–Aptian) Sung Valley ultramafic–alkaline–carbonatite complex is one of several alkaline intrusions that occur in the Shillong Plateau, India. This complex comprises calcite carbonatite and closely associated ultramafic (serpentinized peridotite, pyroxenite and melilitolite) and alkaline rocks (ijolite and nepheline syenite). Field relationship and geochemical characteristics of these rocks do not support a genetic link between carbonatite and associated silicate rocks. There is geochemical evidence that pyroxenite, melilitolite and ijolite of the complex are genetically related. Stable (C and O) and radiogenic (Nd and Sr) isotope data clearly indicate a mantle origin for the carbonatite samples. The carbonatite Nd (+0.7 to +1.8) and Sr (+4.7 to +7.0) compositions overlap the field for Kerguelen ocean island basalts. One sample of ijolite has Nd and Sr isotopic compositions that also plot within the field for Kerguelen ocean island basalts, whereas the other silicate–carbonatite samples indicate involvement with an enriched component. These geochemical and isotopic data indicate that the rocks of the Sung Valley complex were derived from and interacted with an isotopically heterogeneous subcontinental mantle and is consistent with interaction of a mantle plume (e.g. Kerguelen plume) with lithosphere. A U–Pb perovskite age of 115.1±5.1 Ma obtained for a sample of Sung Valley ijolite also supports a temporal link to the Kerguelen plume. The observed geochemical characteristics of the carbonatite rocks indicate derivation by low-degree partial melting (0.1%) of carbonated mantle peridotite. This melt, containing a substantial amount of alkali elements, interacted with peridotite to form metasomatic clinopyroxene and olivine. This process could progressively metasomatize lherzolite to form alkaline wehrlite.     

Fluid inclusions in mantle xenoliths

Fluid inclusions in olivine and pyroxene in mantle-derived ultramafic xenoliths in volcanic rocks contain abundant CO₂-rich fluid inclusions, as well as inclusions of silicate glass, solidified metal sulphide melt and carbonates. Such inclusions represent accidentally trapped samples of fluid- and melt phases present in the upper mantle, and are as such of unique importance for the understanding of mineral–fluid–melt interaction processes in the mantle. Minor volatile species in CO₂-rich fluid inclusions include N₂, CO, SO₂, H₂O and noble gases. In some xenoliths sampled from hydrated mantle-wedges above active subduction zones, water may actually be a dominant fluid species. The distribution of minor volatile species in inclusion fluids can provide information on the oxidation state of the upper mantle, on mantle degassing processes and on recycling of subducted material to the mantle. Melt inclusions in ultramafic xenoliths give information on silicate–sulphide–carbonatite immiscibility relationships within the upper mantle. Recent melt-inclusion studies have indicated that highly silicic melts can coexist with mantle peridotite mineral assemblages. Although trapping-pressures up to 1.4 GPa can be derived from fluid inclusion data, few CO₂-rich fluid inclusions preserve a density representing their initial trapping in the upper mantle, because of leakage or stretching during transport to the surface. However, the distribution of fluid density in populations of modified inclusions may preserve information on volcanic plumbing systems not easily available from their host minerals. As fluid and melt inclusions are integral parts of the phase assemblages of their host xenoliths, and thus of the upper mantle itself, the authors of this review strongly recommend that their study is included in any research project relating to mantle xenoliths.     

Elemental and Sr–Nd isotopic compositional disparity of riverine sediments around the Yellow Sea: Constraints from grain-size and chemical partitioning

To obtain a better understanding of the source compositions of the river sediments around the Yellow Sea and their relationship with source rocks, elements and strontium-neodymium (Sr–Nd) isotopes of different grain-sizes (silt and clay populations) and chemical (labile and residual phases) fractionations in riverine sediments were studied extensively. These results clearly revealed a systematic compositional disparity between Korean river (KR) and Chinese river (CR) sediments, especially in the residual (detrital) fraction. The geochemical dissimilarity between these might reflect inherited signatures of their source rocks but with minor control from chemical weathering. In particular, the remarkable enrichment of some elements (iron (Fe) and magnesium (Mg)) and the behavior of large ion lithophile elements (e.g., barium (Ba), potassium (K) and Sr) during weathering as well as less-radiogenic Sr isotopic compositions implies that CR sediments might be weathering products of relatively more mafic rocks, with abundant ferromagnesian and plagioclase feldspar minerals, compared with KR sediments derived from silicic granites with relatively higher quartz and potassium feldspar contents. This different petrological rationale is clearly evident in an A–CN–K diagram, which estimated the source rock of CR sediments as granodioritic, a composition that reflects accurately the average composition of weathered continental crust in China. The recognition of such geochemical systematics in two river sediments, especially in grain-size and chemically partitioned data, may contribute to the establishment of provenance tracers for the Yellow Sea and East China Sea sediments with multi-sources as well the dust deposition in the western Pacific.     

Trace element partitioning between amphibole and hydrous silicate glasses at 0.6–2.6 GPa

Partitioning behavior between amphibole and silicate glass of thirty-three minor and trace elements(Sc,Ti, V, Cr, Co, Rb, Sr, P, Y, Zr, Nb, Cs, Ba, K, La, Ce, Pr,Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, Pb,Th, and U) have been determined experimentally. Products of crystallization of hydrous basalt melts from 0.6 GPa/860 °C up to 2.6 GPa/970 °C were obtained in a multianvil apparatus. Major and trace element compositions of amphibole and glass were determined with a combination of electron microprobe and laser ablation inductively coupled plasma mass spectrometry. The main mineral phase is calcic amphibole, and the coexisting glass compositions are tonalite, granodiorite, and granite. The compatibility of rare earth elements increase at 915 °C and then decrease at 970 °C, but the compatibility of most of these elements shows a continued, significant increase with increasing pressure. For high-field strength elements, large ion lithophile elements, actinide compatibility decrease with increasing temperature or pressure, but transition metals show a continued increase in compatibility within the temperature–pressure conditions. From mathematical and graphical fitting, we determined best-fit values for the ideal ionic radius(r_0, 1.01–1.04 ?), the strain-free partitioncoefficient(D_0, 1.18–1.58), and apparent Young's modulus(E, 142–370 GPa) for the M4 site in amphibole according to the lattice strain model. The D_0^M4 for rare earth elements rises at 915 °C and then drops at 970 °C at 0.6 GPa.However, the D_0^M4 values are positively proportional to the pressure for rare earth elements in the amphibole-glass pairs at 0.6–2.6 GPa and 970 °C. Furthermore, the derived best-fit values for r_0^M4 and E^M4 are almost constant and trend to increase with rising temperature and pressure,respectively. The partition coefficient is distinctly different for different melt compositions. The rare earth elements become more enriched in amphibole if the quenched glass is granodiorite or granite compared to the tonalitic glasses.     

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface.With the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon burial.As compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon cycle.Soil carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric CO2drawdown.Thus,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively differentiated.In this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North China.Based on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite veins.The modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric CO2.The low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric CO2sink.Nevertheless,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million years.Finally,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.