Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Triassic Nb-enriched basalts, magnesian andesites, and adakites of the Qiangtang terrane (Central Tibet): evidence for metasomatism by slab-derived melts in the mantle wedge

New chronological, geochemical, and isotopic data are reported for Triassic (219–236 Ma) adakite-magnesian andesite-Nb-enriched basaltic rock associations from the Tuotuohe area, central Qiangtang terrane. The adakites and magnesian andesites are characterized by high Sr/Y (25–45), La/Yb (14–42) and Na₂O/K₂O (12–49) ratios, high Al₂O₃ (15.34–18.28 wt%) and moderate to high Sr concentrations (220–498 ppm) and ε_ND (t) (+0.86 to +1.21) values. Low enrichments of Th, Rb relative to Nb, and subequal normalized Nb and La contents, and enrichments of light rare earth elements combine to distinguish a group of Nb-enriched basaltic rocks (NEBs). They have positive ε_ND (t) (+2.57 to +5.16) values. Positive correlations between Th, La and Nb and an absence of negative Nb anomalies on mantle normalized plots indicate the NEBs are products of a mantle source metasomatized by a slab melt rather than by hydrous fluids. A continuous compositional variation between adakites and magnesian andesites confirms slab melt interaction with mantle peridotite. The spatial association of the NEBs with adakites and magnesian andesites define an “adakitic metasomatic volcanic series” recognized in many demonstrably subduction-related environments (e.g., Mindanao arc, Philippines; Kamchatka arc, Russia; and southern Baja California arc, Mexico). The age of the Touhuohe suite, and its correlation with Triassic NEB to the north indicates that volcanism derived from subduction-modified mantle was abundant prior to 220 Ma in the central Qiangtang terrane.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Origin of Fe-Ti Oxide Ores in Mafic Intrusions: Evidence from the Panzhihua Intrusion, SW China

Economic concentrations of Fe–Ti oxides occur as massive,conformable lenses or layers in the lower part of the Panzhihuaintrusion, Emeishan Large Igneous Province, SW China. Mineralchemistry, textures and QUILF equilibria indicate that oxidesin rocks of the intrusion were subjected to extensive subsolidusre-equilibration and exsolution. The primary oxide, reconstructedfrom compositions of titanomagnetite in the ores and associatedintergrowths, is an aluminous titanomagnetite (Usp₄₀) with 40wt % FeO, 34 wt % Fe₂O₃, 16·5 wt % TiO₂, 5·3 wt% Al₂O₃, 3·5 wt % MgO and 0·5 wt % MnO. This compositionis similar to the bulk composition of the oxide ore, as inferredfrom whole-rock data. This similarity strongly suggests thatthe ores formed from accumulation of titanomagnetite crystals,not from immiscible oxide melt as proposed in earlier studies.The occurrence of oxide ores in the lower parts of the Panzhihuaintrusion is best explained by settling and sorting of densetitanomagnetite in the ferrogabbroic parental magma. This magmamust have crystallized Fe–Ti oxides relatively early andabundantly, and is likely to have been enriched in Fe and Tibut poor in SiO₂. These features are consistent with fractionationof mantle-derived melts under relatively high pressures (10kbar), followed by emplacement of the residual magma at 5 kbar.This study provides definitive field and geochemical evidencethat Fe–Ti oxide ores can form by accumulation in ferrogabbro.We suggest that many other massive Fe–Ti oxide depositsmay have formed in a similar fashion and that high concentrationsof phosphorus or carbon, or periodic fluctuation of fO₂ in themagma, are of secondary importance in ore formation. KEY WORDS: ELIP; Fe–Ti oxide ore; layered intrusion; Panzhihua; QUILF     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

The state of land subsidence and prediction approaches due to groundwater withdrawal in China

This article gives a general introduction to land subsidence with the prediction approaches due to withdrawal of groundwater in three subsided/subsiding regions in China: the deltaic plain of Yangtse River (YRDP), North China Plain (NCP), and Fenwei Plain (FP). On YRDP, Shanghai is the typical subsided/subsiding city; on NCP Tianjin is the typical subsided/subsiding city, and on FP Taiyuan is the typical subsided/subsiding city. The subsided area with subsidence over 200 mm on YRDP is about 10,000 km² and the maximum subsided value reached 2.9 m at Shanghai; on NCP the subsided area reached 60,000 km² with the maximum subsidence of 3.9 m at Tianjing; on FP the subsided area is relatively smaller than that on the other two plains and is about 1,135 km² with maximum subsidence of 3.7 m at Taiyuan city. In order to protect the civil and industrial facilities, it is necessary to predict the future development of land subsidence based on present state. Many researchers proposed several approaches to predict the land subsidence due to groundwater withdrawal according to different geological conditions and groundwater withdrawal practice. This article classifies these approaches into five categories: (i) statistical methods; (ii) 1D numerical method; (iii) quasi-3D seepage model; (iv) 3D seepage model; (v) fully coupled 3D model. In China, the former four categories are presently employed in the prediction practice and their merits and demerits are discussed. According to the prediction practice, 3D seepage model is the best method presently.     

Identifying China’s leading world city: a network approach

This paper reports our research on China’s world cities. Formal network analysis of air passenger linkages for recent years among China’s most populous cities and among many of the world’s largest cities allows us to identify the country’s leading world city from among the leading Mainland candidates, Beijing, Shanghai and Guangzhou. We theorize our findings about China’s world cities in relation to both global forces (and China’s increasing entanglement with them) and the policies and actions of the national state. We examine the national and global urban network through a longitudinal, two-level analysis of airline passenger travel for four time points between about 1990 and 2005. We show that Beijing was China’s leading world city at the beginning of the time period, a status it lost nationally in as early as 1995, and then globally 10 years later. On the other hand Shanghai became China’s leading world city, and it acquired this status first nationally in 2000, and then globally in 2005. The changing status of the Chinese capital corresponds to the country’s increasing involvement with the capitalist world economy. Shanghai’s ascendance as the leading world city in China may indicate that global forces have come to play an increasingly important role relative to that of the developmental state.