Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

Glacier change and glacier runoff variation in the Tuotuo River basin,the source region of Yangtze River in western China

Glaciers in the Tuotuo River basin, western China, have been monitored in recent decades by applying topographical maps and high-resolution satellite images. Results indicate that most of glaciers in the Tuotuo River basin have retreated in the period from 1968/1971 to 2001/2002, and their shrinkage area is 3.2% of the total area in the late 1960s. To assess the influence of glacier runoff on river runoff, a modified degree–day model including potential clear-sky direct solar radiation has been applied to the glaciated regions of the river basin over the period 1961–2004. It was found that glacier runoff has increased in the last 44 years, especially in the 1990s when a two-thirds increase in river runoff was derived from the increase in glacier runoff caused by loss of ice mass in the entire Tuotuo River basin.     

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.     

Mapping susceptibility of rainfall-triggered shallow landslides using a probabilistic approach

To prepare a landslide susceptibility map is essential to identify hazardous regions, construct appropriate mitigation facilities, and plan emergency measures for a region prone to landslides triggered by rainfall. The conventional mapping methods require much information about past landslides records and contributing terrace and rainfall. They also rely heavily on the quantity and quality of accessible information and subjectively of the map builder. This paper contributes to a systematic and quantitative assessment of mapping landslide hazards over a region. Geographical Information System is implemented to retrieve relevant parameters from data layers, including the spatial distribution of transient fluid pressures, which is estimated using the TRIGRS program. The factor of safety of each pixel in the study region is calculated analytically. Monte Carlo simulation of random variables is conducted to process the estimation of fluid pressure and factor of safety for multiple times. The failure probability of each pixel is thus estimated. These procedures of mapping landslide potential are demonstrated in a case history. The analysis results reveal a positive correlation between landslide probability and accumulated rainfall. This approach gives simulation results compared to field records. The location and size of actual landslide are well predicted. An explanation for some of the inconsistencies is also provided to emphasize the importance of site information on the accuracy of mapping results.     

Experimental study on the deterioration and natural remediation of the Ariake Sea tidal mud caused by the sea laver treatment acid practice and the upward seepage of pore water liquid

This study presents a laboratory study of the following two aspects: (1) the influence of sea laver treatment acid on the geoenvironmental properties of Ariake Sea tidal mud, and (2) the natural remediation effect on the sea laver treatment acid contaminated Ariake Sea tidal mud caused by the upward seepage of pore water liquid in the mud. Firstly, the mechanisms of the transport of sea laver treatment acid in the Ariake Sea tidal mud and the generation mechanisms of the upward seepage flow in the Ariake Sea tidal mud are discussed. Secondly, a series of one-dimensional laboratory infiltration tests were carried out to investigate the deterioration of the Ariake Sea tidal mud caused by the sea laver acid treatment practice. Test results reveal that the acid treatment practice caused considerable change in the geochemical properties of the mud in terms of increase in sulfide content and decrease in pH value. After the treatment by the sea laver treatment acid, the sulfide content of the mud even exceeded the safe limit value for the benthos, which represents undesirable living condition for benthos. Thirdly, series of laboratory fresh seawater infiltration tests for the deteriorated Iida site mud were conducted to illustrate this natural remediation efficiency. It is found that with the infiltration of the fresh seawater, the sulfide content of the Iida site mud was considerably reduced and pH value increased to an acceptable range for benthos living in the tidal flat mud. With the increase in the infiltration time and the hydraulic gradient, the remediation efficiency could be increased.     

Timing of UHP metamorphism in the Hong’an area,western Dabie Mountains,China: evidence from zircon U–Pb age,trace element and Hf isotope composition

The Hong’an area (western Dabie Mountains) is the westernmost terrane in the Qinling-Dabie-Sulu orogen that preserves UHP eclogites. The ages of the UHP metamorphism have not been well constrained, and thus hinder our understanding of the tectonic evolution of this area. LA-ICPMS U–Pb age, trace element and Hf isotope compositions of zircons of a granitic gneiss and an eclogite from the Xinxian UHP unit in the Hong’an area were analyzed to constrain the age of the UHP metamorphism. Most zircons are unzoned or show sector zoning. They have low trace element concentrations, without significant negative Eu anomalies. These metamorphic zircons can be further subdivided into two groups according to their U–Pb ages, and trace element and Lu–Hf isotope compositions. One group with an average age of 239 ± 2 Ma show relatively high and variable HREE contents (527 ≥ Lu_N ≥ 14) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.00008–0.000931), indicating their growth prior to a great deal of garnet growth in the late stage of continental subduction. The other group yields an average age of 227 ± 2 Ma, and shows consistent low HREE contents and ¹⁷⁶Lu/¹⁷⁷Hf ratios, suggesting their growth with concurrent garnet crystallization and/or recrystallization. These two groups of age are taken as recording the time of prograde HP to UHP and retrograde UHP–HP stages, respectively. A few cores have high Th/U ratios, high trace element contents, and a clear negative Eu anomaly. These features support a magmatic origin of these zircon cores. The upper intercept ages of 771 ± 86 and 752 ± 70 Ma for the granitic gneiss and eclogite, respectively, indicate that their protoliths probably formed as a bimodal suite in rifting zones in the northern margin of the Yangtze Block. Young Hf model ages (T _DM1) of magmatic cores indicate juvenile (mantle-derived) materials were involved in their protolith formation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Distribution of the C37 tetra-unsaturated alkenone in Lake Qinghai, China: A potential lake salinity indicator

The alkenone unsaturation index U^K′₃₇ has been applied to reconstruct past temperature changes in both marine and lacustrine systems. However, few studies have addressed whether the relative abundance of the C_37:4 alkenone to the total C₃₇ production (%C_37:4) can reflect surface salinity changes in lacustrine systems. Here we present long-chain C₃₇ alkenone distribution patterns in surface sediments from Lake Qinghai, China. Surface sediments were sampled over a large range of surface salinity changes (1.7-25 g/l) within Lake Qinghai and its surrounding lakes, while temperature differences at these sampling locations should be relatively small. We have found that %C_37:4 varies from 15% to 49% as surface salinity decreases. We tentatively describe this %C_37:4-salinity link with a general linear regression: %C_37:4 = 53.4 (±7.8) − 1.73 (±0.45) × S (n = 28, r² = 0.62), although step-wise %C_37:4 changes in response to salinity variation may exist. U^K′₃₇ values vary between 0.10 and 0.16 at these sites and the inferred range of lake water temperature changes is ∼2-3 °C, suggesting that U^K′₃₇ largely reflects temperature signal across a large salinity range, consistent with previous findings that U^K′₃₇ can indicate temperature changes over a large diversity of environmental settings. We have also found that U^K′₃₇ values are correlated with salinity changes (r² = 0.4), and thus cannot exclude potential temperature effect on %C_37:4 and salinity effect on U^K′₃₇ in this study. However, even extreme estimates of temperature differences within the lake are still unable to explain the observed %C_37:4 changes. We therefore suggest that %C_37:4 could be used to infer past lake salinity changes at a regional scale.     

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.