Acta Geochimica (v.28, #2)

Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China by Ping Shen; Xiaofeng Wang; Yin Xu; Baoguang Shi; Yongchang Xu (119-124).
The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals: δ $$ D_{CH_4 } $$ >−200‰, −250‰<δ $$ D_{CH_4 } $$ <-−200‰ and δ $$ D_{CH_4 } $$ <−250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δ $$ D_{CH_4 } $$ values are higher than −200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: −250‰<δ $$ D_{CH_4 } $$ <−200‰, the δ $$ D_{CH_4 } $$ values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2-reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δ $$ D_{CH_4 } $$ <−250‰, and relatively heavy carbon isotopic composition. There is a fairly strong negative correlation between the carbon isotopic composition and the hydrogen isotopic composition. The generation mechanism and pathway of carbon, and the hydrogen isotopic composition of biogenic gas may be used to ascertain whether biogenic gas samples from the natural world are of industrial utilization value. In general, the biogenic gas formed by way of acetic fermentation is not propitious to the formation of gas reservoirs.
Keywords: biogenic gas; isotope; generation pathway

Geological, petrological and geochemical studies indicated that there are two distinct types of granitoid rocks: older quartz diorites to granodiorite assemblage and younger granitoids, the latter occurring in two phases. The older granitoids have a meta-aluminous chemistry and a calc-alkaline character, with high MgO, Fe2O3, TiO2, CaO, P2O5, Sr and low SiO2, K2O, and Rb. Their major and trace elements data, together with low 87Sr/86Sr ratios (0.7029±0.0008) are indicative of I-type affinities. The second- and third-phase granitoids range from calc-alkaline to alkaline, respectively. The second-phase granitoids have a peraluminous chemistry and high Sr, Ba, CaO, MgO, Al2O3 and Ti2O and low SiO2, K2O, Nb, Y and Rb relative to the third-phase granitoids. The corundum normative nature and field observations suggested that it was formed by partial melting of the lower crust. The third-phase granitoids are alkaline in nature and characterized by higher SiO2, Rb, Y, Nb and lower MgO, Sr and Ba values than the younger granitoids (phase II). They are A-type granitoids which were generated from below or within the existing continental crust.
Keywords: origin and geochemistry; Pan-African granitoid rocks; Gabal Um Shomer area; southwestern Sinai, Egypt

The Fankou Pb-Zn deposit is a very important and famous deposit in China. The time of Pb-Zn enrichment has been debated for a long time in this deposit. A total of seventeen samples of three sections were taken from the Fankou mine for the study of mineralization time and the mechanism of ore formation. The samples were analyzed by microscope, Soxhlet-extract, GC, and GC/MS methods. The results indicated that organic bulk parameters vary with the Pb-Zn contents in different samples and clearly were influenced by ore sulfide formation. Organically geochemical parameters (MPI 1, CPI) indicate that the paleotemperatures in the Fankou deposit are lower than 80°C in all three sections. Sulfides in the wall rocks might occur mainly during synsedimentation or early diagenesis by BSR or partly by PR, rather than by TSR at such low temperatures, this stage may be the first mineralization stage. Sulfides near the faults might be formed by TSR after sedimentation, this stage may be the second mineralization stage.
Keywords: organic geochemistry; ore formation; bacterial sulfate reduction; thermochemical sulfate reduction; Fankou Pb-Zn deposit, China

The Oban Basement Massif of southeastern Nigeria is composed of metamorphosed rocks including phyllites, schists, gneisses and amphibolites cut by pegmatitic dykes of varying length and thickness, which intruded the metamorphic rocks. Preliminary geochemical study and analysis of these pegmatites from western Oban Massif at Uyanga, Akwa Ibami, Iwuru I, Iwuru II and Igbofia showed that the pegmatites are highly albitized. This is inconsistent with earlier postulations that the pegmatites in this part of Nigeria are barren. Indices of fractionation such as Ba/Rb, K/Rb, Na/K, K/Cs, K/Ba reveal that the pegmatites are mineralized and different discrimination plots show that they are enriched in Li, Be, Sn, Ba, Ta, Ni, Cs, Sn and Zn. Rare metal indicative elements such as Ta, Nb, Rb, Cs, and Sn are enriched in the pegmatites, confirming that the pegmatites are mineralized.
Keywords: Precambrian pegmatite; mineralization; Oban Massif; rare-earth element

Detailed REE and trace elements geochemical studies of the Zhoutan Group metasedimentary rocks in central Jiangxi Province, China, and rock-forming minerals such as garnet were conducted and the results showed that the REEs are partly present in the rock-forming minerals and are dominantly contained in the lattice of accessory minerals. In the process of metamorphism the REEs between garnet porphyroblast and rock and the partitioning of REEs between garnet and the host rock is obviously controlled by the chemical composition of the system. The REEs compositions of metamorphic veins and their minerals display remarked lanthanide tetrad effects and the element pairs Zr-Hf, Y-Ho, Pb-Nd and U-Th have also experienced a certain degree of fractionation with respect to the metasedimentary rocks and they can be used as discriminating indicators to some extent for the occurrence of fluid processes in the process of metamorphism of the Zhoutan Group.
Keywords: REE; garnet; metasedimentary rock; Zhoutan Group; central Jiangxi Province

Disturbance of the zircon U-Pb isotopic system has been investigated extensively, but mostly in lab, in the last decades. Here, we reported a field-based study on intensive sericitization, K-feldsparthization and the impacts of mylonitization on zircons from the Fangcheng syenites. The Fangcheng syenites occur in the eastern part of the Qinling orogen and consist mainly of aegirine-augite syenite, aegirine nepheline syenite, biotite syenite and hornblende nepheline syenite. Zircons from the slightly sericitized aegirine augite syenite are colorless, transparent crystals and exhibit well-developed oscillatory and sector zoning on the cathodoluminescence (CL) images which are typical of magmatic zircons from alkaline rocks. Zircon U-Pb determinations by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) showed that the syenite was formed in Neoproterozoic time, the weighted average of 206Pb/238U ages is 844.3±1.6 Ma (MSWD=0.86). In contrast, the hydrothermally altered zircons (hydrothermal zircon) from the intensively sericitized, K-feldsparthized, and weakly mylonitized aegirine augite syenite are conglomerates, yellowish to brown in color, generally translucent and internally textureless. The CL and backscatter electron (BSE) images of hydrothermal zircons exhibit fractured, textureless or mosaic textures, and occasionally show “sponge texture” with the veinlets and inclusions of K-feldspar; however, relicts of magmatic oscillatory zoning can still be discerned locally in individual grains. LA-ICPMS analyses of the hydrothermal zircons demonstrated that the zircons are chemically inhomogeneous, with enhanced and widely varied Pb, U, and Th contents. The U and Th contents of the hydrothermal zircons are estimated to be 32×10−6−1550×10−6 and 188×10−6−4059×10−6, respectively, with Th/U ratios within the range of 0.7–44.9. 206Pb/238U apparent ages of the hydrothermal zircons are negatively correlated with the contents of U, and radiogenic and common Pb.As the U and Th concentrations of the magmatic zircons are rather low, the α-decay doses (3.65×1014−2.04×1015 α-decay events/mg) are much lower than those at the first percolation point (3.5× 1015 a-decay events/mg), thus, Pb mobility resultant from diffusion could be safely neglected. Disturbance of the U-Pb isotopic system of zircons is most likely to be attributed to the intensive sericitization and K-feldsparthization coupled with mylonitization, the hydrothermal fluids reacted with zircons along the rims and fractures of the distorted zircon crystals, giving rise to the chemically inhomogeneous hydrothermal zircons through a series of complicated mechanisms such as dissolution-reprecipitation. The significance of the U-Pb age (the lower intercept age on the discordia U-Pb plot) of hydrothermal zircons is uncertain. We argued that interpretations of the hydrothermal zircon data as the age of hydrothermal events or hydrothermal ore-forming processes are questionable and hence cautions must be taken.
Keywords: zircon; hydrothermal alteration; mylonitization; U-Pb system; alkali-syenite; Fangcheng

In this study, the author determined fluorine in drinking water and urine of residents who are divided into four age groups (5, 12, 35–44, 65–74 aged), living in Huangling City, Shaanxi Province and at 6 villages of Qin’an County, Gansu Province, P.R.China. Some residents are living in fluorine exposure areas. A total of 929 residents (463 females and 466 males) involved in the study were selected from 7 tap water systems. Drinking water samples were collected from each area and analyzed using the fluoride ion-selective method. No positive correlation relationship was found between fluorine concentrations in urine and those in drinking water in the area where the fluorine concentrations of drinking water are within the range of 1–2 mg/L. The fluorine absorbed by resistents of different ages is different in amount. With the same concentrations of fluorine in drinking water, more fluorine would be absorbed by young residents than old residents. No difference can be seen in absorption amount of fluorine among different genders.
Keywords: fluoride; urinary fluoride; ion-selective method

The purpose of this study is to determine the degree of contamination caused by polycyclic aromatic hydrocarbons (PAHs) in oily sludge and soils around it in the Zhongyuan Oilfield. The contents of polycyclic aromatic hydrocarbons in oily sludge samples were determined with HPLC. The contents of PAHs of oily sludge from three different oil production plants vary from high to low in the order of the Wenming oily sludge dumping site of No. 3 Oil Production Plant (3W)>the Mazhai oily sludge dumping site of No. 3 Oil Production Plant (3M)>the Wen’er oily sludge dumping site of No. 4 Oil Production Plant (4W). Naphthalene, acenaphthylene, acenaphthene, fluorine and phenanthrene are the major pollutants of PAHs in oily sludge. The contents of PAHs in soil samples around the oily sludge dumping sites vary widely from 434.49 to 2408.8 ng/g. Naphthalene, acenaphthene, fluorine, phenanthrene and pyrene are the characteristic factors of PAHs in soil samples of 3M and 3W, and naphthalene, acenaphthene, fluorine and phenanthrene are the characteristic factors of PAHs in soil samples of 4W. According to these data and the ratios of Fl/Py, PAHs in oily sludge samples come mainly from petrogenic sources, and soil samples are divided into petrogenic soil samples and mixed-source soil samples, and both petrogenic and pyrogenic soil samples in terms of the sources of PAHs. The classification by Nemero index P indicates that soils around the oily sludge dumping sites have been seriously polluted.
Keywords: oily sludge; soil; PAH; Nemero index P

Study on the adsorption kinetics of orthophosphate anions on layer double hydroxide by Shuchuan Peng; Lü Lü; Jin Wang; Lu Han; Tianhu Chen; Shaotong Jiang (184-187).
A kinetic study was conducted on the adsorption of orthophosphate anions on layer double hydroxide (LDH). The adsorption has proved itself to be a spontaneous endothermic process and is large in capacity and rate. The adsorption isotherm correlates well with the Freundlich model, and a rise in temperature will lead to an increase in adsorption efficiency. Additionally, the results suggested that the adsorption is an entropy-increasing process and is in good agreement with the pseudo-second order kinetics. The free energy (ΔG) of adsorption of orthophosphate onto LDH varies within the range of −1.75–−3.34 kJ/mol, the enthalpy (ΔH) varies by 7.96 kJ/mol and the entropy (ΔS) by 33.59 kJ/mol. The adsorption activation energy is 8.3 kJ/mol, showing that the adsorption of orthophosphate onto LDH is determined to be a physical adsorption.
Keywords: layer double hydroxide; orthophosphate anion; adsorption

The method of principal component analysis was applied to systematical research on the soil multi-media environment, including soil, surface water, ground water, waterbody sediment and agricultural crops, as well as pollution-inducing wastewater, mullock (or waste ore) and slag in the periphery of a large-sized Pb-Zn mining and smelting plant in a karst area of Guangxi Zhuang Autonomous Region. The results revealed that soils in the area studied have been heavily polluted by Cd, Zn, Pb and Hg, and the levels of these metals in the samples of agricultural crop greatly exceed the standards. The above-mentioned pollutants exist in all soil-multi-media environments. The mullock, slag, wastewater, surface water, ground water, soil, and agricultural crops constitute a composite ecological chain. Therefore, the improper disposal of mullock and slag, and the use of polluted wastewater for agricultural irrigation are the main causes of soil pollution. Heavy metals in the soil have three transition progresses: point (improved soil with slag, ground water inflow plot), linear (river transition) and non-point transition (regional pollution by slag) patterns, and the tailing yard is the most important locus for heavy metals to release into the environment.
Keywords: karst region; Pb-Zn mining and smelting plant; soil; principal component analysis; soil-multi-media environment; heavy meal pollution

With lamprophyre and pyrite from the Laowangzhai gold deposit, Yunnan Province, China, as starting materials, and at pressures from 1.5 to 3.0 GPa and temperatures from 1160 160 to 1560°C, an experimental study was carried out on the liquid immiscibility of lamprophyre-sulfide melt at high temperature and ultra-high pressure in the DS-29A cubic 3600T/6-type high pressure apparatus. Results showed that the liquid immiscibility of lampropyre- sulfide melt in the magmatic system would happen during the early magmatic evolution (high temperature and high pressure conditions) and was controlled by temperature and pressure. The sulfide melt which was separated from the lamprophyric melt would make directional movement in the temperature and pressure field and assemble in the low-temperature and low-pressure region. Because the density of SM is higher than that of the lamprophyric melt, the former would gather together at the bottom of the magma chamber and there would exist a striking boundary between the two melts. On the other hand, the results also suggested that there would be little possibility for lamprophyric magma to carry massive gold, and lamprophyres can’t provide many of ore-forming materials (Au) in the processes of gold mineralization.
Keywords: liquid immiscibility of lamprophyre-sulfide melt; experiment; high temperature and ultra-high pressure

In the second phase of the Chang’E Program an unmanned lunar rover will be launched onto the Moon. When ground scientists get a full understanding of the chemical composition of lunar soil around the rover, they can make more detailed survey plans for the rover and various payloads onboard so as to satisfy their scientific objectives. There is an obvious relationship between the reflectance of lunar soil and its chemical characteristics. Both principal component analysis (PCA) and support vector machine (SVM) models were applied to establishing the relationship between the reflectance spectra and chemical compositions of lunar highland and mare soil samples sent back by Apollo missions 11, 12, 14, 15, 16 and 17 and measured by Lunar Soil Characterization Consortium (LSCC). PCA was used to reduce and select the features of the reflectance spectra of lunar soil samples. Then, these features were put into SVM to estimate the abundances of various chemical components in lunar soil. We also compared the results of our measurement with those obtained by the SVM model [partial least squares (PLS)] and the principal component regression (PCR) model reported in literature. Our studies showed that with the exception of TiO2, the results of prediction of the abundances of chemical compounds in lunar soil by our model are much more reliable than those reported in literature. The reflectance spectra of lunar soil are closely related to the materials from which it was derived.
Keywords: lunar exploration; lunar soil; reflectance spectrum; pattern recognition; PCA; SVM; chemical composition; abundance

The influence of volcanism on paleoclimate in the northeast of China: Insights from Jinchuan peat, Jilin Province, China by Xumei Mao; Shenggao Cheng; Yetang Hong; Yongxuan Zhu; Fenglin Wang (212-219).
Just like contemporary sediments, peat itself is a good repository of information about climate change, the effects of volcanic activity on climate change have been truly recorded in peat, since it is a major archive of volcanic eruption incidents. A section of sand was identified as tephra from the Jinchuan peat, Jilin Province, China, for the grains look like slag with surface bubbles and pits, characterized by high porosity, and loose structure with irregular edges and corners. According to the peat characteristics of uniform deposition, the tephra was dated at 2002–1976 a B.P. by way of linear interpolation, so the time of volcanic eruption was 15 B.C.–26 A.D. (the calibrated age). While the geochemical characteristics of tephra in this study are quite the same as those of tephra from the Jinlongdingzi volcano at Longgang and from alkaline basaltic magma, with the contents of SiO2<55%, and the similar contents to Al2O3 and Fe, but the contents of Na2O>K2O. We speculated that the tephra in this study came from the Longgang volcano group. Compared with 11 recorded volcanic eruption events as shown on the carbon and oxygen isotope curves of the Jinchuan peat cellulose, it is obviously seen that adjacent or large-scale volcanic eruptions are precisely corresponding to the minimum temperature and humidity. It seems that these volcanic eruptions indeed affected the local climate, leading to the drop of regional temperature and humidity. As a result, there was prevailing a cold and dry climate there, and all these changes can be well recorded in peat. So the comparison of volcanic eruption events with information about climate change developed from peat, can provide strong evidence for the impact of volcanism on climate change.
Keywords: tephra; peat; 14C age; volcanic eruption; climate change

A study on the adsorption of chromium on laterite from Guizhou Province, China by Xiaohong Yu; Lijun Zhu; Baiwei Guo; Shouyang He (220-226).
The adsorption behaviors of Cr(VI) on laterite from Guizhou Province were studied in this paper, and the adsorption mechanism was discussed as well. Results showed that different mineral compositions in the laterite would cause differences in the capacity of laterite to absorb Cr(VI). Gibbsite, iron oxide minerals and non-crystalloids are the main contributors to enhancing the capacity of laterite to absorb Cr(VI). The pH of the solution is an important factor affecting the adsorption of Cr(VI) on laterite. Acidic environment (pH=2–5) is favorable to the adsorption of Cr(VI). The amount of adsorbed Cr(VI) decreases with increasing pH of the solution. With increasing initial concentrations of Cr(VI), the amount of adsorbed Cr(VI) increases first, and then decreases. The optimal adsorption concentration of Cr(VI) on laterite is 250 μg/mL. The adsorption of Cr(VI) on laterite is a rapid process, about 80% Cr(VI) will be adsorbed within 2 hours. And the adsorption of Cr(VI) on kaolinite is a slow process.
Keywords: adsorption; laterite; chromium (VI); pH value; isotherm; kinetics

The aquatic environment capacity possesses the largest tolerance to pollutants. We can improve the calculating precision using the conceptual net method. Its basic ways involved in calculation include the following aspects: first, to establish the flow continuity equation, flow motion equation, water quality equation and other mathematical models; at the same time, to conceptualize the reservoir studied, divide the reservoir into several functional areas, and use the one-dimensional section-beginning calculation model to calculate all cross-sections of each functional area; then, to superimpose the environmental capacity of each functional section to get the aquatic environment capacity of the entire two-dimensional space; and finally, to introduce how to make use of the conceptual net to calculate the aquatic environment capacity in terms of the actual reservoir’s situation.
Keywords: conceptual net; reservoir; environmental capacity