Acta Geochimica (v.28, #4)

Studies of polycyclic aromatic hydrocarbons (PAHs) in the surface soil were conducted in Huizhou City, which is located in the Pearl River Delta, South China. Sixteen PAHs in 42 soil samples were detected. The results showed that 4 components of PAHs were detectable in all soil samples, and other 12 components were also detectable to some extent. The total PAHs contents range from 35.40 to 534.5 µg/kg with the mean value of 123.09 µg/kg. Soil in Huizhou was slightly polluted by PAHs according to Maliszewska-Kordybach’s study. It can be confirmed that the increase of PAHs contents in the surface soil of Huizhou City is closely connected to human activities. Multivariate analysis was also made in this study. Principal component analysis was used to constrain their origins, and 3 principal components (PCs) were extracted. The results showed that coal combustion and oil spilling made the major contributions to PAHs. Cluster analysis was made and 16 priority PAHs were classified as 4 sorts, and the result revealed the differences in environmental behavior, chemical properties and sources of PAHs.
Keywords: polycyclic aromatic hydrocarbon; surface soil; Huizhou City; source

The origin of anorthosite and associated igneous gabbronorite and ferrodiorite was investigated through detailed study of a typical massif-type anorthosite complex from Gruber, Central Dronning Maud Land, East Antarctica. Field observations showed that the Gruber Complex is made up of gabbronorite-anorthosite pluton which was intruded by ferrodiorite dykes. Systematic samples collected from the Gruber Complex revealed significant geochemical variations within the region. Four rock types have been identified, based on modal proportions of mineral phases and their geochemistry data. Clinopyroxene-gabbronorite and plagioclase-gabbronorite are the two types of gabbronorite with the dominance of clinopyroxene and plagioclase, respectively. Anorthosite is represented by rocks having predominance of plagioclase with minor clinopyroxene. Ferrodiorite is characterized by modal abundance of orthopyroxene and Fe-Ti oxide. Major and trace element systematics showed that all the four rock types are co-magmatic and are related through fractional crystallization. Based on this study, it is reported that clinopyroxene was the first phase to crystallize followed by plagioclase and then Fe-Ti oxides. Furthermore, trace element composition of the parental melt was calculated using LA-ICPMS analysis of the most primitive, pure clinopyroxene found in the clinopyroxene gabbronorite. Our analyses suggested that the parental melt was similar to that of continental arc basalt and showed signatures of subduction-related metasomatism. Based on mineral chemical and geochemical data, it is interpreted that the parent melt went through changing sequence of crystallization which led to the formation of massive anorthosite.
Keywords: massif-type anorthosite; Gruber; East Antarctica; LA-ICPMS; geochemistry

Study on the mechanism of isotope fractionation in soil water during the evaporation process under equilibrium condition by Xiaoxu Sun; Jiansheng Chen; Hongbing Tan; Wenbo Rao; Yongsen Wang; Xiaoyan Liu; Zhiguo Su (351-357).
In this study, with the method of vacuum extraction, two evaporative processes of soil water and free water under equilibrium condition were simulated. For each sample, water vapor was condensed by liquid nitrogen and was collected in four time intervals. From the analysis of hydrogen and oxygen isotopic compositions of the water collected at different times, it was discovered that the isotope fractionation of soil water also follows the mode, which is just the same as the evaporative process of free water. The relationship between the stable hydrogen and oxygen isotopes in residual water showed that the simulative evaporation line was close to the global meteoric water line (GMWL) under the equilibrium condition at about 20°C. Comparison of the two types of evaporative processes indicated that the isotope fractionation and evaporation velocity of soil water were only slightly modified by the Van der Waals force.
Keywords: soil water; evaporative process; equilibrium condition; Rayleigh fractionation

Fluid inclusions in the leucosomes of Wadi Feiran migmatites showed that CO 2 , H2O and (H2O-CO2) fluids were likely to have been present when partial melting began in these rocks. Low salinity, aqueous fluid, to a lesser extent, CO2-rich fluids are the most abundant fluids. The present study suggests that high-density CO2 inclusions were formed at the earliest stage, while H2O inclusions were formed at the late stage. In an intermediate stage, low-density CO2 and H2O, CO2 inclusions were formed. At the early stage of uplift and during melt crystallization, the CO2-bearing vapour was trapped at grain boundaries. At the late stage of uplift, H2O released at the time of crystallization of the melt was trapped as inclusions.
Keywords: migmatite; fluid inclusion; H2O; CO2 ; Wadi Feiran

In this study, the Al13-oxalate gel synthesized from Al13 solution was characterized by XRD, FTIR and MAS 27Al NMR. The results are: 1) the gel shows obvious XRD diffraction peaks, which is different from common Al gels and their oxalate precipitations; 2) the peak of Al-O stretch vibration of Al13-oxalate complexes at 810 cm−1 indicates that the gel was formed directly by the complexes, and the characteristic peaks of IR and solid-state NMR respectively occur at 725 cm−1 and ∼6.1×10−5 chemical shift, which are respectively assigned to (Al-O)Td vibration and (Al-O)4 tetrahedron, suggesting that the gel has a unique Keggin structure; 3) Al13 polyoxocation can directly form gel with oxalate, even in a high-pH environment (=7.8). This finding provides new evidence for the universality of Al13 in natural environments. Through chemical analysis, the chemical formula of the gel was determined to be AlO4Al12(OH)24(H2O)12(C2O4)7/2.
Keywords: Al13 ; Keggin structure; oxalate; gel

This paper deals with the regional and structural framework of the Cretaceous rocks in the Afikpo Basin located in the southeastern part of the Lower Benue Trough. Results from regional tectonics are presented together with those of the microtectonic analysis of microfaults in the Owutu-Afikpo-Adadama area in the basin.The Owutu-Afikpo-Adadama ridge at the north-central part of the basin marks the boundary between the Late Cenomanian-Turonian-Conianian sediments and the Campanian-Maastrichtian sandstones. This ridge trends N45°E on average and is faulted in three main directions, namely: (1) N-S normal faults; (2) NE-SW strike-slip faults; and (3) NW-SE strike-slip faults. The faulted rocks along these brittle discontinuities are mainly cataclastics with internal fracture cleavage and sigmoidal quartz mosaics that are reminiscent of extensional deformation. The cataclasites often bear slickenside striations.The NE-SW and NW-SE strike-slip faults are the results of the youngest brittle events on the Owutu-Afikpo-Adadama ridge. These faults were reactivated after deposition of the Campanian-Maastrichtain sediments (post-depositional faults) and, therefore, are post-Maastrichtain. Microfault analysis of these fault trends suggests an extensional regime that prevailed in the Lower Benue Trough. These results are of significance because this event is least poorly understood and less documented in contrast to the Cenomanian and Santonian events that affected the older Cretaceous strata in this region.
Keywords: brittle deformation; Afikpo Basin (Southeast Nigeria); Cretaceous extensional regime; Lower Benue Trough; Nigeria

The Precambrian basement complex in the southernmost part of North-Central Nigeria is underlain by migmatitic banded gneisses, granitic intrusions and dykes of dolerite, rhyolite porphyry and pegmatite. The rocks are generally felsic, containing modal and normative hypersthene, as well as normative corundum. The basement complex has experienced high-grade regional metamorphism as indicated by the presence of hypersthene and plagioclase of andesine composition. Anatectic melting is suggested by the occurrence of ptygmatic folds, folded gneissose foliation, numerous quartzo-feldspathic veins and lenses of dark-colured, micaceous schistose rocks. Geochemically, the rocks have magnesian, calc-alkalic and strongly peraluminous characteristics. Their overall characteristics suggest derivation from progressive (fractional) partial melting of pelitic rocks during high-grade regional metamorphism, possibly associated with intense hydrothermal activities. The magnesian characteristics reflect close affinity to relatively hydrous, oxidizing melts and source regions in settings broadly related to subduction.
Keywords: North-Central Nigerian Precambrian basement complex; high-grade regional metamorphism; anatectic melting; magnesian characteristics; strongly peraluminous; subduction-related

Analysis of the ore-controlling structure of the Shihu gold deposit, Hebei Province and deep-seated ore-prospecting prediction by Shuyin Niu; Baode Wang; Aiqun Sun; Chao Chen; Zili Wang; Baojun Ma; Wenxue Wang; Xiaoping Jiang; Yongli Zhao; Yincang Gao; Huabin Liu; Jianping Qiu (386-396).
Under the guidance of the theory of mantle-branch structure-associated metallogenesis and on the basis of the geological characteristics, analysis of the ore-forming and ore-controlling structures, the geochemical characteristics of metallogenesis, the source of ore-forming materials, changes in the physical and chemical conditions of metallogenesis, changes in the vertical width of ore veins, and changes in gold grade of the Shihu gold deposit, the mechanism of its metallogenesis was discussed and the rules of vertical variation of ore veins were summarized in this study. It is pointed out that the orebodies under exploitation at present time should be in the middle and upper portions of gold veins in the Shihu gold mining district. Particularly on the basis of the characteristics of mantle-branch structure-associated metallogenesis, it is indicated that metallogenesis is controlled mainly by such ore-forming conditions as temperature and pressure. Deep-seated ore-forming fluids are characterized mainly by injection and precipitation. So the vein bodies in the adjacent metallogenic structures are of obvious comparability, and there would be great prospects for ore search both at depth and in the periphery of the Shihu gold deposit. Therefore, ore prospecting should be strengthened both at depth and in the peripheries.
Keywords: mantle-branch structure; metallogenesis; ore-controlling structure; ore-search prospect; ore prospecting prediction

Based on the research content and conception of dynamics of tectonic ore-forming processes, with the focus on the dynamics and processes of mineral source, ore formation, transport, accumulation, dissipation and mineralization in response to magmatic invasion and metallogenic fluid under tectonic stress, this paper deals with the ore-finding method of fault tectono-geochemistry and its application on the basis of ore deposit genesis, “giant pressure shadow” structure and ore-finding method of tectonic stress field in the Tongchang orefield, expounds the rules of magmatic emplacement and ore fluid migration and concentration under the control of the structural stress field, hence providing the theoretical basis for the localization and prognosis of concealed ores. The fault tectono-geochemical features show that the Cu-Au polymetallic ore deposits (mineralization) in the orefield are closely related with volcano-(exhalation) sedimentation, magmatism and tectono-reworking. Fault tectono-geochemical anomalies can be applied to prognosis of metallogenetic target areas for ore exploration and can provide strong evidence of “giant pressure shadow” structure. In addition, quite a number of important target areas have been defined in combination with the characteristics of the tectonic stress field, and part of the target areas have been proved by practical activities.
Keywords: tectono-geochemistry; dynamics of tectonic ore-forming processes; prognosis of concealed ores; Tongchang Cu-Au polymetallic orefield

Coalbed methane (CBM) is a kind of burgeoning and enormously potential clean energy resource, and the temperature of the thermogenic CBM generation is close to that of the partial annealing zone (PAZ) of apatite fission tracks (AFT). In this study the thermo-tectonic history of the Huainan Coalfield and the potential CBM resource were studied and discussed by using the AFT method.The AFT data indicate that the apparent ages of AFT vary from 45.5 to 199.1 Ma. They are younger than the ages of their host strata (255–1800 Ma) except one sample, and the single-grain ages of AFT can be classified as a single age group for each sample. In combination with the geological setting, modeling results of the AFT ages, average lengths, and the thermal history based on the AFT single-grain ages and length distributions, some preliminary conclusions can be drawn as follows: (1) at least three thermo-tectonic events (in the periods of ∼240, 140 and 80 Ma, respectively) have occurred in the study area since the Late Paleozoic. The occurrence of both the first (during 240–220 Ma) and second (during 160–120 Ma) thermo-tectonic events is possibly responsible for the establishment of the patterns of gas generation and reservoir formation. The second thermo-tectonic event also led to slight accumulation of hydrocarbons and generation of thermogenic gas; (2) the AFT ages of most coal-bearing strata lie between 50 and 70 Ma. They should represent the cooling ages and the ages of inferred uplift and denudation, as well as the possible CBM release history. Therefore, the maximum burial depth of coal-bearing strata and the denudation thickness of the overlying strata are over 3000 and 2000 m in the Upper Cretaceous and Paleogene series, respectively; and (3) subsequently, a spot of secondary biogenic and scarcely thermogenic gas generation occurred due to negligible sedimentation during the Neogene and Quaternary periods. Thus, it can be presumed that subsequent tectonism would destroy the CBM reservoir after its formation in the Huainan Coalfield, especially in its structural development region. These AFT data may be helpful for a better understanding of the thermo-tectonic history of the Huainan Coalfield, as well as of CBM generation, storage and release in the Huainan Coalfield.
Keywords: apatite fission-track (AFT); thermo-tectonic history; coalbed methane (CBM); Huainan Coalfield

Previous studies showed that water chemistry and concentrations of dissolved organic matter (DOM) could affect its molecular conformation and binding characteristics with hydrophobic organic contaminants (HOCs). However, the conformational change of DOM resultant from water chemistry and concentrations of DOM was not extensively investigated; therefore, the contradictory reports regarding the binding property with HOCs were available in literature. In this study, the effects of ionic strength, pH and DOM concentrations on the fluorescence properties of two humic acids (HA), namely Fluka HA and Amherst HA, were investigated by three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) and steady-state fluorescence polarization (FP) techniques. The results not only corroborated previous observations obtained by other investigators, but revealed some new information about the fluorescence properties and molecular conformation of the humic acids under different water chemistry and DOM concentration conditions, which could shed light on its binding mechanisms and binding properties with HOCs.
Keywords: effect of water chemistry; dissolved organic matter; fluorescence characteristic

To develop synthesized coralline hydroxyl apatite (CHA) bone graft-substitute and measure its physical and chemical characteristics.The CHA bone graft-substitute was synthesized from natural mineral—coralline through hydrothermal exchange process. This process was designed and developed independently by the authors. Its physical and chemical characteristics have been determined and studied using various techniques including Scanning Electron Microscopy (SEM), electron microscope image processing, scanning electron microscope energy spectrography; chemical analysis, ICP-AES, X-ray diffraction, etc. Clinical trials have been conducted.Independently developed CHA bone graft-substitute is white in color; its porosity is 25.87%–53.58%, which is approximate to that of human bones and original coral. It is larger than 3–4 in hardness by Mohs hardness scale and the compressive strength ranges from 4.87 to 12.31 MPa. The chemical compositions of the CHA are 53.13%–64.09% CaO and 35.52%–46.48% P2O5. CaO/P2O5 is 1.143–1.804. ICP-AES analysis detected twenty-four trace elements including Pb, Co, Ni, Ba, Mn, Cr, Th, V, Cu, Ti, K, Mo, Zn, Mg, Nb, Be, Sc, Al, Sr, Na, Li, etc. Ca, P, K, Na, Al and Sr are relatively high while the rest are less than nn×10−6, which is acceptable by human body. The REE level in the CHA bone measured by ICP-MS is 1.433×10−9–2.212×10−9, which is within the acceptable range for human beings.The process of synthesized CHA bone graft-substitute is an innovated independently developed method and concept. Its color, porosity and chemical composition are similar to those of human bones; therefore it has very good biocompatibility and excellent conductivity. Sixty clinical cases have proved that CHA bone graft-substitute has a strong bone-forming ability, no toxicity, no side effect, and better sacralization. It is a fine substitute for bone transplantation.
Keywords: artificially synthesized coral hydroxyapatite bone; physical property; chemical composition; clinical application

Effect of manganese tailings on capsicum growth by Zhengguo Zhou; Longjun Xu; Jinlian Xie; Chenglun Liu (427-431).
The impact of Mn in manganese waste rocks and electrolytic manganese residues on the growth of capsicum was studied via pot experiments. The product yield and manganese nutrition were mainly evaluated in this study. The results showed that the ingredients of manganese tailings were beneficial to the increase of chlorophyll contents in the capsicum. The chlorophyll contents were raised by 12.6%–28.7%, 7.18%–12.1% and 9.70%–13.7%, respectively, corresponding to the idiophase of flower bud, the initial florescence and the fruit expansion stage. Moreover, the additive significantly improved capsicum’s economic features, such as its height, stem width, fruit length and weight and the yield of fresh fruit. These parameters were raised by 11.9%–25%, 18.6%–25.6%, 20.7%–35.4%, 10.4%–27.6% and 11.4%–65.7%, respectively. At the meantime, the manganese taken up by stems and leaves of the capsicum also increased by 11.7%–23.4% and 33.9%–62.8%, respectively. The manganese which remained in the soil was less than that in the original soil due to plant absorption and rainfall loss in pot experiments. It is concluded that both manganese residues and the mixture of manganese waste rock and manganese residue could indeed be made full use of as a fertilizer which can provide Mn nutrition.
Keywords: manganese tailing; capsicum growth; chlorophyll; manganese fertilizer

The Wulong pluton was emplaced in the metamorphic complex of the Mesoproterozoic Foping Group, South Qinling. A few mafic enclaves which are rounded in shape with sharp boundaries with the host granites in the southern part of the pluton. Based on petrography, geochemistry and chronology data, it is indicated that the Wulong pluton shows some adakitic affinities with depletion in HREE (Yb=0.33–0.96 µg/g, Y=4.77–11.2 µg/g); enrichment in Sr (643–1115 µg/g) and Ba (775–1386 µg/g), high Sr/Y ratios (57.3–160) and Y/Yb ratios (11.0–14.3), and slightly negative Eu anomaly (δEu=0.70–0.83). These patterns suggest a feldspar-poor and garnet±amohibole-rich fractionation mineral assemblage. The mafic enclaves have high concentrations of Mg (MgO=4.15%–8.13%), Cr (14.8–371 µg/g), and Ni (20.0–224 µg/g), and high Nb/Ta ratios (15.42–21.9). It seems that the underplating mantle magma was responsible for the generation of the mafic magma. Companied with the results of investigations for the Qinling Orogenic Belt, it was found that partial melting of the thickened lower crust, which was triggered by the underplated mantle-derived magmas, had generated the felsic magma. The Wulong pluton provided evidence for a mixing and mingling process of two kinds of mamma. Its formation probably represents the oceanic slab breakoff during the late orogenic stage in the Qinling area.
Keywords: mafic microgranular enclave; adakite; underplation

Low- and high-concentration nitric wastewater can induce stable nitrite accumulation and realize the nitrification system, with the nitrite accumulation rate between 50% and 90%. In the low-concentration nitrite nitrification system, the average FA concentrations during the period of stable nitrite accumulation remained at 7 to 10 mg/L. In the high-concentration nitrite nitrification system, the nitrogen oxidation activity will not be affected by biomass, the nitrite oxidation activity is related to the system biomass, it is recommended to be measured by FA/MLSS. Keeping the FA sludge load below 0.1 is the precondition of making good nitrite accumulation and nitrogen degradation rate. Nitrite oxidation bacteria cannot be totally eliminated or washed out from the system.
Keywords: nitrification; nitrogen accumulation; free ammonia (FA); inhibition

The authors reviewed the history of geochemistry involved in active volcano monitoring and analyzed the relationship between variations in volcanic gas composition observed at the Changbaishan Volcano Observatory and volcanic activities. It is concluded that both geochemical method and routine gas analysis can provide the information about volcanic activity and earthquake activity, and both of them can play an important role in predicting volcano eruption.
Keywords: geochemistry; volcanic activity