人类世生物地球化学循环及其科学

地球已进入新的地质时代——“人类世”,人类已成为全球变化的主要驱动力。人类活动导致的地球生态系统的生物地球化学过程及关键生源要素的生物地球化学循环的改变直接或间接地影响着地球生态系统的关键功能,给人类福祉和可持续发展带来诸多威胁。本文基于地球系统科学研究的新进展,综述了人类世全球变化特征、生物地球化学循环在地球系统各圈层演化中的作用及其变化规律。特别关注了自然资源开发利用、生产和消费模式改变等人类活动对生物地球化学循环的影响,以及由此产生的气候、生态和环境效应。研究表明,应对人类世全球变化需要系统理解人类活动作为主要驱动力的多要素和多尺度生物地球化学循环过程及其生态和环境效应,基于地球系统科学的理论与方法开展针对人类世社会-生态系统的自然科学和社会科学的交叉融合研究。在文末提出了人类世生物地球化学研究的优先领域和方向,并强调解决受人类活动和气候变化高度影响下人类世生物地球化学循环的各种复杂科学问题的迫切性和重要性。

Chronological Study of Coal-seam Water and its Implication on Gas Production in the South Qinshui Basin

The knowledge of the residence time of formation water is fundamental to understanding the subsurface flow and hydrological setting.To better identify the origin and evolution of coal seam water and its impact on gas storage and production,this study collected coalbed methane co-produced water in the southeast Qinshui Basin and detected chemical and isotopic compositions,especially 36Cl and 129I concentrations.The calculated tracer ages of 129I(5.2–50.6 Ma)and 36Cl(0.13–0.76 Ma)are significantly younger than the age of coal-bearing formation(Pennsylvanian-Cisuralian),indicating freshwater recharge after coal deposition.The model that utilises 129I/I and 36Cl/Cl ratios to constrain the timing of recharge and the proportion of recharge water reveals that over 60%of pre-anthropogenic meteoric water entered coal seams since 10 Ma and mixed with residue initial deposition water,corresponding to the basin inversion in Cenozoic.The spatial distribution of major ion concentrations reveals the primary recharge pathway for meteoric water from coal outcrops at the eastern margin to the basin center.This study demonstrates the occurrence of higher gas production rates from wells that accept water recharge in recent times and suggests the possible potential of the non-stagnant zones for high gas production.

甲烷团簇同位素研究进展及其在表层地球系统碳循环研究中的应用

团簇同位素是当今地球化学研究的前沿领域。有关团簇同位素技术原理、指示意义、模型校正等方面研究已取得初步成果,而在表层地球系统研究领域以及地理、环境和生态等领域的综合应用研究工作亟待加强。在表层地球系统中,碳循环过程涉及广泛且影响深远,而甲烷(CH_(4))作为碳循环中关键环节的重要物质组成,揭示其来源及地球化学过程具有重大意义。甲烷团簇同位素技术的引入将为开展相关研究提供有效工具,该技术在揭示时间-空间不同尺度碳循环研究等领域具有广阔的应用前景。本文综述了团簇同位素的理论基础、测试分析现状及国内外主要研究成果。重点讨论了CH_(4)团簇同位素研究现状、理论模型和同位素不平衡的影响因素,并论述了团簇同位素在天然气、大气和水体CH_(4)成因和转化的应用典型案例。最后提出对开展不同实验室间测试结果对比、测定自然丰度下环境样品、探索准平衡过程的展望,以期对未来应用甲烷及其他物质,如二氧化碳的团簇同位素开展表层地球系统碳循环研究起到一定的借鉴作用。

Zeolite and fungi’s flocculability of simulated wastewater containing heavy metal ions or phosphorus

This paper focuses on the flocculability of simulated wastewater containing heavy metal ions (Fe3+, Cd2+) or phosphorus by zeolite, microbial flocculants (MBF) produced by Aspergillus niger and the composite flocculant composed of zeolite and MBF. The main results are presented as follows: zeolite was a good flocculant when the contamination of the three simulated wastewaters was low, but the treated water is of turbidness and the particles in it are hard to precipitate. The MBF have a good flocculability toward Fe3+ wastewater, as well as particulate matter. Significant changes in flocculability occurred after adding the composite flocculant in different simulated wastewa-ters, the best or least effect respective for Fe3+ and Cd2+ wastewater. The research we have done shows that the method by which the composite flocculant is used to treat the wastewater containing heavy metal ions or phosphorus provides important reference value for practical application.

Effect of Bacillus mucilaginosus on weathering of phosphorite and a preliminary analysis of bacterial proteins

The authors investigated the effect of Bacillus mucilaginosus on weathering of phosphorite. Analysis of different proteins was of significance in exploring the molecular biological mechanism in the bacterial weathering process. The concrete methods are described as follows: Mineral powder was put into liquid culture medium and B. mucilaginosus was incubated in the medium. The control (group) had no mineral powder in the medium. The treatments and controls were cultured simultaneously under the same condition. In a few days, the supernatant was filtrated, the main cations (Ca2+, Mg2+, Na+, Mn2+, Al3+, Fe3+, K+) were measured by ICP-OES, and the contents of water soluble phosphorus (Pws) and silicon (Siws) were determined by colorimetry. The residual solid was weighed on the filter paper, followed by digestion with concentrated HNO3. The concentrations of the main cations and Pws, Siws in the digest liquid were measured by using the method mentioned above. After the supernatant was centrifuged, the precipitation was used to analyze the protein differences between the treatment groups and the control groups by 2-dimentional gel electrophoresis (2-DE). The experimental results showed that apatite and quartz were partially weathered, but kaolinite was dissolved completely. The population of bacteria increased when mineral powder was added in the liquid medium. Software analysis and comparison of the 2-DE pictures of bacterial proteins revealed 1134 visible protein spots in the treatment group, and 729 visible protein spots in the control group. To compare the bacterial protein expression contents of the treatment group with those of the control group, there were 496 different protein spots, including 214 protein spots which indicated that the protein contents increased, 75 protein spots were indicative of a decrease, and 207 proteins were newly synthesized. It is proposed that the increased bacterial contents may be related to some protein expression and activation after the input of mineral powder. Newly synthesized proteins, the increase of expression contents and the reduction of proteins may be connected with bacterial metabolic regulations, cell activation and signal transmission.

Diurnal variations of pCO_2 in relation to environ-mental factors in the cascade reservoirs along the Wujiang River, China

We have investigated the diurnal variations of the pCO2 and related environmental factors in the cascade reservoirs with different trophic levels along Wujiang River. In surface water the pCO2 was 357±11 μatm in Hong-jiadu Reservoir, 338±48 μatm in Dongfeng Reservoir, 682±303 μatm in Wujiangdu Reservoir, and 1677±429 μatm in Liuguang, respectively. The results indicated that these cascade reservoirs had much lower pCO2 values in surface water than river did, and hypereutrophic reservoir showed larger diurnal variations of pCO2 than meso-eutrophic reservoir. In water column, pCO2 tended to increase with the depth. Phytoplankton and the environmental factors such as temperature and pH had different influences on pCO2 diurnal variations due to different trophic levels, and the effect of phytoplankton on pCO2 variation increased with the increase of trophic level in these reservoirs.

Experimental Study on the Electrical Conductivity of Orthopyroxene at High Temperature and High Pressure under Different Oxygen Fugacities

At presure 1.0-4.0 GPa and temperature 1073-1423 K and under oxygen partial pressure conditions, a YJ-3000t multi-anvil solid high-pressure apparatus and Sarltron-1260 Impedance/Gain-Phase analyzer were employed to conduct an in-situ measurement of the electrical conductivity of orthopyroxene. The buffering reagents consist of Ni＋NiO, Fe＋Fe3O4, Fe＋FeO and Mo＋MoO2 in order to control the environmental oxygen fugacity. Experimental results made clear that： （1） within the measuring frequency range from 10-1 to 106 Hz, the complex impedance （R） is of intensive dependence on the frequency; （2） The electrical conductivity （a） tends to increase along to the rise of temperature （T）, and Log a vs. 1/ T fit the Arrenhius linear relations; （3） Under the control of oxygen buffer Fe＋Fe3O4, with the rise of pressure, the activation enthalpy tends to increase whereas the electrical conductivity tends to decrease. The activation energy and activation volume of the main current carders of orthopyroxene have been obtained, which are （1.715±0.035） eV and （0.03±0.01） cm^3/mol, respectively; （4） Under given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, while under given pressure the activation enthalpy tends to decrease with increasing oxygen fugacity; and （5） The sample＇s small polarons mechanism has provided a reasonable explanations to the conduction behavior at high temperature and high pressure.

Seasonal variations in sulfur isotopic composition of dissolved SO_4^(2-) in the Aha Lake, Guiyang and their implications

The Aha Lake is a seasonal anoxic water system in the southwest of Guiyang City, Guizhou Province, China. Seasonal variations in SO42- concentrations and their isotopic compositions in lake water as well as in the tributaries were investigated in this study. The results showed that sulfate concentrations in river water range from 0.94 to 6.52 mmol/L and their δ34S values range from -14.9‰ and 0.9‰, while lake water has sulfate concentrations ranging from 1.91 to 2.79 mmol/L, and δ34S values from -9.8‰ to -5.9‰. It is suggested that coal mining drainage is the major source of SO42- in the Aha Lake. Rainfall, sewage discharge, sulfide oxidation and gypsum dissolution have made only limited contributions. Different depth-dependent distributions of dissolved SO42- and δ34S were de-veloped for both DB and LJK in summer and winter. Due to water overturn, δ34S values display homogenous vertical distributions in winter and spring. While in summer and autumn, significant positive shifts of δ34S were clearly ob-served in epilimnion and bottom strata as a result of water stratification. High δ34S values in epilimnion may result from the retention of rainwater during water stratification. Dissimilatory sulfate reduction by bacteria was thought to be responsible for the increase of δ34S value in hypolimnion.

REE geochemistry of the Zhoutan Group metasedimentary rocks in central Jiangxi Province,Southeast China

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.

Distribution and sequential extraction of some heavy metals in urban soils of Guiyang City,China

Sixty-two soil samples collected from different functional zones of Guiyang were analyzed for total con-centrations and sequential extraction of Cr,Cu,Pb,Zn and Cd by ICP spectrometry. The average total concentrations of Cr,Cu,Pb,Zn and Cd in the soils of Guiyang were 92.9,51.6,44.1,139.3 and 0.28 mg/kg,respectively. The soils have been polluted by Cr,Cu,Pb,Zn and Cd to some extent in comparison with the background values of Guiyang. Significant differences were recognized in the concentrations of Cr,Cu,Pb,Zn and Cd in different functional zones. As for the sequential extraction,Cr,Cu and Zn were present mainly in the residual fraction,and Pb was present mainly in the oxidizable fraction. The reducible fraction of Cd accounts for 47.5%,and the residual fraction is lowest. The mobility and bioavailability of heavy metals follow the order of Cd>Pb>Cu>Cr>Zn.

Stable carbon isotopic composition of soil organic matter in the karst areas of Southwest China

This study dealt with the distribution characteristics of soil organic carbon (SOC) and the variation of stable carbon isotopic composition (δ13C values) with depth in six soil profiles, including two soil types and three vegetation forms in the karst areas of Southwest China. The δ13C values of plant-dominant species, leaf litter and soils were measured using the sealed-tube high-temperature combustion method. Soil organic carbon contents of the limestone soil profiles are all above 11.4 g/kg, with the highest value of 71.1 g/kg in the surface soil. However, the contents vary between 2.9 g/kg and 46.0 g/kg in three yellow soil profiles. The difference between the maximum and minimum δ13C values of soil organic matter (SOM) changes from 2.2‰ to 2.9‰ for the three yellow soil profiles. But it changes from 0.8‰ to 1.6‰ for the limestone soil profiles. The contrast research indicated that there existed significant difference in vertical patterns of organic carbon and δ13C values of SOM between yellow soil and limestone soil. This difference may reflect site-specific factors, such as soil type, vegetation form, soil pH value, and clay content, etc., which control the contents of different organic components comprising SOM and soil carbon turnover rates in the profiles. The vertical variation patterns of stable carbon isotope in SOM have a distinct regional character in the karst areas.

REE Geochemistry of Fluorite from the Maoniuping REE Deposit,Sichuan Province,China:Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based on REE geochemistry, fluorite in the orefleld can be classified as the LREE-rich, LREE-flat and LREE-depleted types. The three types of fluorite formed at different stages from the same hydrothermal fluid source, with the LREE-rich fluorite forming at the relatively early stage, the LREE-flat fluorite in the middle, and the LREE-depleted fluorite at the latest stage. Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color. The mineralization of the Maouiuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.

Organic Carbon Isotope Geochemistry of the Neoproterozoic Doushantuo Formation,South China

The Neoproterozoic Doushantuo Formation on the Yangtze Platform, South China, documents a sedimentary succession with different sedimentary facies from carbonate platform to slope and to deep sea basin, and hosts one of the world-class phosphorite deposits. In these strata, exquisitely preserved fossils have been discovered： the Weng＇an biota. This study presents carbon isotope geochemistry which is associated paired carbonate and organic matter from the Weng＇an section of a carbonate platform （shelf of the Yangtze Platform, Guizhou Province） from the Songtao section and Nanming section of a transition belt （slope of the Yangtze Platform, Guizhou Province） and from the Yanwutan section （basin area of the Yangtze Platform, Hunan Province）. Environmental variations and bio-events on the Yangtze Platform during the Late Neoproterozoic and their causal relationship are discussed. Negative carbon isotope values for carbonate and organic carbon （mean δ^13Corg = -35.0‰） from the uppermost Nantuo Formation are followed by an overall increase in δ^13C up-section. Carbon isotope values vary between -9.9‰ and 3.6‰ for carbonate and between -35.6‰ and -21.5‰ for organic carbon, respectively. Heavier δ^13Ccarb values suggest an increase in organic carbon burial, possibly related to increasing productivity （such as the Weng＇an biota）. The δ^13C values of the sediments from the Doushantuo Formation decreased from the platform via the slope to basin, reflecting a reduced environment with minor dissolved inorganic carbon possibly due to a lower primary productivity. It is deduced that the classical upwelling process, the stratification structure and the hydrothermal eruption are principally important mechanisms to interpret the carbon isotopic compositions of the sediments from the Doushantuo Formation.

Ultraviolet absorbance titration for the determination of conditional stability constants of Hg(Ⅱ) and dissolved organic matter

Strong interaction between natural dissolved organic matter (DOM) and Hg(Ⅱ) may influence the trans- port, conversion, toxicity and bio-validity of mercury in the environment. In this paper ultraviolet (UV) absorbance titration was employed for the first time for the determination of the conditional stability constants of Hg(Ⅱ) and (DOM). With increasing Hg(Ⅱ) concentrations, the UV absorbance of fulvic acid, humic acid, and DOM in river increases progressively. By linear and non-linear model fitting, the conditional stability constants (lgK) of Hg(Ⅱ) and DOM were worked out to be 3.54?4.93 and 3.64?4.85, respectively. The results are consistent with those acquired by the typical fluorescence quenching titration method, with the maximum relative error of lgK being 2.6% and the average relative error being 0.2%. The UV absorbance titration method has the advantages of rapid determination, simple performance, and it will probably become a new approach to studying interactions between DOM and trace metallic ions.

Enrichment and Release of Rare Earth Elements during Weathering of Sedimentary Rocks in Wujiang Catchments

Thirteen weathering profiles of sedimentary rocks such as limestone, dolomitic limestone, dolomite, silicalite, black shale and purple sandrock from Wujiang catchments were selected for study on enrichment and release behavior of rare earth elements （REE） during weathering, and in its impact on plant growth and riverine REE distribution in the catchments with methods of hierachical cluster analysis and mass balance calculation in order to set a basis for riverine material source research and agricultural production. The results show that the enrichment degree of REE in calcareous soils from the Wujiang catchments is much higher than that of limestone, yellow soil, upper continental crust （UCC）,

Simulation of surface runoff in theWujiang River watershed based on GIS

Surface runoff in the Wujiang River watershed was simulated by a GIS-based method using precipitation, hydrology data, and land-use data. The volume of surface runoff is chiefly controlled by climates, topographical characteristics and types of land use at the watershed. Five subwatersheds that can represent the whole watershed were chosen and their average annual precipitation, average annual surface runoff and current land use were calculated respectively in the grid model of the Wujiang River watershed based on the climate and hydrology data from 1965 to 2000 and the land-use data acquired in the year of 2000. Surface runoff is assumed to be a function of precipitation and land use and the multiple regression tool is used to determine the relationship between surface runoff, precipitation and present land use. Thus, the rainfall-runoff model for each land-use type has been established. When calibrating these models, the results show that the percent errors are all below 7%, which indicates that the accuracy of this simulation is high.

Distributions of Picophytoplankton and Phytoplankton Pigments Along a Salinity Gradient in the Changjiang River Estuary, China

We investigated the abundance of different picophytoplankton groups and the phytoplankton pigment ratio in relation to environmental factors such as nutrients and suspended solids along a salinity gradient in the Changjiang River Estuary. The average numbers of Synechococcus spp.(Syn) and picoeukaryotes(Euk) were(2.7 ±5.1) ×103 and(1.1±1.4) ×103 cells m L-1, respectively. Prochlorococcus spp.(Pro) was only found in the high-salinity brackish water with the concentration of 3.0×103 cells m L-1. Syn and Euk numbers both tended to increase offshore and Syn showed a larger variation in cell abundance than Euk. The contribution of picophytoplankton to total phytoplankton biomass increased with increasing salinity and decreasing nutrient concentrations from the estuary to the open ocean. The response of different picophytoplankton groups to environmental variables was different. Water temperature was more important in its control over Euk than over Syn, while nutrients were more important in their influence over Syn than over Euk. Phytoplankton pigment ratios were different in the three different ecological zones along the salinity gradient(i.e., freshwater zone with 0-5 range, fresh and saline water mixing zone with 5-20 range, and high-salinity brackish water zone with 20-32 range), where three different phytoplankton communities were discovered, suggesting that phytoplankton pigment ratios can be considered as a complementary indicator of phytoplankton community structure in the Changjiang River Estuary.

Oxygen isotope and REE geochemistry of metamorphic veins within the Zhoutan Group, central Jiangxi Province

Geochemical studies on REE, trace elements and oxygen isotopes from metamorphic veins and their host metasedimentary rocks in the Zhoutan Group at two localities, Xiangshan and Yihuang, in central Jiangxi Province have been conducted in this paper. The results show that the metamorphic quartz veins inherited the REE and oxygen isotope geochemical characteristics from their host rocks, suggesting that the vein-forming fluids were derived from the host rocks. Additionally, fractionation degrees of the trace element pairs Zr-Hf, Nb-Ta, Y-Ho and U-Th in the veins are different from those of their host rocks. It is also indicated that the veins are the products of the fluids. The metamorphic veins within the Zhoutan Group metasedimentary rocks were formed principally as a result of lateral diffusion of the metamorphic fluids.

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area,Guizhou Province,Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area,the Fe isotope compositions of riverine suspended particulates,lake suspended particulates,lake sediments,porewaters,phytoplanktons,and aerosols in the watersheds of Lake Aha（a mineralized water system）and Lake Hongfeng（a mesotrophic water system）,which are located in the Karst area, southwest China,were investigated.The studied samples displayed a variable range betweenδ^（56）Fe=-2.03‰and 0.36‰.Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks.Fe isotope compositions of riverine Suspended Particulate Matter（SPM）were mainly affected by the types of tributaries.Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negativeδ^（56）Fe values（-0.89‰to-0.31‰）during summer,and there were significant increases ofδ^（56）Fe values in winter,except AR2,which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates,lake sediments,and porewaters.The epilimnetic particulate Fe of Lake Hongfeng hadδ^（56）Fe=-0.04‰to 0.13‰,while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha,ranging from-0.42‰to-0.09‰.Sediments collected from Hou Wu（HW）station of Lake Hongfeng have an averageδ^（56）Fe value of 0.09‰and their corresponding porewaters have lighter Fe isotope compositions,ranging from-0.57‰to-0.31‰;no significant variations have been observed. For the Liang Jiang Kou（LJK）station of Lake Aha,the content of reactive Fe and the concentration of sulfate were all high.Due to the reactive Fe recycling,including dissimilatory Fe reduction,adsorption, and Fe-sulfide formation,porewaters sampled near the sediment surface have been found to have aδ^（56）Fe value as low as-2.03‰and an increase up to 0.12‰,with a burial depth of 10 cm.In contrast,an opposite variation trend was found for LJK sediments.Sediments sampled at 1-cm depth had a value ofδ^（56）Fe=-0.59‰and decrease as low as-1.75‰with burial depth.This investigation demonstrated that significant Fe isotope fractionations occur in surface environments.Fe isotope compositions of particulate Fe were seriously affected by Fe sources,and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments,especially when there are significant amounts of reactive Fe and sulfate.

Biosorption of trace metals from aqueous multimetal solutions by green microalgae

Two strains of green microalgae C.reinhardti and C.pyrenoidosa were examined for their biosorption of Mn2+,Fe2+,Co2+,Ni2+,Cu2+,Zn2+,and Cd2+from aqueous multi-metal solutions.A wide range of biosorption capacities can be observed due to different strains of microalgae and different species of trace metals.This characteristic was ascribed to the distinct components and structures of algal cell walls and the different physicochemical properties of trace metals,such as atomic weight and ion density.C.pyrenoidosa showed higher uptake capacities than C.reinhardti and both of them had a preference for the uptake of cadmium over others in the trace metal solution,suggesting they can be a good biomaterial for biosorption of cadmium.Live microalgal cells displayed a more complex sorption process than dead microalgal cells because of cell assimilation.