洞穴次生化学碳酸盐沉积物-石笋的气候替代指标的意义与不确定性因素

洞穴次生化学碳酸盐(CaCO3)沉积物-石笋、钙华和流石,是一个具有丰富的陆地古气候信息的档案库。洞穴碳酸盐(CaCO3)-石笋古环境重建常用的代用指标有碳、氧稳定同位素、生长速度、纹层厚度和灰度、有机质荧光、微量元素等,利用多种替代指标的环境解译,增加了古气候环境重建的可靠性。本文从测年方法和石笋年代学的研究入手,对石笋的生长速度,沉积速率、纹层厚度、稳定同位素、微量元素等各代用指标指代的气候意义进行了简述,同时,也对洞穴次生化学碳酸盐(CaCO3)沉积物-石笋中各单一代用指标存在的不确定性影响因素进行了探讨。因此,我们认为洞穴动态监测可为洞穴碳酸盐(CaCO3)沉积物的各替代指标的解译提供可靠的依据,充分利用现代洞穴监测的碳酸盐(CaCO3)沉积物的各替代指标,并与现代器测气象资料进行相互对比、并用以校正,是精确或定量解释石笋气候替代指标的关键。     

洞穴滴水-CaCO_3体系氧碳同位素组成的气候意义研究现状和问题

近年来,通过对洞穴滴水-CaCO3体系各项指标的长期监测,以了解现代碳酸钙沉积的形成机制成为了石笋古气候研究的重点。尤其是对滴水-CaCO3体系氧同位素组成(δ18 O)的研究取得了显著的进展。人们在对滴水和CaCO3的δ18 O与古温度关系的研究中,不断地修改普遍使用的关系式,甚至提出了适合自身研究区石笋δ18 O与温度的关系式。无疑这将增加利用石笋氧同位素组成重建本地区古温度的可信度。在对碳同位素组成(δ13 C)的研究中,学者们更加细致地研究了各种影响滴水δ13 C值的因素(如先期碳酸盐沉积PCP、通风条件等),为更好地利用石笋δ13 C重建古气候环境提供了科学支撑。由于洞穴监测条件的限制,至今大多数洞穴都未能建立起完善的自上而下的监测体系,所以对一些δ18 O、δ13 C变化的解译仍然存在多解性和不确定性,有待未来的研究继续加强。     

洞穴上覆土壤层~(210)Pb放射性活度变化特征及其环境意义

土壤210Pb放射性活度变化可以用来指示土壤侵蚀速率变化、计算水土流失速率,但是在其他方面的应用,特别是岩溶环境的应用相对较少。在进行洞穴年轻沉积石笋年代测试过程中,发现目前应用的CIC(恒定初始放射性活度模式)初始活度恒定的假设需要进行验证。通过对广西桂林茅茅头大岩上覆土壤层进行季节采样和210Pb放射性活度、土壤有机质、粒径等分析,发现土壤剖面表层20~30cm内的210Pb放射性活度季节变化明显,可能响应了大气环境、土壤生态环境的变化。但是土壤剖面基底210Pb放射性活度基本保持恒定,说明土壤层厚度大于20~30cm时,土壤层中210 Pb变化对洞穴年轻沉积物表层210Pb活度变化影响不大,洞穴上覆层对洞穴沉积物210Pb放射性活度的影响主要在于土壤有机质和粘粒向下迁移。因此,影响洞穴石笋210Pb放射性活度的关键因素在土壤厚度、土壤中随有机质和粘粒迁移的210 Pb量的变化,进而推广到洞穴年轻沉积物210Pb定年,在土壤层厚度大于20~30cm时,洞穴相对封闭环境下,可以应用CIC模式对洞穴沉积物进行年龄计算。     

总有机碳同位素组成在古环境研究中的应

沉积物或动物化石中的总有机碳同位素组成记录了当时生态植被状况及气候环境信息,对有机碳同位素指标的研究可解译其蕴含的地质历史时期气候和构造事件及变化特征、定量重建古生态系统中植被结构、推断C4植物的起源、扩张等,应用甚为广泛。本文主要概述了总有机碳同位素在古环境研究中应用的基本原理,介绍了在各类载体中获取其数据的实验方法步骤,对其在古环境研究中的地位与作用以例证说明,展示其应用的大好前景。     

喀斯特地区土壤有机质的稳定碳同位素地球化学特征

以喀斯特地区二种主要的土壤类型石灰土和黄壤为例,对三种植被类型下土壤及土壤不同粒径组分中有机质的稳定碳同位素组成(δ13C值)进行了分析,结果显示:石灰土剖面中土壤有机碳含量均大于1.0%,最大值为表层土的7.1%,而三个黄壤剖面中土壤有机碳含量在0.3%～4.6%之间;石灰土剖面中土壤有机质δ13C值的变化范围仅为-24.1‰～-23.0‰,土壤不同粒径组分中有机质的δ13C值变幅也较小;而黄壤剖面中土壤有机质δ13C值的变化范围较大,在-24.5‰～-21.1‰之间,土壤不同粒径组分中有机质的δ13C值变幅也较大。对比研究表明,不同土壤类型中有机质的深度分布特征具有显著差异,土壤有机质的稳定碳同位素地球化学具有明显的区域性特征。     

黄土高原不同植被覆盖下土壤有机碳的分布特征及其同位素组成研究

土壤有机碳（SOC）含量及其8^13C值随深度变化的趋势可以反映植物残体的输入及其在土壤中分解累积特征,有助于揭示SOC循环过程及规律。本研究以黄土高原不同植被类型覆盖条件下的黄土剖面为研究对象,通过测定土壤属性、SOC含量和植物优势种、枯枝落叶、土壤有机质的稳定同位素组成,对该区域SOC深度分布和有机质8”C值组成差...     

重庆地区石笋δ13C记录的全新世气候环境变化

本文利用重庆市青木关镇狮子洞石笋QM09铀系测年数据和氧碳稳定同位素数据,重建了研究区9.4~0 ka BP的古气候环境演化历史。依据狮子洞石笋δ~(13)C记录变化趋势,将其划分为2个阶段:(1)9.4~3.0 ka BP期间,狮子洞石笋δ~(13)C记录除了在4.2 ka BP附近发生一次短暂的偏重事件外,整体变化比较平缓,石笋δ~(13)C值比较偏轻;同时石笋δ~(18)O值在该期也较为偏轻,暗示了此时段季风强盛,气候温暖湿润,地表植被变化稳定。此时人类活动比较弱,对自然环境的影响小,植被变化主要受自然气候环境的影响;(2)3.0~0 ka BP期间,石笋δ~(13)C记录不再呈现如第一阶段般平稳变动的趋势,在3.0 ka BP时开始波动下降,在经历1.7 ka BP大幅下降后,δ~(13)C便频繁波动大幅升降。石笋δ~(18)O记录显示该时段季风减弱,气候变干,植被退化,土壤水中溶解的CO_2含量减少。加之该期人类活动剧烈,地表自然植被遭到破坏,当地无机环境更多的参与到地下水循环体系中来,使得石笋δ~(13)C逐渐加重。     

论泥炭纤维素碳同位素组成作为东亚季风强度变化代用指标的可行性:吉林3个临近发育的泥炭地泥炭剖面的横向比对

降雨量通常与东亚季风强度成正比,而植物纤维素碳同位素组成又与降雨量成反比,因此泥炭纤维素碳同位素比值通常作为东亚季风强度变化的代用指标。由于季风影响的广泛性和区域性,临近发育的泥炭地植物纤维素碳同位素序列应该高度相关。为了验证这种假设,我们系统比较了吉林3处泥炭地3个泥炭剖面苔草纤维素2000年来的碳同位素序列。14 C时标控制的3个序列不呈现有意义的相关关系。不同时段,如过去500年、1000年、1500年和2000年来序列的长期趋势也不相关,序列中包含的周期完全不同。这些事实说明3处剖面苔草纤维素碳同位素比值记录的是当地性的而不是区域性的气候或环境信号,将泥炭纤维素碳同位素比值作为东亚季风强度变化的代用指标的合理性值得怀疑。     

植物硅酸体研究在黄土古气候恢复中的应用

地表植被对环境变化的响应最为敏感 ,沉积物中保存的各种植物残余是古环境研究的良好材料 ,植物硅酸体因其特有的物理化学性质 ,成为古气候信息的绝佳载体。在大量现代植物研究基础上 ,科学家们通过对第三纪以来各种沉积物中硅酸体组合的研究 ,较好地恢复了当时的古植被、古气候及其演化特征 ,在缺乏其它化石依据的黄土地层研究中表现更为突出。由于C3、C4 植物具有明显不同的环境适应性和同位素组成 ,地层中C3、C4 植物硅酸体相对含量和稳定同位素的研究也被成功地应用于古气候恢复中。在现代气候—植被类型和土壤植物硅酸体同位素研究基础上 ,利用数理统计方法 ,建立同位素指标与各种气候因子之间的数学关系 ,将为高分辨率黄土古气候定量研究开辟新的途径。     

用湖泊沉积研究过去气候变化

湖泊沉积是一种其高分辨率的自然档案，记载了丰富的过去气候变迁信息；研究湖泊沉积，从中提取气候代用指标，可以恢复区域过去气候变迁史，进而推断过去全球气候变化。评述了目前研究和应用较多的十几种气候代用指标，如孢粉、碳和氧同位素、微体化石、分子化合物、碳酸钙含量、有机碳含量、藻类、沉积物粒径、矿物组合等；指出了当前特别重要的是要对各种气候代用指标的形成及其变化过程、气候代用指标的具体环境意义作深入细致的研究。     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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