宇宙成因核素10Be的地球化学行为及其在黄土示踪研究中的应用

¹⁰Be是一种典型的长寿命宇宙成因核素,对其在自然界中的分布规律、迁移形式和赋存状态等地球化学行为特征的研究,是利用沉积物¹⁰Be记录进行定年和环境示踪研究的理论基础。其中明确¹⁰Be在不同沉积物中的赋存状态是研究¹⁰Be保存性的基础,而¹⁰Be在固相和液相介质中的分配系数Kd则主要反映了¹⁰Be在固相和液相中的迁移能力,对研究自然界不同沉积物中¹⁰Be的迁移性至关重要,直接影响到沉积物中¹⁰Be环境示踪研究的有效性。本文尝试总结了大气成因¹⁰Be在海洋、河流沉积物和土壤中的赋存状态,分析了¹⁰Be分配系数Kd的分布范围及其主要控制因素。在此基础上以土壤中¹⁰Be的分布特征、迁移规律及影响因素研究为参考实例,对比分析了目前已有对黄土-古土壤序列中¹⁰Be地球化学行为研究取得的主要成果,建议未来应从地球化学机制方面进一步加强对黄土地层序列¹⁰Be分布特征、浓度变化规律及可能影响因素的综合研究,为黄土¹⁰Be示踪研究提供更全面的理论依据。     

大气生成宇宙成因核素~(10)Be在中国黄土中的应用研究进展

中国黄土~(10)Be研究大体上经历了三个阶段:(1)地球化学行为研究:~(10)Be主要吸附于细颗粒及粘土颗粒,在黄土中保存性好,不会发生明显的化学迁移过程;(2)古气候代用指标应用:~(10)Be在黄土和古土壤层中的浓度变化与代表气候变化的深海氧同位素曲线变化一致,且可借此进行黄土年代标尺的建立;(3)地球环境示踪研究:示踪地磁场倒转及漂移事件,恢复古地磁场相对强度变化,以及定量重建黄土高原地区古降水变化历史等。由于近年来黄土~(10)Be环境示踪研究取得了可喜的成果,笔者认为有必要从以上三个方面对中国黄土~(10)Be研究历史进行较为系统的梳理回顾,总结当前最新研究进展,展望未来黄土~(10)Be在环境示踪中的研究方向,希望能使读者在短时间内了解中国黄土~(10)Be研究的发展脉络。     

汉中大佛洞宇宙成因核素26Al/10Be埋藏年龄

汉中天坑群是在我国湿润热带-亚热带岩溶地貌区北界首次发现的岩溶地质景观,已查明区内发育岩溶洞穴160余处,对研究中国南北方乃至全球古地理环境及气候变化具有重要科学价值。目前该区域地貌演化、岩溶洞穴发育研究刚刚起步,尚没有该岩溶区年代学研究成果报道。本文尝试运用加速器质谱仪(AMS)宇宙成因核素~(26)Al/~(10)Be埋藏年龄测试技术,对汉中南郑岩溶洞穴大佛洞内次生沉积石英砾石进行年龄测定,获得~(26)Al/~(10)Be埋藏年龄为(1.07±0.71)Ma,初步限定了汉中岩溶洞穴大佛洞的发育时期;同时获得大佛洞石英砾石样品在埋藏前该流域侵蚀速率为(156.5±73.4)m?Ma-1。     

西藏羊卓雍错沉积物沉积速率的测定

利用~(210)Pb和~(137)Cs测定了西藏羊卓雍错湖泊沉积物的沉积速率。结果表明,羊卓雍错湖心和北部湖区沉积柱中的~(137)Cs都只有一个蓄积峰。假定对应的时标为1963年,据此得出的沉积物累积率分别为0. 014 5 g/(cm~2·a)和0. 025 2g/(cm~2·a),对应的年均沉积速率分别为0. 041 cm/a和0. 068 cm/a;而~(210)Pb的结果显示,羊卓雍错湖心和北部湖区的沉积物累积率分别为0. 014 6 g/(cm~2·a)和0. 014 7 g/(cm~2·a),对应的年均沉积速率分别为0. 040 cm/a和0. 041 cm/a。~(210)Pb和~(137)Cs的定年结果在北部湖区的定年结果差别较大,很可能是由于湖水在北部湖区的渗漏,导致沉积物中Cs的纵向迁移造成的。     

帕米尔高原冰川流域碎屑颗粒的铀同位素组成及其对沉积物搬运的指示

铀(U)同位素作为一种新的地球化学示踪手段,被逐渐用于研究陆地和海洋沉积物的搬运过程。然而,这一新技术能否有效指示不同环境中各类沉积物的搬运还需更多流域数据的支持。本文选取位于帕米尔高原东北部具有显著海拔梯度和气候差异的盖孜河冰川流域作为研究对象,通过该流域河流沉积物细颗粒中的U同位素的活度比((~(234)U/~(238)U)_(AR))的空间变化,探索U同位素指示内陆冰川流域沉积物搬运的可行性。流域内河流沉积物的矿物组成以石英和长石(占51%—77%)为主,表明较弱的风化作用。流域内受冰川侵蚀控制的上游山区支流康西瓦河和木吉河沉积物的(~(234)U/~(238)U)_(AR)范围分别是0.990—1.017和0.988—1.009,盖孜河中下游段河流沉积物的(~(234)U/~(238)U)_(AR)则为0.913—0.997。从上游山区至中下游段显示了一个明显的下降趋势,指示了沉积物搬运过程中(~(234)U/~(238)U)_(AR)的确发生了系统的变化。然而,盖孜河流域碎屑颗粒比表面积和分形维数计算得到的反冲损失参数太低,未能利用U同位素破碎年龄模型获得合理的沉积物搬运时间,该模型如何用到冰川流域尚需更多的研究工作。     

宇宙成因核素26Al/10Be约束贵州涟江流域沉积物埋藏历史

贵州喀斯特地区位于青藏高原向丘陵地貌转换过渡带,区内发育多级层状地貌面,是研究区域构造-气候-剥蚀耦合作用的天然实验场。本文测定了贵州省惠水县境内涟江I级阶地沉积物中原位宇宙成因核素¹⁰Be和²⁶Al浓度,通过暴露-埋藏模型对沉积物埋藏历史和物源进行研究。与前人研究结果相比,涟江流域单核素剥蚀速率（¹⁰Be平均剥蚀速率为10.85±0.97 m/Ma）显著低于贵州高原其他流域。结合双核素暴露-埋藏模型,研究结果表明更新世以来沉积物样品可能经历了复杂暴露-埋藏-再暴露过程,其物源可能是异地埋藏或洞穴堆积等非稳态剥蚀区。宇宙成因核素对²⁶Al-¹⁰Be联用能有效判别非稳态剥蚀过程,弥补了单核素不能表征沉积物埋藏历史的不足。     

10Be和26Al揭示的合黎山西南部侵蚀速率初步研究

地表侵蚀速率是衡量地貌演化的一个重要因子。本研究利用原地宇宙成因核素~(10)Be和26Al对合黎山西南部地表岩石侵蚀速率进行了首次测定。结果显示:约30 ka以来,合黎山西南部的地表岩石侵蚀速率约为24 mm?ka~(-1)。这一结果与已见报道的其他基岩侵蚀速率值一致。这一结果与Small et al获得的非干旱地区的基岩侵蚀速率也基本一致,但是显著高于干旱的南极地区和半干旱的澳大利亚。~(10)Be和26Al获得的侵蚀速率的良好一致性表明本研究中所用侵蚀模式的有效性。所得的侵蚀速率小于Palumbo et al测定的合黎山平均流域侵蚀速率(99 mm?ka-1),原因解释尚待更多地点和样品的研究。     

宇宙成因核素~(10)Be 在全球变化研究中的一些应用

~(10)Be是宇宙射线高能粒子与大气主要成分氮、氧原子核进行散裂反应的产物,通过大气降水沉降到地表。本文介绍了~(10)Be在大气圈降水、极冰、深海沉积物、锰结核、土壤、黄土、湖相沉积物、生物圈等环境系统的分布特征,并对~(10)Be变化与太阳活动变化的关系、~(10)Be产生率与地球磁场极性倒转关系、~(10)Be沉积速率与各种全球传输过程关系,以及~(10)Be作为一种测年工具的应用前景等进行了广泛的论述。     

基于31P-NMR与SMT方法的海河流域典型河流沉积物中磷形态特征研究

利用液相~(31)P核磁共振分析方法和SMT分级方法,对比研究了海河流域典型人工河流子牙新河和滏阳新河、自然河流子牙河表层沉积物中磷形态.结果发现,两条河流沉积物中TC、TN、TP含量均很高,且相关性显著,污染较重且具有同源性.沉积物中总磷在568.2~9171.9mg·kg-1之间,其中以HCl-P为主,占总磷的25.5%~81.8%之间,其次为NaOH-P,所占比例为9.3%~55.5%.使用~(31)P-NMR技术在沉积物中共检测到7类磷化合物:正磷酸盐(Ortho-P)、磷酸单酯(Mono-P)、磷脂(Lipid-P)、DNA磷(DNA-P)、焦磷酸盐(Pyro-P)、膦酸盐(Phon-P)及多聚磷酸盐(Poly-P).Ortho-P和Mono-P分别为总磷和有机磷的主要组成成分,含量分别在113.8~6226.1 mg·kg~(-1_和27.0~1991.9 mg·kg~(-1)之间.子牙河、子牙新河和滏阳新河两条河流在沉积物磷组成方面存在很大的差异子牙新河和滏阳新河沉积物中总磷明显高于子牙河.     

黄土中宇宙成因核素~(10)Be提取条件检验

鉴于利用中国黄土中的宇宙成因核素~(10)Be示踪高分辨率的古地磁场变化研究工作需要高精度、低本底的化学实验结果,为获得现有样品制备流程的详细数据并优化实验流程,文章对酸提取效率进行了检验。通过采用不同温度、不同酸度在加热板和微波消解仪下的提取效率对比检验,获得了不同条件下的可靠实验数据,检验了现有流程提取两次可将样品中90%以上的~(10)Be提取出来,达到实验要求。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.