石笋有机质碳同位素组成研究的进展与挑战

洞穴石笋因其精准的定年和蕴含的多种代用指标,已成为古气候和古环境变化研究的重要载体之一。在石笋研究的多种代用指标中,碳酸盐碳同位素由于受到多重因素的影响,应用其重建过去环境变化历史一直局限在少数几个研究地点。洞穴上覆土壤有机质是洞穴石笋中有机质的重要来源,除此之外,洞穴原位产生的微生物及基岩中的有机质也有贡献。由于主要继承了地表植被和土壤有机质的同位素组成,石笋有机质碳同位素组成的时间序列能够很好地指示地表植被的演变及土壤过程的变化。本文对石笋有机质碳同位素组成的研究现状进行了综述,介绍了最新建立的石笋有机质碳同位素组成分析方法,并指出应用这一指标研究环境变化需要解决的关键问题和未来面临的挑战。     

安固里淖湖积物中总有机碳含量及其碳同位素的环境意义

在探讨有机碳含量及其稳定碳同位素的环境指示意义基础上,对张北高原安固里淖湖泊沉积物进行了分析,重建了安固里淖近400年来的气候环境演变格局。安固里淖沉积物中总有机碳含量的变化间接反映了区域气温的变化,有机碳同位素值的变化与湖泊水位波动导致的湖泊水生植物种类的改变有关。在钻孔岩芯定年的基础上,认为安固里淖地区从约1630AD开始气候逐渐变冷,到1840～1890AD为温度最低点,随后气候变暖;相对于温度的变化过程,从约1630AD开始,气候逐渐向湿润方向发展,到约1770～1840AD期间气候最为湿润,之后气候逐渐变干。     

云南金顶铅锌矿碳、氧、硫同位素地球化学特征及其地质意义

本文对金顶铅锌多金属矿床矿石中硫化物硫同位素及碳酸盐胶结物中碳、氧同位素进行了研究分析,结果表明:成矿流体中的CO2与沉积有机物和海相碳酸盐岩有关,源自碳酸盐岩热解作用和去碳作用以及沉积有机物的氧化作用和脱羧基作用。矿床的矿石矿物组成反映了成矿环境为高氧逸度环境。硫同位素特征研究表明:矿床中石膏矿体中的硫可能来自三叠系古大洋硫酸盐矿物。而金属硫化物矿物中的硫具有多源性,其主要来源为生物或细菌还原地层中膏盐(石膏、硬石膏、有机质等)的还原硫、壳源硫和有机硫。同位素研究表明金顶铅锌多金属矿的成矿物质应源自地壳。     

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。     

封管法制备有机碳稳定同位素样品存在的问题和改进

有机碳稳定同位素的高精度测定是利用地质样品有机碳同位素研究气候和植被变化等的基础。通过实验发现低有机碳含量样品同位素测定误差相对较大,其中样品收集过程是主要的影响因素之一。本文针对这个问题,主要从杂质气体干扰入手,在一步冷冻分离CO_2和H_2O,或分步冷冻分离CO2和H2O的收集方法,以及改变收样管体积三方面进行条件实验研究,讨论了封管法制备有机碳稳定同位素样品气体收集过程对有机碳稳定同位素组成的影响。结果表明:(1)CO_2气体的纯化收集是封管法制备有机碳稳定同位素样品的一个重要步骤,收集时杂质气体含量越高,对样品有机碳稳定同位素组成的影响越大;(2)在相同的杂质气体背景条件下,与一步冷冻分离CO_2和H_2O的方法相比,分步冷冻CO2和H2O的方法能够显著减小杂质气体对有机碳稳定同位素测定的影响;(3)小体积收样管能够显著提高有机碳稳定同位素样品的离子流强度,进而提高低有机碳含量样品的稳定碳同位素测定精度。     

有机氧同位素分馏作用研究进展

植物有机质的氧同位素分馏机制较为复杂,受着多种因素的影响,限制了其在农业、生态学和古环境方面的广泛应用。本文探讨了植物有机质中氧元素的来源、氧同位素分馏机制及影响因素,以期有助于有机氧同位素的应用研究。     

利用Rb/Sr值、有机碳氮同位素及14C重建贵州喀斯特地区古环境变化

本文利用碳酸盐岩风化剖面土壤中Rb/Sr值、有机碳氮的稳定同位素值(δ~(13)C_(org)和δ~(15)N_(org))并结合~(14)C定年结果,讨论了贵州黔西南喀斯特地区晚更新世以来的植被和气候变化情况。结果表明:(1)晚更新世以来,研究区气候在千年尺度上经历了多个冷热、干湿循环过程,植被以C4植物为主;(2)研究区在14 750 a BP时期可能发生过较为极端的气候事件;(3)Rb/Sr值和δ~(13)C_(org)值可以用来指示古环境变化情况,高Rb/Sr值和高δ~(13)C_(org)值指示湿热气候,低Rb/Sr值和低δ~(13)C_(org)值指示干冷气候。     

辽东半岛东岸泥质区有机物分布特征及其环境指示意义

为研究人类活动及鸭绿江陆源输入对河口海岸及陆架泥质区沉积环境的影响,本文通过对2017年于辽东半岛泥质区东部采集的Q02柱与西部Q04柱进行210Pb定年、粒度、总有机碳、总有机氮、δ13C同位素等指标综合分析,利用Meyers研究模型结合C/N值及δ13C同位素含量分析不同物源有机质贡献率。结果表明:（1）两根柱样TOC与TN含量近百年来逐渐升高,C/N值在9~11之间为海陆混合来源。沉积物主要以粉砂及粘土为主,粉砂含量最高,粘土次之,砂含量较少。（2）有机碳来源占比均呈陆源降低海源升高的特点,分别反映了泥质区东部与西部不同主导因素对海域环境的影响。东部沉积环境主要受流域环境变化与海域共同作用,垦荒、自然灾害、日俄战争等事件造成了植被覆盖降低,水库建设减少了陆源有机碳输入;西部沉积环境主要受沿岸人类活动、水体富营养化的影响,"弛禁"政策导致植被覆盖被破坏,港口修建、水产养殖等活动造成水体营养物质增多,引起海洋环境恶化。     

中国第四纪黄土古环境研究若干进展

随着技术进步和多方位研究进展,第四纪古环境研究向着多元古环境替代指标、高分辨率古气候研究、气候变化的多种驱动因素等方面发展。文章总结了中国黄土古环境研究中的主要替代性指标,包括黄土磁化率、黄土粒度、植物硅酸体、孢粉组合、蜗牛化石、碳氧同位素和^10Be、黄土与古土壤。概述了当前对黄土—古土壤的时间标尺、末次冰期的短尺度气候事件以及东亚古季风变化机制的认识。     

稳定碳同位素技术在多环芳烃源解析中的应用进展

多环芳烃是广泛存在于环境中的具有"三致"效应的有机污染物,环境中的多环芳烃来源复杂,传统溯源方法受到环境中降解作用影响,具有较大局限性,而稳定碳同位素技术在多环芳烃源解析中具有较好的应用。该文通过文献综述,梳理比较了多环芳烃单体稳定碳同位素样品提取、净化、洗脱等前处理方法的优缺点,分析了选择不同内标物和分析柱进行样品分析的精确度;阐述了在实验室分析过程中以及环境中可能发生的稳定碳同位素分馏效应;通过相关研究案例分析,总结了稳定碳同位素技术在大气颗粒物、土壤和沉积物等环境样品源解析中的应用可行性。结果表明,稳定碳同位素在特定污染源中组成确定,且具有在污染物迁移和转化过程中不发生显著变化的特点,稳定碳同位素技术能较好应用于多环芳烃源解析,与其他方法结合使用,可以更好地解决复杂样品的溯源问题。     

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.     

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.     

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.     

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.     

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.     

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.     

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.