13.5~2.5 Ma索尔库里盆地沉积物碳氧同位素对古气候演化的记录

索尔库里盆地位于青藏高原东北缘,柴达木盆地的北部,气候恶劣、交通不便,研究资料匮乏。通过对索尔库里北盆地彩虹沟剖面新近纪中后期沉积物的古地磁测年和碳酸盐碳氧同位素质谱分析,揭示了索尔库里盆地13.5~2.5 Ma长序列气候演变过程。13.5~9.2 Ma时期相对冷干,9.2~5.3 Ma时期相对温湿,5.3~3.9 Ma时期相对暖湿,3.9~2.5 Ma时期再次转为冷干。11 Ma左右,青藏高原东北缘隆升到阻止印度洋暖湿气流向北方运输的高度,地处走滑盆地的索尔库里地区逐渐变得极其干旱,标志着亚洲内陆干旱化在此背景下开始。红粘土磁化率和碳氧同位素变化等证据显示,西风在本区贯穿始终,而季风的出现加剧了亚洲内陆古气候的干湿更迭,对区域及全球古气候重建具有重要意义。     

喀斯特坡地土壤硫同位素变化指示的土壤硫循环

用土壤硫形态连续提取方法分离测定了喀斯特坡地土壤总硫、有机硫、SO24-和FeS2的硫同位素组成及其含量.总体来看,土壤剖面表层各形态硫δ34S值FeS2最低,介于-6.86‰~-4.22‰,其次为SO24-(-2.64‰~-1.34‰),第三为总硫(-3.25‰~-1.03‰),最高为有机硫(-1.63‰~0.50‰),随土壤剖面加深各形态硫δ34S值均有增大的趋势.SO24-和FeS2的δ34S值深度分布具有共变性,这与SO24-异化还原有关;而总硫和有机硫的δ34S值随剖面加深而平行增大,则与有机硫循环有关.硫同位素组成可鉴别土壤硫源,同时SO24-异化还原和有机硫矿化有明显的硫同位素分馏,而硫化物氧化及SO24-同化基本不产生同位素分馏,则土壤各形态硫的硫同位素组成的垂直变化可以很好地记录与深度相关的硫循环过程.并且,通过对比各形态硫含量及其硫同位素组成的深度分布特征,也可以很好地判别土壤内部的SO24-和有机硫组分的迁移过程.     

稳定碳同位素在海洋倾倒活动监测中的应用

通过测定倾倒区海域沉积物,产品码头和原油码头的疏浚物的有机碳同位素,分析来自不同区域的样品同位素变化特征,结果显示各区域碳同位素值有较大的差别。倾倒区有机碳同位素在-22.95‰～-23.05‰之内变化;产品码头疏浚物有机碳同位素在-25.20‰～-23.50‰;原油码头疏浚物碳同位素在-22.35‰～-21.89‰。通过碳同位素变化特征可以界定悬沙大致扩散范围。经混合配比实验,得到碳同位素组成与配比系数之间的关系,由此可推算倾倒活动中各码头的倾倒量。     

渤海湾西岸入海河流中有机碳来源及其影响因素分析

基于化学计量特征和不同形态碳的稳定同位素组成,探讨了渤海湾西岸具有不同闸坝控制状态和土地利用方式的两条入海河流(独流减河和捷地减河)水体中有机碳(OC)来源的时空变化及其影响因素。分析结果显示独流减河和捷地减河水体中溶解有机碳同位素组成(δ¹³C_DOC)的变化范围分别为-29.0‰～-24.3‰和-28.4‰～-24.2‰,而颗粒有机碳同位素组成(δ¹³C_POC)的变化范围分别为-36.9‰～-22.0‰和-35.7‰～-20.6‰。自河流上游到近海处,除部分点源受人为因素影响的水体外,两条河流的δ¹³C_DOC值和δ¹³C_POC值均呈增大趋势,且夏季比初春季节偏正。计算结果显示两条河流的有机碳主要来源于浮游生物、水生维管束植物、土壤有机质和城市污水,其相对比例分别为49%～59%、7%～11%、13%～16%和17%～27%。研究表明,河流内部的新陈代谢过程(初级生产和有机质降解)和人为活动(流域土地利用方式和闸...     

粤中长坑金银矿床的碳、氧、氢同位素研究

长坑金银矿床方解石的δ13C值为-3．23‰，方解石和石英的δ18O分别为8．64‰～18．61‰和9．60‰～13．0‰，其范围与其它卡林型金矿相似。结合大本（Ohmoto）模式的理论分析，认为成矿热液的总联同位素组成可大致取为-2‰～－17‰，即碳主要来自地层中的沉积碳酸盐，部分来自有机碳。推导出水岩交换过程中流体氢、氧同位素演化的一般性协变方程并进行了理论模拟，认为成矿流体以燕山晚期一第三纪的加热大气降水或建造水为主。     

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。     

长三角一体化示范区青浦区水体表层沉积物有机质分布特征、来源解析及污染评价

采集了长三角一体化示范区青浦区25个采样点的表层沉积物,分析了样品中总有机碳（TOC）、总氮（TN）、有机碳同位素(δ¹³C)和氮同位素(δ¹⁵N),探讨了研究区域表层沉积物中有机碳的分布特征和潜在来源,并进行了有机污染指数评价.结果表明,青浦区31个采样点表层沉积物中ω（TOC）为0.21%～3.55%,平均值为1.18%;ω（TN）范围为0.02%～0.23%,平均值为0.09%;δ¹³C范围为-28.04‰～-10.80‰,平均值为-22.28‰;δ¹⁵N范围为2.28‰～11.19‰,平均值为5.76‰;且TOC含量与TN含量显著相关;来源分析表明,研究区域表层沉积物中有机质主要受土壤有机质、污水有机质和陆生植物的影响;基于IsoSource软件的贡献率计算结果表明,土壤有机质相对贡献率较高（0.3%～96.8%）,且生活污水对多数采样点有机质来源均有一定的贡献;此外所选端元物质对不同土地利用类型样品中有机质来源贡献具有一定差异性;研究区域表层沉积物中有机污染评价指数范围为0.006～0.7...     

土壤中多环芳烃的稳定碳同位素特征及其对污染源示踪意义

分析了天津市不同功能区土壤中多环芳烃的稳定碳同位素组成特征、土壤中菲、甲基菲、荧葸和芘的δ^13C值范围分别为-29．5‰～-23．2‰、-39．8‰～-23．4‰、-27．2％～-23．6‰和-28．1‰～-22．6‰,不同功能区稳定碳同位素组成的差异反映了PAHs来源的差异．稳定碳同位素组成特征表明,在研究区内,化石燃料燃烧产物的干-湿沉降是土壤PAHs的最主要来源之一,其它可能的来源有污水携带的油污、农作物茎杆及薪柴不完全燃烧产物等．就具体地点而言,土壤PAHs以二元混合输入为主,据此,运用稳定碳同位素组成的二元复合数值模型对不同来源PAHs的相对贡献率进行了估算     

稻草烟尘中正构烷烃和正构脂肪酸的碳同位素

为了查清稻草燃烧烟尘中正构烷烃和正构脂肪酸的碳同位素分馏状况,对我国的6种稻草在明火燃烧和闷烧条件下进行室内模拟试验,并测定了烟尘中两类有机物的单体碳同位素.结果表明,在明火烟尘中,正构烷烃和正构脂肪酸单体的δ13C值分别为-28.6‰～-38.8‰、-29.6‰～-41.9‰;正构烷烃和正构脂肪酸的平均碳同位素组成分别是-32.6‰～-36.4‰、-34.0‰～-36.2‰.在多数稻草的明火烟尘中,正构烷烃总体上比秸秆内同碳数烷烃亏损13C,其δ13C值最大相差4.1‰.大部分正构脂肪酸的单体碳同位素组成比稻草重,二者最大相差6.3‰.在闷烧烟尘中,正构烷烃和正构脂肪酸的单体δ13C值分别为-31.7‰～-39.0‰、-31.3‰～-38.8‰;正构烷烃和正构脂肪酸的平均碳同位素组成分别为-35.1‰～-36.4‰、-34.4‰～-35.6‰.在多数稻草的闷烧烟尘中,正构烷烃的单体碳同位素组成比稻草轻,二者最大相差6.1‰;而正构脂肪酸的单体碳同位素却比稻草重,二者最大相差8.4‰.稻草闷烧时排放的正构烷烃比明火燃烧时排放的更趋向于亏损13C,而高碳数（≥C19）正构脂肪酸的单体碳同位素组成呈现出比明火烟尘偏重的趋势.在稻草烟尘中,正构烷烃和正构脂肪酸的单体碳同位素组成与未燃烧稻草中的对应化合物有显著差别.烟尘中两类有机物相对于稻草而发生了方向相反的碳同位素分馏.     

太原市PM10及其污染源中碳的同位素组成

通过采集太原市PM10及其主要源(煤烟尘、机动车尾气尘、土壤风沙尘)样品,结合离线分步加热氧化法和同位素质谱仪测定了颗粒物中有机碳(OC),元素碳(EC)和总碳(TC)的同位素组成, 并探讨了太原市PM10中碳的来源.结果表明,太原市冬季、春季PM10中OC、EC和TC的碳同位素组成分别是-34.7‰、-23.5‰、-23.9‰和-30.5‰、-23.1‰、-23.9‰; 煤烟尘中OC、EC和TC的碳同位素组成分别是-26.5‰、-23.2‰、-23.6‰,土壤风沙尘分别为-24.6‰、-14.1‰、-17.3‰,汽油车和柴油车尾气尘分别为-27.7‰、-25.5‰、-27.0‰和-25.7‰、-24.3‰、-24.8‰. EC和TC的同位素组成是区分土壤风沙尘较好的标识指标,TC的同位素组成是汽油车尾气尘较好的标识指标;利用二元复合计算公式结果显示土壤风沙尘中OC、EC占TC的百分含量分别为30%、70%;煤烟尘中OC、EC占TC的百分含量分别为11%、89%;汽油车尾气尘中OC、EC占TC的百分含量分别为78%、22%,柴油车尾气尘中OC、EC占TC的百分含量分别为36%、64%;太原市PM10中的TC和EC主要来源于煤烟尘,OC少部分来源于机动车尾气排放,另外还有其他的重要贡献源.     

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.     

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.