基于分步热解技术的沉积岩形态汞同位素分析方法

沉积岩中的汞及其同位素常被用于指示大规模火山活动、海洋氧化还原演变等古环境演化事件,但现有研究主要聚焦总汞含量及相应的总汞同位素组成,缺少形态汞含量及其同位素组成数据,因此无法精准判别古环境中汞的来源、沉积环境和沉积过程。本研究开发了基于热解技术的沉积岩中不同形态汞的分离和同位素分析方法。首先通过沉积岩中典型形态汞（有机质、硫化物和粘土矿物结合态汞）单一标准建立热解温度曲线,然后将上述单一标准物质混合,通过调整升温速率以及形态汞采集的温度范围和时间优化热解分离方法,收集不同温度下析出的气态单质汞进行同位素分析。结果表明,分离的有机质结合态及硫化物结合态汞的δ²⁰²Hg和Δ¹⁹⁹Hg值同参考值的平均差值分别小于0.20‰和0.03‰,因此该分离方法能有效分离上述形态汞并进行汞同位素组成分析。上述方法被进一步应用于分析天然标准物质（黄红壤、水系沉积物、海相沉积岩）的汞形态及其同位素组成,验证了该方法在自然样品中的广泛适用性。     

不同施肥措施对热带地区稻菜轮作体系土壤CH4和N2O排放的影响

研究稻菜轮作模式下土壤甲烷（CH₄）和氧化亚氮（N₂ O）排放对不同施肥措施的响应,对补充我国热带地区CH₄和N₂ O排放研究的不足具有重要的指导意义.在辣椒季设置4种施肥处理：磷钾肥（PK）、氮磷钾肥（NPK）、等氮条件下50%有机肥替代化肥（NPK+M）和100%有机肥替代（M）,水稻种植季未设置施肥处理,研究辣椒季不同施肥条件下CH₄和N₂ O的排放规律以及对早稻生长季水稻产量、CH₄和N₂ O排放的后续影响.采用密闭静态箱-气相色谱法测定稻菜轮作土壤CH₄和N₂ O,同时测定作物产量,并估算全球增温潜势（GWP）和温室气体排放强度（GHGI）.结果表明：①辣椒季和早稻季4种施肥处理下土壤CH₄的累积排放量分别为0.9~2.7 kg ·hm^-2和5.5~8.4 kg ·hm^-2,与NPK处理相比,辣椒季NPK+M和M处理CH₄累积排放量分别减少35.3%和7.6%;而早稻季NPK+M和M处理CH₄累积排放量均增加37.5%和55.1%,其中早稻季M处理达到显著水平.②辣椒季和早稻季4种施肥处理下N₂ O的累积排放量分别为0.5~3.0 kg ·hm^-2和0.3~0.5 kg ·hm^-2,相对NPK处理,辣椒季NPK+M和M处理降低33.7%和16.0%的N₂ O累积排放量,其中NPK+M处理达到显著差异,早稻季NPK+M处理N₂ O累积排放量降低23.5%,M处理却增加9.1%,但均未达到显著水平.③ 4种施肥处理下辣椒和早稻的产量分别为3055.6~37722.5 kg ·hm^-2和5850.9~6994.4 kg ·hm^-2,与NPK处理相比,NPK+M和M处理显著增加辣椒产量.各施肥处理GWP为508.0~1864.4 kg ·hm^-2,NPK+M和M处理相对NPK处理分别下降25.7%和5.7%,其中NPK+M处理达到显著差异.辣椒季各处理的GWP对总GWP的贡献率为69.2%~78.1%,N₂ O对总GWP的贡献率为77.3%~85.3%.辣椒季和早稻季GHGI分别为0.03~0.09 kg ·kg^-1和0.04~0.24 kg ·kg^-1,与NPK处理相比,辣椒季M和NPK+M处理使GHGI显著下降71.5%和54.7%,早稻季NPK+M和M处理GHGI值分别下降44.0%和20.8%,其中NPK+M处理达到显著差异.综合作物产量及温室气体减排效果考虑,化肥和有机肥配施（NPK+M）可推荐为海南稻菜轮作模式下一种最优的减排稳产的施肥措施.     

芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.     

一步法制备乙酸酐新工艺

本文提供了一步法制备乙酸酐的新工艺。它具有工艺简单、反应快、转化率高等优点,是小批量生产乙酸酐的最佳方法。     

Bacterial colonization of the phyllosphere of nineteen plant species and antimicrobial activity of their leaf secondary metabolites against leaf associated bacteria

Summary. The scope of this work was to examine whether leaf constitutive secondary metabolites play a role in determining bacterial colonization of the phyllosphere. To this aim, we surveyed nineteen native or cultivated plant species that share a common bacterial pool in a North Mediterranean area, and estimated the size of total and ice nucleation active (INA) bacterial populations on their leaves. Large differences in the colonization of their phyllosphere were found; the population size of epiphytic bacteria ranged from 7.5 × 10² to 1 × 10⁶ CFU/g fresh weight, in eucalypt and celery, respectively. Species native in Mediterranean-type climate areas, particularly those belonging to the group of aromatic plants, are characterized by scarce presence of INA bacteria. The antibacterial activity of essential oils, surface phenolics and leaf tissue extracts was also estimated against the INA strains P. syringae and E. herbicola, isolated from two of these plant species. E. herbicola proved more sensitive than P. syringae. Of the species examined, oregano [Origanum vulgare L. subsp. hirtum (Link.) Ietswaart], an aromatic plant, had the highest antimicrobial activity, whereas six species showed no activity at all. Further experiments were performed with oregano and bean (Phaseolus vulgaris L.) that represent two extremes in their secondary metabolite content. Both plants were inoculated with P. syringae. By the end of incubation, the bacterial population on bean plants was about 100 times higher than that on oregano leaves. Scanning electron micrographs showed that bacterial growth on oregano leaves was confined to sites away from glandular hairs. Results from the bacterial colonization survey together with those from the toxicity tests showed that all species rich in antibacterial secondary metabolites harbored low leaf bacterial populations. These results provide substantial evidence that leaf secondary metabolites function as constitutive defense chemicals against microbial invasions. However, the fact that species with non- or moderately active leaf secondary metabolites are not always highly colonized suggests mediation of other unknown factors, the contribution of which requires further investigation.     

Validation of a Lagrangian dispersion model implementing different kernel methods for density reconstruction

In this paper the inert version of a Lagrangian particle model named photochemical Lagrangian particle model (PLPM) is described and validated. PLPM implements four density reconstruction algorithms based on the kernel density estimator. All these methods are fully grid-free but they differ each other in considering local or global features of the particles distribution, in treating the Cartesian directions separately or together and in being based on receptors or particles positions in space. Each kernel has been shown to have both advantages and disadvantages, but the overall good performances of the model when compared with the well known Copenhagen and Kincaid data sets are very encouraging in view of its extension to fully chemically active simulations, currently under development.     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

改良剂对4种木本植物的铅锌耐性、亚细胞分布和化学形态的影响

本研究以4种耐铅锌木本植物夹竹桃(Nerium oleander)、栾树(Koelreuteria paniculata)、泡桐(Paulownia)和苎麻(Boehmeria)为材料,在不同改良剂浓度下(CK组:100%铅锌矿渣±少量磷肥、改良一:85%铅锌矿渣±10%泥炭土±5%菌肥±少量磷肥、改良二:75%铅锌矿渣±20%泥炭土±5%菌肥±少量磷肥),进行了耐性木本植物富集与转移能力以及Pb、Zn在4种木本植物不同部位的亚细胞分布和化学形态分析.结果表明:14种植物种植后基质中重金属的浓度基本低于种植前,夹竹桃与苎麻改良一与改良二之间差异不显著,泡桐改良二效果显著优于改良一,栾树改良一效果显著优于改良二;4种植物地上部对Pb、Zn的富集系数都比较低,但具有较高的转移系数,适当的基质改良有利于提高植物对Pb、Zn的富集与转移能力.2Pb、Zn在4种植物各部位的亚细胞分布以细胞壁组分和可溶性组分为主,在线粒体、叶绿体和细胞核等细胞器组分中分布较少;与CK组相比,两改良组使可溶性组分对Pb的滞留作用和细胞壁对Zn的滞留作用在增强.3Pb在植物各部位的化学形态以盐酸、氯化钠和乙醇提取态为主,其他化学形态含量极少;Zn则以残留态、盐酸、醋酸、氯化钠、水和乙醇提取态这6种形态存在,且都具较高分配比例.与CK组相比,两改良组使植物各部位活性较弱的Pb的化学形态比例减少,活性较强的化学形态比例增加;Zn则是根部活性较强的化学形态比例增加,地上部活性较强的化学形态比例减少.     

小清河表层沉积物重污染区重金属赋存形态及风险评价

测定了小清河表层沉积物重污染区间隙水中重金属(Cu、As、Pb、Zn、Cr、Cd和Ni)的质量浓度,采用改进的BCR顺序提取法分析了沉积物中重金属的赋存形态,并分别基于美国水质基准(CCC、CMC)和风险评价编码法(RAC)、潜在生态风险指数法对间隙水和表层沉积物中重金属的毒性及生态风险进行评价.结果表明,小清河沉积物间隙水中的重金属基本不会对水生态系统产生毒性.除As外,表层沉积物中6种重金属的含量显著高于土壤背景值,呈现明显的累积效应.沉积物中Cu、As和Ni主要赋存于残渣态,Pb、Cr主要赋存于可氧化态和残渣态,Zn、Cd以酸可溶解态和可还原态为主.Cd、Zn、Cr和Pb的有效态含量高于残渣态,有较高的二次释放潜力.RAC的评价结果表明,沉积物中Cu、Pb、Cr和As处于无风险到低风险级,Ni处于低风险到中等风险级,Cd处于中等到高风险级,Zn处于中等到极高风险级,不同重金属RAC的平均值依次为CdZnNiAsCuCrPb.潜在生态风险指数法的评价结果表明,沉积物中除Cd有强~很强生态风险外,其他6种重金属均表现为低生态风险,RI值介于136.83~264.83,研究区采样点处于中等~强生态风险.     

镉-八氯代二苯并呋喃复合污染土壤中紫茉莉对镉的修复能力

针对土壤重金属-持久性有机物复合污染日益严重的现象,本研究以镉(Cd)和1,2,3,4,6,7,8,9-八氯代二苯并呋喃(OCDF)为典型的重金属和持久性有机污染物,选取紫茉莉为修复植物,通过温室盆栽实验研究Cd-OCDF复合污染土壤中植物的耐性以及有机物对植物提取土壤中Cd能力的影响.结果表明种植3个月期间,紫茉莉在Cd浓度≤200 mg·kg-1的复合污染土壤中具有较强的耐性,株高和生物量降低有限;与Cd单一污染相比,OCDF对紫茉莉株高、根部生物量无显著影响,Cd浓度200 mg·kg-1,OCDF浓度500μg·kg-1时,OCDF存在使紫茉莉地上生物量降低22.19%,其它处理组,OCDF对紫茉莉地上生物量无显著抑制作用,反而某些处理组增加紫茉莉地上生物量.Cd-OCDF复合污染效应与Cd单一污染相比,Cd浓度为200 mg·kg-1,OCDF浓度为100μg·kg-1时,紫茉莉根部Cd积累量降低了34.44%,Cd浓度为400 mg·kg-1,OCDF浓度为100μg·kg-1时,根部和叶部Cd积累量分别降低了7.93%和18.09%;其它处理组,OCDF不同程度地提高了紫茉莉根、茎、叶提取和积累土壤中Cd的能力.可见,用紫茉莉修复高浓度Cd-OCDF复合污染土壤中的Cd具有实践上的可行性.