北京市夏季臭氧特征及臭氧污染日成因分析

为研究北京市夏季臭氧特征及污染成因,于2017年7月15日至2017年8月10日期间,在北京市城区进行气象要素、臭氧(O3)、氮氧化物(NOx)和一氧化碳(CO)的连续观测,并选取7d(2017年7月20日、30日和8月1日、4~7日)密集采集大气样品进行挥发性有机化合物(VOCs)和含氧挥发性有机化合物(OVOCs)的分析。结果表明,观测期间北京市夏季O3污染严重,臭氧污染日以东南风为主,一般伴随着高温、低湿、低压和高前体物(VOCs、CO和NOx)浓度,占总观测天数的51.8%。密集采样日中臭氧污染日的成因与副热带高压或均压场下的弱高压系统有关。此外,来自河北、内蒙古中部和蒙古国东部途经保定和张家口等地的气流为北京夏季臭氧污染日的形成提供了部分外源,日平均贡献量为16%~37%,最大贡献量为53%,显示区域传输对臭氧污染日形成有重要影响。敏感性试验发现O3的生成主要受VOCs控制,特别是人为源VOCs。以上结果表明,控制北京本地VOCs的人为排放和周边空气质量将有助于降低北京城区的O3浓度。     

Perfluorinated compounds in the surface waters of Puget Sound,Washington and Clayoquot and Barkley Sounds,British Columbia

Perfluorinated compounds (PFCs) are persistent organic contaminants detected in various environmental matrices including sediment, air, biota, and water. The objectives of this study was to evaluate the occurrence of these contaminants within the surface waters of the Pacific Northwest region and through relative concentrations and ratios, to assess their possible sources. Surface waters were extracted and analyzed by liquid chromatography tandem mass spectrometry (LCMSMS). Perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the most commonly detected PFCs. Total PFC concentrations detected ranged from 1.5 to 41 ng L-1. Surprisingly, levels of PFCs in the more urbanized Puget Sound waters were comparable to those measured from the more rural region of Clayoquot and Barkley Sounds in British Columbia. The ratio of PFHpA/PFOA were also similar between the two regions, suggesting that the burden of PFCs throughout the region results from direct input from regional sources.     

典型有机硫化合物热演化的加水热解实验研究

14种典型含硫化合物在 200～ 330 ℃温度区间、在有低硫褐煤和硫抑制剂存在条件下的加水热模拟实验结果表明,大多数结构类型的含硫化合物是结构不稳定的化合物,它们的热稳定性差异很大,不同结构类型的含硫化合物所对应的热解温度不同, 它们在不同温度段产物的分布也不尽相同,这表明单个硫化合物的地球化学行为差异很大,而单个有机硫化合物在有机质热成熟过程中的转换特征基本上可以依据其生成硫化氢、二次含硫化合物以及大分子含硫化合物的量来描述.另一方面,硫化氢作为主要热解产物表明硫化合物分解生成硫化氢是有机硫化合物成熟转化的主要机理性过程.在所调查的化合物中,苯并噻吩、二苯并噻吩、二苯硫和噻蒽等在最高热解温度下也不发生任何化学反应,表明这些化合物代表了稳定型结构的硫化合物,这与这些化合物广泛存在于成熟原油和沉积有机质中的状况是一致的.上述结果还显示含硫化合物的种类和结构类型是受有机质的成熟度或演化阶段控制的.     

黄、渤海二甲基硫化物的浓度分布与迁移转化速率研究

于2015年8-9月对黄、渤海海域进行现场调查,研究了海水中二甲基硫（DMS）、β-二甲巯基丙酸内盐（DMSP）、二甲亚砜（DMSO）的浓度分布、相互关系及影响因素,测定了DMS的生物生产与消耗、光化学氧化和海-气扩散速率,对DMS的迁移转化速率进行综合评价。结果表明:表层海水中DMS、溶解态DMSP（DMSPd）、颗粒态DMSP（DMSPp）、溶解态DMSO（DMSOd）和颗粒态DMSO（DMSOp）浓度的平均值分别为（6.12±3.01）nmol/L、（6.03±3.45）nmol/L、（19.47±9.15）nmol/L、（16.85±8.34）nmol/L和（14.37±7.47）nmol/L,整体呈现近岸高远海低,表层高底层低的趋势。DMS、DMSPd和DMSOp浓度与叶绿素（Chl a）浓度存在显著的相关性。表层海水中DMS光氧化速率顺序为:k_UVA > k_UVB > k_可见,其中UVA波段占光氧化的70.8%。夏季黄、渤海微生物消耗、光氧化及海-气扩散对DMS去除的贡献率分别为32.4%、34.5%和33.1%,表明3种去除途径作用相当。黄、渤海DMS海-气通量变化范围为0.79~48.45 μmol/（m2·d）,平均值为（11.87±11.35）μmol/（m2·d）。     

甘南沼泽沉积脂类生物标志化合物的组成特征

较为系统地分析了寒冷潮湿高原气候条件下形成的沼泽泥炭中脂类化合物，研究了它们的组成，来源和成岩过程，结果表明，正构烷烃，正构烯烃，正构脂肪酸，直链烷基酮和直链烷基醇都由长链组分所构成，这些长链组分来自草本植物，并且得到它们单体碳同位素证据的支持，丰富的奥利烯醇和羽扇烷醇均起源于陆源高等植物，存在很少报道过的一系列藿醇化合物，它们起源于细菌，甾酮和甾醇都以C29组分为主，C28和C29组分主要来自高等植物，而27组分则具有一个细菌源。无奇偶优势的短链正构烷烃，细菌起源的脂肪酸（C14，C15，异构和不饱和脂肪酸），直链烷基－2－酮，藿类和一些甾酮的存在，都说明在这种沉积环境中沉积有机质已经历了强烈改造作用。甾烯酮和甾烯醇分别向它们烷烃的化学和生物化学转化也十分明显。     

Preparation and Structural Investigation of CuCl2 Graphite Intercalation Compounds

Superfine graphite powder was prepared by bali-milling exfoliated graphite containing anhydrous CuCl_2 in planetary ball milling systems.Nano-scale CuCl_2 graphite intercalation compounds were synthesized by heating a mixture of anhydrous CuCl_2 and graphite nanosheets. Scanning electron microscopy,energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy were performed to characterize the microstructures of stage-1 nano-scale CuCl_2 graphite intercalation compounds.The structure and components of the domain wall and core in the nano-scale CuCl_2 graphite intercalation compounds are described.The results show that the content of CuCl_2 in the mixture plays a crucial role in the size of the nano-scale CuCl_2 graphite intercalation compound.     

Establishment and Evaluation of a Method for Analyzing Atmospheric Volatile Organic Compounds

An automated cumulative sampling system and a method that combines a two-step cryo-concentrated system and gas chromatography/mass spectrometry （CCS-GC/MS） are introduced. The method is evaluated by a set of special experiments and the results are presented. The lowest measurement detection limit was expanded from 10^-6 nmol mol^-1 to 10^-12 nmol mol^-1 by using CCS-GC/MS instead of the simpler method of gas chromatography/mass spectrometry （GC/MS）, with the average responsible factor of 39 object compounds being 2.9 × 10^-12. When the volume of air sample reached 1000 cm^3, the lowest detection limit reached up to 7 × 10^-12-40 × 10^-12 nmol mol^-1. The CCS-GC/MS method can potentially identify all objective chemical species in an atmospheric sample, with an average 2.5 s bias error of retention time for 39 gas chromatography （GC） peaks. Within the range 0-400×10^-9 nmol mol^-1, the concentration of 39 kinds of objective compounds can be individually calculated very accurately by a standard curve [average r^2 （coefficient of determination） value of above 0.99]. The recovery efficiency was 88%-111%, with an average of 100.8% ±5.6%. The bias error of precision was 2%-14%, with an average of 6.6%.