Reconstructed mass-spectrometric pattern for characterization of carbon compounds in smoker's lung in situ

BACKGROUND: Cigarette smoke is a major anthropogenic pollutant and contributes to the permanent load of ambient particulate matter in the air, particularly indoors. It is the leading risk factor for premature loss of life due to chronic bronchitis, emphysema and lung cancer. Smoker's lung and graphite pneumoconiosis are pathological states characterized by the deposition of carbonaceous particles. METHODS: Mass spectrometry was used to evaluate unstained lung sections obtained in vivo from a heavy smoker and a patient with occupationally acquired graphite pneumoconiosis. RESULTS AND DISCUSSION: The composition of carbon compounds deposited in lung tissue samples is demonstrated here for the first time. Thirty carbonaceous-containing microareas from ten biopsies (three areas per biopsy) of lung tissues were analyzed mass-spectrometrically. In each case, the samples were taken from a smoker's lung or those demonstrating a graphite pneumoconiosis. The lung-tissue samples were selected by light microscopy before they were evaporated for mass spectrometry. First-order criteria were anionic and cationic mass peaks which occur within the mass patterns in lung tissues of smoker's lung, although not in graphite pneumoconiosis. Second-order criteria were mass peaks from smoker's lung with standard deviations SD < or = 14% of the mean value. First and second-order mass peaks matched the mass peaks of experimental cigarette-smoke condensate in 9 out of 11 peaks. A software program was developed that enabled fast, automated recognition of the typical mass peaks, and thereby confirmed the histological diagnosis of smoker's lung. CONCLUSIONS: The analysis of carbonaceous particles within lung biopsies from a heavy smoker corresponded to the spectra of tobacco condensate and not to the investigated biopsies of graphite peneumoconiosis. RECOMMENDATION AND OUTLOOK: The analyses were performed in order to find out whether mass-spectrometric criteria exist for the differentiation of carbonaceous lung-tissue deposits. Mass spectrometry may be a valuable tool in determining the composition of carbon compounds deposited in human lung tissue. So far, qualitative assessment of the composition of deposits in lung tissue is only possible after the patient is deceased (autopsy).     

超声波萃取—GC／MS测定大气颗粒物中的多环芳烃

采用超声波萃取大气颗粒物样品中的多环芳烃，样品不须纯化，直接可用于GC／MS分析，超声波萃取效率高，萃取时间短；采用MS的SIM方式对多环芳烃进行定性定量，回收率84.5%-108.5%，变异系数3.1%-14.5%。     

大气微生物粒子与飘尘粒子的关系

用ＡＮＤＥＲＳＥＮ生物粒子采样器和光散射气溶胶粒子计数器，在北京西单对大气细菌、真菌和飘尘粒子的浓度、粒度分布及它们之间的关系进行了观测和研究。结果表明，大气细菌的粒度是负偏态分布，大气真菌是对数正态分布，飘尘是正偏态分布。大气细菌浓度与飘尘浓度的比值冬季大，为１１９５３８；夏季小，为２４２１７；年平均比值为６７５１７，＞２．０μｍ的菌尘比值为１５２５３８７，２．０μｍ～８．２μｍ的菌尘比值为３３１８，＞８．２μｍ的菌尘比值为３９４。大气真菌浓度与飘尘浓度的比值冬季大，为２１２７７０；夏季小，为６５５８５；年平均比值为１３５３４４，＜２．０μｍ的菌尘比值为９５２６９８，２．０μｍ～８．２μｍ的菌尘比值为５３４３，＞８．２μｍ的菌尘比值为２６３２。     

Chromatographic measurement of molecular markers of sources of atmospheric aerosol particles

Various organic compounds in aerosol particles in ambient air near a coniferous forest fire in Boulder, Colorado were identified as molecular markers of wood burning and forest fires. Particle samples were collected by filtering small volumes of air. The samples were analysed using thermal desorption followed by gas chromatographic separation and detection, a highly sensitive analytical method. Several compounds unique to softwood combustion were identified in the samples. Additionally, a predominance of odd-carbon-numbered n-alkanes over the corresponding even-carbon-numbered n-alkanes was observed. This predominance is a well-documented molecular pattern indicative of epicutical waxes in plants.     

粘土颗粒吸附直接染料的分形特征

粘土颗粒对直接耐晒黑和直接大红染料的吸附均可分为快速的边缘覆盖和慢速的晶层吸附2个过程,整个吸附过程符合准-二级反应动力学方程式,除了伊利土-直接耐晒黑染料的吸附体系之外,其它体系的吸附过程中以晶层吸附为主的阶段均具有类分形特征.体系的非线性吸附等温线符合Langmuir型吸附等温模式,并且除了蒙脱土吸附直接大红染料之外,也可以用分形Langmuir吸附等温模式获得较好的模拟效果.在不同原始浓度下直接大红染料在粘土颗粒表面发生的边缘覆盖和晶层吸附这2个过程的程度是不同的,从而导致了吸附等温线在原始染料为150mg·L-1时出现最大的吸附量,而且颗粒边缘覆盖的直接大红染料的比例较高.染料进入粘土颗粒的晶层后,扩大了晶层间距,改变了其表面微孔几何结构.颗粒表面棱角变得光滑,结构疏松,片层结构逐渐减少,上述效果在蒙脱土颗粒上或直接耐晒黑染料吸附时表现地更为显著.而且吸附染料后蒙脱土颗粒对N2的吸附量比伊利土下降的幅度小,其比表面积、孔体积和平均孔径的下降比例也比伊利土小,其中平均孔径的差异比较明显.吸附染料之后粘土颗粒表面分形维数Ds均升高了,晶层膨胀和开孔作用抵消了"表面粗糙度屏蔽"、"孔阻塞效应"机理降低Ds的影响.增加了表面粗糙度.     

城市雾天单个矿物颗粒物理和化学特征

应用场发射扫描电镜(FESEM)和带能谱的扫描电镜(SEM-EDX)对北京冬季雾天和正常天气下收集的4个样品进行研究.雾天中矿物颗粒的数量-粒度分布的峰值出现在0.1～0.3 μm和1～2.5 μm之间,并且发现雾天出现的二次矿物颗粒的数量百分含量(4.67%)高于正常天气条件(0.12%).单个矿物颗粒的EDX能谱显示,雾天和正常天气中单个矿物颗粒的主要化学成分有一定的差别,尤其是S元素.矿物颗粒分为9种不同类型:"富Si"、"富Ca"、"富S"、"富Fe""富Mg"、"富Al"、"富Ti"、"富K"和"富Cl",其中雾天"富Ca"中55%的颗粒含有Ca(50%±1.2%)和S(37%±1.6%),"富S"中72%的颗粒含有S(44%±1.5%)和Ca(33%±2%),说明了雾天中绝大部富集S的颗粒物中同时富集Ca,这在一定程度上说明了北京市大气中这些含Ca的碱性矿物对雾水酸性有一定的缓冲作用.雾天样品中S/Ca的平均比值为6.11,如果以冬季正常天气条件下S/Ca的均值0.73为背景值,雾天中S/Ca的比值是冬季正常天气的8倍,可见雾天中颗粒物表面的硫化现象相当严重,同时也显示出雾天SO2向硫酸盐的转化率比较高.     

Superior trichloroethylene removal from water by sulfide-modified nanoscale zero-valent iron/graphene aerogel composite

Sulfide-modified nanoscale zero-valent iron (S-nZVI) is a promising material for removal of organic pollutants from water, but S-nZVI nanoparticles (NPs) easily agglomerate and have poor contact with organic contaminants. Herein, we propose a new S-nZVI/graphene aerogel (S-nZVI/GA) composite which exhibits superior removal capability for trichloroethylene (TCE) from water. Three-dimensional porous graphene aerogel (GA) can improve the efficiency of electron transport, enhance the adsorption of organic pollutants and restrain the agglomeration of the core-shell S-nZVI NPs. The TCE removal rates of FeS, nZVI, GA and S-nZVI were 27.8%, 42%, 63% and 75% in 2?hr, respectively. Furthermore, TCE was completely removed within 50?min by S-nZVI/GA. The TCE removal rate increased with increasing pH and temperature, and TCE removal followed the pseudo-first-order kinetic model. The results demonstrate the great potential of S-nZVI/GA composite as a low-cost, easily separated and superior monolithic adsorbent for removal of organic pollutants.     

异养-自养耦合深度脱氮系统的生物脱氮性能研究

为探究低C/N[ρ（COD_Cr）/ρ（NO₃--N）,下同]水体的脱氮技术,分别以火山岩、火山岩/铁碳颗粒、火山岩/硫磺颗粒、火山岩/铁碳颗粒/硫磺颗粒作为填料构建R1、R2、R3和R4反应器,考察反硝化系统在不同C/N下的脱氮效果.结果表明:①随着进水C/N的降低,R1、R2和R3反应器的NO₃--N去除率逐渐降低,R4反应器则是先升后降;在C/N为1.5~2.0、系统温度为30℃、进水pH为7.0±0.2、HRT（水力停留时间）为4.0 h、进水ρ（NO₃--N）为30 mg/L时,R4反应器中NO₃--N去除率最高,平均值为90.1%.②在R2反应器中,随着反应器的运行,铁碳颗粒自身氧化表面形成氧化膜,使得铁自养反硝化作用不断减弱,脱氮效率与R1反应器相近.③运行前期,R2和R4反应器保持着较高的ρ（NH₄+-N）,随着反应器的运行,4个反应器的ρ（NH₄+-N）相当.④与R3反应器相比,R4反应器中不存在NO₂--N的累积情况,同时铁自养过程产生的碱能被硫自养过程所消耗,系统pH更适合反硝化菌生存.研究显示,C/N为1.5~2.0时,异养-铁-硫自养反硝化系统可提供充足的电子供体,减少对有机碳源的依赖,保证了稳定高效的脱氮效果.      

川南自贡市大气颗粒物污染特征及传输路径与潜在源分析

川南自贡市大气颗粒物污染比较严重, 2015～2018年PM_(10)和PM_(2.5)平均浓度分别为(95.42±9.53)μg·m~(-3)和(65.95±6.98)μg·m~(-3),并有明显的下降趋势,冬季PM_(10)和PM_(2.5)浓度远高于其它季节, 1月平均浓度最高,分别为(138.08±52.29)μg·m~(-3)和(108.50±18.05)μg·m~(-3),夏季平均浓度最低.PM_(2.5)与PM_(10)的平均比值为69.12%,冬季比值约为夏季的1.17倍,空气污染以PM_(2.5)为主.采用拉格朗日混合单粒子轨迹模型(HYSPLIT)和全球资料同化系统的GDAS气象数据,对自贡市细颗粒物(PM_(2.5))浓度和逐日72 h后向轨迹进行计算和聚类研究,利用潜在源贡献分析法(PSCF)和浓度权重轨迹分析法(CWT),探讨不同季节影响自贡市PM_(2.5)浓度的潜在源区以及不同源区的污染贡献.结果表明,自贡市近地面四季多受东南风、偏西风和西北风控制,高浓度PM_(2.5)多出现在0～2 m·s~(-1)的低风速区;不同季节、不同输送路径对自贡PM_(2.5)污染影响的差异显著,春季主要受到来自偏西和偏北方向短距离输送气流的影响,夏季污染轨迹主要来自短距离输送的东南气流,秋季主要受来自资阳,经遂宁、重庆和内江的短距离输送气流的影响,冬季除受到资阳、遂宁和内江等周边城市的影响外,还受到来自西藏中部的远距离输送气流影响;除夏季外,自贡市潜在源区主要位于重庆西部与川南交界区域,冬季的主要贡献区范围最广、贡献程度最大,夏季潜在源区范围最小且贡献程度最弱.     

Fe3O4/CeO2-H2O2非均相类Fenton体系下降解TCE的研究

采用浸渍法成功合成了新型催化剂纳米Fe3O4/CeO_2,并且用Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE进行降解研究,考察了初始pH、H_2O_2浓度、温度及催化剂投加量等因素对于TCE降解效率的影响.实验结果表明,Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE具有较好的去除效果:在初始pH=3,温度50℃,H_2O_2浓度30 mmol·L-1和Fe3O4/CeO_2投加量0.5 mg·L-1时,TCE去除率高达97.29%.同时实验结果表明pH在2~7范围内对TCE均有降解效果,所以相对于传统Fenton体系,该体系拥有更宽pH应用范围.目标污染物的降解符合一级动力学,反应活化能为30.77 k J·mol-1,表明反应易于进行.