宣威肺癌地区室内大气颗粒物理化特征及其毒性研究

发布时间：2018-01-21 12:17

本文关键词： 肺癌燃煤单颗粒毒性相关系数　出处：《中国矿业大学(北京)》2016年博士论文　论文类型：学位论文

【摘要】：本文通过环境科学、单颗粒分析、元素分析与多种生物毒理学研究方法,详细分析了宣威肺癌高发区虎头和对照点肺癌低发区西泽室内大气颗粒物(包括PM10、PM2.5和分级颗粒物)的物理化学特征及其毒性,分析其相互关系,并提出颗粒物毒性表征的方法。研究结果发现:宣威夏季PM10的24小时质量浓度均值区间为203.06μg/m3-365.26μg/m3,高于我国PM10二级标准(150μg/m3);冬季样品中,生物质燃烧产物的质量浓度最大(达到350μg/m3),其次是用电(夜晚燃煤)农户室内颗粒物,最后是燃煤排放颗粒物。夏季样品中,燃煤产物的质量浓度最大(达到350μg/m3),其次是用电和生物质燃烧产物,最后是室外颗粒物。冬夏季节两个采样点颗粒物的平均浓度并无大的波动;冬季宣威地区虎头旧户PM2.5,虎头新户PM2.5和西泽旧户PM10对应的I/O值(室内外颗粒物质量浓度比)分别为1.10,1.78和2.27,都大于1,说明宣威地区室内颗粒物来源于室内污染源。宣威地区虎头室内外PM2.5质量浓度范围为38.54-102.64μg/m3,西泽室内外PM2.5质量浓度范围为32.94μg/m3-54.70μg/m3,其中虎头旧户PM2.5质量浓度明显高于其他采样点。宣威地区虎头室内外PM10质量浓度范围为84.09μg/m3-355.75μg/m3,西泽室内外PM10质量浓度范围为51.23μg/m3-661.49μg/m3,其中西泽旧户白天PM10质量浓度明显高于其他采样点,几乎达到三倍之多,可见相对于燃煤产物,生物质燃烧会产生更多的大气可吸入颗粒物浓度;对于质量浓度均值来说,2013年冬季虎头村PM10均值无论白天还是夜晚都几乎是2011年冬季的1/2,而2013年冬季白天PM2.5均值几乎为2011年冬季的1/3,夜晚几乎相同。三年过去,虎头室内的颗粒物平均浓度都显著降低,相应的污染减小。使用带能谱的透射电镜对宣威各采样点的单颗粒样品进行分析发现,虎头和西泽采样点的单颗粒粒径范围都在0.2μm-3μm,粒径大于2μm的颗粒在两个采样点的数量都比较少。两个采样点的粒度分布规律相似,且粒径在1μm以下的颗粒物数量都比粒径大于1μm的多。虎头和西泽地区样品中硫元素和硅元素最为丰富,西泽作为低肺癌发病率的采样点相比高肺癌发病率地区虎头,其样品中检测到的元素种类少八种,然而只有西泽样品中检测出了砷元素;根据透射电镜及能谱分析结果将宣威地区室内单颗粒样品划分为五种类型:飞灰,有机质(烟尘,焦油球和生物颗粒),矿物颗粒,硫酸盐和混合颗粒物;在两个采样点中混合颗粒为主要颗粒类型,所占的数量也最多。固体单颗粒如飞灰,有机质和矿物颗粒与大气中酸性气体以及空气中的水蒸气接触并反应,形成h+,so42-和no3-等离子,进一步化学反应会产生混合颗粒。大部分混合颗粒物为外混或内混颗粒,内混包括烟尘,有机质,矿物质与硫酸和有机质等的混合;混合颗粒物的老化程度可以参考典型的核壳结构颗粒物及其核壳比。核壳颗粒物的等效粒径范围为0.5μm-2.5μm,平均粒径为1.6μm,几乎所有核壳颗粒的核壳比在0.4到0.8之间,平均比例为0.6。使用质粒dna损伤评价法对宣威地区室内大气颗粒物进行毒性分析,得出在50,100,150,200,250μg/ml剂量下,宣威冬季不同采样点pm10的dna损伤率范围为6%-98%,最高值出现在冬季西泽生物质燃烧产生的颗粒物样品中。宣威夏季不同采样点pm10的dna损伤率范围为24%-72%,最高值出现在夏季虎头燃煤产物中。夏季大气颗粒物dna损伤率整体高于冬季,无论冬季夏季,西泽地区生物质燃烧产生的pm10的dna损伤率都较高。在50,100,150,200,250,500,1000μg/ml剂量下,宣威所有pm10样品的dna损伤率范围从15%到95%,样品的损伤率在50μg/ml到500μg/ml的剂量范围内随剂量增大而增大;虎头村冬季样品中,居民在做饭时采集的颗粒物损伤率明显比不做饭时高。对比虎头和西泽两个采样点白天和夜晚的颗粒物样品,夜晚的颗粒物dna损伤率明显较高,在西泽尤为明显。对比燃煤,生物质燃烧和用电农户大气颗粒物的dna损伤率可以得到,燃煤产物dna损伤率最高,其次是生物质燃烧,最后是用电农户采集的大气颗粒物。宣威地区部分农户没有带烟囱的厨房,而是直接在客厅做饭,对比发现有烟囱的房间采集的大气颗粒物的dna损伤率低于没有烟囱的房间;dna损伤率与质量浓度之间没有明显的相关趋势,主要是因为颗粒物对人体的危害主要是与颗粒物的化学组成和表面吸附的有毒有害物质有关,因此不能仅仅利用颗粒物的质量浓度来评价颗粒物对人体健康的影响。在细胞凋亡实验中,在6.25μg/ml到50μg/ml的剂量范围内,宣威样品的细胞凋亡率较小,且呈现微弱的上升趋势,且宣威室内样品在实验设置的最高剂量下(50μg/ml)的细胞凋亡率最高。在红细胞溶解实验中,在实验所用50、250、500、1000、2000μg/ml各剂量下,宣威样品的红细胞溶剂率较小,说明宣威样品在剂量高达2000μg/ml时都不足以对人血红细胞造成较大的溶解率,则对于宣威样品来说,人体只有在接触足够高浓度的大气颗粒颗粒物后,人体的血红细胞才有可能被溶解损害。使用电感耦合等离子质谱法(icp-ms)对宣威大气颗粒物样品中所含微量元素进行分析,结果得出zn,ti和ni元素的浓度在所有样品中都含量较高,冬季样品中zn元素含量范围是676ppm-16978ppm,ti元素含量范围是577ppm-25560ppm,ni元素含量范围是459ppm-6508ppm。夏季样品的zn元素含量范围是2013ppm-22220ppm,Ti元素含量范围是755ppm-1620ppm,Ni元素含量范围是1058ppm-9200ppm。各元素浓度相对较高的出现在冬季虎头新户样品和冬季西泽旧户样品,且前者所含元素总浓度较高,为81841.96ppm,可能由于冬季虎头新户虽用电做饭,但是每天夜晚燃煤取暖,且屋内不通风。冬季样品总元素含量高于夏季样品,其中,最高值出现在冬季虎头用电农户中,为36590.45ppm。最低值出现在冬季虎头燃煤农户中,为8157.45ppm。夏季样品中元素总含量最高值出现在虎头室外,为30318.82ppm,最低值出现在夏季虎头燃煤农户中,为9226.74 ppm;宣威样品中,Zn元素含量与DNA损伤率呈现正相关,在0.05的显著性水平下相关系数为0.67,说明颗粒物中的水溶性锌有可能是造成质粒DNA氧化性损伤的主要原因之一;将颗粒物中微量元素的含量转换为标准状况下空气中微量元素质量浓度(ng/m3),在大气中浓度最高的三种元素依次为Zn,Ni,Ti,其中Zn元素在空气中的浓度范围为11.1916ng/m3-424.4598ng/m3,Ni元素在空气中的浓度范围为8.9197ng/m3-118.1527 ng/m3,Ti元素在空气中的浓度范围为16.3403ng/m3-639.0148 ng/m3。2013年冬季燃煤室内大气微量元素的含量降低,没有出现质量浓度高于500 ng/m3的的元素,且质量浓度在10ng/m3以下的元素种类更多。在2011年和2013年冬季燃煤室内大气微量元素中,Zn元素含量都为最高,但是在2013年冬季检测到的Zn元素比2011年低一个等级;对比EDX(Energy Dispersive X-ray)和ICP-MS两种方法,其分析结果相互照应。在无机组分方面,将Zn元素作为定义颗粒物毒性的基准元素,使用DNA损伤率与之所有元素之间的相关系数,以及所有与Zn元素有相关性的元素的相关系数可以来表征颗粒物的毒性。
[Abstract]:This article through environmental science, single particle analysis, elemental analysis and various biological toxicology research methods, detailed analysis of lung cancer in high incidence area of the tiger and the control point in low incidence area of lung cancer Cesar indoor atmospheric particles (including PM10, PM2.5 and graded particles) physical and chemical characteristics and toxicity analysis and their relationship, and puts forward the method of particle characterization of toxicity. The results showed: Xuanwei summer PM10 24 hours mean concentration range of 203.06 mu g/m3-365.26 mu g/m3, higher than China's PM10 standard level two (150 g/m3); winter samples, biomass combustion product concentration maximum (up to 350 g/m3), followed by electricity (night coal) indoor particulate matter, finally the emission of particles of coal samples. In summer, the quality of the product (the largest coal concentration reached 350 g/m3), followed by electricity and biomass combustion products, finally the outdoor particulate matter. The season two average concentration of particles is no big fluctuations in winter; the Xuanwei Tiger Old PM2.5, new PM2.5 and Cesar old tiger households households PM10 the corresponding I/O value (indoor and outdoor particle concentration ratio) were 1.10,1.78 and 2.27, are greater than 1, explain the sources of indoor particles in Xuanwei the indoor pollution source. The Xuanwei tiger indoor and outdoor PM2.5 concentration range of 38.54-102.64 g/m3, Cesar indoor and outdoor PM2.5 concentration range of 32.94 g/m3-54.70 g/m3, the old tiger households PM2.5 concentration was significantly higher than that of other sampling points. Xuan Weihai tiger indoor and outdoor PM10 concentration range of 84.09 mu g/m3-355.75 mu g/m3, Cesar indoor PM10 mass concentration of 51.23 Mu g/m3-661.49 mu g/m3, the mass concentration of PM10 during the day old Cesar households was higher than that of other sampling points, almost three times, compared to the visible combustion products Biomass combustion, will produce more atmospheric PM10 concentration; the mean concentration for quality, in the winter of 2013, Steller village PM10 means both day and night is almost in the winter of 2011 1/2, 2013 PM2.5 winter day in the winter of 2011 the mean value is 1/3, the night is almost the same. Over the past three years, the average particle concentration of tiger the indoor were significantly reduced, the corresponding reduction of pollution. With the use of transmission electron microscopy spectrum of single particle Xuanwei samples of each sampling point was found, the tiger and the Cesar sampling point of single particle size in the range of 0.2 M-3 m, the particle size of more than 2 mu m particles in two sampling points the number is less. The size distribution of the two sampling points of similarity in the number and the size of 1 mu m or less than the particle diameter greater than 1 m. The tiger and Cesar area samples of sulfur and silicon is the most abundant, Cesar as low incidence rate of lung cancer with high incidence of lung cancer samples compared to the tiger area, the kinds of elements in samples detected eight samples, but only Cesar detected arsenic; according to transmission electron microscopy and energy spectrum analysis results in Xuanwei indoor single particle samples were divided into five types: fly ash. Organic matter (soot, tar balls and biological particles), mineral particles, sulfate and mixed particles; in two sampling points in the mixed particles as the main types of particles, the number of accounts for the most. The solid particles such as fly ash, organic matter and mineral particles in the atmosphere and acidic gases and water vapor in the air the contact and reaction, the formation of h+, so42- and no3- in plasma, further chemical reactions will produce mixed particles. Most mixed particles for external mixing or mixed particles, including mixed dust, organic matter, mineral acid and sulfur and organic matter mixed ; the aging degree of mixed particles can refer to core-shell structure particles and core-shell ratio. Typical core-shell particles of the equivalent diameter range of 0.5 mu m-2.5 mu m, the average particle size of 1.6 m, almost all the core-shell particles with core-shell ratio between 0.4 to 0.8, the average ratio of 0.6. evaluation of DNA damage plasmid by analyze the toxicity of Xuanwei in atmospheric particulate matter in indoor, obtained 50100150200250 g/ml doses, Xuanwei in different sampling points of PM10 DNA damage rate in the range of 6%-98%, the highest value in biomass combustion in winter Cesar particulate samples. Xuanwei summer in different sampling points of PM10 DNA damage the rate range is 24%-72%, the maximum value appeared in summer. The summer tiger in the residues of atmospheric particulate matter DNA damage rate is higher than that in winter, regardless of winter summer, burning area Cesar biomass of PM10 DNA damage rate are higher. In the 501001502002505001000 g/ml dose, Xuanwei of all PM10 samples DNA damage rate ranges from 15% to 95%, the rate of injury to the sample dose range of 500 g/ml with increasing doses of 50 g/ml increases; Steller village residents in the winter samples, when cooking collected particles damage significantly than cooking high contrast. The tiger and Cesar two sampling points of the day and night particulate samples, night particles DNA damage rate was significantly higher in Xizeyou obviously. Compared with coal, biomass burning and electric household atmospheric particulate DNA damage rate can be obtained, combustion products DNA damage rate is the highest, followed by biomass burning finally is the use of atmospheric particles collected. Some farmers household electrical Xuanwei with no chimney in the kitchen, but the living room directly in the cooking, found that DNA damage the room collected atmospheric particles with the chimney No room rate is lower than the chimney; no obvious correlation between DNA damage rate and the mass concentration of particles is mainly because the harm to human body is mainly toxic and harmful substances in chemical composition and surface adsorption and particle related, so just use particle mass concentrations to evaluate the effects of particulate matter on human health in the cell apoptosis in the experiment, 6.25 g/ml to 50 g/ml within the dose range, the apoptosis rate of Xuanwei samples is small, and showed a weak upward trend, Xuanwei and laboratory samples at the highest dose under the experimental setup (50 g/ml). The apoptosis rate was the highest in red cell lysis experiments. In 5025050010002000 experiments with different doses of g/ml, red blood cell sample solvent Xuanwei rate is smaller, indicating Xuanwei samples at doses up to 2000 g/ml are not enough to cause a larger dissolution of human red blood cells The sample rate, Xuanwei, only in the human body exposed to sufficient atmospheric particulate high concentrations of particles, human red blood cells can be dissolved damage. Using inductively coupled plasma mass spectrometry (ICP-MS) analysis of the trace elements contained in Xuanwei atmospheric particles in the Zn, the concentration of Ti. And the Ni element content in all samples are higher in winter, samples of the Zn element content in the range of 676ppm-16978ppm, the content of Ti is in the range of 577ppm-25560ppm, the content of Ni is in the range of Zn elements in the 459ppm-6508ppm. summer sample range is 2013ppm-22220ppm, the content of Ti is in the range of 755ppm-1620ppm, the content of Ni is in the range of 1058ppm-9200ppm. of each element was relatively high the tiger appeared in winter and winter samples of new households Cesar old household sample, and the elements contained in the total concentration of 81841.96ppm, probably due to the winter Although the new tiger households use electricity for cooking, but every night of coal-fired heating, and the house is not ventilated. The winter samples of total element content is higher than that in summer samples, among them, the highest in winter stellers electricity households, the minimum value for 36590.45ppm. in winter is the highest in the coal tiger farmers, the total content of element 8157.45ppm. in summer samples value the tiger outside, 30318.82ppm, the lowest in the summer stellers coal-fired households, 9226.74 ppm; Xuanwei samples, Zn element content and DNA injury rate showed positive correlation at the 0.05 level correlation coefficient was 0.67, indicating particles in the water soluble zinc may be one of the main causes of oxidative DNA damage plasmid; the content of trace elements in particles into quality concentrations of trace elements in standard condition in the air (ng/m3), the atmospheric concentrations of the three elements of the highest order of Zn, Ni Ti, Zn, the concentration range of elements in the air is 11.1916ng/m3-424.4598ng/m3, the concentration range of Ni elements in the air for 8.9197ng/m3-118.1527 ng/m3, the concentration of Ti elements in the air in order to reduce the 16.3403ng/m3-639.0148 ng/m3.2013 winter indoor coal atmospheric trace element contents, no concentration higher than 500 ng/m3 elements, and the mass concentration in 10ng/m3 the following elements more. Trace elements in the 2011 and 2013 winter indoor coal in the atmosphere, the content of Zn were the highest, but the Zn elements in the winter of 2013 detected a grade lower than 2011; compared with the EDX (Energy Dispersive X-ray) and ICP-MS two methods, the results of each other in the inorganic. The components, the Zn element as a reference element to define the toxic effect of particles using correlation coefficients between DNA and the damage rate of all elements, and The correlation coefficient of all elements associated with the Zn element can be used to characterize the toxicity of particles.

【学位授予单位】：中国矿业大学(北京)
【学位级别】：博士
【学位授予年份】：2016
【分类号】：R122.26;X513

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