Air-Sea Gas Exchange of Typical Trace Organic Pollutants

持久性有机污染物在海-气界面之间的传输对此类化合物在全球环境中的分布是非常重要的，而定量污染物以此机制进行迁移需要准确测量大气和海水中的浓度及经适当方式推导而得的质量传输系数与理化参数来计算求得。本研究旨在分析厦门港秋季大气和海水中有机氯农药（HCHs和DDTs）和多氯联苯（PCBs）的浓度及南海中北部冬季表层海水和底层大气中多环芳烃（PAHs）化合物的浓度，以计算出各化合物的海-气交换通量与方向。于2007年11月采集并分析了厦门内、外港区微表层和次表层海水及大气中的有机氯化合物。厦门港区有机氯化合物海-气交换通量计算采用微表层中真溶解态和大气中气态化合物浓度及经温度校正的无量纲亨利常数带入...Air-sea gas exchange is a very important process influencing the levels and fate of persistent organic pollutants (POPs) in the environment at a global scale. Estimation of the transport of POPs via air-sea exchange requires precise field concentratons and adequate mass transport coefficient and physical-chemical parameters generated proper methods. In this study, concentrations of organchlorine p...学位：博士后院系专业：海洋与环境学院环境科学研究中心_环境科学学号：BH1700006

Influence of UV-irradiation on the Composition of Fatty Acids in the Vegetable Oil

采用酯化衍生-气相色谱/质谱法分析了5种市售植物油中的10种脂肪酸,脂肪酸总量在葵花籽油和玉米油中最高,在花生油和菜籽油中最低,橄榄油居中。组成分布特征以油酸和亚油酸占绝对优势（84.8%~94.7%）,但橄榄油中油酸和亚油酸的比值为1.0,显著高于其他油脂。500 W汞灯作光源,模拟光照24 h后,脂肪酸整体都呈现下降趋势,其中葵花籽油的下降幅度最大（50%）,而玉米油的下降幅度最小（30%）;随光照时间延长,油酸与亚油酸的比值呈逐渐升高的趋势,但反油酸与油酸的比值虽有所降低,但不同油脂之间差异较大。总体而言,光照可以降低植物油的营养价值成分,在贮藏和使用过程中,应尽量避光保存。A total of 10 fatty acids in 5 kinds of vegetable oil bought from local supermarket were analyzed using esterification-GC/MS.The highest concentrations of fatty acids were found in sunflower seed oil and maize oil,followed by olive oil,peanut oil and colza oil.The composition of fatty acids in vegetable oil was characterized by very high oleic acid and linoleic acid,accounting for 84.8%-94.7% of the total fatty acids.The ratio of oleic acid to linoleic acid was 1.0,which was much higher than those in other oils.A 500 W mercury lamp was used to produce UV light source and the irradiation period was set as 0,8,16 and 24 h,respectively.The highest loss of fatty acids was found in sunflower seed oil（around 50%） while the lowest loss was found in maize oil（around 30%）.The ratio of oleic acid to linoleic acid increased with irradiation time,while the ratio of trans oleic acid to oleic acid showed slight decrease trends and varied from oil to oil.In general,the vegetable oil needed to keep in dark place during the storage and in use in order guarantee the quality

武汉月湖水生植被重建过程中浮游植物的动态变化

2004年12月-2005年5月武汉市月湖水生植被重建过程中,对浮游植物进行逐月调查.结果表明,在营养盐浓度较高的条件下,浮游植物仍保持较低的生物量和密度,浮游植物的生长与温度保持一定的相关性,但与湖水营养盐浓度并不存在相关关系.菹草和伊乐藻能使水体的透明度保持较高的状态.浮游植物主要由隐藻和硅藻组成,能形成水华的一些常见种类并未随温度升高而出现,可能与这两种沉水植物的存在改变了浮游植物的群落结构有关.因此,在水温较低的冬季和春季进行水生植被重建是富营养化湖泊治理的有效途径

Seasonal Variations in PM_(10) and Associated Chemical Species in Jiuxian Mountain in Fujian Province

于2011年3月~2012年1月期间在福建德化县九仙山气象站采集大气了PM_(10)样品,分析了九仙山大气PM_(10)中水溶性离子及二元羧酸,; 对其季节分布与来源进行了探讨。结果表明,九仙山大气PM_(10)、水溶性无机离子和有机二元羧酸的季节分布规律较为接近,都表现为春季的浓度显著高于; 其它季节,但9种二元羧酸对PM_(10)的贡献(0.51% 0.41%)显著低于水溶性离子(18.07 %; 8.73%)。其中,水溶性离子组成以NO_3~-和SO_4~(2-)的浓度为最高,其次为Na~+和NH_4~+;阴离子与阳离子当量浓度、NH_4; ~+与SO_4~(2-)当量浓度,以及NH_4~+与NO_3~-当量浓度之间都存在显著正相关关系。有机二元羧酸的组成以乙二酸的浓度为最高,占测量; 二元羧酸总量的75%左右,且随碳数增加呈逐渐递减趋势;来源特征比值(丙二酸/丁二酸、己二酸/壬二酸)、MODIS火点图及后向轨迹图显示,有机二元; 羧酸主要来自大气二次化学反应过程,生物质燃烧的直接贡献很小。PM_(10) samples were collected at the top of Jiuxian Mountain in Fujian; Province from March 2011 to January 2012 and were analyzed for inorganic; water-soluble ions and dicarboxylic acids to investigate their seasonal; variations and sources. The results showed that PM_(10) and its; associated species exhibited much higher levels in the spring than those; in other seasons but the total contribution of the nine species of; dicarboxylic acids to PM_(10) (0.51% 0.41%) was significantly lower; than that of the water-soluble ions (18.07% 8.73%). The water-soluble; ions were characterized by the highest concentrations of SO_4~(2-) and; NO_3~-,followed by Na~+ and NH_4~+. Significant positive correlations; were observed between cation and anion equivalents,as well as between; NH_4~+ and SO_4~(2-) or NO_3~-equivalents. Individual dicarboxylic acid; showed a monotonically decreasing trend with increasing carbon number in; which oxalic acid accounted for approximately 75% of the total; dicarboxylic acids. Characteristic ratios of malonic acid to succinic; acid and adipic acid to azelaic acid,MODIS fire spots,and backward; trajectories showed that dicarboxylic acids mainly originated from; secondary reactions in the atmosphere and that the direct contributions; of open biomass burning to dicarboxylic acid concentrations were; negligible.国家自然科学基金项目; 国家重点研发计划项目; 福建省自然科学基金计划资助项

室内燃烧源排放颗粒物及多环芳烃的粒径分布研究

室内燃烧源排放颗粒物及其多环芳烃（PAHs）的粒径分布是定量评估室内人群呼吸暴露风险的重要参数之一。该研究在再悬浮箱内模拟燃香、燃蚊香、艾灸和吸烟等过程,采用MOUDI采样器采集和分析颗粒物中17种PAHs;同时,采用颗粒物计数器,在实际房间中模拟艾灸和吸烟过程,得到室内颗粒物数浓度的衰减曲线。结果表明,燃烧源烟雾颗粒的排放因子为3.68～22.46 mg/g,颗粒质量粒径呈单峰型,峰值为0.25～0.44μm;US EPA 16种优控PAHs的排放因子为10.52～91.30μg/g,艾绒燃烧排放PAHs的粒径峰值为0.44～1.0μm,略大于其它燃烧源;<1μm颗粒中PAHs的BaP等效毒性当量(BaPTEQ)的贡献占比为85%～98%。来源特征比值的研究显示,艾灸、燃香和吸烟释放的PAHs均归属于生物质燃烧类别。实际室内监测显示,在艾绒和香烟燃烧后室内颗粒物数浓度快速上升,在燃尽时达到峰值,而后在4 h内呈指数规律衰减,且<0.3μm的细颗粒衰减最快。国家自然科学基金项目(41171365

Characteristics of inorganic ions and organic components in PM_(2.5) from biomass burning

为探讨生物质在明火和阴燃两种不同条件下PM_(2.5)及主要成分的排放差异,选取了7种具有代表性的生物质样品(小麦、水稻、马尾松叶、马尾松枝、杂; 草、玉米、棉花)进行了燃烧实验,并对PM_(2.5)样品中的7种主要水溶性离子(Na~+、NH_4~+; 、K~+、Ca~(2+)、Cl~-、NO_3~- 、SO_4~(2-))及有机碳(OC) 、元素碳(EC) 、水溶性有机碳(WSOC); 、有机酸和左旋葡聚糖(LG)等有机成分进行了分析.结果表明,明火和阴燃条件下PM_(2.5)的排放因子分别为2.82~ 7.74; mg·g~(-1)和3.24~ 22.56; mg·g~(-1),阴燃时的排放因子偏高,不同燃料类型也存在一定差异.燃烧排放PM_(2.5)中水溶性离子以Cl~-为最高,占总离子的比例为72; %~; 94%,且与NH_4~+存在显著正相关关系,水溶性离子整体表现为明火条件下的浓度显著高于阴燃条件下的浓度.受阴燃条件下氧气不足的影响,PM_(2; .5)中有机组分的浓度表现为阴燃高于明火,进而导致阴燃时PM_(2.5)的排放因子增加.水稻秸秆燃烧烟尘中3种来源特征比值(LG/PM_(2.5; )、LG/OC和LG/WSOC)仅为小麦和玉米秸秆燃烧排放相应比值均值的0.34、0.24和0.27倍,表明在不同农作物的收获季节采用上述特征比; 值进行生物质燃烧来源估算时,应区别对待.Seven kinds of biomass samples including masson pine needles and; branches,wheat,rice,grass,maize and cotton straw were burned under; flaming and smoldering conditions to investigate the emission factors of; PM_(2.5) and its associated major components including organic carbon; (OC), elemental carbon,water soluble ions,water soluble organ carbon; (WSOC),organic acids and levoglucosan (LG). The results showed that the; emission factors were in the range of 2.82 ~ 7.74 mg·g~(-1) and 3.24 ~; 22.56 mg·g~(-1) for PM_(2.5) from biomass burning in flaming and; smoldering conditions, respectively. The difference between the two; burning conditions varied in different kinds of biomass fuel. The; profiles of water soluble ions in PM_(2.5) were all dominated by; Cl~-,accounting for 72%~ 94% of the total water soluble ions.; Significant positive correlations were only observed between Cl~-and; NH_4~+. The concentrations of water soluble ions were generally higher; in flaming PM_(2.5) than those in smoldering PM_(2.5). The organic; components showed much higher levels in smoldering PM_(2.5) with respect; to those in flaming PM_(2.5) because of incomplete burning. The higher; emission factors of PM_(2.5) under smoldering conditions were mainly due; to the higher emission factors of organic species. Three source; characteristic ratios including LG/PM_(2.5),LG/OC and LG/WSOC in rice; straw burning PM_(2.5) were only 0.34,0.24 and 0.27 times of the mean; ratios in wheat and maize straw burning PM_(2.5),respectively.; Thus,different characteristic ratios are required to estimate biomass; burning contribution in different biomass burning seasons.国家自然科学基金; 国家重点研发计划; 福建省自然科学基金计划项

Particle size distributions of polycyclic aromatic hydrocarbons in rural and urban atmosphere of Tianjin, China

The size distributions of 16 polycyclic aromatic hydrocarbons (PAHs) and particle mass less than 10 mu m in aerodynamic diameter (Dp) were measured using a nine-stage low-volume cascade impactor at rural and urban sites in Tianjin, China in the winter of 2003-2004. The particles exhibited the trimodal distribution with the major peaks occurring at 0.43-2.1 and 9.0-10.0 mu m for both urban and rural sites. The concentrations of the total PAH (sum of 16 PAH compound) at rural site were generally less than those of urban site. Mean fraction of 76.5% and 63.9% of the total PAH were associated with particles of 0.43-2.1 pm at rural and urban sites, respectively. Precipitation, temperature, wind speed and direction were the important meteorological factors influencing the concentration of PAHs in rural and urban sites. The distributions of PAHs concentration with respect to particle size were similar for rural and urban samples. The PAHs concentrations at the height of 40 m were higher than both of 20 and 60 m at urban site, but the mass median diameter (MMD) of total PAH increased with the increasing height. The mid-high molecular weight (278 >= MW >= 202) PAHs were mainly associated with fine particles (Dp = MW >= 178) PAHs were distributed in both of fine and coarse particle. The fraction of PAHs associated with coarse particles (Dp > 2.1 mu m) decreased with increasing molecular weight. The relatively consistent distribution of PAHs seemed to indicate the similar combustion source of PAHs at both of rural and urban sites. The fine differences of concentration and distribution of PAHs at different levels at urban site suggested that the different source and transportation path of particulate PAHs. (c) 2005 Elsevier Ltd. All rights reserved

Application of a Resuspension Test Chamber in PM_(2.5) Source Profile Analysis

为解决PM2.5源解析中无组织排放源的采样问题,在前人基础上发展了一套简便高效的再悬浮采集装置,并对进样量、再悬浮时间等关键运行参数进行了优化,总结了无组织排放源采样分析流程.重复测试表明,双切割头的PM2.5捕集量偏差<8%,粒径分布比率变化不超过5%,显示出再悬浮装置良好的采样平行性和稳定性.将该装置应用于陶瓷工业尘、公路扬尘和二次降尘等3类无组织排放尘及生物质燃烧的源排放再悬浮采样分析,获得了各颗粒源的粒径分布谱和PM2.5无机成分谱,以此对各排放源特征进行有效区分.PM2.5平行样中各化学成分浓度偏差<15%.与其他装置相比,本研究介绍的再悬浮装置简便经济,具有较高的采样效率,在无组织尘排放源谱分析中具有较高的实用价值.A resuspension chamber was developed and optimized to obtain PM2.5 fraction from fugitive sources.In accordance,a basic protocol of sampling and analysis was concluded.Replicate tests showed that mass deviation of PM2.5 between two sampling cascade impactors was less than 8% and size distribution ratios varied by no more than 5%,indicating good sampling parallelism and stability.Chemical profiles and size distribution of three kinds of fugitive dusts(paved road dust,secondary dust and ceramic industrial dust) as well as biomass burning emission had been measured based on the above chamber.The relative standard deviations(RSD%) of inorganic elements in duplicate PM2.5 samples were less than 15%.Comparing with other devices,the resuspension chamber described in this study features convenience and efficiency,and has a high practical value in the source sampling of fugitive dust.环保公益性行业科研专项(201009004);国家自然科学基金项目(40971257

Characteristics and Sources of PM_(10)-bound PAHs During Haze Period in Winter-Spring of Xiamen

采集了厦门市冬春季(2008-12-04~2009-03-20)湖里工业区和大嶝岛旅游区大气PM10样品,用gC-MS定量了PM10负载的19种多环芳烃(PAHS),并结合采样期间气象资料对灰霾期和非灰霾期多环芳烃的差异特征进行对比分析.结果表明,冬春季采样期内,厦门市大气PM10中PAHS的浓度变化范围为12.93~79.27 ng.M-3,平均42.28 ng.M-3,比2004年冬季增长近3倍.灰霾期间PM10中PAHS总的质量浓度明显高于非灰霾期,并且灰霾期间低分子量组分菲、荧蒽和芘的质量分数显著下降,高分子量组分苯并[b]荧蒽、苯并[k]荧、苯并[A]芘、苝、茚并[1,2,3-Cd]芘、苯并[gHI]苝和晕苯的质量分数相对升高.采用特征化合物比值、主成分分析与多元线性回归对来源与贡献率进行了分析和估算.灰霾期间识别出3类污染源:机动车尾气排放+天然气燃烧、煤燃烧和焦炉排放,其贡献率分别为62.7%、28.1%和9.2%;非灰霾期间同样识别出这3类污染源,其贡献率分别为48.6%、36.9%和14.5%.表明厦门市冬春季灰霾期间PM10中PAHS受本地源排放影响相对较多,非灰霾期间受北方燃煤长距离传输影响更显著.PM10 samples were collected at Huli(industrial zone) and Dadeng Island in Xiamen from December 2008 to March 2009.Nineteen polycyclic aromatic hydrocarbons(PAHs) during haze and non-haze periods were determined by GC/MS.Combined with the meteorological data,the differences of chemical composition and source of PAHs were compared.During sampling periods,the concentrations of PM10-bound PAHs ranged from 12.93 to 79.27 ng·m-3 with the average of 42.28 ng·m-3,which were almost three times higher than those in the winter of 2004.PAHs concentrations were much higher during the haze periods than those in the non-haze periods.Meanwhile,during the haze periods the percentages of lower molecular weight PAHs such as Phe,Fluo and Pyr decreased significantly,on the contrary,individual components of BbF,BkF,BaP,Per,Icdp,BghiP and COR were more abundant.The main sources of PAHs were estimated by the Principal Component Analysis method and the contributions of various pollution sources to PAHs were calculated by the Multiple Linear Regression method.Results showed that the main pollutant sources of PM10-bound PAHs in winter-spring of Xiamen during the haze period were vehicle emission plus natural gas,coal combustion and coke oven,their contribution rates were 62.7%,28.1% and 9.2%,respectively.During non-haze periods,the main pollutant sources identified were the same and the contribution rates were 48.6%,36.9% and 14.5%,respectively.In winter-spring of Xiamen,PM10-bound PAHs were more influenced by local emission sources during the haze periods;coal combustion emissions in north China had a big contribution to PAHs during the non-haze periods.环保公益项目(201009004);厦门市科技计划项目(3502Z20093013

Simulation Study of the Emission of Polycyclic Aromatic Hydrocarbons and Sugar Alcohols from Biomass Burning

选择水稻、小麦、玉米及棉花秸秆与马尾松枝,采集模拟燃烧时排放的PM2.5,分析PM2.5中多环芳烃(PAHS)和糖醇类化合物的含量,获得PM2.5及负载的两类化合物的排放因子;采用500 W汞灯直接照射收集了PM2.5的尘膜,获得了中、高环PAHS及左旋葡聚糖的光解动力学.结果表明,PM2.5的排放因子介于(2.26±0.60)g·kg-1(马尾松枝)~(14.33±5.26)g·kg-1(玉米秸秆)之间;19种PAHS的排放因子介于(0.82±0.21)Mg·kg-1(马尾松枝)~(11.14±5.69)Mg·kg-1(棉花秸秆)之间,且以4环类PAHS所占比例最高,介于51%~71%之间(其中马尾松枝燃烧时惹烯的排放因子最大);9种糖醇类化合物的排放因子范围为(52.34±50.16)Mg·kg-1(水稻秸秆)~(238.81±33.62)Mg·kg-1(小麦秸秆),且都以左旋葡聚糖占绝对优势(72%~96%).光照模拟显示,目标化合物的光照损失都遵循拟一级动力学,其中≥4环的PAHS的光解速率常数随着尘膜中PAHS的负载量增大而减小,来源特征比值fluA/(fluA+Py)和IP/(IP+bg P)相对稳定,而左旋葡聚糖的光解速率常数为0.004 5 MIn-1,与苯并[A]蒽的光解速率常数(0.004 1~0.005 0 MIn-1)接近.To measure the emission factors of PM2.5and its associated PAHs and sugar alcohols,Chinese red pine stick and four crop straw including rice,wheat,corn and cotton were burned in a chamber.In addition,the kinetics of certain compounds were obtained through the irradiation of the glass filters with PM2.5loading by 500 W mercury lamp.The emission factors of PM2.5were ranged from( 2.26 ± 0.60) g·kg- 1( Chinese red pine stick) to( 14.33 ± 5.26) g·kg- 1( corn straw).Although the emission factors of the total19 PAHs differed from( 0.82 ± 0.21) mg·kg- 1( Chinese red pine stick) to( 11.14 ± 5.69) mg·kg- 1( cotton straw),4 ring PAHs showed predominance over other PAHs accounting for 51%-71% except Chinese red pine in which retene was the predominant compound.The emission factors of 9 sugar alcohols were ranged from( 52.34 ± 50.16) mg·kg- 1( rice straw) to( 238.81 ± 33.62)mg·kg- 1( wheat straw) with levoglucosan accounting for 72%-96% of the total sugar alcohols.Both the selected PAHs and levoglucosan associated with PM2.5followed the first order kinetics.The photolysis kinetic coefficient of PAHs( ring number≥4) was decreased with the increase of PAHs loading in filters.Two PAHs source characteristic ratios such as Flua /( Flua + Py) and IP /( IP +Bg P) were relative stable during the irradiation.The photolysis kinetic coefficient of levoglucosan( 0.004 5 min- 1) was comparable to benzo[a]anthracene( 0.004 1-0.005 0 min- 1).国家自然科学基金项目(41171365); 环境保护公益性行业科研专项(201009004); 厦门大学山海基金项目(2013SH011