国内民用燃煤烟气中多环芳烃排放因子研究

模拟国内民用燃煤过程.确定燃煤排放烟气中PAHs的排放因子、PAHs在烟气气相与颗粒相之间的分配、特征排放谱以及不同燃烧方式的影响.结果表明:以15种母体PAHs加和计,燃煤排放因子的变化范围为71～882 mg·k8-1,排放因子和有毒PAHs组份排放量由高至低依次为烟煤、蜂窝煤和无烟煤,主要毒性成份存在于颗粒相中.PAH组份的气-固相分配比例与其饱和蒸汽压存在显著的正相关关系.燃煤类型和燃煤中挥发组份对烟气PAHs排放因子、气-固相分配以及排放谱分布具有决定性作用.另外,不同燃烧方式对燃煤排放因子也有一定影响,缺氧条件会导致排放系数升高.     

The study for polyaromatic hydrocarbons decay on Chinese coal soot particles in atmosphere

A study for the photochemical behavior of some polyaromatic hydrocarbons (PAH), for example B(a )P, B( k )F and fluoranthene in coal smoke particles was performed by using indoor Teflon smog chamber.Experiments suggest that the photochemical reaction of PAH is first order reaction and kinetic rates of some PAH were obtained. It was shown that the reaction rate constant is proportional to light intensity and water vapor concentration. Temperature and PAH loading also have influence on PAH decay rate. A model for PAH loss has been set up on the basis of the results of our experiments and the simulating results of this model suggest that coal particle PAH half lives are of the order of a period of days in winter and a few hours in summer. Other factors which may have effect on the photochemical reaction of PAH have also been discussed.     

煤烟粒子中PAHS光化学降解的动力学

 利用TEFLON薄膜室内光化学烟雾箱研究了光强、湿度和温度对燃煤烟颗粒物上多环芳烃（PAH_s）的光化学降解速率的影响。结果表明，PAH_S光解速率常数随光强、湿度和温度的升高而增大。在冬季低光强和低水蒸汽浓度的条件下，PAH_s降解速率很小，可在大气中停留数日，因而可传输较远距离。在夏季高光强和高水蒸汽浓度条件下，PAH_s在数小时内即全部降解。通过对光强、水蒸汽浓度和温度的实验数据进行多元回归，得到了降解速率常数与各参数的函数式，即降解反应的动力学方程式。     

Emission factors of polycyclic aromatic hydrocarbons from domestic coal combustion in China

Domestic coal stove is widely used in China, especially for countryside during heating period of winter, and polycyclic aromatic hydrocarbons （PAHs） are important in flue gas of the stove. By using dilution tunnel system, samples of both gaseous and particulate phases from domestic coal combustion were collected and 18 PAH species were analyzed by GC-MS. The average emission factors of total 18 PAH species was 171.73 mg/kg, ranging from 140.75 to 229.11 mg/kg for bituminous coals, while was 93.98 mg/kg, ranging from 58.48 to 129.47 mg/kg for anthracite coals. PAHs in gaseous phases occupied 95% of the total of PAHs emission of coal combustion. In particulate phase, 3-ring and 4- ring PAHs were the main components, accounting for 80% of the total particulate PAHs. The total toxicity potency evaluated by benzo[a]pyrene-equivalent carcinogenic power, sum of 7 carcinogenic PAH components and 2,3,7,8-tetrachlorodibenzodioxin had a similar tendency. And as a result, the toxic potential of bituminous coal was higher than that of anthracite coal. Efficient emission control should be conducted to reduce PAH emissions in order to protect ecosystem and human health.     

燃煤污染源多环芳烃的排放规律及其分布特征

在对固定污染源烟道气中多环芳烃污染物采样和分析方法进行研究的基础上,对几种不同的燃煤锅炉和炉灶烟道气中的多环芳烃进行了分析测定和评价实验,并探讨了各种锅炉和炉灶多环芳烃的排放规律和分布特征.     

人类活动对查干湖PAHs沉积历史及来源的影响

对查干湖湖心沉积岩芯中16种美国环保署（US EPA）优控多环芳烃（PAHs）含量进行分析,辅以²¹⁰Pb和¹³⁷Cs年代测定,重建查干湖1877—2017年PAHs沉积历史,通过正定矩阵因子分解模型（PMF）定量判别污染源,通过随机影响模型（STIRPAT）和通径分析方法定量分析人类社会经济参数与PAHs沉积历史的影响机理.研究表明：PAHs含量为305.90~1214.42 ng·g^-1,3~4环为优势组分.140年来,PAHs含量变化总体表现为缓慢波动、剧烈波动、快速增加的趋势,20世纪60年代,沉积物中PAHs总量及各组分开始呈较频繁的波动性增大,于2011年达高峰值.查干湖沉积物中PAHs的来源为生物质及煤燃烧、化石燃料燃烧、交通源和石油泄漏,其中燃烧源为主要来源.松原市人口总量和第二产业占GDP比值每提高1%,沉积物中PAHs沉积通量将分别增加8.11%和2.98%,其中能源消费总量通过第二产业占GDP比值对PAHs沉积通量的影响最大.     

海河及渤海表层沉积物中多环芳烃的分布与来源

采集海河和渤海表层沉积物样品,测定16种EPA规定多环芳烃.海河∑PAH含量（干重）范围为445～2185 ng·g-1,平均值为964 ng·g-1;渤海∑PAH含量范围为171～290 ng·g-1,平均值为226 ng·g-1.海河塘沽区段和天津市区段沉积物中∑PAH含量比郊区段含量高.LMW/HMW(低分子质量/高分子质量)和异构体比值分析表明,生物质及煤的燃烧为海河表层沉积物中PAHs主要来源;对于渤海湾大部分区域来说,石油污染是其PAHs的主要来源,而热解来源的PAHs主要以生物质及煤的燃烧为主;滨海旅游度假村附近海域因受旅游活动影响而燃烧源的贡献较大.风险评价表明,海河及部分渤海海域存在潜在生态危害,滨海村附近海域存在潜在生态风险可能性较低.     

天津表层土壤中多环芳烃的主要来源

用主成分分析和多元线性回归分析方法研究了天津3个不同空间区域表土中PAHs的来源及其相对贡献.结果表明:燃煤和炼焦是各区最重要的PAHs释放源.塘沽汉沽高值区尤其如此,其燃煤和炼焦二者合计占总排放贡献的79%,交通源仅占21%.市中心及近郊区交通来源上升到与燃煤来源相当的水平(约各占35%),此外,焚烧产生的PAHs也占很高比例(21%).农村低值区则呈现出更多多源特点;秸秆燃烧是本区独有的,约占总贡献的11%.根据源解析得到的结果与根据燃料用量和排放因子计算的排放结果有一定可比性.     

蚊香燃烧产物中多环芳烃的分布规律及相关性研究

对蚊香燃烧后的烟气和灰烬样品进行采集,利用GC-MS方法分析其中16种优控多环芳烃(PAHs)的含量,并对烟气和灰烬中各PAHs组分及总量间的相关关系进行探讨.结果表明:蚊香烟气中16种PAHs均有检出,排放量较大的组分主要有萘、苊、二氢苊、菲和荧蒽,并以2～3环PAHs为主;灰烬中PAHs也以2～3环化合物为主,但排放总量仅为烟气中的4.7%～21.8%.通过与其他室内燃烧源PAHs排放量的对比发现,蚊香灰烬中总PAHs排放量低于卫生香源和木柴源,但比香烟源高一个数量级以上;烟气中总PAHs排放量低于燃煤源、木柴源和卫生香源,但明显高于烹调源.回归分析结果表明,烟气中总PAHs排放量与灰烬中的排放量表现出明显的线性关系(R2=0.9054).     

淮南煤田石炭-二叠系煤中有害元素分布与富集赋存特征

为调查分析淮南煤田石炭—二叠系有害元素的分布与富集赋存特征,采用ICP-MS对张集矿、潘三矿和顾桥矿共159件样品的煤中微量元素含量进行了测试分析,分析了11种有害元素的含量分布特征、富集特征,利用聚类图谱探讨了有害元素的富集赋存特征。研究结果表明:除As外,绝大多数元素的平均含量均低于地壳丰度,除Ba和As外,绝大多数元素的平均含量均高于中国煤、美国煤和世界;采用地壳丰度作为对比值所得到的富集系数严重偏离了煤中有害元素的分布特征,与中国煤、美国煤和世界煤相对比较,Cd高度富集,Cr、Cu、Ni、Pb、Sn、Ti为轻度富集至富集;不同煤层有害元素的富集程度存在较大的差异,Cd、Cr、Pb、Ni、Sn易出现富集,Cd为典型富集的有害元素,在8煤、7煤、6煤、5煤和4中出现高度富集;不同矿井主采煤层中有害元素富集程度存在差异,明显高度富集的有害元素为Cd、Ti;原煤灰分中的酸性组分超过灰成分的80%,灰成分指数平均碱酸比为9. 64%,煤中有害元素主要为陆源碎屑来源,部分存在自生矿物; As、Ni赋存富集于黄铁矿中,Ba、Mn可能赋存富集于碳酸盐矿物中,Cr可能吸附富集于粘土矿物中、Pb、Sn、Ti可能与硫酸盐矿物有关,Zn、Cu可能赋存在闪锌矿中,Cd可能赋存富集于黄铁矿和吸附富集于粘土矿物中,其富集程度与沉积环境和煤层稳定程度有关。     

洛阳市秋冬季PM2.5中多环芳烃的污染特征、来源解析及健康风险评价

本研究于2018年10月4日至2019年1月30日在洛阳市高新和林校2个采样点位同步连续采集秋冬季PM_2.5样品,使用气相色谱-质谱联用仪（GC-MS）对PM_2.5中优先控制的16种多环芳烃（polycyclic aromatic hydrocarbons,PAHs）进行了分析测定.对优良天和污染天PM_2.5中16种PAHs的质量浓度和组成分布特征进行了研究,利用特征比值法和主成分分析法对其主要来源进行了定性解析,并使用苯并［a］芘（BaP）毒性当量法和增量终生致癌风险模型评估了对人体的健康风险.结果表明在采样期内,高新和林校两个采样点的PM_2.5中16种PAHs质量浓度变化范围分别为24.33~90.26 ng·m^-3和23.81~76.99 ng·m^-3.随着PM_2.5污染程度的加重,PAHs浓度明显升高（污染天为优良天的1.3倍）,不同环数PAHs贡献顺序均为：4环（43%~48%） > 5~6环（32%~35%） > 2~3环（20%~22%）.大气中PAHs主要来自于燃烧源,包括燃煤、生物质燃烧以及机动车排放等,其中燃煤对PAHs污染贡献最大（优良天：49.28%~56.38%,污染天：49.44%~60.60%）.BaP毒性当量浓度表明,污染天存在更高的人体健康风险;增量终生致癌风险结果表明,污染天致癌风险高于优良天,成人呼吸暴露风险高于儿童,在研究区域内不同污染水平下健康风险属于可接受水平（<1×10^-6）.     

利用PUF大气被动采样技术监测中国城市大气中的多环芳烃

利用PUF大气被动采样技术,分冬、春2个季度,对中国32个城市大气中的多环芳烃（PAHs）进行了观测.结果表明,除主要存在于气相中的2～3环PAHs与部分4环PAHs外,PUF被动采样器也可一定程度地采集大气颗粒物中的5～7环PAHs.中国城市大气PAHs的浓度与组成,主要受城市所处的地理位置、气候条件以及能源消费结构的影响.西北、华北、西南和华中地区部分城市大气中PAH总量和高环PAH浓度均较高,华南和东南沿海一带城市则相对较低.在季节变化上,表现为冬季浓度高、春季低.可能是陆源有机质在土壤中早期成岩作用的产物,春季浓度升高反映了土壤颗粒物对大气颗粒物的贡献,与扬尘天气相对应;而芴的浓度在燃煤较多的城市大气中显著增加,与其主要属燃煤成因相一致.研究表明,PUF大气被动器可很好地运用于区域大气PAH污染分布与特征对比研究.     

渤海及邻近海域表层沉积物中多环芳烃的来源解析

利用GC/MS测定了渤海及其邻近海域表层沉积物中的16种优控多环芳烃(PAHs),采用多种数据分析技术解析了PAHs的来源。结果显示:除了萘、苊烯、苊在部分样品中未检出之外,其他13种PAHs在所有样品中均有检出。总PAHs的含量范围为:(148.27~1211.81)10-9,平均值为507.1310-9。TOC(总有机碳)与总PAHs显著相关(R=0.66,P= 0.0002),表明TOC对研究区域PAHs的分布有重要作用。该海域PAHs以高环(4~6环)为主,轻重比值(LMW/HMW)表明该区域的PAHs主要来自高温燃烧源。分子诊断比值分析也表明,PAHs主要来自生物质、煤炭和石油燃烧。主成分分析-多重线性回归分析(PCA-MLR)表明,沉积物中PAHs主要来自煤炭燃烧源、交通源(石油燃烧)、焦化源和石油源,其贡献分别为54.3%,28.6%,13.4%和3.7%。     

室内外PM10中多环芳烃相关关系及来源分析

为研究室内外PM10中多环芳烃相关性和来源特征,于2009年非采暖季、采暖季在天津市某小区36位住户室内和室外进行PM10膜采样,并分析其中12种PAHs浓度.结果表明,非采暖季较采暖季更为良好的室内外通风性,导致非采暖季室内外PM10中PAHs浓度没有显著差异(P>0.05),而采暖季室内PM10中PAHs浓度显著小于室外浓度;非采暖季室内外PM10中各PAHs占总PAHs的质量百分比基本一致,而采暖季其室内外质量百分比有明显不同;采暖季和非采暖季室内外PM10中PAHs的I/O平均值均低于1,但采暖季I/O值小于非采暖季. 对参与者的时间活动模式分析表明,在采暖季和非采暖季,室内吸烟、清洁活动以及烹饪对室内PM10中PAHs浓度变化均没有显著影响(P>0.05). 室内外PAHs浓度线性回归分析表明,室内PM10中5~7环PAHs主要受到室外源的影响,2~4环PAHs主要受到室内源的影响,非采暖季和采暖季室内外PM10中总PAHs的有效穿透因子分别为0.73和0.51. 通过特征比值法对PM10中PAHs来源进行解析得出,燃煤源、柴油机动车是其主要来源.     

Characterization, treatment and releases of PBDEs and PAHs in a typical municipal sewage treatment plant situated beside an urban river, East China

Characterization, treatment and releases of eight polybrominated diphenyl ethers (PBDEs) congeners and sixteen polycyclic aromatic hydrocarbons (PAHs) in wastewater were evaluated along the treatment processes of a typical secondary treatment municipal sewage treatment plant (STP) (in Hefei City) situated the beside Nanfei River, East China. The findings showed that the average concentrations of the total PBDEs in raw wastewater and treated effluent were 188.578 and 36.884 ng/L respectively. Brominated diphenyl ether (BDE) 209 congener, the predominant PBDE in the STP and Nanfei River, could be related to the discharge of car-industry-derived wastes. For PAHs, the average concentrations in raw wastewater and treated effluent were 5758.8 and 2240.4 ng/L respectively, with naphthalene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene being detected at the highest concentrations. PAHs mainly originate from the combustion of biomass/coal and petroleum. The STP reduced about 80% of the PBDEs and 61% of the PAHs, which were eliminated mainly by sedimentation processes. The removal rates of PBDEs/PAHs increased with the increase of their solid-water partitioning coefficients. Accordingly, the STP's effluent, containing some PBDE congeners (e.g., BDE 47, 99 and 209, etc.) and low-molecular-weight PAHs, could be an important contributor of these contaminants' input to Nanfei River. It resulted in a significant increase of PBDE/PAH concentrations and PAH toxicological risk in the river water downstream. About 4.040 kg/yr of PBDEs and 245.324 kg/yr of PAHs could be released into the Nanfei River. The current conventional wastewater treatment processes should be improved to remove the relatively low-molecular-weight PBDEs/PAHs more effectively.     

Polycyclic aromatic hydrocarbon biodegradation and extracellular enzyme secretion in agitated and stationary cultures of Phanerochaete chrysosporium

The extracellular enzyme secretion and biodegradation of polycyclic aromatic hydrocarbons (PAHs) were studied in agitated and shallow stationary liquid cultures of Phanerochaete chrysosporium. Veratryl alcohol and Tween80 were added to cultures as lignin peroxidase (LIP) and manganese peroxidase (MnP) inducer, respectively. Shallow stationary cultures were suitable for the production of enzyme, whereas agitated cultures enhanced overall biodegradation by facilitating interphase mass transfer of PAHs into aqueous phases. The use of a LIP stimulator, veratryl alcohol, did not increase PAH degradation but significantly enhanced LiP activity. In contrast, Tween80 increased both MnP secretion and PAH degradation in shallow stationary cultures. On the other hand, high PAH degradation was observed in agitated cultures in the absence of detectable LIP and MnP activities. The results suggested that extracellular peroxidase activities are not directly related to the PAH degradation, and the increased solubility rather than enzyme activity may be more important in the promotion of PAH degradation.     

淮北煤中12种有害微量元素在煤及其灰中的分布特征

为了解有害微量元素在各煤层中的分布与变化规律,以及在煤燃烧后的煤灰中所发生的迁移与富集情况,采集了淮北煤田不同煤层、不同深度的15个煤样,采用中子活化法对其原煤及灰分中的12 种微量元素(Ag, As,Ba, Co, Cr, Cu, Mn, Mo, Sb, Th, U, V)进行了测试。结果显示:绝大部分有害微量元素的含量都处于n×10 6到n×10 5数量级范围内,不同煤层或同一煤层不同部位中微量元素的含量分布不同;与全国和华北煤中有害微量元素的(平均)含量相比,除Mn低于全国和华北的平均值外,As、Co、Mo、Sb、Th、U与之相近,而Ag、Ba、Cr、Cu、V高于全国和华北煤中的平均值;12种微量元素均在灰分中有所富集,而且富集能力序列为:Cu>Cr>Mn>Mo>Co>Ba>V>Th>As>U>Sb。     

某焦化场地非均质包气带中多环芳烃(PAHs)来源及垂向分布特征

利用某废弃焦化场地内6眼深层采样孔,样品最大采集深度9. 5～42 m不等,分析包气带剖面上16种PAHs分布特征、污染来源以及影响迁移的因素.结果表明,各钻孔ΣPAHs最大含量介于134. 79～11 266. 81 mg·kg^-1之间,主要分布层位为地表以下1～5 m,含量以低环(2+3环)为主,单体以萘含量最高.场地污染主要来自于煤的燃烧源.焦油、沥青及其深加工产物的污染对场地ΣPAHs含量起控制作用.包气带砂卵砾石层作为污染物良好的下渗通道,砂层透镜体通过吸附及截留作用成为PAHs的主要富集层.化产区排放或泄漏的各类油液通过混溶、竞争性吸附等作用增强了PAHs垂向迁移能力,并致使深部包气带受到污染.地表0～1 m土壤受人为扰动、降雨淋滤、降解作用,30 m以下岩层受到地下水溶滤作用,导致低环/高环比例随深度增加呈现先升高后降低的趋势.污染来源、包气带理化指标及水文地质条件等共同作用控制PAHs垂向分布及迁移.     

重庆废弃煤矿区表层土壤多环芳烃污染特征及风险评价

随着煤炭行业的萧条,废弃煤矿逐渐增加。为有效管理和改善矿区废弃地环境生态系统,采集废弃22年的重庆中梁山马家沟煤矿区内18个表层土壤样品和1个煤矸石样品,以及矿区之外的2个背景土壤样品,分析样品中多环芳烃（USEPA 16 PAHs）、正构烷烃（n-alkanes）、汞（Hg）和有机质（OM）含量水平。结果表明,表层土壤中PAHs的平均含量为170.3 ng/g,低于我国正在运行的煤矿区土壤PAHs含量水平,高于山区背景土壤PAHs含量水平。主成分分析（PCA）结果表明煤燃烧释放和原煤残渣分别贡献78.3%和17.6%,是表层土壤中PAHs的主要来源。PAHs与n-alkanes的相关系数r=0.83（P<0.01）,表明土壤中两者具有类似的输入途径和富集行为。PAHs与Hg之间不存在相关性,表明煤矿长期废弃后,这两种与矿区活动释放有关的污染物的环境归趋有显著差异。PAHs和OM之间也不存在相关性,表明与煤矿相关的有机质来源已经被植物、微生物的分泌物质及其残体的有机质替代,生态环境正逐步恢复。风险评价结果表明PAHs含量水平相对安全。值得注意的是,Hg含量超过农用地土壤污染风险筛选值。因此,政府对矿区旧址的土地利用应当基于多污染参数的叠加结果,避免单一指标的片面性评价与诊断。     

Exposure measurement, risk assessment and source identification for exposure of traffic assistants to particle-bound PAHs in Tianjin, China

To investigate the levels of exposure to particulate-bound polycyclic aromatic hydrocarbon(PAH) and to estimate the risk these levels pose to traffic assistants(TAs) in Tianjin(a megacity in North China), a measurement campaign(33 all-day exposure samples, 25 occupational-exposure samples and 10 indoor samples) was conducted to characterize the TAs' exposure to PAHs, assess the cancer risk and identify the potential sources of exposure. The average total exposure concentration of 14 PAHs was approximately 2871 ± 928 ng/m3(on-duty), and 1622 ± 457 ng/m3(all-day). The indoor PAHs level was 1257 ± 107 ng/m3. After 8000 Monte Carlo simulations, the cancer risk resulting from exposure to PAHs was found to be approximately 1.05 × 10-4. A multivariate analysis was applied to identify the potential sources, and the results showed that, in addition to vehicle exhaust, coal combustion and cooking fumes were also another two important contributors to personal PAH exposure. The diagnostic ratios of PAH compounds agree with the source apportionment results derived from principal component analysis.