Characterization of polycyclic aromatic hydrocarbon emissions from diesel engine retrofitted with selective catalytic reduction and continuously regenerating trap

Two after treatment units, selective catalytic reduction (SCR) and continuously regenerating trap (CRT), were independently retrofitted to a diesel engine, with the objective to investigate their impact on the conversion/reduction (CR) of polycyclic aromatic hydrocarbons (PAHs). The experiments were conducted under the European steady state cycle (ESC) first without any retrofits to get baseline emissions, and then with SCR and CRT respectively, on the same engine. The particulate matter (PM)-phase PAHs were trapped in fiberglass filters, whereas gas-phase PAHs were collected in cartridges, and then analyzed using a gas chromatograph-mass spectrometer (GC-MS). Both PM-phase and gas-phase PAHs were greatly reduced with CRT showing respective CR of 90.7% and above 80%, whereas only gas-phase PAHs were abated in the case of SCR, with CR of above 75%. Lower molecular weight (LMW) PAHs were in abundance, while naphthalene exhibited a maximum relative contribution (RC) to LMW-PAHs for all three cases. Further, the CR of naphthalene and anthracene were increased with increasing catalyst temperature of SCR, most likely due to their conversion to solid particles. Moreover, the Benzo[a]Pyrene equivalent (BaP_eq) of PAHs was greatly reduced with CRT, owing to substantial reduction of total PAHs.     

Unregulated emissions from diesel engine with particulate filter using Fe-based fuel borne catalyst

The alteration and formation of toxic compounds and potential changes in the toxicity of emissions when using after-treatment technologies have gained wide attention. Volatile organic compound（VOC）, carbonyl compound and particle-phase polycyclic aromatic hydrocarbon（PAH） emissions were tested at European Steady State Cycle（ESC） to study unregulated emissions from a diesel engine with a fuel-borne catalyst and diesel particulate filter（FBC–DPF）. An Fe-based fuel-borne catalyst was used for this study. According to the results, brake specific emissions of total VOCs without and with DPF were 4.7 and4.9 mg/kWh, respectively, showing a 4.3% increase. Benzene and n-undecane emissions increased and toluene emission decreased, while other individual VOC emissions basically had no change. When retrofitted with the FBC–DPF, total carbonyl compound emission decreased 15.7%, from 25.8 to 21.8 mg/kWh. The two highest carbonyls, formaldehyde and acetaldehyde, were reduced from 20.0 and 3.7 to 16.5 and 3.3 mg/kWh respectively. The specific reactivity（SR） with DPF was reduced from 6.68 to 6.64 mg/kWh. Total particle-phase PAH emissions decreased 66.4% with DPF compared to that without DPF. However, the Benzo[a]pyrene equivalent（BaPeq） with DPF had increased from 0.016 to 0.030 mg/kWh.Fluoranthene and Pyrene had the greatest decrease, 91.1% and 88.4% respectively. The increase of two- and three-ring PAHs with DPF indicates that the fuel-borne catalyst caused some gas-phase PAHs to adsorb on particles. The results of this study expand the knowledge of the effects of using a particulate filter and a Fe-based fuel-borne catalyst on diesel engine unregulated emissions.     

Effect of central ventilation and air conditioner system on the concentration and health risk from airborne polycyclic aromatic hydrocarbons

Central ventilation and air conditioner systems are widely utilized nowadays in public places for air exchange and temperature control,which significantly influences the transfer of pollutants between indoors and outdoors.To study the effect of central ventilation and air conditioner systems on the concentration and health risk from airborne pollutants,a spatial and temporal survey was carried out using polycyclic aromatic hydrocarbons (PAHs) as agent pollutants.During the period when the central ventilation system operated without air conditioning (AC-off period),concentrations of 2-4 ring PAHs in the model supermarket were dominated by outdoor levels,due to the good linearity between indoor air and outdoor air (rp>0.769,p<0.05),and the slopes (1.2-4.54) indicated that ventilating like the model supermarket increased the potential health risks from low molecular weight PAHs.During the period when the central ventilation and air conditioner systems were working simultaneously (AC-on period),although the total levels of PAHs were increased,the concentrations and percentage of the particulate PAHs indoors declined significantly.The BaP equivalency (BaPeq) concentration indicated that utilization of air conditioning reduced the health risks from PAHs in the model supermarket.     

生物柴油对柴油机排放细颗粒物及其中多环芳烃的影响

在柴油发动机台架上,考察普通柴油和2种原料不同的生物柴油(B100-1,大豆油为原料;B100-2,废油为原料)在2个固定转速不同负荷的4个工况点的细颗粒物PM2.5及其中多环芳烃(PAHs)的排放特性.用石英滤膜采集了尾气中的细颗粒物,并用GC/MS分析了颗粒物中的PAHs.生物柴油在高负荷时降低了柴油机PM2.5的排放速率,最大降幅达到了37.3%,在低负荷情况下增加了PM2.5排放速率.在所测试的工况下,生物柴油的颗粒相PAHs的排放速率较普通柴油均有不同程度的降低,最大降幅达到77.6%.生物柴油不但降低了PAHs的排放速率,还降低了PAHs在PM2.5中的质量百分比.B100-2的PM2.5和PAHs的平均排放速率比B100-1分别增加14.7%和17.8%.3种燃料排放PM2.5中的PAHs的主要化合物相似,均以小分子量为主,其中以菲的含量最高,2~3环PAHs超过总排放50%.生物柴油排放的PAHs毒性当量与柴油相比有较大程度地下降.     

Health risk assessment of dietary exposure to polycyclic aromatic hydrocarbons in Taiyuan, China

Sixteen polycyclic aromatic hydrocarbons （PAHs） were determined in 24 duplicate-diet samples from people in Taiyuan during summer and winter in 2009. Dietary intake of PAHs for 2862 participants was subsequently estimated by a survey in Taiyuan. Results from these 24 samples were compared with a raw food study in Taiyuan in 2008. Three main sources of dietary PAHs are vegetables, wheat flour and fruits, the sum of which contributes 75.95% of PAHs in dietary food. Compared to the estimated value in raw food, much more B[a]Peq （benzo[a]pyrene equivalents） were detected in food samples collected in the duplicate-diet study in Taiyuan （60.75 ng/day）. The cooking process may introduce more B[a]Peq into food, and the relative contribution of 16 PAHs in the diet would be changed during the cooking procedure.     

PAHs pollution from traffic sources in air of Hangzhou, China: Trend and influencing factors

Introduction China is experiencing rapid economic and populationgrowth. The rapid growth and increasing fossil fuel energyconsumption have resulted in large amounts of pollutants suchas TSP, SO2, NOx and hydrocarbons to be emitted intoambient atmosphere. Nowadays, national routine monitor haspaid much attention to TSP, SO2 and NOx. Highconcentrations of SO2 and NOx can lead to an increase ofregional levels of acid deposition and tropospheric ozon, thu…     

南黄海中部表层沉积物中多环芳烃分布特征及来源分析

通过对南黄海中部49个表层沉积物样品进行总有机碳,粒度,多环芳烃和甲基菲等GS-MS定量分析,探讨了研究区沉积物中多环芳烃分布特征,分子组成,评估南黄海中部多环芳烃污染水平并识别其来源.研究表明,南黄海中部14种多环芳烃总量(ΣPAHs)在81.63~6567.31 ng/g之间,其中优控多环芳烃(ΣEPA PAHs)11种,含量为29.2~1029.1 ng/g,平均含量255.1 ng/g,与国内外其他地区相比有机污染水平为中-低;苝为研究区内主要多环芳烃,分布较为广泛,其含量占所有PAHs的6.40%~88.85%,低含量苝与人为活动有关,而高含量苝代表了陆源有机质输入;多环芳烃组成,异构体分析和甲基菲特征表明,研究区优控多环芳烃主要为煤和高等植物燃烧或不完全燃烧产物以气溶胶形式输入,但部分样品表现出明显的石油源特性也证实了石油燃料,原油泄露产生的多环芳烃客观存在.     

Concentration and source identification of polycyclic aromatic hydrocarbons and phthalic acid esters in the surface water of the Yangtze River Delta, China

The pollution from polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) in the surface water of the rapidly urbanized Yangtze River Delta region was investigated. Fourteen surface water samples were collected in June 2010. Water samples were liquid-liquid extracted using methylene chloride and analyzed by gas chromatography-mass spectrometry. Concentrations of PAHs and PAEs ranged 12.9-638.1 ng/L and 61-28550 ng/L, respectively. Fluoranthene, naphthalene, pyrene, phenanthrene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate were the most abundant compounds in the samples. The water samples were moderately polluted with benzo[a]pyrene according to China's environmental quality standard for surface water. The two highest concentrations of PAHs and PAEs occurred in samples from Taihu Lake, Wuxi City and the western section of Yangchenghu Lake. Potential sources of pollution at S7 were petroleum combustion and the plastics industry, and at Yangchenghu Lake were petroleum combustion and domestic waste. Pollution in samples from the Beijing-Hangzhou Grand Canal originated from diesel engines. There were no obvious sources of pollution for the other water samples. These results can be used as reference levels for future monitoring programs of pollution from PAHs and PAEs.     

模式采样法采集尾气中BaP的研究

用模式了取样法集汽车柴油发动机尾气中多环茎烃,并重点对ＢａＰ采样方法进行研究,结果表明,该法采样时间仅１－２ｓ,采样体积为３３０ｍｌ（ｓ．次）,回收率７７．６％,９次重复的变异系数为２９．６％,测得ＢａＰ的数据与国际ＩＳＯ规定的ＣＶＳ定容取样法可比。     

车用柴油机燃用棕榈生物柴油的颗粒物排放特性研究

在满足国Ⅳ排放法规的车用柴油机上研究了燃用不同掺混体积比例的棕榈油生物柴油的颗粒物排放特性.试验中棕榈油生物柴油的掺混比例分别为0%、10%、20%、50%和100%,采用DMS500型快速颗粒光谱仪测试分析了发动机在外特性和负荷特性时的颗粒物数量浓度、质量浓度及粒径分布.研究结果表明:随生物柴油掺混比例的增加,颗粒物质量浓度降低.燃用生物柴油后颗粒物的数量浓度在大负荷明显降低,中小负荷呈升高趋势.生物柴油的排气颗粒物呈核态和凝聚态的双峰分布特征,核态数量浓度所占比例高于柴油,凝聚态的质量浓度所占比例略低于柴油.生物柴油颗粒物的几何平均直径小于柴油.     

生物柴油排放微粒特性的试验研究

在1台直喷式增压柴油机上进行了生物柴油和柴油的排放微粒特性试验.用80 L/min定量泵和装有直径90　mm的玻纤滤膜采样器在排气管内采集微粒,利用激光粒度仪和色谱-质谱联用仪,分析了微粒的粒径分布和微粒中的可溶性有机物以及16种多环芳烃.结果表明,生物柴油排放微粒的体积粒径呈单峰分布,其平均直径d₃₂.和中位直径d(0.5)都随转速的增加而减少.高转速时生物柴油排放微粒的d₃₂和d(0.5)均高于柴油,而低转速时均低于柴油.生物柴油的SOF排放质量浓度为12.3～31.5 mg/m³,占微粒质量的38.2％～58.0％,均明显高于柴油.生物柴油排放微粒中的总多环芳烃排放浓度为2.9～4.7 μg/m³,与柴油相比下降29.1％～92.4%.     

津冀辽地区典型湖库沉积物PAHs污染特征及来源解析

采集津冀辽地区典型3湖库（于桥水库、衡水湖和大伙房水库）表层沉积物样品共29个,利用GC-MS检测了16种多环芳烃含量.结果表明,沉积物中ΣPAHs（ng·g^-1）分别是337.3~1604.1（均值820.0）、461.1~1497.5（均值932.3）和102.3~2240.5（均值564.9）.与国内其他河流湖库相比,3个典型湖库PAHs污染均处于中等水平.3个湖库在环数占比上有着一致性,均以高环数的高占比为主.通过特征比值与主成分分析法进行PAHs源解析,结果表明,3湖库污染主要以燃烧源（包括石油类燃烧、煤及生物质燃烧）为主,少部分为石油源.其中汽油和柴油不完全燃烧污染贡献占比51.4%,煤和薪柴燃烧污染来源贡献为22.3%.风险评价结果显示,于桥水库、衡水湖和大伙房水库表层沉积物中PAHs总体处于中等偏低水平,但对Flu、InP和DahA这3类物质的监控应当加强,做好对应应急措施.     

柴油烃族组分对柴油机排放的影响

柴油烃族组分可影响柴油的理化特性,从而影响柴油机的燃烧过程,进而对排放产生重要影响.本研究针对烃族组分含量不同的14种柴油,开展了排放特性的试验研究,基于试验结果采用主成分分析法及回归分析法揭示影响柴油机排放性能的关键组分及作用规律,并得到了柴油机排放与关键组分的经验公式,可在一定程度上预测排放特性.分析结果表明,总芳烃是影响柴油机排放的关键组分,当其含量介于5%～17%时,可使NO_x、soot(碳烟)、CO、HC排放均处于较低水平.此外,多环芳烃对柴油机排放有重要影响,其中的苊类、苊烯类对NO_x、碳烟、CO排放的影响作用更为显著,而其他烃族组分与柴油机排放的规律性相对较差.不同工况下,柴油机排放规律有所不同,在低负荷下柴油机排放对总芳烃含量更加敏感.     

油指纹多元统计分析在鉴别地表水石油类污染来源中的应用研究

采用油指纹多元统计方法,对嘉兴市杭州塘和长山河水系沿岸加油站9个不同来源的轻质柴油进行了分类鉴别,并考察了风化的影响.结果表明:仅基于GC-MS谱图,很难对不同轻质柴油的来源进行鉴别;但基于GC-MS谱图,提取正构烷烃及多环芳烃特征比值,进一步采用多元统计方法,可以对不同来源的轻质柴油进行区分.考虑实际水环境中油污染物会风化,向河水中投入两种轻质柴油,考察了不同初始浓度和不同风化时间下的油指纹变化,发现油污染物初始浓度为0.5 mg·L~(-1)时,所有特征比值在风化过程中均极不稳定,无法用于分类鉴别;油污染物初始浓度达到1.0 mg·L~(-1)及以上时,特征比值C_(17)/Pr、C_(18)/Ph在风化5 d内可用作油指纹的鉴别指标,5 d后无法用于鉴别;特征比值Pr/Ph、(C_(19)+C_(20))/(C_(21)+C_(22))、CPI受风化时间影响小,始终可以作为油指纹鉴别的特征指标.     

Mechanisms of formation of particulate polycyclic aromatic hydrocarbons in relation to the particle size distribution; effects on meso-scale transport

Study of the particle size distribution of an urban aerosol has revealed associations between polycyclic aromatic hydrocarbons (PAHs) and inorganic elements. Two particle size distribution families coexist: the first, having mean particle size less than 1 μm, corresponds to lead and to relatively non-volatile PAHs; the second, with mean particle size greater than 1 μm, corresponds to anthropogenic iron, anthropogenic manganese and to volatile PAHs except fluoranthene.Factor analysis shows that the existence of these two families implies two different mechanisms of particle formation, which both depend on the volatility of the compounds: adsorption of PAHs on preexisting particles corresponding to the fine fraction of aerosols (0.7 μm) and condensation of gaseous compounds leading to the formation of bigger particles (1.5 μm).These results are applied to the evaluation of the relative importance of parameters which determine the PAH concentration variations during meso-scale transport between the source zone and the western Meditteranean Sea: the effect of the specific reactivity of each PAH is predominant while the differences on the deposition rates related to particle size are of minor importance.     

黄淮平原农田土壤中多环芳烃的分布、风险及来源

对227个黄淮平原农田表层土壤样品中16种多环芳烃(PAHs)含量进行了调查,并对其致癌风险和来源等进行了分析.结果表明,有15种PAHs被普遍检出,各单体检出率在23.3%~100%之间(苊烯未检出).土壤中PAHs总量(∑PAHs15)为33.44~1246μg/kg,平均值为152.4±166.2μg/kg,且以4环及4环以上PAHs为主,其中16.7%的样品中PAHs含量达到了污染水平(>200μg/kg),与国内外其他地区相比,黄淮平原农田土壤中PAHs含量处于相对较低水平.黄淮平原农田土壤7种致癌性PAHs毒性当量浓度(TEQBap)占总毒性当量浓度的98.27%,其中苯并(a)芘(Bap)潜在致癌风险最大.同分异构体比值法和主成分分析结果表明黄淮平原农田土壤中PAHs的主要来源是汽油、柴油高温燃烧、以及煤和秸秆燃烧.相关性分析表明有机质含量与∑PAHs15及PAHs单体含量具有显著相关性,表明有机质是影响PAHs在土壤中含量、空间分布及归趋的一个重要因素.     

上海市大气沉降物中多环芳烃赋存特征及其来源

以上海市大气沉降为研究对象,采集了上海市8月、9月、10月3个月的大气沉降物,分析了上海市大气沉降物中16种PAHs的质量浓度、空间分布特征和组成结构,计算了上海市8个采样点∑15PAHs大气沉降物通量.同时,采用正定矩阵因子分解(PMF)模型对大气沉降中的PAHs进行源解析,模型对PAHs的来源有较为细致的判读,结果表明:大气沉降物中∑16PAHs的浓度范围0.458~21.013μg/L,其中,溶解相中∑16PAHs的浓度范围为0.174~0.625μg/L,颗粒相中∑16PAHs的浓度范围为0.275 20.455μg/L.上海市∑15PAHs大气沉降通量在0.24~14.74μg/(m2×d)之间,沉降通量均值为2.77μg/(m2×d).根据PMF模型解析,机动车尾气排放为大气沉降物中PAHs的主要污染物,源贡献率为40.23%,其次,居民烹调、煤炭燃烧、石油挥发泄露和炼焦排放依次占23.73%、14.75%、14.35%和6.92%.     

柴油轿车颗粒多环芳烃的排放特性

以一辆柴油轿车为研究样车,分别使用纯柴油、生物柴油掺混比例为10%的B10燃油,进行了NEDC整车循环工况试验,测取了该车HC、CO、NOx、颗粒等法规限制的排放,利用气相色谱-质谱法对采集的排气颗粒样品进行了分析,重点研究了颗粒中多环芳烃的排放特性.结果表明,与柴油相比,燃用B10燃油的HC、CO、NOx和颗粒等常规排放均有所降低;两种燃料产生的颗粒多环芳烃排放中均以荧蒽和芘最多,与纯柴油相比,燃用B10燃油产生的低环数PAHs排放略有增加,中高环数的PAHs排放降幅明显.苯并[a]芘等效毒性分析结果显示燃用B10燃油的BEQs值比纯柴油降低了21.6%,表明柴油轿车燃用生物柴油后,排气颗粒的多环芳烃毒性有所下降.     

南京大气中多环芳烃的相分布

采用玻璃纤维滤膜(GF)和聚氨基甲酸乙酯泡膜(PUF)同时采集南京大气中颗粒态和气态上的多环芳烃(PAHs),用气质联用仪分析了16种优先控制的PAHs,研究了PAHs在南京大气中的相分布,研究结果表明,颗粒态和气态样品中16种PAHs的平均浓度值分别为20.49ng/m3和182.45ng/m3,2～3环的PAHs主要分布在气态中,而>4环的PAHs主要分布在颗粒态中。     

正丁醇对柴油机颗粒组分与形貌特征的影响

为探讨柴油机燃用正丁醇-柴油混合燃料降低颗粒排放的机理,采用热重分析仪与场发射扫描电子显微镜,重点对正丁醇-柴油混合燃料燃烧的颗粒形貌特征进行研究,分析了颗粒的组分、微观结构以及粒径分布随w(正丁醇)的变化规律. 结果表明:正丁醇-柴油混合燃料燃烧的颗粒呈团簇状结构,随着w(正丁醇)的增加,团聚程度逐渐提高,排列结构更加紧密;颗粒的粒径逐渐减小,柴油、B5、B10〔B5、B10是指w(正丁醇)分别为5%、10%的正丁醇-柴油混合燃料〕燃烧的颗粒平均粒径分别为1.43、0.85、0.52 μm;颗粒中的主要成分为碳烟,其质量分数约为60%,随着w(正丁醇)的增加,碳烟和可溶有机物组分的质量分数有所增加,硫酸盐、金属等不易挥发组分以及金属元素的质量分数逐渐减少. 研究显示,添加正丁醇,可促进颗粒转化、改善颗粒的氧化过程,使颗粒向小粒径方向移动;由于颗粒中可溶有机物组分含量增加,因此提高了颗粒在碰撞过程中凝并的概率,致使颗粒的团聚程度增加.