Variations in traffic-related polycyclic aromatic hydrocarbons in PM2.5 in Kanazawa, Japan, after the implementation of a new vehicle emission regulation

A three-year sampling campaign was conducted at a roadside air pollution monitoring station in the urban area of Kanazawa, Japan. Due to a new emission regulation, PAHs levels decreased over the sampling campaign, exhibiting values of 706 ± 413 pg/m³ in 2017, 559 ± 384 pg/m³ in 2018, and 473 ± 234 pg/m³ in 2019. In each year, similar seasonal variations in PAHs levels were observed, with higher levels observed in winter and lower levels in summer. Among the PAHs isomer ratios, we observed that the ratio of benzo[b]fluoranthene (BbF) and benzo[k]fluoranthene (BkF), [BbF]/([BbF] + [BkF]), and the ratio of indeno[1,2,3-cd]pyrene (IDP) and benzo[ghi]perylene (BgPe), [IDP]/([BgPe] + [IDP]), showed stability over the sampling campaign and were less affected by the new emission regulation, seasonal variations, and regional characteristics. When using the combined ratio ranges of 0.66 - 0.80 ([BbF]/([BbF] + [BkF]) and 0.26-0.49 ([IDP]/([BgPe] + [IDP]), traffic emissions were clearly distinguished from other PAHs emission sources. Principal component analysis (PCA) and positive matrix factorization (PMF) were also performed to further analyse the characteristics of traffic-related PAHs. Overall, this study affirmed the effectiveness of the new emission regulation in the reduction of PAHs emissions and provided a combined range for identifying PAHs traffic emission sources.     

高等植物内源激素与土壤荧蒽、苯并(a)芘污染诱导的剂量-效应关系

以小麦(Triticum acstivnm)为供试植物,草甸棕壤为供试土壤,采用室内培养箱盆栽方法,研究了荧蒽、苯并(a)芘单一及复合污染胁迫与小麦叶片中3种植物内源激素赤霉素(gibberellic acid, GA₃)、细胞分裂素类的玉米素及玉米素核苷总量(zeatin and zeatin riboside, Z&ZR)、脱落酸(abscisic acid, ABA)的污染诱导剂量-效应关系.结果表明,荧蒽单一及与苯并(a)芘复合污染胁迫对小麦体内ABA的合成有明显的诱导作用,并且荧蒽单一污染的诱导作用较强,当荧蒽浓度为16　mg·kg^-1时,ABA含量比对照增加了198％.荧蒽、苯并(a)芘复合污染对GA₃的合成表现为明显的诱导抑制效应,而GA₃对单一污染胁迫响应趋势不明显.荧蒽、苯并(a)芘单一及复合污染胁迫对Z&ZR的合成均产生明显的诱导抑制效应.本研究表明,3种内源激素对土壤低剂量多环芳烃污染指示具有重要作用,其对荧蒽、苯并(a)芘单一及复合污染响应的敏感性顺序为：Z&ZR>ABA>GA₃.     

珠江三角洲地区大气气溶胶中有机污染物背景研究

选择肇庆市鼎湖山自然保护区为珠江三角洲大气气溶胶有机污染评价的区域性环境背景．研究结果表明,珠江三角洲地区大气气溶胶中优控多环芳烃背景值萘、苊、二氢苊、芴、菲、蒽、荧蒽、芘、苯并（a）蒽、、苯并（b）荧蒽、苯并（k）荧蒽、苯并（a）芘、茚并（1,2,3-cd）芘、二苯并（a,h）蒽、苯并（ghi）分别为n.d.、n.d.、tr.、0.14、tr.、0．39、0.53、0.19、1.05、1.82、1.41、0.02、2.29、0.53和2．44ng/m³,总量为10.80ng/m³,其来源主要为高等植物排放.     

Ploidy-, gender-, and dose-dependent alteration of selected biomarkers in Clarias gariepinus treated with benzo[a]pyrene

Naturally-occurring and artificially-induced polyploids have been documented in various fish species but to date no comparison has been reported of the impacts of ploidy on fish biomarker responses to organic pollutants. This study describes effects of ploidy, gender, and dose on biliary fluorescent aromatic compound (FAC) concentrations, hepatic ethoxyresorufin-O-deethylase (EROD) and glutathione S-transferase (GST) activities in one of the most commonly cultured warm-water species, the African catfish Clarias gariepinus. Recently matured male and female diploid and triploid fish were intraperitoneally (i.p.) injected with 0, 5 or 25 mg/kg benzo[a]pyrene (BaP) and liver and gallbladder were sampled 48 hr later. No significant differences were found between ploidies in bile concentrations of 7,8 dihydrodiolbenzo[a]pyrene (7,8D BaP), 1-hydroxybenzo[a]pyrene (1-OH BaP) or 3-hydroxybenzo[a]pyrene (3-OH BaP). However, concentrations of the biliary FACs did differ between males and females at different dose of injection with generally higher concentrations in females at the low dose of BaP and higher concentrations in males at the higher BaP concentration. Hepatic EROD activity did not exhibit gender-dependent difference, whereas it was significantly higher in triploids than diploids. GST activities were not significantly influenced by any of the tested factors. This work advanced our understanding of the role of ploidy, gender, and dose in biotransformation of pollutants in fish.     

武汉城区土壤剖面多环芳烃的分布特征及来源分析

研究分析了位于武汉市城区附近的南望山土壤剖面样品.表层土壤检测到了美国EPA优控的16种多环芳烃,含量为991 ng/g.之外还检测到了联苯、苯并[e]芘、苝、二苯并呋喃、二苯并噻吩、惹烯以及一些多环芳烃的烷基取代物.多环芳烃含量随着深度的增加急剧降低.表层土壤以萤蒽、苯并萤蒽、芘、苯并[a]芘等为主,菲次之.与高环相...     

广西乐业大石围天坑群多环芳烃的干湿沉降

为研究大气多环芳烃(PAHs)的沉降对广西乐业大石围天坑群喀斯特生态环境的影响,选择典型的大石围天坑,采用大气干湿采样器分季节进行了为期1 a(2007-03～2008-03)的大气干湿沉降样品采集,利用气相色谱-质谱联用仪(GC-MS)测定了16种PAHs优先控制污染物.结果表明,大气干湿沉降中PAHs的干湿沉降通量为132.36～1 655.27 ng.(m2.d)-1,平均值为855.00 ng.(m2.d)-1,大石围天坑的PAHs沉降量为51.98 g.a-1;PAHs的组成以苯并[b]荧蒽、、苯并[a]芘、苯并[k]荧蒽、蒽、菲、萘7种为主,占总量PAHs的78.5%;大气PAHs沉降通量的空间分布为东垭口>南垭口>西峰>北垭口;不同季节的沉降通量为春季>夏季>秋季>冬季,春、夏季PAHs沉降通量高于秋、冬季4.6倍,春、夏季以4～6环PAHs为主,而秋、冬季以2～3环PAHs为主;研究区大气PAHs沉降通量与降雨量、风向、风速、温度气象因子及污染源的方位密切相关;大石围天坑群大气PAHs沉降通量在春季、夏季呈季节性增高可能来源于高气温、低海拔的广西工业发达地区.     

废旧汽车拆解区土壤中多环芳烃垂向分布特性

研究分析了废旧汽车拆解区土壤剖面的美国EPA优控的16种多环芳烃的纵向分布.结果表明,表层土壤中16种多环芳烃总含量达到了17 323 ng·g-1,其中芘(Pyr)、苯并[a]蒽(BaA)、芴(Flu)含量最高,分别达到11 820、1 234和1 083 ng·g-1.汽车拆解区表面和土壤深度为10 cm的土壤均达到了重度污染级别;深度在50~350 cm之间的土壤为轻度至中度污染,当土壤深度超过400 cm,土壤基本未受到污染.但是,7种致癌性PAHs(Chr、BaA、BbF、BkF、BaP、DahA、IcdP)总量在土壤深度达到850 cm时仍有34.15 ng·g-1.随着土壤深度的增大,多环芳烃含量急剧降低,当土壤深度超过300 cm,三环的菲(Phe)、荧蒽(Fl)和二氢苊(Ace)成为优势组分.土壤剖面菲(Phe)/蒽(Ant)比值和荧蒽(Fla)/芘(Pyr)、Fluo/Pyr、BaA/(BaA+Chr)等参数表明,土壤表面的多环芳烃主要来源于石油污染.     

金属离子对长期污染土壤中多环芳烃解吸的影响

研究了离子强度、不同金属离子对土壤中PAHs表观解吸水平的影响.根据Pearson原理计算了菲、荧蒽、芘和苯并[k]荧蒽等几种PAHs的碱性特征参数并据此分析了其酸碱性类型.结果表明:实验条件下,解吸液中离子强度并非影响土壤中PAHs解吸的控制要素;不同硬度酸性金属离子与PAHs之间的酸碱作用是影响土壤中PAHs解吸水平变化的关键.硬酸性金属离子Ba2+、Al3+、Ca2+对土壤中PAHs的解吸具有促进作用,软酸性离子Hg2+、Ag+则具有抑制作用,比较而言交界酸性金属离子Cu2+、Fe2+、Zn2+在提高土壤中PAHs解吸上作用更加明显.     

上海工业区玻璃表面多环芳烃分布特征与溯源

利用GC-MS对上海工业区玻璃表面16种优控多环芳烃(PAHs)进行了定量分析.结果表明,宝山工业区、吴泾化工区和金山化工区玻璃表面PAHs平均含量分别为10.66,16.48,31.94mg/m2,工业区附近对照点PAHs平均含量分别为2.7,8.86,4.18mg/m2.各采样点玻璃表面不同环数PAHs分布特征相似,以3环和4环PAHs为主,平均含量分别占∑16PAHs的25%和47%;其次为5环和6环PAHs,分别占∑16PAHs的14%和9%,最低为2环PAHs,仅占5%.单体PAH以Phe、Fluo、Py和Chry为主.源解析表明,玻璃表面PAHs主要来源于煤和焦炭燃烧,部分来源于石油燃烧.质量标准化毒性当量浓度范围在0.07~3.23mg/g之间,对毒性当量贡献最大的单体PAH分别是BaP,BbF,BkF,DahA.     

Semivolatile organic compounds in the ambient air of Denver,Colorado

A filter-polyurethane foam plug high volume air sampler was used to collect the particle (P) and vapor (V) phases of four classes of semivolatile organic compounds (SOC) in Denver, CO: n-alkanes. polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), and organochlorine pesticides. The carbon preference index (CPI) of n-alkanes in the V or P phases alone was skewed by temperature-dependent V/P partitioning; a combined gaseous + particulate CPI was preferred. The CPI suggested that the alkanes in Denver air were predominently petrogenic. Total PCB were calculated as the sum of individual congeners and also as Aroclor equivalents, with good agreement between the two methods. Apparent V/P distributions of these compound classes were expressed as A(TSP)/F, were A and F are the adsorbent- and filter-retained SOC concentrations (ng m⁻³) and TSP is the total suspended particle concentration (μg m⁻³). Values of A(TSP)/F were related to the average sampling temperature (T, K) through: log [A(TSP)/F] = m/T + b. Fitted log A(TSP)/F at 5°C correlated well with p_L⁰ at 5°C, the SOC liquid vapor pressure. No differences were observed in partitioning behavior among the four SOC types.     

青岛近岸表层海水中PAHs的分布特征及物源初步解析

采用固相萃取-高效液相色谱-荧光检测法分析了青岛近岸海水中15种PAHs的质量浓度.结果表明,海水中PAHs的总量变化范围为8.23～272.02 ng.L-1,河口区质量浓度最高,远离城区的清洁区质量浓度最低.就组成特征而言,2～3环PAHs是其主要组分,占总量的质量分数为52.2%～93.8%,4～6环PAHs占总量的质量分数为6.2%～47.8%.表层海水中PAHs总浓度和DOC浓度之间有较好的相关性,相关系数为0.944 3.青岛湾表层海水中PAHs浓度组成相对稳定.利用Fl/(Fl+Py)和An/(An+Ph)分析表层海水中PAHs的来源,结果表明除清洁区表层海水中PAHs主要来源于煤和木材燃烧外,青岛近岸海水中的PAHs主要来源于石油制品和石油燃烧.     

中国主要河流中多环芳烃生态风险的初步评价

以现有的中国主要河流中多环芳烃(PAHs)的浓度数据为基础,通过定义1个危害商,利用商值法筛选出菲、蒽、荧蒽、芘、苯并[a] 蒽、 和苯并[a]芘7种对水生生态具有潜在风险的PAHs.以河流水相中PAHs浓度数据为依据,结合毒性数据库中PAHs水相浓度对水生生物的毒性数据,用概率风险评价法分析了这7种PAHs对水生生物的生态风险.结果表明,7种筛选出的PAHs风险大小依次为：蒽>芘>苯并[a]蒽>荧蒽>苯并[a]芘>菲> .     

Effects of temperature,TSP and per cent non-exchangeable material in determining the gas-particle partitioning of organic compounds

The temperature dependence of the measured, gas-particle partitioning ratio (F_T/TSP)/A_T has been examined for the case when a constant fraction x (%) of a compound is assumed to be bound within the particulate matter, and non-exchangeable with the gas phase. The parameter F_T is the total (exchangeable + non-exchangeable) measured concentration in the atmosphere (ng m⁻³), A_T is the gaseous concentration (ng m⁻³), and TSP is the level of suspended atmospheric particulate matter (μg m⁻³). It is assumed that the true thermodynamic constant K_p depends upon 1/T according to log K_p = m_p/T + b_p where m_p depends on the enthalpy of desorption of the compound of interest, b_p depends in part on other properties of the compound as well as the specific surface area of the particulate matter, and T is the temperature (Kelvin). When K_p or TSP are low, the difference between the measured quantity (F_T/TSP)/A_T and K_p can be significant even when the non-exchangeable fraction x is as low as a few per cent. This approach has been used to examine the PAH data set of Yamasaki et al. [(1982) Env. Sci. Technol.16, 189–194]. It was found that the Yamasaki data set does not allow estimates of x that are consistent with the current understanding of the temperature dependence of log K_p values. A likely reason for this result is some dependence of m_p and b_p on the exact nature of the particulate matter and atmospheric conditions such as relative humidity. It is concluded that estimates of x values for a given compound on actual particulate matter may only be possible by the direct examination of individual particulate matter samples.     

异烟酸铜磁力搅拌微固相萃取-气相色谱法测定土壤中多环芳烃

建立了膜保护异烟酸铜微固相萃取的样品前处理方法,并采用气相色谱氢火焰离子化检测器对土壤中的痕量荧蒽(Flt)、苯并［b］荧蒽(BbF)、苯并［k］荧蒽(BkF)、苯并［a］芘(BaP)进行了测定. 考察了水温、萃取时间和超声洗脱时间等对萃取效果的影响. 结果表明:在最佳试验条件下,Flt的检出限为1.0 ng/g;BbF,BkF和BaP的检出限为2.5 ng/g. Flt的线性范围为2.5～500.0 ng/g;BbF,BkF和BaP的线性范围均为12.5～500.0 ng/g. 相对标准偏差(RSD)为4.4%～13.7%(n9). 采用该方法分析了2种实际土壤中的4种多环芳烃,回收率为34%～90%.      

Pollution characteristics and health risk assessment of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons during heating season in Beijing

Polycyclic aromatic hydrocarbons(PAHs) and their nitrated derivatives(NPAHs) attract continuous attention due to their outstanding carcinogenicity and mutagenicity. In order to investigate the diurnal variations, sources, formation mechanism, and health risk assessment of them in heating season, particulate matter(PM) were collected in Beijing urban area from December 26, 2017 to January 17, 2018. PAHs and NPAHs in PM were quantitatively analyzed via gas chromatography-mass spectrometry(GC-MS). ...     

厦门杏林湾水系表层沉积物中PAHs分析与风险评估

利用ASE-GC-MS(加速溶剂萃取与气相色谱质谱仪联用)方法分析了USEPA(美国环保署)16种优控PAHs在厦门城郊杏林湾水系的19个表层沉积物样点中的含量,并对其组成、来源和风险进行了探讨.结果表明,杏林湾水系表层沉积物中PAHs含量介于413.00~2 748.81 ng·g-1,均值为949.56 ng·g-1;在检测出的13种PAHs中,强致癌性的Bk F和Bghi P检出率高达73.68%,均值分别为69.15 ng·g-1和49.86 ng·g-1;PAHs以2~4环为主,其中2+3环比例均值为61.03%,4环比例均值为23.53%;5和6环均值为15.82%.在所采集的沉积物样品中,中度污染占调查样品数的68.42%,高度污染的占31.58%.利用Ant/(Ant+Phe)和Fla/(Fla+Pyr)比值法和主成分分析方法对杏林湾流域中PAHs其来源进行分析,以及平均沉积物质量基准商(m SQG-Q)法进行生态风险评估,结果表明其PAHs的主要来源为石油源以及石油燃烧源;SQG-Q小于0.50;综合含量、组成特征以及沉积物质量基准商等评价表明,研究区域内靠近杏林工业区一侧的2、3、5和9号采样区以及13号港头采样区表层沉积物中PAHs具有较高的生态安全风险;值得进一步关注.     

长江下游支流水体中多环芳烃的分布及生态风险评估

长江下游地区是我国一个典型的化学工业园区聚集地,化工园区企业生产过程中产生和排放的多环芳烃通过大气沉降、地表径流等方式进入支流水体,并最终汇入长江.本研究选择了典型的支流水体,开展了多环芳烃的分布特征、源解析和生态风险评估研究.结果表明多环芳烃单体以低环为主,总浓度为37.27～285.88 ng·L~(-1),平均值为78.31 ng·L~(-1).PAHs单体浓度范围0～61.35 ng·L~(-1),检出率最低单体为苯并[k]荧蒽和苯并[a]芘,其检出率均为75%.苯并[a]芘是毒性当量因子最大的PAHs,其浓度范围为0～11.08 ng·L~(-1).根据我国《生活饮用水水源水质标准》(CJ 3020-1993)规定,饮用水中苯并[a]芘的限值为10 ng·L~(-1),其中研究区域内无锡市的一个水样(S12)中浓度超出了标准限值,长江下游支流水体的PAHs浓度总体处于低至中等的污染水平.根据比值法和主成分分析的源解析结果,水体中多环芳烃主要受化工排放、汽车尾气的影响,还有部分来自燃煤.生态风险评估结果显示,水体的生态风险处于中等水平,从长期的环境暴露角度出发,应当考虑采取相应地控制措施,防止进一步污染.研究结果可为长江下游支流水环境中多环芳烃风险评估以及化工园区的污染控制提供参考.     

天津地区表层土中芳香烃污染物化学组成及分布特征

分析了天津地区不同环境功能区土壤中多环芳烃污染物的化学组成及其分布状况,并对其可能的污染源作初步分析.结果表明,天津地区不同环境功能区表层土壤样品中均分布有多种类型的烃类污染物,已经检测到的多环芳烃化合物主要包括萘、苊、苊烯、联苯、菲、惹烯、芴、二苯并呋喃(氧芴)、二苯并噻吩(硫芴)、萤蒽、芘、(艹屈)、苯并芴、苯并蒽、苯并萤蒽、苯并芘、(艹屈)、二苯并[a,h]蒽、茚并[1,2,3-cd]芘、苯并[g,h,i](艹屈)、三芳甾烷等系列数100种单体化合物,含量较高的主要有菲、甲基菲、萤蒽、芘、(艹屈)等.这些化合物的组成存在地域上的差异,同一地区不同土地使用情况、不同周围环境的样品中多环芳烃的组成特征也存在较大的差别,表明土壤中多环芳烃的污染源比较复杂,其中主要包括矿物油输入、化石燃料燃烧及木柴燃烧产物等,不同环境功能区各种污染源的贡献存在一定差别.      

生油岩五环芳烃的热演化及成熟度参数

塔里木盆地中生界生油岩中的五环芳烃化合物的热演化呈规律性变化。成熟度较低的样品中的含量较高，苯并芘和苯并荧蒽的含量较低。随着成熟度的增加，含量逐渐下降，而苯并芘和苯并荧蒽的含量不断增多，这表明两者的成因及其演化途径不同。前者可能为有机质早期演化的产物，而后者主要来自环化和芳构化作用。生油层剖面样品分析资料表明，苯并[e]芘／和（苯并[e]芘＋苯并[a]芘）／之比值是良好的成熟度参数，它们可指示生油岩成油高峰期。     

多环芳烃对卤虫无节幼体的光诱导毒性

以卤虫Ⅱ～Ⅲ龄无节幼体为实验材料,在实验室内研究4种多环芳烃的光诱导毒性,比较了在有紫外(UV)和无UV照射条件下多环芳烃对卤虫幼体的存活和几种生理生化指标的影响.结果表明:UV辐射(UVA:476 μw·cm-2;UVB:6.5 μW·cm-2)明显提高了菲、蒽、荧蒽和芘对卤虫幼体的毒性,其24 h LC50值分别是无UV照射条件下LC50值的1/139、1/182、1/102和1/88.UV照射诱导了荧蒽对卤虫幼体的氧化损伤,过氧化物酶(POD)对荧蒽的光诱导毒性较超氧化物歧化酶(SOD)敏感;卤虫幼体的丙二醛(MDA)和Na ·K -ATPase是衡量荧蒽光诱导毒性的较敏感参数.