大同市居民尿中1-羟基芘的十年变化趋势

尿中1-羟基芘可作为人体接触环境中多环芳烃的生物监测指标。我们于2002年12月采集和测定了大同市两个典型功能区居民尿液中的1-羟基芘,并结合过去的研究数据分析了大同市居民尿中1-羟基芘近十年来的变化趋势,也从生物监测的角度反映了近十年来典型煤烟型城市大同空气环境质量的变化情况。     

五种多环芳烃化合物对鲤鱼肝微粒体芳烃羟化酶的诱导

以鲤鱼肝微粒体为实验体系,研究了被五种多环芳烃(PAH)化合物菲、9,10-菲醌、芘、1-羟基芘、苯并芘污染后,其芳烃羟化酶(AHH)的活性变化,发现多环芳烃对AHH的诱导具有良好的剂量效应关系.AHH活性升高的大小可以作为监测多环芳烃对水体污染程度的一种生物指标.五种多环芳烃对AHH诱导能力的大小为1-羟基芘＞苯并芘;9,10-菲醌＞芘＞菲,与其毒性大小相关.     

青岛市松针中多环芳烃污染状况研究

松针、苔藓类等植物可有效的监测环境空气中多环芳烃等有机污染物。为了解青岛市松针中多环芳烃的污染状况，本文使用索氏提取、氧化铝-硅胶净化柱净化、气相色谱-质谱（GC-MS）分析的方法，研究了青岛市6个不同区域的松针中多环芳烃的含量。该方法的提取净化效率在70．8％以上。在6个采样点中，1号采样点松针中的多环芳烃含量最低，平均为7．54ng/g（湿重含量），5号和6号采样点最高，分别为41．0ng/g和39．6ng/g。多环芳烃浓度季节变化规律为春季〉冬季〉夏季；松针中三、四环多环芳烃占总量的82％～90％，苯并（a）芘与多环芳烃总量具有较好的相关性。     

隧道路面沥青摊铺过程空气中TSP和多环芳烃污染研究

分析了隧道沥青摊铺过程环境空气中的TSP及多环芳烃质量浓度。TSP用膜法,中流量采样器采样15 min,重量法分析;超声波萃取,高效液相色法分析多环芳烃。结果表明,摊铺机周围空气中TSP超过8 mg/m3,道路空气中TSP超过3 mg/m3;环境空气中苊烯等12种多环芳烃均有检出,苊烯和艹屈质量浓度较高,苯并[a]芘和二苯并[a,h]蒽质量浓度较低。苯并[a]蒽、苯并[a]芘和二苯并[a,h]蒽超标,对人体健康危害较大。建议加强相关行业PAHs的排放水平及其健康风险研究,制定相关限值标准和沥青摊铺过程环境空气的沥青烟监测方法标准。     

焦化废水中多环芳烃的成分谱及污染特征

液-液萃取-高效液相色谱法分析了焦化废水中EPA优先控制的16种多环芳烃含量,总结出其成分谱及污染特征。结果表明:16种多环芳烃在焦化废水中浓度差异较大,主要以在水中溶解度较大的萘、苊、芴、菲、荧蒽、芘为主。其中萘对多环芳烃总量的贡献最大,占总量的36.70%~86.78%。焦化企业排放废水中6种多环芳烃的总量无超标现象,苯并[a]芘单体超标较普遍。     

广州地区秋冬季细颗粒物PM2.5化学组分分析

分析了广州地区2009年-2010年秋冬季节大气中PM2．5样品的水溶性离子、重金属元素、有机碳/元素碳（OC/EC）、多环芳烃质量浓度和粒径分布。初步掌握了广州地区秋冬季节大气中PM2．5的化学组分和特点，有机质（OM）是广州地区秋冬季PM2．5中最主要的成分，其次是硫酸根离子、硝酸根离子和铵根；PM2．5中有机碳和元素碳的空间分布特征相似，并受一次源排放影响；PM2．5中的重金属含量以铝、锌、铅相对较高，且城区高于城郊；PM2．5中17种多环芳烃、苯并（ a）芘（ BaP）的浓度均为城郊高于市区。     

南宁城市内河水体和表层沉积物中多环芳烃分布特征

采用改进的固相萃取、加速溶剂萃取和高效液相色谱对南宁7条城市内河的水体和表层沉积物样品中6种多环芳烃的残留状况进行了分析测定。检测结果表明,水体中多环芳烃以荧蒽为主,6种多环芳烃在水体中的总残留浓度为26.8～163 ng/L,内河水体各点位苯并[α]芘均超过我国地表水环境质量标准限值,对干流水质存在一定影响。7个点位沉积物中多环芳烃总含量为118.06～416.73μg/kg,6种多环芳烃均有检出。     

焦炉工人PAHs空气日均暴露浓度分析

用个体采样器对100名受试者进行了可吸入颗粒物和气态样品的24h跟踪采集,并通过梯度洗脱一反相HPLC／可编程序荧光检测法定量分析了样品中14种多环芳烃。结果表明,不同受试人员多环芳烃空气日均暴露浓度存在很大差异,其中焦炉工人受多环芳烃中BaP空气日均暴露浓度为0．5μg／m^3～1．7μg／m^3,炼纲厂工作人员和清洁区办公人员的BaP空气日均暴露浓度分别为0．02μg／m^3和0．01μg／m^3。不同受试人员多环芳烃空气日均暴露在PM10及气相中的分配比例也略有不同,焦炉工人的BaP空气日均暴露浓度有近99％来自PM10,一般人群为93％左右。指出2环、3环多环芳烃主要以气态形式存在,4环至6环多环芳烃主要分布在PM10中。     

杭州市大气细颗粒物PM_(2.5)中多环芳烃含量特征研究

按季节对杭州市大气细颗粒物PM2.5中16种多环芳烃(PAHs)的含量在2006年进行了为期一年(样本数n=47)的测定分析.研究表明,杭州市大气PM2.5中PAHs总浓度为40.66ng/m3,以中环或高环为主,分别占总PAHs的32.23%和47.6%;云栖点位(位于风景名胜区内)PM2.5中PAHs浓度高于朝晖点位(位于商业居民混合区);季节变化呈现春季高,秋季低的特点;PM2.5中苯并[a]芘等效毒性(BEQ)为4.50;PM2.5中PAHs的来源不是单一的.     

多环芳烃测定中净化方法的研究

对多环芳烃测定中的净化方法进行研究，为了选出最佳净化柱，在一定条件下分别采用硅胶LC-Si、弗罗里LC-Florisil和C18固相萃取净化柱对一定浓度的多环芳烃标准溶液进行净化，测定吸附后流出液多环芳烃浓度，计算吸附率；测定洗脱后流出液多环芳烃浓度，计算洗脱率。测定结果为硅胶、弗罗里和C18固相萃取净化柱对多环芳烃的吸附率分别在87．1％～100％，99．5％～100％和96．6％～100％之间，洗脱率分别在0～106％，78．7％．109％和79．0％～115％之间。结果表明，GC／MS内标法测定样品中多环芳烃使用最理想的净化柱为弗罗里净化小柱，其次为C18净化小柱，最后为硅胶净化小柱。     

A Pilot Study on Using Urinary 1-Hydroxypyrene Biomarker for Exposure to PAHs in Beijing

To study whether the urinary 1-hydroxypyrene (1-OHP) could be the biomarker of atmospheric PAHs, a small-scale pilot study was carried out on the relation of 1-OHP vs PAHs with the traffic policemen in Beijing of smokers and nonsmokers to be subgroups in both the exposure and control groups. Both the PAHs and 1-OHP were analyzed with high performance liquid chromatography (HPLC). The ambient concentrations of PAHs were different at the different sites (the average sum of PAHs (TPAH) were 12.36, 16.27, 18.37 ng/m³ at the suburban residential, police station and high traffic area, respectively.), but considerably lower than the personal-exposure concentrations (the average TPAH were 65.84 and 47.28 ng/m³ for patrol cars and inspection station, respectively). Pyrene was correlated well with BaP and the summed PAHs (TPAH), with the correlation coefficients (R) of 0.79, 0.87 for ambient level and 0.92, 0.96 for personal exposure, respectively. The average of 1-hydroxypyrene of smokers and nonsmokers were 0.39, 0.15 μmol/mol creatinine in control group and 0.57, 0.33 μmol/mol creatinine in exposure group, respectively. The better correlation of pyrene to BaP and TPAH especially for personal exposure samples indicated that the probability of urinary 1-hydroxypyrene, the metabolite of pyrene, to be the biomarker of total PAH. Nonsmokers in the exposure and control groups had indistinguishable levels of 1-OHP, presumably because the ambient levels of pyrene were so similar (the average were 3.25, 3.20 ng/m³ at the police station and high traffic area, respectively.). Smokers in the control group had significantly higher 1-OHP than that of the nonsmokers, but showed indistinguishable differences in the exposure group. These results suggested that urinary 1-OHP could be a biomarker of PAHs only when the level of PAHs was at a relatively higher level. Smoking as an important influencing factor need to be controlled carefully.     

Air concentrations and urinary metabolites of polycyclic aromatic hydrocarbons among paving and remixing workers

The exposure of paving workers to polycyclic aromatic hydrocarbons (PAH) during stone mastic asphalt (SMA) paving and remixing was evaluated. The effects on the workers' PAH exposure were also evaluated during the use of an industrial by-product, coal fly ash (CFA), instead of limestone as the filler in the SMA. The PAH exposure was measured by personal air sampling and by analysing the levels of urinary naphthols, phenanthrols and 1-hydroxypyrene (1-OHP) in the workers' pre- and post-shift urine samples. The respiratory PAH exposure of the paving workers (geometric mean (GM) 5.7 microg m(-3)) was about ten-fold that of the traffic controllers (GM 0.43 microg m(-3)). The levels of PAH metabolites were significantly higher (p < 0.05) in the post-shift urine samples than in the pre-shift urine samples, and the levels of metabolites in the post-shift urine of paving workers were significantly higher than in that of the controls (p < 0.01). Urinary 1-naphthol correlated well with the airborne concentrations of the two- to three-ring PAHs (r = 0.544, p = 0.003) and naphthalene (r = 0.655, p < 0.001), when non-smoking paving workers were tested. A good correlation was observed between urinary 1-OHP and the airborne concentrations of the four- to six-ring PAHs (r = 0.524, p = 0.003) as well as total PAHs (r = 0.575, p = 0.001). The concentrations of 1-OHP and phenanthrols in the urine of the pavers were significantly higher (p < 0.01) during remixing than during SMA paving. The CFA in the asphalt had no effect on the airborne PAH exposure or on the concentrations of the PAH metabolites in the paving workers' urine.     

DDT, DDE, and 1-hydroxypyrene levels in children (in blood and urine samples) from Chiapas and Oaxaca, Mexico

The aim of this study was to evaluate the DDT, DDE, and 1-hydroxypyrene exposure levels of children living in communities located in southeastern Mexico. The study communities were Lacanja and Victoria in Chiapas state and Ventanilla in Oaxaca state. Children living in Lacanja had total blood DDT levels (mean?±?SD, 29,039.6?±?11,261.4 ng/g lipid) that were significantly higher than those of children in Victoria (10,220.5?±?7,893.1 ng/g lipid) and Ventanilla (11,659.7?±?6,683.7 ng/g lipid). With respect to the 1-hydroxypyrene levels in urine samples, the levels in Lacanja (4.8?±?4.1 μg/L or 4.5?±?3.9 μmol/mol creatinine) and Victoria (4.6?±?3.8 μg/L or 3.9?±?3.0 μmol/mol Cr) were significantly higher than levels found in Ventanilla (3.6?±?1.4 μg/L or 2.5?±?0.5 μmol/mol Cr). In conclusion, our data indicate high levels of exposure in children living in the communities studied in this work. The evidence found in this study could be further used as a trigger to revisit local policies on environmental exposures.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

Road pavers' occupational exposure to asphalt containing waste plastic and tall oil pitch

Waste plastic (WP) and tall oil pitch (T), which are organic recycled industrial by-products, have been used as a binder with bitumen in stone mastic asphalt (SMA) and asphalt concrete (AC). We compared the exposure over one workday in 16 road pavers participating in a survey at four paving sites, using mixes of conventional asphalt (SMA, AC) or mixes containing waste material (SMA-WPT, AC-WPT). The concentrations of 11 aldehydes in air were 515 and 902 microg m(-3) at the SMA-WPT and AC-WPT worksites, being 3 and 13 times greater than at the corresponding worksites laying conventional asphalt. Resin acids (2-42 microg m(-3)), which are known sensitizers, were detected only during laying of AC-WPT. The emission levels (microg m(-3)) of total particulates (300-500), bitumen fumes (60-160), bitumen vapour (80-1120), naphthalene (0.59-1.2), phenanthrene (0.21-0.32), pyrene (<0.015-0.20), benzo(a)pyrene (<0.01) and the sum of 16 PAHs (polycyclic aromatic hydrocarbons, 1.28-2.00) were similar for conventional and WPT asphalts. The dermal deposition of 16 PAHs on exposure pads (on workers' wrist) was low in all pavers (0.7-3.5 ng cm(-2)). Eight OH-PAH biomarkers of naphthalene, phenanthrene and pyrene exposures were quantified in pre- and post-shift urine specimens. The post-shift concentrations (mean +/- SD, micromol mol(-1) creatinine) of 1- plus 2-naphthol; 1-,2-,3-,4- plus 9-phenanthrol; and 1-hydroxypyrene were, respectively, for asphalt workers: 18.1+/- 8.0, 2.41 +/- 0.71 and 0.66+/- 0.58 (smokers); 6.0+/- 2.3, 1.70+/- 0.72 and 0.27+/- 0.15 (non-smokers); WPT asphalt workers: 22.0+/- 9.2, 2.82+/- 1.11 and 0.76+/- 0.18 (smokers); 6.8+/- 2.6, 2.35+/- 0.69 and 0.46+/- 0.13 (non-smokers). The work-related uptake of PAHs was low in all pavers, although it was significantly greater in smokers than in non-smokers. The WPT asphalt workers complained of eye irritation and sore throat more than the pavers who had a much lower exposure to aldehydes and resin acids.     

Seasonal variation for the ratio of BaP to BeP at different sites in Great Xiamen Bay

From March 2008 to February 2009, PM(10) samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) at eight sampling sites in Great Xiamen Bay, China. Analyses of the seasonal and spatial variations of these compounds revealed the following results. Significantly high levels of PAHs were found in the winter compared to the summer, sometimes exceeding 100 ng m(-3), and the spatial variations were influenced most by the sampling site surroundings. Composition profiles of PAHs of an urban and a rural site were shown to be very similar with a positive correlation coefficient larger than 0.9 at the 0.01 level of significance for the same season. Diagnostic ratios, together with principal component and multiple linear regression analysis, showed that more PAHs were from grass/wood/coal combustion in winter than in other seasons. The ratios of benzo[a]pyrene to benzo[e]pyrene (BaP-BeP) in winter and fall were 0.6-1.7 times higher than those in spring and summer, suggesting the importance of local emissions of PAHs. The BaP-BeP ratios in Kinmen were generally lower than those in Xiamen, indicating that the aging degree of PAHs was higher in Kinmen than in Xiamen. The external input of PAHs from upwind urban and industrial areas was one of the key factors causing high levels of PAHs in PM(10) in Great Xiamen Bay in winter.     

Two fish bile reference materials certified for PAH metabolites

Environmental pollution with polycyclic aromatic hydrocarbons (PAHs) from pyrogenic or petrochemical sources is a matter of concern in many aquatic ecosystems. For field monitoring purposes, PAH metabolite levels in fish bile samples can be used as biomarkers of exposure, but previously there were no reference materials for analytical method validation or quality control. In this paper we describe the preparation and certification of two fish bile materials. BCR 720 is a pure bile material from sediment-exposed flounder (Platichthys flesus) and BCR 721 is a pure bile material from oil-exposed plaice (Pleuronectes platessa). Homogeneity and stability tests were carried out and a group of 12 expert laboratories was assembled for the certification measurements. The methods applied were liquid chromatography with fluorescence detection or gas chromatography with mass spectrometric detection. In BCR 720 three PAH metabolites were certified: 1-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo[a]pyrene. In BCR 721 1-hydroxypyrene was certified. The fourth target compound, 2-hydroxynaphthalene, could not be certified, but the results obtained are listed. The major findings from earlier feasibility studies and recommendations for the optimal use of the reference materials are also included.     

Seasonal variation of polycyclic aromatic hydrocarbons in soil and air of Dalian areas, China: an assessment of soil-air exchange

The seasonal variations of concentrations of PAHs in the soil and the air were measured in urban and rural region of Dalian, China in 2007. In soil, mean concentrations of all PAHs in summer were larger than those in winter, whereas the concentrations of heavier weight PAHs in winter were larger than those in summer. Winter/summer concentration ratios for individual PAHs (R(W/S)) increased with the increase of molecular weight of PAHs in soil, indicating that PAHs with high molecular weight were more easily deposited to soil in winter than summer. In air, mean concentrations of all PAHs in winter were larger than those in summer. In comparison with the R(W/S) in soil, all the values of R(W/S) in air were larger than one indicating that the entire individual PAH concentrations in winter were larger than those in summer. The average concentration composition for each PAH compound in soil and air samples was determined and the seasonal change of PAH profile was very small. It was suggested that PAHs in soils and air had the same or similar sources both in winter and summer. The approach to the soil-air equilibrium was assessed by calculating fugacity quotients between soil and air using the soil and air concentrations. The calculated soil-air fugacity quotients indicated that soil acted as a secondary source to the atmosphere for all lighter weight PAHs (two-three rings) and it will continue to be a sink for heavier weight PAHs (five-six rings) in the Dalian environment, both in winter and summer. Medium weight PAHs (four-five rings) were close to the soil-air equilibrium and the tendency shifted between soil and air when season or function region changed. The fugacity quotients of PAHs in summer (mean temperature 298 K) were larger than those in winter (mean temperature 273 K), indicating a higher tendency in summer than winter for PAHs to move from soil to air. The variation of ambient conditions such as temperature, rainfall, etc. can influence the movement of PAHs between soil and air. Most of the fugacity quotients of PAHs for the urban sites were larger than that for the rural site both in winter and summer. This phenomenon may be related with that the temperatures in urban sites were higher than those in the rural site because of the urban heat island effect.     

Evaluation of the urban/rural particle-bound PAH and PCB levels in the northern Spain (Cantabria region)

The aim of the present study was to evaluate the polycyclic aromatic hydrocarbon (PAH) and polychlorinated biphenyl (PCB) levels in PM(10) and PM(2.5), at one rural and three urban sites in the Cantabria region (northern Spain). From all of these pollutants, benzo(a)pyrene is regulated by the EU air quality directives; its target value (1?ng/m(3)) was not exceeded. The concentration values of the studied organic pollutants at the studied sites are in the range of those obtained at other European sites. A comparison between the rural-urban stations was developed: (a) PAH concentration values were lower in the rural site (except for fluorene). Therefore, the contribution of local sources to the urban levels of PAHs seems relevant. Results from the coefficient of divergence show that the urban PAH levels are influenced by different local emission sources. (b) PCB rural concentration values were higher than those found at urban sites. Because no local sources of PCBs were identified in the rural site, the contribution of more distant emission sources (about 40?km) to the PCB levels is considered to be the most important; the long-range transport of PCBs does not seem to be significant. Additionally, local PAH tracers were identified by a triangular diagram: higher molecular weight PAHs in Reinosa, naphthalene in Santander and anthracene/pyrene in Castro Urdiales. A preliminary PAH source apportionment study in the urban sites was conducted by means of diagnostic ratios. The ratios are similar to those reported in areas affected by traffic emissions; they also suggest an industrial emission source at Reinosa.     

Polycyclic aromatic hydrocarbons in sediments and mussels of Corral Bay, south central Chile

PAHs were measured in sediments and mussels (Mytilus chilensis) from Carboneros and Puerto Claro, located in Corral Bay, Valdivia. According to the ratio of phenanthrene/anthracene and fluoranthene/pyrene concentrations, these sites are medium polluted with PAHs originating mainly from pyrolytic sources. Fluoranthene was the major component measured in mussels (3.1-390 ng g(-1) dry weight) and sediments (6.9-74.1 ng g(-1) dry weight). In general, mussels were mainly exposed to the dissolved fraction of the lower molecular weight PAHs (tri- and tetra-aromatics) while the higher molecular ring systems (penta- and hexa-aromatics) were more bioavailable to sediments. Mussel PAHs content was relatively constant, with the exception of the 1999 summer season (March), when higher concentration values were found in both sites; however, PAHs residues in sediments showed a temporal variation.