食品中多环芳烃及卤代多环芳烃的研究进展

综述了多环芳烃及卤代多环芳烃的性质、毒性及国内外食品中的污染情况和研究现状,并对目前的分析测定方法进行了介绍,希望为我国开展食品领域内多环芳烃和卤代多环芳烃的研究提供参考。     

Use of passive samplers to mimic uptake of polycyclic aromatic hydrocarbons by benthic polychaetes

Experiments were conducted to test whether passive samplers made of low-density polyethylene (polyethylene devices, or PEDs) can estimate the extent of uptake of polycyclic aromatic hydrocarbons (PAHs) by benthic polychaetes (Nereis virens) in contaminated marine sediments. For a variety of PAHs, PEDs reached 90% equilibrium with sediment PAHs in 60 days or less. Using 60-day sediment bioaccumulation tests, we have demonstrated a significant relationship between PAH concentrations in the polychaetes and the PEDs (R2 = 0.67, p = 0.002), with the PEDs taking up less PAHs than the polychaetes. Because of this relationship, PEDs can potentially be used in a regulatory context to simulate uptake of bioavailable PAHs in contaminated marine sediments. The PED PAH concentrations were also used to calculate porewater PAH concentrations that allowed for the estimation of a linear free-energy relationship between the lipid-water distribution coefficient (Klip) and the octanol-water distribution coefficient (KOW) for PAH uptake in marine polychaetes (R2 = 0.94, p < 0.0001).     

四种多环芳烃低剂量联合暴露对大鼠毒性作用的初步研究

目的 初步研究4种多环芳烃(苯并[a]芘、苯并[a]蒽、艹屈和苯并[b]荧蒽)低剂量联合暴露的毒性作用。方法 购入50只8周龄SD雄性大鼠,随机分为5组,每组10只,分别按0、10、50、250、1000 μg/kg·BW剂量连续灌胃染毒,基于人体4种多环芳烃的实际暴露量,灌胃剂量的比例设定为苯并[a]芘∶苯并[a]蒽∶艹屈∶苯并[b]荧蒽=0.99∶2.92∶2.68∶1.68。大鼠于染毒30 d后处死,取血清、脏器等生物样本,计算脏器系数,进行大鼠肝脏病理切片观察病理学改变,并检测肝功能相关指标、氧化应激相关指标及脂代谢相关指标。结果 相较于对照组,染毒组大鼠肝脏结构有明显异常,肝窦扩大,肝细胞出现气球样变;1 000 μg/kg·BW组肝脏脏器比显著升高。染毒30 d后1 000 μg/kg·BW组大鼠血清谷草转氨酶均显著上升(P<0.05);染毒组大鼠血清谷胱甘肽过氧化物酶在30 d时显著升高(P<0.05);染毒30 d后,1 000 μg/kg·BW组大鼠血清高密度脂蛋白胆固醇显著下降并且肝脏胆固醇显著上升(P<0.05),250 μg/kg·BW组大鼠血清甘油三酯显著上升(P<0.05),50 μg/kg·BW及以上染毒剂量的染毒组肝脏中TG显著上升(P<0.05)。结论 PAH4低剂量联合暴露对SD雄性大鼠产生了一定程度的肝损伤、氧化应激及脂代谢紊乱等不良影响。     

Adsorption of polycyclic aromatic hydrocarbons by carbon nanomaterials

Carbon nanomaterials are novel manufactured materials, having widespread potential applications. Adsorption of hydrophobic organic compounds (HOCs) by carbon nanomaterials may enhance their toxicity and affect the fate, transformation, and transport of HOCs in the environment. In this research, adsorption of naphthalene, phenanthrene, and pyrene onto six carbon nanomaterials, including fullerenes, single-walled carbon nanotubes, and multiwalled carbon nanotubes was investigated, which is the first systematic study on polycyclic aromatic hydrocarbons (PAHs) sorption by various carbon nanomaterials. All adsorption isotherms were nonlinear and were fitted well by the Polanyi-Manes model (PMM). Through both isotherm modeling and constructing "characteristic curve", Polanyi theory was useful to describe the adsorption process of PAHs by the carbon nanomaterials. The three fitted parameters (Q0, a, and b) of PMM depended on both PAH properties and the nature of carbon nanomaterials. For different PAHs, adsorption seems to relate with their molecular size, i.e., the larger the molecular size, the lower the adsorbed volume capacity (Q0), but higher a and b values. For different carbon nanomaterials, adsorption seems to relate with their surface area, micropore volume, and the volume ratios of mesopore to micropore. Quantitative relationships between these sorbent properties and the estimated parameters of PMM were obtained. These relationships may represent a first fundamental step toward establishing empirical equations for quantitative prediction of PAH adsorption by carbon nanomaterials and possibly other forms of carbonaceous (geo-) sorbents, and for evaluating their environmental impact. In addition, high adsorption capacity of PAHs by carbon nanotubes may add to their high environmental risks once released to the environment, and result in potential alteration of PAHs fate and bioavailability in the environment.     

Aqueous photodegradation of polycyclic aromatic hydrocarbons

Photodegradation of 12 polycyclic aromatic hydrocarbons was studied in aerated pure water, solutions of Suwannee River fulvic acid, and natural waters using polychromatic light (>290 nm). Quantum yields in pure water varied from 3.2 x 10(-5) to 9.2 x 10(-3). No obvious relationships were evident among the quantum yields and molecular properties. Photodegradation rate constants in solutions of Suwannee River fulvic acid or natural waters were largely unchanged compared to rate constants in pure water. Estimates of PAH photodegradation rates in natural waters can thus be obtained employing the quantum yields in pure water, PAH absorption, and solar irradiance. Calculated rate constants for photodegradation in surface waters during the summertime at mid-latitude varied from 3.2 x 10(-3) to 7.6 h(-1).     

Emission of polycyclic aromatic hydrocarbons in China by county

Quantitative relationships among social, economic, and climate parameters, and energy consumption for Chinese provinces, provide data for regression models' estimated rates of energy consumption and emission of polycyclic aromatic hydrocarbons (PAHs) by county. A nonlinear model was used for domestic coal combustion with total population and annual mean temperature as independent variables. Linear regression models were utilized for all other types of fuel consumption. Monte Carlo simulation demonstrated that emission factors, rather than the regression modeling, constitute the main source of uncertainty in prediction. Models were validated using available energy data of several northern and southern counties of China from the literature. The total PAHs produced by each county is approximately equivalent to the sum of the total emission from energy, coke, and aluminum production.     

Spatial and temporal trends of polycyclic aromatic hydrocarbons and other traffic-related airborne pollutants in New York City

Traffic-related air pollutants have been associated with adverse health effects. We hypothesized that exposure to polycyclic aromatic hydrocarbons (PAHs), elemental carbon (EC, diesel indicator), particulate matter (PM2.5), and a suite of metals declined from 1998 to 2006 in NYC due to policy interventions. PAH levels from personal monitoring of pregnant mothers participating in the Columbia's Center for Children's Environmental Health birth cohort study, and EC, PM2.5, and metal data from five New York State Department of Environmental Conservation stationary monitors were compared across sites and over time (1998-2006). Univariate analysis showed a decrease in personal PAHs exposures from 1998 to 2006 (p < 0.0001). After controlling for environmental tobacco smoke, indoor heat, and cooking, year of personal monitoring remained a predictor of decline in sigmaPAHs (beta = -0.269, p < 0.001). Linear trend analysis also suggested that PM2.5 declined (p = 0.09). Concentrations of EC and most metals measured by stationary site monitors, as measured by ANOVA, did not decline. Across stationary sites, levels of airborne EC and metals varied considerably. By contrast PM2.5 levels were highly intercorrelated (values ranged from 0.725 to 0.922, p < 0.01). Further policy initiatives targeting traffic-related air pollutants may be needed for a greater impact on public health.     

Emission of polycyclic aromatic hydrocarbons in China

Emission of 16 polycyclic aromatic hydrocarbons (PAHs) listed as U.S. Environmental Protection Agency (U.S. EPA) priority pollutants from major sources in China were compiled. Geographical distribution and temporal change of the PAH emission, as well as emission profiles, are discussed. It was estimated that the total PAH emission in China was 25,300 tons in 2003. The emission profile featured a relatively higher portion of high molecular weight (HMW) species with carcinogenic potential due to large contributions of domestic coal and coking industry. Among various sources, biomass burning, domestic coal combustion, and coking industry contributed 60%, 20%, and 16% of the total emission, respectively. Total emission, emission density, emission intensity, and emission per capita showed geographical variations. In general, the southeastern provinces were characterized by higher emission density, while those in western and northern China featured higher emission intensity and population-normalized emission. Although energy consumption in China went up continuously during the past two decades, annual emission of PAHs fluctuated depending on the amount of domestic coal consumption, coke production, and the efficiency of energy utilization.     

HPLC-FLD快速测定大豆中的多环芳烃

建立了大豆中多环芳烃的快速检测方法.采用乙腈-四氢呋喃(1+1)提取大豆中的多环芳烃,并用高效液相色谱-荧光光谱(HPLC-FLD)法测定多环芳烃含量.方法检出限和定量限分别为0.07～0.61 μg/kg和0.27 ～ 2.04 μg/kg,线性范围为2～ 200 μg/kg,回收率在81.7％ ～96.5％之间,相对标准偏差在2.10％ ～ 10.44％之间.     

Prediction of personal exposure to PM2.5 and carcinogenic polycyclic aromatic hydrocarbons by their concentrations in residential microenvironments

We measured exposure to fine particles (PM2.5) and polycyclic aromatic hydrocarbons (PAHs), including carcinogenic PAHs, in multiple locations for a diverse population of participants who resided in Shizuoka, Japan. In summer and winter 2002 we surveyed personal concentrations, those of four primary indoor microenvironments-living room, bedroom, kitchen (summer only), and workplace--and those outside the subjects' houses. Concentrations of PM2.5 and PAHs tended to be higher during winter. Median PM2.5 concentration was highest in living room samples during winter but in personal samples during summer. The median PAH concentrations normalized to the cancer potency equivalence factor of benzo[a]pyrene (BaP-TEQ) was highest in the bedroom during winter but outdoors in summer. Personal exposure level profiles differed markedly between smokers and nonsmokers. Personal exposures to BaP ([BaP]p) and BaP-TEQ ([BaP-TEQ]P) in nonsmokers were strongly correlated. Personal exposures of nonsmokers, as calculated from the corresponding time-weighted indoor and outdoor concentrations, were consistent with measured levels of BaP but not PM2.5. Personal exposure of nonsmokers to BaP, as calculated from the time-weighted living room, bedroom, and either workplace or outdoor concentrations, accounted for 92-107% of the measured levels of BaP-TEQ.     

Atmospheric polycyclic aromatic hydrocarbons in north China: a winter-time study

The contamination and outflow of atmospheric polycyclic aromatic hydrocarbons (PAHs) in the Chinese Northern Plain, a region with a total area of 300 000 km2 and a high PAH emission density, were investigated. Polyurethane foam (PUF) and PM10 samples were collected at 46 sites located in urban, rural (towns or villages), and control (remote mountain) areas in the winter from November 2005 to February 2006. The observed concentrations of atmospheric PAHs were generally higher than those reported for developed countries and southern Chinese cities. It was found that there was no significant difference in air PAH concentrations between the urban and the rural areas (514 +/- 563 ng/m3 and 610 +/- 645 ng/ m3, respectively), while the PAH concentrations at the control sites (57.1 +/- 12.6 ng/m3) were 1 order of magnitude lower than those at the other sites. The primary reason for the similarity in PAH concentrations between urban and rural areas was the fact that the predominant sources of biomass and domestic coal combustion were widely spread over the study area. The partition constants (K(PM10)) of PAHs were significantly correlated to the corresponding values of subcooled liquid-vapor pressure (pL0). However, the regression slopes of log K(PM10) versus log pL0 were much steeper than -1, indicating adsorption dominated over absorption. Three distinct patterns of outflow from the study area were identified by forward trajectory and cluster analysis.     

天然生育酚中多环芳烃的脱除方法

多环芳烃是天然生育酚中普遍存在的一种化合物,它是由含有两个及两个以上苯环稠和而成.此类化合物对生物及人类的毒害主要是参与机体的代谢过程,因具有强烈的致癌性、致畸性、致突变性而受到严格限制,目前欧美各国的法规都对生育酚中的多环芳烃采取了近乎苛刻的要求,国内有许多相关生产厂家,因为无法突破此道技术难关,而无法参与欧美市场,因此,寻找到一种既经济又简易可行的脱除方法,是天然生育酚工业化生产中必须要解决的问题,同时也是为人类健康作出必要的保证.本文就当前主要的几家天然生育酚生产商的多环芳烃脱除方法进行了总结与评述,并对比较常用的液液萃取法、吸附剂吸附法、柱层析法和复合脱除法的工业化可行性进行了简要的评价.     

Historical records of airborne polycyclic aromatic hydrocarbons by analyzing dated corks of the bark pocket in a Longpetiole Beech tree

Historical monitoring of airborne polycyclic aromatic hydrocarbons (PAHs) pollution levels was novelly demonstrated by analyzing the dated corks of a bark pocket formed from 1873 to 2003 in a Longpetiole Beech (Fagus longipetiolata) tree trunk sampled from southeastern China. The fundamental studies indicated that the PAHs of log K(oa) < 8.5 are primarily accumulated through interactions with lipid substances in cork and log K(oa) dependent, while the PAHs of log K(oa) > 8.5 existing as particle-phase dependent on log Vp are accumulated through stochastic entrapment by the lenticels on the surface of the cork. The translocation of PAHs by xylem flow and phloem stream as well as radial diffusion from the cork to the inner tissues was not significant, and the cork is most effective for accumulating airborne PAHs. The total concentrations of 16 EPA PAHs (sumPAHs) in the dated corks progressively increased from 43.5 ng/g recorded in the earliest available cork in 1873-1875 to the maximum 345.7 ng/g in 1956-1961, and then gradually decreased to 267.0 ng/g in 2003, while the concentration of perylene (PER) was slightly fluctuating at 0.178 +/- 0.033 ng/g. Moreover, the concentration ratio of sumPAHs to PER increased from 193 to 2431 from 1873 to 2003, indicating a progressive increase in PAH pollution in southeastern China.     

采用GC-MS测定涂层面料中16种多环芳烃的方法

针对纺织品中多环芳烃(PAHs)检测要求,建立了涂层面料经超声提取后液液萃取、固相萃取净化方法,采用气相色谱质谱(GC-MS)测定面料中PAHs含量,并详细考察了该方法的回收率和检出限。结果表明,该方法测定纺织品中PAHs最低检出限(LOD)为0.4～3.8μg/L,最低定量限(LOQ)为1.3～12.2μg/L,加标回收率74.0%～99.0%,相对标准偏差为0.89%～4.94%。检测结果表明,该方法准确,快速,简便可靠,能够满足纺织品及装饰材料中对16种PAHs的检测要求。     

Pyrolytic formation of polycyclic aromatic hydrocarbons from sesquiterpenes

The products of the pyrolysis of four sesquiterpenes, β-caryophyllene, α-cedrene, longifolene and valencene, have been examined. Pyrolysis was carried out at 300, 400 and 500°C, the products determined by GC-MS and then examined for similarities and differences using multivariate data analysis. Analysis showed that longifolene was most resistant and caryophyllene least resistant to pyrolysis with cedrene and valencene occupying intermediate positions. While the compounds were largely unchanged at 300°C, polycyclic aromatic hydrocarbons (PAHs) were major components of the pyrolysates at 400 and 500°C. No less than nine of the 16 EPA priority pollutants were present in the pyrolysates at the higher temperatures.     

8种多环芳烃联合暴露致大鼠肝脏毒性及BMDL推导

目的 探究8种多环芳烃（PAH8）联合暴露的大鼠肝脏毒性,利用基准剂量法（BMD）获得PAH8致肝脏毒性的基准剂量95%置信区间下限值（BMDL）。方法 雄性SD大鼠随机分为5组,每组10只,分别按照0、10、50、250和1 000μg/kg·BW剂量的PAH8连续染毒30 d后处死大鼠,计算脏器系数,进行肝脏病理学检测和油红O染色,检测血清谷丙转氨酶、谷草转氨酶、丙二醛、谷胱甘肽过氧化物酶（GSH-Px）、甘油三酯（TG）、总胆固醇（TC）的水平及肝脏TG、TC含量。选择具有统计学意义、毒理学意义和剂量效应趋势的肝脏毒性数据,利用BMDS 3.2软件进行BMD分析,选择最佳拟合模型得到BMDL值。结果 1 000μg/kg·BW剂量组大鼠肝脏系数较对照组显著升高（P<0.05）。PAH8染毒后部分大鼠肝脏出现细胞水肿、炎性浸润、脂肪变性等病理改变。10～250μg/kg·BW剂量组血清GSH-Px较对照组显著升高（P<0.01）,但1 000μg/kg·BW剂量组GSH-Px显著降低（P<0.001）。肝脏中TC含量呈现剂量效应趋势,1 000μg/kg·BW剂量...