Characterization of polycyclic aromatic hydrocarbons in fog-rain events

Atmospheric polycyclic aromatic hydrocarbons (PAHs) mainly originate from incomplete combustion or pyrolysis of materials containing carbon and hydrogen. They exist in gas and particle phases, as well as dissolved or suspended in precipitation (fog or rain). Current studies in atmospheric PAHs are predominantly focused on fog and rainwater samples. Some sampling difficulties are associated with fog samples. This study presented the first observation of the characteristics of PAHs in fog samples using a solid phase microextraction (SPME) technique. Eighteen fog samples were collected during ten fog events from March to December 2009 in the Shanghai area. PAHs were extracted by SPME and analyzed by gas chromatography-mass spectrometry (GC-MS). As the compounds were partially soluble in water, with solubility decreasing with increasing molecular weight, low molecular weight (LMW) PAH compounds were universally found in the fog water samples. Naphthalene (NaP), phenanthrene (Phe), anthracene (Ant) and fluoranthene (Flo) were dominant compounds in fog water. The total PAH concentration in fog water ranged from 0.03 to 6.67 μg L(-1) (mean of 1.06 μg L(-1)), and was much higher in winter than in summer. The concentration of PAHs in fog or rain water decreased after undergoing a pre-rain or pre-fog wash. The average concentration of PAHs was higher in fog than in rain. Diagnostic ratio analysis suggested that petroleum and combustion were the dominant contributors to PAHs in urban Shanghai. Backward trajectories were calculated to determine the origin of the air masses, showing that air masses were mostly from the northeast territory.     

Fugacity approach to evaluate the sediment-water diffusion of polycyclic aromatic hydrocarbons

Diffusion is an important process for sediment-water exchange and plays a vital role in controlling water quality. Fugacity fraction (ff) was used to estimate the sediment-water diffusion of polycyclic aromatic hydrocarbons (PAHs) between seawater and surficial sediment. A total of 33 surface sediment and sea water samples were collected concurrently from the northeast coastal area in China and 25 PAHs were analyzed including the alkylated and chlorated PAHs. Fugacity fraction was calculated based on the PAH concentrations in water and sediment, octanol-water partition coefficient of PAHs, organic matter content in sediment, and density of sediment. The calculated results showed that ff increased with decreasing molecular weight of PAHs. The low molecular weight PAHs (2-3 rings) transferred from sediment to water and the sediment acted as a secondary source to the water. The medium molecular weight PAHs (4-5 rings) were close to the sediment-water equilibrium and the transfer tendency shifted between sediment and water. The high molecular weight PAHs (5-6 rings) transferred from water into sediment and the sediment acted as a sink. Soot carbon and the difference of PAH concentrations between sediment and water were found to be important factors affecting the sediment-water diffusion. This study provided new insight into the process of sediment-water diffusion, which has a great influence on the quality of water, especially in severely-polluted sediment areas.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from white pine (Pinus strobus) needles and its implications

A supercritical fluid extraction (SFE) method was developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) from fresh and fallen pine needles. Toluene-modified CO2 was used as the extracting fluid, and the extracted PAHs were analyzed by GC-MS. Using a two-stage extraction procedure, a static extraction at 180 degrees C and a dynamic extraction at 60 degrees C, and an in-cell silica gel plug plus a post-oven silica gel column, the extraction and fractionation of PAHs can be accomplished in one step. Over a seven month period, a significant variation was observed for PAHs in urban samples, while PAHs in mountain samples were at much lower levels (by a factor of approximately 8) and showed little seasonal change. Although dry fallen needles and fresh needles contained similar amounts of PAHs, in the fallen needles the lower molecular weight PAHs were partially lost while the higher molecular weight PAHs were slightly enriched. Pollution in urban areas was found to be highly localized, and buildings and trees are believed to be important factors in the restriction of atmospheric PAHs.     

Naphthalene and its biomarkers as measures of occupational exposure to polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) include compounds with two or more fused benzene rings, many of which are carcinogens. Industrial sources produce hundreds of PAH, notably in the coke- and aluminium-producing industries. Because PAH are distributed at varying levels between gaseous and particulate phases, exposure assessment has been problematic. Here, we recommend that occupational exposures to naphthalene be considered as a potential surrogate for occupational PAH exposure for three reasons. Naphthalene is usually the most abundant PAH in a given workplace; naphthalene is present almost entirely in the gaseous phase and is, therefore, easily measured; and naphthalene offers several useful biomarkers, including the urinary metabolites 1- and 2-hydroxynaphthalene. These biomarkers can be used to evaluate total-body exposure to PAH, in much the same way that 1-hydroxypyrene has been applied. Using data from published sources, we show that log-transformed airborne levels of naphthalene are highly correlated with those of total PAH (minus naphthalene) in several industries (creosote impregnation: Pearson r= 0.815, coke production: r= 0.917, iron foundry: r= 0.854, aluminium production: r= 0.933). Furthermore, the slopes of the log-log regressions are close to one indicating that naphthalene levels are proportional to those of total PAH in those industries. We also demonstrate that log-transformed urinary levels of the hydroxynaphthalenes are highly correlated with those of 1-hydroxypyrene among coke oven workers and controls (r= 0.857 and 0.876), again with slopes of log-log regressions close to one. These results support the conjecture that naphthalene is a useful metric for occupational PAH exposure. Since naphthalene has also been shown to be a respiratory carcinogen in several animal studies, it is also argued that naphthalene exposures should be monitored per se in industries with high levels of PAH.     

Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.     

Determination of petroleum hydrocarbons and polycyclic aromatic hydrocarbons in sludge from wastewater treatment basins

Screening by gas chromatography with flame ionization detection and gas chromatography-mass spectrometry has been carried out on sludge extracts of wastewater treatment basins. Soxhlet extraction with trichlorotrifluoroethane was applied. The yields for petroleum hydrocarbons and PAH recovery were high, usually in excess of 90%. The proposed investigations permit a quick assessment of petroleum pollutants in the environment.     

Using discriminant analysis to assess polycyclic aromatic hydrocarbons contamination in Yongding New River

Yongding New River has been polluted by polycyclic aromatic hydrocarbons (PAHs) which are carcinogenic and mutagenic. In three periods (the abundant water period, mean water period, dry water period), ten sites (totally 30 samples) in Yongding New River were clustered into four categories by hierarchical cluster analysis (hierarchical CA). In the same cluster, the samples had the same approximate contamination situation. In order to eliminate the dimensional differences, the data in each sample, containing 16 kinds of PAHs, were standardized with normal standardization and maximum difference standardization. According to the results of the cubic clustering criterion, pseudo F, and pseudo t ² (PST2), the proper number of clustering for the 30 samples is 4. Before conducting hierarchical CA and K-means cluster analysis on the samples, we used principal component analysis to obtain another group data set. This data set was composed of the principal component scores which are uncorrelated variables. Hierarchical CA and K-means cluster analysis were used to classify the two data sets into four categories. With the classification results of hierarchical CA and K-means cluster analysis, discriminant analysis is applied to determine which method was better for normalization of the original data and which one was proper to cluster the samples and establish discriminant functions so that a new sample can be grouped into the right categories.     

Distribution of polycyclic aromatic hydrocarbons in the atmosphere of Hong Kong

This paper reports the monitoring results of eleven polycyclic aromatic hydrocarbons (PAHs), four to six-ring, at two urban sites-Central & Western (CW) and Tsuen Wan (TW) in Hong Kong from January to December 2000; and the findings of a study conducted in 2001 of the partitioning of the gaseous and particulate phases of PAHs. The sum of the eleven PAHs under study (sigmaPAHs) was found to range from 6.46 to 38.8 ng m(-3). The annual mean levels at 12.2 ng m(-3) and 15.8 ng m(-3) for CW and TW respectively are comparable to those recorded for the previous two years and are also within the reported ranges for other metropolitan cities in the Asia Pacific region. Amongst the selected eleven PAHs, fluoranthene and pyrene were the two most abundant found in the urban atmosphere of Hong Kong during the study period accounting for approximately 80%, of the total PAHs. The ratios of benzo(a)pyrene to benzo(g,h,i)perylene (BaP/BghiP) and indeno(1,2,3-cd)pyrene to benzo(g,h,i)perylene (IDP/BghiP) indicate that diesel and gasoline vehicular exhausts were the predominant local emission sources of PAHs. Seasonal variations with high winter to summer ratios for each of the individual PAHs (CW: 1.6-16.7 and TW: 0.82-8.2) and for sigmaPAHs (CW: 1.9 and TW: 1.8) and a spatial variation of BaP amongst the air monitoring stations are noted. Results of correlation studies illustrate that local meteorological conditions such as ambient temperature, solar radiation, wind speed and wind direction have significant impact on the concentrations of atmospheric PAHs accounting for the observed seasonal variations. A snapshot comparison of the concentrations of PAHs at four sites including a roadside site, a rural site and the two regular urban sites CW and TW was also performed using the profiles of PAHs recorded on two particulate episode days in March 2000.     

大气颗粒物中多环芳烃的索氏提取研究

通过对大气颗粒物中多环芳烃的索氏提取过程中的不同阶段的提取液中多环芳烃的分析 ,绘制了索氏提取曲线 ,发现提取效率主要取决于提取循环次数 ,而与提取浸泡时间关系不大。通过比较 1 1种提取液对加标参考物和实验参考物的索氏提取效率 ,发现常用的环己烷、苯等提取液提取效率很低。提取能力的序列为喹啉 乙醇 >吡啶 乙醇 >丙酮>乙醇 >二氯甲烷 >苯 >环己烷 >石油醚 >丙酮 乙醇 环己烷 >氯仿 >四氢呋喃。     

Measurements of polycyclic aromatic hydrocarbons at an industrial site in India

Polycyclic Aromatic Hydrocarbon (PAH) concentrations were measured in Total Suspended Particulate Matter (TSPM) from December 2005 to August 2006 at Nunhai, an industrial site in Agra (India). Particulate matter samples were collected on glass fibre filters using High Volume Sampler (HVS-430) and were extracted using dichloromethane with ultrasonication and analyzed by GC. Total PAH concentration varies between 0.04 to 2.5 microg m(-3) accounting only 1.6 x 10(-3)% of TSPM. The mass distribution in air was dominated by high molecular weight DbA, BghiP, BaP, BkF and IP. Combustion PAH (CPAH) except BeP represents 58% of the total PAH mass and IARC classified total carcinogenic PAH accounting 63% of TPAH concentration. Correlation studies between PAH revealed the contribution of low molecular weight PAH was mainly due to primary emission from diesel exhaust while high molecular weight PAH were formed during combustion. The presence of specific tracers and calculation of characteristic molecular diagnostic ratios Fla/(Fla + Pyr), BaP/(BaP + Chy), BaA/(BaA + Chy), IP/(IP + BghiP), BaP/BghiP and IP/BghiP) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Seasonal variation in atmospheric PAH showed four fold increase in winter concentration than summer. The BaP and relative BaP amount calculated from the measurements suggested that photo-oxidation may also be responsible for the variation in PAH concentrations during winter and summer. Seasonal trends in atmospheric PAH concentration in the study area were influenced by fossil fuel usage for domestic heating, boundary height and temperature.     

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.     

Receptor modeling for source apportionment of polycyclic aromatic hydrocarbons in urban atmosphere

This study reports source apportionment of polycyclic aromatic hydrocarbons (PAHs) in particulate depositions on vegetation foliages near highway in the urban environment of Lucknow city (India) using the principal components analysis/absolute principal components scores (PCA/APCS) receptor modeling approach. The multivariate method enables identification of major PAHs sources along with their quantitative contributions with respect to individual PAH. The PCA identified three major sources of PAHs viz. combustion, vehicular emissions, and diesel based activities. The PCA/APCS receptor modeling approach revealed that the combustion sources (natural gas, wood, coal/coke, biomass) contributed 19–97% of various PAHs, vehicular emissions 0–70%, diesel based sources 0–81% and other miscellaneous sources 0–20% of different PAHs. The contributions of major pyrolytic and petrogenic sources to the total PAHs were 56 and 42%, respectively. Further, the combustion related sources contribute major fraction of the carcinogenic PAHs in the study area. High correlation coefficient (R ² > 0.75 for most PAHs) between the measured and predicted concentrations of PAHs suggests for the applicability of the PCA/APCS receptor modeling approach for estimation of source contribution to the PAHs in particulates.     

Identification of polycyclic aromatic hydrocarbons in unleaded petrol and diesel exhaust emission

Inhalation of emissions from petrol and diesel exhaust particulates is associated with potentially severe biological effects. In the present study, polycyclic aromatic hydrocarbons (PAHs) were identified from smokes released by the automobile exhaust from petrol and diesel. Intensive sampling of unleaded petrol and diesel exhaust were done by using 800-cm³ motor car and 3,455-cm³ vehicle, respectively. The particulate phase of exhaust was collected on Whatman filter paper. Particulate matters were extracted from filter paper by using Soxhlet. PAHs were identified from particulate matter by reverse phase high performance liquid chromatography using C₁₈ column. A total of 14 PAHs were identified in petrol and 13 in case of diesel sample after comparing to standard samples for PAH estimation. These inhalable PAHs released from diesel and petrol exhaust are known to possess mutagenic and carcinogenic activity, which may present a potential risk for the health of inhabitants.     

Alkylphenols and polycyclic aromatic hydrocarbons in eastern Mediterranean Spanish coastal marine bivalves

This paper reports the first results on alkylphenol pollution in edible bivalves from the Spanish coast. Two sampling campaigns (July 2006 and July 2007) were carried out to determine the concentration of nonylphenol (NP), octylphenol (OP), and eight polycyclic aromatic hydrocarbons (PAHs) in wild mussels (Mytilus galloprovincialys) and clams (Donax trunculus) at 14 sampling sites along the eastern Mediterranean Spanish coast. The results show that NP is the predominant alkylphenol, being the port of Valencia the most polluted area (up to 147 ??g/kg wet weight in clams). Moving away from the ports the concentration of NP in bivalves decreased. OP concentration was below its detection limit in most of the studied areas and its maximum concentration (6 ??g/kg w/w) was measured in clams from the port of Sagunto. The presence of low levels of PAHs was observed in most of the studied areas. The total PAHs concentration (i.e., sum of the eight measured PAHs) achieved a maximum value of 10.09 ??g/kg w/w in the north coast of Valencia city. The distribution pattern of the individual PAHs showed that both pollution sources petrogenic and pyrolytic were present in the sampled areas. Fluoranthene was the most abundant PAH in mussels while benzo(b)fluoranthene in clams. The maximum concentration of 10 ??g/kg w/w for benzo(a)pyrene established by the European Commission was never reached, indeed sampled bivalves showed concentrations 10 times lower than this reference value. Thus, they can be considered safe for human consumption. Despite the low contamination levels, the results show an overall pollution of bivalves by alkylphenol and PAHs as well as an increment in the number of polluted areas from 2006 to 2007. Thus, periodical sampling campaigns should be carried out to monitor the long-term tendency of these toxic and persistent pollutants.     

环境空气中多环芳烃的采样与分析技术

文章对环境空气中多环芳烃的采样与分析方法进行了概述,侧重介绍了样品的采集、净化、采样效率的评估方法和采样分析全过程的质量控制.     

Polycyclic aromatic hydrocarbons in pine and spruce shoots-temporal trends and spatial distribution

In the framework of the German environmental specimen bank one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) serve as bioindicators for the atmospheric pollution. Sampling is performed in two urbanized areas in western and eastern Germany (Warndt and Duebener Heide, respectively), and in seven different rural locations. Prior to archiving conifer shoots are continuously analyzed for a set of 17 individual polycyclic aromatic hydrocarbons (PAHs). The results from the two urbanized areas show that the atmospheric contamination with PAH has declined by about 75% between 1985 and 2004 at Warndt and by about 85% between 1991 and 2004 at Duebener Heide. However, summation operatorPAH concentrations stayed virtually constant at both locations since the end of the 1990s at levels of about 100 ng g(-1) wet weight (ww). In spruce shoots from rural areas current concentrations of PAHs are significantly lower and vary between 8 and 61 ng g(-1) ww. In all shoot samples the four low molecular aromatics phenanthrene, fluoranthene, pyrene, and chrysene dominate the pattern by contributing 60 to 90% to summation operatorPAH. The group of high molecular weight aromatics is dominated by benzo[b,j,k]fluoranthene, especially in spruce shoots originating from greater altitudes remarkable amounts of six and seven ringed PAHs could be detected. Despite the strong decrease of PAH concentrations in urban areas patterns of aromatics remained nearly unchanged in the observation period 1985 to 2004.     

Source apportionment of polycyclic aromatic hydrocarbons in the Dahuofang Reservoir, Northeast China

Polycyclic aromatic hydrocarbons (PAHs) in 24 surface sediments from the Dahuofang Reservoir (DHF), the largest man-made lake in Northeast China, were measured. The results showed that the concentrations of 16 US EPA priority PAHs in the sediments ranged from 323 to 912 ng/g dry weight with a mean concentration of 592?±?139 ng/g. The PAH source contributions were estimated based on positive matrix factorization model. The coal combustion contributed to 31 % of the measured PAHs, followed by residential emissions (22 %), biomass burning (21 %), and traffic-related emissions (10 %). Pyrogenic sources contributed ～84 % of anthropogenic PAHs to the sediments, indicating that energy consumption release was a predominant contribution of PAH pollution in DHF. Compared with the results from the urban atmospheric PAHs in the region, there was a low contribution from traffic-related emissions in the sediments possibly due to the low mobility of the traffic-related derived 5+6-ring PAHs and their rapid deposition close to the urban area.     

A source study of atmospheric polycyclic aromatic hydrocarbons in Shenzhen, South China

Air pollution has become a serious problem in the Pearl River Delta, South China, particularly in winter due to the local micrometeorology. In this study, atmospheric polycyclic aromatic hydrocarbons (PAHs) were monitored weekly in Shenzhen during the winter of 2006. Results indicated that the detected PAHs were mainly of vapor phase compounds with phenanthrene dominant. The average vapor phase and particle phase PAHs concentration in Shenzhen was 101.3 and 26.7 ng m^???3, respectively. Meteorological conditions showed great effect on PAH concentrations. The higher PAHs concentrations observed during haze episode might result from the accumulation of pollutants under decreased boundary layer, slower wind speed, and long-term dryness conditions. The sources of PAHs in the air were estimated by principal component analysis in combination with diagnostic ratios. Vehicle exhaust was the major PAHs source in Shenzhen, accounting for 50.0% of the total PAHs emissions, whereas coal combustion and solid waste incineration contributed to 29.4% and 20.6% of the total PAHs concentration, respectively. The results clearly indicated that the increasing solid waste incinerators have become a new important PAHs source in this region.     

Distribution and health-risk of polycyclic aromatic hydrocarbons in soils at a coking plant

Nineteen soil samples were collected in and around Songshan coking plant in Guangdong province of China and analyzed for eighteen polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 2.36 to 1146.39 mg kg(-1) dry weight, varying significantly among the sampling sites, most individual PAHs were correlated with each other. A cluster analysis was performed to examine the correlation of PAH distribution, five groups were observed with sample types in the coking plant. 2-3 ring PAHs were predominant in group I and II, while 4-5 ring PAHs showed great abundance in group III, IV and V, which contributed to the distance from the emission sources in the coking plant and the behaviors of particle-bound and gaseous PAHs. The ratios of Flu?:?(Flu + Pyr), BaA?:?(BaA + Chr), InP?:?(InP + BgP) and Ant?:?(Ant + Phen) ratios were 0.51-0.87, 0.16-0.89, 0.47-0.68 and 0.03-0.60, respectively. The total index of all studied soils was > 6, indicating that the source of the PAHs in coking plant soils were from the pyrolysis processes. Health risk assessments were carried out by dermal PAH exposure data to quantify cancer risk. The resultant lifetime exposure levels due to TEQ(BaP) desorbed onto skin for workers ranged from 2.25 × 10(-7) to 7.86 × 10(-5) mg kg(-1) per day, and the estimated cancer risks were between 8.45 × 10(-6) and 2.94 × 10(-3), indicating that the dermal exposures of PAHs to coking workers might be acceptable in most soil sites.