Role of volcanic dust in the atmospheric transport and deposition of polycyclic aromatic hydrocarbons and mercury

The role of volcanic ash as scavenger of atmospheric pollutants, in their transport and final deposition to the ground is examined. Attention is focused on polycyclic aromatic hydrocarbons (PAHs) and on particulate mercury (Hgp). The ash-fall deposits studied belong to the 2001 and 2002 eruptive activity of Mount Etna, Southern Italy, and were investigated at three (2001) and four (2002) sites downwind of the major tephra dispersal pattern. The dry deposition of mercury and PAHs was determined, and, in particular, a downward flux to the ground of PAHs (approximately 7.29 microg m(-2) per day) and mercury (750 ng m(-2) per day) was estimated in Catania from October 26 to October 28, 2002. Finally, evidence on the anthropogenic origin of PAHs scavenged from the troposphere by volcanic ash is supported by the analysis of PAH compositions in granulometrically homogeneous fractions.     

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.     

Sedimentary record of polycyclic aromatic hydrocarbons in a sediment core from a maar lake, Northeast China: evidence in historical atmospheric deposition

A maar lake is an excellent ecosystem to study the atmospheric deposition of pollutants, as its contaminants are primarily by atmospheric deposition. In this study, a sediment core from Sihailongwan Maar Lake, Northeast China, was collected and the historical atmospherically deposited polycyclic aromatic hydrocarbons (PAHs) were analyzed. The concentrations of TPAHs (the sum of the US EPA proposed 16 priority PAHs, excluding naphthalene and pyrene) ranged from 473.9 to 2289 ng g(-1) with a slow increasing stage in the deeper sediments and a sharp increasing stage in the upper sediments. The input rate of TPAHs, especially that of PAH(9) (the sum of fluoranthene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(ah)anthrathene, and benzo(ghi)perylene), correlated well to the Chinese historical socioeconomic data. This indicates that sediment PAHs were mainly derived from human activities and PAH(9) can be regarded as a better indicator of the local socioeconomic development. Source identification suggested that PAHs were originated primarily from mixed sources (e.g., coal and biomass burning and petroleum combustion), except for perylene which was mostly of diagenetic origin. In addition, the down-core PAHs profile clearly illustrated that PAHs sources in Northeast China experienced a transformation from low- and moderate temperature to high-temperature combustion processes, especially after the late 1980s. Additionally, an ecological risk assessment using two redefined biological thresholds (TEQ(ERL) and TEQ(ERM)) indicated that most of the PAHs measured in the present sediment core would not cause an immediate toxic effect; only FLU and PHEN are a potential source of concern for biological impairment.     

Characteristics and sources of atmospheric polycyclic aromatic hydrocarbons (PAHs) in Shanghai, China

A field campaign was conducted to measure and analyze 13 polycyclic aromatic hydrocarbons (PAHs) in six major zones in the city of Shanghai, P.R. China from August 2006 to April 2007. Ambient air samples were collected seasonally using passive air samplers, and gas chromatography–mass spectroscopy was used in this field campaign. The results showed that there was a sequence of 13 PAHs at Phen > FA > Pyr > Chr > Fl > An > BaA > BbFA > BghiP > IcdP > BkFA > BaP > DahA and the sum of these PAHs is 36.01 ± 10.85 ng/m³ in gas phase. FL, Phen, FA, Pyr, and Chr were the dominant PAHs in gas phase in the city. They contributed 90% of total PAHs in the gas phase. Proportion of measured PAHs with three, four, five, and six rings to total PAHs was 53%, 42%, 3%, and 2%, respectively. The highest concentration of ΣPAHs (the sum of 13 PAHs) occurred in the wintertime and the lowest was in the summer. This investigation suggested that traffic, wood combustion, and metal scrap burn emissions were dominant sources of the concentrations of PAHs in six city zones compared with coal burning and industry emissions. Further, the traffic emission sources of PAHs in the city were attributed mostly to gasoline-powered vehicles compared with diesel-powered vehicles. It was revealed that the seasonal changes in PAHs in the city depended on different source types. Metal scrap burn was found to be the major source of PAHs during the autumn, while the PAH levels in the atmosphere for winter and spring seasons were mainly influenced by wood and biomass combustion. Comparisons of PAHs among different city zones and with several other cities worldwide were also made and discussed.     

Concentrations, sources and temporal trends in atmospheric polycyclic aromatic hydrocarbons in a major conurbation

Concentrations of atmospheric PAH were separately determined in total suspended particulate matter and associated vapour phase in ambient air in Birmingham, UK. Samples of 24 h duration were taken simultaneously at two locations (the Bristol Road Observatory Site, BROS, and the Elms Road Observatory Site, EROS) on 44 separate occasions every one to two weeks between October 1999 and January 2001. BROS was 10 m from the busy Bristol Road, 800 m from EROS that was located within the "green space" of the University of Birmingham campus. With the exception of acenaphthene, average concentrations of all measured PAH at BROS exceed those at EROS, with a paired t-test revealing these roadside increments to be significant (p < 0.05) for 9 out of the 16 target PAH, demonstrating the importance of traffic emissions of PAH. Although the declines were not statistically significant (p > 0.05) except for phenanthrene and fluoranthene, concentrations of individual PAH at EROS between July and December inclusive in 1999 and 2000 fell by between 16 and 54% compared with those during the same months in 1997. Multiple linear regression of PAH concentrations against meteorological variables confirmed the influence of the Bristol Road on BROS but not EROS. Cluster analysis of PAH contamination in individual samples showed there to be two statistically distinct groups of samples. One group contained 15 samples, all of which displayed elevated concentrations. Examination of air mass back trajectory data, revealed that these PAH pollution episodes originate due to the combined effects of meteorology and local traffic emissions, rather than as a result of long-range transport. Eighteen 12 h samples were also taken at EROS over the period of the November Bonfire Night festivals of 1999 and 2000. These revealed significantly elevated PAH concentrations on the nights when ignition of bonfires and fireworks would be anticipated to peak. These results are relevant to assessments of the impact of similar "festivals of fire" elsewhere. In particular, retene (7-isopropyl-1-methylphenanthrene) concentrations were especially elevated, indicating it has possible utility as an indicator of wood combustion emissions.     

Analysis of polycyclic aromatic hydrocarbons in the atmospheric particulate: focused microwaves for a faster extraction method

In this paper, improvements obtained by using focused microwaves for extraction, in the analysis of polycyclic aromatic hydrocarbons (PAHs) adsorbed on particulate matter, are discussed. The method was tested on the following PAHs, which are considered to be among the most harmful with regard to carcinogenicity: benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene. The extraction of PAHs and concentration of the sample can be performed in 3 h with a recovery of at least 70% and a maximum standard deviation of 4%. These steps are followed by clean-up on a SPE (solid-phase extraction) cartridge and analysis by GC-MS. Real samples collected in the urban area of Bari were analysed according to the proposed procedure.     

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.     

Concentration, distribution and source apportionment of atmospheric polycyclic aromatic hydrocarbons in the southeast suburb of Beijing, China

Total suspended particle samples and gas phase samples were collected at three representative sampling sites in the southeastern suburb of Beijing from March 2005 to January 2006. The samples were analyzed for 16 US EPA priority PAHs using GC/MS. Concentrations of Sigma PAHs in particle and gas phases were 0.21-1.18 x 10(3) ng m(-3) and 9.5 x 10(2) ng-1.03 x 10(5) ng m(-3), respectively. PAH concentrations displayed seasonal variation in the order of winter>spring>autumn>summer for particle phase, and winter>autumn>summer>spring for gas phase. Partial correlation analysis indicates that PAH concentrations in particle phase are negatively correlated with temperature and positively correlated with air pollution index of SO(2). No significant correlation is observed between gas phase PAHs and the auxiliary parameters. Sources of PAH are identified through principal component analysis, and source contributions are estimated through multiple linear regression. Major sources of atmospheric PAHs in the study area include coal combustion, coke industry, vehicular emission and natural gas combustion.     

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.     

Transport,deposition and biodegradation of particle bound polycyclic aromatic hydrocarbons in a tidal basin of an industrial watershed

Polycylic aromatic hydrocarbons (PAHs) are commoncontaminants in industrial watersheds. Their origin,transport and fate are important to scientists,environmental managers and citizens. The Philadelphia NavalReserve Basin (RB) is a small semi-enclosed embayment nearthe confluence of the Schuylkill and Delaware Rivers inPennsylvania (USA). We conducted a study at this site todetermine the tidal flux of particles and particle-boundcontaminants associated with the RB. Particle traps wereplaced at the mouth and inside the RB and in the Schuylkilland Delaware Rivers. There was net particle deposition intothe RB, which was determined for three seasons. Spring andfall depositions were highest (1740 and 1230 kg ofparticles, respectively) while winter deposition wasinsignificant. PAH concentrations on settling particlesindicated a net deposition of 12.7 g PAH in fall and 2.1 gPAH in spring over one tidal cycle. There was nosignificant PAH deposition in the winter. Biodegradationrates, calculated from ¹⁴C-labeled PAH substratemineralization, could attenuate only about 0.25% of the PAHdeposited during a tidal cycle in fall. However, in thespring, biodegradation could be responsible for degrading50% of the settling PAHs. The RB appears to be a sink forPAHs in this watershed.     

Determination of n-alkanes and polycyclic aromatic hydrocarbons in atmospheric particulate and vapour phases in Oviedo, Spain, by GC-MS

A GC-MS procedure for the determination of hydrocarbons in air samples from Oviedo, Spain, was developed. Air hydrocarbons were sampled with a high volume sampler equipped with a holder containing a glass fiber filter, to trap the particulate phase, and two polyurethane foams to capture hydrocarbons of the vapour phase. Compounds were extracted with CH2Cl2 by Soxhlet extraction and then fractionated using column chromatography with alumina silica. Analyses of the fractions were performed by GC-MS in the electron ionization mode. PAHs and n-alkanes were the compounds examined in this work. Samples collected in the vicinity of the Faculty of Chemistry (a semi-urban area) were analysed. The total concentration of PAHs in the air samples analysed ranged from 28 to 76 ng m(-3). The total concentration of n-alkanes and PAHs in the vapour phase exceeded the concentration in the particulate phase in the samples analysed.     

Contributions of deposited particles to pine needle polycyclic aromatic hydrocarbons

The contributions of deposited particles (P) to polycyclic aromatic hydrocarbon (PAH) levels in pine (Cedrus deodar) needles sampled from the Dalian region were evaluated by washing off the particles from pine needle surfaces. P values ranged from 4.4 +/- 2.2% for fluorene to 69.9 +/- 4.0% for indeno(1,2,3-cd)pyrene, and positively correlated with the logarithm of octanol-air partition coefficients (log K OA) of each PAH significantly. P and the total levels of 14 PAHs under study ( summation PAHs), that ranged from 490 to 3241 ng g(-1) dw (dry weight) with median value of 1521 ng g(-1) dw, were high for traffic areas, and low for residential or park areas, implying the significant contributions of PAHs in both gas and particle phases emitted by vehicles. However, PAH profiles in pine needles were not significantly altered by the washing, due to the low fractions (2-5%) of the 5- and 6-ring PAHs in summation PAHs. The high wind speed and frequently alternating wind directions in the Dalian spring could quicken the depuration processes of pine needle PAHs. Thus, the local meteorological conditions and source variations should be taken into account when using pine needles to implicate seasonal variations of atmospheric semi-volatile organic compounds.     

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。     

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.     

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.     

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.     

Aliphatic and polycyclic aromatic hydrocarbons in the surface sediments of the Mediterranean: assessment and source recognition of petroleum hydrocarbons

Coastal marine sediment samples were collected from ten sampling stations along the Egyptian Mediterranean coast in April 2010. All sediment samples were analyzed for aliphatic (C7 to C34) and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total aliphatic hydrocarbons ranged from 1621.82 to 9069.99 ng/g (dry weight), while aromatic hydrocarbons (16 PAHs) varied between 208.69 and 1020.02 ng/g with an average of 530.68?±?225.86 ng/g?dwt. Good correlations observed between certain PAH concentrations allowed to identify its origin. The average TOC percent was varied from 0.13 to 1.46 %. Principal component analysis was used to determine the sources of hydrocarbon pollutants in sediments of Mediterranean. Additionally, special PAHs compound ratios suggest the petrogenic origins.     

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.