Lichens to distinguish urban from industrial PAHs

This paper shows that lichens can be used as biomonitors to distinguish urban from industrial polycyclic aromatic hydrocarbons (PAHs). PAHs are atmospheric pollutants originating mainly from incomplete combustion of fuels in vehicles and industry. The occurrence of PAHs in air is a serious health issue in urban areas and industrial areas because some PAHs are carcinogenic. Biomonitoring PAHs with lichens is generally applied for quantification of PAHs. However, the precise sources of PAHs are not well known. Here we use lichen to trace the source of PAHs. PAHs were analyzed in Pyxine subcinerea Stirton, a lichen species collected from twelve sites which vary from urban and industrial to periurban forest area of Haridwar, in the foothills of the Indian Himalayas. Total PAH concentration ranged between 1.25 and 187.3 μg g⁻¹. Results indicate a clear distinction between urban and industrial PAHs profile, using principal component analysis. Lichen sampled from industrial sites exhibited higher concentrations of two-, five-, and six-ringed PAHs, up to 60% of total PAHs, while samples from urban sites were dominated by four-ringed PAHs, predominantly fluoranthene and acenaphthylene. Molecular ratios indicate that combustion was the dominant source of origin of PAHs in industrial area, while urban sites showed mixed origin of PAHs, both pyro- and petrogenic.     

Characterization and sources of PAHs in an urban river system in Beijing,China

Water samples from 20 locations on rivers in the Tongzhou District of Beijing were collected four times from July 2005 to March 2006. In addition, sediment samples were collected in July 2005. All samples were analyzed for 16 US Environmental Protection Agency (EPA) priority pollutants polycyclic aromatic hydrocarbons (PAHs). The concentration, distribution, seasonal variation, and sources of the 16 PAH compounds identified in the water samples, suspended particles, and surface sediments were then evaluated. The concentrations of PAHs in the water and suspended particle and surface sediment samples ranged from 87.3 to 1,890 ng l⁻¹, 1,330 to 27,700 ng g⁻¹, and 156 to 8,650 ng g⁻¹, respectively. These results demonstrated that rivers in the Tongzhou District of Beijing had a high level of PAH pollution, especially in the suspended particles. The highest and lowest concentrations of PAHs in the water samples were observed in summer and spring. However, the seasonal variations in the concentration of PAHs in the suspended particles were more complicated. The dominant compounds in the water, suspended particle, and surface sediment samples were two-, three- and four-ring PAH compounds, respectively. Ratio analysis illustrated that fuel-burning was the primary source of PAHs in the study area. Gasoline, diesel, coal, and coke oven sources were identified and the contributions of the different fuel-burning sources were then calculated using factor analysis and multiple linear regression. These analyses revealed that coal combustion, gasoline combustion plus coke oven emission, and diesel combustion accounted for 38.8%, 38.5%, and 22.7% of the PAHs in suspended particles, respectively.     

京津潮白河多环芳烃及其衍生物分布

采用固相萃取-气相色谱质谱联用仪测定京津潮白河中的多环芳烃(PAHs)及其衍生物(SPAHs)的污染水平,并采用絮凝法分析水样中自由态PAHs/SPAHs和结合态PAHs/SPAHs的分布。结果表明,京津潮白河中PAHs和SPAHs总质量浓度分别为55.06～215.02 ng·L~(-1)和92.37～227.33 ng·L~(-1),上游河段PAHs和SPAHs质量浓度均低于下游河段。7种致癌PAHs占比为22%～41%,需引起重视。本研究中的SPAHs包括三类物质:氧化PAHs(OPAHs)、甲基PAHs(MPAHs)和氯代PAHs(Cl PAHs)。其中,OPAHs对SPAHs贡献最大(59%～71%),其次是Cl PAHs(22%～32%)和MPAHs(7%～14%)。京津潮白河中PAHs和SPAHs主要以自由态形式存在,总浓度可以准确估计污染物的环境风险。     

Evaluation on exposures to particulate matter at a junior secondary school: a comprehensive study on health risks and effective inflammatory responses in Northwestern China

Air pollutant measurement and respiratory inflammatory tests were conducted at a junior secondary school in Xi’an, Northwestern China. Hazardous substances including particulate matters (PMs), black carbon (BC) and particle-bounded polycyclic aromatic hydrocarbons (PAHs) were quantified both indoors and outdoors of the school. Source characterization with organic tracers and particle-size distribution demonstrated that the school’s air was mostly polluted by combustion emissions from the surrounding environment. The evaluation of health assessment related to air quality was conducted by two methods, including potential risk estimation of air pollutants and direct respiratory inflammatory test. The incremental lifetime cancer risks associated with PAHs were estimated and were 1.62 × 10⁻⁶ and 2.34 × 10⁻⁶, respectively, for indoor and outdoor fine PMs. Both the values exceeded the threshold value of 1 × 10⁻⁶, demonstrating that the carcinogenic PAHs are a health threat to the students. Respiratory inflammatory responses of 50 students who studied in the sample classroom were examined with a fractional exhaled nitric oxide (FeNO) test, with the aid of health questionnaires. The average FeNO concentration was 17.4 ± 8.5 ppb, which was slightly lower than the recommended level of 20 ppb established by the American Thoracic Society for children. However, a wide distribution and 6% of the values were > 35 ppb, suggesting that the potentials were still high for eosinophilic inflammation and responsiveness to corticosteroids. A preliminary interpretation of the relationship between air toxins and respiratory inflammatory response demonstrated the high exposure cancer risks and inflammatory responses of the students to PMs in the city.

     

A 25-year record of polycyclic aromatic hydrocarbons in soils amended with sewage sludges

We studied polycyclic aromatic hydrocarbons (PAHs) in crop soils amended with 1000 tonnes dry weight of sewage sludges per 10,000 m² from 1974 to 1992, then after sludges addition from 1993 to 1999. The absence of variations of total PAHs levels of control soils, averaging at 123 μg/Kg, shows the absence of horizontal contamination. During sludges addition, the total PAHs levels in amended soils increased from 232 to 402 μg/Kg. Seven years after sludges addition, it decreased to 275 μg/Kg, which is still more than twice –the levels of control soils. This finding shows that sludges PAHs are preserved in crop soils for long periods of time, on a human scale.     

Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

Comprehensive characterization of PAHs profile in Serbian soils for conventional and organic production: potential sources and risk assessment

This study presents a comprehensive characterization of occurrence and levels of 16 polycyclic aromatic hydrocarbons (PAHs) in arable soils used for conventional and organic production in northern and central part of Serbia as well as cross-border region with Hungary. Furthermore, this study includes a characterization of PAH sources and carcinogenic/non-carcinogenic human health risk for PAHs accumulated in analysed arable soils. The total concentration of 16 PAHs varied between 55 and 4584 µg kg^?1 in agricultural soil used for conventional production and between 90 and 523 µg kg^?1 in agricultural soil used for organic production. High molecular weight (HMW) PAHs were dominant compounds with similar contribution in both soil types (86% and 80% in conventional and in organic soil, respectively). Principal component analysis and diagnostic ratios of selected PAHs were used for identification of PAH sources in the analysed soils. Additionally, positive matrix factorization was applied for quantitative assessment. The results indicated that the major sources of PAHs were vehicle emissions, biomass and wood combustion, accounting for?~?93% of PAHs. Exposure of farmers assessed through carcinogenic (TCR) and non-carcinogenic (THQ) risk did not exceed the acceptable threshold (TCR?<?10^–6 and THQ?<?1). Oral ingestion was the main exposure route which accounted for 57% of TCR and 80% of THQ. It was followed by dermal contact. This investigation gives a valuable data insight into the PAHs presence in arable soils and reveals the absence of environmental and health risk. It also acknowledges the importance of comprehensive monitoring of these persistent pollutants.

     

基于统计方法的辽东湾沉积物中多环芳烃来源特征分析

为研究辽东湾表层沉积物中多环芳烃(PAHs)的来源特征,2014年5月采集了20个辽东湾海域表层沉积物样品,并利用气相色谱质谱联用仪对优先控制的16种PAHs进行测定,采用聚类分析、主成分分析-多元线性回归分析、异构体比值3种统计方法对辽东湾表层沉积物中PAHs来源特征进行了研究。结果表明,辽东湾表层沉积物中PAHs含量范围88.5~199.3 ng·g-1,平均值为(126.3±35.3)ng·g-1,其中,萘、菲和荧蒽是PAHs优势组分。通过统计分析结果表明,辽东湾北部表层沉积物中PAHs含量低于西南部,沉积物中PAHs的来源包括石油燃烧来源、煤炭、木材等生物质燃烧来源和石油来源,其中燃烧来源是主要来源,煤炭、木材等生物质燃烧来源占49.9%,石油燃烧来源和石油来源占50.1%。     

Sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Biobio River in south central Chile

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; there are concerns about them due to their toxic properties. Human activities could significantly contribute to the total PAH burden in river sediments. In this work, we document the analysis of PAHs in sediments taken in the middle stretch of the Biobio River in south central Chile. This river is a principal system, draining more than 24,000 km² and subjected to a diverse variety of human-made stressors (pulp mill and urban effluents, agricultural drainage systems, etc). During 2003, several sediment samples were taken in more than 45 sampling sites located in the river’s middle stretch. Due to the granulometric characteristics (mainly sandy sediments), only 17 samples were analyzed, taking into consideration the presence of a fine section within the sediment sample. Using HPLC with fluorescence detection, 15 EPA priority PAHs and perylene were analyzed. The composition of PAHs in the sediment samples is rather similar between sites and levels averaged 104 ± 78 ng g⁻¹ d.w. The highest levels were detected downstream from an industrial discharge. A good correlation was observed between PAH levels and organic carbon content in the tested sediments; however, concentrations above 134 ng g⁻¹ d.w. did not indicate correlation. The samples PAH ratios (Flu/Pyr and Chr/B(a)A) reveal a strong pyrolytic PAH pattern in the sediments tested, supporting evidence indicating that PAHs come mainly from pyrolytic sources. This result contrasts with previous records that have shown a natural influence in the upper basin and a petrogenic pattern near the mouth.     

室内空气中多环芳烃污染的测量和特征性研究

本文就室内空气中多环芳烃典型污染源－室内燃煤和室内吸烟排放的多环芳烃组成和含量进行了测定，并同室外大气（对照）中多环芳烃组成含量进行了对比，研究了室内环境不同污染源排放多环烃组成和含量的特征性，结果表明，室内燃煤污染同燃煤型室外大气源排放多环芳烃具有相似组成含量特征，而室朵烟草烟雾污染源的多环芳烃组成含量特征，则与室外煤型和交通型均有显著区别。     

Polycyclic aromatic hydrocarbons in household dust near diesel transport routes

A river-dredging project has been undertaken in Nantou, Taiwan. A large number of diesel vehicles carrying gravel and sand shuttle back and forth on the main roads. Ten stations along major thoroughfares were selected as the exposure sites for testing, while a small village located about 9 km from a main traffic route was selected as the control site. Levels of household dust loading at the exposure sites (60.3 mg/m²) were significantly higher than those at the control site (38.2 mg/m²). The loading (μg/m²) of t-PAHs (total polycyclic aromatic hydrocarbons) in the household dust at the exposure sites was significantly higher (P < 0.05) than was the case at the control site. The diagnostic ratios of PAHs showed that diesel emissions were the dominant source of PAHs at the exposure sites. The lack of a significant correlation between the concentrations of Fe and t-PAHs suggested that the t-PAHs in household dust might come from diverse sources. However, a significant correlation (P = 0.003) between the concentrations of Mo and t-PAHs implied that the most of the t-PAHs in the household dust might have resulted from diesel emissions. The lifetime cancer risks of BaP_eq from household dust exposure were markedly higher than those resulting from inhalation exposure.     

Occurrence and particle-size distributions of polycyclic aromatic hydrocarbons in the ambient air of coking plant

The purpose of this study was to characterize the occurrence and size distributions of ten species of polycyclic aromatic hydrocarbons (PAHs) in the ambient air of coking plants. Particulate-matter samples of four size fractions, including ≤2.1, 2.1–4.2, 4.2–10.2, and ≥10.2 μm, were collected using a Staplex234 cascade impactor during August 2009 at two coking plants in Shanxi, China. The PAHs were analyzed by a gas chromatograph equipped with a mass-selective detector. The concentrations of total particulate-matter PAHs were 1,412.7 and 2,241.1 ng/m³ for plants I and II, and the distributions showed a peak within the 0.1–2.1 μm size range for plant I and the 0.1–4.2 μm for plant II. The size distributions of individual PAHs (except fluoranthene) exhibited a considerable peak within the 0.1–2.1 μm size range in coking plant I, which can be explained by the gas–particle partition mechanism. The ambient air of the coking plant was heavily polluted by PAHs associated with fine particles (≤2.1 μm), and benzo[b]fluoranthene made the largest contribution to total PAHs. The exposure levels of coking-plant workers to PAHs associated with fine particles were higher than to PAHs associated with coarse particles. Benzo[b]fluoranthene, benzo[a]pyrene, and dibenzo[a,h]anthracene should be the primary pollutants monitored in the coking plant. This research constitutes a significant contribution to assessing the exposure risk of coking-plant workers and providing basic data for PAH standards for ambient air in coking plants.     

渤海北部典型芳香烃类化合物污染状况及生态风险评价

为探究渤海北部海上油气区及周边近岸海域典型芳香烃类化合物污染状况,2015年5月现场采集了32个站位的海水样品,针对7种苯系物(BTEX)和17种多环芳烃(PAHs)进行测定,并采用商值法和毒性当量法对污染物开展单一和联合生态风险评估。结果显示,研究海域海水中7种苯系物总含量范围为65.1～222.6 ng·L~(-1),以甲苯含量最高,表层含量略低于底层,油气区平均含量低于周边近岸,受到陆源污染输入的影响特征明显。表层海水中ΣPAHs含量范围为98.9～356.0 ng·L~(-1),平均值为184.5 ng·L~(-1),以低环芳烃占优势,总体处于中等水平,比值法判定该海域PAHs可能主要来源于石油及其加工产品。该海域海水中苯并(a)芘的风险商RQ值大于0.1,表现出低度风险,其余3种处于可接受水平。4种芳香烃类化合物联合生态风险等级为低度风险,对生态系统具有潜在的不利影响,但不同区域仍存在一定差异性,海上石油开采与陆源输入是影响该海域个别区域生态风险较高的重要因素。     

Polycyclic aromatic hydrocarbons in medicinal plants from Syria

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (EPA PAHs) in 10 medicinal plants in different used parts of plant (leaves and flowers) have been determined. The analytical method consists of sample preparation by ultrasonic extraction with dichloromethane followed by silica gel clean-up. Subsequently, the analysis was carried out by reversed-phase high-performance liquid chromatography (HPLC) coupled to both ultraviolet and fluorescence detections in series to insure the detection of all 16 EPA PAHs. It was observed that the sum of the 16 PAHs (ΣPAHs) in the investigated medicinal plants ranged from 47 to 890 μg kg^–1 where the highest ΣPAHs was found in Sage plant sample. Light PAHs were dominants in all studied medicinal plants. The sum of eight genotoxic PAHs (ΣPAH8) have shown a better indicator of the degree of contamination with carcinogenic PAHs compared to benzo[a]pyrene in these products.     

气相色谱法估算多环芳烃的辛醇/水分配系数

通过对2－6环多环芳烃（PAHs)气相色谱保留时间（RGC）与HPLC保留值及与辛醇／水分配系数（KOW）对应关系的研究，发现RGC与HPLC保留值主KOW间存在明显的线性相关关系，建立了RGC与KOW间的一元回归方程，并对包括EPA16种优先控制的PAHs在内的33种多环芳烃化合物的KOW值进行估算，估算值的相对误差为0．10％－12．10％，平均值为4．51％。     

绿色食品产地土壤中PAHs测定方法研究

对绿色食品产地土壤中多环芳烃的气相色谱质谱联用分析法进行了研究。样品经索氏提取后硅胶氧化铝复合柱净化,最后用GC/MS内标法进行定性定量分析。方法相关系数除苯并(a,h)蒽的相关系数R2=0.9970外,其余目标化合物的相关系数R2均大于0.9991,各化合物线性关系良好。方法加标回收率大多在70%至90%间,各目标化合物的方法检测限为2.2～40ng/kg。     

Concentrations of polycyclic aromatic hydrocarbons in soils of a mangrove forest affected by forest fire

Surface soils affected by forest fires from Igbanko mangrove forest in Nigeria were analyzed for 16 EPA priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography–mass spectrometry (GC–MS). The total PAHs concentrations in the soils ranged from 63 to 188?µg?kg^?1 dry weight (average: 108?µg?kg^?1). The three predominant PAHs in the soils were naphthalene (Na), fluoranthene (Flu), and benzo(b)fluoranthene (BbF). Compared to the control sample (19?µg?kg^?1), elevated PAHs concentrations were observed in the soils, an indication of some level of PAHs contamination. PAHs source diagnostic ratios of Flu/(Flu?+?Pyr) and Ant/(Ant?+?Phe) indicated that the PAHs have a pyrogenic origin which may have resulted from combustion of grass, wood, or coal. An assessment based on Canadian soil quality guidelines indicated that the studied locations do not pose any serious adverse risk on human health.     

An investigation into the occurrence and distribution of polycyclic aromatic hydrocarbons in two soil size fractions at a former industrial site in NE England,UK using in situ PFE–GC–MS

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in 16 topsoils (0–10 cm) collected across the site of a former tar works in NE England. The soils were prepared in the laboratory to two different particle size fractions: <250 μm (fraction A) and >250 μm to <2 mm (fraction B). Sixteen priority PAHs were analysed in the soils using in situ pressurised fluid extraction (PFE) followed by gas chromatography—mass spectrometry (GC–MS). The average total PAH concentration in the soils ranged from 9.0 to 1,404 mg/kg (soil fraction A) and from 6.6 to 872 mg/kg (soil fraction B). These concentrations are high compared with other industrially contaminated soils reported in the international literature, indicating that the tar works warrants further investigation/remediation. A predominance of higher-molecular-weight compounds was determined in the samples, suggesting that the PAHs were of pyrogenic (anthropogenic) origin. Statistical comparison (t-test) of the mean total PAH concentrations in soil fractions A and B indicated that there was a significant difference (95% confidence interval) between the fractions in all but two of the soil samples. Additionally, comparisons of the distributions of individual PAHs (i.e. 16 PAHs × 16 soil samples) in soil fractions A and B demonstrated generally higher PAH concentrations in fraction A (i.e. 65.8% of all individual PAH concentrations were higher in soil fraction A). This is important because fraction A corresponds to the particle size thought to be most important in terms of human contact with soils and potential threats to human health.     

城市回用水中多环芳烃致癌风险评价

为评价人群暴露于城市回用水中16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)对于人体健康的潜在风险,采用气相色谱-质谱(GC-MS)联用的分析化学方法对不同季节回用水中16种PAHs进行定量分析;在此基础上采用美国国家科学院和国家研究委员会提出的环境健康风险评价方法,分析不同回用条件下具有中国水体基质特色的城市回用水中PAHs健康风险.结果显示,回用水样中16种PAHs的总浓度为1 422.85 ng·L-1,污水处理厂二级出水水样16种PAHs的总浓度为1 791.77 ng ·L-1,经过处理后回用水中PAHs含量有所降低.风险评价分析结果显示,回用水在城市绿化、农业灌溉和景观娱乐3种不同回用途径下多环芳烃的致癌风险分别为788×10-8、2.77×10-6、3.04×10-6,总致癌风险为5.89×10-6.以上结果可以得出,回用水在城市绿化、农田灌溉和景观娱乐接触过程中多环芳烃所增加的致癌风险很低,回用水中多环芳烃的健康风险处于可接受水平.     

Lichens reveal air PAH fractionation in the Himalaya

This paper shows that gas/particulate phase partitioning of polycyclic aromatic hydrocarbons (PAHs) can be monitored using lichens. Anthropogenic sources are responsible for the release of PAHs, which are bioaccumulated in plants at various spatial scales based on their physicochemical properties. Atmospheric PAHs are distributed both in the gaseous and particulate states. Here, a lichen species, Dermatocarpon vellereum Zschacke, has been collected at different altitudes in and around the Rudraprayag valley, located in Central Himalayan region of India, in order to study the spatial distribution of PAHs in the valley. Results show that PAH concentration ranged from 0.136 to 4.96 μg g^?1. Findings reveal that the bioaccumulation of 2- and 3-ringed PAHs was higher in high-altitude samples, whereas bioaccumulation of fluoranthene, a 4-ringed PAH, showed higher concentration in samples from localities away from town centre. 5- and 6-ring PAHs were then confined to the lower altitude at the base of the valley, thus justifying their particulate-bound nature. This is the first report showing the utility of lichen to biomonitor PAHs in the Himalayan ecosystem.