Soil pollution by PAHs in urban soils: a comparison of three European cities

The purpose of this study was to determine the degree of contamination with polycyclic aromatic hydrocarbons (PAHs) in samples of urban soil from three European cities: Glasgow (UK), Torino (Italy) and Ljubljana (Slovenia). Fifteen PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) were measured in urban soil samples, using harmonised sampling, sample extraction and analyte quantification methods. Although the mean concentration of each PAH in urban soils of each city showed a wide range of values, high levels of contamination were only evident in Glasgow, where the sum of concentrations of 15 PAHs was in the range 1487-51,822 microg kg(-1), cf. ranges in the other two cities were about ten-fold lower (89.5-4488 microg kg(-1)). The three predominant PAHs were phenanthrene, fluoranthene and pyrene, with the sum of these compounds about 40% of the total PAH content. These data, together with some special molecular indices based on ratios of selected PAHs, suggest pyrogenic origins, especially motor vehicle exhausts, to be the major sources of PAHs in urban soils of the three cities. The largest concentrations for PAHs were often found in sites close to the historic quarters of the cities. Overall, the different climatic conditions, the organic carbon contents of soil, and the source apportionment were the dominant factors affecting accumulation of PAHs in soil.     

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。     

广东省南海市主干道气溶胶中多环芳烃(PAHs)的研究

气溶胶采样点位于广东省南海市桂江路边缘及两侧 ,采集时间为 2 4 h,连续采集三天。使用仪器为国产大体积采样器。同时在公园内设点采样 ,以作背景研究。样品经超声波抽提和层析柱分离得到正构烷烃、芳烃 (AHs)和极性组分等三种有机组分。对 PAHs进行 GC MS分析 ,气溶胶中具有较高含量的芴、菲、蒽、荧蒽、芘、苯并 [a]蒽、、苯并 [b]荧蒽、苯并 [k]荧蒽、苯并 [a]芘、茚并 [1 ,2 ,3-cd]芘、二苯并 [a,h]蒽、苯并 [g,h,i]等。通过 TSP研究认为 ,主干道的机动车排放和扬尘是气溶胶的主要来源 ,气候改变也是 TSP变化的另一重要因素。     

公园地表土中多环芳烃的分离提取及含量分析

比较加压液体萃取法、超声波辅助萃取技术和微波辅助提取技术对公园地表土中多环芳烃的提取效率,并对目标化学成分进行分析鉴定。以超高效液相色谱-三重四极杆质谱作为分析方法,共分离检测出16种多环芳烃类化合物,分别为萘、苊、苊烯、氟、菲、蒽、荧蒽、芘、苯并[a]蒽、艹屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并[a,h]蒽、茚并[1,2,3-cd]芘和苯并[ghi]苝。结果表明:加压液体萃取法、超声波辅助萃取技术和微波辅助提取技术均可以有效提取公园地表土中多环芳烃类成分。超高效液相色谱-质谱联用技术可以有效地分析公园地表土中多环芳烃类成分。     

Assessment of soil screening levels due to ingestion and dermal absorption of chrysene and benzo[k]fluoranthene and appropriate remediation method for Dorson Abad

For years, the Dorson Abad region has been extremely polluted by Tehran Oil Refinery due to leaking from its underground pipelines, storage tanks, and evaporation ponds. To assess the concentrations of hazardous polycyclic aromatic hydrocarbon (PAH) compounds, soil samples were collected from the grounds at and adjacent to a polluted stream located in the study area. The samples were then analyzed, and the results revealed that 12 of the 16 USEPA PAHs were noticeably present in the soil, which, among them, benzo[k]fluoranthene and chrysene had the highest concentrations with averages of 357.17 and 173.38 mg/kg, respectively. A comparison of the obtained concentrations with the soil screening levels indicated that both benzo[k]fluoranthene and chrysene concentrations were substantially higher than EPA screening level values, signifying the necessity of soil remediation for these contaminants in the area. Techniques such as soil washing/flushing, high temperature thermal desorption, and solidification/stabilization were investigated for treatment of the contaminated soil; solidification/stabilization is recommended as an applicable and cost-effective remediation method for Dorson Abad due to the size of the region, relatively low cost of the binder (cement), and low volatility of benzo[k]fluoranthene and chrysene.     

Determination of Polycyclic Aromatic Hydrocarbons in Rougan, a Traditional Chinese Barbecued Food, by Capillary Gas Chromatography

Several polycyclic aromatic hydrocarbons (PAHs), including those which are carcinogenic, have been detected in rougan, a traditional Chinese barbecued pork dish. The food samples were cleaned up by caustic digestion, solvent extraction, liquid-liquid partition, and column chromatography. The determination was carried out using capillary gas-chromatography with a flame ionization detector. A 25-m HP-1 capillary column was used. Fluorene, phenanthrene, anthracene, benzo[a]anthracene, chrysene and benzo[k]fluoranthene were detected in three of the five samples within the range of 3-17 ng/g. Fluoranthene and pyrene were detected in only two of the samples at similar levels. Two potent carcinogenic compounds, benzo[a]pyrene and benzo[b,j,k]fluoranthene, were not detected in any of the samples. No detectable PAHs have been found in meat cooked without the direct contact of food with flame and smoke. In barbecuing over an open charcoal fire, animal fat and juices dripping onto the open fire probably enhanced the formation of PAHs.     

Multivariate analysis of mixed contaminants (PAHs and heavy metals) at manufactured gas plant site soils

Principal component analysis (PCA) was used to provide an overview of the distribution pattern of polycyclic aromatic hydrocarbons (PAHs) and heavy metals in former manufactured gas plant (MGP) site soils. PCA is the powerful multivariate method to identify the patterns in data and expressing their similarities and differences. Ten PAHs (naphthalene, acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]pyrene) and four toxic heavy metals — lead (Pb), cadmium (Cd), chromium (Cr) and zinc (Zn) — were detected in the site soils. PAH contamination was contributed equally by both low and high molecular weight PAHs. PCA was performed using the varimax rotation method in SPSS, 17.0. Two principal components accounting for 91.7% of the total variance was retained using scree test. Principle component 1 (PC1) substantially explained the dominance of PAH contamination in the MGP site soils. All PAHs, except anthracene, were positively correlated in PC1. There was a common thread in high molecular weight PAHs loadings, where the loadings were inversely proportional to the hydrophobicity and molecular weight of individual PAHs. Anthracene, which was less correlated with other individual PAHs, deviated well from the origin which can be ascribed to its lower toxicity and different origin than its isomer phenanthrene. Among the four major heavy metals studied in MGP sites, Pb, Cd and Cr were negatively correlated in PC1 but showed strong positive correlation in principle component 2 (PC2). Although metals may not have originated directly from gaswork processes, the correlation between PAHs and metals suggests that the materials used in these sites may have contributed to high concentrations of Pb, Cd, Cr and Zn. Thus, multivariate analysis helped to identify the sources of PAHs, heavy metals and their association in MGP site, and thereby better characterise the site risk, which would not be possible if one uses chemical analysis alone.     

Assessment of hydrocarbons concentration in marine fauna due to Tasman Spirit oil spill along the Clifton beach at Karachi coast

On 27 July 2003, Tasman Spirit spilled 31,000 tonnes of crude oil into the sea at the Karachi coast. This disaster badly affected the marine life (Flora and Fauna.) Present research has been proposed to ascertain the level of Polycyclic Aromatic hydrocarbons (PAHs) contamination in different fisheries including Fishes, Crustaceans; Crabs and Shrimps, Mollusks and Echinoderms along with passing time. Heavier components of crude oil such as Polycyclic Aromatic Hydrocarbons (PAHs) appear to cause most damages as these are relatively unreactive and persist in water. High concentrations of toxic PAHs were observed in all the fisheries and shellfishes caught form oil-impacted area. In this study fishes were found most contaminated than shellfishes i.e. summation operator 16 PAH = 1821.24 microg/g and summation operator 1164.34 microg/g, respectively. Naphthalene was found in the range of 0.042-602.23 microg/g. Acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene were detected in the range 0.008-80.03 microg/g, fluoranthene, pyrene, benzo(a)anthracene and chrysene 0.0008-221.32 microg/g, benzo(b) fluoranthene, benzo(k)fluoranthene and benzo(a) pyrene 0.0005-7.71 microg/g, benzo(g,h,i)perylene and indeno(1,2,3-c,d)pyrene 0.02-503.7 microg/g. Dibenzo(a,h)anthracenre was not detected in any specie.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.     

Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

Polycyclic aromatic hydrocarbon levels in European catfish from the upper Po River basin

Polycyclic aromatic hydrocarbons (PAHs) are a major concern in environmental studies as many of them have been labeled as probable carcinogens by the International Agency for Research on Cancer (IARC 1983). Due to their lipophilic properties and resistance to degradation, PAHs can accumulate in organic tissue. As a consequence, alarming concentrations of these compounds have been found in many aquatic species. The European catfish (Silurus glanis) is a top food chain predator that is considered to be a reliable bio-indicator of environmental pollution. From 2009 to 2011, 54 specimens of S. glanis were captured from four different sites covering the area of the Po River basin (Northern Italy). Fish muscles were analyzed in the laboratory to determine the levels of nine PAHs, namely naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, and benz[a]pyrene (BaP), which were detected by high-performance liquid chromatography (HPLC). The total average concentration of PAHs was 26.90?±?49.50 ng g^?1 (min 0.60, max 275.75 ng g^?1). Analysis showed that 9.20 % of the fish muscles exceeded the maximum levels of 2 ng g^?1 set for BaP by European regulations (Commission Regulation (EC), 2006). Values measured for benz[a]pyrene ranged from 0.05 to 8.20 ng g^?1 (mean 1.07?±?1.58 ng g^?1). Chrysene and benz[a]anthracene, both considered potential human carcinogens (PAH2), were found at levels of 4.40 and 0.05 ng g^?1 (mean values), respectively. The highest mean concentration was recorded for anthracene (12.92 ng g^?1), which has been recently included in the list of substances of very high concern (SVHC) as reported by the European Chemicals Agency (ECHA 1–9, 2009).     

Exposure of garbage truck drivers and maintenance personnel at a waste handling centre to polycyclic aromatic hydrocarbons derived from diesel exhaust

Exposure to diesel exhaust was evaluated in summer and winter by measuring vapour and particle phase polycyclic aromatic hydrocarbons (PAHs). Fifteen PAHs were simultaneously determined from the air samples obtained from truck drivers collecting household waste and maintenance personnel at a waste handling centre. The major compounds analysed from the personal air samples of exposed workers were naphthalene, phenanthrene and fluorene. The total PAH exposure (sum of 15 PAHs) of garbage truck drivers ranged from 71 to 2,660 ng m(-3) and from 68 to 900 ng m-3 in the maintenance work. The exposure of garbage truck drivers to benzo[a]pyrene (B[a]P) ranged from the mean of 0.03 to 0.3 ng m(-3) whereas no B[a]P in control samples or in those collected from maintenance workers was detected. A statistically significant difference in diesel-derived PAH exposure between the garbage truck drivers and the control group in both seasons (in summer p = 0.0022, degrees of freedom (df) 70.5; and in winter p < 0.0001, df = 80.4) was observed. Also, a significant difference in PAH exposure between the garbage truck drivers and the maintenance workers (in summer p < 0.0001, df = 50.1; and in winter p < 0.0001, df = 44.2) was obtained.     

Non-occupational exposure to silica dust in vicinity of slate pencil industry, India

Biomonitoring of polycyclic aromatic hydrocarbons (PAHs) in the leaves of Calotropis gigantea R.Br. were performed at seven sites in the surrounding areas of a Thermal Power Plant (TPP), using the gas chromatography and mass spectrometry technique. The primary objective of the study was to monitor the degree of PAHs load in the nearby sites around TPP compared to distant sites. Total PAH (SigmaPAH) concentrations in the leaves ranged from 372.18 (at control site 7) to 4362.35 ng g(-1) d.w. (at highest polluted site 4). The concentration factors ranged from 2.65 to 11.72 for the sites located at 1 km to the point source and 1.0 to 7.08 for distant sites. The share of carcinogenic PAHs to the total PAHs differed with the site, ranging from 10.76% to 26.92%. The sites located closer to TPP have shown higher concentrations of medium and high molecular weight PAHs, which decreased gradually with the distance from the source. The total PAH burden at control site was dominated by the low and medium molecular weight PAHs compounds viz., naphthalene, acenaphthylene, acenaphthene, phenanthrene, fluoranthene, pyrene, chrysene, coronene., whilst at other sites medium and high PAHs viz., fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (e) pyrene and coronene showed the highest values. These results support the biomonitoring ability of Calotropis gigantea R.Br. leaves to monitor PAHs contamination.     

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.     

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。     

Ultrasound-assisted ionic liquid-based microextraction combined with least squares support vector machines regression for the simultaneous determination of aluminum,gallium, and indium in water and coal samples

A new simple and rapid ultrasound-assisted ionic liquid-based microextraction method was applied to preconcentrate aluminum(III), gallium(III), and indium(III) ions from water samples as a prior step to their simultaneous spectrophotometric determination using least squares support vector machines regression. In the novel procedure, 1-hexyl-3-methylimidazolium hexafluorophosphate [C₆MIM][PF₆] was dispersed into the aqueous sample solution as fine droplets by ultrasonication, and the analytes were extracted into the ionic liquid phase after complexation with 1,2,5,8-tetrahydroxy anthraquinone (quinalizarine). After centrifuging, the fine droplets of extractant phase were settled to the bottom of the conical-bottom glass centrifuge tube. The detection limits for Al(III), Ga(III), and In(III) were 1.70, 2.02, and 2.06 ng mL⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of ten replicates, was below 3.2% for all elements. The method was successfully applied for the determination of Al(III), Ga(III), and In(III) in real samples.     

Study of the voltammetric behaviour of the ethalfluralin and methalpropalin and its determination in environmental matrices at hanging mercury drop electrode

An electroanalytical method has been developed for the determination of the herbicides ethalfluralin[N-ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-4-(trifluoromethyl) bezenamine] and methalpropalin [N-(2-methyl-2-propenyl)-2, 6-dinitro-N-propyl-4 (trifluoromethyl) benzenamine] by differential pulse adsorptive stripping voltammetry (DP-AdSV) on a hanging mercury drop electrode (HMDE) with universal buffer as supporting electrolyte. The optimum adsorption conditions were found to be pH 6.0, an accumulation potential of -0.6 V (HMDE vs SCE), an accumulation time of 80 s. and scan rate 45 mVs(-1). Calibration curve is linear in the range 1.30 x 10(-9) to 1.32 x 10(-5) M of ethalfluralin and 1.13 x 10(-5) to 2.0 x 10(-8) M of methalpropalin with detection limits of 1.08 x 10(-9) and 1.87 x 10(-8) M, respectively. The relative SD and correlation coefficients were found to be 1.24%, 0.998 and 1.34%, 0.995, respectively for ten replicates. The method is applied to the determination of the ethalfluralin and methalpropalin in formulations and environmental matrices.     

线性扫描溶出伏安法同时测定水样中铅镉铜锌

通过多壁碳纳米管-Nafion复合膜修饰电极,建立水样中痕量铅、镉、铜、锌同时测定的线性扫描溶出伏安分析法,优化支持电解质及pH值、修饰剂用量、富集电位及时间等测定条件。实验结果表明,在pH 4.0的NaAc-HAc缓冲液中,-1.20V富集5min后,在电位-1.04V、-0.72V、-0.45V及-0.16V附近分别产生锌、镉、铅、铜的灵敏溶出峰,测定各元素的线性关系良好,相对标准偏差均小于5.4%。该法已成功应用于实际水样中痕量铅、镉、铜、锌的同时测定,加标回收率在93.3%~106.7%之间,结果满意。     

化学发光法测定环境水体中的亚硝酸盐氮

利用鲁米诺-铁氰化钾-尿酸化学发光体系,在酸性介质中,NO-2将亚铁氰化钾氧化为铁氰化钾,建立了一种间接测定痕量亚硝酸盐的新方法。     

A simple method for simultaneous determination of some organic liquids in in-process materials and effluents produced in the manufacture of amoxicillin and ampicillin

A simple GC method for simultaneous determination of pivaloylchloride, methylacetoacetate, ethylacetoacetate and 2-ethylhexanoic acid in the presence of each other has been developed using glass column packed with 1% Silicone OV-17 on Gaschrom Q 100-120 mesh with temperature programming. Various performance parameters including precision, linearity and limit of detection have been evaluated. The method was found to be suitable for the analysis of these chemicals in in-process materials and effluents associated with the manufacture of amoxicillin and ampicillin. The run time was less than 15 min. The method has been successfully applied to determine the level of these hazardous organic liquids in real time samples.