Optimization of a solid-phase extraction method using centrifugation for the determination of 16 polycyclic aromatic hydrocarbons in water

A fast and reliable method for the determination of polycyclic aromatic hydrocarbons (PAHs) in water samples by solid-phase extraction (SPE) using centrifugation has been developed and optimized. A silica-based C18 cartridge was used; parameters affecting the extraction procedure such as type and volume of the elution solvent, breakthrough volume of the percolated water sample, drying of the sorbent, and evaporation of the elute have been studied. The innovation of this work was the examination of the use of a centrifugation technique in both the drying and elution steps. When combined with centrifugation, the volume of the elution solvent was reduced to 1 mL and the time for sorbent drying decreased also to 10 min under vacuum. Under optimal conditions, recoveries for the 16 U.S. EPA PAHs were between 70 and 85% and the relative standard deviation varied between 1 and 14%. Surrogate standard recoveries were similarly between 61 and 94% with a relative standard deviation between 2 and 15%. The simplicity of the described method, use of less of organic solvent, short procedure time, and good recoveries demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.     

Accelerated solvent extraction and gas chromatography/mass spectrometry for determination of polycyclic aromatic hydrocarbons in smoked food samples.

Accelerated solvent extraction (ASE) is a new sample extraction method offering a number of advantages such as low pe -extraction cost, reduced solvent and time consumption, and simplified extraction protocols. In this study, the ASE method was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from biological samples. For recovery studies, fish tissues and ground pork were used as sample matrices. Sample aliquots fortified with 16 PAHs were extracted by ASE, and the extracts were treated with sulfuric acid and Florisil, followed by gas chromatography-mass spectrometry analysis. The PAH recoveries by the ASE method were found to be comparable with or better than those by Soxhlet extraction. The extraction and quantitation method was then applied to the determination of PAHs in several smoked meat samples obtained from a local market. Up to 12 PAHs were found to be present at concentrations ranging from 3 to 52 ng/g wet sample.     

安徽省典型城市周边土壤-蔬菜中PAHs的污染特征

研究了安徽省合肥、芜湖和亳州市周边蔬菜地土壤和蔬菜中PAHs的含量及其污染特征。结果表明：安徽省典型蔬菜地土壤中15种PAHs（除萘外）的残留总量在58.2～437.8μg·kg-1之间,三环和四环PAHs占PAHs残留总量的70%以上。胡萝卜、菠菜和茄子体内15种PAHs的含量在23.4～209.1μg·kg-1之间,均值为120.7μg·kg-1,三环和四环PAHs占蔬菜中PAHs富集总量的92.8%～94.4%。不同蔬菜体内8种可疑性致癌PAHs的含量在11.5～17.4μg·kg-1之间,分别占蔬菜中PAHs残留总量的9.80%～13.8%,其中BaP含量在1.69～2.03μg·kg-1之间,低于国家对食品中污染物（BaP）的限量标准（5μg·kg-1）。不同类型PAHs在蔬菜体内的富集系数在0.10～9.20之间,极差达10倍以上,低分子量PAHs在蔬菜体内的富集系数要大于高分子量PAHs。不同PAHs在蔬菜体内的富集系数表现为胡萝卜〉菠菜〉茄子,其中芴在蔬菜体内的富集系数最高。     

影响土壤中PAHs降解的环境因素及促进降解的措施

土壤中的多环芳烃(PAHs)类有机污染物的生物有效性低,不易降解。本文综述了影响污染土壤中多环芳烃降解的环境因素和促进降解措施的研究进展。影响土壤中多环芳烃降解的因素,包括水分、养分、土壤物理条件等;促进土壤中多环芳烃降解的措施有:向污染土壤添加有机溶剂、利用冯顿反应、添加堆肥和有机物料等。从目前研究来看,应当通过促进多环芳烃从土壤上解吸和培育具有较高多环芳烃降解能力的微生物来促进多环芳烃污染土壤的修复。     

Extractability and Subsequent Biodegradation of PAHs from Contaminated Soil

The biodegradation of polyaromatic hydrocarbons (PAHs) has been well documented; however, the biodegradation of PAHs in contaminated soil has proved to be problematic. Sorption of PAHs to soil over time can significantly decrease their availability for extraction much less than for biodegradation. In this study the ability of various organic solvents to extract PAHs from coal tar-contaminated soil obtained from former manufactured gas plant (MGP) sites was investigated. Solvents investigated included acetone/hexane, dichloromethane, ethanol, methanol, toluene, and water. The extraction of MGP soils with solvents was investigated using soxhlet extraction, multiple soxhlet extractions, sonication, and brief agitation at ambient temperature with a range of solvent concentrations. Of particular interest was the documentation of the recalcitrance of PAHs in weathered MGP soils to extraction and to bioremediation, as well as to demonstrate the ease with which PAHs extracted from these soils can be biodegraded. The efficiency of extraction of PAHs from MGP soils was found to be more dependent upon the choice of solvent. The environmentally-benign solvent ethanol, was shown to be equal to if not better than acetone/hexane (the EPA recommended solvent) for the extraction of PAHs from MGP soils, brief contact/agitation times (minutes) using small quantities of ethanol (2 volumes or less) can achieve nearly quantitative extraction of PAHs from MGP soils. Moreover aqueous slurries of an MGP soils experienced less than 10% biodegradation of PAHs in 14 days while in the same period about 95% biodegradation was acieved using PAHs extracted from this soil by ethanol and subsequently added to aqueous bacterial suspensions.     

生物质炭中多环芳烃的潜在环境风险研究进展

作为土壤改良剂和环境污染修复材料,生物质炭在近年来得以广泛应用。生物质炭制备过程中会产生一定量的多环芳烃(PAHs),对其潜在环境负面效应和风险尚缺乏应有的认识。本文总结了生物质炭中PAHs的形成机理、影响因素(包括原材料、裂解温度、裂解升温速率和保留时间等)、总量和生物有效含量及其分析方法,旨在为生物质炭在环境中的安全应用提供理论依据和技术参考。     

Procedure to measure the level of polycyclic aromatic hydrocarbons in wood ashes used as fertilizer in agroforestry soils and their transfer from ashes to water

Before wood ash can be safely used as a fertilizer in soils, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to optimize and characterize extraction methods to isolate and quantitatively measure polycyclic aromatic hydrocarbons (PAHs) concentrations in wood ash that can be used as amendment of soils. It will be then possible to examine the effects of wood ash application on PAHs concentrations in the washing waters with the aim of evaluating their distribution by storage in the different compartments and what influences their stability and persistence. Simple, rapid and inexpensive methods have been set up for the determination of seven polycyclic aromatic hydrocarbons (PAHs) in wood ashes and ash aqueous extracts without interferences from other chemical contaminants using organic solvent extraction and/or SPE techniques and analyzed by an optimized RP-HPLC-FLD method. The feasibility of extraction for the determination of PAHs in wood ashes has been evaluated because PAHs are strongly sorbed to such a matrix, which explains why the PAHs content in ash was seldom studied. The method resulted to be of recoveries ranging from 81 to 97% for the different PAHs, with repeatabilities (RSDs%) better than 6%. Detection levels were from 0.2 to 2.2 microg/kg, while quantification limits were from 0.7 to 5.6 microg/kg, low enough to evaluate the presence of PAHs in wood ashes.     

土壤多环芳烃生物可给性测定的体外胃肠模拟法研究进展

经口摄入是土壤多环芳烃(PAHs)人体暴露的重要途径, 有效评估土中PAHs的生物可给性是全面评估土壤PAHs人体健康风险的重要组成部分。然而, 测定土壤PAHs生物可给性的体外胃肠模拟方法众多, 至今国内外尚缺乏统一标准。由于不同体外模拟方法测定的结果差异较大, 制约了土壤PAHs人体健康风险评估的发展。基于此, 本文综述了PAHs生物可给性测定所用的多种体外胃肠模拟方法及进展, 并针对PAHs生物可给性测定方法存在的问题, 建议未来构建土壤PAHs生物可给性测定标准方法的相关研究应从生理条件、吸附材料的选择、体内模型的验证这三方面综合考虑。综合以上，本文有望对我国污染场地土壤标准体系构建和完善、前瞻性科学管理提供科学依据。     

Comparison of strategies for extraction of high molecular weight polycyclic aromatic hydrocarbons from drinking waters

Simple, rapid, and inexpensive methods have been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in drinking waters without interferences from other chemical contaminants by use of two different extraction techniques and analysis by an optimized reverse-phase (RP) high-performance liquid chromatography followed by fluorescence detection (HPLC-FLD) method. The feasibility of SPE (solid-phase extraction) and SPME (solid-phase microextraction) for the determination of PAH in drinking water samples has been evaluated. Several parameters have been studied and optimized for both extraction procedures. The relationship between the nature of the fibers and the quantity of extracted compounds and the effects of organic solvent, salt addition, sampling temperature, and sampling time was studied for SPME. Acetonitrile percentage added to the sample, sample storage conditions (temperature and time), and type of organic elution solvent and elution volume were evaluated for SPE. The results show that both extraction procedures can be used to determine PAHs in drinking waters, but SPE gives better performance (recovery, precision, and quantification limits) for the determination of PAHs in drinking water at the levels established by the legislation.     

Modeling Surfactant LAS Influenced PAHs Migration in Soil Column

The objective of the present work was to study the transport of Polycyclic Aromatic Hydrocarbons (PAHs) in artificially contaminated and oil field soil columns while Linear Alkylbenzene Sulfonate (LAS) was used as leaching solvent. Through soil column leaching experiments, the through curves (BTCs) of the tracer (Br^?) and PAHs were obtained. The batch equilibrium experiments were conducted. The partition coefficients, and the retardation factor (R) were calculated. Nonlinear least-squares optimization approach was used to fit BTCs of Br^? and PAHs. The symmetrical BTC for Br^? was fitted using equilibrium convention-dispersion equation (CDE) model, and the physical and hydrodynamic parameter, i.e. the dispersion coefficient (D) was calculated. Based on these, the equilibrium and non-equilibrium CDE models were applied to fit the asymmetrical and tailing BTCs of PAHs. Results showed that two-site CDE model is better in fitting the observed data. The concentration distributions of PAHs with leaching time at different depth in the soil column were also estimated using two-site CDE model.     

Estimation of PAH bioavailability to Lepidium sativum using sequential supercritical fluid extraction – a case study with industrial contaminated soils

For the determination of PAH availability to plants a plant accumulation test with Lepidium and sequential supercritical fluid extraction (SSFE) with carbon dioxide as extraction solvent was used, during which the extraction conditions were changed from mild to harsh in order to represent a broad range of potential pollutant-soil interactions. Both approaches were applied in laboratory experiments on industrial contaminated soils which, in addition, were also freshly spiked with PAHs in order to increase the bioavailability. Only Naphthalene, Phenanthrene and, in some cases, Pyrene accumulated from the industrial contaminated soils. Accumulation experiments with spiked industrial soils showed that other PAHs, for example Anthracene, Fluorene and even high weight PAHs like Benzo(a)pyrene, also could be taken up by plants. SSFE extraction data were compared to accumulated amounts of PAHs in the plants. Strong correlations were found for Phenanthrene between plant accumulation and extractability under very mild extraction conditions. For Naphthalene, accumulation did not correlate with its extractability in the industrial soils. The possibility exists that bioavailability in soil was eclipsed by an accumulation in the gas phase due to the high volatility of Naphthalene. Supercritical fluid extraction appears to be a promising tool to estimate Phenanthrene availability to plants, but further studies for the evaluation of other PAHs are recommended. This could be helpful for the determination of the feasibility of phytoremediation applications on industrially contaminated soils.     

土壤中多环芳烃不同前处理分析方法的比较

针对国内缺乏土壤中多环芳烃（PAHs）检测的国家标准方法的现状,以提取效率和回收率作为不同溶剂、不同提取方式前处理优劣的表征,研究了目前国内较常用的3种提取技术（索氏提取、超声波提取、水平振荡提取）和2种不同的提取剂（二氯甲烷、二氯甲烷／丙酮=5：1）对提取效率和回收率的影响。结果表明,以二氯甲烷作为提取溶剂,水平恒温振荡提取4h,可以有效地提取土壤中的15种多环芳烃类污染物。此技术提取时间短,节省提取溶剂且提取效率较高,方法回收率在73．3％－117．5％范围内。     

Spectroscopic determination of poly-aromatic compounds in petroleum contaminated soils

The determination of poly-aromatic hydrocarbons (PAHs) in the soil is of interest because of their carcinogenic and mutagenic activity in biological systems. The present study deals with the rapid application of infrared, fluorescence, synchronous luminescence spectrometries and gas chromatography to detect organic pollutants and their quantity in the soil. Sohxlet extraction followed by column separation was used to isolate organic pollutants. Although several solvent mixtures were used as eluents for the column, the solvent mixture, hexane:dichloromethane (50:50) efficiently extracts the aromatic compounds. Total petroleum hydrocarbons (TPH) measured by IR were found at high concentrations (30810.0 ppm) in the contaminated soil compared with the reference soil (30.0 ppm). Furthermore, the fluorescence results reveal that almost one-fourth of the 30810.0 ppm are aromatic hydrocarbons. In addition, the presence of PAHs such as naphthalene, acenaphthene, fluorene, fluoranthene, phenanthrene, pyrene, benzo(a)pyrene, chrysene, and dibenzo(a,h)anthracene in the polluted soil was determined by using synchronous study.     

PAH release from tar-oil contaminated soil material in response to forced environmental gradients: implications for contaminant transport

Laboratory test systems are frequently used to assess the release of pollutants from contaminated sites. To infer behaviour in the field, all factors that control the release of such pollutants should be considered in the experiment. We carried out column experiments with varying boundary conditions under saturated flow to identify the processes governing the release and to evaluate the effect of environmental conditions on several polycyclic aromatic hydrocarbons (PAHs). We compared the results with groundwater concentrations monitored in the field. The contaminated soil material originated from a former tar‐processing site. The effluent was analysed in response to forced variations in flow velocity, residence time, ionic strength and temperature. Interruptions to the flow had no effect on concentrations, which were close to those predicted by Raoult’s law. We conclude that release of PAHs is controlled by equilibrium dissolution according to Raoult’s law at moderate ionic strength. Diminishing the ionic strength by a pulse of pure water, however, results in a marked increase in the concentrations of exported PAHs. We attribute this to PAHs being bound to mobile particles. The effect was larger in the column percolated with fast flow, suggesting that the release of carriers is controlled by shear stress. An increase of temperature by 10 K resulted in marked increases in concentrations of the PAHs in the outflow between 6 and 160%. Concentrations in the groundwater correlate well with those in the outflow from the columns with similar ionic strength and temperature. We were able to identify the processes governing the release of PAHs under various conditions and to explain the concentrations observed in the field. The study illustrates that column outflow experiments, which support decisions in risk assessment, must be designed appropriately.     

SFE-plus-C(18) lipid cleanup and selective extraction method for GC/MS quantitation of polycyclic aromatic hydrocarbons in smoked meat

In biological matrixes lipid material often poses an interference problem for determinations of nonpolar compounds, e.g., polycyclic aromatic hydrocarbons (PAHs). A newly developed supercritical fluid extraction plus adsorbent method, "SFE-plus-C(18)", offers selective extraction of PAHs in lipid-rich biological matrixes without the need for supplementary cleanup. This method eliminates the use of large volumes of toxic solvent and lengthy lipid removal procedures. This study reports the first application of the SFE-plus-C(18) method to the analysis of a genuine food product, i.e., smoked meat (beef). The procedure employs the addition of C(18) adsorbent beads to the initial sample slurry of pureed smoked meat prior to supercritical CO(2) extraction and GC/MS quantitation. During SF extraction, indigenous lipids are preferentially retained on the beads, and PAHs are selectively extracted with supercritical CO(2). In a comparison of determinations of PAHs by SFE-plus-C(18) vs the conventional SFE method, only 11-17% of the indigenous lipids observed by the conventional SFE method were co-extracted using the SFE-plus-C(18) method. The PAHs in smoked meat could thus be determined efficiently in the presence of a reduced background of co-extracted lipids. Out of 10 targeted PAHs, seven were detected with a range of 10.0-26.0 ng/g in the smoked meat sample. The other three PAHs were not present above the detection limit of the instrument (2.5-4.1 pg). The recoveries of PAHs obtained using the conventional SFE method were 63-94% lower than those achieved by SFE-plus-C(18).     

土壤样品中多环芳烃分析方法研究进展

概述了国内外土壤样品中多环芳烃(PAHs)测定方法的研究状况,其中提取方法包括加速溶剂萃取方法、固相微萃取方法、超临界流体萃取方法、亚临界水萃取方法和流化床提取方法等,测定方法有HPLC法、GC法和免疫分析法等。重点介绍了PAHs的提取过程,同时总结了各种方法的优缺点。     

Seasonal variations of concentrations, profiles and possible sources of polycyclic aromatic hydrocarbons in sediments from Taihu Lake, China

Purpose

Obtaining a better understanding of the concentrations and origins of polycyclic aromatic hydrocarbons (PAHs) in the sediments Taihu Lake, China, is of paramount importance for the environmental protection and remediation of this lake. To investigate temporal and spatial variations in PAH concentrations, composition and possible source categories, 29 sediment samples were collected from Taihu Lake during both the flooding and dry seasons of the lake.

Materials and methods

Fifteen US Environmental Protection Agency priority PAHs were detected in 58 surface sediments (29 for each season) by gas chromatograph/mass selective detection, following extraction by accelerated solvent extraction.

Results and discussion

The concentrations of the total and individual PAHs in the flooding season were higher than those in the dry season, suggesting that high levels of fishing activity may be an important contributor to PAH pollution in the flooding season. The fractions of high molecular weight PAHs in the flooding season ranged from 63?% to 71?% and were higher than those in the dry season (which ranged from 52?% to 65?%). These results indicate that vehicle exhaust may be a more important pollutant source in the flooding season than in the dry season. Diagnostic ratios, principal component analysis and hierarchical cluster analysis were used to study possible source categories in the different seasons. Consistent results were obtained for all techniques. Seasonal and spatial variations were also investigated by the coefficient of divergence method. The results of previous studies support the conclusion of source identification.

Conclusions

Vehicle emissions were the dominant contributor to PAHs in the flooding season, while PAHs in the dry season sediments may have come from multiple sources. The findings of this study may provide a theoretical basis for seasonal PAH control strategies for Taihu Lake.     

Partial Least Square Regression Method for the Detection of Polycyclic Aromatic Hydrocarbons in the Soil Environment Using Laser-Induced Fluorescence Spectroscopy

Polycyclic aromatic hydrocarbons (PAHs) are currently of great concern due to their potential carcinogenicity. The standard methods of identification and quantification of PAHs are costly and time–consuming. Laser–induced fluorescence (LIF) spectroscopy can overcome these limitations and make it possible to simultaneously identify and quantify several PAHs without the aid of chemical pre-processing steps. LIF system and multivariate chemometric analysis, especially the partial least square (PLS) regression method, have been employed to investigate the potential correlations between LIF data and soil properties, especially their physical composition and moisture content, and confirm the capability for the detection of PAHs in soils, using the soil samples artificially comprised of sand and silt/clay. Phenanthrene and pyrene were selected as representative PAHs. The diffuse reflectance has also been recorded to investigate the capability to normalize the LIF data. Data analysis, through a multivariate chemometric analysis, showed significant statistical correlations between the LIF intensity and the PAH concentrations in soil samples. The LIF intensity has been shown to depend on the sample properties, with the diffuse reflectance at 532 nm also depending on these factors. It has been demonstrated that the errors induced by the physical composition could be reduced by dividing the LIF intensity by the diffuse reflectance at 532 nm. The LIF concentration data were compared with those measured by high performance liquid chromatography (HPLC), with values of correlation coefficient (R) of 0.96 and 0.90 for phenanthrene and pyrene, respectively. The results obtained through a data analysis algorithm, based on the linear mixture model and the normalization by diffuse reflectance, demonstrated that the PAHs in artificial soil samples could be discriminated and quantified by LIF spectroscopy.     

Rapid magnetic solid-phase extraction based on magnetic multiwalled carbon nanotubes for the determination of polycyclic aromatic hydrocarbons in edible oils

In this study, magnetic multiwalled carbon nanotubes were fabricated by a simple method and applied to magnetic solid-phase extraction (MSPE) of eight heavy molecular weight polycyclic aromatic hydrocarbons (PAHs) including chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene from edible oil samples. Several parameters affecting the extraction efficiency were investigated, including the type and volume of desorption solvent, extraction and desorption time, washing solution and the amount of sorbent. Under the optimized conditions, a simple and effective method for the determination of PAHs in edible oils was developed by coupling with gas chromatography-mass spectrometry (GC-MS). The whole pretreatment process was rapid, and it can be accomplished within 10 min. The limits of quantitation for the target PAHs were found to be 0.34-2.9 ng/g. The recoveries in oil sample were in the range 87.8-122.3% with the RSDs less than 6.8% (intraday) and 9.6% (interday). This method was successfully applied to the analysis of PAHs in seven kinds of edible oils from local markets.     

Quantitative determination of PAHs in biochar: a prerequisite to ensure its quality and safe application

Biochar is increasingly promoted as a beneficial soil conditioner. However, it may contain residues of polycyclic aromatic hydrocarbons (PAHs) as a result of its production by pyrolysis. To date, analytical methods to analyze PAHs in biochar quantitatively are hardly available. This study presents an optimized and validated procedure to quantify the 16 U.S. EPA PAHs in biochar. PAHs were best extracted with Soxhlet for 36 h using 100% toluene. Average absolute recoveries of isotope labeled internal standards used for each analyte from three different biochars ranged from 42% to 72%, and relative recoveries were between 71% and 105%. The limits of detection were biochar-dependent, but on average a factor of >50 lower than quantified PAH concentrations (9-355 mg kg(dry weight)(-1)). The established method prepares the ground for a harmonized protocol for PAH analysis of biochars, a necessity for biochar quality control, registration, and legislation.