Analytical methods for the determination of emerging organic contaminants in the atmosphere

Concerns over the occurrence and transport of emerging organic contaminants (EOCs) from local sources to remote regions have resulted in wide developments in sampling strategy and analytical methodology for the determination of trace concentrations of EOCs in the atmosphere. This article discusses developments in the determination of EOCs in ambient air which includes polyfluorinated alkyl substances (PFASs), brominated-flame retardants (BFRs), synthesis musk fragrances, and alkylphenols (APs). References were mainly summarized from the past 5 years (2002 up to present) on new developments of sampling methods, extraction, separation/fractionation and/or applications of new technologies for sampling and determination.     

Determination of currently used pesticides in biota

Although pesticides enable control of the quantity and quality of farm products and food, and help to limit diseases in humans transmitted by insects and rodents, they are regarded as among the most dangerous environmental contaminants because of their tendency to bioaccumulate, and their mobility and long-term effects on living organisms. In the past decade, more analytical methods for accurate identification and quantitative determination of traces of pesticides in biota have been developed to improve our understanding of their risk to ecosystems and humans. Because sample preparation is often the rate-determining step in analysis of pesticides in biological samples, this review first discusses extraction and clean-up procedures, after a brief introduction to the classes, and the methods used in the analysis of pesticides in biota. The analytical methods, especially chromatographic techniques and immunoassay-based methods, are reviewed in detail, and their corresponding advantages, limitations, applications, and prospects are also discussed. This review mainly covers reports published since 2008 on methods for analysis of currently used pesticides in biota.     

A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m³ h^–1) (urban site) or a low-volume pump (2.3 m³ h^–1) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m^–3 of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19–5130 ng m^–3) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.     

Isotachophoretic determination of amines from workroom air

Eight different isotachophoretic systems for the analysis of 27 aliphatic amines are described. Complete methods including sampling and analysis procedures for the determination of eight amines in workroom air are also given. Different systems for the generation of gaseous amine standards in air are discussed, as well as sampling with washing bottles, adsorption tubes and liquid dosimeters. The methods were used in industrial environments. The isotachophoretic method is compared with gas and high-performance liquid chromatography.     

Sorbent-based sampling methods for volatile and semi-volatile organic compounds in air. Part 2. Sorbent selection and other aspects of optimizing air monitoring methods

Sorbent tubes/traps are widely used in combination with gas chromatographic (GC) analytical methods to monitor the vapour-phase fraction of organic compounds in air. Applications range from atmospheric research and ambient air monitoring (indoor and outdoor) to occupational hygiene (personal exposure assessment) and measuring chemical emission levels. Part 1 of this paper reviewed the main sorbent-based air sampling strategies including active (pumped) tube monitoring, diffusive (passive) sampling onto sorbent tubes/cartridges plus sorbent trapping/focusing of whole air samples that are either collected in containers (such as canisters or bags) or monitored online. Options for subsequent extraction and transfer to GC(MS) analysis were also summarised and the trend to thermal desorption (TD)-based methods and away from solvent extraction was explained. As a result of this trend, demand for TD-compatible sorbents (alternatives to traditional charcoal) is growing. Part 2 of this paper therefore continues with a summary of TD-compatible sorbents, their respective advantages and limitations and considerations for sorbent selection. Other analytical considerations for optimizing sorbent-based air monitoring methods are also discussed together with recent technical developments and sampling accessories which have extended the application range of sorbent trapping technology generally.     

Determination of volatile organic compounds in ambient air. Comparison of methods

Two analytical methods for the determination of benzene vapour in ambient air are compared in this paper. The methods differ from each other in the sampling technique, type of sorbent, method of extraction and method of detection. The investigation of the methods using various techniques for sample analysing showed a significant influence of the way in which the analysis is carried out, on the final result of the analysis. Calculation of the standard deviations, relative standard deviations and confidence intervals allowed for assessment of the precision and repeatability of the methods. Of the two examined methods, that using an automated system of contaminant sampling and thermodesorption was more precise. This method has been applied to measurements of concentrations of benzene, toluene and xylenes in ambient air.     

Long-term sampling: Suitable monitoring strategy for determination of semi-volatile PAHs at outdoor and indoor sites

Summary A new, molecular diffusion-based, sampling device (Analyst 2) has been used for the determination of semi-volatile PAHs in air. It has been developed from a previous model (Analyst), which is suitable for volatile hydrocarbons. The new model is capable of collecting enough gaseous PAHs for GC-MS analysis of enriched samples after 2 months exposure to both urban and suburban air. The adsorbent material adopted for enriching PAHs from air (Carbopack C) gives good recoveries of analytes from naphthalene to chrysene when a single solvent extraction is run at ambient temperature. The results of an experiment for assessing the internal consistency of this device are presented here. Data collected indicate that the “uptake rate” is constant for a 6-month sampling period. Results are also presented and discussed for indoor and outdoor determination of volatile PAHs, collected at both urban and suburban sites over a 12-month period in 2-monthly steps.     

Novel Sampling for the Determination of Naphthalene in Air by Gas Chromatography–Mass Spectrometry

Here are reported two new sampling method approaches for the determination of naphthalene in ambient air for concentrations from 0.25 to 18.7?µg/L. The first method used for gas phase naphthalene analysis produced an average recovery of 88.8% and the second method using headspace sampling produced an average recovery of 93.8%. The second method showed better recovery than the former, so it was used for subsequent comparative gas-phase determination of naphthalene. The second method was validated at various naphthalene concentrations and humidity using a naphthalene gas generator to produce various naphthalene standards and a naphthalene-monitoring instrument. The naphthalene concentrations generated using the gas generator and determined second sampling method with gas chromatography–mass spectrometry (GC–MS) were compared to the sensor measurements and were in good agreement. In summary, the sampling methods presented provided reliable gas-phase naphthalene determination when coupled with GC–MS.     

Flow-Injection Methods in Water Analysis—Recent Developments

Widespread demand for the analysis and control of water quality and supply for human activity and ecosystem sustainability has necessitated the continuous improvement of water analysis methods in terms of their reliability, efficiency, and costs. To satisfy these requirements, flow-injection analysis using different detection methods has successfully been developed in recent decades. This review, based on about 100 original research papers, presents the achievements in this field over the past ten years. Various methodologies for establishing flow-injection measurements are reviewed, together with microfluidics and portable systems. The developed applications mostly concern not only the determination of inorganic analytes but also the speciation analysis of different elements, and the determination of several total indices of water quality. Examples of the determination of organic residues (e.g., pesticides, phenolic compounds, and surfactants) in natural surface waters, seawater, groundwater, and drinking water have also been identified. Usually, changes in the format of manual procedures for flow-injection determination results in the improvement of various operational parameters, such as the limits of detection, the sampling rate, or selectivity in different matrices.     

GC-MS法测定大气样品的前处理研究--碳化纤维树脂捕集大气中痕量多环芳烃

研究了碳化纤维树脂吸附载体采集大气中多环芳烃(PAHs)的性能、样品前处理条件和毛细管气相色谱－质谱联用仪检测PAHs的,地具有代表性的多个采样点进行了实地采样、分析,证明碳化纤维树脂吸附载体是一种性能独特的固相吸附剂,建立的样品前处理方法可行,分析数据可靠,可用于大气中PAHs的检测。     

Passive sampling and/or extraction techniques in environmental analysis: a review

The current state-of-the-art of passive sampling and/or extraction methods for long-term monitoring of pollutants in different environmental compartments is discussed in this review. Passive dosimeters that have been successfully used to monitor organic and inorganic contaminants in air, water, sediments, and soil are presented. The application of new approaches to the determination of pollutants at the sampling stage is discussed. The main milestones in the development of passive techniques for sampling and/or extraction of analytes, and in biomonitors used in environmental analysis, are summarized in this review. Passive samplers and biomonitors are compared.     

Some Aspects of Analysis of Single Fibers in Environmental and Biological Samples

Abstract

Nuclepore filters were used for sampling and evaluation of fibrous particles in ambient air, in liquids and in biological materials. The fiber counting and fiber size measurements were done by means of SEM-methods. The number of fibers and the distributions of fiber lengths and diameters were plotted. The specific identifications of asbestos, glass and other mineral fibrous particles were made by electron microprobe analysis. Certain elements proved to be approximative identification factors for different fibrous minerals in ambient air, in liquids, on material surfaces, or in biological materials.

For ambient air, asbestos, glass, and many other inorganic fibrous particles were found in the urban atmosphere as well as in the atmosphere of remote regions. Fibrous gypsum, fibrous ammonium sulfates, fibrous silicates, fibrous mica, and quartz were identified among these particles. Even in remote ambient air, relatively high concentrations of inorganic fibrous particles could be measured.     

Improved accuracy in the determination of polycyclic aromatic hydrocarbons in air using 24 h sampling on a mixed bed followed by thermal desorption capillary gas chromatography-mass spectrometry

A new sampling method for the determination of polycyclic aromatic hydrocarbons (PAHs) in ambient air is described. The method is based on active sampling on sorption tubes consisting of polydimethylsiloxane (PDMS) foam, PDMS particles and a TENAX TA bed. After sampling, the solutes are quantitatively recovered by thermal desorption and analysed by capillary GC-MS. The new sampling method has been compared to the classical method using high-volume sampling on a glass fiber filter followed by polyurethane foam for 24h sampling of ambient air. Volumes enriched were 144 l on the mixed bed and 1296 m3 with the classical method. The concentrations measured using the new method were significantly higher that the values obtained using the classical method, i.e. a factor 1.2-3 for the high molecular weight PAHs and up to 35 times for naphthalene and 23 times for acenaphthene. The total toxicity equivalence value (TEQ) for PAHs was ca. two times higher compared to the conventional method, illustrating that the concentrations of PAHs in ambient air have been underestimated until now. Some figures of merit (mean value for 17 PAHs) of the method are repeatability 7.4%, detection limit 13 pg/m3, accuracy 105.6% and linearity 0.996. The method also opens interesting perspectives for the determination of other semi-volatile persistent organic pollutants (POPs) in air as illustrated with the analysis of polychlorinated biphenyls (PCBs) at a workplace during removal of transformer oil.     

甲醛监测方法及仪器

介绍了甲醛检测方法的新进展和常用的仪器,指出发展灵敏度高、选择性好、能够实现现场分析或长期稳定地实时在线监测的新方法和新仪器仍然是空气中甲醛监测研究的一个重要方向。     

实时直接分析质谱在农药检测中的应用

实时直接分析(Direct analysis in real time,DART)作为一种原位电离技术发展迅猛,其与质谱联用已成为热门的分析技术并广泛应用于法庭科学领域,如食品安全、爆炸物检测、毒物毒品分析和药物分析等方面。目前农药的常规检测方法已非常成熟,但引入原位电离-质谱联用技术可以拓宽检测范围,缩短检测时限。该文从实时直接分析质谱(DART-MS)技术的工作原理、检测条件优化及其在农药检测方面的应用进行综述,并对DART-MS的应用前景进行了展望。     

Experimental choices for the determination of carbonyl compounds in air

The analysis of carbonyls in ambient air has received a great deal of scientific attention with the advancement of analytical techniques and increased demand for the build-up of its data base. In this review article, we have attempted to provide some insight into the relative performance of different instrumental approaches available for the analysis of ambient carbonyls with a major emphasis on high performance liquid chromatographic and gas chromatographic methods. Reported in several international standard procedures, derivatization of carbonyls with 2,4-dinitrophenylhydrazine (2,4-DNPH) with either an impinger or cartridges is the most commonly used method of HPLC detection. In this respect, a number of alternative hydrazine reagents have also been discussed for use with HPLC. In contrast, GC methods based on the combined application of adsorptive enrichment on solid sorbents and thermal desorption are examined with regard to their suitability for carbonyl analysis in air. Particular emphasis has been directed towards the advantages and drawbacks of these different instrumental techniques for ambient carbonyls. Based on this comparative approach, we discuss the suitability for each method for carbonyl analysis.     

Determination of complex mixtures of volatile organic compounds in ambient air: an overview

This article reviews developments in the sampling and analysis of volatile organic compounds (VOCs) in ambient air since the 1970s, particularly in the field of environmental monitoring. Global monitoring of biogenic and anthropogenic VOC emissions is briefly described. Approaches used for environmental monitoring of VOCs and industrial hygiene VOC exposure assessments are compared. The historical development of the sampling and analytical methods used is discussed, and the relative advantages and disadvantages of sorbent and canister methods are identified. Overall, there is considerable variability in the reliability of VOC estimates and inventories. In general, canister methods provide superior precision and accuracy and are particulary useful for the analysis of complex mixtures of VOCs. Details of canister methods are reviewed in a companion paper. C. C. Austin is an Invited Scientist of the National Research Council of Canada.     

Assessing the transfer of pesticides to the atmosphere during and after application. Development of a multiresidue method using adsorption on Tenax and thermal desorption-GC/MS

An air sampling and analytical method based on adsorption on porous polymer (Tenax TA) followed by automatic thermal desorption (ATD) and GC/MS analysis was developed for ten pesticides commonly used on major crops in Britanny and some of their metabolites in air (from spray drift and volatilisation transfer processes): alachlor, atrazine (and two major degradation products: deethylatrazine and deisopropylatrazine), carbofuran, cyprodinil, epoxyconazole, iprodione (and 3,5-dichloroaniline), lindane (and -HCH, its isomer), metolachlor, terbuconazole and trifluralin. This method was established with special consideration for optimal thermal desorption conditions, linear ranges, limits of detection and quantification. Moreover, collection efficiencies of Tenax TA at room temperature were examined. This method was then applied to the determination of ambient pesticide levels during the spraying season at a rural area. The method was also applied to determine the vertical gradient of alachlor concentrations on a treated maize parcel to evaluate volatilisation fluxes.