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This paper discusses the occurrence of organic contaminants bonded to particulate matter (PM) in ambient air. We describe the presence and concentration levels of contaminants mainly reported in atmospheres close to factories or at locations influenced by them, and the relationship between factory emissions and the type of organic contaminants found in PM samples from the surrounding air. Many organic contaminants have been found in these types of samples, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs). Their sources, fates and distributions in the ambient atmosphere are therefore well known. However, in addition to these most studied compounds, others are also of concern nowadays due to their detection and toxic effects on the environment. The continuous updating of regulations on these contaminants and the appearance of new air pollutants make it important to be aware of their occurrence. This will help to either establish new guidelines for the newer contaminants or reassess existing limitations for known ones. Moreover, if we know their occurrence, we can analyse their sources, destinations and distributions in the outdoor air.

Plastic additives include several kinds of chemicals that are added to the polymer matrix to improve the final product quality and prevent deterioration effects. They are used in a large quantity of materials, so their presence in the environment is expected. This study has developed and validated a method based on gas chromatography-mass spectrometry after pressurised liquid extraction to determine sixteen plastic additives including UV-stabilizers, aromatic and phenolic antioxidants and some of their degradation products in particulate matter (PM10) from outdoor air. Apparent recoveries were above 85% for most of compounds and low detection limits (pg m−3) were achieved. This is the first study to determine these types of contaminant in the PM10 of outdoor air from two locations surrounded by different industries. Various compounds were found in almost all samples; BHT, BHT-Q, 2,4-DTBP, BHT-CHO, UV320, UV328, Irgafos168 and Iragonx1076, with concentrations ranging from Estimated daily intakes (EDIs) via ambient inhalation were calculated for each polymer additive and for different subpopulation groups classified by age. Two possible exposure scenarios (low, based on geometric mean, and high, 95th percentile) were simulated, and 0.51 ng kgbw−1 day−1 was the EDI in the worst case scenario for children.

Two analytical methods for determining levels of 1,3-butadiene in urban and industrial atmospheres were evaluated in this study. Both methods are extensively used for determining the concentration of volatile organic compounds in the atmosphere and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method uses activated charcoal as the sorbent and involves liquid desorption with carbon disulfide. The second involves the use of a multi-sorbent bed with two graphitised carbons and a carbon molecular sieve as the sorbent, with thermal desorption. Special attention was paid to the optimization of the sampling procedure through the study of sample volume, the stability of 1,3-butadiene once inside the sampling tube and the humidity effect. In the end, the thermal desorption method showed better repeatability and limits of detection and quantification for 1,3-butadiene than the liquid desorption method, which makes the thermal desorption method more suitable for analysing air samples from both industrial and urban atmospheres. However, sampling must be performed with a pre-tube filled with a drying agent to prevent the loss of the adsorption capacity of the solid adsorbent caused by water vapour. The thermal desorption method has successfully been applied to determine of 1,3-butadiene inside a 1,3-butadiene production plant and at three locations in the vicinity of the same plant.

Benzothiazole (BTHs), benzotriazole (BTRs) and benzenesulfonamide (BSAs) derivates are high production volume chemicals and they are used in several industrial and household applications, therefore it is expected their occurrence in various environments, especially water and air. In this study we developed a method based on gas chromatography-mass spectrometry (GC-MS) combined with pressurised liquid extraction (PLE) to simultaneously determine four BTR, five BTH and six BSA derivates in the particulate matter (PM10) of outdoor air samples collected in quartz fibre filters (QFFs). To the best of our knowledge, this is the first time these compounds have been determined in open ambient environments. Under optimised conditions, method recoveries at the lower and upper concentration levels (0.8 and 4.2 ng m−3) ranged from 70 to 120%, except for 1-H-benzothiazole and 2-chlorobenzothiazole, which were about 50%. The repeatability of the method was usually below 20% (n = 3, %RSD) for both concentration levels. This method enables the contaminants to be detected at pg m−3 concentration levels. Several samples from two different sites influenced by local industries showed that BTRs, followed by BTHs, were the most detected compounds, whereas BSAs were hardly found. The most frequently determined compounds were 1-H-benzothiazole, 2-chlorobenzothiazole, 1-H-benzotriazole, 2-hydroxibenzothiazole, 5,6-dimethyl-1-H-benzotriazole and the isomers 4- and 5-methyl-1-H-benzotriazole. With the concentrations found, the human exposure assessment and health risk characterization via ambient inhalation were also evaluated taking into account different subpopulation groups classified by age for the two sampling points.

A multi-residue method based on gas chromatography-mass spectrometry combined with pressurised liquid extraction was developed to determine seven organophosphate esters (OPEs), six phthalate esters (PAEs), four benzotriazoles (BTRs), five benzothiazoles (BTHs) and four benzenesulfonamides (BSAs) in particulate matter samples from outdoor air. All of these compounds are among the named high-production volume chemicals (HPVCs) and some of them have shown to be harmful to human, therefore they have been subject for legal regulation in order to control their production and usage. Under optimised conditions, high recovery values (>80%) and low detection limits (pg m−3) were obtained for most of the compounds with accuracy values between 83% and 118%. Some samples from two locations surrounded by different industry activities showed the widespread occurrence of all the PAEs, followed by some OPEs. Diethylhexyl phthalate (DEHP) was the most abundant compound with concentrations ranging from 1.9 to 97.7 ng m−3. With the concentrations found, estimated daily intakes through outdoor inhalation were calculated for each contaminant and for different population groups classified by age (infants, children and adults) in two possible exposure scenarios (low and high). Then, hazard quotients and carcinogenic risks were estimated for several compounds, those that had toxicological parameters available. This preliminary result showed no significant risks via ambient inhalation for the exposed population, however more research is needed to confirm the present results.

This study describes the humidity effect in the sampling process by adsorbent tubes followed by thermal desorption and gas chromatography-mass spectrometry (TD-GC-MS) for the determination of volatile organic compounds (VOCs) in air samples and evaluates possible solutions to this problem. Two multi-sorbent bed tubes, Tenax TA/Carbograph 1TD and Carbotrap B/Carbopack X/Carboxen 569, were tested in order to evaluate their behaviour in the presence of environmental humidity. Humidity problems were demonstrated with carbon-based tubes, while Tenax-based tubes did not display any influence. Silica gel, a molecular sieve and CaCl2 were tried out as materials for drying tube to remove air humidity, placed prior to the sampling tube to prevent water from entering. The pre-tubes filled with 0.5g of CaCl2 showed the best results with respect to their blanks, the analytes recoveries and their ability to remove ambient humidity. To avoid the possible agglomeration of CaCl2 during the sampling process in high relative humidity atmospheres, 0.1g of diatomaceous earth were mixed with the desiccant agent. The applicability of the CaCl2 pre-tube as drying agent prior to Carbotrap B/Carbopack X/Carboxen 569 tubes was tested in urban and industrial locations with samplings of air at high relative humidity. In addition, the results were compared with those obtained using Tenax TA/Carbograph 1TD tubes.

Different analytical techniques can be used to chemically characterize the atmospheric particulate matter, and to provide information about the concentration range, sources, fates and distributions of different atmospheric pollutants. This review describes the available and currently most-used analytical methods for PM characterization. Although it is not an exhaustive study about the whole characterization of the air PM, some particular case studies are presented. Most of the methods described are mainly based on gas chromatography, although techniques such as liquid chromatography or others, such as Fourier transform infrared spectroscopy, are also presented. Moreover, sample pre-treatments, extraction and clean-up techniques and the mentioned determination techniques are described and discussed, showing their main features as well as their advantages and drawbacks. Therefore, this review could be a useful guide for readers to choose the most suitable techniques for their purposes since it reports different advances in PM characterization during the last decade.