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Polycyclic aromatic hydrocarbons (PAHs) were assessed in 65 atmospheric particulate matter (PM10) samples collected at a coastal urban area of Southwest Atlantic Europe during the 1-year period. Analytical methodology was successfully validated in terms of limits of detection and quantification, linearity, precision and trueness by using ERM CZ100 reference material and analytical recovery studies. Status of PM10-bound PAHs and their relationship with other PM10 constituents (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) in an area where few data are available is provided. Benzo(b)fluoranthene (BbF) and benzo(e)pyrene (BeP) were observed to be predominant in all samples analysed with average concentrations of 1.6 and 1.5 ng m−3, respectively. Furthermore, high RSDs were achieved for PAHs during the sampling period, which reflects inherent heterogeneity of the atmospheric particles besides weather conditions variations. Statistical significant seasonal changes in PAH concentrations during summer and winter seasons were not found. Data obtained from molecular PAH indices, univariate analysis, principal component analysis (PCA) and cluster analysis (CA) suggested a pyrogenic origin derived from the continuous harbour activity and marine and road traffic emissions at the studied urban site throughout the year. Additionally, major ion and metal(oid) concentrations in PM10 samples were also used as tracers of PAH origin and for PM10 source exploration. Linear and quadratic models have shown that the PAH concentrations exhibited correlation with some metals (Ba, Bi, Cu, Pb, Sb and Zn) and NO3− concentrations. Finally, carcinogenic and mutagenic potencies and inhalation cancer risk (ILCRinh) posed by PM10-bound PAHs were assessed.

Due to the exponential growth of the SARS-CoV-2 pandemic in Spain (2020), the Spanish Government adopted lockdown measures as mitigating strategies to reduce the spread of the pandemic from 14 March. In this paper, we report the results of the change in air quality at two Atlantic Coastal European cities (Northwest Spain) during five lockdown weeks. The temporal evolution of gaseous (nitrogen oxides, comprising NOx, NO, and NO2, sulfur dioxide, SO2, carbon monoxide, CO, and ozone, O3) and particulate matter (PM10, PM2.5, and equivalent black carbon, eBC) pollutants were recorded before (7 February to 13 March 2020) and during the first five lockdown weeks (14 March to 20 April 2020) at seven air quality monitoring stations (urban background, traffic, and industrial) in the cities of A Coruña and Vigo. The influences of the backward trajectories and meteorological parameters on air pollutant concentrations were considered during the studied period. The temporal trends indicate that the concentrations of almost all species steadily decreased during the lockdown period with statistical significance, with respect to the pre-lockdown period. In this context, great reductions were observed for pollutants related mainly to fossil fuel combustion, road traffic, and shipping emissions (−38 to −78% for NO, −22 to −69% for NO2, −26 to −75% for NOx, −3 to −77% for SO2, −21% for CO, −25 to −49% for PM10, −10 to −38% for PM2.5, and −29 to −51% for eBC). Conversely, O3 concentrations increased from +5 to +16%. Finally, pollutant concentration data for 14 March to 20 April of 2020 were compared with those of the previous two years. The results show that the overall air pollutants levels were higher during 2018–2019 than during the lockdown period.

In this study, a characterization of particulate matter (PM 10 ) is performed in a suburban area in Northwestern Spain (A Coruna, Galicia), in order to establish the interrelationships between major components, as well as between these components and submicron particles. 140 PM 10 samples were collected from April 2014 to January 2015 and numerous chemical parameters, such as carbonaceous fraction, including water-soluble organic carbon (WSOC), major ions, and carbon and nitrogen isotopic ratios, were determined. Data on ultrafine particles for one season were also recorded. Nanoparticle modes showed a correlation between them and with all of the carbonaceous fractions (especially elemental carbon and Aitken mode) and some meteorological parameters (humidity and solar radiation). Their correlations suggested the possible influence of a few industrial sources, depending on the prevailing winds. Isotopic data indicated the presence of a significant input from combustion sources during the cold period and primary biogenic input during the spring, reinforced by OC/EC ratios and WSOC values. Organic carbon (OC), the main component of carbonaceous fraction, correlates seasonally with elemental carbon (EC), setting a fitting to a potential equation during the winter. These parameters also suggested a significant presence of secondary organic aerosol in the area, except in the spring. A high contribution of secondary inorganic aerosol was also observed, with ammonium sulfate (all of the seasons), sodium nitrate with a marine contribution (except in the autumn), and potassium sulfate (except in the spring) as the main species. The Atlantic Ocean's influence was observed as a contribution of sea salt to PM 10 of 23.4% on average, up to 84.5% on certain days, and a strong relationship between sea salt and secondary aerosol.

Atmospheric particle-bound mercury (PHg) quantification, at a pg m&minus, 3 level, has been assessed in particulate matter samples (PM10) at several sites (industrial, urban and sub-urban sites) of Atlantic coastal European region during 13 months by using a direct thermo-desorption method. Analytical method validation was assessed using 1648a and ERM CZ120 reference materials. The limits of detection and quantification were 0.25 pg m&minus, 3 and 0.43 pg m&minus, 3, respectively. Repeatability of the method was generally below 12.6%. PHg concentrations varied between 1.5&ndash, 30.8, 1.5&ndash, 75.3 and 2.27&ndash, 33.7 pg m&minus, 3 at urban, sub-urban and industrial sites, respectively. PHg concentration varied from 7.2 pg m&minus, 3 (urban site) to 16.3 pg m&minus, 3 (suburban site) during winter season, while PHg concentrations varied from 9.9 pg m&minus, 3 (urban site) to 19.3 pg m&minus, 3 (suburban site) during the summer. Other trace elements, major ions, black carbon (BC) and UV-absorbing particulate matter (UV PM) was also assessed at several sites. Average concentrations for trace metals (Al, As, Bi, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Si, Sr, V and Zn) ranged from 0.08 ng m&minus, 3 (Bi) at suburban site to 1.11 &micro, g m&minus, 3 (Fe) at industrial site. Average concentrations for major ions (including Na+, K+, Ca2+, NH4+, Mg2+, Cl&minus, NO3&minus, and SO42&minus, ) ranged from 200 ng m&minus, 3 (K+) to 5332 ng m&minus, 3 (SO42&minus, ) at urban site, 166 ng m&minus, 3 (Mg2+) to 4425 ng m&minus, ) at suburban site and 592 ng m&minus, 3 (K+) to 5853 ng m&minus, 3 (Cl&minus, ) at industrial site. Results of univariate analysis and principal component analysis (PCA) suggested crustal, marine and anthropogenic sources of PHg in PM10 at several sites studied. Toxicity prediction of PHg, by using hazard quotient, suggested no non-carcinogenic risk for adults.

An in-tube solid phase microextraction, coupled with high-performance liquid chromatography with diode array detection (IT-SPME-HPLC-DAD) method, has been developed for the simultaneous determination of 13 diesters (from dimethyl to dioctylphthalate plus diisobutyl, benzylbutyl, di-2-ethylhexyl, diisononyl and diisodecylphthalate) and 2 monoesters of phthalic acid (mono-butyl and mono-(2-ethylhexyl) phthalate) in particulate matter (PM 10 ). Triethylamine at pH = 3 was used as an ion-pair reagent with a double function, of regulating the chromatographic retention of the monoesters and the most hydrophilic diesters on a monolithic silica column, and of improving their extraction on a porous polymer with divinylbenzene-4-vinylpyridine capillary. The chromatographic separation was achieved in 13 min. A previous ultrasound-assisted extraction from PM 10 filters was also optimized using methanol as solvent. The method detection limits were 0.09–0.52 ng m −3 , the inter-day precision at concentration of 20 ng mL −1 was between 4.2% and 12.7% (n = 15), and the average recovery was 87.3%. The average absolute IT-SPME recovery was 26.2% and the linear range reached up to 109 ng m −3 for most analytes. The method was applied to PM 10 samples from different environments collected in Galicia (Spain). DiBP was the major phthalate, followed by its isomer DnBP in urban sites and by DEP in the suburban area. In all samples, DEHP quantified correlates with the isomers of dibutylphthalate. Total PAE concentration was between 14.5 and 245.5 ng m −3 . To the best of our knowledge, this is the first time that a method allows the simultaneous determination of 13 phthalates and their degradation products in particulate matter.

Polycyclic aromatic hydrocarbons (PAHs) inhalation bioaccessibility was assessed in 65 atmospheric particulate matter samples (PM10) collected at an Atlantic coastal European urban site. The proposed method consists on a physiologically based extraction (PBET) by using Gamble's solution followed by a vortex assisted liquid-liquid micro-extraction (VALLME) and quantification by high performance liquid chromatography with fluorescence detection (HPLC-FLD). The use of a micro-extraction technique combined with FLD detection, provides a simple, fast, sensitive, accurate and low-cost methodology to PAHs quantification in bioaccessible fractions. Accuracy of the bioaccessibility study was assessed by means of a mass balance approaches using a PM10 filter and a certified reference material (ERM-CZ100). High-moderate inhalation bioaccessibilities were found for phenanthrene (Phe), fluoranthene (Ft) and pyrene (Pyr) (average ratios in the 52-65% range); while dibenz (a,h)anthracene (DBahA), indeno (1,2,3-cd)pyrene (IP) and benzo (g,h,i)perylene (BghiP) were observed to be less bioaccessibles (average ratios in the 11-14% range). Relationship between PM10 composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and PAHs bioaccessibility ratios was also assessed. Principal Component Analysis (PCA) showed that PAHs bioaccessibility percentage is dependent on anthropogenic (eBC, UVPM and Sb concentrations) and marine sources of PM10. Predicted PAHs bioaccessibilities after applying a multiple linear regression model based on marine and anthropogenic source of PM10 could also be established. Health risk assessment of target PM10-associated PAHs via inhalation was assessed considering bioaccessibility concentrations by using hazard index (HI) and BaP equivalent concentration (BaPeq) approaches, suggesting no carcinogenic risk in the area during the sampling campaign.

A novel single-step method was developed for the determination of 15 polycyclic aromatic hydrocarbons (PAHs) at ultratrace levels in rainwater by on-line in-tube solid-phase microextraction (IT-SPME) coupled to high-performance liquid chromatography-photodiode array-fluorescence detection. This paper is focused on a study of the IT-SPME coupling and optimization, its application to rainwater and other environmental waters and the stability of PAH rainwater solutions. In order to solve the different extractive behavior of PAHs, several IT-SPME parameters were optimized, with the type and percentage of organic modifier playing a decisive role. In the kinetic study on stability of PAH solutions, the organic modifier has proven to be effective as a preservative, avoiding the loss of the higher-molecular weight PAHs. The proposed method presents a wide interval of linearity (10–1500 ng L −1 ) and a good relative standard deviation between 3.4% and 14.6% for the PAHs analyzed. Detection and quantification limits between 2.3 and 28 ng L −1 and 5.7 and 65 ng L −1 were obtained respectively, taking into account the values of the procedure blanks. Recoveries for different kinds of real water samples were within the range of 72–110%. Low and medium-molecular weight PAHs predominate in daily and monthly rainwater samples analyzed. In comparison with other methods reported, the proposed method achieves a significant reduction of the sample volume, the organic solvent consumption and time of sample treatment, allowing a cost-effective analysis of environmental waters. The method is especially suitable for samples from the precipitation events of low intensity or short duration for which sample volume is limiting.

In-tube solid-phase microextraction (in-tube SPME or IT-SPME) is a sample preparation technique which has demonstrated over time its ability to couple with liquid chromatography (LC), as well as its advantages as a miniaturized technique. However, the in-tube SPME perspectives in the forthcoming years depend on solutions that can be brought to the environmental, industrial, food and biomedical analysis. The purpose of this scoping review is to examine the strengths and weaknesses of this technique during the period 2009 to 2015 in order to identify research gaps that should be addressed in the future, as well as the tendencies that are meant to strengthen the technique. In terms of methodological aspects, this scoping review shows the in-tube SPME strengths in the coupling with LC (LC-mass spectrometry, capillary LC, ultra-high-pressure LC), in the new performances (magnetic IT-SPME and electrochemically controlled in-tube SPME) and in the wide range of development of coatings and capillaries. Concerning the applicability, most in-tube SPME studies (around 80%) carry out environmental and biomedical analyses, a lower number food analyses and few industrial analyses. Some promising studies in proteomics have been performed. The review makes a critical description of parameters used in the optimization of in-tube SPME methods, highlighting the importance of some of them (i.e. type of capillary coatings). Commercial capillaries in environmental analysis and laboratory-prepared capillaries in biomedical analysis have been employed with good results. The most consolidated configuration is in-valve mode, however the cycle mode configuration is frequently chosen for biomedical analysis. This scoping review revealed that some aspects such as the combination of in-tube SPME with other sample treatment techniques for the analysis of solid samples should be developed in depth in the near future.

This article consists of a review of the methodologies proposed for analysis of surfactants. The main changes and advances are described with regard to three relevant aspects, the analysis of surfactants in industrial and commercial products, in environmental matrices, as well as the determination of their residual products. Chromatographic techniques, and more specifically liquid chromatography coupled to mass spectrometry, allow the identification of mixtures of homologs and/or ethoxymers from different classes of surfactants. Depending on the complexity of the matrices and concentration levels, multistage sample treatments are applied, sometimes including miniaturized techniques. Tensammetric techniques in environmental matrices and selective electrodes in commercial products are used for the determination of ionic and nonionic surfactants. Different reagents were proposed for the formation of complexes with target surfactants and further measurement by spectrophotometric techniques. High-production-volume surfactants, such as linear alkylbenzene sulfonate, ethoxylates alcohols, dialkyldimethyl ammonium, benzalkonium chloride are analyzed in detergents, pharmaceutical or cosmetic products. Information on the concentration of surfactants in solid and liquid matrices from wastewater treatment plants is useful to evaluate the biodegradation efficiency. 1,4-dioxane, alkylamines and other compounds from raw materials or by-products are found in technical products and formulations.

Six phthalic acid esters were determined in rainwater samples, from which a very low sample volume was collected. This method combines on-line in-tube solid-phase microextraction coupled to high-performance liquid chromatography with a diode-array detector. In order to obtain a short analysis time and to reduce the consumption of organic solvents, two chromatographic phases (C18 monolithic and cyanopropyl silica) are compared. Although three critical pairs are found, faster separation, good resolution and lower pressures are achieved using C18 monolithic column. In order to achieve a simple and sensitive method, two commercial capillaries (a porous polymer with divinylbenzene-4-vinylpyridine and a liquid-phase capillary with 95% poly(dimethylsiloxane)-5% poly(diphenylsiloxane)) are tested for the extraction process. Due to great differences of hydrophobicity among the six phthalates, the selection of a modifier is necessary for a good extraction. The best conditions are achieved using 5 mL of sample containing 40% methanol in a 70 cm-long porous polymer capillary. The procedural blanks are controlled and taken into account in the calculation of the detection limits. Except for dimethylphthalate, the method detection limits are in the range from 0.2 to 0.9 ng mL-1 and the inter-day precision is between 5.3% and 12.5%. The recoveries were within the range of 71%-101%. Rainwater samples are analyzed in order to examine the dilution effect and washout of phthalates in the atmosphere. Dibutyl phthalate is the predominant phthalate found and di-(2-ethylhexyl) phthalate is detected in all analyzed samples.