Multi-class organic pollutants in atmospheric particulate matter (PM2.5) from a Southwestern Europe industrial area: Levels, sources and human health risk.

The occurrence of 50 multi-class pollutants comprising 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 12 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols was studied in atmospheric particulate matter (PM2.5) samples collected at an industrial area focused on automotive manufacturing located at the Southwestern Atlantic European region (Vigo city, Spain) during 1-year period. Among all quantitated pollutants in PM2.5 samples, bisphenol A (BPA) was the most predominant with an average concentration of 6180 pg m-3, followed by PAHs comprising benzo(b+j)fluoranthene (BbF + BjF) and benzo(g,h,i)perylene (BghiP), accounting for 546 pg m-3 and 413 pg m-3 respectively. In addition, two OPFRs concerning tris(chloropropyl) phosphate (TCPP) and triphenyl phosphine oxide (TPPO) were the next following the concentration order, accounting for 411 pg m-3 and 367 pg m-3 respectively; being butyl benzyl phthalate (BBP) the most profuse PAE (56.1 pg m-3 by average). High relative standard deviations (RSDs) were observed during the whole sampling period, while statistically significant differences were only observed for PAHs concentrations during cold and warm seasons. Furthermore, some water-soluble ions and metal(oid)s were analysed in PM2.5 samples to be used as PM source tracers, whose concentrations were quite below the target levels set in the current legislation. Data obtained from principal component analysis (PCA) and PAHs molecular indices suggested a pyrogenic and petrogenic origin for PAHs, whereas occurrence of the remaining compounds seems to be attributed to resources used in the automotive industrial activity settled in the sampling area. Moreover, although a substantial anthropogenic source to PM2.5 in the area was observed, marine and soil resuspension contributions were also accounted. Finally, carcinogenic and non-carcinogenic risks posed by PM2.5-bound pollutants inhalation were assessed, being both averages within the safe level considering the whole period.

Validation of the analytical methodology used in obtaining the oral bioavailability of organic target pollutants in atmospheric particulate matter (PM10) applying an in-vitro method.

In recent years, scientists have started evaluating the portion of PM-bound pollutants that may be liberated (bioaccessible fraction) in human fluids and spread through the digestive system ultimately entering systemic circulation (known as the bioavailable fraction). In the current research, an analytical procedure was validated and applied to characterize the oral bioavailable fraction of PM10 samples. The approach encompassed the determination of 49 organic contaminants. The proposed method aims to biomimetic complete mouth-gastric-intestinal system basing on an adaptation of the unified bioaccessibility method (UBM) modified by the inclusion of a dialysis membrane to mimic intestinal absorption and obtain the orally bioavailable fractions. It was followed by a vortex-assisted liquid-liquid extraction (VALLE) step, using gas chromatography-tandem mass spectrometry (GC-MS/MS). Analytical procedure was effectively validated by employing selected reaction monitoring (SRM) mode in MS/MS, matrix-matched calibration, and deuterium-labelled surrogate standards. This approach ensured heightened sensitivity, minimized matrix effects, and compensated for any losses during the process. The validation process covered various aspects, including studying linearity, determining detection and quantification limits, assessing analytical recoveries at three concentration levels, and evaluating precision both within a single day and across multiple days. The validated method was applied to PM10 samples, revealing that polycyclic aromatic hydrocarbons (PAHs) were the most frequently detected, with significant seasonal variations in their concentrations. Organophosphorus flame retardants (OPFRs) like TCPP were also detected in bioavailable fractions, highlighting their potential health impact. Bisphenols, SMCs, and PAEs were not detected, suggesting low levels in the studied urban area. Further research is needed to understand the bioavailability of PM-bound pollutants in different environments.

Oxidative potential of the inhalation bioaccessible fraction of PM10 and bioaccessible concentrations of polycyclic aromatic hydrocarbons and metal(oid)s in PM10.

Atmospheric particulate matter (PM) has been related to numerous adverse health effects in humans. Nowadays, it is believed that one of the possible mechanisms of toxicity could be the oxidative stress, which involves the development of reactive oxygen species (ROS). Different assays have been proposed to characterize oxidative stress, such as dithiothreitol (DTT) and ascorbic acid (AA) acellular assays (OPDTT and OPAA), as a metric more relevant than PM mass measurement for PM toxicity. This study evaluates the OP of the bioaccessible fraction of 65 PM10 samples collected at an Atlantic Coastal European urban site using DTT and AA assays. A physiologically based extraction (PBET) using Gamble's solution (GS) as a simulated lung fluid (SLF) was used for the assessment of the bioaccessible fraction of PM10. The use of the bioaccessible fraction, instead of the fraction assessed using conventional phosphate buffer and ultrasounds assisted extraction (UAE), was compared for OP assessment. Correlations between OPDTT and OPAA, as well as total and bioaccessible concentrations of polycyclic aromatic hydrocarbons (PAHs) and metal(oid)s, were investigated to explore the association between those compounds and OP. A correlation was found between both OP (OPDTT and OPAA) and total and bioaccessible concentrations of PAHs and several metal(oid)s such as As, Bi, Cd, Cu, Ni, and V. Additionally, OPDTT was found to be related to the level of K+.

A multi-residue method for the analysis of organic pollutants released from atmospheric PM2.5 in simulated biological fluids: Inhalation bioaccessibility and bioavailability estimation.

BACKGROUND: In recent decades, there has been a growing interest within the scientific community regarding the study of the fraction that could be released in simulated biological fluids to estimate in vitro bioaccessibility and bioavailability of compounds. Concerning particulate matter (PM), studies were essentially focused on metal (oid)s probably due to more complex methodologies needed for organic compounds, requiring extraction and pre-concentration steps from simulated fluids, followed by chromatographic analysis. Thus, the development of a simple and sensitive methodology for the analysis of multi-class organic compounds released in different inhalation simulated fluids would represent a great contribution to the field. RESULTS: In this work, a methodology for the analysis of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols released in simulated fluids from PM2.5 samples was developed. After a physiologically based extraction test (PBET) by using artificial lysosomal fluid (ALF) and a simulated body fluid (SBF, filling a dialysis membrane) to obtain in vitro inhalation bioaccessible and bioavailable fractions, respectively; compounds were determined by a vortex-assisted liquid-liquid extraction (VALLE) and a subsequent analysis by programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). Experimental conditions concerning VALLE extraction (extraction time and amount of NaCl (g)) were optimized by using a central composite design (CCD), best MS/MS transitions were selected and matrix-matched calibration combined with use of labelled subrogate standards provided high sensitivity, minimization of matrix effects and recovering losses compensation. SIGNIFICANCE: The successful validation results obtained for most of the compounds demonstrated the effectiveness of the proposed methodology for the analysis of multi-class organic pollutants released in ALF and SBF for inhalation bioaccessibility and bioavailability assessment, respectively. Furthermore, applicability of the method was proved by analysing 20 p.m.2.5 samples, being the proposed in vitro PBET dialyzability approach for assessing organic pollutant's inhalation bioavailability applied to PM2.5 samples for the first time.

In-vitro inhalation bioavailability estimation of Metal(oid)s in atmospheric particulate matter (PM2.5) using simulated alveolar lysosomal fluid: A dialyzability approach.

A novel in-vitro method, by using synthetic body fluids, human physiological conditions and a simulated air-blood barrier (by using a dialysis membrane) has been developed and applied to assess in-vitro inhalation bioavailability of metal(oid)s associated to particulate matter (PM2,5) samples collected from an industrial site of the Northwest of Spain. A validated analytical methodology based on inductively coupled plasma mass spectrometry (ICP-MS) was used to analyse metal(oid)s concentrations in bioavailable fractions. This approach would be a more realistic human health risk assessment since considering processes that occur in human body in contrast the overestimation derived from current models (which consider environmental concentrations). Metal(oid)s such as Cu and Mo seemed to be the most bioavailable (mean in-vitro bioavailability ratios higher than 70%); Ba, Cd, Mn, Pb, Rb, Sb, Sn, V and Zn shown mean ratios between 20 and 60%, while low in-vitro bioavailability ratios (less than 20%) were observed for metal(oid)s such as Al, Co, Cr, Fe, Ni, Ti, and Tl. Health risk assessment via inhalation based on hazard carcinogenic and non-carcinogenic indexes (HIc and HInc, respectively) were performed considering three exposure scenarios using both inhalation bioavailable and total metal(oid)s concentrations in PM2.5 samples, suggesting no risk to human health. The influence of chemical composition on in-vitro bioavailability ratios was obtained, pointing out that inhalation ratios of Al, Ba, Cr, Cu, Fe, Ni, Pb and V seem to be affected by sea salt and/or crustal and/or biogenic and/or anthropogenic content of PM2.5.

Inhalation bioaccessibility of multi-class organic pollutants associated to atmospheric PM2.5: Correlation with PM2.5 properties and health risk assessment.

Inhalation exposure to fine particulate matter (PM2.5) represents a global concern due to the adverse effects in human health. In the last years, scientific community has been adopted the assessment of the PM2.5-bound pollutant fraction that could be released (bioaccessible fraction) in simulated lung fluids (SLFs) to achieve a better understanding of PM risk assessment and toxicological studies. Thus, bioaccessibility of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols in PM2.5 samples was evaluated. The proposed method consists of a physiologically based extraction test (PBET) by using artificial lysosomal fluid (ALF) to obtain bioaccessible fractions, followed by a vortex-assisted liquid-liquid microextraction (VALLME) and a final analysis by programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). The highest inhalation bioaccessibility ratio was found for bisphenol A (BPA) with an average of 83%, followed by OPFRs, PAEs and PAHs (with average bioaccessibilities of 68%, 41% and 34%, respectively). Correlations between PM2.5 composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and bioaccessibility ratios were also assessed. Principal Component Analysis (PCA) suggested that PAHs, PAES and OPFRs bioaccessibility ratios could be positively correlated with PM2.5 carbonaceous content. Furthermore, both inverse and positive correlations on PAHs, PAEs and OPFRs bioaccessibilites could be accounted for some major ions and metal (oid)s associated to PM2.5, whereas no correlations comprising considered PM2.5 major ions and metal (oid)s contents and BPA bioaccessibility was observed. In addition, health risk assessment of target PM2.5-associated PAHs via inhalation was assessed in the study area considering both total and bioaccessible concentrations, being averaged human health risks within the safe carcinogenic and non-carcinogenic levels.