Oxidative potential of particulate matter and its association to respiratory health endpoints in high-altitude cities in Bolivia.

Exposure to particulate matter (PM) pollution is a significant health risk, driving the search for innovative metrics that more accurately reflect the potential harm to human health. Among these, oxidative potential (OP) has emerged as a promising health-based metric, yet its application and relevance across different environments remain to be further explored. This study, set in two high-altitude Bolivian cities, aims to identify the most significant sources of PM-induced oxidation in the lungs and assess the utility of OP in assessing PM health impacts. Utilizing two distinct assays, OPDTT and OPDCFH, we measured the OP of PM samples, while also examining the associations between PM mass, OP, and black carbon (BC) concentrations with hospital visits for acute respiratory infections (ARI) and pneumonia over a range of exposure lags (0-2 weeks) using a Poisson regression model adjusted for meteorological conditions. The analysis also leveraged Positive Matrix Factorization (PMF) to link these health outcomes to specific PM sources, building on a prior source apportionment study utilizing the same dataset. Our findings highlight anthropogenic combustion, particularly from traffic and biomass burning, as the primary contributors to OP in these urban sites. Significant correlations were observed between both OPDTT and PM2.5 concentration exposure and ARI hospital visits, alongside a notable association with pneumonia cases and OPDTT levels. Furthermore, PMF analysis demonstrated a clear link between traffic-related pollution and increased hospital admissions for respiratory issues, affirming the health impact of these sources. These results underscore the potential of OPDTT as a valuable metric for assessing the health risks associated with acute PM exposure, showcasing its broader application in environmental health studies.

Local incomplete combustion emissions define the PM2.5 oxidative potential in Northern India.

The oxidative potential (OP) of particulate matter (PM) is a major driver of PM-associated health effects. In India, the emission sources defining PM-OP, and their local/regional nature, are yet to be established. Here, to address this gap we determine the geographical origin, sources of PM, and its OP at five Indo-Gangetic Plain sites inside and outside Delhi. Our findings reveal that although uniformly high PM concentrations are recorded across the entire region, local emission sources and formation processes dominate PM pollution. Specifically, ammonium chloride, and organic aerosols (OA) from traffic exhaust, residential heating, and oxidation of unsaturated vapors from fossil fuels are the dominant PM sources inside Delhi. Ammonium sulfate and nitrate, and secondary OA from biomass burning vapors, are produced outside Delhi. Nevertheless, PM-OP is overwhelmingly driven by OA from incomplete combustion of biomass and fossil fuels, including traffic. These findings suggest that addressing local inefficient combustion processes can effectively mitigate PM health exposure in northern India.

Disentangling fine particles (PM2.5) composition in Hanoi, Vietnam: Emission sources and oxidative potential.

A comprehensive chemical characterization of fine particulate matter (PM2.5) was conducted at an urban site in one of the most densely populated cities of Vietnam, Hanoi. Chemical analysis of a series of 57 daily PM2.5 samples obtained in 2019-2020 included the quantification of a detailed set of chemical tracers as well as the oxidative potential (OP), which estimates the ability of PM to catalyze reactive oxygen species (ROS) generation in vivo as an initial step of health effects due to oxidative stress. The PM2.5 concentrations ranged from 8.3 to 148 µg m-3, with an annual average of 40.2 ± 26.3 µg m-3 (from September 2019 to December 2020). Our results obtained by applying the Positive Matrix Factorization (PMF) source-receptor apportionment model showed the contribution of nine PM2.5 sources. The main anthropogenic sources contributing to the PM mass concentrations were heavy fuel oil (HFO) combustion (25.3 %), biomass burning (20 %), primary traffic (7.6 %) and long-range transport aerosols (10.6 %). The OP activities were evaluated for the first time in an urban site in Vietnam. The average OPv levels obtained in our study were 3.9 ± 2.4 and 4.5 ± 3.2 nmol min-1 m-3 for OPDTT and OPAA, respectively. We assessed the contribution to OPDTT and OPAA of each PM2.5 source by applying multilinear regression models. It shows that the sources associated with human activities (HFO combustion, biomass burning and primary traffic) are the sources driving OP exposure, suggesting that they should be the first sources to be controlled in future mitigation strategies. This study gives for the first time an extensive and long-term chemical characterization of PM2.5, providing also a link between emission sources, ambient concentrations and exposure to air pollution at an urban site in Hanoi, Vietnam.

Prenatal Exposure to PM2.5 Oxidative Potential and Lung Function in Infants and Preschool- Age Children: A Prospective Study.

BACKGROUND: Fine particulate matter (PM2.5) has been found to be detrimental to respiratory health of children, but few studies have examined the effects of prenatal PM2.5 oxidative potential (OP) on lung function in infants and preschool children. OBJECTIVES: We estimated the associations of personal exposure to PM2.5 and OP during pregnancy on offspring objective lung function parameters and compared the strengths of associations between both exposure metrics. METHODS: We used data from 356 mother-child pairs from the SEPAGES cohort. PM filters collected twice during a week were analyzed for OP, using the dithiothreitol (DTT) and the ascorbic acid (AA) assays, quantifying the exposure of each pregnant woman. Lung function was assessed with tidal breathing analysis (TBFVL) and nitrogen multiple-breath washout (N2MBW) test, performed at 6 wk, and airwave oscillometry (AOS) performed at 3 y. Associations of prenatal PM2.5 mass and OP with lung function parameters were estimated using multiple linear regressions. RESULTS: In neonates, an interquartile (IQR) increase in OPvDTT (0.89 nmol/min/m3) was associated with a decrease in functional residual capacity (FRC) measured by N2MBW [ß=-2.26mL; 95% confidence interval (CI): -4.68, 0.15]. Associations with PM2.5 showed similar patterns in comparison with OPvDTT but of smaller magnitude. Lung clearance index (LCI) and TBFVL parameters did not show any clear association with the exposures considered. At 3 y, increased frequency-dependent resistance of the lungs (Rrs7-19) from AOS tended to be associated with higher OPvDTT (ß=0.09 hPa×s/L; 95% CI: -0.06, 0.24) and OPvAA (IQR=1.14 nmol/min/m3; ß=0.12 hPa×s/L; 95% CI: -0.04, 0.27) but not with PM2.5 (IQR=6.9 µg/m3; ß=0.02 hPa×s/L; 95% CI: -0.13, 0.16). Results for FRC and Rrs7-19 remained similar in OP models adjusted on PM2.5. DISCUSSION: Prenatal exposure to OPvDTT was associated with several offspring lung function parameters over time, all related to lung volumes. https://doi.org/10.1289/EHP11155.

Personal exposure to PM2.5 oxidative potential and its association to birth outcomes.

BACKGROUND: Prenatal exposure to fine particulate matter (PM2.5) assessed through its mass concentration has been associated with foetal growth restriction in studies based on outdoor levels. Oxidative potential of PM2.5 (OP) is an emerging metric a priori relevant to mechanisms of action of PM on health, with very limited evidence to indicate its role on birth outcomes. OBJECTIVES: We investigated the association of OP with birth outcomes and compared it with that of PM2.5 mass concentration. METHODS: 405 pregnant women from SEPAGES cohort (Grenoble area) carried PM2.5 personal dosimeters for one or two one-week periods. OP was measured using dithiothreitol (DTT) and ascorbic acid (AA) assays from the collected filters. Associations of each exposure metric with offspring weight, height, and head circumference at birth were estimated adjusting for potential confounders. RESULTS: The correlation between PM2.5 mass concentration and [Formula: see text] was 0.7. An interquartile range increase in .. was associated with reduced weight (adjusted change, -64 g, -166 to -11, p = 0.02) and height (-4 mm, -6 to -1, p = 0.01) at birth. PM2.5 mass concentration showed similar associations with weight (-53 g, -99 to -8, p = 0.02) and height (-2 mm, -5 to 0, p = 0.05). In birth height models mutually adjusted for the two exposure metrics, the association with [Formula: see text] was less attenuated than that with mass concentration, while for weight both effect sizes attenuated similarly. There was no clear evidence of associations with head circumference for any metric, nor for [Formula: see text] with any growth parameter. IMPACT: PM2.5 pregnancy exposure assessed from personal dosimeters was associated with altered foetal growth. Personal OP exposure was associated with foetal growth restrictions, specifically decreased weight and height at birth, possibly to a larger extent than PM2.5 mass concentration alone. These results support OP assessed from DTT as being a health-relevant metric. Larger scale cohort studies are recommended to support our findings.

Evaluation of the Sources, Precursors, and Processing of Aerosols at a High-Altitude Tropical Site.

This work presents the results from a set of aerosol- and gas-phase measurements collected during the BIO-MAÏDO field campaign in Réunion between March 8 and April 5, 2019. Several offline and online sampling devices were installed at the Maïdo Observatory (MO), a remote high-altitude site in the Southern Hemisphere, allowing the physical and chemical characterization of atmospheric aerosols and gases. The evaluation of short-lived gas-phase measurements allows us to conclude that air masses sampled during this period contained little or no anthropogenic influence. The dominance of sulfate and organic species in the submicron fraction of the aerosol is similar to that measured at other coastal sites. Carboxylic acids on PM10 showed a significant contribution of oxalic acid, a typical tracer of aqueous processed air masses, increasing at the end of the campaign. This result agrees with the positive matrix factorization analysis of the submicron organic aerosol, where more oxidized organic aerosols (MOOAs) dominated the organic aerosol with an increasing contribution toward the end of the campaign. Using a combination of air mass trajectories (model predictions), it was possible to assess the impact of aqueous phase processing on the formation of secondary organic aerosols (SOAs). Our results show how specific chemical signatures and physical properties of air masses, possibly affected by cloud processing, can be identified at Réunion. These changes in properties are represented by a shift in aerosol size distribution to large diameters and an increased contribution of secondary sulfate and organic aerosols after cloud processing.

Modelling aerosol molecular markers in a 3D air quality model: Focus on anthropogenic organic markers.

We developed and implemented in the 3D air quality model CHIMERE the formation of several key anthropogenic aerosol markers including one primary anthropogenic marker (levoglucosan) and 4 secondary anthropogenic markers (nitrophenols, nitroguaiacols, methylnitrocatechols and phthalic acid). Modelled concentrations have been compared to measurements performed at 12 locations in France for levoglucosan in winter 2014-15, and at a sub-urban station in the Paris region over the whole year 2015 for secondary molecular markers. While a good estimation of levoglucosan concentrations by the model has been obtained for a few sites, a strong underestimation was simulated for most of the stations especially for western locations due to a probable underestimation of residential wood burning emissions. The simulated ratio between wood burning organic matter and particulate phase levoglucosan is constant only at high OM values (>10 µg m-3) indicating that using marker contribution ratio may be valid only under certain conditions. Concentrations of secondary markers were well reproduced by the model for nitrophenols and nitroguaiacols but were underestimated for methylnitrocatechols and phthalic acid highlighting missing formation pathways and/or precursor emissions. By comparing modelled to measured Gas/Particle Partitioning (GPP) of markers, the simulated partitioning of Semi-Volatile Organic Compounds (SVOCs) was evaluated. Except for nitroguaiacols and nitrophenols when ideality was assumed, the GPP for all the markers was underestimated and mainly driven by the hydrophilic partitioning. SVOCs GPP, and more generally of all SVOC contributing to the formation of SOA, could therefore be significantly underestimated by air quality models, especially when only the partitioning on the organic phase is considered. Our results show that marker modelling can give insights on some processes (such as precursor emissions or missing mechanisms) involved in SOA formation and could prove especially useful to evaluate the GPP in 3D air quality models.

Equal abundance of summertime natural and wintertime anthropogenic Arctic organic aerosols.

Aerosols play an important yet uncertain role in modulating the radiation balance of the sensitive Arctic atmosphere. Organic aerosol is one of the most abundant, yet least understood, fractions of the Arctic aerosol mass. Here we use data from eight observatories that represent the entire Arctic to reveal the annual cycles in anthropogenic and biogenic sources of organic aerosol. We show that during winter, the organic aerosol in the Arctic is dominated by anthropogenic emissions, mainly from Eurasia, which consist of both direct combustion emissions and long-range transported, aged pollution. In summer, the decreasing anthropogenic pollution is replaced by natural emissions. These include marine secondary, biogenic secondary and primary biological emissions, which have the potential to be important to Arctic climate by modifying the cloud condensation nuclei properties and acting as ice-nucleating particles. Their source strength or atmospheric processing is sensitive to nutrient availability, solar radiation, temperature and snow cover. Our results provide a comprehensive understanding of the current pan-Arctic organic aerosol, which can be used to support modelling efforts that aim to quantify the climate impacts of emissions in this sensitive region.

Emission factors and chemical characterization of particulate emissions from garden green waste burning.

This work provides an evaluation of the emission factors (EFs) of typical garden waste burning (fallen leaves and hedge trimming) in terms of particulate matter (PM), elemental and organic carbon (EC-OC) together with a detailed chemical characterization of 88 particle-bound organic species including polycyclic aromatic hydrocarbons (PAHs), levoglucosan and its isomers, lignin breakdown products (methoxyphenols), cholesterol, alkanes, polyols and sugars. Furthermore, wood-log based burning experiments have been performed to highlight key indicators or chemical patterns of both, green waste and wood burning (residential heating) sources, that may be used for PM source apportionment purposes. Two residential log wood combustion appliances, wood stove (RWS) and fireplace, under different output conditions (nominal and reduced) and wood log moisture content (mix of beech, oak and hornbeam), have been tested. Open wood burning experiments using wood logs were also performed. Green waste burning EFs obtained were comparable to the available literature data for open-air biomass burning. For PM and for most of the organic species studied, they were about 2 to 30 times higher than those observed for wood log combustion experiments. Though, poor performance wood combustions (open-air wood log burning, fireplace and RWS in reduced output) showed comparable EFs for levoglucosan and its isomers, methoxyphenols, polyols, PAHs and sugars. Toxic PAH equivalent benzo[a]pyrene EFs were even 3-10 times higher for the fireplace and open-air wood log burning. These results highlighted the impact of the nature of the fuel burnt and the combustion performances on the emissions. Different chemical fingerprints between both biomass burning sources were highlighted with notably a predominance of odd high-molecular weight n-alkanes (higher carbon preference index, CPI), lower levoglucosan/mannosan ratio and lower sinapylaldehyde abundance for green waste burning. However, the use of such indicators seems limited, especially if applied alone, for a clear discrimination of both sources in ambient air.

Geochemistry and oxidative potential of the respirable fraction of powdered mined Chinese coals.

This study evaluates geochemical and oxidative potential (OP) properties of the respirable (finer than 4 µm) fractions of 22 powdered coal samples from channel profiles (CP4) in Chinese mined coals. The CP4 fractions extracted from milled samples of 22 different coals were mineralogically and geochemically analysed and the relationships with the OP evaluated. The evaluation between CP4/CP demonstrated that CP4 increased concentrations of anatase, Cs, W, Zn and Zr, whereas sulphates, Fe, S, Mo, Mn, Hf and Ge decreased their CP4 concentrations. OP results from ascorbic acid (AA), glutathione (GSH) and dithiothreitol (DTT) tests evidenced a clear link between specific inorganic components of CP4 with OPAA and the organic fraction of OPGSH and OPDTT. Correlation analyses were performed for OP indicators and the geochemical patterns of CP4. These were compared with respirable dust samples from prior studies. They indicate that Fe (r = 0.83), pyrite (r = 0.66) and sulphate minerals (r = 0.42) (tracing acidic species from pyrite oxidation), followed by S (r = 0.50) and ash yield (r = 0.46), and, to a much lesser extent, Ti, anatase, U, Mo, V and Pb, are clearly linked with OPAA. Moreover, OPGSH correlation was identified by organic matter, as moisture (r = 0.73), Na (r = 0.56) and B (r = 0.51), and to a lesser extent by the coarse particle size, Ca and carbonate minerals. In addition, Mg (r = 0.70), B (r = 0.47), Na (r = 0.59), Mn, Ba, quartz, particle size and Sr regulate OPDTT correlations. These became more noticeable when the analysis was done for samples of the same type of coal rank, in this case, bituminous.

Sources of particulate-matter air pollution and its oxidative potential in Europe.

Particulate matter is a component of ambient air pollution that has been linked to millions of annual premature deaths globally1-3. Assessments of the chronic and acute effects of particulate matter on human health tend to be based on mass concentration, with particle size and composition also thought to play a part4. Oxidative potential has been suggested to be one of the many possible drivers of the acute health effects of particulate matter, but the link remains uncertain5-8. Studies investigating the particulate-matter components that manifest an oxidative activity have yielded conflicting results7. In consequence, there is still much to be learned about the sources of particulate matter that may control the oxidative potential concentration7. Here we use field observations and air-quality modelling to quantify the major primary and secondary sources of particulate matter and of oxidative potential in Europe. We find that secondary inorganic components, crustal material and secondary biogenic organic aerosols control the mass concentration of particulate matter. By contrast, oxidative potential concentration is associated mostly with anthropogenic sources, in particular with fine-mode secondary organic aerosols largely from residential biomass burning and coarse-mode metals from vehicular non-exhaust emissions. Our results suggest that mitigation strategies aimed at reducing the mass concentrations of particulate matter alone may not reduce the oxidative potential concentration. If the oxidative potential can be linked to major health impacts, it may be more effective to control specific sources of particulate matter rather than overall particulate mass.

Oxidative stress-induced inflammation in susceptible airways by anthropogenic aerosol.

Ambient air pollution is one of the leading five health risks worldwide. One of the most harmful air pollutants is particulate matter (PM), which has different physical characteristics (particle size and number, surface area and morphology) and a highly complex and variable chemical composition. Our goal was first to comparatively assess the effects of exposure to PM regarding cytotoxicity, release of pro-inflammatory mediators and gene expression in human bronchial epithelia (HBE) reflecting normal and compromised health status. Second, we aimed at evaluating the impact of various PM components from anthropogenic and biogenic sources on the cellular responses. Air-liquid interface (ALI) cultures of fully differentiated HBE derived from normal and cystic fibrosis (CF) donor lungs were exposed at the apical cell surface to water-soluble PM filter extracts for 4 h. The particle dose deposited on cells was 0.9-2.5 and 8.8-25.4 µg per cm2 of cell culture area for low and high PM doses, respectively. Both normal and CF HBE show a clear dose-response relationship with increasing cytotoxicity at higher PM concentrations. The concurrently enhanced release of pro-inflammatory mediators at higher PM exposure levels links cytotoxicity to inflammatory processes. Further, the PM exposure deregulates genes involved in oxidative stress and inflammatory pathways leading to an imbalance of the antioxidant system. Moreover, we identify compromised defense against PM in CF epithelia promoting exacerbation and aggravation of disease. We also demonstrate that the adverse health outcome induced by PM exposure in normal and particularly in susceptible bronchial epithelia is magnified by anthropogenic PM components. Thus, including health-relevant PM components in regulatory guidelines will result in substantial human health benefits and improve protection of the vulnerable population.

Substantial brown carbon emissions from wintertime residential wood burning over France.

Brown carbon (BrC) is known to absorb light at subvisible wavelengths but its optical properties and sources are still poorly documented, leading to large uncertainties in climate studies. Here, we show its major wintertime contribution to total aerosol absorption at 370 nm (18-42%) at 9 different French sites. Moreover, an excellent correlation with levoglucosan (r2 = 0.9 and slope = 22.2 at 370 nm), suggesting important contribution of wood burning emissions to ambient BrC aerosols in France. At all sites, BrC peaks were mainly observed during late evening, linking to local intense residential wood burning during this time period. Furthermore, the geographic origin analysis also highlighted the high potential contribution of local and/or small-regional emissions to BrC. Focusing on the Paris region, twice higher BrC mass absorption efficiency value was obtained for less oxidized biomass burning organic aerosols (BBOA) compared to more oxidized BBOA (e.g., about 4.9 ± 0.2 vs. 2.0 ± 0.1 m2 g-1, respectively, at 370 nm). Finally, the BBOA direct radiative effect was found to be 40% higher when these two BBOA fractions are treated as light-absorbing species, compared to the non-absorbing BBOA scenario.

Variability of the Atmospheric PM10 Microbiome in Three Climatic Regions of France.

Primary Biogenic Organic Aerosols (PBOA) were recently shown to be produced by only a few types of microorganisms, emitted by the surrounding vegetation in the case of a regionally homogeneous field site. This study presents the first comprehensive description of the structure and main sources of airborne microbial communities associated with temporal trends in Sugar Compounds (SC) concentrations of PM10 in 3 sites under a climatic gradient in France. By combining sugar chemistry and DNA Metabarcoding approaches, we intended to identify PM10-associated microbial communities and their main sources at three sampling-sites in France, under different climates, during the summer of 2018. This study accounted also for the interannual variability in summer airborne microbial community structure (bacteria and fungi only) associated with PM10-SC concentrations during a 2 consecutive years' survey at one site. Our results showed that temporal changes in PM10-SC in the three sites are associated with the abundance of only a few specific taxa of airborne fungi and bacterial. These taxa differ significantly between the 3 climatic regions studied. The microbial communities structure associated with SC concentrations of PM10 during a consecutive 2-year study remained stable in the rural area. Atmospheric concentration levels of PM10-SC species varied significantly between the 3 study sites, but with no clear difference according to site typology (rural vs. urban), suggesting that SC emissions are related to regional rather than local climatic characteristics. The overall microbial beta diversity in PM10 samples is significantly different from that of the main vegetation around the urban sites studied. This indicates that the airborne microorganisms at these urban sites are not solely from the immediate surrounding vegetation, which contrasts with observations at the scale of a regionally homogeneous rural site in 2017. These results improve our understanding of the spatial behavior of tracers of PBOA emission sources, which need to be better characterized to further implement this important mass fraction of Organic Matter (OM) in Chemical Transport models (CTM).

Source apportionment of fine particulate matter in a Middle Eastern Metropolis, Tehran-Iran, using PMF with organic and inorganic markers.

With over 8 million inhabitants and 4 million motor vehicles on the streets, Tehran is one of the most crowded and polluted cities in the Middle East. Frequent exceedances of national daily PM2.5 limit have been reported in this city during the last decade, yet, the chemical composition and sources of fine particles are poorly determined. In the present study, 24-hour PM2.5 samples were collected at two urban sites during two separate campaigns, a one-year period from 2014 to 2015 and another three-month period at the beginning of 2017. Concentrations of organic carbon (OC), elemental carbon (EC), inorganic ions, trace metals and specific organic molecular markers were measured by chemical analysis of filter samples. The dominant mass components were organic matter (OM), sulfate and EC. With a 20% water-soluble organic carbon (WSOC) fraction, the predominance of primary anthropogenic sources (i.e. fossil fuel combustion) was anticipated. A positive matrix factorization (PMF) analysis using the ME-2 (Multilinear Engine-2) solver was then applied to this dataset. 5 factors were identified by Marker-PMF, named as traffic exhaust (TE), biomass burning (BB), industries (Ind.), nitrate-rich and sulfate-rich. Another 4 factors were identified by Metal-PMF, including, dust, vehicles (traffic non-exhaust, TNE), industries (Ind.) and heavy fuel combustion (HFC). Traffic exhaust was the dominant source with 44.5% contribution to total quantified PM2.5 mass. Sulfate-rich (24.2%) and nitrate-rich (18.4%) factors were the next major contributing sources. Dust (4.4%) and biomass burning (6.7%) also had small contributions while the total share of all other factors was < 2%. Investigating the correlations of different factors between the two sampling sites showed that traffic emissions and biomass burning were local, whereas dust, heavy fuel combustion and industrial sources were regional. Results of this study indicate that gas- and particle-phase pollutants emitted from fossil fuel combustion (mobile and stationary) are the principal origin of both primary and secondary fine aerosols in Tehran.

Methods to Investigate the Global Atmospheric Microbiome.

The interplay between microbes and atmospheric physical and chemical conditions is an open field of research that can only be fully addressed using multidisciplinary approaches. The lack of coordinated efforts to gather data at representative temporal and spatial scales limits aerobiology to help understand large scale patterns of global microbial biodiversity and its causal relationships with the environmental context. This paper presents the sampling strategy and analytical protocols developed in order to integrate different fields of research such as microbiology, -omics biology, atmospheric chemistry, physics and meteorology to characterize atmospheric microbial life. These include control of chemical and microbial contaminations from sampling to analysis and identification of experimental procedures for characterizing airborne microbial biodiversity and its functioning from the atmospheric samples collected at remote sites from low cell density environments. We used high-volume sampling strategy to address both chemical and microbial composition of the atmosphere, because it can help overcome low aerosol and microbial cell concentrations. To account for contaminations, exposed and unexposed control filters were processed along with the samples. We present a method that allows for the extraction of chemical and biological data from the same quartz filters. We tested different sampling times, extraction kits and methods to optimize DNA yield from filters. Based on our results, we recommend supplementary sterilization steps to reduce filter contamination induced by handling and transport. These include manipulation under laminar flow hoods and UV sterilization. In terms of DNA extraction, we recommend a vortex step and a heating step to reduce binding to the quartz fibers of the filters. These steps have led to a 10-fold increase in DNA yield, allowing for downstream omics analysis of air samples. Based on our results, our method can be integrated into pre-existing long-term monitoring field protocols for the atmosphere both in terms of atmospheric chemistry and biology. We recommend using standardized air volumes and to develop standard operating protocols for field users to better control the operational quality.

Aniline-based catalysts as promising tools to improve analysis of carbonyl compounds through derivatization techniques: preliminary results using dansylacetamidooxyamine derivatization and LC-fluorescence.

Derivatization techniques based on α-effect amines and H+ catalysis are commonly used for the measurement of carbonyl compounds (CCs), whether in environmental, food, or biological samples. Here, we investigated the potential of aniline-based catalysts to improve derivatization rates of selected carbonyls by using dansylacetamidooxyamine (DNSAOA) as a reagent. Kinetic experiments were performed in aqueous solutions by varying catalyst and CC concentrations and delivered insights into the reaction mechanism. Using anilinium acetate (AnAc), rate constants varied linearly with the catalyst concentration with rate enhancements toward H+-catalyzed reactions as high as ca. 90 and 200 for acetone and benzaldehyde, respectively. Owing to contamination problems when using AnAc, anilinium chloride (AnCl) was chosen for the optimized analysis of real samples at low concentration. Rate enhancements for derivatization reaction of 4.4 (methylglyoxal), 6.0 (glyoxal), 12 (acetone), 20 (formaldehyde), and 47 (hydroxyacetaldehyde) were obtained using 0.1 M AnCl. The optimized method was successfully applied to the determination of the above compounds in natural snow and meltwater samples. Limits of detection (LODs) and limits of quantification (LOQs) were in the 2-14 and 7-41 nM range, respectively, i.e., low enough to allow for the analysis of most natural samples. Satisfactory relative recoveries (92.8 ± 3.8-118.3 ± 4.4%) and intra-day precision (2.7-11.3%) were achieved. Finally, we think that this approach could be applied not only to every α-effect nitrogen reagent-with the most evident profit of lowering derivatization times and particularly those required for low-reactive ketones-but also to the derivatization of CCs onto coated solid sorbents.

Speciation of organic fraction does matter for source apportionment. Part 1: A one-year campaign in Grenoble (France).

PM10 source apportionment was performed by positive matrix factorization (PMF) using specific primary and secondary organic molecular markers on samples collected over a one year period (2013) at an urban station in Grenoble (France). The results provided a 9-factor optimum solution, including sources rarely apportioned in the literature, such as two types of primary biogenic organic aerosols (fungal spores and plant debris), as well as specific biogenic and anthropogenic secondary organic aerosols (SOA). These sources were identified thanks to the use of key organic markers, namely, polyols, odd number higher alkanes, and several SOA markers related to the oxidation of isoprene, α-pinene, toluene and polycyclic aromatic hydrocarbons (PAHs). Primary and secondary biogenic contributions together accounted for at least 68% of the total organic carbon (OC) in the summer, while anthropogenic primary and secondary sources represented at least 71% of OC during wintertime. A very significant contribution of anthropogenic SOA was estimated in the winter during an intense PM pollution event (PM10>50µgm-3 for several days; 18% of PM10 and 42% of OC). Specific meteorological conditions with a stagnation of pollutants over 10days and possibly Fenton-like chemistry and self-amplification cycle of SOA formation could explain such high anthropogenic SOA concentrations during this period. Finally, PMF outputs were also used to investigate the origins of humic-like substances (HuLiS), which represented 16% of OC on an annual average basis. The results indicated that HuLiS were mainly associated with biomass burning (22%), secondary inorganic (22%), mineral dust (15%) and biogenic SOA (14%) factors. This study is probably the first to state that HuLiS are significantly associated with mineral dust.

The importance of simulated lung fluid (SLF) extractions for a more relevant evaluation of the oxidative potential of particulate matter.

Particulate matter (PM) induces oxidative stress in vivo, leading to adverse health effects. Oxidative potential (OP) of PM is increasingly studied as a relevant metric for health impact (instead of PM mass concentration) as much of the ambient particle mass do not contribute to PM toxicity. Several assays have been developed to quantify PM oxidative potential and a widely used one is the acellular dithiothreitol (DTT) assay. However in such assays, particles are usually extracted with methanol or Milli-Q water which is unrepresentative of physiological conditions. For this purpose, OPDTT measurements after simulated lung fluids (SLF) extraction, in order to look at the impact of simulated lung fluid constituents, were compared to Milli-Q water extraction measurements. Our major finding is a significant decrease of the OPDTT when the artificial lysosomal fluid (ALF) solution was used. Indeed, ligand compounds are present in the SLF solutions and some induce a decrease of the OP when compared to water extraction. Our results suggest that the effect of ligands and complexation in lining fluids towards PM contaminants probably has been underestimated and should be investigated further.