Altitudinal and Chiral Signature of Persistent Organochlorine Pesticides in Air, Soil, and Spruce Needles (<i>Picea abies</i>) of the Alps

The present study investigated the distribution, transportation, and biodegradation of the selected chiral persistent organochlorine pesticides (OCP) in the Alps. In the complex environment, we found the movement and fate of OCP could be defined by many factors. Taking HCE as an example, below the timberline its accumulation from air into SPMD increased with altitude and seasonally changed, but the trends reversed above the timberline. In soil, the tendency of HCE concentrations vs organic materials followed a sigmoid curve, and HCE concentration-altitude correlations are positive in central Alps but negative in southern Alps. The HCE enantiomeric ratios (ERs) in soil correlated to HCE isomers concentrations, the humus pH values, and the sampling site altitudes. HCE shift from humus to mineral soil can also be traced by ERs. The altitudinal and longitudinal trends in needles suggested that α-HCH has a more complex movement than HCE in Alps. In conclusion, altitude conducted condensation, plant canopies, organic material in soil, and geographic specific precipitations may affect OCP distributions and transportation, whereas altitude conducted temperature and soil pH could dictate their fate in the environment

Chemical Fingerprinting of Biomass Burning Organic Aerosols from Sugar Cane Combustion: Complementary Findings from Field and Laboratory Studies

Agricultural fires are a major source of biomass-burning organic aerosols (BBOAs) with impacts on health, the environment, and climate. In this study, globally relevant BBOA emissions from the combustion of sugar cane in both field and laboratory experiments were analyzed using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry. The derived chemical fingerprints of fresh emissions were evaluated using targeted and nontargeted evaluation approaches. The open-field sugar cane burning experiments revealed the high chemical complexity of combustion emissions, including compounds derived from the pyrolysis of (hemi)cellulose, lignin, and further biomass, such as pyridine and oxime derivatives, methoxyphenols, and methoxybenzenes, as well as triterpenoids. In comparison, laboratory experiments could only partially model the complexity of real combustion events. Our results showed high variability between the conducted field and laboratory experiments, which we, among others, discuss in terms of differences in combustion conditions, fuel composition, and atmospheric processing. We conclude that both field and laboratory studies have their merits and should be applied complementarily. While field studies under real-world conditions are essential to assess the general impact on air quality, climate, and environment, laboratory studies are better suited to investigate specific emissions of different biomass types under controlled conditions

Photochemical Aging Induces Changes in the Effective Densities, Morphologies, and Optical Properties of Combustion Aerosol Particles

Effective density (ρeff) is an important property describing particle transportation in the atmosphere and in the human respiratory tract. In this study, the particle size dependency of ρeff was determined for fresh and photochemically aged particles from residential combustion of wood logs and brown coal, as well as from an aerosol standard (CAST) burner. ρeff increased considerably due to photochemical aging, especially for soot agglomerates larger than 100 nm in mobility diameter. The increase depends on the presence of condensable vapors and agglomerate size and can be explained by collapsing of chain-like agglomerates and filling of their voids and formation of secondary coating. The measured and modeled particle optical properties suggest that while light absorption, scattering, and the single-scattering albedo of soot particle increase during photochemical processing, their radiative forcing remains positive until the amount of nonabsorbing coating exceeds approximately 90% of the particle mass

Effective Density and Morphology of Particles Emitted from Small-Scale Combustion of Various Wood Fuels

The effective density of fine particles emitted from small-scale wood combustion of various fuels were determined with a system consisting of an aerosol particle mass analyzer and a scanning mobility particle sizer (APM-SMPS). A novel sampling chamber was combined to the system to enable measurements of highly fluctuating combustion processes. In addition, mass-mobility exponents (relates mass and mobility size) were determined from the density data to describe the shape of the particles. Particle size, type of fuel, combustion phase, and combustion conditions were found to have an effect on the effective density and the particle shape. For example, steady combustion phase produced agglomerates with effective density of roughly 1 g cm^–3 for small particles, decreasing to 0.25 g cm^–3 for 400 nm particles. The effective density was higher for particles emitted from glowing embers phase (ca. 1–2 g cm^–3), and a clear size dependency was not observed as the particles were nearly spherical in shape. This study shows that a single value cannot be used for the effective density of particles emitted from wood combustion

Photochemical Aging Induces Changes in the Effective Densities, Morphologies, and Optical Properties of Combustion Aerosol Particles

Effective density (ρeff) is an important property describing particle transportation in the atmosphere and in the human respiratory tract. In this study, the particle size dependency of ρeff was determined for fresh and photochemically aged particles from residential combustion of wood logs and brown coal, as well as from an aerosol standard (CAST) burner. ρeff increased considerably due to photochemical aging, especially for soot agglomerates larger than 100 nm in mobility diameter. The increase depends on the presence of condensable vapors and agglomerate size and can be explained by collapsing of chain-like agglomerates and filling of their voids and formation of secondary coating. The measured and modeled particle optical properties suggest that while light absorption, scattering, and the single-scattering albedo of soot particle increase during photochemical processing, their radiative forcing remains positive until the amount of nonabsorbing coating exceeds approximately 90% of the particle mass

On the Complementarity and Informative Value of Different Electron Ionization Mass Spectrometric Techniques for the Chemical Analysis of Secondary Organic Aerosols

The atmospheric aging of volatile organic compounds leads to the formation of complex mixtures of highly oxidized secondary organic aerosols (SOAs). State-of-the-art mass spectrometry (MS) has become a pivotal tool for their chemical characterization. In this study, we characterized the chemical complexity of naphthalene-derived SOA by three different time-of-flight (TOF) mass spectrometric techniques applying electron ionization: high-resolution–TOF–aerosol MS (AMS), direct inlet probe (DIP)–high-resolution TOFMS, and thermal desorptioncomprehensive two-dimensional gas chromatographyTOFMS (GC × GC). We discuss AMS as an online, DIP as an atline, and GC × GC as an offline technique to compare their informative value for studying the oxidation state, volatility, and molecular composition of laboratory-generated SOA. For GC × GC, the accessible organic content was limited to (semi-)­volatile compounds and supported a reliable assignment of the molecular composition. DIP and AMS were used to derive secondary parameters such as O/C and H/C ratios, the general functionality of the compound classes and their abundance upon photochemical aging. Thereby, while the induced pyrolysis in the AMS extended the accessibility range to polar, high-molecular-weight compounds, thermal fragmentation also led to limited molecular information. For DIP, low-volatility compounds could be volatilized and the high mass resolution was useful to resolve isobaric mass fragments and assign reliable sum formulas of fragments and molecular ions. Although no single technique can provide information to describe the full chemical complexity of the SOA, AMS, DIP, and GC × GC in their complementarity are well suited to investigate the impact of SOA on health and environment

Summary of the main HFO- and DF-particle exposure effects.

<p>The arrows indicate the direction of regulation for cellular functions derived from the most statistically significant enriched Gene Ontology terms from the transcriptome, proteome, and metabolome (details in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>).</p><p>^x BEAS-2B up, A549 down</p><p>* BEAS-2B down, A549 up</p><p>Summary of the main HFO- and DF-particle exposure effects.</p

Experimental set-up and global omics analyses.

<p>(A) An 80 KW common-rail-ship diesel engine was operated with heavy fuel oil (HFO) or refined diesel fuel (DF). The exhaust aerosols were diluted and cooled with clean air. On-line real-time mass spectrometry, particle-sizing, sensor IR-spectrometry and other techniques were used to characterise the chemical composition and physical properties of the particles and gas phase. Filter sampling of the particulate matter (PM) was performed to further characterise the PM composition. Lung cells were synchronously exposed at the air-liquid-interface (ALI) to aerosol or particle-filtered aerosol as a reference. The cellular responses were characterised in triplicate at the transcriptome (BEAS-2B), proteome and metabolome (A549) levels with stable isotope labelling (SILAC and ¹³C₆-glucose). (B) Heatmap showing the global regulation of the transcriptome, proteome and metabolome.</p

Chemical and physical aerosol characterisation.

<p>(A) The ship diesel engine was operated for 4 h in accordance with the IMO-test cycle. (B) Approximately 28 ng/cm² and 56 ng/cm² were delivered to the cells from DF and HFO, respectively, with different size distributions. The HFO predominantly contained particles <50 nm, and the DF predominantly contained particles >200 nm, both in mass and number. (C) Number of chemical species in the EA particles. (D) Transmission electron microscope (TEM) images and energy-dispersive X-ray (EDX) spectra of DF-EA and HFO-EA; heavy elements (black speckles, arrow); and contributions of the elements V, P, Fe and Ni in the HFO particles using EDX (* = grid-material). (E) Exemplary EA concentrations (right) and concentration ratios (left) for particulate matter-bound species. For all experiments, n = 3.</p

Effects of shipping particles on lung cells.

<p>The net effects from the particles were referenced against the gaseous phase of the emissions. (A) Number of the regulated components in the transcriptome shows more genes regulated by the DF than the HFO particles (in BEAS-2B cells). Similar results were observed for the proteome (B) and metabolome (C) (in A549 cells). (D) Meta-analyses for the transcriptome and proteome using the combined Gene Ontology (GO) term analysis of the 10% most regulated transcripts and proteins. Individual GO terms are listed in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>; the hierarchical pathways are indicated on the right. (E) Gene regulation of Wiki-pathway bioactivation; (F) gene regulation of Wiki-pathway inflammation; g, secreted metabolites; and h, metabolic flux measurements using ¹³C-labelled glucose. For all experiments, n = 3.</p