Snow scavenging and phase partitioning of nitrated and oxygenated aromatic hydrocarbons in polluted and remote environments in central Europe and the European Arctic

Nitrated and oxygenated polycyclic aromatic hydrocarbons (N/OPAHs) are emitted in combustion processes and formed in polluted air. Their environmental cycling through wet deposition has hardly been studied. Fresh snow samples at urban and rural sites in central Europe, as well as surface snow from a remote site in Svalbard, were analysed for 17 NPAHs, 8 OPAHs, and 11 nitrated mono-aromatic hydrocarbons (NMAHs), of which most N/OPAHs as well as nitrocatechols, nitrosalicylic acids, and 4-nitroguaiacol are studied for the first time in precipitation. In order to better understand the scavenging mechanisms, the particulate mass fractions (θ) at 273&thinsp;K were predicted using a multi-phase gas-particle partitioning model based on polyparameter linear free energy relationships.  ∑NPAH concentrations were 1.2&ndash;17.6 and 8.8–19.1&thinsp;ng&thinsp;L&minus;1 at urban and rural sites, whereas  ∑OPAHs were 79.8&ndash;955.2 and 343.3&ndash;1757.4&thinsp;ng&thinsp;L−1 at these sites, respectively. 9,10-anthraquinone was predominant in snow aqueous and particulate phases. NPAHs were only found in the particulate phase with 9-nitroanthracene being predominant followed by 2-nitrofluoranthene. Among NMAHs, 4-nitrophenol showed the highest abundance in both phases. The levels found for nitrophenols were in the same range or lower than those reported in the 1980s and 1990s. The lowest levels of  ∑ N/OPAHs and  ∑ NMAHs were found at the remote site (3.5 and 390.5&thinsp;ng&thinsp;L&minus;1, respectively). N/OPAHs preferentially partitioned in snow particulate phase in accordance with predicted θ, whereas NMAHs were predominant in the aqueous phase, regardless of θ. It is concluded that the phase distribution of non-polar N/OPAHs in snow is determined by their gas-particle partitioning prior to snow scavenging, whereas that for polar particulate phase substances, i.e. NMAHs, is determined by an interplay between gas-particle partitioning in the aerosol and dissolution during in- or below-cloud scavenging.</p

Revolatilisation of soil-accumulated pollutants triggered by the summer monsoon in India

Persistent organic pollutants that have accumulated in soils can be remobilised by volatilisation in response to chemical equilibrium with the atmosphere. Clean air masses from the Indian Ocean, advected with the onset of the summer monsoon, are found to reduce concentrations of hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives, endosulfan and polychlorinated biphenyls (PCBs) in air at a mountain site (all in the range 5–20&thinsp;pg&thinsp;m−3) by 77&thinsp;%, 70&thinsp;%, 82&thinsp;% and 45&thinsp;%, respectively. The analysis of fugacities in soil and air suggest that the arrival of summer monsoon triggers net volatilisation or enhances ongoing revolatilisation of the now-banned chemicals HCH and PCBs from background soils in southern India. The response of the air–soil exchange was modelled using a regional air pollution model, WRF-Chem PAH/POP. The results suggest that the air is increasingly polluted during transport by the south-westerly monsoon winds across the subcontinent. Using a multidecadal multimedia mass balance model, it is found that air–surface exchange of HCH and DDT have declined since the ban of these substances from agriculture, but remobilisation of higher chlorinated PCBs may have reached a historical high, 40 years after peak emission.</p

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides in background air in central Europe - investigating parameters affecting wet scavenging of polycyclic aromatic hydrocarbons

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides (CPs) were measured in air and precipitation at a background site in central Europe. Sigma PAH concentrations in air and rainwater ranged from 0.7 to 327.9 ng m(-3) and below limit of quantification (< LOQ) to 2.1 x 10(3) ng L-1. The concentrations of PCBs and CPs in rainwater were < LOQ. Sigma PCB and Sigma CP concentrations in air ranged from < LOQ to 44.6 and < LOQ to 351.7 pg m(-3), respectively. The potential relationships between PAH wet scavenging and particulate matter and rainwater properties were investigated. The concentrations of ionic species in particulate matter and rainwater were significantly correlated, highlighting the importance of particle scavenging process. Overall, higher scavenging efficiencies were found for relatively less volatile PAHs, underlining the effect of analyte gas-particle partitioning on scavenging process. The particulate matter removal by rain, and consequently PAH wet scavenging, was more effective when the concentrations of ionic species were high. In addition, the elemental and organic carbon contents of the particulate matter were found to influence the PAH scavenging

Composition and mass size distribution of nitrated and oxygenated aromatic compounds in ambient particulate matter from southern and central Europe - implications for the origin

Nitro-monoaromatic hydrocarbons (NMAHs), such as nitrocatechols, nitrophenols and nitrosalicylic acids, are important constituents of atmospheric particulate matter (PM) water-soluble organic carbon (WSOC) and humic-like substances (HULIS). Nitrated and oxygenated derivatives of polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are toxic and ubiquitous in the ambient air; due to their light absorption properties, together with NMAHs, they are part of aerosol brown carbon (BrC). We investigated the winter concentrations of these substance classes in size-resolved PM from two urban sites in central and southern Europe, i.e. Mainz (MZ), Germany, and Thessaloniki (TK), Greece. The total concentration of 11 NMAHs (∑11NMAH concentrations) measured in PM10 and total PM were 0.51-8.38 and 12.1-72.1 ng m-3 at the MZ and TK sites, respectively, whereas ∑7OPAHs were 47-1636 and 858-4306 pg m-3, and ∑8NPAHs were -3, respectively. NMAHs contributed 0.4% and 1.8% to the HULIS mass at MZ and TK, respectively. The mass size distributions of the individual substances generally peaked in the smallest or second smallest size fraction i.e. < 0.49 or 0.49-0.95 µm. The mass median diameter (MMD) of NMAHs was 0.10 and 0.27 µm at MZ and TK, respectively, while the MMDs of NPAHs and OPAHs were both 0.06 mu m at MZ and 0.12 and 0.10 µm at TK. Correlation analysis between NMAHs, NPAHs, and OPAHs from one side and WSOC, HULIS, sulfate, and potassium from the other suggested that fresh biomass burning (BB) and fossil fuel combustion emissions dominated at the TK site, while aged air masses were predominant at the MZ site

Nitro-polycyclic aromatic hydrocarbons - gas-particle partitioning, mass size distribution, and formation along transport in marine and continental background air

Nitro-polycyclic aromatic hydrocarbons (NPAH) are ubiquitous in polluted air but little is known about their abundance in background air. NPAHs were studied at one marine and one continental background site, i.e. a coastal site in the southern Aegean Sea (summer 2012) and a site in the central Great Hungarian Plain (summer 2013), together with the parent compounds, PAHs. A Lagrangian particle dispersion model was used to track air mass history. Based on Lagrangian particle statistics, the urban influence on samples was quantified for the first time as a fractional dose to which the collected volume of air had been exposed. At the remote marine site, the 3–4-ring NPAH (sum of 11 targeted species) concentration was 23.7 pg m−3 while the concentration of 4-ring PAHs (6 species) was 426 pg m−3. The most abundant NPAHs were 2-nitrofluoranthene (2NFLT) and 3-nitrophenanthrene. Urban fractional doses in the range of < 0.002–5.4 % were calculated. At the continental site, the Σ11 3–4-ring NPAH and Σ6 4-ring PAH were 58 and 663 pg m−3, respectively, with 9-nitroanthracene and 2NFLT being the most concentrated amongst the targeted NPAHs. The NPAH levels observed in the marine background air are the lowest ever reported and remarkably lower, by more than 1 order of magnitude, than 1 decade before. Day–night variation of NPAHs at the continental site reflected shorter lifetime during the day, possibly because of photolysis of some NPAHs. The yields of formation of 2NFLT and 2-nitropyrene (2NPYR) in marine air seem to be close to the yields for OH-initiated photochemistry observed in laboratory experiments under high NOx conditions. Good agreement is found for the prediction of NPAH gas–particle partitioning using a multi-phase poly-parameter linear free-energy relationship. Sorption to soot is found to be less significant for gas–particle partitioning of NPAHs than for PAHs. The NPAH levels determined in the south-eastern outflow of Europe confirm intercontinental transport potential

Evaluation of models for gas-particle partitioning of nitro- and oxy-aromatic hydrocarbons

Gas-particle partitioning is an important mechanism affecting the transport and fate of semi-volatile organic compounds (SOCs). The preferential partitioning of SOCs in the atmosphere depends on parameters such as the compound’s molecular structure as well as particulate matter physical and chemical properties. This can be explained by various empirical and theoretical models based on single- or poly-parameter linear free energy relationship (ppLFER). To explain the SOC partitioning, each model considers one or more of the compound’s physico-chemical properties or particulate matter characteristics. Despite the past efforts in determining the most appropriate model, discrepancies remain between the model prediction and observation because some models neglect certain intermolecular interactions. The aim of the present research was to apply a dual-phase as well as a multi-phase ppLFER model to predict gas-particle partitioning of nitro- and oxy- aromatic hydrocarbons. To this end, air samples (gas and particulate phase) were collected from urban and non-urban sites in Germany, France, and India. The poster will present the model predictions versus observations, and discuss their structural differences in details

One-year measurements of secondary organic aerosol (SOA) markers in the Paris region (France): Concentrations, gas/particle partitioning and SOA source apportionment

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Evaluation of a conceptual model for gas-particle partitioning of polycyclic aromatic hydrocarbons using polyparameter linear free energy relationships

A model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35–0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03–1.40 and 0.94–1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected