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1.
Online chemical characterization and sources of submicron aerosol in the major mediterranean port city of Piraeus, Greece
Iasonas Stavroulas, Georgios Grivas, Eleni Liakakou, Panayiotis Kalkavouras, Aikaterini Bougiatioti, Dimitris G. Kaskaoutis, Maria Lianou, Kyriaki Papoutsidaki, M. Tsagkaraki, Evangelos Gerasopoulos, Pavlos Zarmpas, Nikolaos Mihalopoulos, 2021, original scientific article

Abstract: Port cities are affected by a wide array of emissions, including those from the shipping, road transport, and residential sectors; therefore, the characterization and apportionment of such sources in a high temporal resolution is crucial. This study presents measurements of fine aerosol chemical composition in Piraeus, one of the largest European ports, during two monthly periods (winter vs. summer) in 2018–2019, using online instrumentation (Aerosol Chemical Speciation Monitor—ACSM, 7-λ aethalometer). PMF source apportionment was performed on the ACSM mass spectra to quantify organic aerosol (OA) components, while equivalent black carbon (BC) was decomposed to its fossil fuel combustion and biomass burning (BB) fractions. The combined traffic, shipping and, especially, residential emissions led to considerably elevated submicron aerosol levels (22.8 μg m−3) in winter, which frequently became episodic late at night under stagnant conditions. Carbonaceous compounds comprised the major portion of this submicron aerosol in winter, with mean OA and BC contributions of 61% (13.9 μg m−3) and 16% (3.7 μg m−3), respectively. The contribution of BB to BC concentrations was considerable and spatially uniform. OA related to BB emissions (fresh and processed) and hydrocarbon-like OA (from vehicular traffic and port-related fossil fuel emissions including shipping) accounted for 37% and 30% of OA, respectively. In summer, the average PM1 concentration was significantly lower (14.8 μg m−3) and less variable, especially for the components associated with secondary aerosols (such as OA and sulfate). The effect of the port sector was evident in summer and maintained BC concentrations at high levels (2.8 μg m−3), despite the absence of BB and improved atmospheric dispersion. Oxygenated components yielded over 70% of OA in summer, with the more oxidized secondary component of regional origin being dominant (41%) despite the intensity of local sources, in the Piraeus environment. In general, with respect to local sources that can be the target of mitigation policies, this work highlights the importance of port-related activities but also reveals the extensive wintertime impact of residential wood burning. While a separation of the BB source is feasible, more research is needed on how to disentangle the short-term effects of different fossil-fuel combustion sources.
Keywords: Athens, harbor, shipping emissions, PM1, chemical speciation, organic aerosol, black carbon, ACSM, aethalometer, PMF
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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2.
Absorption enhancement of black carbon particles in a Mediterranean city and countryside : effect of particulate matter chemistry, ageing and trend analysis
Jesús Yus-Díez, Marta Via, Andrés Alastuey, Angeliki Karanasiou, Maria Cruz Minguillon, Noemí Perez, Xavier Querol, Cristina Reche, Matic Ivančič, Martin Rigler, 2022, original scientific article

Abstract: Abstract. Black carbon (BC) is recognized as the most important warming agent among atmospheric aerosol particles. The absorption efficiency of pure BC is rather well-known, nevertheless the mixing of BC with other aerosol particles can enhance the BC light absorption efficiency, thus directly affecting Earth's radiative balance. The effects on climate of the BC absorption enhancement due to the mixing with these aerosols are not yet well constrained because these effects depend on the availability of material for mixing with BC, thus creating regional variations. Here we present the mass absorption cross-section (MAC) and absorption enhancement of BC particles (Eabs), at different wavelengths (from 370 to 880 nm for online measurements and at 637 nm for offline measurements) measured at two sites in the western Mediterranean, namely Barcelona (BCN; urban background) and Montseny (MSY; regional background). The Eabs values ranged between 1.24 and 1.51 at the urban station, depending on the season and wavelength used as well as on the pure BC MAC used as a reference. The largest contribution to Eabs was due to the internal mixing of BC particles with other aerosol compounds, on average between a 91 % and a 100 % at 370 and 880 nm, respectively. Additionally, 14.5 % and 4.6 % of the total enhancement at the short ultraviolet (UV) wavelength (370 nm) was due to externally mixed brown carbon (BrC) particles during the cold and the warm period, respectively. On average, at the MSY station, a higher Eabs value was observed (1.83 at 637 nm) compared to BCN (1.37 at 637 nm), which was associated with the higher fraction of organic aerosols (OA) available for BC coating at the regional station, as denoted by the higher organic carbon to elemental carbon (OC:EC) ratio observed at MSY compared to BCN. At both BCN and MSY, Eabs showed an exponential increase with the amount of non-refractory (NR) material available for coating (RNR-PM). The Eabs at 637 nm at the MSY regional station reached values up to 3 during episodes with high RNR-PM, whereas in BCN, Eabs kept values lower than 2 due to the lower relative amount of coating materials measured at BCN compared to MSY. The main sources of OA influencing Eabs throughout the year were hydrocarbon OA (HOA) and cooking-related OA (COA), i.e. primary OA (POA) from traffic and cooking emissions, respectively, at both 370 and 880 nm. At the short UV wavelength (370 nm), a strong contribution to Eabs from biomass burning OA (BBOA) and less oxidized oxygenated OA (LO-OOA) sources was observed in the colder period. Moreover, we found an increase of Eabs with the ageing state of the particles, especially during the colder period. This increase of Eabs with particle ageing was associated with a larger relative amount of secondary OA (SOA) compared to POA. The availability of a long dataset at both stations from offline measurements enabled a decade-long trend analysis of Eabs at 637 nm, that showed statistically significant (s.s.) positive trends of Eabs during the warmer months at the MSY station. This s.s. positive trend in MSY mirrored the observed increase of the OC:EC ratio over time. Moreover, in BCN during the COVID-19 lockdown period in spring 2020 we observed a sharp increase of Eabs due to the observed sharp increase of the OC:EC ratio. Our results show similar values of Eabs to those found in the literature for similar background stations.
Keywords: black carbomn, coating, organic aerosol, light absorption
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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3.
Development and evaluation of an improved offline aerosol mass spectrometry technique
Christina Vasilakopoulou, Kalliopi Florou, Christos Kaltsonoudis, Iasonas Stavroulas, Nikolaos Mihalopoulos, Spyros N. Pandis, 2023, original scientific article

Abstract: Abstract. The offline aerosol mass spectrometry technique is a useful tool for the source apportionment of organic aerosol (OA) in areas and periods during which an aerosol mass spectrometer (AMS) is not available. However, the technique is based on the extraction of aerosol samples in water, while several atmospheric OA components are partially or fully insoluble in water. In this work an improved offline technique was developed and evaluated in an effort to capture most of the partially soluble and insoluble organic aerosol material, reducing significantly the uncertainty of the corresponding source apportionment. A major advantage of the proposed approach is that no corrections are needed for the offline analysis to account for the limited water solubility of some OA components. The improved offline AMS analysis was tested in three campaigns: two during winter and one during summer. Collocated online AMS measurements were performed for the evaluation of the offline method. Source apportionment analysis was performed separately for the online and the offline measurements using positive matrix factorization (PMF). The PMF results showed that the fractional contribution of each factor to the total OA differed between the online and the offline PMF results by less than 15 %. The differences in the AMS spectra of the factors of the two approaches could be significant, suggesting that the use of factor profiles from the literature in the offline analysis may lead to complications. Part of the good agreement between the online and the offline PMF results is due to the ability of the improved offline AMS technique to capture a bigger part of the OA, including insoluble organic material. This was evident by the significant fraction of submicrometer suspended insoluble particles present in the water extract and by the reduced insoluble material on the filters after the extraction process. More than half of the elemental carbon (EC) was on average missing from the filters after the water extraction. Significant EC concentrations were measured in the produced aerosol that was used as input to the AMS during the offline analysis.
Keywords: organic aerosol, receptor modeling, offline PMF, Greece
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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4.
5.
The effect of the averaging period for PMF analysis of aerosol mass spectrometer measurements during offline applications
Christina Vasilakopoulou, Iasonas Stavroulas, Nikolaos Mihalopoulos, Spyros N. Pandis, 2022, original scientific article

Abstract: Offline aerosol mass spectrometer (AMS) measurements can provide valuable information about ambient organic aerosols in areas and periods in which online AMS measurements are not available. However, these offline measurements have a low temporal resolution, as they are based on filter samples usually collected over 24 h. In this study, we examine whether and how this low time resolution affects source apportionment results. We used a five-month period (November 2016–March 2017) of online measurements in Athens, Greece, and performed positive matrix factorization (PMF) analysis to both the original dataset, which consists of 30 min measurements, and to time averages from 1 up to 24 h. The 30 min results indicated that five factors were able to represent the ambient organic aerosol (OA): a biomass burning organic aerosol factor (BBOA), which contributed 16 % of the total OA; hydrocarbon-like OA (HOA) (29 %); cooking OA (COA) (20 %); more-oxygenated OA (MO-OOA) (18 %); and less-oxygenated OA (LO-OOA) (17 %). Use of the daily averages resulted in estimated average contributions that were within 8 % of the total OA compared with the high-resolution analysis for the five-month period. The most important difference was for the BBOA contribution, which was overestimated (25 % for low resolution versus 17 % for high resolution) when daily averages were used. The estimated secondary OA varied from 35 % to 28 % when the averaging interval varied between 30 min and 24 h. The high-resolution results are expected to be more accurate, both because they are based on much larger datasets and because they are based on additional information about the temporal source variability. The error for the low-resolution analysis was much higher for individual days, and its results for high-concentration days in particular are quite uncertain. The low-resolution analysis introduces errors in the determined AMS profiles for the BBOA and LO-OOA factors but determines the rest relatively accurately (theta angle around 10∘ or less).
Keywords: AMS, offline PMF, ACSM, organic aerosols
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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6.
Rolling vs. seasonal PMF : real-world multi-site and synthetic dataset comparison
Marta Via, Gang Chen, Francesco Canonaco, Kaspar Rudolf Daellenbach, Benjamin Chazeau, Hasna Chebaicheb, Jianhui Jiang, Hannes Keernik, Chunshui Lin, Nicolas Marchand, 2022, original scientific article

Abstract: Abstract. Particulate matter (PM) has become a major concern in terms of human health and climate impact. In particular, the source apportionment (SA) of organic aerosols (OA) present in submicron particles (PM1) has gained relevance as an atmospheric research field due to the diversity and complexity of its primary sources and secondary formation processes. Moreover, relatively simple but robust instruments such as the Aerosol Chemical Speciation Monitor (ACSM) are now widely available for the near-real-time online determination of the composition of the non-refractory PM1. One of the most used tools for SA purposes is the source-receptor positive matrix factorisation (PMF) model. Even though the recently developed rolling PMF technique has already been used for OA SA on ACSM datasets, no study has assessed its added value compared to the more common seasonal PMF method using a practical approach yet. In this paper, both techniques were applied to a synthetic dataset and to nine European ACSM datasets in order to spot the main output discrepancies between methods. The main advantage of the synthetic dataset approach was that the methods' outputs could be compared to the expected “true” values, i.e. the original synthetic dataset values. This approach revealed similar apportionment results amongst methods, although the rolling PMF profile's adaptability feature proved to be advantageous, as it generated output profiles that moved nearer to the truth points. Nevertheless, these results highlighted the impact of the profile anchor on the solution, as the use of a different anchor with respect to the truth led to significantly different results in both methods. In the multi-site study, while differences were generally not significant when considering year-long periods, their importance grew towards shorter time spans, as in intra-month or intra-day cycles. As far as correlation with external measurements is concerned, rolling PMF performed better than seasonal PMF globally for the ambient datasets investigated here, especially in periods between seasons. The results of this multi-site comparison coincide with the synthetic dataset in terms of rolling–seasonal similarity and rolling PMF reporting moderate improvements. Altogether, the results of this study provide solid evidence of the robustness of both methods and of the overall efficiency of the recently proposed rolling PMF approach.
Keywords: particulate matter, synthetic dataset comparison, source apportionment, organic aerosols
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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7.
Increase in secondary organic aerosol in an urban environment : Increase in secondary organic aerosol in an urban environment
Marta Via, Maria Cruz Minguillon, Cristina Reche, Xavier Querol, Andrés Alastuey, 2021, original scientific article

Abstract: The evolution of fine aerosol (PM1) species as well as the contribution of potential sources to the total organic aerosol (OA) at an urban background site in Barcelona, in the western Mediterranean basin (WMB) was investigated. For this purpose, a quadrupole aerosol chemical speciation monitor (Q-ACSM) was deployed to acquire real-time measurements for two 1-year periods: May 2014–May 2015 (period A) and September 2017–October 2018 (period B). Total PM1 concentrations showed a slight decrease (from 10.1 to 9.6 μgm�3 from A to B), although the relative contribution of inorganic and organic compounds varied significantly. Regarding inorganic compounds, SO42- , black carbon(BC) and NH4+ showed a significant decrease from period A to B (21 %, 18% and 9 %, respectively), whilst NO3- concentrations were higher in B (8 %). Source apportionment revealed OA contained 46% and 70% secondary OA (SOA) in periods A and B, respectively. Two secondary oxygenated OA sources (OOA) were differentiated by their oxidation status (i.e. ageing): less oxidized (LO-OOA) and more oxidized (MO-OOA). Disregarding winter periods, when LO-OOA production was not favoured, LO-OOA transformation into MO-OOA was found to be more effective in period B. The lowest LO-OOA-to-MO-OOA ratio, excluding winter, was in September–October 2018 (0.65), implying an accumulation of aged OA after the high temperature and solar radiation conditions in the summer season. In addition to temperature, SOA (sum of OOA factors) was enhanced by exposure to NOx-polluted ambient and other pollutants, especially to O3 and during afternoon hours. The anthropogenic primary OA sources identified, cooking-related OA (COA), hydrocarbon-like OA (HOA), and biomass burning OA (BBOA), decreased from period A to B in both absolute concentrations and relative contribution (as a whole, 44% and 30 %, respectively). However, their concentrations and proportion to OA grew rapidly during highly polluted episodes. The influence of certain atmospheric episodes on OA sources was also assessed. Both SOA factors were boosted with long- and medium-range circulations, especially those coming from inland Europe and the Mediterranean (triggering mainly MO-OOA) and summer breeze-driven regional circulation (mainly LO-OOA). In contrast, POA was enhanced either during air-renewal episodes or stagnation anticyclonic events.
Keywords: aerosol, organic aerosol, source apportionment, PM1, particulate matter
Published in RUNG: 10.05.2024; Views: 11; Downloads: 0
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8.
Exhaled volatile organic compounds and respiratory disease : recent progress and future outlook
Maria Chiara Magnano, Waqar Ahmed, Ran Wang, Martina Bergant Marušič, Stephen J. Fowler, Iain R. White, 2024, review article

Abstract: The theoretical basis of eVOCs as biomarkers for respiratory disease diagnosis is described, followed by a review of the potential biomarkers that have been proposed as targets from in vitro studies. The utility of these targets is then discussed based on comparison with results from clinical breath studies. The current status of breath research is summarised for various diseases, with emphasis placed on quantitative and targeted studies. Potential for bias highlights several important concepts related to standardization, including practices adopted for compound identification, correction for background inspired VOC levels and computation of mixing ratios. The compiled results underline the need for targeted studies across different analytical platforms to understand how sampling and analytical factors impact eVOC quantification. The impact of environmental VOCs as confounders in breath analysis is discussed alongside the potential that eVOCs have as biomarkers of air pollution exposure and future perspectives on clinical breath sampling are provided.
Keywords: breath analysis, disease diagnosis, exhaled volatile organic compounds, respiratory disease, environmental exposure analysis, breath analysis
Published in RUNG: 06.05.2024; Views: 110; Downloads: 1
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9.
Effective microorganisms technology applied to sewage sludge and tested in short exposure on Lepidium sativum
Tanja Buh, Leja Goljat, Darian Rampih, Petra Makorič, Sara Pignattelli, 2024, original scientific article

Abstract: Sewage sludge has fertilizer properties and can supply a large amount of necessary nutrients to the crops, because it is full of organic matter, carbon, nitrogen and other nutrients, but on the other hand, it also contains a lot of toxic compounds, derived from its origin, such as heavy metals, antibiotics and microplastics. Effective microorganisms are a collection of naturally occurring beneficial microorganisms that are able to coexist and are commonly used in agriculture and gardening to improve plant performance and production. In this study, increasing concentrations of sewage sludge alone and added with effective microorganisms were evaluated in a short exposure on Lepidium sativum L. Parameters that were evaluated are: (i) percentage inhibition of germination, (ii) root length, (iii) biomass, (iv) soil pH, (v) total organic carbon and nitrogen both at soil and at root level. Results carried out from our experiment highlighted that effective microorganisms when coupled with sludge are able to restore biometric parameters by resetting seeds germinability inhibition and improving root elongation more than 50% when compared with plants added only with sludge, restoring the values almost of those to the control plants, as well as for soil pH values. Total organic carbon and total nitrogen are boosted at soil level almost at 50% when compared with the same concentrations added only with sludge, while at root level they appear decreased only in plants directly added with sludge treated with effective microorganisms
Keywords: sewage sludge, effective microorganism, total organic carbon, total nitrogen, germinability, short plants exposure, acute toxicity, biomass, pH
Published in RUNG: 12.04.2024; Views: 302; Downloads: 0
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10.
High charge carrier mobility in thin films of quasi-two-dimensional polyacetylenes with sulphuric inter-chain linkers
Nadiia Pastukhova, Gvido Bratina, Egon Pavlica, 2023, published scientific conference contribution abstract

Abstract: Quasi-two-dimensional conjugated polymers (q2DCP) have been described and recognised as crystalline, one- or two-layer polymer nanosheets prepared by arranging linear conjugated polymer chains in a 2D plane via non-covalent interchain interactions.[1,2] The extension of polymer dimensionality to two dimensions improves the alignment of individual polymer layers and overcomes the limitations associated with charge carrier hopping between polymer chains in one-dimensional and crosslinked polymers [3] Compared to other two-dimensional materials such as graphene or transition metal dichalcogenides, q2DCPs offer a high degree of flexibility in chemical design and are compatible with liquid-based processing methods. Various q2DCPs have been synthesized by surface active monolayer-assisted interfacial synthesis (SMAIS) [5] The photoreaction of these materials is of particular interest due to their tunable properties such as band gap and associated wavelength-dependent photoexcitation, which enables a wide range of applications in optoelectronic devices. Using time-of-flight photoconductivity measurements (TOF-PC) [4], we investigate the charge transport properties of 2D polyacetylene prepared by the SMAIS method. A typical TOFP measurement of q2D polyacetylene is shown in Figure 1, using a focused nanosecond pulse laser at 325 nm and an electrode spacing of 250 µm. From the polarity of the bias voltage and the duration of the photocurrent, we can determine the polarity, velocity, and mobility of the photo-excited carriers as a function of the applied bias voltage and excitation wavelength. and observed electron mobility of 250 cm2/Vs, which is in the range of the most advanced organic single-crystal small-molecule semiconductors and almost an order of magnitude higher than linear polymeric semiconductors. We investigated the optical absorption and transmission on a lateral scale using scanning near-field optical microscopy (SNOM).
Keywords: 2D polymers, organic semiconductors, q2DPA, SNOM, time-of-flight photoconductivity
Published in RUNG: 25.03.2024; Views: 332; Downloads: 1
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