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

Toxicity and Clinical Results after Proton Therapy for Pediatric Medulloblastoma: A Multi-Centric Retrospective Study

Medulloblastoma is the most common malignant brain tumor in children. Even if current treatment dramatically improves the prognosis, survivors often develop long-term treatment-related sequelae. The current radiotherapy standard for medulloblastoma is craniospinal irradiation with a boost to the primary tumor site and to any metastatic sites. Proton therapy (PT) has similar efficacy compared to traditional photon-based radiotherapy but might achieve lower toxicity rates. We report on our multi-centric experience with 43 children with medulloblastoma (median age at diagnosis 8.7 years, IQR 6.6, M/F 23/20; 26 high-risk, 14 standard-risk, 3 ex-infant), who received active scanning PT between 2015 and 2021, with a focus on PT-related acute-subacute toxicity, as well as some preliminary data on late toxicity. Most acute toxicities were mild and manageable with supportive therapy. Hematological toxicity was limited, even among HR patients who underwent hematopoietic stem-cell transplantation before PT. Preliminary data on late sequelae were also encouraging, although a longer follow-up is needed

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 K were predicted using a multi-phase gas-particle partitioning model based on polyparameter linear free energy relationships. ∑NPAH concentrations were 1.2–17.6 and 8.8–19.1 ng L−1 at urban and rural sites, whereas ∑OPAHs were 79.8–955.2 and 343.3–1757.4 ng 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 ng L−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

Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((−)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(&minus;)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning

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

Erratum: Electrocaloric cooling: The importance of electric-energy recovery and heat regeneration

Original article: EPL, 111 (2015) 5700

Electrocaloric cooling: The importance of electric-energy recovery and heat regeneration

Here we explore the effect of electric-energy recovery and heat regeneration on the energy efficiency of an electrocaloric-cooling system. Furthermore, the influence of the polarization-electric field hysteresis on the energy efficiency of the system is analysed. For the purposes of the analysis, the properties of (1 – x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-100xPT) with x = 0, $x=0.1$ , and $x=0.35$ are characterized. We show that if no heat is regenerated, even small irreversibilities in the electric circuit used to recover the electric energy can cause a significant drop in the achievable energy efficiency. On the other hand, when a heat regeneration process is considered and a realistic value for the degree of electric-energy recovery equal to 80% is assumed, the limit for the energy efficiency of a system employing PMN ceramics is estimated to be equal to 81% of the efficiency of a Carnot heat pump