Consequences of the Direct Reduction and Electric Steelmaking Grid Creation on the Italian Steel Sector

The consequences on the Italian steel sector following the conversion of the sole integrated steel plant and the establishment of a direct reduction/electric arc furnace (DR/EAF) grid in the period 2022–2050 were analyzed. Imported natural gas (pathway 0), green hydrogen (pathway 1) and biomethane (pathway 2) were studied as possible reducing gases to be exploited in the DR plant and to be introduced as a methane substitute in EAFs. The results showed that the environmental targets for the sustainable development scenario could be achieved in both 2030 and 2050. In particular, the main reduction would occur by 2030 as a result of the cease of the integrated plant itself, allowing for an overall reduction of 71% of the CO2 emitted in 2022. On the other hand, reaching the maximum production capacity of the DR plants by 2050 (6 Mton) would result in final emission reductions of 25%, 80% and 35% for pathways 0, 1 and 2, respectively. Finally, the creation of a DR/EAF grid would increase the energy demand burden, especially for pathway 1, which would require three times as much green energy as pathway 0 and/or 2 (36 TWh/y vs. ca. 12 TWh/y

Peeking into the Femtosecond Hot-Carrier Dynamics Reveals Unexpected Mechanisms in Plasmonic Photocatalysis

Plasmonic-driven photocatalysis may lead to reaction selectivity that cannot be otherwise achieved. A fundamental role is played by hot carriers, i.e., electrons and holes generated upon plasmonic decay within the metal nanostructure interacting with molecular species. Understanding the elusive microscopic mechanism behind such selectivity is a key step in the rational design of hot-carrier reactions. To accomplish that, we present state-of-the-art multiscale simulations, going beyond density functional theory, of hot-carrier injections for the rate-determining step of a photocatalytic reaction. We focus on carbon dioxide reduction, for which it was experimentally shown that the presence of a rhodium nanocube under illumination leads to the selective production of methane against carbon monoxide. We show that selectivity is due to a (predominantly) direct hole injection from rhodium to the reaction intermediate CHO. Unexpectedly, such an injection does not promote the selective reaction path by favoring proper bond breaking but rather by promoting bonding of the proper molecular fragment to the surface

Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO₃ with Acids under Ambient Conditions

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth’s atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.</p

Local and regional components of aerosol in a heavily trafficked street canyon in central London derived from PMF and cluster analysis of single-particle ATOFMS spectra.

Positive matrix factorization (PMF) has been applied to single particle ATOFMS spectra collected on a six lane heavily trafficked road in central London (Marylebone Road), which well represents an urban street canyon. PMF analysis successfully extracted 11 factors from mass spectra of about 700,000 particles as a complement to information on particle types (from K-means cluster analysis). The factors were associated with specific sources and represent the contribution of different traffic related components (i.e., lubricating oils, fresh elemental carbon, organonitrogen and aromatic compounds), secondary aerosol locally produced (i.e., nitrate, oxidized organic aerosol and oxidized organonitrogen compounds), urban background together with regional transport (aged elemental carbon and ammonium) and fresh sea spray. An important result from this study is the evidence that rapid chemical processes occur in the street canyon with production of secondary particles from road traffic emissions. These locally generated particles, together with aging processes, dramatically affected aerosol composition producing internally mixed particles. These processes may become important with stagnant air conditions and in countries where gasoline vehicles are predominant and need to be considered when quantifying the impact of traffic emissions.This is the author accepted manuscript. The final version is available via ACS at http://pubs.acs.org/doi/abs/10.1021/es506249z

Simultaneous Detection of Alkylamines in the Surface Ocean and Atmosphere of the Antarctic Sympagic Environment

Measurements of alkylamines from seawater and atmospheric samples collected simultaneously across the Antarctic Peninsula, South Orkney and South Georgia Islands are reported. Concentrations of mono-, di-, and trimethylamine (MMA, DMA, and TMA, respectively), and their precursors, the quarternary amines glycine betaine and choline, were enhanced in sympagic seawater samples relative to ice-devoid pelagic ones, suggesting the microbiota of sea ice and sea ice-influenced ocean is a major source of these compounds. Primary sea-spray aerosol particles artificially generated by bubbling seawater samples were investigated by aerosol time-of-flight mass spectrometry (ATOFMS) of single particles; their mixing state indicated that alkylamines were aerosolized with sea spray from dissolved and particulate organic nitrogen pools. Despite this unequivocal sea spray-associated source of alkylamines, ATOFMS analyses of ambient aerosols in the sympagic region indicated that the majority (75–89%) of aerosol alkylamines were of secondary origin, that is, incorporated into the aerosol after gaseous air–sea exchange. These findings show that sympagic seawater properties are a source of alkylamines influencing the biogenic aerosol fluxed from the ocean into the boundary layer; these organic nitrogen compounds should be considered when assessing secondary aerosol formation processes in Antarctica

Hyperspectral Imaging Techniques for Rapid Identification of Arabidopsis Mutants with Altered Leaf Pigment Status

The spectral reflectance signature of living organisms provides information that closely reflects their physiological status. Because of its high potential for the estimation of geomorphic biological parameters, particularly of gross photosynthesis of plants, two-dimensional spectroscopy, via the use of hyperspectral instruments, has been widely used in remote sensing applications. In genetics research, in contrast, the reflectance phenotype has rarely been the subject of quantitative analysis; its potential for illuminating the pathway leading from the gene to phenotype remains largely unexplored. In this study, we employed hyperspectral imaging techniques to identify Arabidopsis mutants with altered leaf pigment status. The techniques are comprised of two modes; the first is referred to as the ‘targeted mode’ and the second as the ‘non-targeted mode’. The ‘targeted’ mode is aimed at visualizing individual concentrations and compositional parameters of leaf pigments based on reflectance indices (RIs) developed for Chls a and b, carotenoids and anthocyanins. The ‘non-targeted’ mode highlights differences in reflectance spectra of leaf samples relative to reference spectra from the wild-type leaves. Through the latter approach, three mutant lines with weak irregular reflectance phenotypes, that are hardly identifiable by simple observation, were isolated. Analysis of these and other mutants revealed that the RI-based targeted pigment estimation was robust at least against changes in trichome density, but was confounded by genetic defects in chloroplast photorelocation movement. Notwithstanding such a limitation, the techniques presented here provide rapid and high-sensitive means to identify genetic mechanisms that coordinate leaf pigment status with developmental stages and/or environmental stress conditions

Synergic estimation of columnar integrated aerosol properties and their vertical resolved profiles in respect to the scenarios of dust intrusions over Granada

This is a preprint version of a paper accepted to be published in "Mandija, F.; et al. Synergic estimation of columnar integrated aerosol properties and their vertical resolved profiles in respect to the scenarios of dust intrusions over Granada. Atmospheric Environment, 145: 439-454 (2016)", doi: https://doi.org/10.1016/j.atmosenv.2016.09.045In this paper, we present a study of the columnar and vertically resolved aerosol optical properties over Granada (Spain) during dust events detected during July-August in the period 2012e2013. For this purpose, we classified the events according to their origins and pathways. The analyzed aerosol prop- erties include; columnar aerosol optical properties like aerosol optical depth (AOD) and Angstrom exponent (AE), as well as the lidar products, like backscatter-related Angstrom exponent and linear particle depolarization ratio (LDPR). The lidar profiles are used for determination of the geometrical structure of dust layers and the aerosol optical parameters inside dust layers. There are identified 58 dusty days over Granada during the periods July-August, 2012e2013. In 71% of the dust, event analyzed the dust plume over Granada is located between 3000 and 4000 m a.g.l. Mean values of AOD500 according to the Atlantic and Mediterranean pathway were 0.28 ± 0.10 and 0.93 ± 0.17. Meanwhile, the mean values of AE440-870 were 0.57 ± 0.25 and 0.43 ± 0.20. Three region are identified as the main dust sources affecting the dust intrusions over Granada. Two principal pathways of air masses during dust intrusion over Granada were observed: through Atlantic (52.7%) and through Mediterranean (47.3%). Air masses which come through the Mediterranean present larger AOD and lower Angstrom exponent values than those air masses coming through Atlantic. Lidar measurements show different vertical distributions on particle backscatter coefficient, during different scenarios of dust intrusions. The lidar profiles indicate that average base and top heights of all dust during the investigation period were 2.1 ± 0.7 and 4.8 ± 0.9 km, and their center of mass and thickness were 3.3 ± 0.7 and 2.8 ± 1.0 km a.g.l. The AE355/532 profiles for the dust intrusions present some differences depending on the source regions and path followed by the dust. On the other hand, the profiles of LPDRat 532 nm were more similar for all scenarios.This work was supported by the Andalusia Regional Government through project P12-RNM-2409, by the Spanish Ministry of Economy and Competitiveness through project CGL2013-45410-R and by the European Union's Horizon 2020 Research and Innovation Programme through project ACTRIS-2 (grant agreement No. 654109)

Measurements of particulate methanesulfonic acid above the remote Arctic Ocean using a high resolution aerosol mass spectrometer

Methanesulfonic acid (MSA) is an important product from the oxidation of dimethyl sulfide (DMS), and thus is often used as a tracer for marine biogenic sources and secondary organic aerosol. MSA also contributes to aerosol mass and potentially to the formation of cloud condensation nuclei and new particles. However, measurements of MSA at high temporal resolution in the remote Arctic are scarce, which limits our understanding of its formation, climate change impact and regional transport. Here, we applied a validated quantification method to determine the mass concentration of MSA and non-sea salt sulfate (nss-SO4) in PM2.5 in the marine boundary layer, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during a research cruise to the Arctic and North Atlantic Ocean, between 55 ◦N and 68 ◦N (26th May to June 23, 2022). With this method, the concen�trations of MSA in the remote Arctic marine boundary layer were determined for the first time. Results show that the average MSA concentration was 0.025 ± 0.03 μg m− 3 , ranging from <0.01 to 0.32 μg m− 3 . The lowest MSA level was found towards the northern leg of the cruise (near Sisimut (67 ◦N)) with air masses from sea ice over the northern polar region, and the highest MSA concentrations were observed over the Atlantic open ocean. The diurnal cycles of gas MSA, particulate MSA and nss-SO4 peaked in the afternoon, about one hour later than that of peak of solar radiation, which suggests that photochemical process is an important mechanism for the conversion of DMS into MSA above the remote ocean. The mass ratio of MSA to nss-SO4 (MSA/nss-SO4) presents a tem�perature dependence, which indicates that the addition branching pathway favors MSA formation, while thermal decay of intermediate radicals could be a possible pathway for sulfate formation. Finally, we found that the MSA/ nss-SO4 ratio is around 0.22-0.25 in the remote northern marine atmosphere

Untangling the influence of Antarctic and Southern Ocean life on clouds

Polar environments are among the fastest changing regions on the planet. It is a crucial time to make significant improvements in our understanding of how ocean and ice biogeochemical processes are linked with the atmosphere. This is especially true over Antarctica and the Southern Ocean where observations are severely limited and the environment is far from anthropogenic influences. In this commentary, we outline major gaps in our knowledge, emerging research priorities, and upcoming opportunities and needs. We then give an overview of the large-scale measurement campaigns planned across Antarctica and the Southern Ocean in the next 5 years that will address the key issues. Until we do this, climate models will likely continue to exhibit biases in the simulated energy balance over this delicate region. Addressing these issues will require an international and interdisciplinary approach which we hope to foster and facilitate with ongoing community activities and collaborations

Fostering multidisciplinary research on interactions between chemistry, biology, and physics within the coupled cryosphere-atmosphere system

The cryosphere, which comprises a large portion of Earth’s surface, is rapidly changing as a consequence of global climate change. Ice, snow, and frozen ground in the polar and alpine regions of the planet are known to directly impact atmospheric composition, which for example is observed in the large influence of ice and snow on polar boundary layer chemistry. Atmospheric inputs to the cryosphere, including aerosols, nutrients, and contaminants, are also changing in the anthropocene thus driving cryosphere-atmosphere feedbacks whose understanding is crucial for understanding future climate. Here, we present the Cryosphere and ATmospheric Chemistry initiative (CATCH) which is focused on developing new multidisciplinary research approaches studying interactions of chemistry, biology, and physics within the coupled cryosphere – atmosphere system and their sensitivity to environmental change. We identify four key science areas: (1) micro-scale processes in snow and ice, (2) the coupled cryosphere-atmosphere system, (3) cryospheric change and feedbacks, and (4) improved decisions and stakeholder engagement. To pursue these goals CATCH will foster an international, multidisciplinary research community, shed light on new research needs, support the acquisition of new knowledge, train the next generation of leading scientists, and establish interactions between the science community and society