Evolution under dark conditions of particles from old and modern diesel vehicles in a new environmental chamber characterized with fresh exhaust emissions

Atmospheric particles have several impacts on health and the environment, especially in urban areas. Parts of those particles are not fresh and have undergone atmospheric chemical and physical processes. Due to a lack of representativeness of experimental conditions and experimental artifacts such as particle wall losses in chambers, there are uncertainties on the effects of physical processes (condensation, nucleation and coagulation) and their role in particle evolution from modern vehicles. This study develops a new method to correct wall losses, accounting for size dependence and experiment-to-experiment variations. It is applied to the evolution of fresh diesel exhaust particles to characterize the physical processes which they undergo. The correction method is based on the black carbon decay and a size-dependent coefficient to correct particle distributions. Six diesel passenger cars, Euro 3 to Euro 6, were driven on a chassis dynamometer with Artemis Urban cold start and Artemis Motorway cycles. Exhaust was injected in an 8 m3 chamber with Teflon walls. The physical evolution of particles was characterized during 6 to 10 h. Increase in particle mass is observed even without photochemical reactions due to the presence of intermediate-volatility organic compounds and semi-volatile organic compounds. These compounds were quantified at emission and induce a particle mass increase up to 17 % h−1, mainly for the older vehicles (Euro 3 and Euro 4). Condensation is 4 times faster when the available particle surface is multiplied by 6.5. If initial particle number concentration is below [8–9] × 104 cm−3, a nucleation mode seems to be present but not measured by a scanning mobility particle sizer (SMPS). The growth of nucleation-mode particles results in an increase in measured [PN]. Above this threshold, particle number concentration decreases due to coagulation, up to −27 % h−1. Under those conditions, the chamber and experimental setup are well suited to characterizing and quantifying the process of coagulation.

Evolution of OH reactivity in NO-free volatile organic compound photooxidation investigated by the fully explicit GECKO-A model

OH reactivity (OHR) is an important control on the oxidative capacity in the atmosphere but remains poorly constrained in many environments, such as remote, rural, and urban atmospheres, as well as laboratory experiment setups under low-NO conditions. For an improved understanding of OHR, its evolution during oxidation of volatile organic compounds (VOCs) is a major aspect requiring better quantification. We use the fully explicit Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model to study the OHR evolution in the NO-free photooxidation of several VOCs, including decane (an alkane), m-xylene (an aromatic), and isoprene (an alkene). Oxidation progressively produces more saturated and functionalized species. Total organic OHR (including precursor and products, OHRVOC) first increases for decane (as functionalization increases OH rate coefficients) and m-xylene (as much more reactive oxygenated alkenes are formed). For isoprene, C=C bond consumption leads to a rapid drop in OHRVOC before significant production of the first main saturated multifunctional product, i.e., isoprene epoxydiol. The saturated multifunctional species in the oxidation of different precursors have similar average OHRVOC per C atom. The latter oxidation follows a similar course for different precursors, involving fragmentation of multifunctional species to eventual oxidation of C1 and C2 fragments to CO2, leading to a similar evolution of OHRVOC per C atom. An upper limit of the total OH consumption during complete oxidation to CO2 is roughly three per C atom. We also explore the trends in radical recycling ratios. We show that differences in the evolution of OHRVOC between the atmosphere and an environmental chamber, and between the atmosphere and an oxidation flow reactor (OFR), can be substantial, with the former being even larger, but these differences are often smaller than between precursors. The Teflon wall losses of oxygenated VOCs in chambers result in large deviations of OHRVOC from atmospheric conditions, especially for the oxidation of larger precursors, where multifunctional species may suffer substantial wall losses, resulting in significant underestimation of OHRVOC. For OFR, the deviations of OHRVOC evolution from the atmospheric case are mainly due to significant OHR contribution from RO2 and lack of efficient organic photolysis. The former can be avoided by lowering the UV lamp setting in OFR, while the latter is shown to be very difficult to avoid. However, the former may significantly offset the slowdown in fragmentation of multifunctional species due to lack of efficient organic photolysis.

Evolution under dark conditions of particles from old and modern diesel vehicles, in a new environmental chamber characterized with fresh exhaust emissions

Atmospheric particles have several impacts on health and environment, especially in urban areas. Part of those particles is not fresh, and has undergone atmospheric chemical and physical processes. Due to not representative experimental conditions, and experimental artifacts such as particle wall losses in chambers, there are uncertainties on the effects of physical processes (condensation, nucleation and coagulation) and how they act on particles from modern vehicles. This study develops a new method to correct wall losses, accounting for size dependence and experiment-to-experiment variations, and applies it to the evolution of fresh diesel exhaust particles to characterize the physical processes acting on them. The correction method is based on the black carbon decay and a size-dependent coefficient to correct particle distributions. Exhaust from 6 diesel passenger cars, Euro 3 to Euro 6, driven on a chassis dynamometer with Artemis Urban cold start and Artemis Motorway cycles, was injected in an 8 m3 chamber with Teflon walls. The physical evolution of particles was characterized during 6 to 10 hours. Condensation occurs even without photochemical reactions, due to the presence of intermediate volatility organic compounds and semi-volatile organic compounds which were quantified at emission, and induces a particle mass increase up to 17 %.h−1, mainly for the older vehicles (Euro 3 and Euro 4). Condensation is 4 times faster when the available particle surface if multiplied by 3. If initial particle number concentration is below [8–9] × 104 #.cm−3, it can increase up to 25 %.h−1 due to nucleation or condensation on particles below 14 nm. Above this threshold, particle number concentration decreases due to coagulation, up to −27 %.h−1.

Evolution of OH reactivity in low-NO volatile organic compound photooxidation investigated by the fully explicit GECKO-A model

OH reactivity (OHR) is an important control on the oxidative capacity in the atmosphere but remains poorly constrained. For an improved understanding of OHR, its evolution during oxidation of volatile organic compounds (VOCs) is a major aspect requiring better quantification. We use the fully explicit Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model to study the OHR evolution in the low-NO photooxidation of several VOCs, including decane (an alkane), m-xylene (an aromatic), and isoprene (an alkene). Oxidation progressively produces more saturated and functionalized species. Total organic OHR (including precursor and products, OHRVOC) first increases for decane (as functionalization increases OH rate coefficients), and m-xylene (as much more reactive oxygenated alkenes are formed). For isoprene, C=C bond consumption leads to a rapid drop in OHRVOC before significant production of the first main saturated multifunctional product, i.e., isoprene epoxydiol. The saturated multifunctional species in the oxidation of different precursors have similar average OHRVOC per C atom. The latter oxidation follows a similar course for different precursors, involving fragmentation of multifunctional species to eventual oxidation of C1 and C2 fragments to CO2, leading to a similar evolution of OHRVOC per C atom. An upper limit of the total OH consumption during complete oxidation to CO2 is roughly 3 per C atom. We also explore the trends in radical recycling ratios. We show that differences in the evolution of OHRVOC between the atmosphere and an environmental chamber, and between the atmosphere and an oxidation flow reactor (OFR) can be substantial, with the former being even larger, but these differences are often smaller than between precursors. The Teflon wall losses of oxygenated VOCs in chambers result in substantial deviations of OHRVOC from atmospheric conditions, especially for the oxidation of larger precursors, where multifunctional species may suffer near-complete wall losses, resulting in significant underestimation of OHRVOC. For OFR, the deviations of OHRVOC evolution from the atmospheric case are mainly due to significant OHR contribution from RO2 and lack of efficient organic photolysis. The former can be avoided by lowering the UV lamp setting in OFR, while the latter is shown to be very difficult to avoid. However, the former may significantly offset the slowdown in fragmentation of multifunctional species due to lack of efficient organic photolysis.

Multidomain ribosomal protein trees and the planctobacterial origin of neomura (eukaryotes, archaebacteria)

Palaeontologically, eubacteria are > 3× older than neomura (eukaryotes, archaebacteria). Cell biology contrasts ancestral eubacterial murein peptidoglycan walls and derived neomuran N-linked glycoprotein coats/walls. Misinterpreting long stems connecting clade neomura to eubacteria on ribosomal sequence trees (plus misinterpreted protein paralogue trees) obscured this historical pattern. Universal multiprotein ribosomal protein (RP) trees, more accurate than rRNA trees, are taxonomically undersampled. To reduce contradictions with genically richer eukaryote trees and improve eubacterial phylogeny, we constructed site-heterogeneous and maximum-likelihood universal three-domain, two-domain, and single-domain trees for 143 eukaryotes (branching now congruent with 187-protein trees), 60 archaebacteria, and 151 taxonomically representative eubacteria, using 51 and 26 RPs. Site-heterogeneous trees greatly improve eubacterial phylogeny and higher classification, e.g. showing gracilicute monophyly, that many ‘rDNA-phyla’ belong in Proteobacteria, and reveal robust new phyla Synthermota and Aquithermota. Monoderm Posibacteria and Mollicutes (two separate wall losses) are both polyphyletic: multiple outer membrane losses in Endobacteria occurred separately from Actinobacteria; neither phylum is related to Chloroflexi, the most divergent prokaryotes, which originated photosynthesis (new model proposed). RP trees support an eozoan root for eukaryotes and are consistent with archaebacteria being their sisters and rooted between Filarchaeota (=Proteoarchaeota, including ‘Asgardia’) and Euryarchaeota sensu-lato (including ultrasimplified ‘DPANN’ whose long branches often distort trees). Two-domain trees group eukaryotes within Planctobacteria, and archaebacteria with Planctobacteria/Sphingobacteria. Integrated molecular/palaeontological evidence favours negibacterial ancestors for neomura and all life. Unique presence of key pre-neomuran characters favours Planctobacteria only as ancestral to neomura, which apparently arose by coevolutionary repercussions (explained here in detail, including RP replacement) of simultaneous outer membrane and murein loss. Planctobacterial C-1 methanotrophic enzymes are likely ancestral to archaebacterial methanogenesis and β-propeller-α-solenoid proteins to eukaryotic vesicle coats, nuclear-pore-complexes, and intraciliary transport. Planctobacterial chaperone-independent 4/5-protofilament microtubules and MamK actin-ancestors prepared for eukaryote intracellular motility, mitosis, cytokinesis, and phagocytosis. We refute numerous wrong ideas about the universal tree.

Secondary organic aerosol formation from evaporated biofuels: comparison to gasoline and correction for vapor wall losses

With an ongoing interest in displacing petroleum-based sources of energy with biofuels, we measure and model the formation and composition of secondary organic aerosol (SOA) from organic compounds present in biofuels.

MODE SELECTION BY OHMIC LOSSES IN LONGITUDINALLY CORRUGATED CAVITIES OF SUB-THz SECOND-HARMONIC GYROTRONS

Ohmic wall losses are proposed as a means for improving the mode selection in a cylindrical gyrotron cavity with longitudinal wedge-shaped corrugations. Such losses depend on mode frequency and geometrical parameters of the corrugations. For cavity of the 0.4-THz second-harmonic gyrotron we find the corrugation depth, which corresponds to maximum ohmic losses of the competing modes excited at the first (fundamental) cyclotron resonance, as well as to reasonably low losses of the operating mode. For this depth, we determine the number of corrugations and their width, which ensure the maximum enhancement of the ohmic wall losses of the fundamental modes with respect to those of the operating second-harmonic mode, together with minimum conversion of the operating second-harmonic mode to higher Bloch harmonics. Parameters of the corrugations in hand are practicable.