Rate enhancement in collisions of sulfuric acid molecules due to long-range intermolecular forces

Collisions of molecules and clusters play a key role in determining the rate of atmospheric new particle formation and growth. Traditionally the statistics of these collisions are taken from kinetic gas theory assuming spherical noninteracting particles, which may significantly underestimate the collision coefficients for most atmospherically relevant molecules. Such systematic errors in predicted new particle formation rates will also affect large-scale climate models. We studied the statistics of collisions of sulfuric acid molecules in a vacuum using atomistic molecular dynamics simulations. We found that the effective collision cross section of the H2SO4 molecule, as described by an optimized potentials for liquid simulation (OPLS). OPLS all-atom force field, is significantly larger than the hard-sphere diameter assigned to the molecule based on the liquid density of sulfuric acid. As a consequence, the actual collision coefficient is enhanced by a factor of 2.2 at 300 K compared with kinetic gas theory. This enhancement factor obtained from atomistic simulation is consistent with the discrepancy observed between experimental formation rates of clusters containing sulfuric acid and calculated formation rates using hard-sphere kinetics. We find reasonable agreement with an enhancement factor calculated from the Langevin model of capture, based on the attractive part of the atomistic intermolecular potential of mean force.Peer reviewe

Ambient sesquiterpene concentration and its link to air ion measurements

International audienceAmbient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol?1 (1.24 eV) and of 960 kJ mol?1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. The estimated concentration is found to reveal the same seasonal pattern as emission measurements conducted at shoot level. As expected for biogenic VOCs, the concentration is obtained highest during summer (maximum values of about 100 pptv) and smallest during winter (minimum less than 1 pptv). Because of the sesquiterpenes high reactivity and its low ambient concentrations, this approach can be a first step in understanding their emission and their impact on atmospheric chemistry in more detail. The findings presented are highly relevant for emission budgets too, since boreal forests are extended over large areas of the globe

Criegee Intermediates React with Ozone

We have investigated the reaction of the one-carbon stabilized Criegee intermediate (H_2COO, formaldehyde oxide) with ozone, theoretically, using high level coupled cluster ab initio methods. Key to the reactivity of the Criegee intermediate with ozone is the strongly exothermic formation of an intermediate consisting of five oxygen and one carbon atoms (H_2CO_5) in a six-membered ring structure. This intermediate proceeds via a spin-allowed route over two transition states with low energy barriers to form molecular oxygen and formaldehyde. The reaction may contribute to the loss of these biradicals in the atmosphere

Evidence of strong stabilizing effects on the evolution of boreoeutherian (Mammalia) dental proportions.

The dentition is an extremely important organ in mammals with variation in timing and sequence of eruption, crown morphology, and tooth size enabling a range of behavioral, dietary, and functional adaptations across the class. Within this suite of variable mammalian dental phenotypes, relative sizes of teeth reflect variation in the underlying genetic and developmental mechanisms. Two ratios of postcanine tooth lengths capture the relative size of premolars to molars (premolar-molar module, PMM), and among the three molars (molar module component, MMC), and are known to be heritable, independent of body size, and to vary significantly across primates. Here, we explore how these dental traits vary across mammals more broadly, focusing on terrestrial taxa in the clade of Boreoeutheria (Euarchontoglires and Laurasiatheria). We measured the postcanine teeth of N = 1,523 boreoeutherian mammals spanning six orders, 14 families, 36 genera, and 49 species to test hypotheses about associations between dental proportions and phylogenetic relatedness, diet, and life history in mammals. Boreoeutherian postcanine dental proportions sampled in this study carry conserved phylogenetic signal and are not associated with variation in diet. The incorporation of paleontological data provides further evidence that dental proportions may be slower to change than is dietary specialization. These results have implications for our understanding of dental variation and dietary adaptation in mammals

Oldest known pantherine skull and evolution of the tiger

The tiger is one of the most iconic extant animals, and its origin and evolution have been intensely debated. Fossils attributable to extant pantherine species-lineages are less than 2 MYA and the earliest tiger fossils are from the Calabrian, Lower Pleistocene. Molecular studies predict a much younger age for the divergence of modern tiger subspecies at <100 KYA, although their cranial morphology is readily distinguishable, indicating that early Pleistocene tigers would likely have differed markedly anatomically from extant tigers. Such inferences are hampered by the fact that well-known fossil tiger material is middle to late Pleistocene in age. Here we describe a new species of pantherine cat from Longdan, Gansu Province, China, Panthera zdanskyi sp. nov. With an estimated age of 2.55–2.16 MYA it represents the oldest complete skull of a pantherine cat hitherto found. Although smaller, it appears morphologically to be surprisingly similar to modern tigers considering its age. Morphological, morphometric, and cladistic analyses are congruent in confirming its very close affinity to the tiger, and it may be regarded as the most primitive species of the tiger lineage, demonstrating the first unequivocal presence of a modern pantherine species-lineage in the basal stage of the Pleistocene (Gelasian; traditionally considered to be Late Pliocene). This find supports a north-central Chinese origin of the tiger lineage, and demonstrates that various parts of the cranium, mandible, and dentition evolved at different rates. An increase in size and a reduction in the relative size of parts of the dentition appear to have been prominent features of tiger evolution, whereas the distinctive cranial morphology of modern tigers was established very early in their evolutionary history. The evolutionary trend of increasing size in the tiger lineage is likely coupled to the evolution of its primary prey species

Atmospheric gaseous hydrochloric and hydrobromic acid in urban Beijing, China : detection, source identification and potential atmospheric impacts

Gaseous hydrochloric (HCl) and hydrobromic acid (HBr) are vital halogen species that play essential roles in tropospheric physicochemical processes. Yet, the majority of the current studies on these halogen species were conducted in marine or coastal areas. Detection and source identification of HCl and HBr in inland urban areas remain scarce, thus limiting the full understanding of halogen chemistry and potential atmospheric impacts in the environments with limited influence from the marine sources. Here, both gaseous HCl and HBr were concurrently measured in urban Beijing, China, during winter and early spring of 2019. We observed significant HCl and HBr concentrations ranging from a minimum value at 1 x 10(8) molecules cm(-3) (4 ppt) and 4 x 10(7) molecules cm 3 (1 ppt) up to 6 x 10(9) molecules cm(-3) (222 ppt) and 1 x 10(9) molecules cm(-3) (37 ppt), respectively. The HCl and HBr concentrations are enhanced along with the increase of atmospheric temperature, UVB and levels of gaseous HNO3. Based on the air mass analysis and high correlations of HCl and HBr with the burning indicators (HCN and HCNO), gaseous HCl and HBr are found to be related to anthropogenic burning aerosols. The gas-particle partitioning may also play a dominant role in the elevated daytime HCl and HBr. During the daytime, the reactions of HCl and HBr with OH radicals lead to significant production of atomic Cl and Br, up to 2 x 10(4) molecules cm(-3) s(-1) and 8 x 10(4) molecules cm(-3) s(-1), respectively. The production rate of atomic Br (via HBr + OH) is 2-3 times higher than that of atomic Cl (via HCl + OH), highlighting the potential importance of bromine chemistry in the urban area. On polluted days, the production rates of atomic Cl and Br are faster than those on clean days. Furthermore, our observations of elevated HCl and HBr may suggest an important recycling pathway of halogen species in inland megacities and may provide a plausible explanation for the widespread halogen chemistry, which could affect the atmospheric oxidation in China.Peer reviewe

The Effect of Inappropriate Calibration: Three Case Studies in Molecular Ecology

Time-scales estimated from sequence data play an important role in molecular ecology. They can be used to draw correlations between evolutionary and palaeoclimatic events, to measure the tempo of speciation, and to study the demographic history of an endangered species. In all of these studies, it is paramount to have accurate estimates of time-scales and substitution rates. Molecular ecological studies typically focus on intraspecific data that have evolved on genealogical scales, but often these studies inappropriately employ deep fossil calibrations or canonical substitution rates (e.g., 1% per million years for birds and mammals) for calibrating estimates of divergence times. These approaches can yield misleading estimates of molecular time-scales, with significant impacts on subsequent evolutionary and ecological inferences. We illustrate this calibration problem using three case studies: avian speciation in the late Pleistocene, the demographic history of bowhead whales, and the Pleistocene biogeography of brown bears. For each data set, we compare the date estimates that are obtained using internal and external calibration points. In all three cases, the conclusions are significantly altered by the application of revised, internally-calibrated substitution rates. Collectively, the results emphasise the importance of judicious selection of calibrations for analyses of recent evolutionary events

Evolution of Skull and Mandible Shape in Cats (Carnivora: Felidae)

The felid family consists of two major subgroups, the sabretoothed and the feline cats, to which all extant species belong, and are the most anatomically derived of all carnivores for predation on large prey with a precision killing bite. There has been much controversy and uncertainty about why the skulls and mandibles of sabretoothed and feline cats evolved to become so anatomically divergent, but previous models have focused on single characters and no unifying hypothesis of evolutionary shape changes has been formulated. Here I show that the shape of the skull and mandible in derived sabrecats occupy entirely different positions within overall morphospace from feline cats, and that the evolution of skull and mandible shape has followed very different paths in the two subgroups. When normalised for body-size differences, evolution of bite forces differ markedly in the two groups, and are much lower in derived sabrecats, and they show a significant relationship with size and cranial shape, whereas no such relationship is present in feline cats. Evolution of skull and mandible shape in modern cats has been governed by the need for uniform powerful biting irrespective of body size, whereas in sabrecats, shape evolution was governed by selective pressures for efficient predation with hypertrophied upper canines at high gape angles, and bite forces were secondary and became progressively weaker during sabrecat evolution. The current study emphasises combinations of new techniques for morphological shape analysis and biomechanical studies to formulate evolutionary hypotheses for difficult groups

Reticulate evolution: frequent introgressive hybridization among chinese hares (genus lepus) revealed by analyses of multiple mitochondrial and nuclear DNA loci

<p>Abstract</p> <p>Background</p> <p>Interspecific hybridization may lead to the introgression of genes and genomes across species barriers and contribute to a reticulate evolutionary pattern and thus taxonomic uncertainties. Since several previous studies have demonstrated that introgressive hybridization has occurred among some species within <it>Lepus</it>, therefore it is possible that introgressive hybridization events also occur among Chinese <it>Lepus </it>species and contribute to the current taxonomic confusion.</p> <p>Results</p> <p>Data from four mtDNA genes, from 116 individuals, and one nuclear gene, from 119 individuals, provides the first evidence of frequent introgression events via historical and recent interspecific hybridizations among six Chinese <it>Lepus </it>species. Remarkably, the mtDNA of <it>L. mandshuricus </it>was completely replaced by mtDNA from <it>L. timidus </it>and <it>L. sinensis</it>. Analysis of the nuclear DNA sequence revealed a high proportion of heterozygous genotypes containing alleles from two divergent clades and that several haplotypes were shared among species, suggesting repeated and recent introgression. Furthermore, results from the present analyses suggest that Chinese hares belong to eight species.</p> <p>Conclusion</p> <p>This study provides a framework for understanding the patterns of speciation and the taxonomy of this clade. The existence of morphological intermediates and atypical mitochondrial gene genealogies resulting from frequent hybridization events likely contribute to the current taxonomic confusion of Chinese hares. The present study also demonstrated that nuclear gene sequence could offer a powerful complementary data set with mtDNA in tracing a complete evolutionary history of recently diverged species.</p