Abstract. Typical tropospheric temperatures render possible phase
states of amorphous organic aerosol (OA) particles of solid, semisolid, and
liquid. This will affect the multiphase oxidation kinetics involving the
organic condensed-phase and gaseous oxidants and radicals. To quantify this
effect, we determined the reactive uptake coefficients (γ) of
O3, NO3, and OH by substrate films composed of single and binary OA
surrogate species under dry conditions for temperatures from 213 to 313 K. A
temperature-controlled coated-wall flow reactor coupled to a chemical
ionization mass spectrometer was applied to determine γ with
consideration of gas diffusion transport limitation and gas flow entrance
effects, which can impact heterogeneous reaction kinetics. The phase state
of the organic substrates was probed via the poke-flow technique, allowing
the estimation of the substrates' glass transition temperatures. γ
values for O3 and OH uptake to a canola oil substrate, NO3 uptake
to a levoglucosan and a levoglucosan / xylitol substrate, and OH uptake to a
glucose and glucose / 1,2,6-hexanetriol substrate have been determined as a
function of temperature. We observed the greatest changes in γ with
temperature for substrates that experienced the largest changes in viscosity
as a result of a solid-to-liquid phase transition. Organic substrates that
maintain a semisolid or solid phase state and as such a relatively higher
viscosity do not display large variations in heterogeneous reactivity. From
213 to 293 K, γ values of O3 with canola oil, of NO3
with a levoglucosan / xylitol mixture, and of OH with a
glucose / 1,2,6-hexanetriol mixture and canola oil, increase by about a factor
of 34, 3, 2, and 5, respectively, due to a solid-to-liquid phase transition
of the substrate. These results demonstrate that the surface and bulk
lifetime of the OA surrogate species can significantly increase due to the
slowed heterogeneous kinetics when OA species are solid or highly viscous in
the middle and upper troposphere. This experimental study will further our
understanding of the chemical evolution of OA particles with subsequent
important consequences for source apportionment, air quality, and climate.
Organic aerosol (OA) is ubiquitous in the atmosphere and, during transport, can experience chemical transformation with consequences for air quality and climate. Prediction of the chemical evolution of OA depends on its reactivity with atmospheric oxidants such as the OH radical. OA particles undergo amorphous phase transitions from liquid to solid (glassy) states in response to temperature changes, which, in turn, will impact its reactivity toward OH oxidation. To improve the predictability of OA reactivity toward OH oxidation, the reactive uptake coefficients (γ) of OH radicals reacting with triacontane and squalane serving as amorphous OA surrogates were measured at temperatures from 213−293 K. γ increases strongest with temperature when the organic species is in the liquid phase, compared to when being in the semisolid or solid phase. The resistor model is applied, accounting for the amorphous phase state changes using the organic species' glass transition temperature and fragility, to evaluate the physicochemical parameters of the temperature dependent OH uptake process. This allows for the derivation of a semiempirical formula, applicable to models, to predict the degree of oxidation and chemical lifetime of the condensed-phase organic species for typical tropospheric temperature and humidity when OA particle viscosity is known.
Application of X-STRs as complements of autosomal STR application in the forensic genetics has become a tendency for kinship testing, especially in deficiency paternity cases. Recently, a novel kit of 19 X-STR loci was developed, which permitted the analysis of 19 STR in the same PCR reaction, and these markers can be clustered into seven groups for the physical linkage. The objective of this study was to evaluate the allele and haplotype diversity of 19 X-STR loci in the Uygur (n = 220) and Tibetan nationality (n = 270) and to estimate the usefulness for complex kinship analysis. In the Tibetan and Uygur populations, a total of alleles of all loci were 188 and 212, with the allele frequencies ranged from 0.0037 to 0.5593 and from 0.0045 to 0.5409, respectively. Compared with previous studies, DXS10135 was the most polymorphic locus in the two population groups, whereas the least variant locus was DXS10164 in the Uygur population and DXS7423 in the Tibetan nationality. Haplotype diversity obtained in this investigation was greater than 0.9 across all LGs. This study indicated the new kit could be used as a supplementary tool in kinship testing in China. In addition, the data sets can be used as supplementary national X-STR references to enlarge the database.
The Y‐chromosome short tandem repeats (Y‐STRs) loci with different mutation rates existing in the Y chromosome non‐recombination region (NRY) allow to be applied in human forensics, genealogical researches, historical investigations and evolutionary studies. Currently, there is a high demand for pedigree search to narrow the scope of crime investigations. However, the commonly used Y‐STRs kits generally contain Y‐STRs with high mutation rates that could cause individuals from the same pedigree to display different haplotypes. Herein, we put forward a new strategy of Slowly Mutating (SM) Y‐STRs plus Y‐SNPs typing, which could not only improve the resolution and accuracy of pedigree search, but also be applicable to evolutionary research. First, we developed a nine SM Y‐STRs assay by evaluating their mutation rates in 210 pedigrees. Then the gene diversity and efficiency of the SM Y‐STRs and 172 Y‐SNPs sets were investigated by 2304 unrelated males from 24 populations. Furthermore, network and time estimation analyses were performed to evaluate the new strategy's capability to reconstruct phylogenetic tree and reliability to infer the time to the most recent common ancestor (TMRCA). The nine SM Y‐STRs assay even had a higher resolution and a comparable capacity of revealing population genetic differentiation compared to 172 Y‐SNPs system. This new strategy could optimize the phylogenetic tree generated by commonly used Y‐STR panels and obtain a quite consistent time estimations with the published dating.
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