Abundance of NO3 derived organo-nitrates and their importance in the atmosphere

The chemistry of the nitrate radical and its contribution to organo-nitrate formation in the troposphere has been investigated using a mesoscale 3-D chemistry and transport model, WRF-Chem-CRI. The model-measurement comparisons of NO2, ozone and night-time N2O5 mixing ratios show good agreement supporting the model’s ability to represent nitrate (NO3) chemistry reasonably. Thirty-nine organo-nitrates in the model are formed exclusively either from the reaction of RO2 with NO or by the reaction of NO3 with alkenes. Temporal analysis highlighted a significant contribution of NO3-derived organo-nitrates, even during daylight hours. Night-time NO3-derived organo-nitrates were found to be 3-fold higher than that in the daytime. The reactivity of daytime NO3 could be more competitive than previously thought, with losses due to reaction with VOCs (and subsequent organo-nitrate formation) likely to be just as important as photolysis. This has highlighted the significance of NO3 in daytime organo-nitrate formation, with potential implications for air quality, climate and human health. Estimated atmospheric lifetimes of organo-nitrates showed that the organo-nitrates act as NOx reservoirs, with particularly short-lived species impacting on air quality as contributors to downwind ozone formation

Population Genetics of Perennial Ryegrass (\u3cem\u3eLolium Perenne\u3c/em\u3e L.): Differentiation of Pasture and Turf Cultivars

Cultivar differentiation using molecular markers to assess genetic variation may be of value in obtaining or protecting plant breeders rights. A knowledge of genetic variation and how it is structured within perennial ryegrass (Lolium perenne L.) populations will also help us understand the consequences to fitness and adaptation when implementing molecular breeding strategies. In a study of the population genetic structure of a number of perennial ryegrass varieties we examined the cultivar differentiation potential of marker technology

Measured solid state and subcooled liquid vapour pressures of nitroaromatics using Knudsen effusion mass spectrometry

Knudsen effusion mass spectrometry (KEMS) was used to measure the solid state saturation vapour pressure (PsatS) of a range of atmospherically relevant nitroaromatic compounds over the temperature range from 298 to 328 K. The selection of species analysed contained a range of geometric isomers and differing functionalities, allowing for the impacts of these factors on saturation vapour pressure (Psat) to be probed. Three subsets of nitroaromatics were investigated: nitrophenols, nitrobenzaldehydes and nitrobenzoic acids. The PsatS values were converted to subcooled liquid saturation vapour pressure (PsatL) values using experimental enthalpy of fusion and melting point values measured using differential scanning calorimetry (DSC). The PsatL values were compared to those estimated by predictive techniques and, with a few exceptions, were found to be up to 7 orders of magnitude lower. The large differences between the estimated PsatL and the experimental values can be attributed to the predictive techniques not containing parameters to adequately account for functional group positioning around an aromatic ring, or the interactions between said groups. When comparing the experimental PsatS of the measured compounds, the ability to hydrogen bond (H bond) and the strength of the H bond formed appear to have the strongest influence on the magnitude of the Psat, with steric effects and molecular weight also being major factors. Comparisons were made between the KEMS system and data from diffusion-controlled evaporation rates of single particles in an electrodynamic balance (EDB). The KEMS and the EDB showed good agreement with each other for the compounds investigated

The influence of the addition of isoprene on the volatility of particles formed from the photo-oxidation of anthropogenic–biogenic mixtures

In this study, we investigate the influence of isoprene on the volatility of secondary organic aerosol (SOA) formed during the photo-oxidation of mixtures of anthropogenic and biogenic precursors. The SOA particle volatility was quantified using two independent experimental techniques (using a thermal denuder and the Filter Inlet for Gas and Aerosols iodide high-resolution time-of-flight Chemical Ionisation Mass Spectrometer – FIGAERO-CIMS) in mixtures of α-pinene/isoprene, o-cresol/isoprene, and α-pinene/o-cresol/isoprene. Single-precursor experiments at various initial concentrations and results from previous α-pinene/o-cresol experiments were used as a reference. The oxidation of isoprene did not result in the formation of detectable SOA particle mass in single-precursor experiments. However, isoprene-derived products were identified in the mixed systems, likely due to the increase in the total absorptive mass. The addition of isoprene resulted in mixture-dependent influence on the SOA particle volatility. Isoprene made no major change to the volatility of α-pinene SOA particles, though changes in the SOA particle composition were observed and the volatility was reasonably predicted based on the additivity. Isoprene addition increased o-cresol SOA particle volatility by ∼5/15 % of the total mass/signal, respectively, indicating a potential to increase the overall volatility that cannot be predicted based on the additivity. The addition of isoprene to the α-pinene/o-cresol system (i.e. α-pinene/o-cresol/isoprene) resulted in slightly fewer volatile particles than those measured in the α-pinene/o-cresol systems. The measured volatility in the α-pinene/o-cresol/isoprene system had an ∼6 % higher low volatile organic compound (LVOC) mass/signal compared to that predicted assuming additivity with a correspondingly lower semi-volatile organic compound (SVOC) fraction. This suggests that any effects that could increase the SOA volatility from the addition of isoprene are likely outweighed by the formation of lower-volatility compounds in more complex anthropogenic–biogenic precursor mixtures. Detailed chemical composition measurements support the measured volatility distribution changes and showed an abundance of unique-to-the-mixture products appearing in all the mixed systems accounting for around 30 %–40 % of the total particle-phase signal. Our results demonstrate that the SOA particle volatility and its prediction can be affected by the interactions of the oxidized products in mixed-precursor systems, and further mechanistic understanding is required to improve their representation in chemical transport models.</p

Gene-Associated Single Nucleotide Polymorphism Discovery in White Clover (\u3cem\u3eT. Repens\u3c/em\u3e L.)

Single nucleotide polymorphism (SNP) discovery permits the discovery of molecular marker variation associated with functionally-defined genes. SNP markers have been developed for the temperate pasture legume crop white clover (Trifolium repens) using public and proprietary genic sequences correlated with key agronomic traits of interest

Application of Molecular Technologies in Forage Plant Breeding

Key points A range of molecular breeding technologies have been developed for forage plant species including both transgenic and non-transgenic methodologies. The application of these technologies has the potential to greatly increase the range of genetic variation that is available for incorporation into breeding programs and subsequent delivery to producers in the form of improved germplasm. Further developments in detailing the phenotypic effect of genes and alleles both through research in target species and through inference from results from model species will further refine the delivery of new forage cultivars

Genetic Variation in the Perennial Ryegrass Fungal Endophyte \u3cem\u3eNeotyphodium Lolii\u3c/em\u3e

The common fungal endophytes (Neotyphodium species) of temperate pasture grasses are associated with improved tolerance to water and nutrient stress and resistance to insect pests, but are also the causal agents of animal toxicoses. Considerable variation exists among grass-endophyte associations for these beneficial and detrimental agronomic traits. The extent to which this variation may be attributed to the endophyte genotype, the host genotype or environmental interactions is currently unknown. The development of molecular genetic markers for endophytes based on simple sequence repeat (SSR) loci and the demonstration of the specific detection of endophytes in planta with these markers (van Zijll de Jong et al., 2005) allows efficient assessment of endophyte diversity in grass populations

Enhanced ozone loss by active inorganic bromine chemistry in the tropical troposphere

Abstract Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss (Theys et al., 2011) although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17-€“1.64 pptv BrO and 3.6-8 pptv total inorganic Br from these four species throughout the troposphere causes 10-20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br- and Cl-ˆ’) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species