Key Role of NO3 Radicals in the Production of Isoprene Nitrates and Nitrooxyorganosulfates in Beijing.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

Investigation of East Asian Emissions of CFC-11 Using Atmospheric Observations in Taiwan.

Recent findings of an unexpected slowdown in the decline of CFC-11 mixing ratios in the atmosphere have led to the conclusion that global CFC-11 emissions have increased over the past decade and have been attributed in part to eastern China. This study independently assesses these findings by evaluating enhancements of CFC-11 mixing ratios in air samples collected in Taiwan between 2014 and 2018. Using the NAME (Numerical Atmospheric Modeling Environment) particle dispersion model, we find the likely source of the enhanced CFC-11 observed in Taiwan to be East China. Other halogenated trace gases were also measured, and there were positive interspecies correlations between CFC-11 and CHCl3, CCl4, HCFC-141b, HCFC-142b, CH2Cl2, and HCFC-22, indicating co-location of the emissions of these compounds. These correlations in combination with published emission estimates of CH2Cl2 and HCFC-22 from China, and of CHCl3 and CCl4 from eastern China, are used to estimate CFC-11 emissions. Within the uncertainties, these estimates do not differ for eastern China and the whole of China, so we combine them to derive a mean estimate that we term as being from "(eastern) China". For 2014-2018, we estimate an emission of 19 ± 5 Gg year-1 (gigagrams per year) of CFC-11 from (eastern) China, approximately one-quarter of global emissions. Comparing this to previously reported CFC-11 emissions estimated for earlier years, we estimate CFC-11 emissions from (eastern) China to have increased by 7 ± 5 Gg year-1 from the 2008-2011 average to the 2014-2018 average, which is 50 ± 40% of the estimated increase in global CFC-11 emissions and is consistent with the emission increases attributed to this region in an earlier study.

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

An improved dual channel PERCA instrument for atmospheric measurements of peroxy radicals.

This paper describes a new dual-channel PEroxy RadiCal Amplification (PERCA) instrument, which has been designed to improve the time resolution and signal to noise and to reduce the interference caused by variations in ambient ozone concentrations. The instrument was run at the Weybourne Atmospheric Observatory (WAO), North Norfolk, during WAOWEX (Weybourne Atmospheric Observatory Winter Experiment) in January/February 2002 and INSPECTRO (Influence of clouds on the spectral actinic flux in the lower troposphere) in September 2002. The performance of the instrument is assessed and compared to that of a single channel instrument. In particular, it is shown how the precision is greatly improved in fluctuating background ozone conditions. In addition the improved time response of the instrument allows changes in peroxy radical concentrations to be related to rapid changes in nitric oxide concentrations and the ozone photolysis frequency, j(O(1)D).

Airborne measurements of peroxy radicals using the PERCA technique.

The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO2) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO2 yield with an improved 'Luminox' LMA-3 NO2 detector. NO2 from the amplification chemistry is distinguished from other sources of NO2 reaching the detector by periodically injecting CO approximately 1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically approximately 260 (ground level) to approximately 200 (7,000 m). This variation with altitude is less than the variation associated with the 'age' of the PFA inlet material where the amplification chemistry occurs; CL's of approximately 200 with old tubing to approximately 300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH3I in air, producing CH3O2 in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO2 + RO2) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.