Formaldehyde, glyoxal, and methylglyoxal in air and cloudwater at a rural mountain site in central Virginia

As part of the Shenandoah Cloud and Photochemistry Experiment (SCAPE), we measured formaldehyde (HCHO), glyoxal (CHOCHO), and methylglyoxal (CH3C(O)CHO) concentrations in air and cloudwater at Pinnacles (elevation 1037 m) in Shenandoah National Park during September 1990. Mean gas‐phase concentrations of HCHO and CHOCHO were 980 and 44 pptv, respectively. The concentration of CH3C(O)CHO rarely exceeded the detection limit of 50 pptv. Mean cloudwater concentrations of HCHO and CHOCHO were 9 and 2 μM, respectively; the mean CH3C(O)CHO concentration was below its detection limit of 0.3 μM. The maximum carbonyl concentrations were observed during stagnation events with high O3, peroxides, and CO. Outside of these events the carbonyls did not correlate significantly with O3, CO, or NOy. Carbonyl concentrations and concentration ratios were consistent with a major source for the carbonyls from isoprene oxidation. Oxidation of CH4 supplies a significant background of HCHO. The carbonyl concentrations were indistinguishable in two size fractions of cloudwater having a cut at d=18 μm. Gas‐ and aqueous‐phase concentrations of HCHO from samples collected during a nighttime cloud event agree with thermodynamic equilibria within a factor of 2. Samples collected during a daytime cloud event show HCHO supersaturation by up to a factor of 4. Positive artifacts in the cloudwater samples due to hydrolysis of hydroxymethylhydroperoxide (HOCH2OOH) could perhaps account for this discrepancy

Two-hundred-year record of biogenic sulfur in a south Greenland ice core (20D)

The concentration of methanesulfonic acid (MSA) was determined in a shallow south central Greenland ice core(20D). This study provides a high-resolution record of the DMS-derived biogenic sulfur in Greenland precipitation over the past 200 years. The mean concentration of MSA is 3.30 ppb(σ = 2.38 ppb,n = 1134). The general trend of MSA is an increase from 3.01 to 4.10 ppb between 1767 and 1900, followed by a steady decrease to 2.34 ppb at the present time. This trend is in marked contrast to that of non-sea-salt sulfate (nss SO42-), which increases dramatically after 1900 due to the input of anthropogenic sulfur. The MSA fraction ((MSA/(MSA+ nss SO42-))* 100) ranges from a mean of 15% in preindustrial ice to less than 5% in recent ice. These MSA fraction suggest that approximately 5 to 40% of the sulfur in recent Greenland ice is of biological origin. It is suggested that there is a significant low-latitude component to the biogenic sulfur in the core and that variations in the MSA fraction reflect changes in the relative strengths of low- and high-latitude inputs. The data shown o evidence for a strong dependence of dimethyl sulfide(DMS) emissions on sea surface temperature during the last century. There is also no indication that the yield of MSA from DMS oxidation has been altered by increased NOx levels over the North Atlantic during this period

Regional and hemispheric influences on measured spring peroxyacetyl nitrate (PAN) mixing ratios at the Auchencorth UK EMEP supersite

AbstractThis work presents 15-min averaged measurements of peroxyacetyl nitrate (PAN) obtained during spring 2014 (24/04/2014 – 06/05/2014) at the Auchencorth UK EMEP supersite (southeast Scotland). The aim of this analysis was to investigate the conditions producing the distribution of PAN mixing ratios at the supersite in spring 2014. Air mass back trajectories showed the majority of air masses to have spent substantial time over the UK, continental Europe or Scandinavia prior to arrival at Auchencorth. The median and 95th percentile PAN mixing ratios observed were 0.46ppb and 1.03ppb, respectively. The median mixing ratio was elevated compared with previous PAN measurements during springtime (April–May) in southeast Scotland (corresponding median mixing ratios April–May 1994–1998: 0.1–0.3ppb), which is hypothesised to be due to conditions conducive to regional (European) photochemical PAN production. Additionally, PAN mixing ratios during regionally influenced conditions (0.4–1.5ppb) were substantially more elevated from hemispheric background mixing ratios (0.4–0.6ppb) than for ozone (O3, regional: 10–45ppb, hemispheric: 30–40ppb). PAN and O3 both impact upon vegetation and human health and it is necessary to understand the extent to which hemispheric and regional processes contribute to their abundances in different locations. Regional processes can both increase and decrease PAN and O3 mixing ratios compared to imported hemispheric background mixing ratios. This study concludes that during the measurement period in spring 2014 at the Auchencorth supersite, regional PAN and O3 modifying processes enhanced PAN mixing ratios more than for O3