ALBERT

Description: Dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in late summer (February–March) over the Chatham Rise in the South West Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in late winter (August–September) 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim, and 24 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 12 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent MAX-DOAS observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal 〉 1 over Chatham Rise but 〈 1 at Cape Grim, suggesting different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1–3 ppt of dicarbonyls observed, corresponding to 11 and 17% of the observed glyoxal and 28 and 10% of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Glyoxal surface observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter, however satellite vertical column densities exceeded the surface observations by more than 1.5 × 1014 molecules cm−2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption, or use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much needed data to verify the presence of these short lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.

Description: Marine nitrogen fixation is co-limited by the supply of iron and phosphorus in large areas of the global ocean. Up to 75 % of marine nitrogen fixation may be limited by iron supply due to the relatively high iron requirements of planktonic diazotrophs (Berman-Frank et al., 2001). The deposition of soluble aerosol iron can initiate nitrogen fixation and trigger toxic algal blooms in nitrate-poor tropical waters. There is a large variability in estimates of soluble iron, related to the mixing of aerosol iron sources. Most studies assume that mineral dust represents the primary source of soluble iron in the atmosphere. However, seasonal biomass burning in tropical regions is a potential source of aerosol iron that could explain the large variability of soluble iron in those regions. To investigate aerosol iron sources to the adjacent tropical waters of Australia, the fractional solubility of aerosol iron was determined during the Savannah Fires in the Early Dry Season (SAFIRED) campaign at Gunn Point, Northern Territory, Australia during the dry season in 2014. The source of particulate matter less than 10 µm (PM10) aerosol iron was a mixture of mineral dust, fresh biomass burning aerosol, sea spray and anthropogenic pollution. The mean soluble and total aerosol iron concentrations were 40 and 500 ng m−3 respectively. Fractional Fe solubility was relativity high for the majority of the campaign and averaged 8 % but dropped to 3 % during the largest and most proximal fire event. Fractional Fe solubility and proxies for biomass burning (elemental carbon, levoglucosan, oxalate and carbon monoxide) were unrelated throughout the campaign. An explanation of the lack of correlation between fractional Fe solubility and elemental carbon at the biomass burning source is due to the physical properties of elemental carbon, i.e., fresh elemental carbon aerosols are initially hydrophobic, however they can disperse in water after aging and coating with water soluble species in the atmosphere. Combustion aerosols are thought to have a high factional Fe solubility, which can increase during atmospheric transport from the source. Although, biomass burning derived particles may not be a direct source of soluble iron, they can act indirectly as a surface for aerosols iron to bind during atmospheric transport and subsequently be released to the ocean upon deposition. In addition, biomass burning derived aerosols can indirectly impact the fractional solubility of mineral dust. Fractional Fe solubility was highest during dust events at Gunn Point, and could have been enhanced by mixing with biomass burning derived aerosols. Iron in dust may be more soluble in the tropics compared to higher latitudes due to the presence higher concentrations of biomass burring derived reactive organic species in the atmosphere, such as oxalate, and their potential to enhance the fractional Fe solubility of mineral dust. As the aerosol loading is dominated by biomass burning emissions over the tropical waters in the dry season, additions of biomass burning derived soluble iron could have harmful consequences for initiating nitrogen fixing toxic algal blooms. Future research is required to quantify biomass burning derived particle sources of soluble iron over tropical waters.

Description: The dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high-performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in summer (February–March) over the Chatham Rise in the south-west Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in the late winter (August–September) of 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim and 23 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 10 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal 〉 1 over Chatham Rise but 〈 1 at Cape Grim suggest that a different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper-estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1–3 ppt of dicarbonyls observed, corresponding to 10% and 17% of the observed glyoxal and 29 and 10% of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Surface-level glyoxal observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter; however, satellite vertical column densities exceeded the surface observations by more than 1.5 × 1014 molecules cm−2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or it may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption or the use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much-needed data to verify the presence of these short-lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.