scholarly journals Seasonal in situ observations of glyoxal and methylglyoxal over the temperate oceans of the Southern Hemisphere

2014 ◽  
Vol 14 (15) ◽  
pp. 21659-21708 ◽  
Author(s):  
S. J. Lawson ◽  
P. W. Selleck ◽  
I. E. Galbally ◽  
M. D. Keywood ◽  
M. J. Harvey ◽  
...  

Abstract. 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.

2015 ◽  
Vol 15 (1) ◽  
pp. 223-240 ◽  
Author(s):  
S. J. Lawson ◽  
P. W. Selleck ◽  
I. E. Galbally ◽  
M. D. Keywood ◽  
M. J. Harvey ◽  
...  

Abstract. 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.


2015 ◽  
Vol 15 (9) ◽  
pp. 5083-5097 ◽  
Author(s):  
M. D. Shaw ◽  
J. D. Lee ◽  
B. Davison ◽  
A. Vaughan ◽  
R. M. Purvis ◽  
...  

Abstract. Highly spatially resolved mixing ratios of benzene and toluene, nitrogen oxides (NOx) and ozone (O3) were measured in the atmospheric boundary layer above Greater London during the period 24 June to 9 July 2013 using a Dornier 228 aircraft. Toluene and benzene were determined in situ using a proton transfer reaction mass spectrometer (PTR-MS), NOx by dual-channel NOx chemiluminescence and O3 mixing ratios by UV absorption. Average mixing ratios observed over inner London at 360 ± 10 m a.g.l. were 0.20 ± 0.05, 0.28 ± 0.07, 13.2 ± 8.6, 21.0 ± 7.3 and 34.3 ± 15.2 ppbv for benzene, toluene, NO, NO2 and NOx respectively. Linear regression analysis between NO2, benzene and toluene mixing ratios yields a strong covariance, indicating that these compounds predominantly share the same or co-located sources within the city. Average mixing ratios measured at 360 ± 10 m a.g.l. over outer London were always lower than over inner London. Where traffic densities were highest, the toluene / benzene (T / B) concentration ratios were highest (average of 1.8 ± 0.5 ppbv ppbv-1), indicative of strong local sources. Daytime maxima in NOx, benzene and toluene mixing ratios were observed in the morning (~ 40 ppbv NOx, ~ 350 pptv toluene and ~ 200 pptv benzene) and in the mid-afternoon for ozone (~ 40 ppbv O3), all at 360 ± 10 m a.g.l.


2018 ◽  
Vol 40 ◽  
pp. 63 ◽  
Author(s):  
Rayonil Gomes Carneiro ◽  
Alice Henkes ◽  
Gilberto Fisch ◽  
Camilla Kassar Borges

In the present study, the evolution the diurnal cycle of planetary boundary layer in the wet season at Amazon region during a period of intense observations carried out in the GOAmazon Project 2014/2015 (Green Ocean Amazon).The analysis includes radiosonde and remote sensing data. In general case, the results of the daily cycle in the wet season indicate a Nocturnal boundary layer with a small oscillation in its depth and with a tardy erosion. The convective boundary layer did not present great depth, responding to the low values of sensible heat of the wet season. A comparison between the different techniques(in situ observations and remote sensing)  for estimating the planetary boundary layer is also presented.


2002 ◽  
Vol 2 (5) ◽  
pp. 1599-1633 ◽  
Author(s):  
M. Seifert ◽  
J. Ström ◽  
R. Krejci ◽  
A. Minikin ◽  
A. Petzold ◽  
...  

Abstract. In situ observations of aerosol particles contained in cirrus crystals are presented and compared to interstitial aerosol size distributions (non-activated particles in between the cirrus crystals). The observations were conducted in cirrus clouds in the Southern and Northern Hemisphere mid-latitudes during the INCA project. The first campaign in March and April 2000 was performed from Punta Arenas, Chile (54° S) in pristine air. The second campaign in September and October 2000 was performed from Prestwick, Scotland (53° N) in the vicinity of the North Atlantic flight corridor. Size distribution measurements of crystal residuals (particles remaining after evaporation of the crystals) show that small aerosol particles (Dp < 0.1µm) dominate the number density of residuals. The crystal residual size distributions were significantly different in the two campaigns. On average the residual size distributions were shifted towards larger sizes in the Southern Hemisphere. For a given integral residual number density, the calculated particle volume was on average three times larger in the Southern Hemisphere. This may be of significance to the vertical redistribution of aerosol mass by clouds in the tropopause region. In both campaigns the mean residual size increased with increasing crystal number density. The observations of ambient aerosol particles were consistent with the expected higher pollution level in the Northern Hemisphere. The fraction of residual particles only contributes to approximately a percent or less of the total number of particles, which is the sum of the residual and interstitial particles.


2010 ◽  
Vol 10 (8) ◽  
pp. 3615-3627 ◽  
Author(s):  
C. D. Homan ◽  
C. M. Volk ◽  
A. C. Kuhn ◽  
A. Werner ◽  
J. Baehr ◽  
...  

Abstract. We present airborne in situ measurements made during the AMMA (African Monsoon Multidisciplinary Analysis)/SCOUT-O3 campaign between 31 July and 17 August 2006 on board the M55 Geophysica aircraft, based in Ouagadougou, Burkina Faso. CO2 and N2O were measured with the High Altitude Gas Analyzer (HAGAR), CO was measured with the Cryogenically Operated Laser Diode (COLD) instrument, and O3 with the Fast Ozone ANalyzer (FOZAN). We analyse the data obtained during five local flights to study the dominant transport processes controlling the tropical tropopause layer (TTL, here ~350–375 K) and lower stratosphere above West-Africa: deep convection up to the level of main convective outflow, overshooting of deep convection, and horizontal inmixing across the subtropical tropopause. Besides, we examine the morphology of the stratospheric subtropical barrier. Except for the flight of 13 August, distinct minima in CO2 mixing ratios indicate convective outflow of boundary layer air in the TTL. The CO2 profiles show that the level of main convective outflow was mostly located at potential temperatures between 350 and 360 K, and for 11 August reached up to 370 K. While the CO2 minima indicate quite significant convective influence, the O3 profiles suggest that the observed convective signatures were mostly not fresh, but of older origin (several days or more). When compared with the mean O3 profile measured during a previous campaign over Darwin in November 2005, the O3 minimum at the main convective outflow level was less pronounced over Ouagadougou. Furthermore O3 mixing ratios were much higher throughout the whole TTL and, unlike over Darwin, rarely showed low values observed in the regional boundary layer. Signatures of irreversible mixing following overshooting of convective air were scarce in the tracer data. Some small signatures indicative of this process were found in CO2 profiles between 390 and 410 K during the flights of 4 and 8 August, and in CO data at 410 K on 7 August. However, the absence of expected corresponding signatures in other tracer data makes this evidence inconclusive, and overall there is little indication from the observations that overshooting convection has a profound impact on gas-phase tracer TTL composition during AMMA. We find the amount of photochemically aged air isentropically mixed into the TTL across the subtropical tropopause to be not significant. Using the N2O observations we estimate the fraction of aged extratropical stratospheric air in the TTL to be 0.0±0.1 up to 370 K during the local flights. Above the TTL this fraction increases to 0.3±0.1 at 390 K. The subtropical barrier, as indicated by the slope of the correlation between N2O and O3 between 415 and 490 K, does not appear as a sharp border between the tropics and extratropics, but rather as a gradual transition region between 10° N and 25° N where isentropic mixing between these two regions may occur.


2019 ◽  
Author(s):  
Xiaoyi Zhao ◽  
Debora Griffin ◽  
Vitali Fioletov ◽  
Chris McLinden ◽  
Jonathan Davies ◽  
...  

Abstract. Pandora spectrometers can retrieve nitrogen dioxide (NO2) vertical column densities (VCDs) via two viewing geometries: direct-sun and zenith-sky. The direct-sun NO2 VCD measurements have high quality (0.1 DU accuracy in clear-sky conditions) and do not rely on any radiative transfer model to calculate air mass factors (AMFs); however, they are not available when the sun is obscured by clouds. To perform NO2 measurements in cloudy conditions, a simple but robust NO2 retrieval algorithm is developed for Pandora zenith-sky measurements. This algorithm derives empirical zenith-sky NO2 AMFs from coincident high-quality direct-sun NO2 observations. Moreover, the retrieved Pandora zenith-sky NO2 VCD data are converted to surface NO2 concentrations with a scaling algorithm that uses chemical-transport-model predictions and satellite measurements as inputs. NO2 VCDs and surface concentrations are retrieved from Pandora zenith-sky measurements made in Toronto, Canada, from 2015 to 2017. The retrieved Pandora zenith-sky NO2 data (VCD and surface concentration) show good agreement with both satellite and in situ measurements. The diurnal and seasonal variations of derived Pandora zenith-sky surface NO2 data also agree well with in situ measurements (diurnal difference within ±2 ppbv). Overall, this work shows that the new Pandora zenith-sky NO2 products have the potential to be used in various applications such as future satellite validation in moderate cloudy scenes and air quality monitoring.


2010 ◽  
Vol 3 (3) ◽  
pp. 1359-1421
Author(s):  
R. Hommel ◽  
C. Timmreck ◽  
H. F. Graf

Abstract. In this paper we investigate results from a middle-atmosphere aerosol-climate model which has been developed to study the evolution of stratospheric aerosols. Here we focus on the stratospheric background period and evaluate several key quantities of the global dispersion of stratospheric aerosols and their precursors with observations and other model studies. It is shown that the model fairly well reproduces in situ observations of the aerosol size and number concentrations in the upper troposphere and lower stratosphere (UT/LS). Compared to measurements from the limb-sounding SAGE II satellite instrument, modelled integrated aerosol quantities are more biased the lower the moment of the aerosol population. Both findings are consistent with earlier work analysing the quality of SAGE II retrieved e.g. aerosol surface area densities from the volcanically unperturbed stratosphere (SPARC/ASAP, 2006; Thomason et al., 2008; Wurl et al., 2010). The model suggests that new particles are formed over large areas of the LS, albeit nucleation rates in the upper troposphere are at least one order of magnitude larger than those in the stratosphere. Hence, we suggest that both tropospheric sulphate aerosols and particles formed in situ in the LS are maintaining the stability of the stratospheric aerosol layer also in the absence of direct stratospheric emissions from volcanoes. Particle size distributions are clearly bimodal, except in the upper branches of the stratospheric aerosol layer where aerosols evaporate. Modelled concentrations of condensation nuclei (CN) are lesser than measured in regions of the aerosol layer where aerosol mixing ratios are largest, due to an overpredicted particle growth by coagulation. Transport regimes of tropical stratospheric aerosol have been identified from modelled aerosol mixing ratios and correspond to those deduced from satellite extinction measurements. We found that convective updraft in the Asian Monsoon region significantly contributes to both stratospheric aerosol load and size. The timing of formation and descend of layers of fine mode particles in the winter and spring polar stratosphere (CN layer) are reproduced by the model. Far above the tropopause where nucleation is inhibited due to with height increasing stratospheric temperatures, planetary wave mixing transports significant amounts of fine mode particles from the polar stratosphere to mid-latitudes. In those regions enhanced condensation rates of sulphuric acid vapour counteracts the evaporation of aerosols, hence prolonging the aerosol lifetime in the upper branches of the stratospheric aerosol layer. Measurements of the aerosol precursors SO2 and sulphuric acid vapour are fairly well reproduced by the model throughout the stratosphere.


2020 ◽  
Author(s):  
Michał Gałkowski ◽  
Armin Jordan ◽  
Michael Rothe ◽  
Julia Marshall ◽  
Frank-Thomas Koch ◽  
...  

Abstract. The intensive measurement campaign CoMet 1.0 (Carbon dioxide and Methane mission) took place during May and June 2018, with a focus on greenhouse gases over Europe. CoMet 1.0 aimed at characterising the distribution of CH4 and CO2 over significant regional sources with the use of a fleet of research aircraft, as well as validating remote sensing measurements from state-of-the-art instrumentation installed on-board against a set of independent in-situ observations. Here we present the results of over 55 hours of accurate and precise in situ measurements of CO2, CH4 and CO mixing ratios made during CoMet 1.0 flights with a cavity ring-down spectrometer aboard the German research aircraft HALO, together with results from analyses of 96 discrete air samples collected aboard the same platform. A careful in-flight calibration strategy together with post-flight quality assessment made it possible to determine both the single measurement precision as well as biases against respective WMO scales. We compare the result of greenhouse gas observations against two of the available global modelling systems, namely Jena CarboScope and CAMS (Copernicus Atmosphere Monitoring Service). We find overall good agreement between the global models and the observed mixing ratios in the free-tropospheric range, characterised by very low bias values for the CAMS CH4 and the CarboScope CO2 products, with a mean free tropospheric offset of 0 (14) ppb and 0.8 (1.3) ppm respectively, with the quoted number giving the standard uncertainty in the final digits for the numerical value. Higher bias is observed for CAMS CO2 (equal to 3.7 (1.5) ppm), and for CO the model-observation mismatch is variable with height (with offset equal to −1.0 (8.8)). We also present laboratory analyses of air samples collected throughout the flights, which include information on the isotopic composition of CH_4, and we demonstrate the potential of simultaneously measuring δ13C-CH4 and δ2H-CH4 from air to determine the sources of enhanced methane signals using even a limited amount of discrete samples. Using flasks collected during two flights over the Upper Silesian Coal Basin (USCB, southern Poland), one of the strongest methane-emitting regions in the European Union, we were able to use the Miller-Tans approach to derive the isotopic signature of the measured source, with values of δ2H equal to −224.7 (6.6) permil and δ13C to −50.9 (1.1) permil, giving significantly lower d2H values compared to previous studies in the area.


2010 ◽  
Vol 10 (2) ◽  
pp. 3173-3187
Author(s):  
T. Warneke ◽  
A. K. Petersen ◽  
C. Gerbig ◽  
A. Jordan ◽  
C. Rödenbeck ◽  
...  

Abstract. The first ground-based remote sensing measurements of the column averaged volume mixing ratio of CO2 (XCO2) for the inner tropics have been obtained at Paramaribo, Suriname (5.8° N, 55.2° W). The remote sensing observations are complemented by surface air-samples collected at the site, analyzed for CO2 and 13CO2. The surface in-situ measurements are strongly influenced by local sources. From the isotopic composition of the air samples the local source component is suggested to be dominated by the terrestrial biosphere. Using δ13C from the NOAA/ESRL stations Ascension Is. (ASC), 7.9° S, 14.4° W, and Ragged Point (RPB), 7.9° S, 14.4° W, the data has been corrected for the local source component. Due to the migration of the ITCZ over the measurement site the probed air masses belong to the Northern or Southern Hemisphere depending on the time of the year. Comparison to analyzed CO2 fields based on TM3 model simulations using optimized fluxes indicate agreement for XCO2 as well as for the corrected CO2 mixing ratios at the surface for the long dry season, when Paramaribo belongs to the Southern Hemisphere. A slightly worse agreement during the short dry season is attributed to a larger representation error during this time of the year. Overall the comparison demonstrates that the TM3 model is capable to simulate surface concentrations as well as column densities of CO2 correctly at the same location.


2020 ◽  
Author(s):  
Ji Sung Na ◽  
Taekyun Kim ◽  
Emilia Kyung Jin ◽  
Seung-Tae Yoon ◽  
Won Sang Lee ◽  
...  

Abstract. The role of the refreezing effect in the ice shelf–ocean boundary layer (IOBL) flow with a super-cooled, plume beneath the ice shelf is investigated using the large-eddy simulation. To reveal the detailed physical processes and characteristics of the IOBL flow, a model domain is initialized and forced by in situ observations and a comparison is made between two simulations, one with the refreezing effect and one without. The simulated velocity, potential temperature, and salinity field are validated with in situ observations performed in Terra Nova Bay in the western Ross Sea in 2016/2017, confirming that the vertical structures in the simulation results agree well with observations. In particular, it is evident that, when the refreezing effect is considered, the IOBL flow can be more realistically resolved, especially upward advection from the sub-ice shelf plume and the ice front eddy. Beneath the ice shelf, two district regions (the inner and outer regions) are identified based on flow characteristics and the refreezing pattern. In the inner region, stratification and stable conditions are observed with negative momentum flux and low refreezing rates. Meanwhile, in the outer region, high shear impact and unstable conditions with a heat flux of −9 to −52 W m−2 are observed, demonstrating the high refreezing rate and the entrainment of super-cooled water from the sub-ice shelf plume. A total of 94 % of the refreezing events occur in the outer region, with a maximum refreezing rate of 1.86 m yr−1 at the ice front.


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