scholarly journals A broadband cavity ringdown spectrometer for in-situ measurements of atmospheric trace gases

2005 ◽  
Vol 5 (3) ◽  
pp. 3491-3532 ◽  
Author(s):  
M. Bitter ◽  
S. M. Ball ◽  
I. M. Povey ◽  
R. L. Jones
Keyword(s):  
Boundary Layer ◽  
Water Vapour ◽  
Marine Boundary Layer ◽  
Thermal Dissociation ◽  
Optical Absorption Spectroscopy ◽  
Integration Time ◽  
Research Station ◽  
Absorption Bands ◽  
Optical Extinction ◽  
Cavity Ringdown

Abstract. This paper describes a broadband cavity ringdown spectrometer and its deployment during the 2002 North Atlantic Marine Boundary Layer Experiment (NAMBLEX) to measure ambient concentrations of NO3, N2O5, I2 and OIO at the Mace Head Atmospheric Research Station, Co. Galway, Ireland. The effective absorption path lengths accessible with the spectrometer generally exceeded 10 km, enabling sensitive localised ''point'' measurements of atmospheric absorbers to be made adjacent to the other instruments monitoring chemically related species at the same site. For the majority of observations, the spectrometer was used in an open path configuration thereby avoiding surface losses of reactive species. A subset of observations targeted the N2O5 molecule by detecting the additional NO3 formed by the thermal dissociation of N2O5. In all cases the concentrations of the atmospheric absorbers were retrieved by fitting the differential structure in the broadband cavity ringdown spectra using a methodology adapted from long path differential optical absorption spectroscopy. The uncertainty of the retrieval depends crucially on the correct treatment and fitting of the absorption bands due to water vapour, a topic that is discussed in the context of analysing broadband cavity ringdown spectra. The quality of the measurements and the retrieval method are illustrated with representative spectra acquired during NAMBLEX in spectral regions around 660 nm (NO3 and N2O5) and 570 nm (I2 and OIO). Typical detection limits were 1 pptv for NO3 in an integration time of 100 s, 4 pptv for OIO and 20 pptv for I2 in an integration time of 10 min. Additionally, the concentrations of atmospheric water vapour and the aerosol optical extinction were retrieved in both spectral regions. A companion paper in this issue presents the time series of the measurements and discusses their significance for understanding the variability of short lived nitrogen and iodine compounds in the marine boundary layer.

scholarly journals A broadband cavity ringdown spectrometer for in-situ measurements of atmospheric trace gases

2005 ◽  
Vol 5 (9) ◽  
pp. 2547-2560 ◽  
Author(s):  
M. Bitter ◽  
S. M. Ball ◽  
I. M. Povey ◽  
R. L. Jones
Keyword(s):  
Boundary Layer ◽  
Water Vapour ◽  
Marine Boundary Layer ◽  
Thermal Dissociation ◽  
Optical Absorption Spectroscopy ◽  
Integration Time ◽  
Research Station ◽  
Absorption Bands ◽  
Optical Extinction ◽  
Cavity Ringdown

Abstract. This paper describes a broadband cavity ringdown spectrometer and its deployment during the 2002 North Atlantic Marine Boundary Layer Experiment (NAMBLEX) to measure ambient concentrations of NO3, N2O5, I2 and OIO at the Mace Head Atmospheric Research Station, Co. Galway, Ireland. The effective absorption path lengths accessible with the spectrometer generally exceeded 10 km, enabling sensitive localised ``point" measurements of atmospheric absorbers to be made adjacent to the other instruments monitoring chemically related species at the same site. For the majority of observations, the spectrometer was used in an open path configuration thereby avoiding surface losses of reactive species. A subset of observations targeted the N2O5 molecule by detecting the additional NO3 formed by the thermal dissociation of N2O5. In all cases the concentrations of the atmospheric absorbers were retrieved by fitting the differential structure in the broadband cavity ringdown spectra using a methodology adapted from long path differential optical absorption spectroscopy. The uncertainty of the retrieval depends crucially on the correct treatment and fitting of the absorption bands due to water vapour, a topic that is discussed in the context of analysing broadband cavity ringdown spectra. The quality of the measurements and the retrieval method are illustrated with representative spectra acquired during NAMBLEX in spectral regions around 660 nm (NO3 and N2O5) and 570 nm (I2 and OIO). Typical detection limits were 1 pptv for NO3 in an integration time of 100 s, 4 pptv for OIO and 20 pptv for I2 in an integration time of 10 min. Additionally, the concentrations of atmospheric water vapour and the aerosol optical extinction were retrieved in both spectral regions. A companion paper in this issue presents the time series of the measurements and discusses their significance for understanding the variability of short lived nitrogen and iodine compounds in the marine boundary layer.

scholarly journals A novel instrument for measurements of BrO with LED based Cavity-Enhanced Differential Optical Absorption Spectoscopy

2013 ◽  
Vol 6 (4) ◽  
pp. 6047-6096
Author(s):  
D. J. Hoch ◽  
J. Buxmann ◽  
H. Sihler ◽  
D. Pöhler ◽  
C. Zetzsch ◽  
...  
Keyword(s):  
Optical Absorption ◽  
Marine Boundary Layer ◽  
Detection Limits ◽  
High Sensitivity ◽  
Field Measurements ◽  
Reaction Chamber ◽  
Optical Absorption Spectroscopy ◽  
Integration Time ◽  
Polar Regions ◽  
Chamber Studies

Abstract. The chemistry of the troposphere and specifically the global tropospheric ozone budget is affected by reactive halogen species like Bromine monoxide (BrO) or Chlorine monoxide (ClO). Especially BrO plays an important role in the processes of ozone destruction, disturbance of NOx and HOx chemistry, oxidation of DMS, and the deposition of elementary mercury. In the troposphere BrO has been detected in polar regions, at salt lakes, in volcanic plumes, and in the marine boundary layer. For a better understanding of these processes field measurements as well as reaction-chamber studies are performed. In both cases instruments with high spatial resolution and high sensitivity are necessary. A Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) instrument with an open path measurement cell was designed and applied. For the first time, a CE-DOAS instrument is presented using an UV-LED in the 325–365 nm wavelength range. In laboratory studies, BrO as well as HONO, HCHO, O3, and O4, could be reliable determined at detection limits of 20 ppt for BrO, 9.1 ppb for HCHO, 970 ppt for HONO, and 91 ppb for O3, for five minutes integration time, respectively. The best detection limits were achieved for BrO (11 ppt), HCHO (5.1 ppb), HONO (490 ppt), and O3 (59 ppb) for integration times of 81 min or less. Comparison with established White-System DOAS and O3 monitor demonstrate the reliability of the instrument.

scholarly journals Airborne DOAS measurements in Arctic: vertical distributions of aerosol extinction coefficient and NO<sub>2</sub> concentration

2011 ◽  
Vol 11 (5) ◽  
pp. 13525-13574
Author(s):  
A. Merlaud ◽  
M. Van Roozendael ◽  
N. Theys ◽  
C. Fayt ◽  
C. Hermans ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Scattered Light ◽  
Optical Absorption Spectroscopy ◽  
North Coast ◽  
Aerosol Extinction ◽  
Back Trajectories ◽  
The North ◽  
Source Regions ◽  
Vertical Distributions

Abstract. We report airborne differential optical absorption spectroscopy (DOAS) measurements of aerosol extinction and NO2 tropospheric profiles performed off the North coast of Norway in April 2008. The DOAS instrument was installed on the Safire ATR-42 aircraft during the POLARCAT-France spring campaign and recorded scattered light spectra in near-limb geometry using a scanning telescope. We use O4 slant column measurements to derive the aerosol extinction at 360 nm. Regularization is based on the maximum a posteriori solution, for which we compare a linear and a logarithmic approach. The latter inherently constrains the solution to positive values and yields aerosol extinction profiles more consistent with independently measured size distributions. Two soundings are presented, performed on 8 April 2008 above 71° N, 22° E and on 9 April 2008 above 70° N, 17.8° E. The first profile shows aerosol extinction and NO2 in the marine boundary layer with respective values of 0.04±0.005 km−1 and 1.9±0.3 × 109 molec cm−3. A second extinction layer of 0.01±0.003 km−1 is found at 4 km altitude. During the second sounding, clouds prevented us to retrieve profile parts under 3 km altitude but a layer with enhanced extinction (0.025±0.005 km−1) and NO2 (1.95±0.2 × 109 molec cm−3) is clearly detected at 4 km altitude. From CO and ozone in-situ measurements complemented by back-trajectories, we interpret the measurements in the free troposphere as, for the first sounding, a mix between stratospheric and polluted air from Northern Europe and for the second sounding, polluted air from Central Europe containing NO2. Considering the boundary layer measurements of the first flight, modeled source regions indicate closer sources, especially the Kola Peninsula smelters, which can explain the NO2 enhancement not correlated with a CO increase at the same altitude.

scholarly journals Concentrations of OH and HO<sub>2</sub> radicals during NAMBLEX: measurements and steady state analysis

2005 ◽  
Vol 5 (6) ◽  
pp. 12403-12464 ◽  
Author(s):  
S. C. Smith ◽  
J. D. Lee ◽  
W. J. Bloss ◽  
G. P. Johnson ◽  
D. E. Heard
Keyword(s):  
Boundary Layer ◽  
Steady State ◽  
Detection Limit ◽  
Diurnal Variation ◽  
Marine Boundary Layer ◽  
Chemical Conversion ◽  
Early Morning ◽  
Research Station ◽  
Solar Noon ◽  
Mean Concentration

Abstract. OH and HO2 concentrations were measured simultaneously at the Mace Head Atmospheric Research Station in the summer of 2002 during the NAMBLEX (North Atlantic Marine Boundary Layer EXperiment) field campaign. OH was measured by laser-induced fluorescence employing the FAGE (Fluorescence Assay by Gas Expansion) technique, with a mean daytime detection limit of 2.7×105 molecule cm−3 (5 min acquisition period; signal-to-noise ratio = 1). HO2 was detected as OH following its chemical conversion through addition of NO, with a mean detection limit of 4.4×106 molecule cm−3. The diurnal variation of OH was measured on 24 days, and that of HO2 on 17 days. The local solar noon OH concentrations ranged between (3–8)×106 molecule cm−3, with a 24 h mean concentration of 9.1×105 molecule cm−3. The local solar noon HO2 concentrations were (0.9–2.1)×108 molecule cm−3 (3.5–8.2 pptv), with a 24 h mean concentration of 4.2×107 molecule cm−3. HO2 radicals in the range (2–3)×107 molecule cm−3 were observed at night. During NAMBLEX, a comprehensive suite of supporting measurements enabled a detailed study of the behaviour of HOx radicals under primarily clean marine conditions. Case study periods highlight the typical radical levels observed under different conditions. Steady state expressions are used to calculate OH and HO2 concentrations and to evaluate the effect of different free-radical sources and sinks. The diurnally averaged calculated to measured OH ratio was 1.04±0.36, but the ratio displays a distinct diurnal variation, being less than 1 during the early morning and late afternoon/evening, and greater than 1 in the middle of the day. For HO2 there was an overprediction, with the agreement between calculated and measured concentrations improved by including reaction with measured IO and BrO radicals and uptake to aerosols. Increasing the concentration of IO radicals included in the calculations to above that measured by a DOAS instrument with an absorption path located mainly over the ocean, reflecting the domination of the inter-tidal region as an iodine source at Mace Head, led to further improvement. The results are compared with previous measurements at Mace Head, and elsewhere in the remote marine boundary layer.

scholarly journals On the relative absorption strengths of water vapour in the blue wavelength range

2015 ◽  
Vol 8 (6) ◽  
pp. 5895-5936 ◽  
Author(s):  
J. Lampel ◽  
D. Pöhler ◽  
J. Tschritter ◽  
U. Frieß ◽  
U. Platt
Keyword(s):  
Water Vapour ◽  
Cross Sections ◽  
Spectral Region ◽  
Field Measurements ◽  
Optical Absorption Spectroscopy ◽  
Absorption Cross ◽  
Absorption Bands ◽  
Blue Wavelength ◽  
Water Vapour Absorption ◽  
Density Ratios

Abstract. In recent updates of the HITRAN water vapour H2O spectroscopic compilation covering the blue spectral region (here: 394–480 nm) significant changes for the absorption bands at 416 and 426 nm were reported. In order to investigate the consistency of the different cross-sections calculated from these compilations, H2O vapour column density ratios for different spectral intervals were retrieved from Long-path and Multi-Axis – Differential Optical Absorption Spectroscopy (DOAS) measurements. We observed a significant improvement of the DOAS evaluation when using the updated HITRAN water vapour absorption cross-sections for the calculation of the reference spectra. In particular the magnitudes of the residual spectra as well as the fit errors were reduced. However we also found that the best match between measurement and model is reached when the absorption cross-section of groups of lines are scaled by factors ranging from 0.5 and 1.9, suggesting that the HITRAN water vapour absorption compilation still needs significant corrections. For this spectral region we present correction factors for HITRAN 2009, HITRAN 2012, HITEMP and BT2 derived from field measurements. Additionally, upper limits for water vapour absorption in the UV-A range from 330–390 nm are given.

scholarly journals In situ measurements of molecular iodine in the marine boundary layer: the link to macroalgae and the implications for O<sub>3</sub>, IO, OIO and NO<sub>x</sub>

2010 ◽  
Vol 10 (1) ◽  
pp. 361-390
Author(s):  
R.-J. Huang ◽  
K. Seitz ◽  
J. Buxmann ◽  
D. Poehler ◽  
K. E. Hornsby ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Single Point ◽  
Molecular Iodine ◽  
In Situ Measurements ◽  
Gas Chromatography Mass Spectrometry ◽  
Optical Absorption Spectroscopy ◽  
Mixing Ratios ◽  
Concentration Levels

Abstract. "Single-point" in situ measurements of molecular iodine (I2) were carried out in the coastal marine boundary layer (MBL) using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. Comparison measurements were taken at Mace Head and Mweenish Bay, on the West Coast of Ireland. The observed mixing ratios of I2 at Mweenish Bay are much higher than that at Mace Head, indicating the emissions of I2 are correlated with the local algal biomass density and algae species. The concentration levels of I2 were found to correlate inversely with tidal height and correlate positively with the concentration levels of O3 in the surrounding air. However, the released I2 can also lead to O3 destruction via the reaction of O3 with iodine atoms that are formed by the photolysis of I2 during the day and via the reaction of I2 with NOx at night. IO and OIO were measured by long-path differential optical absorption spectroscopy (LP-DOAS). The results show that the concentrations of both daytime and nighttime IO are correlated with the mixing ratios of I2. OIO was observed not only during the day but also, for the first time at both Mace Head and Mweenish Bay, at night. In addition, I2 was measured simultaneously by the LP-DOAS technique and compared with the "single-point" in situ measurement. The results suggest that the local algae sources dominate the inorganic iodine chemistry at Mace Head and Mweenish Bay.

scholarly journals Meridional and vertical variations of the water vapour isotopic composition in the marine boundary layer over the Atlantic and Southern Ocean

2020 ◽  
Vol 20 (9) ◽  
pp. 5811-5835 ◽  
Author(s):  
Iris Thurnherr ◽  
Anna Kozachek ◽  
Pascal Graf ◽  
Yongbiao Weng ◽  
Dimitri Bolshiyanov ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Time Series ◽  
Wind Speed ◽  
Southern Ocean ◽  
Water Vapour ◽  
Turbulent Mixing ◽  
Large Scale ◽  
Marine Boundary Layer ◽  
Sea Spray ◽  
Moisture Source

Abstract. Stable water isotopologues (SWIs) are useful tracers of moist diabatic processes in the atmospheric water cycle. They provide a framework to analyse moist processes on a range of timescales from large-scale moisture transport to cloud formation, precipitation and small-scale turbulent mixing. Laser spectrometric measurements on research vessels produce high-resolution time series of the variability of the water vapour isotopic composition in the marine boundary layer. In this study, we present a 5-month continuous time series of such ship-based measurements of δ2H and δ18O from the Antarctic Circumnavigation Expedition (ACE) in the Atlantic and the Southern Ocean in the time period from November 2016 to April 2017. We analyse the drivers of meridional SWI variations in the marine boundary layer across diverse climate zones in the Atlantic and Southern Ocean using Lagrangian moisture source diagnostics and relate vertical SWI differences to near-surface wind speed and ocean surface state. The median values of δ18O, δ2H and deuterium excess during ACE decrease continuously from low to high latitudes. These meridional SWI distributions reflect climatic conditions at the measurement and moisture source locations, such as air temperature, specific humidity and relative humidity with respect to sea surface temperature. The SWI variability at a given latitude is highest in the extratropics and polar regions with decreasing values equatorwards. This meridional distribution of SWI variability is explained by the variability in moisture source locations and its associated environmental conditions as well as transport processes. The westward-located moisture sources of water vapour in the extratropics are highly variable in extent and latitude due to the frequent passage of cyclones and thus widen the range of encountered SWI values in the marine boundary layer. Moisture loss during transport further contributes to the high SWI variability in the extratropics. In the subtropics and tropics, persistent anticyclones lead to well-confined narrow easterly moisture source regions, which is reflected in the weak SWI variability in these regions. Thus, the expected range of SWI signals at a given latitude strongly depends on the large-scale circulation. Furthermore, the ACE SWI time series recorded at 8.0 and 13.5 m above the ocean surface provide estimates of vertical SWI gradients in the lowermost marine boundary layer. On average, the vertical gradients with height found during ACE are -0.1‰m-1 for δ18O, -0.5‰m-1 for δ2H and 0.3 ‰ m−1 for deuterium excess. Careful calibration and post-processing of the SWI data and a detailed uncertainty analysis provide a solid basis for the presented gradients. Using sea spray concentrations and sea state conditions, we show that the vertical SWI gradients are particularly large during high wind speed conditions with increased contribution of sea spray evaporation or during low wind speed conditions due to weak vertical turbulent mixing. Although further SWI measurements at a higher vertical resolution are required to validate these findings, the simultaneous SWI measurements at several heights during ACE show the potential of SWIs as tracers for vertical mixing and sea spray evaporation in the lowermost marine boundary layer.

scholarly journals Measurements and modelling of molecular iodine emissions, transport and photodestruction in the coastal region around Roscoff

2010 ◽  
Vol 10 (23) ◽  
pp. 11823-11838 ◽  
Author(s):  
R. J. Leigh ◽  
S. M. Ball ◽  
J. Whitehead ◽  
C. Leblanc ◽  
A. J. L. Shillings ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Coastal Region ◽  
Molecular Iodine ◽  
Transport Processes ◽  
Optical Absorption Spectroscopy ◽  
Emission Rates ◽  
Cavity Ringdown Spectroscopy ◽  
The Relationship

Abstract. Iodine emissions from the dominant six macroalgal species in the coastal regions around Roscoff, France, have been modelled to support the Reactive Halogens in the Marine Boundary Layer Experiment (RHaMBLe) undertaken in September 2006. A two-dimensional model is used to explore the relationship between geographically resolved regional emissions (based on maps of seaweed beds in the area and seaweed I2 emission rates previously measured in the laboratory) and in situ point and line measurements of I2 performed respectively by a broadband cavity ringdown spectroscopy (BBCRDS) instrument sited on the shoreline and a long-path differential optical absorption spectroscopy (LP-DOAS) instrument sampling over an extended light path to an off-shore island. The modelled point and line I2 concentrations compare quantitatively with BBCRDS and LP-DOAS measurements, and provide a link between emission fields and the different measurement geometries used to quantify atmospheric I2 concentrations during RHaMBLe. Total I2 emissions over the 100 km2 region around Roscoff are calculated to be 1.7×1019 molecules per second during the lowest tides. During the night, the model replicates I2 concentrations up to 50 pptv measured along the LP-DOAS instrument's line of sight, and predicts spikes of several hundred pptv in certain conditions. Point I2 concentrations up to 50 pptv are also calculated at the measurement site, in broad agreement with the BBCRDS observations. Daytime measured concentrations of I2 at the site correlate with modelled production and transport processes. However substantial recycling of the photodissociated I2 is required for the model to quantitatively match measured concentrations. This result corroborates previous modelling of iodine and NOx chemistry in the semi-polluted marine boundary layer which proposed a mechanism for recycling I2 via the formation, transport and subsequent reactions of the IONO2 reservoir compound. The methodology presented in this paper provides a tool for linking spatially distinct measurements to inhomogeneous and temporally varying emission fields.

scholarly journals The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

2011 ◽  
Vol 4 (11) ◽  
pp. 2421-2439 ◽  
Author(s):  
S. Coburn ◽  
B. Dix ◽  
R. Sinreich ◽  
R. Volkamer
Keyword(s):  
Gulf Of Mexico ◽  
Marine Boundary Layer ◽  
Optical Resolution ◽  
Stray Light ◽  
Detection Sensitivity ◽  
Optical Absorption Spectroscopy ◽  
Integration Time ◽  
Vertical Column ◽  
Residual Spectrum ◽  
Bromine Oxide

Abstract. We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and the oxygen dimer (O4) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10−6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise). Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMSNLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMSFWHM. The non-linearity of our detector is low (∼10−2) yet – unless actively controlled – is sufficiently large to create RMSNLin of up to 2 × 10−4. The optical resolution is sensitive to temperature changes (0.03 detector pixels °C−1 at 334 nm), and temperature variations of 0.1°C can cause RMSFWHM of ~1 × 10−4. Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s the instrument can reach RMS noise of 3 × 10−5, and typical RMS in field measurements ranged from 6 × 10−5 to 1.4 × 10−4. The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 1013 molec cm−2, 8 × 1012 molec cm−2 and 4 × 1014 molec cm−2, respectively. HCHO and NO2 were also detected with typical MBL VCDs of 1 × 1016 and 3 × 1015 molec cm−2. These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly discussed. The CU GMAX-DOAS has great potential to investigate RMS-limited problems, like the abundance and variability of trace gases in the MBL and possibly the free troposphere (FT).

scholarly journals Measurements of diurnal variations and eddy covariance (EC) fluxes of glyoxal in the tropical marine boundary layer: description of the Fast LED-CE-DOAS instrument

2014 ◽  
Vol 7 (10) ◽  
pp. 3579-3595 ◽  
Author(s):  
S. Coburn ◽  
I. Ortega ◽  
R. Thalman ◽  
B. Blomquist ◽  
C. W. Fairall ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Eddy Covariance ◽  
Marine Boundary Layer ◽  
Light Emitting Diode ◽  
Chemical Properties ◽  
Diurnal Variations ◽  
Optical Absorption Spectroscopy ◽  
Tropical Ocean ◽  
Mixing Ratios ◽  
Fast Light

Abstract. Here we present first eddy covariance (EC) measurements of fluxes of glyoxal, the smallest α-dicarbonyl product of hydrocarbon oxidation, and a precursor for secondary organic aerosol (SOA). The unique physical and chemical properties of glyoxal – i.e., high solubility in water (effective Henry's law constant, KH = 4.2 × 105 M atm−1) and short atmospheric lifetime (~2 h at solar noon) – make it a unique indicator species for organic carbon oxidation in the marine atmosphere. Previous reports of elevated glyoxal over oceans remain unexplained by atmospheric models. Here we describe a Fast Light-Emitting Diode Cavity-Enhanced Differential Optical Absorption Spectroscopy (Fast LED-CE-DOAS) instrument to measure diurnal variations and EC fluxes of glyoxal and inform about its unknown sources. The fast in situ sensor is described, and first results are presented from a cruise deployment over the eastern tropical Pacific Ocean (20° N to 10° S; 133 to 85° W) as part of the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO) field experiment (January to March 2012). The Fast LED-CE-DOAS is a multispectral sensor that selectively and simultaneously measures glyoxal (CHOCHO), nitrogen dioxide (NO2), oxygen dimers (O4), and water vapor (H2O) with ~2 Hz time resolution (Nyquist frequency ~1 Hz) and a precision of ~40 pptv Hz−0.5 for glyoxal. The instrument is demonstrated to be a "white-noise" sensor suitable for EC flux measurements. Fluxes of glyoxal are calculated, along with fluxes of NO2, H2O, and O4, which are used to aid the interpretation of the glyoxal fluxes. Further, highly sensitive and inherently calibrated glyoxal measurements are obtained from temporal averaging of data (e.g., detection limit smaller than 2.5 pptv in an hour). The campaign average mixing ratio in the Southern Hemisphere (SH) is found to be 43 ± 9 pptv glyoxal, which is higher than the Northern Hemisphere (NH) average of 32 ± 6 pptv (error reflects variability over multiple days). The diurnal variation of glyoxal in the marine boundary layer (MBL) is measured for the first time, and mixing ratios vary by ~8 pptv (NH) and ~12 pptv (SH) over the course of 24 h. Consistently, maxima are observed at sunrise (NH: 35 ± 5 pptv; SH: 47 ± 7 pptv), and minima at dusk (NH: 27 ± 5 pptv; SH: 35 ± 8 pptv). In both hemispheres, the daytime flux was directed from the atmosphere into the ocean, indicating that the ocean is a net sink for glyoxal during the day. After sunset the ocean was a source for glyoxal to the atmosphere (positive flux) in the SH; this primary ocean source was operative throughout the night. In the NH, the nighttime flux was positive only shortly after sunset and negative during most of the night. Positive EC fluxes of soluble glyoxal over oceans indicate the presence of an ocean surface organic microlayer (SML) and locate a glyoxal source within the SML. The origin of most atmospheric glyoxal, and possibly other oxygenated hydrocarbons over tropical oceans, remains unexplained and warrants further investigation.

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