skip to main content

Title: Dried, closed-path eddy covariance method for measuring carbon dioxide flux over sea ice

Abstract. The Arctic marine environment plays an important role inthe global carbon cycle. However, there remain large uncertainties in howsea ice affects air–sea fluxes of carbon dioxide (CO2), partially dueto disagreement between the two main methods (enclosure and eddy covariance)for measuring CO2 flux (FCO2). The enclosure method has appearedto produce more credible FCO2 than eddy covariance (EC), but is notsuited for collecting long-term, ecosystem-scale flux datasets in suchremote regions. Here we describe the design and performance of an EC systemto measure FCO2 over landfast sea ice that addresses the shortcomingsof previous EC systems. The system was installed on a 10m tower onQikirtaarjuk Island – a small rock outcrop in Dease Strait located roughly35km west of Cambridge Bay, Nunavut, in the Canadian Arctic Archipelago. Thesystem incorporates recent developments in the field of air–sea gasexchange by measuring atmospheric more » CO2 using a closed-path infrared gasanalyzer (IRGA) with a dried sample airstream, thus avoiding the known watervapor issues associated with using open-path IRGAs in low-flux environments.A description of the methods and the results from 4 months of continuousflux measurements from May through August 2017 are presented, highlightingthe winter to summer transition from ice cover to open water. We show thatthe dried, closed-path EC system greatly reduces the magnitude of measuredFCO2 compared to simultaneous open-path EC measurements, and for thefirst time reconciles EC and enclosure flux measurements over sea ice. Thisnovel EC installation is capable of operating year-round on solar and windpower, and therefore promises to deliver new insights into the magnitude ofCO2 fluxes and their driving processes through the annual sea icecycle.

« less
Award ID(s):
Publication Date:
Journal Name:
Atmospheric Measurement Techniques
Page Range or eLocation-ID:
6075 to 6090
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract. Photoacoustic spectroscopy (PAS) has become a popular technique for measuringabsorption of light by atmospheric aerosols in both the laboratory andfield campaigns. It has low detection limits, measures suspended aerosols,and is insensitive to scattering. But PAS requires rigorous calibration to beapplied quantitatively. Often, a PAS instrument is either filled with a gasof known concentration and absorption cross section, such that the absorptionin the cell can be calculated from the product of the two, or the absorptionis measured independently with a technique such as cavity ring-downspectroscopy. Then, the PAS signal can be regressed upon the known absorptionto determine a calibration slope that reflects the sensitivity constant ofthe cell and microphone. Ozone has been used for calibrating PAS instrumentsdue to its well-known UV–visible absorption spectrum and the ease with whichit can be generated. However, it is known to photodissociate up toapproximately 1120nm via the O3 + hν(>1.1eV)O2(3Σg-) + O(3P) pathway, which is likely tolead to inaccuracies in aerosol measurements. Two recent studies haveinvestigated the use of O3 for PASmore »calibration but have reachedseemingly contradictory conclusions with one finding that it results in asensitivity that is a factor of 2 low and the other concluding that it isaccurate. The present work is meant to add to this discussion by exploringthe extent to which O3 photodissociates in the PAS cell and the rolethat the identity of the bath gas plays in determining the PAS sensitivity.We find a 5% loss in PAS signal attributable to photodissociation at 532nmin N2 but no loss in a 5% mixture of O2 in N2.Furthermore, we discovered a dramatic increase of more than a factor of 2in the PAS sensitivity as we increased the O2 fraction in the bathgas, which reached an asymptote near 100% O2 that nearly matched thesensitivity measured with both NO2 and nigrosin particles. Weinterpret this dependence with a kinetic model that suggests the reason forthe observed results is a more efficient transfer of energy from excitedO3 to O2 than to N2 by a factor of 22–55 depending onexcitation wavelength. Notably, the two prior studies on this topic useddifferent bath gas compositions, and although the results presented here donot fully resolve the differences in their results, they may at leastpartially explain them.

    « less
  2. Abstract. Chemical ionization massspectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compoundsin the atmosphere. A major limitation of these instruments is the uncertaintyin their sensitivity to many of the detected ions. We describe thedevelopment of a new high-resolution time-of-flight chemical ionization massspectrometer that operates in one of two ionization modes: using eitherammonium ion ligand-switching reactions such as for NH4+ CIMS orproton transfer reactions such as for proton-transfer-reaction massspectrometer (PTR-MS). Switching between the modes can be done within 2 min.The NH4+ CIMS mode of the new instrument has sensitivities of upto 67 000 dcps ppbv−1 (duty-cycle-corrected ion counts per second perpart per billion by volume) and detection limits between 1 and 60 pptv at2σ for a 1 s integration time for numerous oxygenated volatileorganic compounds. We present a mass spectrometric voltage scanning procedurebased on collision-induced dissociation that allows us to determine thestability of ammonium-organic ions detected by the NH4+more »xmlns:xlink="" xlink:href="amt-12-1861-2019-ie00005.svg" width="24pt" height="15pt" src="amt-12-1861-2019-ie00005.png"/> CIMS instrument.Using this procedure, we can effectively constrain the sensitivity of theammonia chemical ionization mass spectrometer to a wide range of detectedoxidized volatile organic compounds for which no calibration standards exist.We demonstrate the application of this procedure by quantifying thecomposition of secondary organic aerosols in a series of laboratoryexperiments.

    « less
  3. Abstract. Triplet excited states of organic matter are formed when colored organicmatter (i.e., brown carbon) absorbs light. While these “triplets” can beimportant photooxidants in atmospheric drops and particles (e.g., theyrapidly oxidize phenols), very little is known about their reactivity towardmany classes of organic compounds in the atmosphere. Here we measure thebimolecular rate constants of the triplet excited state of benzophenone(3BP), a model species, with 17 water-solubleC3C6 alkenes that have either been found in theatmosphere or are reasonable surrogates for identified species. Measured rateconstants (kALK+3BP) vary by a factor of 30 and are in therange of (0.24–7.5) ×109 M−1 s−1. Biogenic alkenesfound in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, andmethyl jasmonate – react rapidly, with rate constants above 1×109 M−1 s−1. Rate constants depend on alkene characteristicssuch as the location of the double bond, stereochemistry, and alkylsubstitution on the double bond. There is a reasonable correlation betweenkALK+3BP and the calculated one-electron oxidation potential(OP) of the alkenes (more »class="inline-formula">R2=0.58); in contrast, rate constants are notcorrelated with bond dissociation enthalpies, bond dissociation freeenergies, or computed energy barriers for hydrogen abstraction. Using the OPrelationship, we estimate aqueous rate constants for a number of unsaturatedisoprene and limonene oxidation products with 3BP: values are inthe range of (0.080–1.7) ×109 M−1 s−1, withgenerally faster values for limonene products. Rate constants with lessreactive triplets, which are probably more environmentally relevant, arelikely roughly 25 times slower. Using our predicted rate constants, alongwith values for other reactions from the literature, we conclude thattriplets are probably minor oxidants for isoprene- and limonene-relatedcompounds in cloudy or foggy atmospheres, except in cases in which the tripletsare very reactive.

    « less
  4. Abstract. Following the Budyko framework, the soil wetting ratio (the ratio betweensoil wetting and precipitation) as a function of the soil storage index (theratio between soil wetting capacity and precipitation) is derived from theSoil Conservation Service Curve Number (SCS-CN) method and the variableinfiltration capacity (VIC) type of model. For the SCS-CN method, the soilwetting ratio approaches 1 when the soil storage index approaches ,due to the limitation of the SCS-CN method in which the initial soil moisturecondition is not explicitly represented. However, for the VIC type of model,the soil wetting ratio equals the soil storage index when the soil storageindex is lower than a certain value, due to the finite upper bound of thegeneralized Pareto distribution function of storage capacity. In this paper,a new distribution function, supported on a semi-infinite interval x[0,), is proposed for describing the spatial distribution of storagecapacity. From this new distribution function, an equation is derived for therelationship between the soil wetting ratio and the storage index. In thederived equation, the soil wetting ratio approaches 0 as the storage indexapproaches 0; when the storage index tendsmore »to infinity, the soil wettingratio approaches a certain value (≤1) depending on the initial storage.Moreover, the derived equation leads to the exact SCS-CN method when initialwater storage is 0. Therefore, the new distribution function for soil waterstorage capacity explains the SCS-CN method as a saturation excess runoffmodel and unifies the surface runoff modeling of the SCS-CN method and theVIC type of model.

    « less
  5. Abstract. A large array of proxy recordssuggests that the “4.2ka event” marks an approximately300-year long period (∼3.9 to 4.2ka) ofmajor climate change across the globe. However, the climatic manifestation ofthis event, including its onset, duration, and termination, remains lessclear in the Indian summer monsoon (ISM) domain. Here, we present new oxygenisotope (δ18O) data from a pair of speleothems (ML.1 and ML.2)from Mawmluh Cave, Meghalaya, India, that provide a high-resolution record ofISM variability during a period (∼3.78 and 4.44ka) that fullyencompasses the 4.2ka event. The sub-annually to annually resolved ML.1δ18O record is constrained by 18 230Th dates with anaverage dating error of ±13 years (2σ) and a resolution of ∼40 years, which allows us to characterize the ISM variability withunprecedented detail. The inferred pattern of ISM variability during theperiod contemporaneous with the 4.2ka event shares broad similarities andkey differences with the previous reconstructions of ISM from the MawmluhCave and other proxy records from the region. Our data suggest that the ISMintensity, in the context of the length of our record, abruptly decreased at∼4.0ka (±13more »xlink:href="cp-14-1869-2018-ie00001.svg" width="32pt" height="10pt" src="cp-14-1869-2018-ie00001.png"/> years), marking the onset of a multi-centennialperiod of relatively reduced ISM, which was punctuated by at least twomulti-decadal droughts between ∼3.9 and 4.0ka. The latter stands outin contrast with some previous proxy reconstructions of the ISM, in which the4.2ka event has been depicted as a singular multi-centennial drought.

    « less