ALBERT

Description: Processes of cobalt (Co) entrainment from shelf sediments over the Kerguelen Plateau were studied during the KEOPS (Kerguelen Ocean Plateau compared Study) in order to explain the exceptionally high dissolved cobalt concentrations that have been measured in the surface waters above the Kerguelen Plateau, and in intermediate and deep waters above its eastern slope. Lateral advection and dissolution of Co contained in basalt sediments around Heard Island, a main source of lithogenic Co in the study area, were shown to imprint the process of surface enrichment over the plateau. Dissolved Co enrichment was strongest at the intercept of the eastern slope with intermediate and deep waters, probably due to more efficient mobilisation of the sediments in the slope current, in addition to advection of Co-enriched and low oxygenated ocean water-masses. In surface waters, strong sedimentary Co inputs were estimated to be much higher than biological Co uptake in phytoplankton blooms, underlining the potential role of cobalt as lithogenic tracer. Based on a simple, steady state balance equation of the external input of dissolved iron over the plateau, the fertilization of iron inferred by using Co as a tracer of basalt sources is estimated to be 28 × 102 ± 21 × 102 ton yr−1 in surface waters of the Kerguelen Plateau. This estimate is consistent with preceding ones and the required iron supply matching the phytoplankton demand.

Description: The organic speciation of dissolved cobalt was investigated in the subtropical region of the southeastern Atlantic, and in the Antarctic Circumpolar Current (ACC) and the northern Weddell Gyre in the Southern Ocean between 33°58′S and 57°33′S along the Greenwich Meridian during the austral summer of 2008. The organic speciation of cobalt was determined by Competing Ligand Exchange Adsorptive Cathodic Stripping Voltammetry (CLE-AdCSV) using nioxime as a competing ligand. The conditional stability constants (log K'CoL) of the organic complexes of Co ranged between 17.9 and 20.1, and the concentrations of the organic ligands (L) between 26 and 73 pM. Most dissolved cobalt (DCo) was organically complexed in the water-column (60 to ≥99.9 %). There were clear vertical and meridional patterns in the distribution of L and the organic speciation of DCo along the section. These patterns suggested a biological source of the organic ligands in the surface waters of the subtropical domain and northern subantarctic region, potentially driven by the cyanobacteria, and a removal of the organic Co by direct or indirect biological uptake. The highest L:DCo ratio (e.g. 5.81 ± 1.07 pM pM–1) observed in these surface waters reflected the combined effects of ligand production and consumption of DCo. As a result of these combined effects, the calculated concentrations of free, unbound Co ([Co′]) in subtropical and subantarctic surface waters were very low, generally between 10–19 and 10–17 M. In intermediate and deep waters, the South African margins can be a source of organic ligands, as it was suggested to be for DCo (Bown et al., 2011), although a significant portion of DCo (up to 15 %) can be stabilized and transported as inorganic species in those DCo-enriched water-masses. Contrastingly, the distribution of L did not suggest an intense biological production of L around the Antarctic Polar Front where a diatom bloom had recently occurred. Here [Co′] can be several orders of magnitude higher than those reported in the subtropical domain, suggesting that cobalt limitation was unlikely in the ACC domain. The almost invariant L:DCo ratio of ~1 recorded in these surface waters also reflected the conservative behaviours of both the organic ligands and DCo. In deeper waters relatively higher ligand concentrations were observed in waters previously identified as DCo sources (Bown et al., 2011). At those depths the eastward increase of DCo could be associated with a large scale transport and remineralisation of DCo as organic complexes; here, the fraction stabilized as inorganic Co was much lower but still significant (up to 25 %) in the low oxygenated Upper Circumpolar Deep Waters. The organic speciation may thus be a central factor in the biogeochemical cycle of DCo in those areas, playing a major role in the bioavailability and the geochemistry of Co.

Description: We present an evaluation of aircraft observations of the carbon and greenhouse gases (CO2, CH4, N2O, and CO) using a direct-absorption pulsed quantum cascade laser spectrometer (QCLS) operated during the HIPPO and CalNex airborne experiments. The QCLS made continuous 1 Hz measurements with 1-sigma Allan precisions of 20, 0.5, 0.09, and 0.15 ppb for CO2, CH4, N2O, and CO, respectively, over 〉 500 flight hours on 79 research flights. The QCLS measurements are compared to two vacuum ultraviolet (VUV) CO instruments (CalNex and HIPPO), a cavity ring-down spectrometer (CRDS) measuring CO2 and CH4 (CalNex), two broadband non-dispersive infrared spectrometers (NDIR) measuring CO2 (HIPPO), two onboard gas chromatographs measuring a variety of chemical species including CH4, N2O, and CO (HIPPO), and various flask-based measurements of all four species. QCLS measurements are tied to NOAA and WMO standards using an in-flight calibration system and mean differences when compared to NOAA CCG flask data over the 59 HIPPO research flights were 100, 1, 1, and 2 ppb for CO2, CH4, N2O, and CO, respectively. The details of the end-to-end calibration procedures and the data quality-assurance and quality-control (QA/QC) are presented. Specifically, we discuss our practices for the traceability of standards given uncertainties in calibration cylinders, isotopic and surface effects for the long-lived greenhouse gas tracers, interpolation techniques for in-flight calibrations, and the effects of instrument linearity on retrieved mole fractions.

Description: Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial results from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes in climate models.

Description: A quantum cascade laser based absorption spectrometer for continuous and direct measurements of NO and NO2 was employed at the high-altitude monitoring site Jungfraujoch (3580 m a.s.l., Switzerland) during a three month campaign in Spring/Summer 2012. The total reactive nitrogen, NOy, was also measured in the form of NO after conversion on a gold catalyst. The aim was to assess the suitability of the instrument for long-term monitoring of the main reactive nitrogen species under predominantly free tropospheric air conditions. A precision (1σ) of 10 and 3 ppt for NO and NO2 was achieved with 180 s averaging time under field conditions. The linear dynamic range of the instrument has been verified for both species from the detection limit to ≈45 ppbv. The spectrometer shared a common sampling inlet with a chemiluminescence-based analyzer. The comparison of the time series shows excellent agreement between the two techniques and demonstrates the adequacy of the laser spectroscopic approach for this kind of demanding environmental applications.

Description: Droplets produced in a cloud condensation nucleus chamber as a function of supersaturation have been separated from unactivated aerosol particles using counterflow virtual impaction. Residual material after droplets were evaporated was chemically analyzed with an Aerodyne Aerosol Mass Spectrometer and the Particle Analysis by Laser Mass Spectrometry instrument. Experiments were initially conducted to verify activation conditions for monodisperse ammonium sulfate particles and to determine the resulting droplet size distribution as a function of supersaturation. Based on the observed droplet size, the counterflow virtual impactor cut-size was set to differentiate droplets from unactivated interstitial particles. Validation experiments were then performed to verify that only droplets with sufficient size passed through the counterflow virtual impactor for subsequent analysis. A two-component external mixture of monodisperse particles was also exposed to a supersaturation which would activate one of the types (ammonium sulfate) but not the other (polystyrene latex spheres). The mass spectrum observed after separation indicated only the former, validating separation of droplets from unactivated particles. Results from atmospheric measurements using this technique indicate that aerosol particles often activate predominantly as a function of particle size. Chemical composition is not irrelevant, however, and we observed enhancement of sulfate in droplet residuals using single particle analysis.

Description: Forest fires in Alaska and West Canada represent important sources of aerosols and trace gases in North America. Among the largest uncertainties when modeling forest fire effects are the timing and injection height of biomass burning emissions. Here we simulate CO and aerosols over North America during the 2004 fire season, using the GEOS-Chem chemical transport model. We apply different temporal distributions and injection height profiles to the biomass burning emissions, and compare model results with satellite-, aircraft-, and ground-based measurements. We find that averaged over the fire season, the use of finer temporal resolved biomass burning emissions usually decreases CO and aerosol concentrations near the fire source region, and often enhances long-range transport. Among the individual temporal constraints, switching from monthly to 8-day time intervals for emissions has the largest effect on CO and aerosol distributions, and shows better agreement with measured day-to-day variability. Injection height substantially modifies the surface concentrations and vertical profiles of pollutants near the source region. In comparison with CO, the simulation of black carbon aerosol is more sensitive to the temporal and injection height distribution of emissions. The use of MISR-derived injection height improves agreement with surface aerosol measurements near the fire source. Our results indicate that the discrepancies between model simulations and MOPITT CO measurements near the Hudson Bay can not be attributed solely to the representation of injection height within the model. Frequent occurrence of strong convection in North America during summer tends to limit the influence of injection height distribution of fire emissions in Alaska and West Canada on CO and aerosol distributions over eastern North America.

Description: The organic speciation of dissolved cobalt (DCo) was investigated in the subtropical region of the southeastern Atlantic, and in the Southern Ocean in the Antarctic Circumpolar Current (ACC) and the northern Weddell Gyre, between 34°25´ S and 57°33´ S along the Greenwich Meridian during the austral summer of 2008. The organic speciation of dissolved cobalt was determined by competing ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) using nioxime as a competing ligand. The concentrations of the organic ligands (L) ranged between 26 and 73 pM, and the conditional stability constants (log K'CoL) of the organic complexes of Co between 17.9 and 20.1. Most dissolved cobalt was organically complexed in the water-column (60 to 〉99.9%). There were clear vertical and meridional patterns in the distribution of L and the organic speciation of DCo along the section. These patterns suggest a biological source of the organic ligands in the surface waters of the subtropical domain and northern subantarctic region, potentially driven by the cyanobacteria, and a removal of the organic Co by direct or indirect biological uptake. The highest L:DCo ratio (5.81 ± 1.07 pM pM−1) observed in these surface waters reflected the combined effects of ligand production and DCo consumption. As a result of these combined effects, the calculated concentrations of inorganic Co ([Co']) were very low in the subtropical and subantarctic surface waters, generally between 10−19 and 10−17 M. In intermediate and deep waters, the South African margins can be a source of organic ligands, as it was suggested to be for DCo (Bown et al., 2011), although a significant portion of DCo (up to 15%) can be stabilized and transported as inorganic species in those DCo-enriched water-masses. Contrastingly, the distribution of L does not suggest an intense biological production of L around the Antarctic Polar Front where a diatom bloom had recently occurred. Here [Co'] can be several orders of magnitude higher than those reported in the subtropical domain, suggesting that cobalt limitation was unlikely in the ACC domain. The almost invariant L:DCo ratio of ~1 recorded in these surface waters also reflected the conservative behaviours of both L and DCo. In deeper waters higher ligand concentrations were observed in waters previously identified as DCo sources (Bown et al., 2011). At those depths the eastward increase of DCo from the Drake Passage to the Greenwich Meridian could be associated with a large scale transport and remineralisation of DCo as organic complexes; here, the fraction stabilized as inorganic Co was also significant (up to 25%) in the low oxygenated Upper Circumpolar Deep Waters. Organic speciation may thus be a central factor in the biogeochemical cycle of DCo in those areas, playing a major role in the bioavailability and the geochemistry of Co.

Description: We present a novel spectral method to measure atmospheric carbon dioxide (CO2) with high precision and stability without resorting to calibration tanks during long-term operation. This spectral null method improves precision by reducing spectral proportional noise associated with laser emission instabilities. We employ sealed quartz cells with known CO2 column densities to serve as the permanent internal references in the null method, which improve the instrument's stability and accuracy. A prototype instrument – ABsolute Carbon dioxide (ABC) is developed using this new approach. The instrument has a one-second precision of 0.02 ppm, which averages down to 0.007 ppm within one minute. Long-term stability of within 0.1 ppm is achieved without any calibrations for over a one-month period. These results have the potential for eliminating the need for calibration cylinders for high accuracy field measurements of carbon dioxide.

Description: A quantum cascade laser based absorption spectrometer for continuous and direct measurements of NO and NO2 was employed at the high-altitude monitoring site Jungfraujoch (3580 m a.s.l., Switzerland) during a three-month campaign in spring/summer 2012. The total reactive nitrogen, NOy, was also measured in the form of NO after conversion on a gold catalyst. The aim was to assess the suitability of the instrument for long-term monitoring of the main reactive nitrogen species under predominantly free tropospheric air conditions. A precision (1σ) of 10 and 3 ppt for NO and NO2 was achieved under field conditions after 180 s averaging time. The linear dynamic range of the instrument has been verified for both species from the detection limit up to 45 ppb. The spectrometer shared a common sampling inlet with a chemiluminescence-based analyzer. The comparison of the time series shows excellent agreement between the two techniques and demonstrates the adequacy of the laser spectroscopic approach for this kind of demanding environmental applications.