ALBERT

Description: Dimethyl sulphide (DMS) is an important precursor of cloud condensation nuclei (CCN), particularly in the remote marine atmosphere. The SE Pacific is consistently covered with a persistent stratocumulus layer that increases the albedo over this large area. It is not certain whether the source of CCN to these clouds is natural and oceanic or anthropogenic and terrestrial. This unknown currently limits our ability to reliably model either the cloud behaviour or the oceanic heat budget of the region. In order to better constrain the marine source of CCN it is necessary to have an improved understanding of the sea-air flux of DMS. Of the factors that govern the magnitude of this flux, the greatest unknown is the surface seawater DMS concentration. In the study area there is a paucity of such data, although previous measurements suggest that the concentration can be substantially variable. In the last decade a number of climatologies and algorithms have been devised to predict seawater DMS. Here we test some of these by comparing predictions with measurements of surface seawater made during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in October and November of 2008. We conclude that none of the algorithms reproduce local variability in seawater DMS very well. From these findings, we recommend the best algorithm choice for the SE Pacific and suggest lines of investigation for future work.

Description: Dimethylsulfide (DMS) is biologically produced in the surface ocean and is the dominant natural source of sulfur to the atmosphere. Although DMS is an algal by-product, the ratio of DMS to chlorophyll (DMS:Chl) varies widely in the surface ocean. This is presumably because dimethylsulfoniopropionate (DMSP), the major precursor of DMS, DMSP-lyases, which catalyze the conversion of DMSP to DMS, and Chl vary as well with taxonomic composition than with the physiological state of the algal assemblage. Here we use remote sensing of Chl and phytoplankton dominance from PHYSAT with in-situ measured DMS concentrations to assess on an unprecedented spatial scale the affect of species composition on the DMS:Chl ratio in the surface ocean. Meridional distributions at 22° W in the Atlantic, and 95° W and 110° W in the Pacific, showed the same marked drop in DMS:Chl ratios near the equator, down to few mmol g−1, yet the basins exhibited different species dominance signatures. Hence, our results suggest that species composition was of secondary importance in controlling DMS and DMS:Chl variations in equatorial upwellings as well as physiological shifts in algal DMS production since mixed layer growth conditions (i.e., nutrient stress, temperature and light) were relatively homogeneous over the eastern equatorial Pacific. In the Indian sector of the Southern Ocean, warm core eddies with contrasting PHYSAT signatures displayed similar DMS levels. However, DMS:Chl ratios in eddies dominated by Synechococcus (SYN) were about 50% lower than that found in eddies showing nanoeucayotes or Phaeocystis-like signatures. DMS:Chl ratios varied with latitude in SYN dominated regions with ratios at low latitudes (away from equatorial upwellings) about twice that found at high northern and southern latitudes. This is the sole piece of coherent observations which indicates that species composition and growth conditions affect the large-scale dynamics of the DMS:Chl ratio. Overall, it appears that the DMS:Chl ratio is not consistent within specific phytoplankton groups determined from space. So DMS concentrations can not be derived from water-leaving radiance spectra obtained simultaneously from ocean color sensor measurements of Chl concentrations and dominant phytoplankton functional types. To proceed with the global investigation and better discriminate between factors affecting DMS:Chl ratios in the surface ocean, we recommend the use of PHYSAT records with higher spatial resolution in conjunction with other satellite products (e.g. particulate backscattering coefficients and indices of phytoplankton physiology and bloom status).

Description: Laboratory work is reported here establishing iodide ion chemical ionization mass spectrometry (I− CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO2NO2, PNA). A~dynamic calibration source for HO2NO2, HO2, and HONO was developed and calibrated using a~novel total NOy detector (NOy CaRDS). Photochemical sources of these species were used for the calibration and validation of the I− CIMS instrument for detection of HO2NO2. A dual inlet system was developed to determine differences in the instrument response when using a heated inlet dissociator (150 °C) and a "cold" room-temperature inlet. HO2NO2 was detected as I-HO2− (m/z 160), NO3− (m/z 62) and I-HO2NO2− (m/z 206). The I− CIMS normalized sensitivity to peroxynitric acid was 2.0 Hz pptv−1 with a detection limit (3σ) of 40 pptv via detection of the I-HO2− (m/z 160) cluster ion using an inlet dissociator at a temperature of 150 °C. Alternatively, PNA was detected via I− CIMS with a cold inlet at both the NO3− (m/z 62) and I-HO2NO2− (m/z 206) ions with normalized detection sensitivities of 144 and 0.4 Hz pptv−1 respectively. The cold inlet sensitivity of iodide CIMS towards the detection of HO2 radicals, also via detection at the I-HO2− cluster ion, a potential HO2NO2 interference, was approximately 2.6 Hz pptv−1 with an instrumental detection limit (3σ) of 20 pptv. Ambient observations of HO2NO2 using I− CIMS were made during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO2NO2 as high as 1.5 ppbv during the 2013 study. A comparison of HO2NO2 observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO2NO2 mixing ratio, but a significant difference os several hours in the timing of the observed maxima. Observations of vertical gradients suggest that the ground snow surface potentially serves as both a net sink and source of HO2NO2 depending on time of day. Sensitivity tests using a chemical box model indicate that the lifetime of HO2NO2 with respect to deposition has a non-negligible impact on ozone production rates on the order of 10%.

Description: Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site in June–July of 2010 during CalNex and a site in an oil and gas producing region in January–February of 2013 during UBWOS 2013 will be discussed. Although the VOC compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 ppb in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (〉 8%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of 〉 10). Inclusion of recent findings on additional precursors and formation pathways of formic acid in the box model increases modeled formic acid concentrations for UBWOS 2013 and CalNex by a factor of 6.4 and 4.5, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 21 and 47% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be −7 and 0–6% in UBWOS 2013 and CalNex, respectively. We observe that air-snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (∼20% in total). In total, 50–57% in UBWOS 2013 and 48–53% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic acid and to narrow the gaps between measurements and model results.

Description: Dimethylsulfoniopropionate (DMSP) is produced in surface seawater by phytoplankton. Phytoplankton culture experiments have shown that nanoeucaryotes (NANO) display much higher mean DMSP-to-Carbon or DMSP-to-Chlorophyll (Chl) ratios than Prochlorococcus (PRO), Synechococcus (SYN) or diatoms (DIAT). Moreover, the DMSP-lyase activity of algae which cleaves DMSP into dimethylsulfide (DMS) is even more group specific than DMSP itself. Ship-based observations have shown at limited spatial scales, that sea surface DMS-to-Chl ratios (DMS:Chl) are dependent on the composition of phytoplankton groups. Here we use satellite remote sensing of Chl (from SeaWiFS) and of Phytoplankton Group Dominance (PGD from PHYSAT) with ship-based sea surface DMS concentrations (8 cruises in total) to assess this dependence on an unprecedented spatial scale. PHYSAT provides PGD (either NANO, PRO, SYN, DIAT, Phaeocystis (PHAEO) or coccolithophores (COC)) in each satellite pixel (1/4° horizontal resolution). While there are identification errors in the PHYSAT method, it is important to note that these errors are lowest for NANO PGD which we typify by high DMSP:Chl. In summer, in the Indian sector of the Southern Ocean, we find that mean DMS:Chl associated with NANO + PHAEO and PRO + SYN + DIAT are 13.6±8.4 mmol g−1 (n=34) and 7.3±4.8 mmol g−1 (n=24), respectively. That is a statistically significant difference (P

Description: Dimethyl sulphide (DMS) is an important precursor of cloud condensation nuclei (CCN), particularly in the remote marine atmosphere. The SE Pacific is consistently covered with a persistent stratocumulus layer that increases the albedo over this large area. It is not certain whether the source of CCN to these clouds is natural and oceanic or anthropogenic and terrestrial. This unknown currently limits our ability to reliably model either the cloud behaviour or the oceanic heat budget of the region. In order to better constrain the marine source of CCN, it is necessary to have an improved understanding of the sea-air flux of DMS. Of the factors that govern the magnitude of this flux, the greatest unknown is the surface seawater DMS concentration. In the study area, there is a paucity of such data, although previous measurements suggest that the concentration can be substantially variable. In order to overcome such data scarcity, a number of climatologies and algorithms have been devised in the last decade to predict seawater DMS. Here we test some of these in the SE Pacific by comparing predictions with measurements of surface seawater made during the Vamos Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in October and November of 2008. We conclude that none of the existing algorithms reproduce local variability in seawater DMS in this region very well. From these findings, we recommend the best algorithm choice for the SE Pacific and suggest lines of investigation for future work.

Description: Atmospheric aerosol vertical distributions were measured above Svalbard, Norway, in April 2011 during the Cooperative Investigation of Climate-Cryosphere Interactions campaign (CICCI). Measurements were made of the particle number concentration and the aerosol light absorption coefficient at three wavelengths. A filter sample was collected on each flight at the altitude of maximum particle number concentration. The filters were analyzed for major anions and cations. The aerosol payload was flown in a NOAA/PMEL MANTA Unmanned Aerial System (UAS). A total of 18 flights were flown during the campaign totaling 38 flight hours. The data show frequent aerosol layers aloft with high particle number concentration (1000 cm−3) and enhanced aerosol light absorption (1 Mm−1). Air mass histories of these aerosol layers were assessed using FLEXPART particle dispersion modeling. The data contribute to an assessment of sources of BC to the Arctic and potential climate impacts.

Description: The spatial extent and temporal behaviour of quasi-periodic (QP) intensity modulations of 0.5-2 kHz ELF-VLF signals were investigated in a comparative study of data collected at the Antarctic stations of South Pole (L=14), Halley (L=4), and Siple (L=4). Frequently, the waveforms of ELF-VLF signals simultaneously received at each site were identical. Although of similar frequency structure, the waveforms of the accompanying Pc3 magnetic pulsations did not show a one-to-one association. Whereas both are dayside phenomena, QP emissions occur over a smaller range of local times, and have a maximum of occurrence later in the day closer to local noon. QP emissions are identified with the periodic modulation of the electron pitch-angle distribution by the propagation of ULF compressional fast-mode waves through a region. However, contrary to previous ideas, rising-tone emissions do not represent the frequency-time signatures of such waves. In addition to generation close to the equatorial plane, we propose an additional high-latitude source of QP emissions. These emissions are associated with regions of minimum B produced by the dayside compression of the magnetosphere close to the magnetopause. Model magnetic field calculations of these minimum-B regions as a function of magnetic local time and invariant latitude are presented.

Description: Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June–July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January–February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (〉 99%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of 〉 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0–6 and 0–5% in UBWOS 2013 and CalNex, respectively. We observe that air–snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (~ 20% in total). In total, 53–59 in UBWOS 2013 and 50–55% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic acid and to narrow the gaps between measurements and model results.

Description: Atmospheric aerosol vertical distributions were measured above Svalbard, Norway in April 2011 during the Cooperative Investigation of Climate-Cryosphere Interactions campaign (CICCI). Measurements were made of the particle number concentration and the aerosol light absorption coefficient at three wavelengths. A filter sample was collected on each flight at the altitude of maximum particle number concentration. The filters were analyzed for major anions and cations. The aerosol payload was flown in a NOAA/PMEL MANTA Unmanned Aerial System (UAS). A total of 18 flights were flown during the campaign totaling 38 flight hours. The data show frequent aerosol layers aloft with high particle number concentration (1000 cm−3 and enhanced aerosol light absorption (1 Mm−1). Air mass histories of these aerosol layers were assessed using FLEXPART particle dispersion modeling. The data contribute to an assessment of sources of BC to the Arctic and potential climate impacts.