Hydrogen Sulfide and Radon in and Over the Western North Atlantic Ocean

Atmospheric measurements of radon and hydrogen sulfide, and seawater measurements of total sulfide, free sulfide, and carbonyl sulfide, were made on a cruise in the western North Atlantic Ocean (October 24 to November 9, 1989). Measured values for 222Rn ranged from 3 to 70 pCi m−3, those for atmospheric hydrogen sulfide from 1 to 85 parts per trillion, and those for dissolved total and free sulfide in seawater from 33 to 930 pmol L−1 and 0 to 73 pmol L−1, respectively. A positive correlation between 222Rn and atmospheric H2S was observed. Both 222Rn and H2S were high in air masses traced back to North America. Measurements in seawater showed that uncomplexed sulfides were approximately 13% of total sulfide at 2 m depth. Atmospheric H2S and dissolved H2S in seawater were usually not far from saturation equilibrium. Our results indicate that the ocean acted at some times as a source of atmospheric H2S but more frequently as a sink. Hydrolysis of COS and atmospheric deposition of H2S both may contribute to the budget of dissolved sulfide in seawater of the western North Atlantic Ocean. On a global scale the ocean/atmosphere exchange of H2S appears to play a minor role in the atmospheric sulfur cycle

Hitting all Maximal Independent Sets of a Bipartite Graph

We prove that given a bipartite graph G with vertex set V and an integer k, deciding whether there exists a subset of V of size k hitting all maximal independent sets of G is complete for the class Sigma_2^P.Comment: v3: minor chang

Size distribution and hygroscopic properties of aerosol particles from dry-season biomass burning in Amazonia

International audienceAerosol particle number size distributions and hygroscopic properties were measured at a pasture site in the southwestern Amazon region (Rondonia). The measurements were performed 11 September-14 November 2002 as part of LBA-SMOCC (Large scale Biosphere atmosphere experiment in Amazonia - SMOke aerosols, Clouds, rainfall and Climate), and cover the later part of the dry season (with heavy biomass burning), a transition period, and the onset of the wet period. Particle number size distributions were measured with a DMPS (Differential Mobility Particle Sizer, 3-850nm) and an APS (Aerodynamic Particle Sizer), extending the distributions up to 3.3 µm in diameter. An H-TDMA (Hygroscopic Tandem Differential Mobility Analyzer) measured the hygroscopic diameter growth factors (Gf) at 90% relative humidity (RH), for particles with dry diameters (dp) between 20-440 nm, and at several occasions RH scans (30-90% RH) were performed for 165nm particles. These data provide the most extensive characterization of Amazonian biomass burning aerosol, with respect to particle number size distributions and hygroscopic properties, presented until now. The evolution of the convective boundary layer over the course of the day causes a distinct diel variation in the aerosol physical properties, which was used to get information about the properties of the aerosol at higher altitudes. The number size distributions averaged over the three defined time periods showed three modes; a nucleation mode with geometrical median diameters (GMD) of ~12 nm, an Aitken mode (GMD=61-92 nm) and an accumulation mode (GMD=128-190 nm). The two larger modes were shifted towards larger GMD with increasing influence from biomass burning. The hygroscopic growth at 90% RH revealed a somewhat external mixture with two groups of particles; here denoted nearly hydrophobic (Gf~1.09 for 100 nm particles) and moderately hygroscopic (Gf~1.26). While the hygroscopic growth factors were surprisingly similar over the periods, the number fraction of particles belonging to each hygroscopic group varied more, with the dry period aerosol being more dominated by nearly hydrophobic particles. As a result the total particle water uptake rose going into the cleaner period. The fraction of moderately hygroscopic particles was consistently larger for particles in the accumulation mode compared to the Aitken mode for all periods. Scanning the H-TDMA over RH (30-90% RH) showed no deliquescence behavior. A parameterization of both Gf(RH) and Gf(dp), is given

Small-scale mixing processes enhancing troposphere-to-stratosphere transport by pyro-cumulonimbus storms

Deep convection induced by large forest fires is an efficient mechanism for transport of aerosol particles and trace gases into the upper troposphere and lower stratosphere (UT/LS). For many pyro-cumulonimbus clouds (pyroCbs) as well as other cases of severe convection without fire forcing, radiometric observations of cloud tops in the thermal infrared (IR) reveal characteristic structures, featuring a region of relatively high brightness temperatures (warm center) surrounded by a U-shaped region of low brightness temperatures. We performed a numerical simulation of a specific case study of pyroCb using a non-hydrostatic cloud resolving model with a two-moment cloud microphysics parameterization and a prognostic turbulence scheme. The model is able to reproduce the thermal IR structure as observed from satellite radiometry. Our findings establish a close link between the observed temperature pattern and small-scale mixing processes atop and downwind of the overshooting dome of the pyroCb. Such small-scale mixing processes are strongly enhanced by the formation and breaking of a stationary gravity wave induced by the overshoot. They are found to increase the stratospheric penetration of the smoke by up to almost 30 K and thus are of major significance for irreversible transport of forest fire smoke into the lower stratosphere

Dark Production: A Significant Source of Oceanic COS

Carbonyl sulfide (COS) in air and dissolved in seawater was determined during a cruise in August 1999 in the Sargasso Sea in the northwest Atlantic Ocean. Dissolved concentrations at the sea surface displayed only a weak diel cycle with a mean of 8.6 ± 2.8 pmol dm−3 owing to low abundance of photochemical precursors and high temperatures causing rapid hydrolysis. Depth profiles measured over the oceanic mixed layer revealed significant vertical gradients of COS concentration with higher values at the surface, suggesting that the rate of photochemical production at the surface exceeds the rate of vertical mixing. The mean atmospheric mixing ratio was 486 ± 40 ppt, and calculated sea-air fluxes ranged from 0.03 to 0.8 g COS km−2 d−1. COS dark production, estimated from the predawn COS concentration at the surface and the hydrolysis constant, contributed significantly to the total amount of COS produced. A strong temperature dependence of the COS dark production rate q was found by comparing previously published values. The data further indicate an approximately first-order relationship between q and chromophoric dissolved organic matter (CDOM) absorbance at 350 nm, a350, which is used as a proxy for the CDOM content of the water but is likely to covary with other parameters, such as biological activity, that could also affect COS dark production. Together with known functions for COS hydrolysis and solubility, the parameterization of dark production as a function of temperature and a350 allows for the prediction of COS concentrations and saturation ratios as a function of physical and optical seawater properties in the absence of photoproduction. This is used to estimate a lower limit of 0.056 Tg COS yr−1 to the annual COS flux from the ocean to the atmosphere

Physical properties of the sub-micrometer aerosol over the Amazon rain forest during the wet-to-dry season transition - comparison of modeled and measured CCN concentrations

Sub-micrometer atmospheric aerosol particles were studied in the Amazon region, 125 km northeast of Manaus, Brazil (-1°55.2'S, 59°28.1'W). The measurements were performed during the wet-to-dry transition period, 4-28 July 2001 as part of the LBA (Large-Scale Biosphere Atmosphere Experiment in Amazonia) CLAIRE-2001 (Cooperative LBA Airborne Regional Experiment) experiment. The number size distribution was measured with two parallel differential mobility analyzers, the hygroscopic growth at 90% RH with a Hygroscopic Tandem Mobility Analyzer (H-TDMA) and the concentrations of cloud condensation nuclei (CCN) with a cloud condensation nuclei counter. A model was developed that uses the H-TDMA data to predict the number of soluble molecules or ions in the individual particles and the corresponding minimum particle diameter for activation into a cloud droplet at a certain supersaturation. Integrating the number size distribution above this diameter, CCN concentrations were predicted with a time resolution of 10 min and compared to the measured concentrations. During the study period, three different air masses were identified and compared: clean background, air influenced by aged biomass burning, and moderately polluted air from recent local biomass burning. For the clean period 2001, similar number size distributions and hygroscopic behavior were observed as during the wet season at the same site in 1998, with mostly internally mixed particles of low diameter growth factor (~1.3 taken from dry to 90% RH). During the periods influenced by biomass burning the hygroscopic growth changed slightly, but the largest difference was seen in the number size distribution. The CCN model was found to be successful in predicting the measured CCN concentrations, typically within 25%. A sensitivity study showed relatively small dependence on the assumption of which model salt that was used to predict CCN concentrations from H-TDMA data. One strength of using H-TDMA data to predict CCN concentrations is that the model can also take into account soluble organic compounds, insofar as they go into solution at 90% RH. Another advantage is the higher time resolution compared to using size-resolved chemical composition data

Aerosol particle number size distributions and particulate light absorption at the ZOTTO tall tower (Siberia), 2006–2009

This paper analyses aerosol particle number size distributions, particulate absorption at 570 nm wavelength and carbon monoxide (CO) measured between September 2006 and January 2010 at heights of 50 and 300 m at the Zotino Tall Tower Facility (ZOTTO) in Siberia (60.8° N; 89.35° E). Average number, surface and volume concentrations are broadly comparable to former studies covering shorter observation periods. Fits of multiple lognormal distributions yielded three maxima in probability distribution of geometric mean diameters in the Aitken and accumulation size range and a possible secondary maximum in the nucleation size range below 25 nm. The seasonal cycle of particulate absorption shows maximum concentrations in high winter (December) and minimum concentrations in mid-summer (July). The 90th percentile, however, indicates a secondary maximum in July/August that is likely related to forest fires. The strongly combustion derived CO shows a single winter maximum and a late summer minimum, albeit with a considerably smaller seasonal swing than the particle data due to its longer atmospheric lifetime. Total volume and even more so total number show a more complex seasonal variation with maxima in winter, spring, and summer. A cluster analysis of back trajectories and vertical profiles of the pseudo-potential temperature yielded ten clusters with three levels of particle number concentration: Low concentrations in Arctic air masses (400–500 cm−3), mid-level concentrations for zonally advected air masses from westerly directions between 55° and 65° N (600–800 cm−3), and high concentrations for air masses advected from the belt of industrial and population centers in Siberia and Kazakhstan (1200 cm−3). The observational data is representative for large parts of the troposphere over Siberia and might be particularly useful for the validation of global aerosol transport models

The Chisholm firestorm: observed microstructure, precipitation and lightning activity of a pyro-Cb

International audienceA fire storm that occured on 28 May 2001 devastated the town of Chisholm, ~150 km north of Edmonton, Alberta, induced a violent fire-invigorated cumulonimbus cloud. This pyro-cumulonimbus (pyro-Cb) had overshooting tops of 2.5?3 km above the tropopause, and injected massive amounts of smoke into the lower stratosphere. Fortunately, this event occurred under good coverage of radar, rain gauge, lightning and satellite measurements, which allowed in-depth documentation of the event. The combination of heat and smoke created a cloud with extremely small drops, which ascended rapidly in violent updrafts. There appeared to be little freezing up to the homogeneous freezing isotherm level of ?38°C. A cloud with such small and short-lived highly supercooled drops is incapable of producing precipitation except for few large graupel and hail, which produced the observed radar echoes and charged the cloud with positive lightning. The small cloud drops froze homogeneously to equally small ice particles, for which there is no mechanism to aggregate into precipitation particles that hence remain in the anvil. The small precipitation efficiency implies that only a small fraction of the smoke is scavenged, so that most of it is exhausted through the anvil to the upper troposphere and lower stratosphere. Comparisons with other cases suggest that a pyro-Cb does not have to be as violent as the Chisholm case to have strongly suppressed precipitation. However, this level of convective vigor is necessary to create the overshooting updraft that injects the smoke into the lower stratosphere

Comparison of different Aethalometer correction schemes and a reference multi-wavelength absorption technique for ambient aerosol data

Deriving absorption coefficients from Aethalometer attenuation data requires different corrections to compensate for artifacts related to filter-loading effects, scattering by filter fibers, and scattering by aerosol particles. In this study, two different correction schemes were applied to seven-wavelength Aethalometer data, using multi-angle absorption photometer (MAAP) data as a reference absorption measurement at 637 nm. The compensation algorithms were compared to five-wavelength offline absorption measurements obtained with a multi-wavelength absorbance analyzer (MWAA), which serves as a multiple-wavelength reference measurement. The online measurements took place in the Amazon rainforest, from the wet-to-dry transition season to the dry season (June\u2013September 2014). The mean absorption coefficient (at 637 nm) during this period was 1.8 +/-2.1Mm-1, with a maximum of 15.9Mm-1. Under these conditions, the filter-loading compensation was negligible. One of the correction schemes was found to artificially increase the short-wavelength absorption coefficients. It was found that accounting for the aerosol optical properties in the scattering compensation significantly affects the absorption \uc5ngstr\uf6m exponent (\ue5ABS/ retrievals. Proper Aethalometer data compensation schemes are crucial to retrieve the correct \ue5ABS, which is commonly implemented in brown carbon contribution calculations. Additionally, we found that the wavelength dependence of uncompensated Aethalometer attenuation data significantly correlates with the \ue5ABS retrieved from offline MWAA measurements