Tropospheric Boundary Layer Research Articles

Observing low-altitude features in ozone concentrations in a shoreline environment via uncrewed aerial systems

Abstract. Ozone is a pollutant formed in the atmosphere by photochemical processes involving nitrogen oxides (NOx) and volatile organic compounds (VOCs) when exposed to sunlight. Tropospheric boundary layer ozone is regularly measured at ground stations and sampled infrequently through balloon, lidar, and crewed aircraft platforms, which have demonstrated characteristic patterns with altitude. Here, to better resolve vertical profiles of ozone within the atmospheric boundary layer, we developed and evaluated an uncrewed aircraft system (UAS) platform for measuring ozone and meteorological parameters of temperature, pressure, and humidity. To evaluate this approach, a UAS was flown with a portable ozone monitor and a meteorological temperature and humidity sensor to compare to tall tower measurements in northern Wisconsin. In June 2020, as a part of the WiscoDISCO20 campaign, a DJI M600 hexacopter UAS was flown with the same sensors to measure Lake Michigan shoreline ozone concentrations. This latter UAS experiment revealed a low-altitude structure in ozone concentrations in a shoreline environment showing the highest ozone at altitudes from 20–100 m a.g.l. These first such measurements of low-altitude ozone via a UAS in the Great Lakes region revealed a very shallow layer of ozone-rich air lying above the surface.

YEAST IN SOUTHWEST MONSOON RAINWATER

Strong evidence of the presence of bacteria and fungi in the tropospheric boundary layer is available in the literature. We report successful isolation of unique morphotypes of wild ascomycetous yeasts from rainwater samples collected directly in sterile containers, taking extreme care to avoid ambient contamination. Direct and quick visualization of fresh rainwater samples under a phase contrast microscope indicated the sporadic presence of yeast cells. Further confirmation of the presence of yeast was obtained by plating of rainwater on a medium with antibiotics to generate pure colonies. We described their characteristics while molecular identification revealed it as Candida tropicalis. Yeast species could contribute valuable knowledge about yeast transportation in the atmosphere. However, knowledge is insufficient about the yeast deposited from the atmosphere and its transportation across the atmosphere. We report and discuss these interesting and exciting results which are useful in understanding the microbiological dimension of meteorology and the southwest monsoon rainfall in the light of present discourse on global warming and climate change. We offer a tentative model for a possible source, role, and fate of the yeasts in rainwater.

Observational evidence of a long-term increase in precipitation due to urbanization effects and its implications for sustainable urban living

Although projected precipitation increases in East Asia due to future climate change have aroused concern, less attention has been paid by the scientific community and public to the potential long-term increase in precipitation due to rapid urbanization. A ten-year precipitation dataset was analysed for both a rapidly urbanized megacity and nearby suburban/rural stations in southern China. Rapid urbanization in the megacity was evident from satellite observations. A statistically significant, long-term, increasing trend of precipitation existed only at the megacity station (45.6mm per decade) and not at the other stations. The increase was attributed to thermal and dynamical modifications of the tropospheric boundary layer related to urbanization, which was confirmed by the results of our WRF-SLUCM simulations. The results also suggested that a long-term regional increase in precipitation, caused by greenhouse gas-induced climate change, for instance, was not evident within the study period. The urbanization-induced increase was found to be higher than the precipitation increase (18.3mm per decade) expected from future climate change. The direct climate impacts due to rapid urbanization is highlighted with strong implications for urban sustainable development and the planning of effective adaptation strategies for issues such as coastal defenses, mosquito-borne disease spread and heat stress mortality.

Uncertainty Evaluation of Friction Velocity Measurements by Oil-Film Interferometry

Wind loads on structures and the wind environment around buildings are based on tests in boundary layer wind tunnels with corresponding scale parameters. The lower part of the troposphere boundary layer was simulated inside a small wind tunnel located at the Wind Engineering Centre of the Université de Moncton. The correct scale ratios of the boundary layer thickness combined with the roughness height are two of the most important scales to match. For small wind tunnels, roughness parameters related to the model boundary layer can be difficult to measure since scale ratios for wind load studies are expected to be in the range of 400–1000. Oil-film interferometry was used to determine the roughness parameters (shear stress, friction velocity, and roughness height) of the forced turbulent boundary layer inside the wind tunnel. In this work, the International Organization for Standardization (ISO) Guide to Expression of Uncertainty in Measurements was used to evaluate the standard uncertainty of the roughness parameters on the bottom wall of the wind tunnel. The standard uncertainty of the roughness parameters depends strongly on the oil viscosity and on the accurate measurement of the fringe spacing. Results show that the standard uncertainty of the shear stress and friction velocity determined by the interferometry technique can be less than 5% when the oil viscosity and the fringe spacing can be accurately measured with a standard uncertainty lower than 4% and 1%, respectively.

Carbon monoxide total column retrievals from TROPOMI shortwave infrared measurements

Abstract. The Tropospheric Monitoring Instrument (TROPOMI) spectrometer is the single payload of the Copernicus Sentinel 5 Precursor (S5P) mission. It measures Earth radiance spectra in the shortwave infrared spectral range around 2.3 µm with a dedicated instrument module. These measurements provide carbon monoxide (CO) total column densities over land, which for clear sky conditions are highly sensitive to the tropospheric boundary layer. For cloudy atmospheres over land and ocean, the column sensitivity changes according to the light path through the atmosphere. In this study, we present the physics-based operational S5P algorithm to infer atmospheric CO columns satisfying the envisaged accuracy ( < 15 %) and precision ( < 10 %) both for clear sky and cloudy observations with low cloud height. Here, methane absorption in the 2.3 µm range is combined with methane abundances from a global chemical transport model to infer information on atmospheric scattering. For efficient processing, we deploy a linearized two-stream radiative transfer model as forward model and a profile scaling approach to adjust the CO abundance in the inversion. Based on generic measurement ensembles, including clear sky and cloudy observations, we estimated the CO retrieval precision to be ≤ 11 % for surface albedo ≥ 0.03 and solar zenith angle ≤ 70°. CO biases of ≤ 3 % are introduced by inaccuracies in the methane a priori knowledge. For strongly enhanced CO concentrations in the tropospheric boundary layer and for cloudy conditions, CO errors in the order of 8 % can be introduced by the retrieval of cloud parameters of our algorithm. Moreover, we estimated the effect of a distorted spectral instrument response due to the inhomogeneous illumination of the instrument entrance slit in the flight direction to be < 2 % with pseudo-random characteristics when averaging over space and time. Finally, the CO data exploitation is demonstrated for a TROPOMI orbit of simulated shortwave infrared measurements. Overall, the study demonstrates that for an instrument that performs in compliance with the pre-flight specifications, the CO product will meet the required product performance well.

Air quality impact of a middle size airport within an urban context through EDMS simulation

The air quality impact of an airport due to both ground sources and air traffic emissions within the troposphere boundary layer is a relevant topic at a local scale, especially where the airport is surrounded by urbanized areas. The work analyses the emissions from the Amerigo Vespucci airport in Florence, Italy. The comparison between the present and the future layout of the airport, which is under project, is addressed, providing a possible tool to guide local air pollution prevention strategies within the framework of the strategic transport infrastructures development.The emission scenarios of the present and future airport layouts were estimated with EDMS 5.1.3, the software package issued by FAA (Federal Aviation Administration) which is an US-EPA (Environmental Protection Agency) preferred model for airport emissions evaluation. The total yearly emissions of NOX,CO,SOX,VOCs and PM10 have been assessed, divided into the main phases of the LTO (landing and takeoff) cycle, provided for each aircraft. The results show that the takeoff phase is mainly responsible for NOX,SOX and PM10 contributions.The AERMOD dispersion model was run over one year to evaluate the concentrations of those pollutants, modelled as chemically inert. The maximum concentrations occur close to the gate and the ground movement areas. However, the air quality standards ruled by Directive 50/2008/EU are never reached except for NOX, which shows an overall maximum of the annual average of about 40μg/m3, close to the standard for the vegetation health (50μg/m3).

Atmospheric composition and thermodynamic retrievals from the ARIES airborne TIR-FTS system – Part 2: Validation and results from aircraft campaigns

Abstract. This study validates trace gas and thermodynamic retrievals from nadir infrared spectroscopic measurements recorded by the UK Met Office Airborne Research Interferometer Evaluation System (ARIES) – a thermal infrared, Fourier transform spectrometer (TIR-FTS) on the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 aircraft. Trace-gas-concentration and thermodynamic profiles have been retrieved and validated for this study throughout the troposphere and planetary boundary layer (PBL) over a range of environmental variability using data from aircraft campaigns over and around London, the US Gulf Coast, and the Arctic Circle during the Clear air for London (ClearfLo), Joint Airborne IASI (Infrared Atmospheric Sounding Interferometer) Validation Experiment (JAIVEx), and Measurements, process studies, and Modelling (MAMM) aircraft campaigns, respectively. Vertically resolved retrievals of temperature and water vapour (H2O), and partial-column retrievals of methane (CH4), carbon monoxide (CO), and ozone (O3) (over both land and sea) were compared to corresponding measurements from high-precision in situ analysers and dropsondes operated on the FAAM aircraft. Average degrees of freedom for signal (DOFS) over a 0–9 km column range were found to be 4.97, 3.11, 0.91, 1.10, and 1.62 for temperature, H2O, CH4, CO, and O3, respectively, when retrieved on 10 vertical levels. Partial-column mean biases (and bias standard error) between the surface and ~ 9 km, when averaged across all flight campaigns, were found to be −0.7(±0.3) K, −479(±56) ppm, −11(±2) ppb, −3.3(±1.0) ppb, and +3.5(±1.0) ppb, respectively, whilst the typical a posteriori (total) uncertainties for individually retrieved profiles were 0.4, 9.5, 5.0, 21.2, and 15.0 %, respectively. Averaging kernels (AKs) derived for progressively lower altitudes show improving sensitivity to lower atmospheric layers when flying at lower altitudes. Temperature and H2O display significant vertically resolved sensitivity throughout the column, whilst trace gases are usefully retrieved only as partial-column quantities, with maximal sensitivity for trace gases other than H2O within a layer 1 and 2 km below the aircraft. This study demonstrates the valuable atmospheric composition information content that can be obtained by ARIES nadir TIR remote sensing for atmospheric process studies.

Atmospheric composition and thermodynamic retrievals from the ARIES airborne FTS system – Part 1: Technical aspects and simulated capability

Abstract. In this study we present an assessment of the retrieval capability of the Airborne Research Interferometer Evaluation System (ARIES): an airborne remote-sensing Fourier transform spectrometer (FTS) operated on the UK Facility for Airborne Atmospheric Measurement (FAAM) aircraft. Simulated maximum a posteriori retrievals of partial column trace gas concentrations, and thermodynamic vertical profiles throughout the troposphere and planetary boundary layer have been performed here for simulated infrared spectra representative of the ARIES system operating in the nadir-viewing geometry. We also describe the operational and technical aspects of the pre-processing necessary for routine retrieval from the FAAM platform and the selection and construction of a priori information. As exemplars of the capability of the ARIES retrieval system, simulated retrievals of temperature, water vapour (H2O), carbon monoxide (CO), ozone (O3), and methane (CH4), and their corresponding sources of error and potential vertical sensitivity, are discussed for ARIES scenes across typical global environments. The maximum Degrees of Freedom for Signal (DOFS) for the retrievals, assuming a flight altitude of 7 km, were 3.99, 2.97, 0.85, 0.96, and 1.45 for temperature, H2O, CO, O3, and CH4, respectively, for the a priori constraints specified. Retrievals of temperature display significant vertical sensitivity (DOFS in the range 2.6 to 4.0 across the altitude range) as well as excellent simulated accuracy, with the vertical sensitivity for H2O also extending to lower altitudes (DOFS ranging from 1.6 to 3.0). It was found that the maximum sensitivity for CO, O3, and CH4 was approximately 1–2 km below the simulated altitudes in all scenarios. Comparisons of retrieved and simulated-truth partial atmospheric columns are used to assess the capability of the ARIES measurement system. Maximum mean biases (and bias standard deviations) in partial columns (i.e. below aircraft total columns) were found to be +0.06 (±0.02 at 1σ)%, +3.95 (±3.11)%, +3.74 (±2.97)%, −8.26 (±4.64)%, and +3.01 (±2.61)% for temperature, H2O, CO, O3, and CH4, respectively, illustrating that the retrieval system performs well compared to an optimal scheme. The maximum total a posteriori retrieval errors across the partial columns were also calculated, and were found to be 0.20, 22.57, 18.22, 17.61, and 16.42% for temperature, H2O, CO, O3, and CH4, respectively.

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

Abstract. Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

Formation of Gas-Phase Bromine from Interaction of Ozone with Frozen and Liquid NaCl/NaBr Solutions: Quantitative Separation of Surficial Chemistry from Bulk-Phase Reaction

The formation kinetics of gas-phase bromine (Br(2)) from interaction of gas-phase ozone (O(3)) with frozen and liquid solutions of NaCl (0.55 M) and NaBr (largely from 1.7 to 8.5 mM) have been studied from -40 to 0 °C in a coated-wall flow tube coupled to a chemical ionization mass spectrometer. The reactive uptake coefficient for O(3) is deduced from the product formation rate and then studied as a function of experimental conditions. In particular, for both the liquid and frozen solutions, we find that the uptake coefficient is inversely dependent on the gas-phase O(3) concentration in a manner that is quantitatively consistent with both surface- and bulk-phase kinetics. The reaction is fastest on acidic media (pH of the starting solution down to 2) but also proceeds at an appreciable rate on neutral substrates. Above 253 K, the uptake coefficient increases with increasing temperature on frozen solutions, consistent with an increasing brine content. The similarity of the absolute magnitude and form of the kinetics on the frozen and liquid substrates suggests that the reaction on the frozen solution is occurring with the associated brine, and not with the ice bulk or a quasi-liquid layer existing on the ice. The implications of these results to bromine activation in the tropospheric boundary layer are made.

Thermal and photochemical oxidation of self-assembled monolayers on alumina particles exposed to nitrogen dioxide

Alumina is an important component of airborne dust particles as well as of building materials and soils found in the tropospheric boundary layer. While the uptake and reactions of oxides of nitrogen and their photochemistry on alumina have been reported in the past, little is known about the chemistry when organics are also present. Fourier transform infrared (FTIR) spectroscopy at ∼23 °C was used to study reactions of NO(2) on γ-Al(2)O(3) particles that had been derivatized using 7-octenyltrichlorosilane to form a self-assembled monolayer (SAM). For comparison, the reactions with untreated γ-Al(2)O(3) were also studied. In both cases, the particles were exposed to water vapor prior to NO(2) to provide adsorbed water for reaction. As expected, surface-bound HONO, NO(2)(-), and NO(3)(-) were formed. Surprisingly, oxidation of the organic by surface-bound nitrogen oxides was observed in the dark, forming organo-nitrogen products identified as nitronates (R(2)C[double bond, length as m-dash]NO(2)(-)). Oxidation was more rapid under irradiation (λ > 290 nm) and formed organic nitrates and carbonyl compounds and/or peroxy nitrates in addition to the products observed in the dark. Mass spectrometry of the gas phase during irradiation revealed the production of NO, CO(2), and CO. These studies provide evidence for oxidation of organic compounds on particles and boundary layer surfaces that are exposed to air containing oxides of nitrogen, as well as new pathways for the formation of nitrogen-containing compounds on these surfaces.

Observation of halogen species in the Amundsen Gulf, Arctic, by active long-path differential optical absorption spectroscopy

In the polar tropospheric boundary layer, reactive halogen species (RHS) are responsible for ozone depletion as well as the oxidation of elemental mercury and dimethyl sulphide. After polar sunrise, air masses enriched in reactive bromine cover areas of several million square kilometers. Still, the source and release mechanisms of halogens are not completely understood. We report measurements of halogen oxides performed in the Amundsen Gulf, Arctic, during spring 2008. Active long-path differential optical absorption spectroscopy (LP-DOAS) measurements were set up offshore, several kilometers from the coast, directly on the sea ice, which was never done before. High bromine oxide concentrations were detected frequently during sunlight hours with a characteristic daily cycle showing morning and evening maxima and a minimum at noon. The, so far, highest observed average mixing ratio in the polar boundary layer of 41 pmol/mol (equal to pptv) was detected. Only short sea ice contact is required to release high amounts of bromine. An observed linear decrease of maximum bromine oxide levels with ambient temperature during sunlight, between -24 degrees C and -15 degrees C, provides indications on the conditions required for the emission of RHS. In addition, the data indicate the presence of reactive chlorine in the Arctic boundary layer. In contrast to Antarctica, iodine oxide was not detected above a detection limit of 0.3 pmol/mol.

The development of extremely dry surface air due to vertical exchanges under the exit region of a jet streak

Observations and numerical model simulations indicate that anomalous surface drying is strongly forced by mass and momentum adjustments under the right exit region of a polar jet streak overtaking and modifying a weak surface cold front. This drying event, which was associated with a wildfire in south-central New Jersey, is related to multi-scale atmospheric forcing that began far upstream and was likely not coupled to the classic cold conveyor belt model, as described by Carlson (Mon Wea Rev 108:1498–1509, 1980). The analyses indicate that both deep tropospheric circulations and boundary layer dry air advection occur in tandem to create a favorable environment for two closely associated extreme surface drying events. The first drying event occurs when lower tropospheric air is transported downwards in the descending branch of the low-level cold front’s thermally direct circulation. This low-level circulation, which is vertically separated from the upper-level jet, is still enhanced by the hydrostatic pressure rises under the velocity convergence in the equatorward exit region of the polar jet. The upper-level convergence phases with the low-level cold air advection to intensify the low-level isallobaric wind. Dry air increases at low levels in conjunction with the isallobaric divergence behind the low-level cold front. Sinking air occurs within the 100-hPa layer centered just above 900 hPa as a result of the isallobaric divergence. The shallow descending circulation within the upstream side of this low-level front produces the first injection of dry air into the surface layer independently of deep-boundary layer mixing. Surface moisture divergence and shallow sinking sustain the dry cold front in the boundary layer. The descending air in the upper tropospheric jet circulation does not immediately couple to the deepening boundary layer accompanying the cold front’s circulation. A second drying event occurs at the surface shortly thereafter, when surface heating deepens the well-mixed layer, such that the boundary layer behind the low-level front (i.e., within its trailing descending air) is linked to the dry air under the jet’s equatorward exit region descending branch. Thus, the first drying event is created by the low-level direct circulation in a region of isallobaric divergence, while the second drying event is created by the coupling between the upper level indirect circulation and the deepening convective boundary layer. The two dry events combine to create a favorable environment for an isolated wildfire as both dry air and increasing surface winds develop during maximum surface heating.

Chasing quicksilver northward: mercury chemistry in the Arctic troposphere

Environmental Context. ‘Mercurial storms rage over the Arctic’ wrote Fred Pearce in New Scientist in June of 1997: he was referring to the recent discovery by Bill Schroeder and his colleagues (Nature, Vol. 394, 1998) of periods soon after Arctic dawn when the concentration of mercury in the atmosphere literally plummets to levels so low that they can be undetectable, even by the most sensitive of modern instruments. A decade and many measurement campaigns later, we think we understand how these so-called depletion events occur, if not all the mechanisms that go towards providing the conditions for them to happen. Nor do we really know what happens to the mercury removed from the atmosphere; the fear is that it is deposited and enters the Arctic ecosystem, where it is potentially extremely harmful. The present study questions whether that fear is grounded. Abstract. The tropospheric boundary layer chemistry of Hg has been simulated using a two-phase photochemical box model to see if our current (experimental and theoretical) understanding of Hg(g)0 reaction rates can account for the depletion events seen during Arctic spring, when the so-called ‘bromine explosion’ in the model is constrained by the measured ozone depletion rate. The simulations reveal that the observed rate of Hg(g)0 depletion can be accounted for; however, the measured concentrations of gas-phase oxidised Hg and HgP (Hg associated with particulate matter) cannot. Simulating the emission of Hg(g)0 from the snow pack to mimic the observed concentration recovery after a depletion event suggests the net Hg deposition from a depletion event is all but irrelevant.

New Experimental and Theoretical Approach to the Heterogeneous Hydrolysis of NO2: Key Role of Molecular Nitric Acid and Its Complexes

Although heterogeneous chemistry on surfaces in the troposphere is known to be important, there are currently only a few techniques available for studying the nature of surface-adsorbed species as well as their chemistry and photochemistry under atmospheric conditions of 1 atm pressure and in the presence of water vapor. We report here a new laboratory approach using a combination of long path Fourier transform infrared spectroscopy (FTIR) and attenuated total reflectance (ATR) FTIR that allows the simultaneous observation and measurement of gases and surface species. Theory is used to identify the surface-adsorbed intermediates and products, and to estimate their relative concentrations. At intermediate relative humidities typical of the tropospheric boundary layer, the nitric acid formed during NO2 heterogeneous hydrolysis is shown to exist both as nitrate ions from the dissociation of nitric acid formed on the surface and as molecular nitric acid. In both cases, the ions and HNO3 are complexed to water molecules. Upon pumping, water is selectively removed, shifting the NO(3-)-HNO3(H2O)y equilibria toward more dehydrated forms of HNO3 and ultimately to nitric acid dimers. Irradiation of the nitric acid-water film using 300-400 nm radiation generates gaseous NO, while irradiation at 254 nm generates both NO and HONO, resulting in conversion of surface-adsorbed nitrogen oxides into photochemically active NO(x). These studies suggest that the assumption that deposition or formation of nitric acid provides a permanent removal mechanism from the atmosphere may not be correct. Furthermore, a potential role of surface-adsorbed nitric acid and other species formed during the heterogeneous hydrolysis of NO2 in the oxidation of organics on surfaces, and in the generation of gas-phase HONO on local to global scales, should be considered.

Iodine oxide in the Dead Sea Valley: Evidence for inorganic sources of boundary layer IO

The importance of iodine oxide (IO) in tropospheric boundary layer chemistry has been well established in the last decade. Iodine‐containing radicals have been detected in regions of high biological productivity. To date, most explanations assume biogenic precursors (e.g., emission of iodocarbons). In a 2 week field campaign at the Dead Sea, Israel, IO was found to exceed the detection limit (0.3–2 parts per trillion (ppt)) almost daily, with peak levels topping 10 ppt. Macro algae are nonexistent because of the water's high salinity. The Dead Sea's microbiology is discussed in detail, and organic sources of iodine oxide are found to be of minor importance. Thus the site can be treated as a unique place for the investigation of inorganic sources of IO. Such processes have recently been included in model studies. Our study focuses on the first direct evidence for inorganic sources of reactive boundary layer iodine. Heterogeneous iodine release induced by photolysis, liquid phase ozone reactions, or catalytic HOX interactions are discussed as well as NOx chemistry.

Hygroscopic properties of different aerosol types over the Atlantic and Indian Oceans

Abstract. Hygroscopic properties of atmospheric particles were studied in the marine tropospheric boundary layer over the Atlantic and Indian Oceans during two consecutive field studies: the Aerosols99 cruise (Atlantic Ocean) from 15 January to 20 February 1999, and the INDOEX cruise (Indian Ocean Experiment) from 23 February to 30 March 1999. The hygroscopic properties were compared to optical and chemical properties, such as absorption, chemical inorganic composition, and mass concentration of organic and elemental carbon, to identify the influence of these parameters on hygroscopicity. During the two field studies, four types of aerosol-sampling instruments were used on board the NOAA (National Oceanic and Atmospheric Administration) Research Vessel Ronald H. Brown: Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA), seven-stage cascade impactor, two-stage cascade impactor, and Particle Soot Absorption Photometer (PSAP). The HTDMA was used to determine the hygroscopic properties of atmospheric particles at initial dry sizes (Dp) of 50, 150, and 250 nm and at relative humidities (RH) of 30, 55, 75, and 90%. Simultaneously, a seven-stage cascade impactor of which 3 stages were in the sub-mm size range was used to determine the molar composition of the major inorganic ions such as ammonium and sulfate ions. A two-stage cascade impactor (1 in the sub-mm size range, 1 in the sup-mm size range) was used to determine the mass concentration of organic and elemental carbon. The PSAP was used (at a wavelength of 565 nm) to measure the light absorption coefficient of the aerosol. During the two field studies, air masses of several different origins passed the ship's cruise path. The occurrence of different air masses was classified into special time periods signifying the origin of the observed aerosol. All time periods showed a group of particles with high hygroscopic growth. The measured average hygroscopic growth factors defined by the ratio of dry and wet particle diameter at 90% RH ranged from 1.6 to 2.0, depending on the dry particle size and on the type of air mass. Particles with low hygroscopic growth occurred only when continentally influenced air masses arrived at the ship's position. Distinctions in hygroscopic growth of particles of different air masses were more significant for small relative humidities (30% or 55% RH). High concentrations of elemental carbon corresponded with high light absorption coefficients and with the occurrence of less-hygroscopic and nearly hydrophobic particle fractions in the hygroscopic growth distributions. A key finding is that clean marine air masses that had no land contact for five to six days could clearly be distinguished from polluted air masses that had passed over a continent several days before reaching the ship.

Acid Dissociation of HBr on a Model Ice Surface

The acid ionization of HBr on ice is important in connection with the rapid springtime ozone depletion in the Arctic tropospheric boundary layer. The interaction of HBr with an ice surface is studied theoretically via electronic structure calculations on a semiconstrained HBr.(H 2 O) 1 3 model cluster at the MP2 level of theory using effective core potentials for all the heavy atoms. The heterolytic dissociation of HBr to form a H 3 O + .Br - contact ion pair is not found to occur atop this model ice lattice system, but it is found to be barrierless and energetically spontaneous when assisted by a single extra-lattice water molecule.

Antarctic springtime depletion of atmospheric mercury.

Unlike other heavy metals that are inherently associated with atmospheric aerosols, mercury in ambient air exists predominantly in the gaseous elemental form. Because of its prolonged atmospheric residence time, elemental mercury vapor is distributed on a global scale. Recently, Canadian researchers have discovered that total gaseous mercury levels in the lower tropospheric boundary layer in the Canadian Arctic are often significantly depleted during the months after polar sunrise. A possible explanation may involve oxidation of elemental mercury, followed by adsorption and deposition of the oxidized form, leading to an increased input of atmospheric mercury into the Arctic ecosystem. Here we present the first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period between January 2000 and January 2001 at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W). We report that mercury depletion events also occur in the Antarctic after polar sunrise and compare our measurements with a data setfrom Alert, Nunavut, Canada. We also present indications that BrO radicals and ozone play a key role in the boundary-layer chemistry during springtime mercury depletion events in the Antarctic troposphere.

In‐situ measurement of atmospheric NO3 and N2O5 via cavity ring‐down spectroscopy

We report the application of cavity ring‐down spectroscopy (CaRDS), a high‐sensitivity absorption technique, to the in‐situ detection of both NO3 and N2O5 in ambient air. The detection limit for NO3, measuring absorption in its strong, 662‐nm band, is 0.3 pptv at STP (50 s integration time). Heating the air flow through the inlet thermally dissociates N2O5 to yield NO3, whose detection gives the ambient concentration of N2O5. The instrument was successfully field tested in March–April, 2001 at a site in the tropospheric boundary layer in Boulder, Colorado. This study is the first fast‐response (5s‐1 min), in‐situ detection of NO3. It is also the first in‐situ detection of N2O5 and the first observation of this species in the troposphere. Both NO3 and N2O5 showed considerable temporal variability, highlighting the need for a fast‐response instrument.