ALBERT

Beschreibung: This paper presents a summary of the measurements that were made during the heavily-instrumented Reactive Halogens in the Marine Boundary Layer (RHaMBLe) coastal study in Roscoff on the North West coast of France. It was clearly demonstrated that iodine-mediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I2, by macroalgal species fully or partially exposed by the receding waterline. Ultrafine particle concentrations strongly correlate with the rapidly recycled reactive iodine species, IO, produced at high concentrations following photolysis of I2. The heterogeneous macroalgal I2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques. Apparent particle emission fluxes were associated with an enhanced apparent depositional flux of ozone, consistent with both a direct O3 deposition to macroalgae and involvement of O3 in iodine photochemistry and subsequent particle formation below the measurement height. The magnitude of the particle formation events was observed to be greatest at the lowest tides with higher concentrations of ultrafine particles growing to much larger sizes, probably by the condensation of anthropogenically-formed condensable material. At such sizes the particles should be able to act as cloud condensation nuclei at reasonable atmospheric supersaturations.

Beschreibung: STEREO has now completed the first two years of its mission, moving from close proximity to Earth in 2006/2007 to more than 50 degrees longitudinal separation from Earth in 2009. During this time, several large-scale structures have been observed in situ. Given the prevailing solar minimum conditions, these structures have been predominantly coronal hole-associated solar wind, slow solar wind, their interfaces, and the occasional transient event. In this paper, we extend earlier solar wind composition studies into the current solar minimum using high-resolution (1-h) sampling times for the charge state analysis. We examine 2-year trends for iron charge states and solar wind proton speeds, and present a case study of Carrington Rotation 2064 (December 2007) which includes minor ion (He, Fe, O) kinetic and Fe composition parameters in comparison with proton and magnetic field signatures at large-scale structures observed during this interval.

Beschreibung: Simulated primary organic aerosols (POA), as well as other particulates and trace gases, in the vicinity of Mexico City are evaluated using measurements collected during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaigns. Since the emission inventories, transport, and turbulent mixing will directly affect predictions of total organic matter and consequently total particulate matter, our objective is to assess the uncertainties in predicted POA before testing and evaluating the performance of secondary organic aerosol (SOA) treatments. Carbon monoxide (CO) is well simulated on most days both over the city and downwind, indicating that transport and mixing processes were usually consistent with the meteorological conditions observed during MILAGRO. Predicted and observed elemental carbon (EC) in the city was similar, but larger errors occurred at remote locations since the overall CO/EC emission ratios in the national emission inventory were lower than in the metropolitan emission inventory. Components of organic aerosols derived from Positive Matrix Factorization of data from several Aerodyne Aerosol Mass Spectrometer instruments deployed both at ground sites and on research aircraft are used to evaluate the model. Modeled POA was consistently lower than the measured organic matter at the ground sites, which is consistent with the expectation that SOA should be a large fraction of the total organic matter mass. A much better agreement was found when modeled POA was compared with the sum of "primary anthropogenic" and "biomass burning" components derived from Positive Matrix Factorization (PMF) on most days, especially at the surface sites, suggesting that the overall magnitude of primary organic particulates released was reasonable. However, simulated POA from anthropogenic sources was often lower than "primary anthropogenic" components derived from PMF, consistent with two recent reports that these emissions are underestimated. The modeled POA was greater than the total observed organic matter when the aircraft flew directly downwind of large fires, suggesting that biomass burning emission estimates from some large fires may be too high.

Beschreibung: Simulated primary organic aerosols (POA), as well as other particulates and trace gases, in the vicinity of Mexico City are evaluated using measurements collected during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaigns. Since the emission inventories and dilution will directly affect predictions of total organic matter and consequently total particulate matter, our objective is to assess the uncertainties in predicted POA before testing and evaluating the performance of secondary organic aerosol (SOA) treatments. Carbon monoxide (CO) is well simulated on most days both over the city and downwind, indicating that transport and mixing processes were usually consistent with the meteorological conditions observed during MILAGRO. Predicted and observed elemental carbon (EC) in the city was similar, but larger errors occurred at remote locations since the overall CO/EC emission ratios in the national emission inventory were lower than in the metropolitan emission inventory. Components of organic aerosols derived from Positive Matrix Factorization of data from several Aerodyne Aerosol Mass Spectrometer instruments deployed both at ground sites and on research aircraft are used to evaluate the model. Modeled POA was consistently lower than the measured organic matter at the ground sites, which is consistent with the expectation that SOA should be a large fraction of the total organic matter mass. A much better agreement was found when modeled POA was compared with the sum of measured "primary anthropogenic" and "biomass burning" components on most days, suggesting that the overall magnitude of primary organic particulates released was reasonable. The modeled POA was greater than the total observed organic matter when the aircraft flew directly downwind of large fires, suggesting that biomass burning emission estimates from some large fires may be too high. Predicted total observed organic carbon (TOOC) was also analyzed to assess how emission inventory estimates of volatile organic compounds may impact predictions of SOA.

Beschreibung: GEM/POPs was developed to simulate the transport, deposition and partitioning of semi-volatile persistent organic pollutants (POPs) in the atmosphere within the framework of Canadian weather forecasting model GEM. In addition to the general processes such as anthropogenic emissions, atmosphere/water and atmosphere/soil exchanges, GEM/POPs incorporates a dynamic aerosol module to provide the aerosol surface areas for the semi-volatile POPs to partition between gaseous and particle phases and a mechanism for particle-bound POPs to be removed. Simulation results of three PCBs (28, 153 and 180) for year 2000 indicate that the model captured the main features of global atmospheric PCBs when compared with observations from EMEP, IADN and Alert stations. The annual averaged concentrations and the fractionation of the three PCBs as a function of latitudes are agreed reasonably well with observations. The impacts of atmospheric aerosols on the transports and partitioning of the three PCBs are reasonably simulated. The ratio of particulate to gaseous PCBs ranges from less than 0.1 for PCB28 to as high as 100 for PCB180, increasing from the warm lower latitudes to the cold high latitudes. Application of GEM/POPs in a study of the global transports and budgets of various PCBs accompanies this paper.

Beschreibung: The input of nitrogen (N) to ecosystems has increased dramatically over the past decades. While total (wet + dry) N deposition has been extensively determined in temperate regions, only very few data sets of N wet deposition exist for tropical ecosystems, and moreover, reliable experimental information about N dry deposition in tropical environments is lacking. In this study we estimate dry and wet deposition of inorganic N for a remote pasture site in the Amazon Basin based on in-situ measurements. The measurements covered the late dry (biomass burning) season, a transition period and the onset of the wet season (clean conditions) (12 September to 14 November 2002) and were a part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate) 2002 campaign. Ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), nitrogen dioxide (NO2), nitric oxide (NO), ozone (O3), aerosol ammonium (NH4+) and aerosol nitrate (NO3-) were measured in real-time, accompanied by simultaneous meteorological measurements. Dry deposition fluxes of NO2 and HNO3 are inferred using the ''big leaf multiple resistance approach'' and particle deposition fluxes are derived using an established empirical parameterization. Bi-directional surface-atmosphere exchange fluxes of NH3 and HONO are estimated by applying a ''canopy compensation point model''. N dry and wet deposition is dominated by NH3 and NH4+, which is largely the consequence of biomass burning during the dry season. The grass surface appeared to have a strong potential for daytime NH3 emission, owing to high canopy compensation points, which are related to high surface temperatures and to direct NH3 emissions from cattle excreta. NO2 also significantly accounted for N dry deposition, whereas HNO3, HONO and N-containing aerosol species were only minor contributors. Ignoring NH3 emission from the vegetation surface, the annual net N deposition rate is estimated to be about −11 kgN ha-1 yr-1. If on the other hand, surface-atmosphere exchange of NH3 is considered to be bi-directional, the annual net N budget at the pasture site is estimated to range from −2.15 to −4.25 kgN ha-1 yr-1.

Beschreibung: GEM/POPs was developed to simulate the transport, deposition and partitioning of semi-volatile persistent organic pollutants (POPs) in the atmosphere within the framework of Canadian weather forecasting model GEM. In addition to the general processes such as anthropogenic emissions, atmosphere/water and atmosphere/soil exchanges, GEM/POPs incorporates a dynamic aerosol module to provide the aerosol surface areas for the semi-volatile POPs to partition between gaseous and particle phases and a mechanism for particle-bound POPs to be removed. Simulation results of three PCBs (28, 153 and 180) for the year 2000 indicate that the model captured the main features of global atmospheric PCBs when compared with observations from EMEP, IADN and Alert stations. The annual averaged concentrations and the fractionation of the three PCBs as a function of latitudes agreed reasonably well with observations. The impacts of atmospheric aerosols on the transports and partitioning of the three PCBs are reasonably simulated. The ratio of particulate to gaseous PCBs in the atmospheric column ranges from less than 0.1 for PCB28 to as high as 100 for PCB180, increasing from the warm lower latitudes to the cold high latitudes. Application of GEM/POPs in a study of the global transports and budgets of various PCBs accompanies this paper.

Beschreibung: Global transports and budgets of three PCBs were investigated with a 3-D dynamic model for semi-volatile persistent organic pollutants – GEM/POPs. Dominant pathways were identified for PCB transports in the atmosphere with a transport flux peaking below 8 km for gaseous and 14 km for particulate PCB28, and peaking below 4 km for gaseous and 6 km for particulate PCB180. The inter-continental transports of PCBs in the Northern Hemisphere (NH) are dominated in the zonal direction with their route changes regulated seasonally by the variation of westerly jet. The transport pathways from Europe and North Atlantic contributed the most PCBs to the Arctic. Inter-hemispheric transports of PCBs originated from the regions of Europe, Asia and North America in three different flow-paths, accompanying with easterly jet, Asian monsoon winds and trade winds. PCBs from the Southern Hemisphere (SH) could also be exported into the NH. According to the PCB emissions of year 2000, Europe, North America and Asia are the three largest sources of the three PCBs, contributing to the global background concentrations in the atmosphere, soil and water. Globally, PCB28 in soil and water has become a comparable source to the anthropogenic emissions while heavier PCBs such as PCB153 and 180 are still transporting into soil and water. For all three congeners, particulate PCBs are concentrated in the higher levels than gaseous PCBs. More than half of the particulate PCB28 could reach up to the stratosphere, while most of the heavier counter-parts (PCB153 and PCB180) are stored in the troposphere including boundary layer with more than 99% gaseous PCB180 below 6 km.

Beschreibung: Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.

Beschreibung: Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.