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Impacts of electronically photo-excited NO2 on air pollution in the South Coast Air Basin of California

A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2) and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB). Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating two summer episodes. First, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 8-h average ozone and particulate matter concentrations. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx) and volatile organic compounds (VOC) emissions. Isopleths are obtained using 1987 emissions, to represent past conditions, and 2005, to represent current conditions in the SoCAB. Results show that the sensitivity of modeled pollutant control strategies due to photoexcitation decreases with the decrease in baseline emissions from 1987 to 2005. Results show that including NO2 photo-excitation, increases the sensitivity of ozone concentration with respect to changes in NOx emissions for both years. In particular, decreasing NOx emissions in 2005 when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to ozone relative reduction factors that are 15% lower than in a case without photo-excited NO2. This implies that photoexcitation increases the effectiveness in reducing ozone through NOx emissions reductions alone, which has implications for the assessment of future emission control strategies. However, there is still disagreement with respect to the reaction rate constant for the formation of OH. Therefore, further studies are required to reduce the uncertainty in the reaction rate constant before this new mechanism is fully implemented in regulatory applications.
Mercury emission and speciation of coal-fired power plants in China

Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of Selective Catalytic Reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92–27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66–94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.
Integrated water vapor above Ny Ålesund, Spitsbergen: a multi-sensor intercomparison

Water vapor is an important constituent of the atmosphere. Because of its abundance and its radiative properties it plays an important role for the radiation budget of the atmosphere and has major influence on weather and climate. In this work integrated water vapor (IWV) derived from the measurements of three satellite sensors, GOME, SCIAMACHY and AMSU-B, two ground based sensors, a Fourier-transform spectrometer (FTIR), a microwave radiometer for O3 (RAM) and IWV inferred from GPS zenith path delay (ZPD) measurements, are compared to radio-sonde measurements above Ny Ålesund, 79° N. All six remote sensors exploit different principles and work in different wavelength regions. All remote sensing instruments reproduce the sonde measurements very well and are highly correlated when compared with the radio-sonde measurements. The ground-based FTIR shows very little scatter of about 10%. The GPS performs similar to the FTIR at all times except for very low IWV, where the scatter exceeds 50% of the measured IWV. The other remote sensing instruments show scatter of about 20% (standard deviation). The ground-based RAM performs similar to the satellite instruments, despite the fact that the retrieval of IWV is just a by-product of this ozone sensor.
Gaseous elemental mercury depletion events observed at Cape Point during 2007–2008

Gaseous mercury in the marine boundary layer has been measured with a 15 min temporal resolution at the Global Atmosphere Watch station Cape Point since March 2007. The most prominent features of the data until July 2008 are the frequent occurrences of pollution (PEs) and depletion events (DEs). Both types of events originate mostly within a short transport distance (up to about 100 km), which are embedded in air masses ranging from marine background to continental. The Hg/CO emission ratios observed during the PEs are within the range reported for biomass burning and industrial/urban emissions. The depletion of gaseous mercury during the DEs is in many cases almost complete and suggests an atmospheric residence time of elemental mercury as short as a few dozens of hours, which is in contrast to the commonly used estimate of approximately 1 year. The DEs observed at Cape Point are not accompanied by simultaneous depletion of ozone which distinguishes them from the halogen driven atmospheric mercury depletion events (AMDEs) observed in Polar Regions. Nonetheless, DEs similar to those observed at Cape Point have also been observed at other places in the marine boundary layer. Additional measurements of mercury speciation and of possible mercury oxidants are hence called for to reveal the chemical mechanism of the newly observed DEs and to assess its importance on larger scales.
An aerosol chamber investigation of the heterogeneous ice nucleating potential of refractory nanoparticles

Nanoparticles of iron oxide (crystalline and amorphous), silicon oxide and magnesium oxide were investigated for their propensity to nucleate ice over the temperature range 180–250 K, using the AIDA chamber in Karlsruhe, Germany. All samples were observed to initiate ice formation via the deposition mode at threshold ice super-saturations (RHithresh) ranging from 105% to 140% for temperatures below 220 K. Approximately 10% of amorphous Fe2O3 particles (modal diameter = 30 nm) generated in situ from a photochemical aerosol reactor, led to ice nucleation at RHithresh = 140% at an initial chamber temperature of 182 K. Quantitative analysis using a singular hypothesis treatment provided a fitted function [ns(190 K)=10(3.33×sice)+8.16] for the variation in ice-active surface site density (ns:m−2) with ice saturation (sice) for Fe2O3 nanoparticles. This was implemented in an aerosol-cloud model to determine a predicted deposition (mass accommodation) coefficient for water vapour on ice of 0.1 at temperatures appropriate for the upper atmosphere. Classical nucleation theory was used to determine representative contact angles (θ) for the different particle compositions. For the in situ generated Fe2O3 particles, a slight inverse temperature dependence was observed with θ = 10.5° at 182 K, decreasing to 9.0° at 200 K (compared with 10.2° and 11.4° respectively for the SiO2 and MgO particle samples at the higher temperature). These observations indicate that such refractory nanoparticles are relatively efficient materials for the nucleation of ice under the conditions studied in the chamber which correspond to cirrus cloud formation in the upper troposphere. The results also show that Fe2O3 particles do not act as ice nuclei under conditions pertinent for tropospheric mixed phase clouds, which necessarily form above ~233 K. At the lower temperatures (<150 K) where noctilucent clouds form during summer months in the high latitude mesosphere, higher contact angles would be expected, which may reduce the effectiveness of these particles as ice nuclei in this part of the atmosphere.
Chirality and the origin of atmospheric humic-like substances

Aerosol water extracts and atmospheric humic-like substances (HULIS) obtained from PM2.5-fraction aerosol samples collected in a rural/continental background environment and in an urban environment in spring and summer, and at a tropical site that was heavily impacted by biomass burning were studied. HULIS was obtained as the water-soluble, methanol-elutable material isolated from a solid-phase extraction procedure. The mean organic matter-to-organic carbon mass conversion factor and the standard deviation of 2.04±0.06 were derived for HULIS from biomass burning. Mean atmospheric concentrations of HULIS for the rural and urban environments and for the biomass burning during daylight periods and nights, were 1.65, 2.2, 43, and 60 μg m−3, respectively. This and other abundances indicate that intense emission sources and/or formation mechanisms of HULIS operate in biomass burning. Mean contributions of C in HULIS (HULIS-C) to water-soluble organic carbon (WSOC) were 35, 48, 63, and 76%, respectively, for the sample set listed. HULIS-C is the major component of the WSOC in tropical biomass burning. The data also suggest that HULIS most likely do not share common origin in the three environments studied. Differentiation among the possible formation processes was attempted by investigating the optical activity of HULIS through their (electronic and vibrational) circular dichroism properties. The urban HULIS did not show optical activity, which is in line with the concept of their major airborne formation from anthropogenic aromatics. The rural HULIS revealed weak optical activity, which may be associated with one of their important formation pathways by photo-oxidation and oligomerisation, i.e., with the formation from chiral biogenic precursors with one of the enantiomers slightly enriched. The The biomass burning of HULIS exhibited a strong effect in the vibrational circular dichroism as a clear distinction from the other two types. This was related to the contribution of the thermal degradation products of lignins and cellulose. The biomass burning of HULIS resemble Suwannee River Fulvic Acid standard more closely in some aspects than the urban and rural types of HULIS, which may be related to their common origin from plant material.
Contributions from DMS and ship emissions to CCN observed over the summertime North Pacific

Measurements of cloud condensation nuclei (CCN) made over the North Pacific Ocean in July 2002 are analysed with concurrent measurements of aerosol number, mass and composition. Overall the CCN are controlled by the sulphate, including one case that suggests particle nucleation and growth resulting from dimethyl sulphide oxidation that enhanced CCN concentrations. Hourly CCN concentrations are correlated with concentrations of sulphate plus methanesulphonic acid (MSA) over the entire study period (r2=0.43 and 0.52 for supersaturations of 0.34% and 0.19%, respectively), and are not well correlated with other organics (r2<0.2). One case study reveals elevated mass and number concentrations of ultrafine and fine organic particles due to regional ship emissions, identified through quadrupole aerosol mass spectrometer (Q-AMS) measurements, during which organic mass concentrations are correlated with CCN values (r2=0.39 and 0.46 for supersaturations of 0.19% and 0.34%, respectively). The evolution of the time series and mass distributions of organics, sulphate and MSA over this timeframe indicate that the regional distribution of small, diffuse ship-sourced organic particles act as condensation sites for sulphur species, resulting in a subsequent increase in number concentrations of CCN. We conclude that, where present, direct emissions of anthropogenic organic particles may exert a strong control on marine CCN concentrations once diffused into the marine atmosphere, by acting as condensation sites for biogenic and anthropogenic sulphur species.
Measurements of volatile organic compounds in the middle of Central East China during Mount Tai Experiment 2006 (MTX2006): observation of regional background and impact of biomass burning

The measurement of volatile organic compounds (VOCs) was carried out at the summit of Mount Tai, located in the center of the Central East China (CEC) region, in June 2006 as part of the Mount Tai Experiment 2006 (MTX2006), which focused on the ozone and aerosol chemistry in the region. Temporal variations of simple VOCs between 2 June and 28 June revealed the characteristics of an aged air mass with minimum local influence. A comparison of VOCs observed at Mount Tai with other Chinese sites revealed relatively similar VOC levels to remote sites and, as expected, a lower level compared to more polluted sites. However, relatively high acetylene and benzene levels at Mount Tai were evidently indicated from comparison with normalized VOC profile by ethane suggested for Beijing. Owing to a shift in boundary layer height, we observed considerable differences between daytime and nighttime VOC mixing ratios. This suggests that the site potentially has a very useful characteristic of being able to measure regional polluted air and the free troposphere regional background air quality. Influence of emissions from biomass burning in the region was evidently found to be extensive during the first half of the campaign (2–15 June), using fire spot data coupling with backward trajectory analysis. Agricultural residue burning was suggested as the primary source of emissions elucidated by the slope of the correlation plot between CH3Cl and CO obtained during the first half of the campaign.
Inverse modeling of European CH4 emissions: sensitivity to the observational network

Inverse modeling is widely employed to provide "top-down" emission estimates using atmospheric measurements. Here, we analyze the dependence of derived CH4 emissions on the sampling frequency and density of the observational surface network, using the TM5-4DVAR inverse modeling system and synthetic observations. This sensitivity study focuses on Europe. The synthetic observations are created by TM5 forward model simulations. The inversions of these synthetic observations are performed using virtually no knowledge on the a priori spatial and temporal distribution of emissions, i.e. the emissions are derived mainly from the atmospheric signal detected by the measurement network. Using the European network of stations for which continuous or weekly flask measurements are available for 2001, the synthetic experiments can retrieve the "true" annual total emissions for single countries such as France within 20%, and for all North West European countries together within ~5%. However, larger deviations are obtained for South and East European countries due to the scarcity of stations in the measurement network. Upgrading flask sites to stations with continuous measurements leads to an improvement for central Europe in emission estimates. For realistic emission estimates over the whole European domain, however, a major extension of the number of stations in the existing network is required. We demonstrate the potential of an extended network of a total of ~60 European stations to provide realistic emission estimates over the whole European domain.
Aerosol hygroscopicity at high (99 to 100%) relative humidities

The hygroscopicity of an aerosol strongly influences its effects on climate and, for smaller particles, atmospheric lifetime. While many aerosol hygroscopicity measurements have been made at lower relative humidities (RH) and under cloud formation conditions (RH>100%), relatively few have been made at high RH (99 to 100%), where the Kelvin (curvature) effect is comparable to the Raoult (solute) effect. We measured the size of droplets at high RH that had formed on particles composed of one of seven compounds with dry diameters between 0.1 and 0.5 μm. We report the hygroscopicity of these compounds using a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term. For inorganic compounds, hygroscopicity could reliably be predicted using water activity data (measured in macroscopic solutions) and assuming a surface tension of pure water. In contrast, most organics exhibited a slight to mild increase in hygroscopicity with droplet diameter. This trend was strongest for sodium dodecyl sulfate (SDS), the most surface-active compound studied. The results suggest that, for single-component aerosols at high RH, partitioning of solute to the particle-air interface reduces particle hygroscopicity by reducing the bulk solute concentration. This partitioning effect is more important than the increase in hygroscopicity due to surface tension reduction. Furthermore, we found no evidence that micellization limits SDS activity in micron-sized solution droplets, as observed in macroscopic solutions. We conclude that while the high-RH hygroscopicity of inorganic compounds can be reliably predicted using readily available data, surface-activity parameters obtained from macroscopic solutions with organic solutes may be inappropriate for calculations involving micron-sized droplets.