bluuebunny/crossref_metadata_2025 huggingface dataset:
Impacts of electronically photo-excited NO2 on air pollution in the South Coast Air Basin of California
Authors: Ensberg J. J. , Carreras-Sospedra M. , Dabdub D.
Published: April 2010

Abstract. 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.
Integrated water vapor above Ny Ålesund, Spitsbergen: a multi-sensor intercomparison
Authors: Pałm M. , Melsheimer C. , Noël S. , Heise S. , Notholt J. , Burrows J. , Schrems O.
Published: April 2010

Abstract. 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.
An aerosol chamber investigation of the heterogeneous ice nucleating potential of refractory nanoparticles
Authors: Saunders R. W. , Möhler O. , Schnaiter M. , Benz S. , Wagner R. , Saathoff H. , Connolly P. J. , Burgess R. , Murray B. J. , Gallagher M. , Wills R. , Plane J. M. C.
Published: April 2010

Abstract. 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.
Aerosol hygroscopicity at high (99 to 100%) relative humidities
Authors: Ruehl C. R. , Chuang P. Y. , Nenes A.
Published: April 2010

Abstract. 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.
Biomass burning aerosol emissions from vegetation fires: particle number and mass emission factors and size distributions
Authors: Janhäll S. , Andreae M. O. , Pöschl U.
Published: April 2010

Abstract. Aerosol emissions from vegetation fires have a large impact on air quality and climate. In this study, we use published experimental data and different fitting procedures to derive dynamic particle number and mass emission factors (EFPN, EFPM) related to the fuel type, burning conditions and the mass of dry fuel burned, as well as characteristic CO-referenced emission ratios (PN/CO, PM/CO). Moreover, we explore and characterize the variability of the particle size distribution of fresh smoke, which is typically dominated by a lognormal accumulation mode with count median diameter around 120 nm (depending on age, fuel and combustion efficiency), and its effect on the relationship between particle number and mass emission factors. For the particle number emission factor of vegetation fires, we found no dependence on fuel type and obtained the following parameterization as a function of modified combustion efficiency (MCE): EFPN=34×1015×(1−MCE) kg−1±1015 kg−1 with regard to dry fuel mass (d.m.). For the fine particle mass emission factors (EFPM) we obtained (86–85×MCE) g kg−1±3 g kg−1 as an average for all investigated fires; (93–90×MCE) g kg−1±4 g kg−1 for forest; (67–65×MCE) g kg−1±2 g kg−1 for savanna; (63–62×MCE) g kg−1±1 g kg−1 for grass. For the PN/CO emission ratio we obtained an average of (34±16) cm−3 ppb−1 exhibiting no systematic dependence on fuel type or combustion efficiency. The average PM/CO emission ratios were (0.09±0.04) g g−1 for all investigated fires; (0.13±0.05) g g−1 for forest; (0.08±0.03) g g−1 for savanna; and (0.07±0.03) g g−1 for grass. The results are consistent with each other, given that particles from forest fires are on average larger than those from savanna and grass fires. This assumption and the above parameterizations represent the current state of knowledge, but they are based on a rather limited amount of experimental data which should be complemented by further measurements. Nevertheless, the presented parameterizations appear sufficiently robust for exploring the influence of vegetation fires on aerosol particle number and mass concentrations in regional and global model studies.
Measurements of OH and HO2 yields from the gas phase ozonolysis of isoprene
Authors: Malkin T. L. , Goddard A. , Heard D. E. , Seakins P. W.
Published: April 2010

Abstract. The reactions of ozone with alkenes are an important source of hydroxyl (OH) radicals; however, quantification of their importance is hindered by uncertainties in the absolute OH yield. Hydroxyl radical yields for the gas-phase ozonolysis of isoprene are determined in this paper by four different methods: (1) The use of cyclohexane as an OH scavenger, and the production of cyclohexanone, (2) The use of 1,3,5-trimethylbenzene as an OH tracer, and the diminution in its concentration, (3) A kinetic method in which the OH yield was obtained by performing a series of pseudo-first-order experiments in the presence or absence of an OH scavenger (cyclohexane), (4) The OH and HO2 yields were determined by fitting the temporal OH and HO2 profiles following direct detection of absolute OH and HO2 concentrations by laser induced fluorescence at low pressure (Fluorescence Assay by Gas Expansion- FAGE). The following OH yields for the ozonolysis of isoprene were obtained, relative to alkene consumed, for each method: (1) Scavenger (0.25±0.04), (2) Tracer (0.25±0.03), (3) Kinetic study (0.27±0.02), and (4) Direct observation (0.26±0.02), the error being one standard deviation. An averaged OH yield of 0.26±0.02 is recommended at room temperature and atmospheric pressure and this result is compared with recent literature determinations. The HO2 yield was directly determined for the first time using FAGE to be 0.26±0.03.
The 16-day wave in the Arctic and Antarctic mesosphere and lower thermosphere
Authors: Day K. A. , Mitchell N. J.
Published: April 2010

Abstract. The 16-day planetary wave in the polar mesosphere and lower thermosphere has been investigated using meteor radars at Esrange (68° N, 21° E) in the Arctic and Rothera (68° S, 68° W) in the Antarctic. The measurements span the 10-year interval from October 1999 to July 2009 and the 5-year interval February 2005 to July 2009, respectively. The height range covered is about 80–100 km. In both polar regions the wave is seen to occur in intermittent bursts, where wave amplitudes typically reach a maximum of about 15 m s−1, and never more than about 20 m s−1. Horizontal wind variance within a wave-period range of 12 to 20 days is used as a proxy for the activity of the 16-day wave. Wave activity is strong for 3 to 4 months in winter, where it is present across the entire height range observed and monthly wave variance reaches about 65 m2 s−2. Some weak and intermittent activity is observed throughout the other seasons including summer. However, there is a high degree of inter-annual variability and in some individual years wave activity is almost absent. The data are used to construct a representative climatology for the Arctic and Antarctic. The seasonal cycle of the 16-day wave is found to be very similar in both polar regions. The 16-day wave has slightly greater amplitudes in the zonal component of the winds than in the meridional. Mesospheric temperatures measured by the radars were used to further investigate the 16-day wave. The temperatures reveal a clear signature of the 16-day wave. Temperature amplitudes are generally only a few Kelvin but occasional bursts of up to 10 K have been observed. Observations of the wave in summer are sometimes consistent with the suggestion of ducting from the winter hemisphere.
Atmospheric oxygen and carbon dioxide observations from two European coastal stations 2000–2005: continental influence, trend changes and APO climatology
Authors: Sirignano C. , Neubert R. E. M. , Rödenbeck C. , Meijer H. A. J.
Published: April 2010

Abstract. Seeking for baseline conditions has biased the atmospheric carbon dioxide (CO2) and later on also oxygen (O2) monitoring networks towards remote marine stations, missing part of the variability that is due to regional anthropogenic as well as land biotic activity. We present here a five-year record of atmospheric CO2 concentrations and oxygen/nitrogen (O2/N2) ratio measurements from the coastal stations Lutjewad (LUT), The Netherlands and Mace Head (MHD), Ireland, derived from flask samples. O2/N2 ratios, a proxy for O2 concentrations, concurrently measured with CO2 concentrations, help determine regional CO2 fluxes by separating land fluxes from sea fluxes. Mace Head is the closest marine baseline station to Lutjewad, located at the same latitude, and therefore is taken as a reference. During the studied period, from 2000 until 2005, we observed an average increase of CO2 in the atmosphere of (1.7±0.2) ppm y−1, and a change of the O2/N2 ratio of (−20±1) per meg y−1. The difference between the CO2 summer minimum and the winter maximum is 14.4 ppm and 16.1 ppm at Mace Head and Lutjewad, respectively, while the paraphase variation in the O2 signal equals 113 per meg and 153 per meg, respectively. We also studied the atmospheric potential oxygen (APO) tracer at both stations. By this analysis, evidence has been found that we need to be careful when using APO close to anthropogenic CO2 sources. It could be biased by combustion-derived CO2, and models need to take into account daily and seasonal variations in the anthropogenic CO2 production in order to be able to simulate APO over the continents.
BVOC ecosystem flux measurements at a high latitude wetland site
Authors: Holst T. , Arneth A. , Hayward S. , Ekberg A. , Mastepanov M. , Jackowicz-Korczynski M. , Friborg T. , Crill P. M. , Bäckstrand K.
Published: April 2010

Abstract. In this study, we present summertime concentrations and fluxes of biogenic volatile organic compounds (BVOCs) measured at a sub-arctic wetland in northern Sweden using a disjunct eddy-covariance (DEC) technique based on a proton transfer reaction mass spectrometer (PTR-MS). The vegetation at the site was dominated by Sphagnum, Carex and \\textit{Eriophorum} spp. The measurements reported here cover a period of 50 days (1 August to 19 September 2006), approximately one half of the growing season at the site, and allowed to investigate the effect of day-to-day variation in weather as well as of vegetation senescence on daily BVOC fluxes, and on their temperature and light responses. The sensitivity drift of the DEC system was assessed by comparing H3O+-ion cluster formed with water molecules (H3O+(H2O) at m37) with water vapour concentration measurements made using an adjacent humidity sensor, and the applicability of the DEC method was analysed by a comparison of sensible heat fluxes for high frequency and DEC data obtained from the sonic anemometer. These analyses showed no significant PTR-MS sensor drift over a period of several weeks and only a small flux-loss due to high-frequency spectrum omissions. This loss was within the range expected from other studies and the theoretical considerations. Standardised (20 °C and 1000 μmol m−2 s−1 PAR) summer isoprene emission rates found in this study of 329 μg C m−2 (ground area) h−1 were comparable with findings from more southern boreal forests, and fen-like ecosystems. On a diel scale, measured fluxes indicated a stronger temperature dependence than emissions from temperate or (sub)tropical ecosystems. For the first time, to our knowledge, we report ecosystem methanol fluxes from a sub-arctic ecosystem. Maximum daytime emission fluxes were around 270 μg m−2 h−1 (ca. 100 μg C m−2 h−1), and during most nights small negative fluxes directed from the atmosphere to the surface were observed.
Measurements of electric charge separated during the formation of rime by the accretion of supercooled droplets
Authors: Lighezzolo R. A. , Pereyra R. G. , Avila E. E.
Published: April 2010

Abstract. In these experiments, the electric charge carried by single particles ejected from the surface of a graupel particle growing by riming was measured. Simulated graupel pellets were grown by accretion of supercooled water drops, at temperatures ranging from −2 to −10 °C in a wind tunnel at air velocities between 5 and 10 m s−1, with the goal of studying the charging of graupel pellets under conditions of secondary ice crystal production (Hallett-Mossop mechanism). The graupel, and induction rings upstream and downstream of the graupel, were connected to electrometers and analyzing circuits of sufficient sensitivity and speed to measure, correlate and display individual charging events. The results suggest that fewer than 1% of the ejected particles carry a measurable electric charge (>2 fC). Further, it was observed that the graupel pellets acquire a positive charge and the average charge of a single splinter ejected is −14 fC. This mechanism of ejection of charged particles seems adequate to account for a positive charge of around 1 pC that individual precipitation particles of mm-size could acquire in the lower part of the cloud, which in turn could contribute to the lower positive charge region of thunderstorms.
Source-receptor relationships for airborne measurements of CO2, CO and O3 above Siberia: a cluster-based approach
Authors: Paris J.-D. , Stohl A. , Ciais P. , Nédélec P. , Belan B. D. , Arshinov M. Yu. , Ramonet M.
Published: April 2010

Abstract. We analysed results of three intensive aircraft campaigns above Siberia (April and September 2006, August 2007) with a total of ~70 h of continuous CO2, CO and O3 measurements. The flight route consists of consecutive ascents and descents between Novosibirsk (55° N, 82° E) and Yakutsk (62° N, 129° E). We performed retroplume calculations with the Lagrangian particle dispersion model FLEXPART for many short segments along the flight tracks. To reduce the extremely rich information on source regions provided by the model calculation into a small number of distinct cases, we performed a statistical clustering – to our knowledge for the first time – into potential source regions of the footprint emission sensitivities obtained from the model calculations. This technique not only worked well to separate source region influences but also resulted in clearly distinct tracer concentrations for the various clusters obtained. High CO and O3 concentrations were found associated with agricultural fire plumes originating from Kazakhstan in September 2006. A statistical analysis indicates that summer uptake of CO2 is largely explained (~50% of variance) by air mass exposure to uptake by Siberian and sub-arctic ecosystems. This resulted in an average 5 to 10 ppm difference with overlaying air masses. Stratosphere-troposphere exchange is found to strongly influence the observed O3 mixing ratios in spring, but not in summer. European emissions contributed to high O3 concentrations above Siberia in April 2006 and August 2007, while emissions from North Eastern China also contributed to higher O3 mixing ratios in summer, but tend to lower mixing ratios in spring, when the airmass aerosol burden is important. In the lower troposphere, large-scale deposition processes in the boreal and sub-arctic boundary layer is a large O3 sink, resulting in a ~20 ppb difference with overlaying air masses. Lagrangian footprint clustering is very promising and could also be advantageously applied to the interpretation of ground based measurements including calculation of tracers' sources and sinks.
A review of natural aerosol interactions and feedbacks within the Earth system
Authors: Carslaw K. S. , Boucher O. , Spracklen D. V. , Mann G. W. , Rae J. G. L. , Woodward S. , Kulmala M.
Published: April 2010

Abstract. The natural environment is a major source of atmospheric aerosols, including dust, secondary organic material from terrestrial biogenic emissions, carbonaceous particles from wildfires, and sulphate from marine phytoplankton dimethyl sulphide emissions. These aerosols also have a significant effect on many components of the Earth system such as the atmospheric radiative balance and photosynthetically available radiation entering the biosphere, the supply of nutrients to the ocean, and the albedo of snow and ice. The physical and biological systems that produce these aerosols can be highly susceptible to modification due to climate change so there is the potential for important climate feedbacks. We review the impact of these natural systems on atmospheric aerosol based on observations and models, including the potential for long term changes in emissions and the feedbacks on climate. The number of drivers of change is very large and the various systems are strongly coupled. There have therefore been very few studies that integrate the various effects to estimate climate feedback factors. Nevertheless, available observations and model studies suggest that the regional radiative perturbations are potentially several Watts per square metre due to changes in these natural aerosol emissions in a future climate. Taking into account only the direct radiative effect of changes in the atmospheric burden of natural aerosols, and neglecting potentially large effects on other parts of the Earth system, a global mean radiative perturbation approaching 1 W m−2 is possible by the end of the century. The level of scientific understanding of the climate drivers, interactions and impacts is very low.
Impact of energetic particle precipitation on stratospheric polar constituents: an assessment using monitoring and assimilation of operational MIPAS data
Authors: Robichaud A. , Ménard R. , Chabrillat S. , de Grandpré J. , Rochon Y. J. , Yang Y. , Charette C.
Published: April 2010

Abstract. In 2003, strong energetic particle precipitation (EPP) events occurred producing massive amounts of ionization which affected the polar region significantly perturbing its chemical state down to the middle stratosphere. These events and their effects are generally left unaccounted for in current models of stratospheric chemistry and large differences between observations and models are then noted. In this study, we use a coupled 3-D stratospheric dynamical-chemical model and assimilation system to ingest MIPAS temperature and chemical observations. The goal is to gain further understanding of assimilation and monitoring processes during EPP events and their impacts on the stratospheric polar chemistry. Moreover, we investigate the feasibility of assimilating valid "outlier" observations associated with such events. We use OmF (Observation minus Forecast) residuals as they filter out phenomena well reproduced by the model (such as gas phase chemistry, transport, diurnal and seasonal cycles) thus revealing a clear trace of the EPP. Inspection of OmF statistics in both passive (without chemical assimilation) and active (with chemical assimilation) cases altogether provides a powerful diagnostic tool to assess the model and assimilation system. We also show that passive OmF can permit a satisfactory evaluation of the ozone partial column loss due to EPP effects. Results suggest a small but significant loss of 5–6 DU (Dobson Units) during an EPP-IE (EPP Indirect Effects) event in the Antarctic winter of 2003, and about only 1 DU for the SPE (Solar Proton Event) of October/November 2003. Despite large differences between the model and MIPAS chemical observations (NO2, HNO3, CH4 and O3), we demonstrate that a careful assimilation with only gas phase chemistry included in the model (i.e. no provision for EPP) and with relaxed quality control nearly eliminated the short-term bias and significantly reduced the standard deviation error of the constituents below 1 hPa.
Light absorption by organic carbon from wood combustion
Authors: Chen Y. , Bond T. C.
Published: April 2010

Abstract. Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While black carbon (BC) is highly absorbing, some organic carbon (OC) also has significant absorption, especially at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to positive direct aerosol radiative forcing. Quantification of that absorption is necessary so that radiative-transfer models can evaluate the net radiative effect of OC. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble OC contributes to light absorption at both ultraviolet and visible wavelengths. However, a larger portion of the absorption comes from OC that is extractable only by methanol. Absorption spectra of water-soluble OC are similar to literature reports. We compare spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating OC with higher absorption; changing wood temperature from a devolatilizing state of 210 °C to a near-flaming state of 360 °C causes about a factor of four increase in mass-normalized absorption at visible wavelengths. A clear-sky radiative transfer model suggests that, despite the absorption, both high-temperature and low-temperature OC result in negative top-of-atmosphere radiative forcing over a surface with an albedo of 0.19 and positive radiative forcing over bright surfaces. Unless absorption by real ambient aerosol is higher than that measured here, it probably affects global average clear-sky forcing very little, but could be important in energy balances over bright surfaces.
The exchange of SVOCs across the air-sea interface in Singapore's coastal environment
Authors: He J. , Balasubramanian R.
Published: April 2010

Abstract. Coastal areas are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs, OCPs and PCBs from atmospheric inputs. Dry particulate and wet depositions, and air-water diffusive exchange in the Singapore's south coastal area, where most of chemical and oil refinery industries are situated in, were estimated. Based on a yearly dataset, the mean annual dry particulate deposition fluxes of ∑16-PAHs, ∑7 OCPs and ∑21 PCBs were 1328.8±961.1 μg m−2 y−1, 5421.4±3426.7 ng m−2 y−1 and 811.8±578.3 ng m−2 y−1, and the wet deposition of ∑16-PAHs and ∑7 OCPs were 6667.1±1745.2 and 115.4±98.3 μg m−2 y−1, respectively. Seasonal variation of atmospheric depositions was influenced by meteorological conditions. Air-water gas exchange fluxes were shown to be negative values for PAHs, HCHs and DDXs, indicating Singapore's south coast as a sink for the above-mentioned SVOCs. The relative contribution of each depositional process to the total atmospheric input was assessed by annual fluxes. The profile of dry particulate deposition, wet deposition and gas exchange fluxes seemed to be correlated with individual pollutant's properties such as molecular weight and Henry's law constant, etc. For the water column partitioning, the organic carbon-normalized partition coefficients between particulate and dissolved phases (KOC) for both PAHs and OCPs were obtained. The relationships between KOC of PAHs and OCPs and their respective octanol-water partition coefficient (KOW) were examined. In addition, both adsorption onto combustion-derived soot carbon and absorption into natural organic matter for PAHs in marine water column were investigated. Enrichment factors in the sea-surface microlayer (SML) of the particulate phase were 1.2–7.1 and 3.0–4.9 for PAHs and OCPs, and those of dissolved phase were 1.1–4.9 and 1.6–4.2 for PAHs and OCPs, respectively. These enrichment factors are relatively higher than those reported for nearby coastal areas, which are most likely due to more organic surfactants floating in the south coastal surface of Singapore.
Temporal variability, sources, and sinks of C1-C5 alkyl nitrates in coastal New England
Authors: Russo R. S. , Zhou Y. , Haase K. B. , Wingenter O. W. , Frinak E. K. , Mao H. , Talbot R. W. , Sive B. C.
Published: April 2010

Abstract. Seven C1-C5 alkyl nitrates were measured both on the mainland and off the coast of New Hampshire using gas chromatographic techniques. Five separate data sets are presented to characterize the seasonal and diurnal trends and the major sources and loss processes of these compounds. Based on in situ measurements conducted at the University of New Hampshire (UNH) Atmospheric Observing Station at Thompson Farm (TF) located in southeast NH during winter (January–February) 2002, summer (June–August) 2002, summer (July–August) 2004, and on daily canister samples collected at midday from January 2004–February 2008, the median total alkyl nitrate mixing ratio (ΣRONO2) was 23–25 pptv in winter and 14–16 pptv in summer. During summers 2002 and 2004, MeONO2 decreased overnight and reached minimum hourly average mixing ratios in the early morning. Comparison with wind speed and trace gas trends suggested that dry deposition contributed to the early morning MeONO2 minimum which is a previously unaccounted for removal mechanism. The mean dry deposition rate and velocity of MeONO2 was estimated to be −0.5 nmol m−2 hr−1 and 0.13 cm s−1, respectively. Results from ambient air and surface seawater measurements made onboard the NOAA R/V Ronald H. Brown in the Gulf of Maine during the 2002 New England Air Quality Study and from ambient canister samples collected throughout the Great Bay estuary in August 2003 are also presented. Comparisons between the alkyl nitrate trends with anthropogenic and marine tracers suggest that a marine source of alkyl nitrates is not significant in coastal New England. Given the apparent prominence of a secondary source, comparisons between observed and predicted alkyl nitrate/parent hydrocarbon ratios were made which demonstrated that background mixing ratios have a continuous and prevalent influence on the alkyl nitrate distribution.
Atmospheric data over a solar cycle: no connection between galactic cosmic rays and new particle formation
Authors: Kulmala M. , Riipinen I. , Nieminen T. , Hulkkonen M. , Sogacheva L. , Manninen H. E. , Paasonen P. , Petäjä T. , Dal Maso M. , Aalto P. P. , Viljanen A. , Usoskin I. , Vainio R. , Mirme S. , Mirme A. , Minikin A. , Petzold A. , Hõrrak U. , Plaß-Dülmer C. , Birmili W. , Kerminen V.-M.
Published: April 2010

Abstract. Aerosol particles affect the Earth's radiative balance by directly scattering and absorbing solar radiation and, indirectly, through their activation into cloud droplets. Both effects are known with considerable uncertainty only, and translate into even bigger uncertainties in future climate predictions. More than a decade ago, variations in galactic cosmic rays were suggested to closely correlate with variations in atmospheric cloud cover and therefore constitute a driving force behind aerosol-cloud-climate interactions. Later, the enhancement of atmospheric aerosol particle formation by ions generated from cosmic rays was proposed as a physical mechanism explaining this correlation. Here, we report unique observations on atmospheric aerosol formation based on measurements at the SMEAR II station, Finland, over a solar cycle (years 1996–2008) that shed new light on these presumed relationships. Our analysis shows that none of the quantities related to aerosol formation correlates with the cosmic ray-induced ionisation intensity (CRII). We also examined the contribution of ions to new particle formation on the basis of novel ground-based and airborne observations. A consistent result is that ion-induced formation contributes typically significantly less than 10% to the number of new particles, which would explain the missing correlation between CRII and aerosol formation. Our main conclusion is that galactic cosmic rays appear to play a minor role for atmospheric aerosol formation events, and so for the connected aerosol-climate effects as well.
The municipal solid waste landfill as a source of ozone-depleting substances in the United States and United Kingdom
Authors: Hodson E. L. , Martin D. , Prinn R. G.
Published: April 2010

Abstract. This study provides observation-based national estimates of CFC-11, CFC-12, CFC-113, and 1,1,1-trichloroethane emissions for the United States (US) and United Kingdom (UK) from municipal solid waste (MSW) landfills. The scarcity of national estimates has lead to the assumption that a significant fraction of the lingering ozone-depleting substance (ODS) emissions, which have been detected in industrialized countries, could be emitted from landfills. Spatial coverage was achieved through sampling at seven landfills in Massachusetts and through data provided by nine UK landfills. Linear least square regressions of recovered ODS vs. CH4 were used in combination with national estimates of landfill CH4 emissions to estimate 2006 national US and UK ODS landfill emissions. The ODS landfill emission estimates were then compared to recent estimates of total US and UK ODS emissions. US ODS landfill emissions are 0.4%–1% (0.006–0.09 Gg/year) of total US emissions. UK ODS landfill emission estimates are 1% (0.008 Gg/year) and 6% (0.03 Gg/year) of total UK CFC-11 and CFC-12 emissions, respectively. This indicates that landfills are only a minor source of lingering ODS emissions in the US, but may be more significant for CFC-12 emissions in the UK. The implication is that the majority of current ODS emissions in industrialized countries is likely coming from equipment still in use.
Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals
Authors: Antiñolo M. , Jiménez E. , Notario A. , Martínez E. , Albaladejo J.
Published: April 2010

Abstract. The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263–371 K) and pressure (50–215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work for the detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10−11 cm3 molecule−1 s−1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kCl(CF3CH2CHO) = (0.259±0.050); kCl(CF3(CH2)2CHO) = (1.28±0.24). A slightly positive temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence over the range investigated. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) = (4.4±1.0)×10−11 exp{−(316±68)/T} cm3 molecule−1 s−1 kCl(CF3(CH2)2CHO) = (2.9±0.7)×10−10 exp{−(625±80)/T} cm3 molecule−1 s−1 kOH(CF3CH2CHO) = (7.8±2.2)×10−12 exp{−(314±90)/T} cm3 molecule−1 s−1 The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)x CHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere.
Estimations of climate sensitivity based on top-of-atmosphere radiation imbalance
Authors: Lin B. , Chambers L. ,   P. Stackhouse Jr., Wielicki B. , Hu Y. , Minnis P. , Loeb N. , Sun W. , Potter G. , Min Q. , Schuster G. , Fan T.-F.
Published: April 2010

Abstract. Large climate feedback uncertainties limit the accuracy in predicting the response of the Earth's climate to the increase of CO2 concentration within the atmosphere. This study explores a potential to reduce uncertainties in climate sensitivity estimations using energy balance analysis, especially top-of-atmosphere (TOA) radiation imbalance. The time-scales studied generally cover from decade to century, that is, middle-range climate sensitivity is considered, which is directly related to the climate issue caused by atmospheric CO2 change. The significant difference between current analysis and previous energy balance models is that the current study targets at the boundary condition problem instead of solving the initial condition problem. Additionally, climate system memory and deep ocean heat transport are considered. The climate feedbacks are obtained based on the constraints of the TOA radiation imbalance and surface temperature measurements of the present climate. In this study, the TOA imbalance value of 0.85 W/m2 is used. Note that this imbalance value has large uncertainties. Based on this value, a positive climate feedback with a feedback coefficient ranging from −1.3 to −1.0 W/m2/K is found. The range of feedback coefficient is determined by climate system memory. The longer the memory, the stronger the positive feedback. The estimated time constant of the climate is large (70~120 years) mainly owing to the deep ocean heat transport, implying that the system may be not in an equilibrium state under the external forcing during the industrial era. For the doubled-CO2 climate (or 3.7 W/m2 forcing), the estimated global warming would be 3.1 K if the current estimate of 0.85 W/m2 TOA net radiative heating could be confirmed. With accurate long-term measurements of TOA radiation, the analysis method suggested by this study provides a great potential in the estimations of middle-range climate sensitivity.
Saharan dust infrared optical depth and altitude retrieved from AIRS: a focus over North Atlantic – comparison to MODIS and CALIPSO
Authors: Peyridieu S. , Chédin A. , Tanré D. , Capelle V. , Pierangelo C. , Lamquin N. , Armante R.
Published: April 2010

Abstract. Monthly mean infrared (10 μm) dust layer aerosol optical depth (AOD) and mean altitude are simultaneously retrieved over the tropics (30° S–30° N) from almost seven years of Atmospheric Infrared Sounder (AIRS) observations covering the period January 2003 to September 2009. The method developed relies on the construction of look-up-tables computed for a large selection of atmospheric situations and follows two main steps: first, determination of the observed atmospheric thermodynamic situation and, second, determination of the dust properties. A very good agreement is found between AIRS-retrieved AODs and visible optical depths from the Moderate resolution Imaging Spectroradiometer (MODIS/Aqua) during the main (summer) dust season, in particular for three regions of the tropical North Atlantic and one region of the north-western Indian Ocean. Outside this season, differences are mostly due to the sensitivity of MODIS to aerosol species other than dust and to the more specific sensitivity of AIRS to the dust coarse mode. AIRS-retrieved dust layer mean altitudes are compared to the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP/CALIPSO) aerosol mean layer altitude for the period June 2006 to June 2009. Results for a region of the north tropical Atlantic downwind of the Sahara show a good agreement between the two products (σ≈360 m). Differences observed in the peak-to-trough seasonal amplitude, smaller from AIRS, are principally attributed to the large difference in spatial sampling of the two instruments. They also come from the intrinsic limit in sensitivity of the passive infrared sounders for low altitudes. These results demonstrate the capability of high resolution infrared sounders to measure not only dust aerosol AOD but also the mean dust layer altitude.
A numerical evaluation of global oceanic emissions of α-pinene and isoprene
Authors: Luo G. , Yu F.
Published: April 2010

Abstract. A numerical evaluation of global oceanic emissions of α-pinene and isoprene based on both "bottom-up" and "top-down" methods is presented. We infer that the global "bottom-up" oceanic emissions of α-pinene and isoprene are 0.013 TgC yr−1 and 0.32 TgC yr−1, respectively. By constraining global chemistry model simulations with the shipborne measurement of Organics over the Ocean Modifying Particles in both Hemispheres summer cruise, we derived the global "top-down" oceanic α-pinene source of 29.5 TgC yr−1 and isoprene source of 11.6 TgC yr−1. Both the "bottom-up" and "top-down" values are subject to large uncertainties. The incomplete understanding of the in-situ phytoplankton communities and their range of emission potentials significantly impact the estimated global "bottom-up" oceanic emissions, while the estimated total amounts of the global "top-down" oceanic sources can be influenced by emission parameterizations, model and input data spatial resolutions, boundary layer mixing processes, and the treatments of chemical reactions. The global oceanic α-pinene source and its impact on organic aerosol formation is significant based on "top-down" method, but is negligible based on "bottom-up" approach. Our research highlights the importance of carrying out further research (especially measurements) to resolve the large offset in the derived oceanic organic emission based on two different approaches.
MAX-DOAS measurements in southern China: retrieval of aerosol extinctions and validation using ground-based in-situ data
Authors: Li X. , Brauers T. , Shao M. , Garland R. M. , Wagner T. , Deutschmann T. , Wahner A.
Published: April 2010

Abstract. We performed MAX-DOAS measurements during the PRiDe-PRD2006 campaign in the Pearl River Delta region 50 km north of Guangzhou, China, for 4 weeks in June 2006. We used an instrument sampling at 7 different elevation angles between 3° and 90°. During 9 cloud-free days, differential slant column densities (DSCDs) of O4 (O2 dimer) absorptions between 351 nm and 389 nm were evaluated for 6 elevation angles. Here, we show that radiative transfer modeling of the DSCDS can be used to retrieve the aerosol extinction and the height of the boundary layer. A comparison of the aerosol extinction with simultaneously recorded, ground based nephelometer data shows excellent agreement.
Midlatitude stratosphere – troposphere exchange as diagnosed by MLS O3 and MOPITT CO assimilated fields
Authors: El Amraoui L. , Attié J.-L. , Semane N. , Claeyman M. , Peuch V.-H. , Warner J. , Ricaud P. , Cammas J.-P. , Piacentini A. , Josse B. , Cariolle D. , Massart S. , Bencherif H.
Published: April 2010

Abstract. This paper presents a comprehensive characterization of a very deep stratospheric intrusion which occurred over the British Isles on 15 August 2007. The signature of this event is diagnosed using ozonesonde measurements over Lerwick, UK (60.14° N, 1.19° W) and is also well characterized using meteorological analyses from the global operational weather prediction model of Météo-France, ARPEGE. Modelled as well as assimilated fields of both ozone (O3) and carbon monoxide (CO) have been used in order to better document this event. O3 and CO from Aura/MLS and Terra/MOPITT instruments, respectively, are assimilated into the three-dimensional chemical transport model MOCAGE of Météo-France using a variational 3-D-FGAT (First Guess at Appropriate Time) method. The validation of O3 and CO assimilated fields is done using self-consistency diagnostics and by comparison with independent observations such as MOZAIC (O3 and CO), AIRS (CO) and OMI (O3). It particularly shows in the upper troposphere and lower stratosphere region that the assimilated fields are closer to MOZAIC than the free model run. The O3 bias between MOZAIC and the analyses is −11.5 ppbv with a RMS of 22.4 ppbv and a correlation coefficient of 0.93, whereas between MOZAIC and the free model run, the corresponding values are 33 ppbv, 38.5 ppbv and 0.83, respectively. In the same way, for CO, the bias, RMS and correlation coefficient between MOZAIC and the analyses are −3.16 ppbv, 13 ppbv and 0.79, respectively, whereas between MOZAIC and the free model they are 6.3 ppbv, 16.6 ppbv and 0.71, respectively. The paper also presents a demonstration of the capability of O3 and CO assimilated fields to better describe a stratosphere-troposphere exchange (STE) event in comparison with the free run modelled O3 and CO fields. Although the assimilation of MLS data improves the distribution of O3 above the tropopause compared to the free model run, it is not sufficient to reproduce the STE event well. Assimilated MOPITT CO allows a better qualitative description of the stratospheric intrusion event. The MOPITT CO analyses appear more promising than the MLS O3 analyses in terms of their ability to capture a deep STE event. Therefore, the results of this study open the perspectives for using MOPITT CO in the STE studies.