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Characterisation of individual aerosol particles collected during a haze episode in Incheon, Korea using the quantitative ED-EPMA technique

A quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), called low-Z particle EPMA, was used to analyse individual aerosol particles collected in Incheon, Korea on 13–18 October 2008 (a typical haze episode occurred from 15 to 18 October). Overall 3600 individual particles in PM2.5-10 and PM1.0-2.5 fractions from 12 aerosol samples collected on haze and non-haze days were analysed. The analysed particles were classified, based on their X-ray spectral data together with their secondary electron images. The major particle types included organic carbon (OC), elemental carbon (EC), sea-salt, mineral dust (such as aluminosilicate, SiO2, CaCO3/CaMgCO3, etc.), (NH4)2SO4/NH4HSO4-containing, K-containing, Fe-rich and fly ash particles. Their relative number abundance results showed that OC particles were significantly increased while sea-salts and mineral dust particles were significantly decreased (especially in PM1.0-2.5 fraction) when haze occurred. For the other particle types (except Fe-rich particles in PM2.5-10 fraction), there were no significant differences in their relative abundances between haze and non-haze samples. On non-haze days, the nitrate-containing reacted sea-salt and mineral dust particles in PM1.0-2.5 fraction significantly outnumbered the sulfate-containing ones, whereas it was the reverse on haze days, implying that on haze days there were special sources or formation mechanisms for fine aerosol particles (≤2.5 μm in aerodynamic diameter). The emission of air pollutants from motor vehicles and stagnant meteorological conditions, such as low wind speed and high relative humidity, might be responsible for the elevated level of OC particles on haze days.
Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

Nitric acid (HNO3) or nitrate (NO3−) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we measured nitrogen (N) and oxygen (O) isotopic composition of NO3− in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3− formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3− (versus air N2) ranged from −4.9 to +10.1&permil;, and averaged +3.9&permil; in 2008 and +3.3&permil; in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3− were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5&permil; (average +65.0&permil; and +67.0&permil; in 2008 and 2009, respectively), a range being lower than those reported for high latitude and polar areas. Sixteen percent of δ18O values was observed lower than the expected minimum of +55&permil; at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3−. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3− in a N-polluted city.
Assessment of the CALIPSO Lidar 532 nm attenuated backscatter calibration using the NASA LaRC airborne High Spectral Resolution Lidar

The Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument on the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) spacecraft has provided global, high-resolution vertical profiles of aerosols and clouds since it became operational on 13 June 2006. On 14 June 2006, the NASA Langley Research Center (LaRC) High Spectral Resolution Lidar (HSRL) was deployed aboard the NASA Langley B-200 aircraft for the first of a series of 86 underflights of the CALIPSO satellite to provide validation measurements for the CALIOP data products. To better assess the range of conditions under which CALIOP data products are produced, these validation flights were conducted under both daytime and nighttime lighting conditions, in multiple seasons, and over a large range of latitudes and aerosol and cloud conditions. This paper presents a quantitative assessment of the CALIOP 532 nm calibration (through the 532 nm total attenuated backscatter) using internally calibrated airborne HSRL underflight data and is the most extensive study of CALIOP 532 nm calibration. Results show that HSRL and CALIOP 532 nm total attenuated backscatter agree on average within 2.7% ± 2.1% (CALIOP lower) at night and within 2.9% ± 3.9% (CALIOP lower) during the day, demonstrating the accuracy of the CALIOP 532 nm calibration algorithms. Additionally, comparisons with HSRL show consistency of the CALIOP calibration before and after the laser switch in 2009 as well as improvements in the daytime version 3.01 calibration scheme compared with the version 2 calibration scheme. Potential biases and uncertainties in the methodology relevant to validating satellite lidar measurements with an airborne lidar system are discussed and found to be less than 4.5% ± 3.2% for this validation effort with HSRL. Results from this study are also compared with prior assessments of the CALIOP 532 nm attenuated backscatter calibration.
The Chemistry of Atmosphere-Forest Exchange (CAFE) Model – Part 2: Application to BEARPEX-2007 observations

In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm (~29 °C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes.
Emulating coupled atmosphere-ocean and carbon cycle models with a simpler model, MAGICC6 – Part 1: Model description and calibration

Current scientific knowledge on the future response of the climate system to human-induced perturbations is comprehensively captured by various model intercomparison efforts. In the preparation of the Fourth Assessment Report (AR4) of the Intergovernmental Panel on Climate Change (IPCC), intercomparisons were organized for atmosphere-ocean general circulation models (AOGCMs) and carbon cycle models, named "CMIP3" and "C4MIP", respectively. Despite their tremendous value for the scientific community and policy makers alike, there are some difficulties in interpreting the results. For example, radiative forcings were not standardized across the various AOGCM integrations and carbon cycle runs, and, in some models, key forcings were omitted. Furthermore, the AOGCM analysis of plausible emissions pathways was restricted to only three SRES scenarios. This study attempts to address these issues. We present an updated version of MAGICC, the simple carbon cycle-climate model used in past IPCC Assessment Reports with enhanced representation of time-varying climate sensitivities, carbon cycle feedbacks, aerosol forcings and ocean heat uptake characteristics. This new version, MAGICC6, is successfully calibrated against the higher complexity AOGCMs and carbon cycle models. Parameterizations of MAGICC6 are provided. The mean of the emulations presented here using MAGICC6 deviates from the mean AOGCM responses by only 2.2% on average for the SRES scenarios. This enhanced emulation skill in comparison to previous calibrations is primarily due to: making a "like-with-like comparison" using AOGCM-specific subsets of forcings; employing a new calibration procedure; as well as the fact that the updated simple climate model can now successfully emulate some of the climate-state dependent effective climate sensitivities of AOGCMs. The diagnosed effective climate sensitivity at the time of CO2 doubling for the AOGCMs is on average 2.88 °C, about 0.33 °C cooler than the mean of the reported slab ocean climate sensitivities. In the companion paper (Part 2) of this study, we examine the combined climate system and carbon cycle emulations for the complete range of IPCC SRES emissions scenarios and the new RCP pathways.
Quantitative assessment of upstream source influences on total gaseous mercury observations in Ontario, Canada

Hourly total gaseous mercury (TGM) concentrations at three monitoring sites (receptors) in Ontario were predicted for four selected periods at different seasons in 2002 using the Stochastic Time-Inverted Lagrangian Transport (STILT) model, which transports Lagrangian air parcels backward in time from the receptors to provide linkages to the source region in the upwind area. The STILT model was modified to deal with Hg deposition and high stack Hg emissions. The model-predicted Hg concentrations were compared with observations at three monitoring sites. Estimates of transport errors (uncertainties in simulated concentrations due to errors in wind fields) are also provided that suggest such errors can reach approximately 10% of simulated concentrations. Results from a CMAQ chemical transport model (CTM) simulation in which the same emission and meteorology inputs were used are also reported. The comparisons show that STILT-predicted Hg concentrations usually agree better with observations than CMAQ except for a subset of cases that are subject to biases in the coarsely resolved boundary conditions. In these comparisons STILT captures high frequency concentration variations better than the Eulerian CTM, likely due to its ability to account for the sub-grid scale position of the receptor site and to minimize numerical diffusion. Thus it is particularly valuable for the interpretation of plumes (short-term concentration variations) that require the use of finer mesh sizes or controls on numerical diffusion in Eulerian models. We report quantitative assessments of the relative importance of different upstream sources for the selected episodes, based on emission fluxes and STILT footprints. The STILT simulations indicate that natural sources (which include re-emission from historical anthropogenic activities) contribute much more than current-day anthropogenic emissions to the Hg concentrations observed at the three sites.
Effects of absorbing aerosols in cloudy skies: a satellite study over the Atlantic Ocean

We present a method for deriving the radiative effects of absorbing aerosols in cloudy scenes from satellite retrievals only. We use data of 2005–2007 from various passive sensors aboard satellites of the "A-Train" constellation. The study area is restricted to the tropical- and subtropical Atlantic Ocean. To identify the dependence of the local planetary albedo in cloudy scenes on cloud liquid water path and aerosol optical depth (AOD), we perform a multiple linear regression. The OMI UV-Aerosolindex serves as an indicator for absorbing-aerosol presence. In our method, the aerosol influences the local planetary albedo through direct- (scattering and absorption) and indirect (Twomey) aerosol effects. We find an increase of the local planetary albedo (LPA) with increasing AOD of mostly scattering aerosol and a decrease of the LPA with increasing AOD of mostly absorbing aerosol. These results allow us to derive the direct aerosol effect of absorbing aerosols in cloudy scenes, with the effect of cloudy-scene aerosol absorption in the tropical- and subtropical Atlantic contributing (+21.2 ± 11.1)×10−3 Wm−2 to the global top of the atmosphere radiative forcing.
Quantifying immediate radiative forcing by black carbon and organic matter with the Specific Forcing Pulse

Climatic effects of short-lived climate forcers (SLCFs) differ from those of long-lived greenhouse gases, because they occur rapidly after emission and because they depend upon the region of emission. The distinctive temporal and spatial nature of these impacts is not captured by measures that rely on global averages or long time integrations. Here, we propose a simple measure, the Specific Forcing Pulse (SFP), to quantify climate warming or cooling by these pollutants, where we define "immediate" as occurring primarily within the first year after emission. SFP is the amount of energy added to or removed from a receptor region in the Earth-atmosphere system by a chemical species, per mass of emission in a source region. We limit the application of SFP to species that remain in the atmosphere for less than one year. Metrics used in policy discussions, such as total forcing or global warming potential, are easily derived from SFP. However, SFP conveys purely physical information without incurring the policy implications of choosing a time horizon for the global warming potential. Using one model (Community Atmosphere Model, or CAM), we calculate values of SFP for black carbon (BC) and organic matter (OM) emitted from 23 source-region combinations. Global SFP for both atmosphere and cryosphere impacts is divided among receptor latitudes. SFP is usually greater for open-burning emissions than for energy-related (fossil-fuel and biofuel) emissions because of the timing of emission. Global SFP for BC varies by about 45% for energy-related emissions from different regions. This variation would be larger except for compensating effects. When emitted aerosol has larger cryosphere forcing, it often has lower atmosphere forcing because of less deep convection and a shorter atmospheric lifetime. A single model result is insufficient to capture uncertainty. We develop a best estimate and uncertainties for SFP by combining forcing results from 12 additional models. We outline a framework for combining a large number of simple models with a smaller number of enhanced models that have greater complexity. Adjustments for black carbon internal mixing and for regional variability are discussed. Emitting regions with more deep convection have greater model diversity. Our best estimate of global-mean SFP is +1.03 ± 0.52 GJ g−1 for direct atmosphere forcing of black carbon, +1.15 ± 0.53 GJ g−1 for black carbon including direct and cryosphere forcing, and −0.064 (−0.02, −0.13) GJ g−1 for organic matter. These values depend on the region and timing of emission. The lowest OM:BC mass ratio required to produce a neutral effect on top-of-atmosphere direct forcing is 15:1 for any region. Any lower ratio results in positive direct forcing. However, important processes, particularly cloud changes that tend toward cooling, have not been included here. Global-average SFP for energy-related emissions can be converted to a 100-year GWP of about 740 ± 370 for BC without snow forcing, and 830 ± 440 with snow forcing. 100-year GWP for OM is −46 (−18, −92). Best estimates of atmospheric radiative impact (without snow forcing) by black and organic matter are +0.47 ± 0.26 W m−2 and −0.17 (−0.07, −0.35) W m−2 for BC and OM, respectively, assuming total emission rates of 7.4 and 45 Tg yr−1. Anthropogenic forcing is +0.40 ± 0.18 W m−2 and −0.13 (−0.05, −0.25) W m−2 for BC and OM, respectively, assuming anthropogenic emission rates of 6.3 and 32.6 Tg yr−1. Black carbon forcing is only 18% higher than that given by the Intergovernmental Panel on Climate Change (IPCC), although the value presented here includes enhanced absorption due to internal mixing.
Chemical, physical, and optical evolution of biomass burning aerosols: a case study

In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols from a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (HR-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While these types of extensive BB events are not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). The average EBRI for a mixed population of aerosols dominated by open fires was m = 1.53(±0.03) + 0.07i(±0.03), during the smoldering phase of the fires we found the EBRI to be m = 1.54(±0.01) + 0.04i(±0.01) compared to m = 1.49(±0.01) + 0.02i(±0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.
Oxygen isotopic signature of CO2 from combustion processes

For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7&permil; was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio-chemical compounds to individual combustion products released from the involved material became obvious.