scispace - formally typeset
Search or ask a question

Showing papers in "Atmospheric Chemistry and Physics in 2012"


Journal ArticleDOI
TL;DR: In this paper, the ice nucleation active surface site (INAS) density is discussed as a simple and empirical normalized measure for ice nucleization activity, and the authors compare the results obtained with different methodologies.
Abstract: . A small subset of the atmospheric aerosol population has the ability to induce ice formation at conditions under which ice would not form without them (heterogeneous ice nucleation). While no closed theoretical description of this process and the requirements for good ice nuclei is available, numerous studies have attempted to quantify the ice nucleation ability of different particles empirically in laboratory experiments. In this article, an overview of these results is provided. Ice nucleation "onset" conditions for various mineral dust, soot, biological, organic and ammonium sulfate particles are summarized. Typical temperature-supersaturation regions can be identified for the "onset" of ice nucleation of these different particle types, but the various particle sizes and activated fractions reported in different studies have to be taken into account when comparing results obtained with different methodologies. When intercomparing only data obtained under the same conditions, it is found that dust mineralogy is not a consistent predictor of higher or lower ice nucleation ability. However, the broad majority of studies agrees on a reduction of deposition nucleation by various coatings on mineral dust. The ice nucleation active surface site (INAS) density is discussed as a simple and empirical normalized measure for ice nucleation activity. For most immersion and condensation freezing measurements on mineral dust, estimates of the temperature-dependent INAS density agree within about two orders of magnitude. For deposition nucleation on dust, the spread is significantly larger, but a general trend of increasing INAS densities with increasing supersaturation is found. For soot, the presently available results are divergent. Estimated average INAS densities are high for ice-nucleation active bacteria at high subzero temperatures. At the same time, it is shown that INAS densities of some other biological aerosols, like certain pollen grains, fungal spores and diatoms, tend to be similar to those of dust. These particles may owe their high ice nucleation onsets to their large sizes. Surface-area-dependent parameterizations of heterogeneous ice nucleation are discussed. For immersion freezing on mineral dust, fitted INAS densities are available, but should not be used outside the temperature interval of the data they were based on. Classical nucleation theory, if employed with only one fitted contact angle, does not reproduce the observed temperature dependence for immersion nucleation, the temperature and supersaturation dependence for deposition nucleation, and the time dependence of ice nucleation. Formulations of classical nucleation theory with distributions of contact angles offer possibilities to overcome these weaknesses.

946 citations


Journal ArticleDOI
TL;DR: In this article, the daily concentrations of major inorganic water-soluble constituents, mineral aerosol, organic carbon (OC) and elemental carbon (EC) in ambient PM10 samples were investigated from 16 urban, rural and remote sites in various regions of China, and were compared with global aerosol measurements.
Abstract: . From 2006 to 2007, the daily concentrations of major inorganic water-soluble constituents, mineral aerosol, organic carbon (OC) and elemental carbon (EC) in ambient PM10 samples were investigated from 16 urban, rural and remote sites in various regions of China, and were compared with global aerosol measurements. A large difference between urban and rural chemical species was found, normally with 1.5 to 2.5 factors higher in urban than in rural sites. Optically-scattering aerosols, such as sulfate (~16%), OC (~15%), nitrate (~7%), ammonium (~5%) and mineral aerosol (~35%) in most circumstance, are majorities of the total aerosols, indicating a dominant scattering feature of aerosols in China. Of the total OC, ~55%–60% can be attributed to the formation of the secondary organic carbon (SOC). The absorbing aerosol EC only accounts for ~3.5% of the total PM10. Seasonally, maximum concentrations of most aerosol species were found in winter while mineral aerosol peaks in spring. In addition to the regular seasonal maximum, secondary peaks were found for sulfate and ammonium in summer and for OC and EC in May and June. This can be considered as a typical seasonal pattern in various aerosol components in China. Aerosol acidity was normally neutral in most of urban areas, but becomes some acidic in rural areas. Based on the surface visibility observations from 681 meteorological stations in China between 1957 and 2005, four major haze areas are identified with similar visibility changes, namely, (1) Hua Bei Plain in N. China, and the Guanzhong Plain; (2) E. China with the main body in the Yangtze River Delta area; (3) S. China with most areas of Guangdong and the Pearl River Delta area; (4) The Si Chuan Basin in S.W. China. The degradation of visibility in these areas is linked with the emission changes and high PM concentrations. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and weather-climate effects, and in validating atmospheric models.

766 citations


Journal ArticleDOI
TL;DR: The Meteorological Synthesizing Centre-West (MSC-W) of the European Monitoring and Evaluation Programme (EMEP) has been performing model calculations in support of the Convention on Long Range Transboundary Air Pollution (CLRTAP) for more than 30 years as mentioned in this paper.
Abstract: The Meteorological Synthesizing Centre-West (MSC-W) of the European Monitoring and Evaluation Programme (EMEP) has been performing model calculations in support of the Convention on Long Range Transboundary Air Pollution (CLRTAP) for more than 30 years The EMEP MSC-W chemical transport model is still one of the key tools within European air pollution policy assessments Traditionally, the model has covered all of Europe with a resolution of about 50 km x 50 km, and extending vertically from ground level to the tropopause (100 hPa) The model has changed extensively over the last ten years, however, with flexible processing of chemical schemes, meteorological inputs, and with nesting capability: the code is now applied on scales ranging from local (ca 5 km grid size) to global (with 1 degree resolution) The model is used to simulate photo-oxidants and both inorganic and organic aerosols In 2008 the EMEP model was released for the first time as public domain code, along with all required input data for model runs for one year The second release of the EMEP MSC-W model became available in mid 2011, and a new release is targeted for summer 2012 This publication is in-tended to document this third release of the EMEP MSC-W model The model formulations are given, along with details of input data-sets which are used, and a brief background on some of the choices made in the formulation is presented The model code itself is available at wwwemepint, along with the data required to run for a full year over Europe

587 citations


Journal ArticleDOI
TL;DR: For example, the European Monitoring and Evaluation Programme (EMEP) data has been used to evaluate the regional and spatial trends of air pollution during a period of nearly 40 years as mentioned in this paper.
Abstract: . European scale harmonized monitoring of atmospheric composition was initiated in the early 1970s, and the activity has generated a comprehensive dataset (available at http://www.emep.int ) which allows the evaluation of regional and spatial trends of air pollution during a period of nearly 40 yr. Results from the monitoring made within EMEP, the European Monitoring and Evaluation Programme, show large reductions in ambient concentrations and deposition of sulphur species during the last decades. Reductions are in the order of 70–90% since the year 1980, and correspond well with reported emission changes. Also reduction in emissions of nitrogen oxides (NOx) are reflected in the measurements, with an average decrease of nitrogen dioxide and nitrate in precipitation by about 23% and 25% respectively since 1990. Only minor reductions are however seen since the late 1990s. The concentrations of total nitrate in air have decreased on average only by 8% since 1990, and fewer sites show a significant trend. A majority of the EMEP sites show a decreasing trend in reduced nitrogen both in air and precipitation on the order of 25% since 1990. Deposition of base cations has decreased during the past 30 yr, and the pH in precipitation has increased across Europe. Large inter annual variations in the particulate matter mass concentrations reflect meteorological variability, but still there is a relatively clear overall decrease at several sites during the last decade. With few observations going back to the 1990s, the observed chemical composition is applied to document a change in particulate matter (PM) mass even since 1980. These data indicate an overall reduction of about 5 μg m−3 from sulphate alone. Despite the significant reductions in sulphur emissions, sulphate still remains one of the single most important compounds contributing to regional scale aerosol mass concentration. Long-term ozone trends at EMEP sites show a mixed pattern. The year-to-year variability in ozone due to varying meteorological conditions is substantial, making it hard to separate the trends caused by emission change from other effects. For the Nordic countries the data indicate a reduced occurrence of very low concentrations. The most pronounced change in the frequency distribution is seen at sites in the UK and the Netherlands, showing a reduction in the higher values. Smaller changes are seen in Germany, while in Switzerland and Austria, no change is seen in the frequency distribution of ozone. The lack of long-term data series is a major obstacle for studying trends in volatile organic compounds (VOC). The scatter in the data is large, and significant changes are only found for certain components and stations. Concentrations of the heavy metals lead and cadmium have decreased in both air and precipitation during the last 20 yr, with reductions in the order of 80–90% for Pb and 64–84% for Cd (precipitation and air respectively). The measurements of total gaseous mercury indicate a dramatic decrease in concentrations during 1980 to about 1993. Trends in hexachlorocyclohexanes (HCHs) show a significant decrease in annual average air concentrations. For other persistent organic pollutants (POPs) the patterns is mixed, and differs between sites and between measurements in air versus precipitation.

544 citations


Journal ArticleDOI
TL;DR: In this article, the authors determined the emissions into the atmosphere of two isotopes, the noble gas xenon-133 (133Xe) and the aerosol-bound caesium-137 (137Cs), which have very different release characteristics as well as behavior in the atmosphere.
Abstract: . On 11 March 2011, an earthquake occurred about 130 km off the Pacific coast of Japan's main island Honshu, followed by a large tsunami. The resulting loss of electric power at the Fukushima Dai-ichi nuclear power plant developed into a disaster causing massive release of radioactivity into the atmosphere. In this study, we determine the emissions into the atmosphere of two isotopes, the noble gas xenon-133 (133Xe) and the aerosol-bound caesium-137 (137Cs), which have very different release characteristics as well as behavior in the atmosphere. To determine radionuclide emissions as a function of height and time until 20 April, we made a first guess of release rates based on fuel inventories and documented accident events at the site. This first guess was subsequently improved by inverse modeling, which combined it with the results of an atmospheric transport model, FLEXPART, and measurement data from several dozen stations in Japan, North America and other regions. We used both atmospheric activity concentration measurements as well as, for 137Cs, measurements of bulk deposition. Regarding 133Xe, we find a total release of 15.3 (uncertainty range 12.2–18.3) EBq, which is more than twice as high as the total release from Chernobyl and likely the largest radioactive noble gas release in history. The entire noble gas inventory of reactor units 1–3 was set free into the atmosphere between 11 and 15 March 2011. In fact, our release estimate is higher than the entire estimated 133Xe inventory of the Fukushima Dai-ichi nuclear power plant, which we explain with the decay of iodine-133 (half-life of 20.8 h) into 133Xe. There is strong evidence that the 133Xe release started before the first active venting was made, possibly indicating structural damage to reactor components and/or leaks due to overpressure which would have allowed early release of noble gases. For 137Cs, the inversion results give a total emission of 36.6 (20.1–53.1) PBq, or about 43% of the estimated Chernobyl emission. Our results indicate that 137Cs emissions peaked on 14–15 March but were generally high from 12 until 19 March, when they suddenly dropped by orders of magnitude at the time when spraying of water on the spent-fuel pool of unit 4 started. This indicates that emissions may not have originated only from the damaged reactor cores, but also from the spent-fuel pool of unit 4. This would also confirm that the spraying was an effective countermeasure. We explore the main dispersion and deposition patterns of the radioactive cloud, both regionally for Japan as well as for the entire Northern Hemisphere. While at first sight it seemed fortunate that westerly winds prevailed most of the time during the accident, a different picture emerges from our detailed analysis. Exactly during and following the period of the strongest 137Cs emissions on 14 and 15 March as well as after another period with strong emissions on 19 March, the radioactive plume was advected over Eastern Honshu Island, where precipitation deposited a large fraction of 137Cs on land surfaces. Radioactive clouds reached North America on 15 March and Europe on 22 March. By middle of April, 133Xe was fairly uniformly distributed in the middle latitudes of the entire Northern Hemisphere and was for the first time also measured in the Southern Hemisphere (Darwin station, Australia). In general, simulated and observed concentrations of 133Xe and 137Cs both at Japanese as well as at remote sites were in good quantitative agreement. Altogether, we estimate that 6.4 PBq of 137Cs, or 18% of the total fallout until 20 April, were deposited over Japanese land areas, while most of the rest fell over the North Pacific Ocean. Only 0.7 PBq, or 1.9% of the total fallout were deposited on land areas other than Japan.

517 citations


Journal ArticleDOI
TL;DR: In this article, the authors use a 2D-Voxidation space to describe organic-aerosol chemical evolution, based on two coordinates, volatility and the degree of oxidation, which can be constrained observationally or specified for known molecules.
Abstract: We discuss the use of a two-dimensional volatility-oxidation space (2-D-VBS) to describe organic- aerosol chemical evolution. The space is built around two coordinates, volatility and the degree of oxidation, both of which can be constrained observationally or specified for known molecules. Earlier work presented the thermodynam- ics of organics forming the foundation of this 2-D-VBS, al- lowing us to define the average composition (C, H, and O) of organics, including organic aerosol (OA) based on volatility and oxidation state. Here we discuss how we can analyze ex- perimental data, using the 2-D-VBS to gain fundamental in- sight into organic-aerosol chemistry. We first present a well- understood "traditional" secondary organic aerosol (SOA) system - SOA from -pinene + ozone, and then turn to two examples of "non-traditional" SOA formation - SOA from wood smoke and dilute diesel-engine emissions. Finally, we discuss the broader implications of this analysis.

448 citations


Journal ArticleDOI
TL;DR: In this article, the authors present a method for estimating cooking organic aerosol in ambient datasets based on the fractions of organic mass fragments at m/z 55 and 57: their data points fall into a V-shape in a scatter plot, with strongly influenced HOA data aligned to right arm and strongly influenced COA data points aligned to the left arm.
Abstract: . PM1 (particulate matter with an aerodynamic diameter This paper presents a method for estimating cooking organic aerosol in ambient datasets based on the fractions of organic mass fragments at m/z 55 and 57: their data points fall into a V-shape in a scatter plot, with strongly influenced HOA data aligned to the right arm and strongly influenced COA data points aligned to the left arm. HR data show that this differentiation is mainly driven by the oxygen-containing ions C3H3O+ and C3H5O+, even though their contributions to m/z 55 and 57 are low compared to the reduced ions C4H7+ and C4H9+. A simple estimation method based on the markers m/z 55, 57, and 44 is developed here and allows for a first-order-estimation of COA in urban air. This study emphasizes the importance of cooking activities for ambient air quality and confirms the importance of chemical composition measurements with a high mass and time resolution.

401 citations


Journal ArticleDOI
TL;DR: In this paper, an empirical gas-particle partitioning relationship log 10(K 1 ) = (10±1)- (2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM 2.5 in µg m 3, and T in K.
Abstract: Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM 2.5), and temperature (T ) at five sites in North America to derive an empirical gas-particle partitioning relationship log 10(K 1 ) = (10±1)- (2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in µg m 3 , and T in K. This relationship is within the range of previ- ous work but is based on far more extensive data from mul- tiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) be- tween the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with lit- tle aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more effi- cient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North Ameri- can surface sites suggests that subsidence from the free tro- posphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associ- ated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduc- tion of Hg(II) emitted from coal combustion and by assum- ing that anthropogenic particulate Hg(p) behaves as semi- volatile Hg(II) rather than as a refractory particulate compo- nent. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout al- gorithm. The observed wintertime minimum in wet depo- sition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

354 citations


Journal ArticleDOI
TL;DR: In this paper, the first ambient measurements using nitrate ion based Chemical Ionization with the Atmospheric Pressure interface Time-Of-Flight mass spectrometer (CI-APi-TOF) for sulphuric acid and neutral cluster detection are presented.
Abstract: . The first ambient measurements using nitrate ion based Chemical Ionization with the Atmospheric Pressure interface Time-Of-Flight mass spectrometer (CI-APi-TOF) for sulphuric acid and neutral cluster detection are presented. We have found CI-APi-TOF a highly stable and sensitive tool for molecular sulphuric acid detection. The lowest limit of detection for sulphuric acid was determined to be 3.6 × 104 molecules cm−3 for 15 min averaging. Signals from sulphuric acid clusters up to tetramer containing ammonia were also obtained but these were found to result from naturally charged clusters formed by ion induced clustering in the atmosphere during nucleation. Opposite to earlier studies with cluster mass spectrometers, we had no indication of neutral clusters. The reason is either less efficient charging of clusters in comparison to molecular sulphuric acid, or the low concentration of neutral clusters at our measurement site during these particular nucleation events. We show that utilizing high resolution mass spectrometry is crucial in separating the weak sulfuric acid cluster signal from other compounds.

353 citations


Journal ArticleDOI
TL;DR: This work quantifies the rate of DTT loss from individual redox-active species that are common in ambient particulate matter and tests how the DTT assay is affected by EDTA, a chelator that is sometimes used in the assay.
Abstract: The rate of consumption of dithiothreitol (DTT) is increasingly used to measure the oxidative potential of particulate matter (PM), which has been linked to the adverse health effects of PM. While several quinones are known to be very reactive in the DTT assay, it is unclear what other chemical species might contribute to the loss of DTT in PM extracts. To address this question, we quantify the rate of DTT loss from individual redox-active species that are common in ambient particulate matter. While most past research has indicated that the DTT assay is not sensitive to metals, our results show that seven out of the ten transition metals tested do oxidize DTT, as do three out of the five quinones tested. While metals are less efficient at oxidizing DTT compared to the most reactive quinones, concentrations of soluble transition metals in fine particulate matter are generally much higher than those of quinones. The net result is that metals appear to dominate the DTT response for typical ambient PM(2.5) samples. Based on particulate concentrations of quinones and soluble metals from the literature, and our measured DTT responses for these species, we estimate that for typical PM(2.5) samples approximately 80 % of DTT loss is from transition metals (especially copper and manganese), while quinones account for approximately 20 %. We find a similar result for DTT loss measured in a small set of PM(2.5) samples from the San Joaquin Valley of California. Because of the important contribution from metals, we also tested how the DTT assay is affected by EDTA, a chelator that is sometimes used in the assay. EDTA significantly suppresses the response from both metals and quinones; we therefore recommend that EDTA should not be included in the DTT assay.

351 citations


Journal ArticleDOI
TL;DR: In this article, the authors apply a newly developed aerosol optical depth (AOD) retrieval algorithm over land and ocean to investigate the distribution of AOD, and to identify emerging patterns and trends in global and regional aerosol loading during its 13-yr mission.
Abstract: . Both sensor calibration and satellite retrieval algorithm play an important role in the ability to determine accurately long-term trends from satellite data. Owing to the unprecedented accuracy and long-term stability of its radiometric calibration, SeaWiFS measurements exhibit minimal uncertainty with respect to sensor calibration. In this study, we take advantage of this well-calibrated set of measurements by applying a newly-developed aerosol optical depth (AOD) retrieval algorithm over land and ocean to investigate the distribution of AOD, and to identify emerging patterns and trends in global and regional aerosol loading during its 13-yr mission. Our correlation analysis between climatic indices (such as ENSO) and AOD suggests strong relationships for Saharan dust export as well as biomass-burning activity in the tropics, associated with large-scale feedbacks. The results also indicate that the averaged AOD trend over global ocean is weakly positive from 1998 to 2010 and comparable to that observed by MODIS but opposite in sign to that observed by AVHRR during overlapping years. On regional scales, distinct tendencies are found for different regions associated with natural and anthropogenic aerosol emission and transport. For example, large upward trends are found over the Arabian Peninsula that indicate a strengthening of the seasonal cycle of dust emission and transport processes over the whole region as well as over downwind oceanic regions. In contrast, a negative-neutral tendency is observed over the desert/arid Saharan region as well as in the associated dust outflow over the north Atlantic. Additionally, we found decreasing trends over the eastern US and Europe, and increasing trends over countries such as China and India that are experiencing rapid economic development. In general, these results are consistent with those derived from ground-based AERONET measurements.

Journal ArticleDOI
TL;DR: In this paper, a new parameterization of soil NOx emissions (SNOx) implemented within a global chemical transport model (GEOS-Chem) is presented, which represents available nitrogen (N) in soils using biome specific emission factors, online wet-and dry-deposition of N, and fertilizer and manure N derived from a spatially explicit dataset, distributed using seasonality derived from data obtained by the Moderate Resolution Imaging Spectrometer.
Abstract: . Soils have been identified as a major source (~15%) of global nitrogen oxide (NOx) emissions. Parameterizations of soil NOx emissions (SNOx) commonly used in the current generation of chemical transport models were designed to capture mean seasonal behaviour. These parameterizations do not, however, respond quantitatively to the meteorological triggers that are observed to result in pulsed SNOx. Here we present a new parameterization of SNOx implemented within a global chemical transport model (GEOS-Chem). The parameterization represents available nitrogen (N) in soils using biome specific emission factors, online wet- and dry-deposition of N, and fertilizer and manure N derived from a spatially explicit dataset, distributed using seasonality derived from data obtained by the Moderate Resolution Imaging Spectrometer. Moreover, it represents the functional form of emissions derived from point measurements and ecosystem scale experiments including pulsing following soil wetting by rain or irrigation, and emissions that are a smooth function of soil moisture as well as temperature between 0 and 30 °C. This parameterization yields global above-soil SNOx of 10.7 Tg N yr−1, including 1.8 Tg N yr−1 from fertilizer N input (1.5% of applied N) and 0.5 Tg N yr−1 from atmospheric N deposition. Over the United States (US) Great Plains region, SNOx are predicted to comprise 15–40% of the tropospheric NO2 column and increase column variability by a factor of 2–4 during the summer months due to chemical fertilizer application and warm temperatures. SNOx enhancements of 50–80% of the simulated NO2 column are predicted over the African Sahel during the monsoon onset (April–June). In this region the day-to-day variability of column NO2 is increased by a factor of 5 due to pulsed-N emissions. We evaluate the model by comparison with observations of NO2 column density from the Ozone Monitoring Instrument (OMI). We find that the model is able to reproduce the observed interannual variability of NO2 (induced by pulsed-N emissions) over the US Great Plains. We also show that the OMI mean (median) NO2 observed during the overpass following first rainfall over the Sahel is 49% (23%) higher than in the five days preceding. The measured NO2 on the day after rainfall is still 23% (5%) higher, providing a direct measure of the pulse's decay time of 1–2 days. This is consistent with the pulsing representation used in our parameterization and much shorter than 5–14 day pulse decay length used in current models.

Journal ArticleDOI
TL;DR: The second version of the global aerosol-climate model ECHAM-HAM was introduced and evaluated in this article, where a new parameterization for aerosol nucleation and water uptake, an explicit treatment of secondary organic aerosols, modified emission calculations for sea salt and mineral dust, coupling of aerosol microphysics to a two-moment stratiform cloud micro-physics scheme, and alternative wet scavenging parameterizations were introduced.
Abstract: . This paper introduces and evaluates the second version of the global aerosol-climate model ECHAM-HAM. Major changes have been brought into the model, including new parameterizations for aerosol nucleation and water uptake, an explicit treatment of secondary organic aerosols, modified emission calculations for sea salt and mineral dust, the coupling of aerosol microphysics to a two-moment stratiform cloud microphysics scheme, and alternative wet scavenging parameterizations. These revisions extend the model's capability to represent details of the aerosol lifecycle and its interaction with climate. Nudged simulations of the year 2000 are carried out to compare the aerosol properties and global distribution in HAM1 and HAM2, and to evaluate them against various observations. Sensitivity experiments are performed to help identify the impact of each individual update in model formulation. Results indicate that from HAM1 to HAM2 there is a marked weakening of aerosol water uptake in the lower troposphere, reducing the total aerosol water burden from 75 Tg to 51 Tg. The main reason is the newly introduced κ-Kohler-theory-based water uptake scheme uses a lower value for the maximum relative humidity cutoff. Particulate organic matter loading in HAM2 is considerably higher in the upper troposphere, because the explicit treatment of secondary organic aerosols allows highly volatile oxidation products of the precursors to be vertically transported to regions of very low temperature and to form aerosols there. Sulfate, black carbon, particulate organic matter and mineral dust in HAM2 have longer lifetimes than in HAM1 because of weaker in-cloud scavenging, which is in turn related to lower autoconversion efficiency in the newly introduced two-moment cloud microphysics scheme. Modification in the sea salt emission scheme causes a significant increase in the ratio (from 1.6 to 7.7) between accumulation mode and coarse mode emission fluxes of aerosol number concentration. This leads to a general increase in the number concentration of smaller particles over the oceans in HAM2, as reflected by the higher Angstrom parameters. Evaluation against observation reveals that in terms of model performance, main improvements in HAM2 include a marked decrease of the systematic negative bias in the absorption aerosol optical depth, as well as smaller biases over the oceans in Angstrom parameter and in the accumulation mode number concentration. The simulated geographical distribution of aerosol optical depth (AOD) is better correlated with the MODIS data, while the surface aerosol mass concentrations are very similar to those in the old version. The total aerosol water content in HAM2 is considerably closer to the multi-model average from Phase I of the AeroCom intercomparison project. Model deficiencies that require further efforts in the future include (i) positive biases in AOD over the ocean, (ii) negative biases in AOD and aerosol mass concentration in high-latitude regions, and (iii) negative biases in particle number concentration, especially that of the Aitken mode, in the lower troposphere in heavily polluted regions.

Journal ArticleDOI
TL;DR: This article measured a suite of gases and aerosols emitted from an 81 hectare pre-scribed fire in chaparral fuels on the central coast of Cali-fornia, US on 17 November 2009.
Abstract: Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the pro- duction and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare pre- scribed fire in chaparral fuels on the central coast of Cali- fornia, US on 17 November 2009. We also measured physi- cal and chemical changes that occurred in the isolated down- wind plume in the first 4 h after emission. The measure- ments were carried out onboard a Twin Otter aircraft outfit- ted with an airborne Fourier transform infrared spectrome- ter (AFTIR), aerosol mass spectrometer (AMS), single par- ticle soot photometer (SP2), nephelometer, LiCor CO2 an- alyzer, a chemiluminescence ozone instrument, and a wing- mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; or- ganic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative hu- midity, barometric pressure, and three-dimensional wind ve- locity. The molar ratio of excess O3 to excess CO in the plume (1O3/1CO) increased from 5.13 (±1.13)◊ 10 3 to 10.2 (±2.16)◊ 10 2 in 4.5 h following smoke emis- sion. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73± 0.43 and 7.34± 3.03 (re- spectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97)◊ 10 6 molec cm 3 , consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammo- nium increase was a factor of 3.90± 2.93 in about 4 h, but accounted for just 36 % of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles be- low the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first 4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a fac- tor of 2.50± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary forma- tion of OA closely tracked the increase in scattering. In the California plume, however, 1OA/1CO2 decreased sharply for the first hour and then increased slowly with a net de- crease of 20 % over 4 h. The fraction of thickly coated rBC particles increased up to 85 % over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of par- ticle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies

Journal ArticleDOI
TL;DR: In this paper, the GEOS-Chem global chemical transport model was used to simulate nitrogen deposition over the US in 2006-2008 by using 1/2°×2/3° horizontal resolution over North America and adjacent oceans.
Abstract: . We simulate nitrogen deposition over the US in 2006–2008 by using the GEOS-Chem global chemical transport model at 1/2°×2/3° horizontal resolution over North America and adjacent oceans. US emissions of NOx and NH3 in the model are 6.7 and 2.9 Tg N a−1 respectively, including a 20% natural contribution for each. Ammonia emissions are a factor of 3 lower in winter than summer, providing a good match to US network observations of NHx (≡NH3 gas + ammonium aerosol) and ammonium wet deposition fluxes. Model comparisons to observed deposition fluxes and surface air concentrations of oxidized nitrogen species (NOy) show overall good agreement but excessive wintertime HNO3 production over the US Midwest and Northeast. This suggests a model overestimate N2O5 hydrolysis in aerosols, and a possible factor is inhibition by aerosol nitrate. Model results indicate a total nitrogen deposition flux of 6.5 Tg N a−1 over the contiguous US, including 4.2 as NOy and 2.3 as NHx. Domestic anthropogenic, foreign anthropogenic, and natural sources contribute respectively 78%, 6%, and 16% of total nitrogen deposition over the contiguous US in the model. The domestic anthropogenic contribution generally exceeds 70% in the east and in populated areas of the west, and is typically 50–70% in remote areas of the west. Total nitrogen deposition in the model exceeds 10 kg N ha−1 a−1 over 35% of the contiguous US.

Journal ArticleDOI
TL;DR: In this paper, the authors synthesize the available scientific information connecting atmospheric nucleation with subsequent cloud condensation nuclei (CCN) formation and discuss the potential climatic implications.
Abstract: . This paper synthesizes the available scientific information connecting atmospheric nucleation with subsequent cloud condensation nuclei (CCN) formation. We review both observations and model studies related to this topic, and discuss the potential climatic implications. We conclude that CCN production associated with atmospheric nucleation is both frequent and widespread phenomenon in many types of continental boundary layers, and probably also over a large fraction of the free troposphere. The contribution of nucleation to the global CCN budget spans a relatively large uncertainty range, which, together with our poor understanding of aerosol-cloud interactions, results in major uncertainties in the radiative forcing by atmospheric aerosols. In order to better quantify the role of atmospheric nucleation in CCN formation and Earth System behavior, more information is needed on (i) the factors controlling atmospheric CCN production and (ii) the properties of both primary and secondary CCN and their interconnections. In future investigations, more emphasis should be put on combining field measurements with regional and large-scale model studies.

Journal ArticleDOI
TL;DR: In this article, chemical weather forecasting models are described and compared on regional and continental scales in Europe, and the most prominent gaps of knowledge are highlighted for the following selected focus areas: emission inventories, the integration of numerical weather prediction and atmospheric chemical transport models, boundary conditions and nesting of models, data assimilation of the various chemical species, improved understanding and parameterization of physical processes, better evaluation of models against data and the construction of model ensembles.
Abstract: Numerical models that combine weather forecasting and atmospheric chemistry are here referred to as chemical weather forecasting models. Eighteen operational chemical weather forecasting models on regional and continental scales in Europe are described and compared in this article. Topics discussed in this article include how weather forecasting and atmospheric chemistry models are integrated into chemical weather forecasting systems, how physical processes are incorporated into the models through parameterization schemes, how the model architecture affects the predicted variables, and how air chemistry and aerosol processes are formulated. In addition, we discuss sensitivity analysis and evaluation of the models, user operational requirements, such as model availability and documentation, and output availability and dissemination. In this manner, this article allows for the evaluation of the relative strengths and weaknesses of the various modelling systems and modelling approaches. Finally, this article highlights the most prominent gaps of knowledge for chemical weather forecasting models and suggests potential priorities for future research directions, for the following selected focus areas: emission inventories, the integration of numerical weather prediction and atmospheric chemical transport models, boundary conditions and nesting of models, data assimilation of the various chemical species, improved understanding and parameterization of physical processes, better evaluation of models against data and the construction of model ensembles. © 2012 Author(s).

Journal ArticleDOI
TL;DR: In this article, satellite observations of tropospheric NO2 vertical column densities over the United States (US) for 2005-2011 are evaluated using the OMI Berkeley High Resolution (BEHR) retrieval algorithm.
Abstract: . Observations of tropospheric NO2 vertical column densities over the United States (US) for 2005–2011 are evaluated using the OMI Berkeley High Resolution (BEHR) retrieval algorithm. We assess changes in NO2 on day-of-week and interannual timescales to assess the impact of changes in emissions from mobile and non-mobile sources on the observed trends. We observe consistent decreases in cities across the US, with an average total reduction of 32 ± 7% across the 7 yr. Changes for large power plants have been more variable (−26 ± 12%) due to regionally-specific regulation policies. An increasing trend of 10–20% in background NO2 columns in the northwestern US is observed. We examine the impact of the economic recession on emissions and find that decreases in NO2 column densities over cities were moderate prior to the recession (−6 ± 5% yr−1), larger during the recession (−8 ± 5% yr−1), and then smaller after the recession (−3 ± 4% yr−1). Differences in the trends observed on weekdays and weekends indicate that prior to the economic recession, NO2 reductions were dominated by technological improvements to the light-duty vehicle fleet but that a decrease in diesel truck activity has contributed to emission reductions since the recession. We use the satellite observations to estimate a 34% decrease in NO2 from mobile sources in cities for 2005–2011 and use that value to infer changes in non-mobile sources. We find that reductions in NO2 from non-mobile sources in cities have been both more modest and more variable than NO2 reductions from mobile sources (−10 ± 13%).

Journal ArticleDOI
TL;DR: In this paper, the authors presented a method for the evaluation of the exhaust emissions of marine traffic, based on the messages provided by the Automatic Identification System (AIS), which enable the positioning of ship emissions with a high spatial resolution (typically a few tens of metres).
Abstract: . A method is presented for the evaluation of the exhaust emissions of marine traffic, based on the messages provided by the Automatic Identification System (AIS), which enable the positioning of ship emissions with a high spatial resolution (typically a few tens of metres). The model also takes into account the detailed technical data of each individual vessel. The previously developed model was applicable for evaluating the emissions of NOx, SOx and CO2. This paper addresses a substantial extension of the modelling system, to allow also for the mass-based emissions of particulate matter (PM) and carbon monoxide (CO). The presented Ship Traffic Emissions Assessment Model (STEAM2) allows for the influences of accurate travel routes and ship speed, engine load, fuel sulphur content, multiengine setups, abatement methods and waves. We address in particular the modeling of the influence on the emissions of both engine load and the sulphur content of the fuel. The presented methodology can be used to evaluate the total PM emissions, and those of organic carbon, elemental carbon, ash and hydrated sulphate. We have evaluated the performance of the extended model against available experimental data on engine power, fuel consumption and the composition-resolved emissions of PM. We have also compared the annually averaged emission values with those of the corresponding EMEP inventory, As example results, the geographical distributions of the emissions of PM and CO are presented for the marine regions of the Baltic Sea surrounding the Danish Straits.

Journal ArticleDOI
TL;DR: In this article, changes in baseline (here understood as representative of continental to hemispheric scales) tropospheric O3 concentrations that have occurred at northern midlatitudes over the past six decades are quantified from available measurement records with the goal of providing benchmarks to which retrospective model calculations of the global O3 distribution can be compared.
Abstract: . Changes in baseline (here understood as representative of continental to hemispheric scales) tropospheric O3 concentrations that have occurred at northern mid-latitudes over the past six decades are quantified from available measurement records with the goal of providing benchmarks to which retrospective model calculations of the global O3 distribution can be compared. Eleven data sets (ten ground-based and one airborne) including six European (beginning in the 1950's and before), three North American (beginning in 1984) and two Asian (beginning in 1991) are analyzed. When the full time periods of the data records are considered a consistent picture emerges; O3 has increased at all sites in all seasons at approximately 1% yr−1 relative to the site's 2000 yr mixing ratio in each season. For perspective, this rate of increase sustained from 1950 to 2000 corresponds to an approximate doubling. There is little if any evidence for statistically significant differences in average rates of increase among the sites, regardless of varying length of data records. At most sites (most definitively at the European sites) the rate of increase has slowed over the last decade (possibly longer), to the extent that at present O3 is decreasing at some sites in some seasons, particularly in summer. The average rate of increase before 2000 shows significant seasonal differences (1.08 ± 0.09, 0.89 ± 0.10, 0.85 ± 0.11 and 1.21 ± 0.12% yr−1 in spring, summer, autumn and winter, respectively, over North America and Europe).

Journal ArticleDOI
TL;DR: In this paper, the authors examined surface air temperature trends over global land from 1901-2009 and found that the warming trend was particularly enhanced, in the boreal cold season (November to March) over semi-arid regions (with precipitation of 200-600 mm yr −1 ) showing a temperature increase of 1.53 °C as compared to the global annual mean temperature increase 1.13 °C over land.
Abstract: . This study examined surface air temperature trends over global land from 1901–2009. It is found that the warming trend was particularly enhanced, in the boreal cold season (November to March) over semi-arid regions (with precipitation of 200–600 mm yr −1 ) showing a temperature increase of 1.53 °C as compared to the global annual mean temperature increase of 1.13 °C over land. In mid-latitude semi-arid areas of Europe, Asia, and North America, temperatures in the cold season increased by 1.41, 2.42, and 1.5 °C, respectively. The semi-arid regions contribute 44.46% to global annual-mean land-surface temperature trend. The mid-latitude semi-arid regions in the Northern Hemisphere contribute by 27.0% of the total, with the mid-latitude semi-arid areas in Europe, Asia, and North America accounting for 6.29%, 13.81%, and 6.85%, respectively. Such enhanced semi-arid warming (ESAW) imply drier and warmer trend of these regions.

Journal ArticleDOI
TL;DR: In this paper, the authors used a coupled atmosphere-ocean global climate model (CSIRO-Mk3.6) to investigate the drivers of trends in summer rainfall and circulation in the vicinity of northern Australia.
Abstract: . We use a coupled atmosphere-ocean global climate model (CSIRO-Mk3.6) to investigate the drivers of trends in summer rainfall and circulation in the vicinity of northern Australia. As part of the Coupled Model Intercomparison Project Phase 5 (CMIP5), we perform a 10-member 21st century ensemble driven by Representative Concentration Pathway 4.5 (RCP4.5). To investigate the roles of different forcing agents, we also perform multiple 10-member ensembles of historical climate change, which are analysed for the period 1951–2010. The historical runs include ensembles driven by "all forcings" (HIST), all forcings except anthropogenic aerosols (NO_AA) and forcing only from long-lived greenhouse gases (GHGAS). Anthropogenic aerosol-induced effects in a warming climate are calculated from the difference of HIST minus NO_AA. CSIRO-Mk3.6 simulates a strong summer rainfall decrease over north-western Australia (NWA) in RCP4.5, whereas simulated trends in HIST are weakly positive (but insignificant) during 1951–2010. The weak rainfall trends in HIST are due to compensating effects of different forcing agents: there is a significant decrease in GHGAS, offset by an aerosol-induced increase. Observations show a significant increase of summer rainfall over NWA during the last few decades. The large magnitude of the observed NWA rainfall trend is not captured by 440 unforced 60-yr trends calculated from a 500-yr pre-industrial control run, even though the model's decadal variability appears to be realistic. This suggests that the observed trend includes a forced component, despite the fact that the model does not simulate the magnitude of the observed rainfall increase in response to "all forcings" (HIST). We investigate the mechanism of simulated and observed NWA rainfall changes by exploring changes in circulation over the Indo-Pacific region. The key circulation feature associated with the rainfall increase in reanalyses is a lower-tropospheric cyclonic circulation trend off the coast of NWA, which enhances the monsoonal flow. The model shows an aerosol-induced cyclonic circulation trend off the coast of NWA in HIST minus NO_AA, whereas GHGAS shows an anticyclonic circulation trend. This explains why the aerosol-induced effect is an increase of rainfall over NWA, and the greenhouse gas-induced effect is of opposite sign. Possible explanations for the cyclonic (anticyclonic) circulation trend in HIST minus NO_AA (GHGAS) involve changes in the Walker circulation or the local Hadley circulation. In either case, a plausible atmospheric mechanism is that the circulation anomaly is a Rossby wave response to convective heating anomalies south of the Equator. We also discuss the possible role of air-sea interactions, e.g. an increase (decrease) of sea-surface temperatures off the coast of NWA in HIST minus NO_AA (GHGAS). Further research is needed to better understand the mechanisms and the extent to which these are model-dependent. In summary, our results suggest that anthropogenic aerosols may have "masked" greenhouse gas-induced changes in rainfall over NWA and in circulation over the wider Indo-Pacific region. Due to the opposing effects of greenhouse gases and anthropogenic aerosols, future trends may be very different from trends observed over the last few decades.

Journal ArticleDOI
TL;DR: In this paper, it was shown that water has been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves, and the ice nuclei have to be easily-suspendable macromolecules located on the pollen.
Abstract: . The ice nucleation of bioaerosols (bacteria, pollen, spores, etc.) is a topic of growing interest, since their impact on ice cloud formation and thus on radiative forcing, an important parameter in global climate, is not yet fully understood. Here we show that pollen of different species strongly differ in their ice nucleation behaviour. The average freezing temperatures in laboratory experiments range from 240 to 255 K. As the most efficient nuclei (silver birch, Scots pine and common juniper pollen) have a distribution area up to the Northern timberline, their ice nucleation activity might be a cryoprotective mechanism. Far more intriguingly, it has turned out that water, which has been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves. The ice nuclei have to be easily-suspendable macromolecules located on the pollen. Once extracted, they can be distributed further through the atmosphere than the heavy pollen grains and so presumably augment the impact of pollen on ice cloud formation even in the upper troposphere. Our experiments lead to the conclusion that pollen ice nuclei, in contrast to bacterial and fungal ice nucleating proteins, are non-proteinaceous compounds.

Journal ArticleDOI
TL;DR: In this article, a spectroscopic analysis of 115 wintertime particulate matter samples collected in rural California showed that wood smoke absorbs solar radiation with a strong spectral selectivity, consistent with prior work that has demonstrated that organic carbon (OC), in addition to black carbon (BC), appreciably absorb solar radiation in the visible and ultraviolet spectral regions.
Abstract: . A spectroscopic analysis of 115 wintertime particulate matter samples collected in rural California shows that wood smoke absorbs solar radiation with a strong spectral selectivity. This is consistent with prior work that has demonstrated that organic carbon (OC), in addition to black carbon (BC), appreciably absorbs solar radiation in the visible and ultraviolet spectral regions. We apportion light absorption to OC and BC and find that the absorption Angstrom exponent of the light-absorbing OC in these samples ranges from 3.0 to 7.4 and averages 5.0. Further, we calculate that OC would account for 14% and BC would account for 86% of solar radiation absorbed by the wood smoke in the atmosphere (integrated over the solar spectrum from 300 to 2500 nm). OC would contribute 49% of the wood smoke particulate matter absorption of ultraviolet solar radiation at wavelengths below 400 nm and, therefore, may affect tropospheric photochemistry. These results illustrate that BC is the dominant light-absorbing particulate matter species in atmospheres burdened with residential wood smoke and OC absorption is secondary but not insignificant. Further, these results add to the growing body of evidence that light-absorbing OC is ubiquitous in atmospheres influenced by biomass burning and may be important to include when considering particulate matter effects on climate.

Journal ArticleDOI
TL;DR: In this paper, the authors used formation free energies calculated by quantum chemical methods to estimate the evaporation rates of species from sulfuric acid clusters containing ammonia or dimethylamine.
Abstract: . Atmospheric new particle formation is an important source of atmospheric aerosols. Large efforts have been made during the past few years to identify which molecules are behind this phenomenon, but the actual birth mechanism of the particles is not yet well known. Quantum chemical calculations have proven to be a powerful tool to gain new insights into the very first steps of particle formation. In the present study we use formation free energies calculated by quantum chemical methods to estimate the evaporation rates of species from sulfuric acid clusters containing ammonia or dimethylamine. We have found that dimethylamine forms much more stable clusters with sulphuric acid than ammonia does. On the other hand, the existence of a very deep local minimum for clusters with two sulfuric acid molecules and two dimethylamine molecules hinders their growth to larger clusters. These results indicate that other compounds may be needed to make clusters grow to larger sizes (containing more than three sulfuric acid molecules).

Journal ArticleDOI
TL;DR: The authors used in situ observations from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network, the Midwest Ammonia Monitoring Project, 11 surface site campaigns as well as Infrared Atmospheric Sounding Interferometer (IASI) satellite measurements with the GEOS-Chem model to investigate inorganic aerosol loading and atmospheric ammonia concentrations over the United States.
Abstract: We use in situ observations from the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network, the Midwest Ammonia Monitoring Project, 11 surface site campaigns as well as Infrared Atmospheric Sounding Interferometer (IASI) satellite measurements with the GEOS-Chem model to investigate inorganic aerosol loading and atmospheric ammonia concentrations over the United States IASI observations suggest that current ammonia emissions are underestimated in California and in the springtime in the Midwest In California this underestimate likely drives the underestimate in nitrate formation in the GEOS-Chem model However in the remaining continental United States we find that the nitrate simulation is biased high (normalized mean bias > = 10) year-round, except in Spring (due to the underestimate in ammonia in this season) None of the uncertainties in precursor emissions, the uptake efficiency of N2O5 on aerosols, OH concentrations, the reaction rate for the formation of nitric acid, or the dry deposition velocity of nitric acid are able to explain this bias We find that reducing nitric acid concentrations to 75% of their simulated values corrects the bias in nitrate (as well as ammonium) in the US However the mechanism for this potential reduction is unclear and may be a combination of errors in chemistry, deposition and sub-grid near-surface gradients This "updated" simulation reproduces PM and ammonia loading and captures the strong seasonal and spatial gradients in gas-particle partitioning across the United States We estimate that nitrogen makes up 15−35% of inorganic fine PM mass over the US, and that this fraction is likely to increase in the coming decade, both with decreases in sulfur emissions and increases in ammonia emissions

Journal ArticleDOI
TL;DR: In this paper, the observed OH exhibited a weak dependence on NOx in contrast to model predictions, reaching a factor of 8 at 0.02 ppb NO, while modelled and measured OH agree well at NO mixing ratios above 1 ppb.
Abstract: . Ambient OH and HO2 concentrations were measured by laser induced fluorescence (LIF) during the PRIDE-PRD2006 (Program of Regional Integrated Experiments of Air Quality over the Pearl River Delta, 2006) campaign at a rural site downwind of the megacity of Guangzhou in Southern China. The observed OH concentrations reached daily peak values of (15–26) × 106 cm−3 which are among the highest values so far reported for urban and suburban areas. The observed OH shows a consistent high correlation with j(O1D) over a broad range of NOx conditions. The correlation cannot be reproduced by model simulations, indicating that OH stabilizing processes are missing in current models. The observed OH exhibited a weak dependence on NOx in contrast to model predictions. While modelled and measured OH agree well at NO mixing ratios above 1 ppb, a continuously increasing underprediction of the observed OH is found towards lower NO concentrations, reaching a factor of 8 at 0.02 ppb NO. A dependence of the modelled-to-measured OH ratio on isoprene cannot be concluded from the PRD data. However, the magnitude of the ratio fits into the isoprene dependent trend that was reported from other campaigns in forested regions. Hofzumahaus et al. (2009) proposed an unknown OH recycling process without NO, in order to explain the high OH levels at PRD in the presence of high VOC reactivity and low NO. Taking a recently discovered interference in the LIF measurement of HO2 into account, the need for an additional HO2 → OH recycling process persists, but the required source strength may be up to 20% larger than previously determined. Recently postulated isoprene mechanisms by Lelieveld et al. (2008) and Peeters and Muller (2010) lead to significant enhancements of OH expected for PRD, but an underprediction of the observed OH by a factor of two remains at low NO (0.1–0.2 ppb). If the photolysis of hydroperoxy aldehydes from isoprene is as efficient as proposed by Peeters and Muller (2010), the corresponding OH formation at PRD would be more important than the primary OH production from ozone and HONO. While the new isoprene mechanisms need to be confirmed by laboratory experiments, there is probably need for other, so far unidentified chemical processes to explain entirely the high OH levels observed in Southern China.

Journal ArticleDOI
TL;DR: The Atmospheric Cluster Dynamics Code (ACDC) as mentioned in this paper was created to study the first steps of atmospheric new particle formation by examining the formation of molecular clusters from atmospherically relevant molecules.
Abstract: . The Atmospheric Cluster Dynamics Code (ACDC) is presented and explored. This program was created to study the first steps of atmospheric new particle formation by examining the formation of molecular clusters from atmospherically relevant molecules. The program models the cluster kinetics by explicit solution of the birth–death equations, using an efficient computer script for their generation and the MATLAB ode15s routine for their solution. Through the use of evaporation rate coefficients derived from formation free energies calculated by quantum chemical methods for clusters containing dimethylamine or ammonia and sulphuric acid, we have explored the effect of changing various parameters at atmospherically relevant monomer concentrations. We have included in our model clusters with 0–4 base molecules and 0–4 sulfuric acid molecules for which we have commensurable quantum chemical data. The tests demonstrate that large effects can be seen for even small changes in different parameters, due to the non-linearity of the system. In particular, changing the temperature had a significant impact on the steady-state concentrations of all clusters, while the boundary effects (allowing clusters to grow to sizes beyond the largest cluster that the code keeps track of, or forbidding such processes), coagulation sink terms, non-monomer collisions, sticking probabilities and monomer concentrations did not show as large effects under the conditions studied. Removal of coagulation sink terms prevented the system from reaching the steady state when all the initial cluster concentrations were set to the default value of 1 m−3, which is probably an effect caused by studying only relatively small cluster sizes.

Journal ArticleDOI
TL;DR: Wang et al. as mentioned in this paper investigated both the wet and dry atmospheric deposition of different reactive nitrogen (N) species during a three-year observation campaign at ten selected sites in Northern China.
Abstract: . Emissions of reactive nitrogen (N) species can affect surrounding ecosystems via atmospheric deposition. However, few long-term and multi-site measurements have focused on both the wet and the dry deposition of individual N species in large areas of Northern China. Thus, the magnitude of atmospheric deposition of various N species in Northern China remains uncertain. In this study, the wet and dry atmospheric deposition of different N species was investigated during a three-year observation campaign at ten selected sites in Northern China. The results indicate that N deposition levels in Northern China were high with a ten-site, three-year average of 60.6 kg N ha−1 yr−1. The deposition levels showed spatial and temporal variation in the range of 28.5–100.4 kg N ha−1 yr−1. Of the annual total deposition, 40% was deposited via precipitation, and the remaining 60% was comprised of dry-deposited forms. Compared with gaseous N species, particulate N species were not the major contributor of dry-deposited N; they contributed approximately 10% to the total flux. On an annual basis, oxidized species accounted for 21% of total N deposition, thereby implying that other forms of gaseous N, such as NH3, comprised a dominant portion of the total flux. The contribution of NO3− to N deposition was enhanced in certain urban and industrial areas, possibly due to the fossil fuse combustion. As expected, the total N deposition in Northern China was significantly larger than the values reported by national scale monitoring networks in Europe, North America and East Asia because of high rates of wet deposition and gaseous NH3 dry deposition. Taken together, these findings show that NH3 emissions should be abated to mitigate high N deposition and associated potential impacts on ecosystems in Northern China. The present results improve our understanding of spatio-temporal variations of magnitudes, pathways and species of deposited N in the target areas, and are important not only to inform conservation and regulatory bodies but also to initiate further detailed studies. Uncertainties among current observations underscore the need to quantify the impact of vegetation on dry deposition and to refine the simulation of dry deposition velocity.

Journal ArticleDOI
TL;DR: In this paper, the authors investigated the air pollution characteristics of synoptic-scale circulation in the Beijing megacity, and provided quantitative evaluation of the impacts of circulation patterns on air quality during the 2008 Beijing Summer Olympics.
Abstract: . This study investigated the air pollution characteristics of synoptic-scale circulation in the Beijing megacity, and provided quantitative evaluation of the impacts of circulation patterns on air quality during the 2008 Beijing Summer Olympics. Nine weather circulation types (CTs) were objectively identified over the North China region during 2000–2009, using obliquely rotated T-mode principal component analysis (PCA). The resulting CTs were examined in relation to the local meteorology, regional transport pathways, and air quality parameters, respectively. The FLEXPART-WRF model was used to calculate 48-h backward plume trajectories for each CT. Each CT was characterized with distinct local meteorology and air mass origin. CT 1 (high pressure to the west with a strong pressure gradient) was characterized by a northwestern air mass origin, with the smallest local and southeasterly air mass sources, and CT 6 (high pressure to the northwest) had air mass sources mostly from the north and east. On the contrary, CTs 5, 8, and 9 (weak pressure field, high pressure to the east, and low pressure to the northwest, respectively) were characterized by southern and southeastern trajectories, which indicated a greater influence of high pollutant emission sources. In turn, poor air quality in Beijing (high loadings of PM10, BC, SO2, NO2, NOx, O3, AOD, and low visibility) was associated with these CTs. Good air quality in Beijing was associated with CTs 1 and 6. The average visibilities (with ±1σ) in Beijing for CTs 1 and 6 during 2000–2009 were 18.5 ± 8.3 km and 14.3 ± 8.5 km, respectively. In contrast, low visibility values of 6.0 ± 3.5 km, 6.6 ± 3.7 km, and 6.7 ± 3.6 km were found in CTs 5, 8, and 9, respectively. The mean concentrations of PM10 for CTs 1, 6, 5, 8, and 9 during 2005–2009 were 90.3 ± 76.3 μg m−3, 111.7 ± 89.6 μg m−3, 173.4 ± 105.8 μg m−3, 158.4 ± 90.0 μg m−3, and 151.2 ± 93.1 μg m−3, respectively. Analysis of the relationship between circulation pattern and air quality during the emission control period suggests that CTs are the primary drivers of day-to-day variations in pollutant concentrations over Beijing and its vicinity. During the Olympics period, the frequency of CT 6 was twice that of the mean in August from 2000 to 2009. This CT had northerly transport pathways and favorable meteorological conditions (e.g. frequent precipitation) for clean air during the Olympics. Assuming that relationships between CTs and air quality parameters in the same season are fixed in different years, the relative contributions of synoptic circulation to decreases in PM10, BC, SO2, NO2, NOx, CO, and horizontal light extinction during the Olympics were estimated as 19 ± 14%, 18 ± 13%, 41 ± 36%, 12 ± 7%, 10 ± 5%, 19 ± 11%, and 54 ± 25%, respectively.