A multi-model evaluation of aerosols over South Asia: common problems and possible causes

Atmospheric pollution over South Asia attracts special attention due to its effects on regional climate, water cycle and human health. These effects are potentially growing owing to rising trends of anthropogenic aerosol emissions. In this study, the spatio-temporal aerosol distributions over South Asia from seven global aerosol models are evaluated against aerosol retrievals from NASA satellite sensors and ground-based measurements for the period of 2000–2007. Overall, substantial underestimations of aerosol loading over South Asia are found systematically in most model simulations. Averaged over the entire South Asia, the annual mean aerosol optical depth (AOD) is underestimated by a range 15 to 44% across models compared to MISR (Multi-angle Imaging SpectroRadiometer), which is the lowest bound among various satellite AOD retrievals (from MISR, SeaWiFS (Sea-Viewing Wide Field-of-View Sensor), MODIS (Moderate Resolution Imaging Spectroradiometer) Aqua and Terra). In particular during the post-monsoon and wintertime periods (i.e., October–January), when agricultural waste burning and anthropogenic emissions dominate, models fail to capture AOD and aerosol absorption optical depth (AAOD) over the Indo–Gangetic Plain (IGP) compared to ground-based Aerosol Robotic Network (AERONET) sunphotometer measurements. The underestimations of aerosol loading in models generally occur in the lower troposphere (below 2 km) based on the comparisons of aerosol extinction profiles calculated by the models with those from Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) data. Furthermore, surface concentrations of all aerosol components (sulfate, nitrate, organic aerosol (OA) and black carbon (BC)) from the models are found much lower than in situ measurements in winter. Several possible causes for these common problems of underestimating aerosols in models during the post-monsoon and wintertime periods are identified: the aerosol hygroscopic growth and formation of secondary inorganic aerosol are suppressed in the models because relative humidity (RH) is biased far too low in the boundary layer and thus foggy conditions are poorly represented in current models, the nitrate aerosol is either missing or inadequately accounted for, and emissions from agricultural waste burning and biofuel usage are too low in the emission inventories. These common problems and possible causes found in multiple models point out directions for future model improvements in this important region.

Spatial evaluation of volcanic ash forecasts using satellite observations

The decision to close airspace in the event of a volcanic eruption is based on hazard maps of predicted ash extent. These are produced using output from volcanic ash transport and dispersion (VATD)models. In this paper an objectivemetric to evaluate the spatial accuracy of VATD simulations relative to satellite retrievals of volcanic ash is presented. The 5 metric is based on the fractions skill score (FSS). Thismeasure of skill provides more information than traditional point-bypoint metrics, such as success index and Pearson correlation coefficient, as it takes into the account spatial scale overwhich skill is being assessed. The FSS determines the scale overwhich a simulation has skill and can differentiate between a "near miss" and a forecast that is badly misplaced. The 10 idealised scenarios presented show that even simulations with considerable displacement errors have useful skill when evaluated over neighbourhood scales of 200–700km2. This method could be used to compare forecasts produced by different VATDs or using different model parameters, assess the impact of assimilating satellite retrieved ash data and evaluate VATD forecasts over a long time period.

Evaluating the climate and air quality impacts of short-lived pollutants

This paper presents a summary of the work done within the European Union's Seventh Framework Programme project ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants). ECLIPSE had a unique systematic concept for designing a realistic and effective mitigation scenario for short-lived climate pollutants (SLCPs; methane, aerosols and ozone, and their precursor species) and quantifying its climate and air quality impacts, and this paper presents the results in the context of this overarching strategy. The first step in ECLIPSE was to create a new emission inventory based on current legislation (CLE) for the recent past and until 2050. Substantial progress compared to previous work was made by including previously unaccounted types of sources such as flaring of gas associated with oil production, and wick lamps. These emission data were used for present-day reference simulations with four advanced Earth system models (ESMs) and six chemistry transport models (CTMs). The model simulations were compared with a variety of ground-based and satellite observational data sets from Asia, Europe and the Arctic. It was found that the models still underestimate the measured seasonality of aerosols in the Arctic but to a lesser extent than in previous studies. Problems likely related to the emissions were identified for northern Russia and India, in particular. To estimate the climate impacts of SLCPs, ECLIPSE followed two paths of research: the first path calculated radiative forcing (RF) values for a large matrix of SLCP species emissions, for different seasons and regions independently. Based on these RF calculations, the Global Temperature change Potential metric for a time horizon of 20 years (GTP20) was calculated for each SLCP emission type. This climate metric was then used in an integrated assessment model to identify all emission mitigation measures with a beneficial air quality and short-term (20-year) climate impact. These measures together defined a SLCP mitigation (MIT) scenario. Compared to CLE, the MIT scenario would reduce global methane (CH4) and black carbon (BC) emissions by about 50 and 80 %, respectively. For CH4, measures on shale gas production, waste management and coal mines were most important. For non-CH4 SLCPs, elimination of high-emitting vehicles and wick lamps, as well as reducing emissions from gas flaring, coal and biomass stoves, agricultural waste, solvents and diesel engines were most important. These measures lead to large reductions in calculated surface concentrations of ozone and particulate matter. We estimate that in the EU, the loss of statistical life expectancy due to air pollution was 7.5 months in 2010, which will be reduced to 5.2 months by 2030 in the CLE scenario. The MIT scenario would reduce this value by another 0.9 to 4.3 months. Substantially larger reductions due to the mitigation are found for China (1.8 months) and India (11–12 months). The climate metrics cannot fully quantify the climate response. Therefore, a second research path was taken. Transient climate ensemble simulations with the four ESMs were run for the CLE and MIT scenarios, to determine the climate impacts of the mitigation. In these simulations, the CLE scenario resulted in a surface temperature increase of 0.70 ± 0.14 K between the years 2006 and 2050. For the decade 2041–2050, the warming was reduced by 0.22 ± 0.07 K in the MIT scenario, and this result was in almost exact agreement with the response calculated based on the emission metrics (reduced warming of 0.22 ± 0.09 K). The metrics calculations suggest that non-CH4 SLCPs contribute ~ 22 % to this response and CH4 78 %. This could not be fully confirmed by the transient simulations, which attributed about 90 % of the temperature response to CH4 reductions. Attribution of the observed temperature response to non-CH4 SLCP emission reductions and BC specifically is hampered in the transient simulations by small forcing and co-emitted species of the emission basket chosen. Nevertheless, an important conclusion is that our mitigation basket as a whole would lead to clear benefits for both air quality and climate. The climate response from BC reductions in our study is smaller than reported previously, possibly because our study is one of the first to use fully coupled climate models, where unforced variability and sea ice responses cause relatively strong temperature fluctuations that may counteract (and, thus, mask) the impacts of small emission reductions. The temperature responses to the mitigation were generally stronger over the continents than over the oceans, and with a warming reduction of 0.44 K (0.39–0.49) K the largest over the Arctic. Our calculations suggest particularly beneficial climate responses in southern Europe, where surface warming was reduced by about 0.3 K and precipitation rates were increased by about 15 (6–21) mm yr−1 (more than 4 % of total precipitation) from spring to autumn. Thus, the mitigation could help to alleviate expected future drought and water shortages in the Mediterranean area. We also report other important results of the ECLIPSE project.

Advanced source apportionment of size-resolved trace elements at multiple sites in London during winter

Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

Modelled and observed changes in aerosols and surface solar radiation over Europe between 1960 and 2009

Substantial changes in anthropogenic aerosols and precursor gas emissions have occurred over recent decades due to the implementation of air pollution control legislation and economic growth. The response of atmospheric aerosols to these changes and the impact on climate are poorly constrained, particularly in studies using detailed aerosol chemistry–climate models. Here we compare the HadGEM3-UKCA (Hadley Centre Global Environment Model-United Kingdom Chemistry and Aerosols) coupled chemistry–climate model for the period 1960–2009 against extensive ground-based observations of sulfate aerosol mass (1978–2009), total suspended particle matter (SPM, 1978–1998), PM10 (1997–2009), aerosol optical depth (AOD, 2000–2009), aerosol size distributions (2008–2009) and surface solar radiation (SSR, 1960–2009) over Europe. The model underestimates observed sulfate aerosol mass (normalised mean bias factor (NMBF) = −0.4), SPM (NMBF = −0.9), PM10 (NMBF = −0.2), aerosol number concentrations (N30 NMBF = −0.85; N50 NMBF = −0.65; and N100 NMBF = −0.96) and AOD (NMBF = −0.01) but slightly overpredicts SSR (NMBF = 0.02). Trends in aerosol over the observational period are well simulated by the model, with observed (simulated) changes in sulfate of −68 % (−78 %), SPM of −42 % (−20 %), PM10 of −9 % (−8 %) and AOD of −11 % (−14 %). Discrepancies in the magnitude of simulated aerosol mass do not affect the ability of the model to reproduce the observed SSR trends. The positive change in observed European SSR (5 %) during 1990–2009 ("brightening") is better reproduced by the model when aerosol radiative effects (ARE) are included (3 %), compared to simulations where ARE are excluded (0.2 %). The simulated top-of-the-atmosphere aerosol radiative forcing over Europe under all-sky conditions increased by > 3.0 W m−2 during the period 1970–2009 in response to changes in anthropogenic emissions and aerosol concentrations.

Current model capabilities for simulating black carbon and sulfate concentrations in the Arctic atmosphere: a multi-model evaluation using a comprehensive measurement data set

The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of 2 years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC or rBC and sulfate concentrations quite well, compared to previous comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January–March underestimated by 59 and 37 % for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44 % for July–September), but with overestimates as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is 3 times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modeling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

Methane cross-validation between three Fourier Transform Spectrometers: SCISAT ACE-FTS, GOSAT TANSO-FTS, and ground-based FTS measurements in the Canadian high Arctic

We present cross-validation of remote sensing measurements of methane profiles in the Canadian high Arctic. Accurate and precise measurements of methane are essential to understand quantitatively its role in the climate system and in global change. Here, we show a cross-validation between three datasets: two from spaceborne instruments and one from a ground-based instrument. All are Fourier Transform Spectrometers (FTSs). We consider the Canadian SCISAT Atmospheric Chemistry Experiment (ACE)-FTS, a solar occultation infrared spectrometer operating since 2004, and the thermal infrared band of the Japanese Greenhouse Gases Observing Satellite (GOSAT) Thermal And Near infrared Sensor for carbon Observation (TANSO)-FTS, a nadir/off-nadir scanning FTS instrument operating at solar and terrestrial infrared wavelengths, since 2009. The ground-based instrument is a Bruker 125HR Fourier Transform Infrared (FTIR) spectrometer, measuring mid-infrared solar absorption spectra at the Polar Environment Atmospheric Research Laboratory (PEARL) Ridge Lab at Eureka, Nunavut (80° N, 86° W) since 2006. For each pair of instruments, measurements are collocated within 500 km and 24 h. An additional criterion based on potential vorticity values was found not to significantly affect differences between measurements. Profiles are regridded to a common vertical grid for each comparison set. To account for differing vertical resolutions, ACE-FTS measurements are smoothed to the resolution of either PEARL-FTS or TANSO-FTS, and PEARL-FTS measurements are smoothed to the TANSO-FTS resolution. Differences for each pair are examined in terms of profile and partial columns. During the period considered, the number of collocations for each pair is large enough to obtain a good sample size (from several hundred to tens of thousands depending on pair and configuration). Considering full profiles, the degrees of freedom for signal (DOFS) are between 0.2 and 0.7 for TANSO-FTS and between 1.5 and 3 for PEARL-FTS, while ACE-FTS has considerably more information (roughly 1° of freedom per altitude level). We take partial columns between roughly 5 and 30 km for the ACE-FTS–PEARL-FTS comparison, and between 5 and 10 km for the other pairs. The DOFS for the partial columns are between 1.2 and 2 for PEARL-FTS collocated with ACE-FTS, between 0.1 and 0.5 for PEARL-FTS collocated with TANSO-FTS or for TANSO-FTS collocated with either other instrument, while ACE-FTS has much higher information content. For all pairs, the partial column differences are within ± 3 × 1022 molecules cm−2. Expressed as median ± median absolute deviation (expressed in absolute or relative terms), these differences are 0.11 ± 9.60 × 10^20 molecules cm−2 (0.012 ± 1.018 %) for TANSO-FTS–PEARL-FTS, −2.6 ± 2.6 × 10^21 molecules cm−2 (−1.6 ± 1.6 %) for ACE-FTS–PEARL-FTS, and 7.4 ± 6.0 × 10^20 molecules cm−2 (0.78 ± 0.64 %) for TANSO-FTS–ACE-FTS. The differences for ACE-FTS–PEARL-FTS and TANSO-FTS–PEARL-FTS partial columns decrease significantly as a function of PEARL partial columns, whereas the range of partial column values for TANSO-FTS–ACE-FTS collocations is too small to draw any conclusion on its dependence on ACE-FTS partial columns.

The status and challenge of global fire modelling

Biomass burning impacts vegetation dynamics, biogeochemical cycling, atmospheric chemistry, and climate, with sometimes deleterious socio-economic impacts. Under future climate projections it is often expected that the risk of wildfires will increase. Our ability to predict the magnitude and geographic pattern of future fire impacts rests on our ability to model fire regimes, either using well-founded empirical relationships or process-based models with good predictive skill. A large variety of models exist today and it is still unclear which type of model or degree of complexity is required to model fire adequately at regional to global scales. This is the central question underpinning the creation of the Fire Model Intercomparison Project - FireMIP, an international project to compare and evaluate existing global fire models against benchmark data sets for present-day and historical conditions. In this paper we summarise the current state-of-the-art in fire regime modelling and model evaluation, and outline what essons may be learned from FireMIP.

Climatology and variability of trace gases in extratropical double-tropopause regions from MLS, HIRDLS, and ACE-FTS measurements

Upper tropospheric and lower stratospheric measurements from the Aura Microwave Limb Sounder (MLS), the Aura High Resolution Dynamics Limb Sounder (HIRDLS), and the Atmospheric Chemistry Experiment-Fourier transform spectrometer (ACE-FTS) are used to present the first global climatological comparison of extratropical, nonpolar trace gas distributions in double-tropopause (DT) and single-tropopause (ST) regions. Stratospheric tracers, O3, HNO3, and HCl, have lower mixing ratios ∼2–8 km above the primary (lowermost) tropopause in DT than in ST regions in all seasons, with maximum Northern Hemisphere (NH) differences near 50% in winter and 30% in summer. Southern Hemisphere winter differences are somewhat smaller, but summer differences are similar in the two hemispheres. H2O in DT regions of both hemispheres shows strong negative anomalies in November through February and positive anomalies in July through October, reflecting the strong seasonal cycle in H2O near the tropical tropopause. CO and other tropospheric tracers examined have higher DT than ST values 2–7 km above the primary tropopause, with the largest differences in winter. Large DT-ST differences extend to high NH latitudes in fall and winter, with longitudinal maxima in regions associated with enhanced wave activity and subtropical jet variations. Results for O3 and HNO3 agree closely between MLS and HIRDLS, and differences from ACE-FTS are consistent with its sparse and irregular midlatitude sampling. Consistent signatures in climatological trace gas fields provide strong evidence that transport from the tropical upper troposphere into the layer between double tropopauses is an important pathway for stratosphere-troposphere exchange.

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.

Inter-comparison of stratospheric mean-meridional circulation and eddy mixing among six reanalysis data sets

The stratospheric mean-meridional circulation (MMC) and eddy mixing are compared among six meteorological reanalysis data sets: NCEP-NCAR, NCEP-CFSR, ERA-40, ERA-Interim, JRA-25, and JRA-55 for the period 1979–2012. The reanalysis data sets produced using advanced systems (i.e., NCEP-CFSR, ERA-Interim, and JRA-55) generally reveal a weaker MMC in the Northern Hemisphere (NH) compared with those produced using older systems (i.e., NCEP/NCAR, ERA-40, and JRA-25). The mean mixing strength differs largely among the data products. In the NH lower stratosphere, the contribution of planetary-scale mixing is larger in the new data sets than in the old data sets, whereas that of small-scale mixing is weaker in the new data sets. Conventional data assimilation techniques introduce analysis increments without maintaining physical balance, which may have caused an overly strong MMC and spurious small-scale eddies in the old data sets. At the NH mid-latitudes, only ERA-Interim reveals a weakening MMC trend in the deep branch of the Brewer–Dobson circulation (BDC). The relative importance of the eddy mixing compared with the mean-meridional transport in the subtropical lower stratosphere shows increasing trends in ERA-Interim and JRA-55; this together with the weakened MMC in the deep branch may imply an increasing age-of-air (AoA) in the NH middle stratosphere in ERA-Interim. Overall, discrepancies between the different variables and trends therein as derived from the different reanalyses are still relatively large, suggesting that more investments in these products are needed in order to obtain a consolidated picture of observed changes in the BDC and the mechanisms that drive them.

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of Sao Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that Sao Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. On the other hand, Sao Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in Sao Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in Sao Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at Sao Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved

Gas-Phase Nucleophilic and Elimination Reactions in Simple Alkyl Nitrates

There has been increasing interest in the gas-phase reactivity of alkyl nitrates because of their well-known applications as explosives and because of then role in atmospheric and in marine processes This manuscript describes an experimental study by FT-ICR techniques of the gas-phase reactions of OH(-) and F(-) with methyl and ethyl Innate For methyl nitrate, the main reaction channel is found to be an elimination process promoted by abstraction of an a proton from the methyl group. Nucleophilic displacement of nitrate anion through an S(N)2 process at the carbon center Is also found to he an important reaction channel with methyl nitrate In ethyl nitrate, Ruination of NO(3)(-) is greatly enhanced and this is attributed to the ease of an E2-type elimination process promoted by proton abstraction at the beta position of the ethyl group. Theoretical calculations at the MP2/6-311+G(3df,2p)//MP2/6-31+G(d) level of theory ale consistent with the relative importance of the reaction channels and suggest that these reactions proceed through a double well potential The calculations also predict that nucleophilic attack by OH(-) at the nitrogen center (Sn2@N) is energetically the rueful ad pathway but experiments with (18)OH(-) showed no evidence for this channel. Single-point calculations reveal a strong preference for approach to the emboli center and may explain the lack of reactivity at the nitrogen center. Calculations were also carried out or NH(2)(-) and SH(-) to establish the reactivity pattern to provide a better understanding of environmentally relevant nitrate esters.

Predicting and characterizing new molecular species at a high-level theoretical approach: HSeCl, HClSe, and SeCl

New molecular species HSeCl, HClSe, and SeCl were investigated at a high level of theory, CCSD(T), with a series of correlation consistent basis sets with extrapolation to the CBS limit. Account has been taken for valence-only and core-valence correlation effects, and of anharmonic effects on the vibrational frequencies. HSeCl is 43.25 kcal mol (1) more stable than HClSe. A barrier (Delta G(#)) of 47.20 kcal mol (1) separates these species. Internuclear distances are generally overestimated by 0.008 angstrom in the valence-only correlation calculations. Inclusion of anharmonicity leads to much improved vibrational frequencies. For SeCl, we estimate Delta H(f) (0 K) = 23.96 and Delta H(f) (298.15 K) = 24.64 kcal mol (1); for HSeCl, we had 4.20 and 4.97 kcal mol (1), respectively. (C) 2010 Elsevier B.V. All rights reserved.