A Simple Kinetic Model for Autoxidation of S(IV) Oxides Catalyzed by Iron and/or Manganese Ions

The reaction kinetics of S(IV) autoxidation catalyzed by single metal ions of Mn(II) and Fe(II) or Fe(III) and by a mixture of Mn(II) and Fe(II) under the conditions representative for acidified atmospheric liquid water was investigated. A simple power law kinetic model based on the stability constants for metal-sulfito complexes formed during the first step of a radical chain mechanism predicts well the kinetics for the reactions catalyzed by single metal ions. The calculated stability constants for iron (5.7×10³ dm³ mol^–1) and manganese (10×10⁴ dm³ mol^–1) sulfito complexes are close to those reported in the literature. The catalytic synergism between Mn(II) and Fe(II) was confirmed. For this system the following power law rate equation was suggested:r_tot = S_Fe · r_Fe + S_Mn · r_Mn ,where r_Fe and r_Mn are the reaction rates in the presence of Fe(II) and Mn(II), respectively. S_Fe and S_Mn are proportional factors, which account for the synergistic effect. The proposed power law rate equation predicts the reaction kinetics very well. The values of S_Fe (1.35) and S_Mn (15) indicate that the influence of Fe(II)/Fe(III) on Mn(II)/Mn(III) cycling is larger than, vice versa, agreeing with the reaction mechanism proposed for the S(IV) autoxidation catalyzed by mixed metal ions.     

Theoretical studies on OH and Cl initiated hydrogen atom abstraction of HFE-227pc (CF3OCF2CHF2)

The kinetics of hydrogen atom abstraction reactions of HFE-227pc by OH and Cl was studied by ab initio method. The structural optimization and frequency calculation of the titled compound and the species formed during the abstraction reactions were performed with density functional theory using hybrid meta density functional MPWB1K with 6–31?+?G(d,p) basis set. The energy of the species was further refined by making a single point energy calculation at G3B3 level of theory. The standard enthalpies of formation of reactant and the radical formed after H-atom abstraction was calculated using isodesmic method. The rate constants of abstraction reactions were calculated using Conventional Transition State Theory (CTST) and were found to be 1.5?×?10^?15 and 0.53?×?10^?16 cm³molecule^?1 s^?1 for OH and Cl respectively. The calculated value for the abstraction by OH is close to the experimental value of 2.26?×?10^?15 cm³molecule^?1 s^?1 whereas the same for Cl is found to be about five times lower than that of 2.70?×?10^?16 cm³molecule^?1 s^?1. The theoretical studies yielded the enthalpies of formation and the rate constants that are vital in determining the lifetime of HFE-227pc.     

South Atlantic Ocean cyclogenesis climatology simulated by regional climate model (RegCM3)

A detailed climatology of the cyclogenesis over the Southern Atlantic Ocean (SAO) from 1990 to 1999 and how it is simulated by the RegCM3 (Regional Climate Model) is presented here. The simulation used as initial and boundary conditions the National Centers for Environmental Prediction—Department of Energy (NCEP/DOE) reanalysis. The cyclones were identified with an automatic scheme that searches for cyclonic relative vorticity (ζ₁₀) obtained from a 10-m height wind field. All the systems with ζ₁₀ ≤ ?1.5 × 10^?5 s^?1 and lifetime equal or larger than 24 h were considered in the climatology. Over SAO, in 10 years were detected 2,760 and 2,787 cyclogeneses in the simulation and NCEP, respectively, with an annual mean of 276.0 ± 11.2 and 278.7 ± 11.1. This result suggests that the RegCM3 has a good skill to simulate the cyclogenesis climatology. However, the larger model underestimations (?9.8%) are found for the initially stronger systems (ζ₁₀ ≤ ?2.5 × 10^?5 s^?1). It was noted that over the SAO the annual cycle of the cyclogenesis depends of its initial intensity. Considering the systems initiate with ζ₁₀ ≤ ?1.5 × 10^?5 s^?1, the annual cycle is not well defined and the higher frequency occurs in the autumn (summer) in the NCEP (RegCM3). The stronger systems (ζ₁₀ ≤ ?2.5 × 10^?5 s^?1) have a well-characterized high frequency of cyclogenesis during the winter in both NCEP and RegCM3. This work confirms the existence of three cyclogenetic regions in the west sector of the SAO, near the South America east coast and shows that RegCM3 is able to reproduce the main features of these cyclogenetic areas.     

Ecological limits to terrestrial biological carbon dioxide removal

Terrestrial biological atmospheric carbon dioxide removal (BCDR) through bioenergy with carbon capture and storage (BECS), afforestation/reforestation, and forest and soil management is a family of proposed climate change mitigation strategies. Very high sequestration potentials for these strategies have been reported, but there has been no systematic analysis of the potential ecological limits to and environmental impacts of implementation at the scale relevant to climate change mitigation. In this analysis, we identified site-specific aspects of land, water, nutrients, and habitat that will affect local project-scale carbon sequestration and ecological impacts. Using this framework, we estimated global-scale land and resource requirements for BCDR, implemented at a rate of 1 Pg C y^?1. We estimate that removing 1 Pg C y^?1 via tropical afforestation would require at least 7?×?10⁶ ha y^?1 of land, 0.09 Tg y^?1 of nitrogen, and 0.2 Tg y^?1 of phosphorous, and would increase evapotranspiration from those lands by almost 50 %. Switchgrass BECS would require at least 2?×?10⁸ ha of land (20 times U.S. area currently under bioethanol production) and 20 Tg y^?1 of nitrogen (20 % of global fertilizer nitrogen production), consuming 4?×?10¹²?m³ y^?1 of water. While BCDR promises some direct (climate) and ancillary (restoration, habitat protection) benefits, Pg C-scale implementation may be constrained by ecological factors, and may compromise the ultimate goals of climate change mitigation.     

Photochemical activation of chlorine by iron-oxide aerosol

The photochemical activation of chlorine by dissolved iron in artificial sea-salt aerosol droplets and by highly dispersed iron oxide (Fe₂O₃) aerosol particles (mainly hematite, specific surface ~150 m² g^?1) exposed to gaseous HCl, was investigated in humidified air in a Teflon simulation chamber. Employing the radical-clock technique, we quantified the production of gaseous atomic chlorine (Cl) from the irradiated aerosol. When the salt aerosol contained Fe₂O₃ at pH 6, no significant Cl production was observed, even if the dissolution of iron was forced by “weathering” (repeatedly freezing and thawing for five times). Adjusting the pH in the stock suspension to 2.6, 2.2, and 1.9 and equilibrating for one week resulted in a quantifiable amount of dissolved iron (0.03, 0.2, and 0.6 mmol L^?1, respectively) and in gaseous Cl production rates of ~1.6, 6, and 8?×?10²¹ atoms cm^?2 h^?1, respectively. In a further series of experiments, the pure Fe₂O₃ aerosol was exposed to various levels of gaseous hydrogen chloride (HCl). The resulting Cl production rates ranged from 8?×?10²⁰ Cl atoms cm^?2 h^?1 (at ~4 ppb HCl) to 5?×?10²² Cl atoms cm^?2 h^?1 (at ~350 ppb HCl) and confirmed the uptake and conversion of HCl to atomic Cl (at HCl to Cl conversion yields of 2–5 %, depending on the relative humidity). The Fe₂O₃ experiments indicate that iron-induced Cl formation may be important for highly soluble combustion-aerosol particles in marine environments in the presence of gaseous HCl.     

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.     

The impacts of urbanization on air quality over the Pearl River Delta in winter: roles of urban land use and emission distribution

In this study, ideal but realistic numerical experiments are performed to explore the relative effects of changes in land use and emission distribution on air quality in the Pearl River Delta (PRD) region in winter. The experiments are accomplished using the Lagrangian particle transport and dispersion model FLEXPART coupled with the Weather Research and Forecasting model under different scenarios. Experiment results show that the maximum changes in daily mean air pollution concentration (as represented by SO₂ concentration) caused by land use change alone reaches up to 2?×?10^?6 g m^?3, whereas changes in concentrations due to the anthropogenic emission distribution are characterized by a maximum value of 6?×?10^?6 g m^?3. Such results reflect that, although the impacts of land use change on air quality are non-negligible, the emission distribution exerts a more significant influence on air quality than land use change. This provides clear implications for policy makers to control urban air pollution over the PRD region, especially for the urban planning in spatial arrangements for reasonable emissions.     

Biogenic hydrogen sulphide emissions and non-sea sulfate aerosols over the Indian Sundarban mangrove forest

Temporal variations in atmospheric hydrogen sulphide concentrations and its biosphere-atmosphere exchanges were studied in the World’s largest mangrove ecosystem, Sundarbans, India. The results were used to understand the possible contribution of H₂S fluxes in the formation of atmospheric aerosol of different size classes (e.g. accumulation, nucleation and coarse mode). The mixing ratio of hydrogen sulphide (H₂S) over the Sundarban mangrove atmosphere was found maximum during the post-monsoon season (October to January) with a mean value of 0.59?±?0.02 ppb and the minimum during pre-monsoon (February to May) with a mean value of 0.26?±?0.01 ppb. This forest acted as a perennial source of H₂S and the sediment-air emission flux ranged between 1213?±?276 μg S m^?2 d^?1(December) and 457?±?114 μg S m^?2 d^?1 (August) with an annual mean of 768?±?240 μg S m^?2d^?1. The total annual emissions of H₂S from the Indian Sundarban were estimated to be 1.2?±?0.6 Tg S. The accumulation mode of aerosols was found to be more enriched with non-sea salt sulfate with an average loading of 5.74 μg m^?3 followed by the coarse mode (5.18 μg m^?3) and nucleation mode (1.18 μg m^?3). However, the relative contribution of Non-sea salt sulfate aerosol to total sulfate aerosol was highest in the nucleation mode (83%) followed by the accumulation (73%) and coarse mode (58%). Significant positive relations between H₂S flux and different modes of NSS indicated the likely link between H₂S, a dominant precursor for the non-sea salt sulfate, and non-sea sulfate aerosol particles. An increase in H₂S emissions from the mangrove could result in an increase in enhanced NSS in aerosol and associated cloud albedo, and a decrease in the amount of incoming solar radiation reaching the Sundarban mangrove forest.     

Meteorological aspects of an abnormal cooling event over Iran in April 2009

During the period from 12 to 15 April, 2009 nearly the entire Iran, apart from the southern border, experienced an advective cooling event. While winter freezing concerns are typical, the nature of this freezing event was unusual with respect to its date of occurrence and accompanying synoptic meteorological situation. To analyze the freezing event, the relevant meteorological data at multiple levels of the atmosphere were examined from the NCEP/NCAR reanalysis dataset. The results showed that a polar vortex was responsible for the freezing event over the country extending southward extraordinarily in such a way that its ridge influenced most parts of Iran. This was recognized as an abnormal extension of a polar vortex in the recent years. The sea-level pressure fields indicated that a ridge of large-scale anticyclone centered over Black Sea extended southward and prevailed over most parts of Iran. This resulted in the formation of a severe cold air advection from high latitudes (Polar region) over Iran. During the study period, moisture pumping was observed from the Arabian Sea and Persian Gulf. The winds at 1000 hPa level blew with a magnitude of 10 m s^?1 toward south in the region of convergence (between ?2 × 10^?6 s^?1 and ?12 × 10^?6 s^?1). The vertical profiles of temperature and humidity also indicated that the ICE structural icing occurred at multiple levels of the atmosphere, i.e, from 800 hPa through 400 hPa levels. In addition to the carburetor (or induction), icing occurred between 900 and 700 hPa levels in the selected radiosonde stations during the study period. In addition, the HYSPLIT backward trajectory model outputs were in quite good agreement with the observed synoptic features.     

Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

Seasonal and annual trends of carbonaceous species of PM<Subscript>10</Subscript> over a megacity Delhi,India during 2010–2017

PM₁₀ samples were collected to characterize the seasonal and annual trends of carbonaceous content in PM₁₀ at an urban site of megacity Delhi, India from January 2010 to December 2017. Organic carbon (OC) and elemental carbon (EC) concentrations were quantified by thermal-optical transmission (TOT) method of PM₁₀ samples collected at Delhi. The average concentrations of PM₁₀, OC, EC and TCA (total carbonaceous aerosol) were 222?±?87 (range: 48.2–583.8 μg m^?3), 25.6?±?14.0 (range: 4.2–82.5 μg m^?3), 8.7?±?5.8 (range: 0.8–35.6 μg m^?3) and 54.7?±?30.6 μg m^?3 (range: 8.4–175.2 μg m^?3), respectively during entire sampling period. The average secondary organic carbon (SOC) concentration ranged from 2.5–9.1 μg m^?3 in PM₁₀, accounting from 14 to 28% of total OC mass concentration of PM₁₀. Significant seasonal variations were recorded in concentrations of PM₁₀, OC, EC and TCA with maxima during winter and minima during monsoon seasons. In the present study, the positive linear trend between OC and EC were recorded during winter (R²?=?0.53), summer (R²?=?0.59) and monsoon (R²?=?0.78) seasons. This behaviour suggests the contribution of similar sources and common atmospheric processes in both the fractions. OC/EC weight ratio suggested that vehicular emissions, fossil fuel combustion and biomass burning could be the major sources of carbonaceous aerosols of PM₁₀ at the megacity Delhi, India. Trajectory analysis indicates that the air mass approches to the sampling site is mainly from Indo Gangetic plain (IGP) region (Uttar Pradesh, Haryana and Punjab etc.), Thar desert, Afghanistan, Pakistan and surrounding areas.     

A nocturnal atmospheric loss of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> in the remote marine boundary layer

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH₂I₂) and chloro-iodomethane (CH₂ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH₂I₂ and CH₂ICl in air and of CH₂I₂ in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH₂I₂ was lower in amplitude than that of CH₂ICl, despite its faster photolysis rate. We speculate that night-time loss of CH₂I₂ occurs due to reaction with NO₃ radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k _CH2I2+NO3 of ≤4 × 10^?13 cm³ molecule^?1 s^?1; a previous kinetic study carried out at ≤100 Torr found k _CH2I2+NO3 of 4 × 10^?13 cm³ molecule^?1 s^?1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/? 0.8 nmol m^?2 d^?1 for CH₂I₂ and 3.7 +/? 0.8 nmol m^?2 d^?1 for CH₂ICl), we show that the model overestimates night-time CH₂I₂ by >60 % but reaches good agreement with the measurements when the CH₂I₂ + NO₃ reaction is included at 2–4 × 10^?13 cm³ molecule^?1 s^?1. We conclude that the reaction has a significant effect on CH₂I₂ and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.     

Evaluating observed and projected future climate changes for the Arctic using the K?ppen-Trewartha climate classification

The ecosystems in the Arctic region are known to be very sensitive to climate changes. The accelerated warming for the past several decades has profoundly influenced the lives of the native populations and ecosystems in the Arctic. Given that the K?ppen-Trewartha (K-T) climate classification is based on reliable variations of land-surface types (especially vegetation), this study used the K-T scheme to evaluate climate changes and their impact on vegetation for the Arctic (north of 50°N) by analyzing observations as well as model simulations for the period 1900–2099. The models include 16 fully coupled global climate models from the Intergovernmental Panel on Climate Change Fourth Assessment. By the end of this century, the annual-mean surface temperature averaged over Arctic land regions is projected to increase by 3.1, 4.6 and 5.3°C under the Special Report on Emissions Scenario (SRES) B1, A1b, and A2 emission scenarios, respectively. Increasing temperature favors a northward expansion of temperate climate (i.e., Dc and Do in the K-T classification) and boreal oceanic climate (i.e., Eo) types into areas previously covered by boreal continental climate (i.e., Ec) and tundra; and tundra into areas occupied by permanent ice. The tundra region is projected to shrink by ?1.86?×?10⁶?km² (?33.0%) in B1, ?2.4?×?10⁶?km² (?42.6%) in A1b, and ?2.5?×?10⁶?km² (?44.2%) in A2 scenarios by the end of this century. The Ec climate type retreats at least 5° poleward of its present location, resulting in ?18.9, ?30.2, and ?37.1% declines in areal coverage under the B1, A1b and A2 scenarios, respectively. The temperate climate types (Dc and Do) advance and take over the area previously covered by Ec. The area covered by Dc climate expands by 4.61?×?10⁶?km² (84.6%) in B1, 6.88?×?10⁶?km² (126.4%) in A1b, and 8.16?×?10⁶?km² (149.6%) in A2 scenarios. The projected redistributions of K-T climate types also differ regionally. In northern Europe and Alaska, the warming may cause more rapid expansion of temperate climate types. Overall, the climate types in 25, 39.1, and 45% of the entire Arctic region are projected to change by the end of this century under the B1, A1b, and A2 scenarios, respectively. Because the K-T climate classification was constructed on the basis of vegetation types, and each K-T climate type is closely associated with certain prevalent vegetation species, the projected large shift in climate types suggests extensive broad-scale redistribution of prevalent ecoregions in the Arctic.     

Ionic and elemental composition of PM<Subscript>2.5</Subscript> aerosols over the Caribbean Sea in the Tropical Atlantic

To characterize atmospheric particulate matter equal or less than 2.5 μm in diameter (PM_2.5) over the Tropical Atlantic Ocean, aerosol sampling was carried out in Puerto Rico during August and September, 2006. Aerosols were analyzed by ion chromatography for water-soluble inorganic and organic ions (including Na⁺, NH₄ ⁺, Mg²⁺, Ca²⁺, K⁺, Cl^?, SO₄ ^2?, NH₄ ⁺, F^?, methanesulfonate (MSA), and oxalate), by inductive coupled plasma mass spectrometry (ICPMS) for trace elements (Al, Fe, Zn, Mn, Cu, Ni, V, Pb, Cr, Sb, Co, Sc, Cd), and by scanning electron microscopy for individual aerosol particle composition and morphology. The results show that the dominant cations in aerosols were Na⁺, (mean: 631 ng m^?3), accounting for 63.8 % of the total cation and NH₄ ⁺ (mean: 164 ng m^?3), accounting for 13.8 % of the total cation measured in this study. The main inorganic anions were Cl^? (576 ng m^?3, 54.1 %) and SO₄ ^2? (596 ng m^?3, 38.0 %). The main organic anion was oxalate (18 ng m^?3). Crustal enrichment factor calculations identified 62 % of the trace elements measured (Cu, Ni, V, Co, Al, Mn, Fe, Sc, and Cr) with crustal origin. Single particle analysis demonstrated that 40 % of the aerosol particles examined were Cl^? rich particles as sodium chloride from seawater and 34 % of the total particles were Si-rich particles, mainly in the form of aluminosilicates from dust material. Based on the combination of air-mass trajectories, cluster analysis and principal component analysis, the major sources of these PM_2.5 particles include marine, Saharan dust and biomass burning from West Africa; however, volcanic emissions from the Soufriere Hills in Montserrat had significant impact on aerosol composition in this region at the time of sample collection.     

Increasing trend of northeast monsoon rainfall over the equatorial Indian Ocean and peninsular India

Peninsular India and Sri Lanka receive major part of their annual rainfall during the northeast monsoon season (October–December). The long-term trend in the northeast monsoon rainfall over the Indian Ocean and peninsular India is examined in the vicinity of global warming scenario using the Global Precipitation Climatology Project (GPCP) dataset available for the period 1979–2010. The result shows a significant increasing trend in rainfall rate of about 0.5 mm day^?1 decade^?1 over a large region bounded by 10 °S–10 °N and 55 °E–100 °E. The interannual variability of seasonal rainfall rate over peninsular India using conventional rain gauge data is also investigated in conjunction to the Indian Ocean dipole. The homogeneous rain gauge data developed by Indian Institute of Tropical Meteorology over peninsular India also exhibit the considerable upward rainfall trend of about 0.4 mm day^?1 decade^?1 during this period. The associated outgoing longwave radiation shows coherent decrease in the order of 2 W?m^?2 decade^?1 over the rainfall increase region.     

Chemical characteristics of atmospheric bulk deposition in a semi-rural area of the <Emphasis Type="Bold">Po Valley</Emphasis> (Italy)

This study provides an analysis of a five-year time series chemical composition of the bulk deposition (2009–2013), collected within a farm surrounded by industrial and urban settlements in a semi-rural area of the Po Valley, with the aim of characterizing potential emission sources affecting precipitation composition at the site. Most monitoring efforts in this region, recognized as one of the most polluted in the world both due to the intense industrialisation and urbanisation as well as to frequent air stagnation conditions, are presently devoted more to gaseous and particulate pollutants than to precipitation chemistry. The bulk deposition samples were very concentrated in chemical species, both acidic and alkaline, high compared to other polluted sites in the world and to locations in the same district. The mean ions concentrations (in μeq l^?1) are: NO₃ ^? (243) > SO₄ ^2? (220) > PO₄ ^3? (176) > Cl^? (153) > NO₂ ^? (29) > F^? (2.6); NH₄ ⁺ (504) > Ca²⁺ (489) > K⁺ (151) > Na⁺ (127) > Mg²⁺ (127). pH data shows a trend toward slightly alkaline conditions attributed to the large presence of ammonium and crustal elements, in spite of high concentrations of nitrates and sulphates. The relevant concentrations of Ca²⁺ and Mg²⁺ further suggests that these alkaline conditions might be due to the correspondingly significant concentrations of carbonates/bicarbonates in our dataset. While back-trajectories analysis suggests the stronger importance of local resuspension over long-range transport, statistical analyses on ion composition highlight the key role exerted by agricultural activity, especially in the case of NH₄ ⁺, K⁺, Ca²⁺ and PO₄ ^3? (especially linked to fertilisation practices and soil resuspension due to mechanical operations). Apart from Na⁺ and Cl^? ions which correlate well as expected, indicating their likely common origin from marine salt, the identification of the origin of the other ions is very complex due to the contribution of diverse local sources, such as industrial and residential settlements.     

Aqueous Oxidation of Sulfur(IV) Catalyzed by Manganese(II): A Generalized Simple Kinetic Model

The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO ₃ ⁻ up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation

Assessment of PM<Subscript>2.5</Subscript> chemical compositions in Delhi: primary vs secondary emissions and contribution to light extinction coefficient and visibility degradation

Haze-fog conditions over northern India are associated with visibility degradation and severe attenuation of solar radiation by airborne particles with various chemical compositions. PM_2.5 samples have been collected in Delhi, India from December 2011 to November 2012 and analyzed for carbonaceous and inorganic species. PM₁₀ measurements were made simultaneously such that PM_10–2.5 could be estimated by difference. This study analyzes the temporal variation of PM_2.5 and carbonaceous particles (CP), focusing on identification of the primary and secondary aerosol emissions, estimations of light extinction coefficient (b_ext) and the contributions by the major PM_2.5 chemical components. The annual mean concentrations of PM_2.5, organic carbon (OC), elemental carbon (EC) and PM_10–2.5 were found to be 153.6 ± 59.8, 33.5 ± 15.9, 6.9 ± 3.9 and 91.1 ± 99.9 μg m^?3, respectively. Total CP, secondary organic aerosols and major anions (e.g., SO₄ ^2? and NO₃ ^?) maximize during the post-monsoon and winter due to fossil fuel combustion and biomass burning. PM_10–2.5 is more abundant during the pre-monsoon and post-monsoon. The OC/EC varies from 2.45 to 9.26 (mean of 5.18 ± 1.47), indicating the influence of multiple combustion sources. The b_ext exhibits highest values (910 ± 280 and 1221 ± 371 Mm^?1) in post-monsoon and winter and lowest in monsoon (363 ± 110 and 457 ± 133 Mm^?1) as estimated via the original and revised IMPROVE algorithms, respectively. Organic matter (OM =1.6 × OC) accounts for ~39 % and ~48 % of the b_ext, followed by (NH₄)₂SO₄ (~21 % and ~24 %) and EC (~13 % and ~10 %), according to the original and revised algorithms, respectively. The b_ext estimates via the two IMPROVE versions are highly correlated (R² = 0.95, root mean square error = 38 % and mean bias error = 28 %) and are strongly related to visibility impairment (r = ?0.72), mostly associated with anthropogenic rather than natural PM contributions. Therefore, reduction of CP and precursor gas emissions represents an urgent opportunity for air quality improvement across Delhi.     

Atmospheric ionic species in PM2.5 and PM1 aerosols in the ambient air of eastern central India

This study elucidates the characteristics of ambient PM_2.5 (fine) and PM₁ (submicron) samples collected between July 2009 and June 2010 in Raipur, India, in terms of water soluble ions, i.e. Na⁺, NH ₄ ⁺ , K⁺, Mg²⁺, Ca²⁺, Cl^?, NO ₃ ^? and SO ₄ ^2? . The total number of PM_2.5 and PM₁ samples collected with eight stage cascade impactor was 120. Annual mean concentrations of PM_2.5 and PM₁ were 150.9?±?78.6 μg/m³ and 72.5?±?39.0 μg/m³, respectively. The higher particulate matter (PM) mass concentrations during the winter season are essentially due to the increase of biomass burning and temperature inversion. Out of above 8 ions, the most abundant ions were SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ for both PM_2.5 and PM₁ aerosols; their average concentrations were 7.86?±?5.86 μg/m³, 3.12?±?2.63 μg/m³ and 1.94?±?1.28 μg/m³ for PM_2.5, and 5.61?±?3.79 μg/m³, 1.81?±?1.21 μg/m³ and 1.26?±?0.88 μg/m³ for PM₁, respectively. The major secondary species SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ accounted for 5.81%, 1.88% and 1.40% of the total mass of PM_2.5 and 11.10%, 2.68%, and 2.48% of the total mass of PM₁, respectively. The source identification was conducted for the ionic species in PM_2.5 and PM₁ aerosols. The results are discussed by the way of correlations and principal component analysis. Spearman correlation indicated that Cl^? and K⁺ in PM_2.5 and PM₁ can be originated from similar type of sources. Principal component analysis reveals that there are two major sources (anthropogenic and natural such as soil derived particles) for PM_2.5 and PM₁ fractions.     

Analysis of chemical characteristics of PM<Subscript>2.5</Subscript> in Beijing over a 1-year period

Beijing is one of the largest and most densely populated cities in China. PM_2.5 (fine particulates with aerodynamic diameters less than 2.5 μm) pollution has been a serious problem in Beijing in recent years. To study the temporal and spatial variations in the chemical components of PM_2.5 and to discuss the formation mechanisms of secondary particles, SO₂, NO₂, PM_2.5, and chemical components of PM_2.5 were measured at four sites in Beijing, Dingling (DL), Chegongzhuang (CG), Fangshan (FS), and Yufa (YF), over four seasons from 2012 to 2013. Fifteen chemical components, including organic carbon (OC), elemental carbon (EC), K⁺, NH₄ ⁺, NO₃ ^?, SO₄ ^2?, Cl^?, Al, Ca, Fe, Mg, Na, Pb, Si, and Zn, were selected for analysis. Overall, OC, SO₄ ^2?, NO₃ ^?, and NH₄ ⁺ were dominant among 15 components, the annual average concentrations of which were 22.62 ± 21.86, 19.39 ± 21.06, 18.89 ± 19.82, and 13.20 ± 12.80 μg·m^?3, respectively. Compared with previous studies, the concentrations of NH₄ ⁺ were significantly higher in this study. In winter, the average concentrations of OC and EC were, respectively, 3 and 2.5 times higher than in summer, a result of coal combustion during winter. The average OC/EC ratios over the four sites were 4.9, 7.0, 8.1, and 8.4 in spring, summer, autumn, and winter, respectively. The annual average [NO₃ ^?]/[SO₄ ^2?] ratios in DL, CG, FS, and YF were 1.01, 1.25, 1.08, and 1.12, respectively, which were significantly higher than previous studies in Beijing, indicating that the contribution ratio of mobile source increased in recent years in Beijing. Analysis of correlations between temperature and relative humidity and between SOR ([SO₄ ^2?]/([SO₄ ^2?] + [SO₂])) and NOR ([NO₃ ^?]/([NO₃ ^?] + [NO₂])) indicated that gas-phase oxidation reactions were the major formation mechanism of SO₄ ^2? in spring and summer in urban Beijing, whereas slow gas-phase oxidation reactions and heterogeneous reactions both occurred in autumn and winter. NO₃ ^? was mainly formed through year-round heterogeneous reactions in urban Beijing.