Time-dependent uptake of NO3 by sea salt

Using a coated-insert flow tube reactor coupled to a low-energy electron-impact mass spectrometer with molecular beam sampling, we studied uptake of NO₃ by sea salt at room temperature and [NO₃]?=?8?10¹¹???4?10¹³ molecule cm^?3. The radical uptake coefficient γ(t) is time dependent: its initial value (γ _ini) decreases exponentially with the characteristic time (τ) to its steady-state value (γ _ss) at given [NO₃]. The parameters γ _ini, γ _ss and τ depend on [NO₃], whereas γ _ss is water vapor independent at [H₂O]?=?8?10¹²???1.6?10¹⁵ molecule cm^?3 and RH ≤ 0.5 %. HCl and NO₂ are uptake products detected in the gas phase. We used these findings to estimate γ values under tropospheric conditions for urban coastal and remote marine environments: at high NO₃ (~90 ppt), the time dependence becomes important, and the γ value averaged over the aerosol lifetime is 4?10^?3; at low NO₃ (~1 ppt), the radical uptake is time independent and proceeds faster with γ _ini?=?8?10^?3     

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.     

Seasonal characteristics of tropical marine boundary layer air measured at the Cape Verde Atmospheric Observatory

Observations of the tropical atmosphere are fundamental to the understanding of global changes in air quality, atmospheric oxidation capacity and climate, yet the tropics are under-populated with long-term measurements. The first three years (October 2006–September 2009) of meteorological, trace gas and particulate data from the global WMO/Global Atmospheric Watch (GAW) Cape Verde Atmospheric Observatory Humberto Duarte Fonseca (CVAO; 16° 51′ N, 24° 52′ W) are presented, along with a characterisation of the origin and pathways of air masses arriving at the station using the NAME dispersion model and simulations of dust deposition using the COSMO-MUSCAT dust model. The observations show a strong influence from Saharan dust in winter with a maximum in super-micron aerosol and particulate iron and aluminium. The dust model results match the magnitude and daily variations of dust events, but in the region of the CVAO underestimate the measured aerosol optical thickness (AOT) because of contributions from other aerosol. The NAME model also captured the dust events, giving confidence in its ability to correctly identify air mass origins and pathways in this region. Dissolution experiments on collected dust samples showed a strong correlation between soluble Fe and Al and measured solubilities were lower at high atmospheric dust concentrations. Fine mode aerosol at the CVAO contains a significant fraction of non-sea salt components including dicarboxylic acids, methanesulfonic acid and aliphatic amines, all believed to be of oceanic origin. A marine influence is also apparent in the year-round presence of iodine and bromine monoxide (IO and BrO), with IO suggested to be confined mainly to the surface few hundred metres but BrO well mixed in the boundary layer. Enhanced CO₂ and CH₄ and depleted oxygen concentrations are markers for air-sea exchange over the nearby northwest African coastal upwelling area. Long-range transport results in generally higher levels of O₃ and anthropogenic non-methane hydrocarbons (NMHC) in air originating from North America. Ozone/CO ratios were highest (up to 0.42) in relatively fresh European air masses. In air heavily influenced by Saharan dust the O₃/CO ratio was as low as 0.13, possibly indicating O₃ uptake to dust. Nitrogen oxides (NO_x and NO_y) show generally higher concentrations in winter when air mass origins are predominantly from Africa. High photochemical activity at the site is shown by maximum spring/summer concentrations of OH and HO₂ of 9?×?10⁶ molecule cm^?3 and 6?×?10⁸ molecule cm^?3, respectively. After the primary photolysis source, the most important controls on the HO_x budget in this region are IO and BrO chemistry, the abundance of HCHO, and uptake of HO_x to aerosol.     

Effect of temperature on the methyl chloride production rate in a marine phytoplankton, <Emphasis Type="Italic">Phaeodactylum tricornutum</Emphasis>

Methyl halides such as methyl chloride (CH₃Cl) are known to be important carriers of halogen from the ocean to the atmosphere, and the halogens they release into the stratosphere by photolysis catalyze ozone depletion. Marine phytoplankton have been reported as a source of CH₃Cl, but the effects of environmental temperature on the CH₃Cl production by phytoplankton have not been investigated. In this study, we investigated the effects of temperature on the production of CH₃Cl in the culture of a marine diatom, Phaeodactylum tricornutum CCMP 630, incubated at 10, 15, 20, 25, and 30 °C. CH₃Cl concentrations in cultured samples were determined using purge and trap gas chromatograph–mass spectrometry. Phytoplankton growth was monitored by measuring the chlorophyll a concentrations. CH₃Cl production was observed for several weeks at four different temperatures ranging from 10 to 25 °C. The CH₃Cl production from P. tricornutum was increased with increasing temperature from 10 to 25 °C, and the maximum production rate for CH₃Cl was 0.21~0.26 μmol (g chlorophyll a)^?1 d^?1 at 25 °C, which was several times higher than that at 10 °C (~0.03 μmol (g chlorophyll a)^?1 d^?1). The Arrhenius equation was successfully used to characterize the effects of temperature on the production rates of CH₃Cl in the culture of P. tricornutum. Our results suggest that water temperature directly affects CH₃Cl production derived from P. tricornutum and that water temperature would be a significant factor for estimating the emissions of CH₃Cl from marine environments.     

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.     

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.     

Effect of surface albedo, water vapour, and atmospheric aerosols on the cloud-free shortwave radiative budget in the Arctic

This study is based on ground-based measurements of downward surface shortwave irradiance (SW), columnar water vapour (wv), and aerosol optical depth (τ) obtained at Thule Air Base (Greenland) in 2007–2010, together with MODIS observations of the surface shortwave albedo (A). Radiative transfer model calculations are used in combination with measurements to separate the radiative effect of A (ΔSW_A), wv (ΔSW_wv), and aerosols (ΔSW_τ) in modulating SW in cloud-free conditions. The shortwave radiation at the surface is mainly affected by water vapour absorption, which produces a reduction of SW as low as ?100 Wm^?2 (?18%). The seasonal change of A produces an increase of SW by up to +25 Wm^?2 (+4.5%). The annual mean radiative effect is estimated to be ?(21–22) Wm^?2 for wv, and +(2–3) Wm^?2 for A. An increase by +0.065 cm in the annual mean wv, to which corresponds an absolute increase in ΔSW_wv by 0.93 Wm^?2 (4.3%), has been observed to occur between 2007 and 2010. In the same period, the annual mean A has decreased by ?0.027, with a corresponding decrease in ΔSW_A by 0.41 Wm^?2 (?14.9%). Atmospheric aerosols produce a reduction of SW as low as ?32 Wm^?2 (?6.7%). The instantaneous aerosol radiative forcing (RF_τ) reaches values of ?28 Wm^?2 and shows a strong dependency on surface albedo. The derived radiative forcing efficiency (FE_τ) for solar zenith angles between 55° and 70° is estimated to be (?120.6 ± 4.3) for 0.1 < A < 0.2, and (?41.2 ± 1.6) Wm^?2 for 0.5 < A < 0.6.     

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.     

Emission estimates of methyl chloride from industrial sources in China based on high frequency atmospheric observations

Methyl Chloride (CH₃Cl) is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion (Carpenter et al. 2014). In the global CH₃Cl budget, the atmospheric CH₃Cl emissions is predominantly maintained by natural sources, of which magnitudes have been relatively well-constrained. However, significant uncertainties still remain in the CH₃Cl emission strengths from anthropogenic sources. High-frequency and high-precision in situ measurements of atmospheric CH₃Cl concentrations obtained since 2008 at Gosan station (a remote background site in the East Asia) reveal significant pollution events superimposed on the seasonally varying regional background levels. Back trajectory statistics showed that air masses corresponding to the observed CH₃Cl enhancement largely originated from regions of intensive industrial activities in China. Based on an inter-species correlation method, estimates of CH₃Cl emissions from manufacturing industries including coal combustion, use of feedstocks, or process agents in chemical production for China (2008–2012) are 297 ± 71 Gg yr.^?1 in 2008 to 480 ± 99 Gg yr.^?1 in 2009, followed by a gradual decrease of about 25% between 2009 and 2012 (398 ± 92 Gg yr.^?1 for 2010; 286 ± 68 Gg yr.^?1 for 2011; 358 ± 92 Gg yr.^?1 for 2012). The annual average of industrial CH₃Cl emissions for 2008–2012 (363 ± 85 Gg yr.^?1) in China is comparable to the known total global anthropogenic CH₃Cl emissions accounting only for coal combustion and indoor biofuel use. This may suggest that unless emissions from the chemical industry are accounted for, global anthropogenic emissions of CH₃Cl have been substantially underestimated. In particular, since industrial production and use of CH₃Cl have not been regulated under the Montreal Protocol (MP) or its successor amendments, continuous monitoring of Chinese CH₃Cl outflow is important to properly evaluate its anthropogenic emissions.     

Cloud condensation nuclei (CCN) concentration in the Brazilian northeast semi-arid region: the influence of local circulation

Ground-based aerosol instrumentation covering particle size diameters from 25 nm to 32 µm was deployed to determine aerosol concentration and cloud condensation nuclei (CCN)-activation properties at water vapor supersaturations in the range of S = 0.20–1.50 % in the remote Brazilian northeast semi-arid region (NEB) in coastal (maritime) and continental (inland) regimes. The instruments measured aerosol number concentration and activation spectra for CCN and revealed that aerosol properties are sensitive with respect to the sources as a function of the local wind circulation system. The observations show that coastal aerosol total number concentrations are above 3,000 cm^?3 on average, exhibiting concentration peaks depending on the time of the day in a consistent daily pattern. The variation on aerosol concentration has also influences on the fraction of particles active as CCN. At 1.0 % water vapor supersaturation, the fraction can reach as high as 80 %. Inland aerosol total concentrations were about 1,800–1,900 cm^?3 and did not show much diurnal variation. The fraction of particles active as CCN observed inland depend on the history of the air masses, and was much higher when air masses were originated over the sea. It was found that (NH₄)₂SO₄ and NaCl are the major soluble inorganic fraction of the aerosols at the coast. The major fraction of NaCl was present in the coarse mode, while ammonium sulfate dominates the inorganic fraction at the submicron range, with about 10 % of the total aerosol mass at 0.32 µm. Inorganic compounds are almost absent in particles with sizes around 0.1 μm. The study suggests that the air masses with high concentration of CCN originate at the sea. The feasible explanation lies in the fact that the NEB’s beaches have a particular morphology that produces a wide surf zone and creates a large load of aerosols when combined with strong and permanent winds of the region.     

Measurements of CO,HCN, and C2H6 Total Columns in Smoke Plumes Transported from the 2010 Russian Boreal Forest Fires to the Canadian High Arctic

In August 2010, simultaneous enhancements of aerosol optical depth and total columns of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C₂H₆) were observed at the Polar Environment Atmospheric Research Laboratory (PEARL, 80.05°N, ?86.42°W, 0.61 km above sea level, Eureka, Nunavut, Canada). Moderate Resolution Imaging Spectroradiometer (MODIS) hot spots, Ozone Monitoring Instrument (OMI) aerosol index maps, and Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) back-trajectories were used to attribute these enhancements to an intense boreal fire event occurring in Russia. A ground-based Fourier Transform InfraRed (FTIR) spectrometer at PEARL provided vertically integrated measurements of trace gases transported in smoke plumes. We derived HCN and C₂H₆ equivalent emission ratios with respect to CO of 0.0054?±?0.0022 and 0.0108?±?0.0036, respectively, and converted them into equivalent emission factors of 0.66?±?0.27 g kg^?1 and 1.47?±?0.50 g kg^?1 (in grams of gas per kilogram of dry biomass burnt, with one-sigma uncertainties). These emission factors add new observations to the relatively sparse datasets available and can be used to improve the simulation of biomass burning fire emissions in chemical transport models. These emission factors for the boreal forest are in agreement with the mean values recently reported in a compilation study.     

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.     

The characteristics of ultraviolet radiation in arid and semi-arid regions of China

Measurements of the broadband global solar radiation (R _S) and total ultraviolet radiation (the sum of UV-A and UV-B) were conducted from 2005 to 2010 at 9 sites in arid and semi-arid regions of China. These data were used to determine the temporal variability of UV and UV/R _S and their dependence on the water vapor content and clearness index. The dependence of UV/R _S on aerosol optical depth (AOD) and water vapor content was also investigated. In addition, a simple and efficient empirically model suited for all-weather conditions was developed to estimate UV from R _s. The annual average daily UV level in arid and semi-arid areas is 0.61 and 0.59 MJ m^?2 d^?1, respectively. The highest value (0.66?±?0.25 MJ m^?2 d^?1) was recorded at an arid area at Linze. The lowest value (0.53?±?0.22 MJ m^?2 d^?1) was recorded at a semi-arid area at Ansai. The highest daily value of UV radiation was measured in May, whereas the lowest value was measured in December. The monthly variation of the UV/R _s ratio ranged from 0.41 in Aksu to 0.35 in Qira. The monthly mean value of UV/R _s gradually increased from November and then decreased in August. A small decreasing trend of UV/R _s was observed in the arid and semi-arid regions due to recently increasing amounts of fine aerosol. A simple and efficient empirically model suit for all-weather condition was developed to estimate UV from R _s. The slope a and intercept b of the regression line between the estimated and measured values were close to 1 and zero, respectively. The relative error between the estimated and measured values was less than 11.5%. Application of the model to data collected from different locations in this region also resulted in reasonable estimates of UV.     

A semi-continuous measurement of gaseous ammonia and particulate ammonium concentrations in PM<Subscript>2.5</Subscript> in the ambient atmosphere

Ammonia has a short residence time in the atmosphere and rapidly neutralizes acid gases that occur near its source, requiring a rapid measurement system for ammonia and particulate ammonium concentrations to better understand their sources, temporal variation of ammonia emissions, and the formation of secondary ammonium aerosols. A semi-continuous measurement system, consisting of a diffusion scrubber, a particle growth chamber, an air-liquid separator, and a fluorescent detector, was developed to determine both gaseous ammonia (NH₃) and particulate ammonium (NH ₄ ⁺ ) in PM_2.5 in the ambient atmosphere of Gwangju, South Korea, during the months of March, April, July, and September of 2007. During the sampling periods, the average concentrations of ammonia and ammonium were found to be 2.33?±?1.29 μg/m³ and 1.89?±?0.99 μg/m³, respectively. Although the average gaseous ammonia concentration was highest in March, the particulate ammonium concentration was higher during the warmer season, reaching 2.08?±?1.07 μg/m³ and 2.32?±?0.94 μg/m³ in April and July, respectively, while only 1.68?±?0.61 μg/m³ in March and 1.24?±?0.99 μg/m³ in September. It is proposed that the higher availability of acid species during the warmer months produced a significant amount of particulate ammonium sulfate. Diurnal fluctuation of ammonia and ammonium during the warmer months showed that their peak time occurred at approximately 10:00 am. Both ammonia and ammonium concentrations were better correlated during the warmer months than during the cooler months. Further, the data suggest that the ammonia and ammonium were measured under well dispersed conditions, and multiple sources contributed to the ammonia at the sampling site.     

Formation of carbonyls and hydroperoxyenals (HPALDs) from the OH radical reaction of isoprene for low-NOx conditions: influence of temperature and water vapour content

The formation of gas-phase products from the reaction of OH radicals with isoprene for low-NO_x conditions ([NO_x] ≤ 10¹⁰ molecule cm^?3) has been studied in an atmospheric pressure flow tube (Institute for Tropospheric Research-Laminar Flow Tube, IfT-LFT) operating in the temperature range of 293–343 K and a relative humidity of < 0.5 % up to 50 %. The photolysis of H₂O₂ or ozone photolysis in the presence of water vapour served as the NO_x-free OH radical sources. For dry conditions at 293 K, the measured yields of methyl vinyl ketone (MVK), 0.07?±?0.02, and methacrolein (MACR), 0.12?±?0.04, were in reasonable agreement with literature data. Beside the C₄-carbonyls, further product signals have been attributed tentatively to glycolaldehyde, methylglyoxal, hydroxyacetone, 3-methylfuran, C₅-hydroperoxyenals (HPALDs) and C₅-hydroxy-hydroperoxides. A simplified, “classical” reaction mechanism without efficient HPALD production describes well the observed yield for MVK and MACR. Unexpected high MVK and MACR yields of up to 0.65 in total were measured under conditions of a relative humidity of 50 % using both OH radical sources and two different measurement techniques for organics (proton transfer reaction mass spectrometry and gas chromatography with flame ionization detector). The reaction mechanism applied is not able to describe the strong increase of MVK and MACR yields with increasing water vapour content. The signal attributed to the HPALDs showed a distinct rise of about one order of magnitude increasing the temperature from 293 K to 343 K. A rough estimate leads to a HPALD yield of 0.32 at 343 K with an uncertainty of a factor of two. The results of this study do not support a predominant formation of HPALDs under atmospheric conditions in low-NO_x areas. The surprisingly high MVK and MACR yields measured for a relative humidity of 50 % and the formation of glycolaldehyde, methylglyoxal and hydroxyacetone necessitate further research.     

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.     

Impacts of Aerosol Loading on Surface Precipitation from Deep Convective Systems over North Central Mongolia

The impacts of aerosol loading on surface precipitation from mid-latitude deep convective systems are examined using a bin microphysics model. For this, a precipitation case over north central Mongolia, which is a high-altitude inland region, on 21 August 2014 is simulated with aerosol number concentrations of 150, 300, 600, 1200, 2400, and 4800 cm^?3. The surface precipitation amount slightly decreases with increasing aerosol number concentration in the range of 150–600 cm^?3, while it notably increases in the range of 600–4800 cm^?3 (22% increase with eightfold aerosol loading). We attempt to explain why the surface precipitation amount increases with increasing aerosol number concentration in the range of 600–4800 cm^?3. A higher aerosol number concentration results in more drops of small sizes. More drops of small sizes grow through condensation while being transported upward and some of them freeze, thus increasing the mass content of ice crystals. The increased ice crystal mass content leads to an increase in the mass content of small-sized snow particles largely through deposition, and the increased mass content of small-sized snow particles leads to an increase in the mass content of large-sized snow particles largely through riming. In addition, more drops of small sizes increase the mass content of supercooled drops, which also leads to an increase in the mass content of large-sized snow particles through riming. The increased mass content of large-sized snow particles resulting from these pathways contributes to a larger surface precipitation amount through melting and collision-coalescence.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

Unique isoprene oxidation products demonstrate chlorine atom chemistry occurs in the Houston,Texas urban area

As part of the 2000 Texas Air Quality Study (TexAQS), we studied the isoprene oxidation process under ambient conditions to discern the presence of chlorine atom (Cl) chemistry in the Houston, Texas urban area. By measuring chloromethylbutenone (CMBO) and an isomer of chloromethylbutenal (CMBA), we clearly observed sixteen episodes of active Cl chemistry during the 24-day experiment. Estimated median Cl concentration during each of these episodes was between the detection limit of ~10² atoms cm⁻³ and 50 _{- 30} ^{+ 70} ×10⁴ 50_{ - 30}^{ + 70} \times {10^4} atoms cm⁻³. Cl concentration during all the episodes averaged 7.6 _{- 2.0} ^{+ 4.7} ×10⁴ 7.6_{ - 2.0}^{ + 4.7} \times {10^4} atoms cm⁻³ and thus amounted to less than 3% of the OH concentration during the same periods. During the episodes, the fraction of oxidation chemistry initiated by Cl ranged from 3–43% and was strongly dependent on the quantity and type of hydrocarbons present in the atmosphere. Because of its intermittent presence and low concentration, Cl is not a broadly influential oxidant in the Houston, Texas urban area.     

Continuous observations of water-soluble ions in PM2.5 at Mount Tai (1534 m a.s.l.) in central-eastern China

Near real-time measurements of PM_2.5 ionic compositions were performed at the summit of the highest mountain in the central-eastern plains in the spring and summer of 2007 in order to characterize aerosol composition and its interaction with clouds. The average concentrations of total water soluble ions were 27.5 and 36.7 μg?m^?3, accounting for 44% and 62% of the PM_2.5 mass concentration in the spring and summer, respectively. A diurnal pattern of SO ₄ ^2- , NH ₄ ⁺ and NO ₃ ^- was observed in both campaigns and attributed to the upslope/downslope transport of air mass and the development of the planetary boundary layer (PBL). The average SO₂ oxidation ratio (SOR) in summer was 57% (±27%), more than twice that in spring 24% (±16%); the fine nitrate oxidation ratio (NOR) was comparable in the two seasons (9?±?6% and 11?±?10% in summer and spring, respectively). This result indicates strong summertime production of sulfate aerosol. A principal component analysis shows that short-range and long-range transport of pollution, cloud processing, and crustal source were the main factors affecting the variability of the measured ions (and other trace gases and aerosols) at Mt. Tai. Strong indications of biomass burning were observed in summer. Cloud scavenging rates showed larger variations for different ions and in different cloud events. The elevated concentrations of the water soluble ions at Mt. Tai indicate serious aerosol pollution over the North China plain of eastern China.