Three-dimensional characterization of the ammonia plume from a beef cattle feedlot

In Canada approximately 45% of ammonia (NH₃) emissions are attributed to dairy and beef cattle industries. The present study focused on NH₃ emissions from a beef feedlot with a one-time capacity of 17,220 head. The aim was to improve the Canadian NH₃ emission inventories and air quality forecasting capabilities. A Cessna 207, equipped with a fast-response NH₃/NO_y detector and a quadrupole aerosol mass spectrometer, was flown in a grid pattern covering an area of 8 × 8 km centered on a feedlot (800 × 800 m) at altitudes ranging from 30 to 300 m above ground. Stationary ground measurements of NH₃ concentration and turbulence parameters were made downwind of the feedlot. Three flights were conducted under varying meteorological conditions, ranging from very calm to windy with near-neutral stratification. NH₃ mixing ratios up to 100 ppbv were recorded on the calm day, up to 300 m above ground. An average feedlot NH₃ emission rate of 76 ± 4 μg m^?2 s^?1 (equivalent to 10.2 g head^?1 h^?1) was estimated. Characteristics of the measured NH₃ plume were compared to those predicted by a Lagrangian dispersion model. The spatially integrated pattern of NH₃ concentrations predicted and measured agreed but the measured was often more complex than the predicted spatial distribution. The study suggests that the export of NH₃ through advection accounted for about 90% of the emissions from the feedlot, chemical transformation was insignificant, and dry deposition accounted for the remaining 10%.     

A four-year size-segregated characterization study of particles PM10, PM2.5 and PM1 depending on air mass origin at Melpitz

PM₁₀ measurements were started in November 1992 at Melpitz site. The mean PM₁₀ concentration in 1993 was 38 μg m^?3 in the summer season (May until October) and about 44 μg m^?3 in the winter season (November until April). The mean PM₁₀ level decreased until 1999 and varies now in ranges from 20–34 μg m^?3 to 17–24 μg m^?3 (minimum and maximum mean values for 1999–2008) in winter and summer seasons, respectively. High volume filter samples of particles PM₁₀, PM_2.5 and PM₁ were characterized for mass, water-soluble ions, organic and elemental carbon from 2004 until 2008. The percentage of PM_2.5 in PM₁₀ varies between summer (71.6%) and winter seasons (81.9%). Mean concentrations of PM₁₀, PM_2.5 and PM₁ in Melpitz were 20, 15, and 13 μg m^?3 in 2004, 22, 18, and 13 μg m^?3 in 2005, 24, 19, and 12 μg m^?3 in 2006 and 22, 17, and 12 μg m^?3 in 2007, respectively. In the four winters the rural background concentration PM₁₀ at Melpitz exceeded the daily 50 μg m^?3 limit for Europe on 8, 8, 7 and 6 days, respectively.Findings for a simple two-sector-classification of the samples (May 2004 until April 2008) using 96-h backward trajectories for the identification of source regions are: Air masses were transported most of time (60%) from the western sector and secondly (17%) from the eastern sector. The lowest daily mean mass concentration PM₁₀ were found during western inflow in summer (17 μg m^?3) containing low amounts of sulphate (2.4 μg m^?3), nitrate (1.7 μg m^?3), ammonium (1.1 μg m^?3) and TC (3.7 μg m^?3). In opposite the highest mean mass concentration PM₁₀ was found during eastern inflow in winter (35 μg m^?3) with high amounts of sulphate (6.1 μg m^?3), nitrate (5.4 μg m^?3), ammonium (3.8 μg m^?3) and TC (9.4 μg m^?3). An estimation of secondary formed OC (SOA) shows 0.8–0.9 μg m^?3 for air masses from West and 2.1–2.2 μg m^?3 from East. The seasonal difference can be neglected.The half-hourly measurements of the particle mass concentration PM₁₀ evaluated as mean daily courses using a TEOM^® show low values (14–21 μg m^?3) in summer and winter for air masses transported from West and the highest concentrations (31–38 μg m^?3) in winter for air masses from East.The results demonstrate the influence of meteorological parameters on long-range transport, secondary particle mass formation and re-emission which modify mass concentration and composition of PM₁₀, PM_2.5 and PM₁. Melpitz site is located in the East of Germany faraway from strong local anthropogenic emissions (rural background). Therefore, this site is suitable for investigation of the influence of long-range transport of air pollution in continental air masses from the East with source regions inside and outside of the European Union.     

Long-range transport episodes of fine particles in southern Finland during 1999–2007

The frequency, strength and sources of long-range transport (LRT) episodes of fine particles (PM_2.5) were studied in southern Finland using air quality monitoring results, backward air mass trajectories, remote sensing of fire hot spots, transport and dispersion modelling of smoke and chemical analysis of particle samples (black carbon, monosaccharide anhydrides, oxalate, succinate, malonate, SO₄^2?, NO₃^?, K⁺ and NH₄⁺). At an urban background site in Helsinki, the daily WHO guideline value (24-h PM_2.5 mean 25 μg m^?3) was exceeded during 1–7 LRT episodes per year in 1999–2007. The 24-h mean maximum concentrations varied between 25 and 49 μg m^?3 during the episodes, which was 3–6 times higher than the local mean concentration (8.7 μg m^?3) in 1999–2007. The highest particle concentrations (max. 1-h mean 163 μg m^?3) and the longest episodes (max. 9 days) were mainly caused by the emissions from open biomass burning, especially during springs and late-summers in 2002 and 2006. During the period 2001–2007, the satellite remote sensing of active fire hot spots and transport and dispersion modelling of smoke indicated that approximately half of the episodes were caused partly by the emissions from wildfires and/or agricultural waste burning in fields in Eastern Europe, especially in Russia, Belarus and Ukraine. Other episodes were mainly caused by the LRT of ordinary anthropogenic pollutants, e.g. from energy production, traffic, industry and wood combustion. During those ‘other episodes’, air masses also arrived from Eastern Europe, including Poland. The highest concentrations of biomass-burning tracers, such as monosaccharide anhydrides (levoglucosan + mannosan + galactosan) and K⁺, were observed during open biomass-burning episodes, but quite high values were also measured during some winter episodes due to wood combustion emissions. Our results indicate that open biomass burning in Eastern Europe causes high fine particle concentration peaks in large areas of Europe almost every year.     

Experimental and statistical analyses to characterize in-vehicle fine particulate matter behavior inside public transit buses operating on B20-grade biodiesel fuel

This paper presents results from an in-vehicle air quality study of public transit buses in Toledo, Ohio, involving continuous monitoring, and experimental and statistical analyses to understand in-vehicle particulate matter (PM) behavior inside buses operating on B20-grade biodiesel fuel. The study also focused on evaluating the effects of vehicle’s fuel type, operating periods, operation status, passenger counts, traffic conditions, and the seasonal and meteorological variation on particulates with aerodynamic diameter less than 1 micron (PM_1.0). The study found that the average PM_1.0 mass concentrations in B20-grade biodiesel-fueled bus compartments were approximately 15 μg m^?3, while PM_2.5 and PM₁₀ concentration averages were approximately 19 μg m^?3 and 37 μg m^?3, respectively. It was also observed that average hourly concentration trends of PM_1.0 and PM_2.5 followed a “μ-shaped” pattern during transit hours.Experimental analyses revealed that the in-vehicle PM_1.0 mass concentrations were higher inside diesel-fueled buses (10.0–71.0 μg m^?3 with a mean of 31.8 μg m^?3) as compared to biodiesel buses (3.3–33.5 μg m^?3 with a mean of 15.3 μg m^?3) when the windows were kept open. Vehicle idling conditions and open door status were found to facilitate smaller particle concentrations inside the cabin, while closed door facilitated larger particle concentrations suggesting that smaller particles were originating outside the vehicle and larger particles were formed within the cabin, potentially from passenger activity. The study also found that PM_1.0 mass concentrations at the back of bus compartment (5.7–39.1 μg m^?3 with a mean of 28.3 μg m^?3) were higher than the concentrations in the front (5.7–25.9 μg m^?3 with a mean of 21.9 μg m^?3), and the mass concentrations inside the bus compartment were generally 30–70% lower than the just-outside concentrations. Further, bus route, window position, and time of day were found to affect the in-vehicle PM concentrations significantly. Overall, the in-vehicle PM_1.0 concentrations inside the buses operating on B20-grade biodiesel ranged from 0.7 μg m^?3 to 243 μg m^?3, with a median of 11.6 μg m^?3.Statistical models developed to study the effects of vehicle operation and ambient conditions on in-vehicle PM concentrations suggested that while open door status was the most important influencing variable for finer particles and higher passenger activity resulted in higher coarse particles concentrations inside the vehicle compartments, ambient PM concentrations contributed to all PM fractions inside the bus irrespective of particle size.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Chemical and strontium isotope characterization of rainwater in Beijing,China

Major ion concentrations and Sr isotope ratios (⁸⁷Sr/⁸⁶Sr) were measured in rainwater samples collected at an urban site in Beijing over a period of one year. The pH value and major ion concentrations of samples varied considerably, and about 50% of the rainwater studied here were acidic rain with pH values less than 5.0. Ca²⁺ and NH₄⁺ were the dominant cations in rainwaters and their volume weighted mean (VWM) values were 608 μeq l^?1 (14–1781 μeq l^?1) and 186 μeq l^?1 (48–672 μeq l^?1), respectively. SO₄^2? was the predominant anion with VWM value of 316 μeq l^?1 (65–987 μeq l^?1), next was NO₃^? with VWM value of 109 μeq l^?1 (30–382 μeq l^?1).Using Na as an indicator of marine origin, and Al for the terrestrial inputs, the proportions of sea salt and terrestrial elements were estimated from elemental ratios. More than 99% of Ca²⁺ and 98% of SO₄^2? in rainwater samples are non-sea-salt origin. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize the different sources based on the data sets of this study and those from literatures. Such sources include sea salts (⁸⁷Sr/⁸⁶Sr～0.90917), soluble soil dust minerals originating from either local or the desert and loess areas (～0.7111), and anthropogenic sources (fertilizers, coal combustion and automobile exhausts). The high concentrations of alkaline ions (mainly Ca²⁺) in Beijing atmosphere have played an important role to neutralize the acidity of rainwater. However, it is worth noting that there is a remarkable acidification trend of rainwater in Beijing recent years.     

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Two-week average concentrations of ozone (O₃), nitric acid vapor (HNO₃) and ammonia (NH₃) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O₃, 1.0-3.8 μg m⁻³ for HNO₃, and 2.6-5.2 μg m⁻³ for NH₃. Calculated O₃ exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha⁻¹ for maximum values, and 0.4-8 kg N ha⁻¹ for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O₃ human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O₃.     

Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

Year-long continuous personal exposure to PM2.5 recorded by a fast responding portable nephelometer

Personal exposure to particulate matter of aerodynamic diameter under 2.5 μm (PM_2.5) was monitored using a DustTrak nephelometer. The battery-operated unit, worn by an adult individual for a period of approximately one year, logged integrated average PM_2.5 concentrations over 5 min intervals. A detailed time-activity diary was used to record the experimental subject’s movement and the microenvironments visited. Altogether 239 days covering all the months (except April) were available for the analysis. In total, 60 463 acceptable 5-min averages were obtained. The dataset was divided into 7 indoor and 4 outdoor microenvironments. Of the total time, 84% was spent indoors, 10.9% outdoors and 5.1% in transport. The indoor 5-min PM_2.5 average was higher (55.7 μg m^?3) than the outdoor value (49.8 μg m^?3). The highest 5-min PM_2.5 average concentration was detected in restaurant microenvironments (1103 μg m^?3), the second highest 5-min average concentration was recorded in indoor spaces heated by stoves burning solid fuels (420 μg m^?3). The lowest 5-min mean aerosol concentrations were detected outdoors in rural/natural environments (25 μg m^?3) and indoors at the monitored person’s home (36 μg m^?3). Outdoor and indoor concentrations of PM_2.5 measured by the nephelometer at home and during movement in the vicinity of the experimental subject’s home were compared with those of the nearest fixed-site monitor of the national air quality monitoring network. The high correlation coefficient (0.78) between the personal and fixed-site monitor aerosol concentrations suggested that fixed-site monitor data can be used as proxies for personal exposure in residential and some other microenvironments. Collocated measurements with a reference method (β-attenuation) showed a non-linear systematic bias of the light-scattering method, limiting the use of direct concentration readings for exact exposure analysis.     

Deposition processes of ionic constituents to snow cover

Atmospheric deposition is an important removal process of aerosol particles and gases from the atmosphere. To elucidate the relative contributions of wet and dry processes and in-cloud and below-cloud scavenging based on deposition amounts in winter at Mt. Tateyama, central Japan, we obtained daily samples (December, 2006–March, 2007) of size-segregated aerosol particles and precipitation at Senjyugahara (SJ; 475 m a.s.l.) and vertical samples of spring snow cover at Murododaira (MR, 2450 m a.s.l., 13 km distance from SJ) on the western flank of Mt. Tateyama. The NH₄⁺ and nssSO₄^2? in aerosols were mostly found in the fine fraction (<2 μm), although Na⁺, NO₃^?, and nssCa²⁺ were mainly detected in the coarse fraction (>2 μm). Average ionic concentrations (μg g^?1) in precipitation at SJ were higher about 3.8 for Na⁺ and nssCa²⁺, 3.4 for NO₃^?, 3.7 for NH₄⁺, 2.5 for nssSO₄^2? than those at MR, whereas cumulative precipitation amounts at SJ and MR were, respectively, 84 and 175 cm of water equivalent. Wet and dry deposition amounts during the study period were estimated for sites using size-segregated aerosol data, winter averages of HNO₃, NH₃, and SO₂ concentrations, and dry deposition velocities. Particle-dry deposition comprised about 3% (Na⁺) to 11% (NH₄⁺) of the total deposition at MR. The maximum amounts of gas dry deposition were estimated, respectively, as 4, 13, and 3% of the total deposition at MR for NH₄⁺, NO₃^?, and nssSO₄^2?. The relative contributions of below-cloud scavenging (BCS) between MR and SJ were estimated as considering the wet only deposition amount at MR. Higher contributions of BCS were obtained for Na⁺ (56%) and nssCa²⁺ (45%), whereas BCSs for NH₄⁺, NO₃^?, and nssSO₄^2? were lower than 28%. Ionic constituents existing predominantly in the coarse fraction showed a large contribution of BCS.     

Combined effects of nitrogen addition and organic matter manipulation on soil respiration in a Chinese pine forest

The response of soil respiration (Rs) to nitrogen (N) addition is one of the uncertainties in modelling ecosystem carbon (C). We reported on a long-term nitrogen (N) addition experiment using urea (CO(NH₂)₂) fertilizer in which Rs was continuously measured after N addition during the growing season in a Chinese pine forest. Four levels of N addition, i.e. no added N (N0: 0 g N m⁻² year⁻¹), low-N (N1: 5 g N m⁻² year⁻¹), medium-N (N2: 10 g N m⁻² year⁻¹), and high-N (N3: 15 g N m⁻² year⁻¹), and three organic matter treatments, i.e. both aboveground litter and belowground root removal (LRE), only aboveground litter removal (LE), and intact soil (CK), were examined. The Rs was measured continuously for 3 days following each N addition application and was measured approximately 3–5 times during the rest of each month from July to October 2012. N addition inhibited microbial heterotrophic respiration by suppressing soil microbial biomass, but stimulated root respiration and CO₂ release from litter decomposition by increasing either root biomass or microbial biomass. When litter and/or root were removed, the “priming” effect of N addition on the Rs disappeared more quickly than intact soil. This is likely to provide a point of view for why Rs varies so much in response to exogenous N and also has implications for future determination of sampling interval of Rs measurement.

     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Seabird feathers as monitors of the levels and persistence of heavy metal pollution after the Prestige oil spill

We measured heavy metal concentrations in yellow-legged gulls (n = 196) and European shags (n = 189) in order to assess the temporal pattern of contaminant exposure following the Prestige oil spill in November 2002. We analysed Pb, Cu, Zn, Cr, Ni and V levels in chick feathers sampled at four colonies during seven post-spill years (2003-2009), and compared results with pre-spill levels obtained from feathers of juvenile shag corpses (grown in spring/summer 2002). Following the Prestige wreck, Cu (4.3-10 μg g⁻¹) and Pb concentrations (1.0-1.4 μg g⁻¹) were, respectively, between two and five times higher than pre-spill levels (1.5-3.6 and 0.1-0.4 μg g⁻¹), but returned to previous background concentrations after three years. Our study highlights the suitability of chick feathers of seabirds for assessing the impact of oil spills on heavy metal contamination, and provides the best evidence to date on the persistence of oil pollution after the Prestige incident.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Physicochemical variations in atmospheric aerosols recorded at sea onboard the Atlantic–Mediterranean 2008 Scholar Ship cruise (Part I): Particle mass concentrations,size ratios,and main chemical components

We report on ambient atmospheric aerosols present at sea during the Atlantic–Mediterranean voyage of Oceanic II (The Scholar Ship) in spring 2008. A record was obtained of hourly PM₁₀, PM_2.5, and PM₁ particle size fraction concentrations and 24-h filter samples for chemical analysis which allowed for comparison between levels of crustal particles, sea spray, total carbon, and secondary inorganic aerosols. On-board monitoring was continuous from the equatorial Atlantic to the Straits of Gibraltar, across the Mediterranean to Istanbul, and back via Lisbon to the English Channel. Initially clean air in the open Atlantic registered PM₁₀ levels <10 μg m^?3 but became progressively polluted by increasingly coarse PM as the ship approached land. Away from major port cities, the main sources of atmospheric contamination identified were dust intrusions from North Africa (NAF), smoke plumes from biomass burning in sub-Saharan Africa and Russia, industrial sulphate clouds and other regional pollution sources transported from Europe, sea spray during rough seas, and plumes emanating from islands. Under dry NAF intrusions PM₁₀ daily mean levels averaged 40–60 μg m^?3 (30–40 μg m^?3 PM_2.5; c. 20 μg m^?3 PM₁), peaking briefly to >120 μg m^?3 (hourly mean) when the ship passed through curtains of higher dust concentrations amassed at the frontal edge of the dust cloud. PM₁/PM₁₀ ratios ranged from very low during desert dust intrusions (0.3–0.4) to very high during anthropogenic pollution plume events (0.8–1).     

Growing season methane budget of an Inner Mongolian steppe

We present a methane (CH₄) budget for the area of the Baiyinxile Livestock Farm, which comprises approximately 1/3 of the Xilin river catchment in central Inner Mongolia, P.R. China. The budget calculations comprise the contributions of natural sources and sinks as well as sources related to the main land-use in this region (non-nomadic pastoralism) during the growing season (May–September). We identified as important CH₄ sources floodplains (mean 1.55 ± 0.97 mg CH₄–C m^?2 h^?1) and domestic ruminants, which are mainly sheep in this area. Within the floodplain significant differences between investigated positions were detected, whereby only positions close-by the river or bayous emitted large amounts of CH₄ (mean up to 6.21 ± 1.83 mg CH₄–C m^?2 h^?1). Further CH₄ sources were sheepfolds (0.08–0.91 mg CH₄–C m^?2 h^?1) and pasture faeces (1.34 ± 0.22 mg CH₄–C g^?1 faeces dry weight), but they did not play a significant role for the CH₄ budget. In contrast, dung heaps were not a net source of CH₄ (0.0 ± 0.2 for an old and 0.0 ± 0.3 μg CH₄–C kg^?1 h^?1 for a new dung heap). Trace gas measurements along two landscape transects (volcano, hill slope) revealed expectedly a mean CH₄ uptake (volcano: 76.5 ± 4.3; hill: 28.3 ± 5.3 μg CH₄–C m^?2 h^?1), which is typical for the aerobic soils in this and other steppe ecosystems. The observed fluxes were rarely influenced by topography.The CH₄ emissions from the floodplain and the sheep were not compensated by the CH₄ oxidation of aerobic steppe soils and thus, this managed semi-arid grassland did not serve as a terrestrial sink, but as a source for this globally important greenhouse gas. The source strength amounted to 1.5–3.6 kg CH₄–C ha^?1 during the growing season, corresponding to 3.5–8.7 kg C ha^?1 yr^?1.     

Quantitative chemical composition and characteristics of aerosols over western India: One-year record of temporal variability

One-year quantitative chemical data set consisting of water-soluble constituents (NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₃^?, SO₄^2? and HCO₃^?), crustal and trace elements (Al, Fe, Ca, Mg, K, Mn, Zn, Pb) and carbonaceous species (OC, EC) in ambient aerosols, collected over an urban site located in a high-dust semi-arid region of western India, reveals excellent linear relationship (r² = 0.92; slope = 0.96 ± 0.05) between gravimetrically assessed TSP (total suspended particulates) and chemically analyzed aerosol mass. The TSP abundance ranging from 60 to 250 μg m^?3, over a period of 12 months (January–December), is dominated by mineral dust (～70%); whereas contribution from sea-salts, anthropogenic and carbonaceous species exhibits significant temporal variability depending upon the wind regimes. The mineral dust is enriched in Ca, Mg and Fe with respect to upper continental crust (UCC); whereas Zn and Pb exhibit a characteristic anthropogenic source and high enrichment factors. The carbonaceous species show significant seasonality; with dominance of OC (range: 4.6–28 μg m^?3; average: 12.8 μg m^?3; SD: 6.8) and minor contribution from EC (range: 0.3–4.4 μg m^?3; average: 2.4 μg m^?3; SD: 1.4). The observed concentrations are significantly lower than those reported for the metro cities in South Asia but the OC/EC ratios (range: 4.3–35; average: 8.3; SD: 5.7) are significantly higher than the characteristic ratio (～2–4) reported for the urban atmosphere. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and climate change. This study could also be useful in understanding the physical and optical aerosol properties documented from the same site and thus, in validating regional climate models.     

Copper-induced response of physiological parameters and antioxidant enzymes in the aquatic macrophyte Potamogeton pusillus

Bioaccumulation and toxicity of copper was evaluated on Potamogeton pusillus L. The effect of copper (5–100 μg L^?1) applied for several days was assessed by measuring changes in the chlorophyll's, phaeophytin's, malondialdehyde, electrical conductivity, glutathione peroxidase (GPX), glutathione reductase (GR) and guaiacol peroxidase (POD) activities. Plants accumulated copper with a maximum of 162 μg g^?1 dw after 7-days exposure at 100 μg L^?1, however most of the metal was accumulated after 1-day exposure. The toxic effect caused by Cu was evident by the reduction of photosynthetic pigments, increase of malondialdehyde and electrical conductivity. P. pusillus shows Cu-induced oxidative stress by modulating antioxidant enzymes like GPX, GR and POD. Antioxidant enzymes activity increased significantly after exposure to 40 μg L^?1 during 24 h, followed by a drop at longer times. Thus, P. pusillus is proposed as a good biomonitor for the assessment of metal pollution in aquatic ecosystems.     

Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent

A nanocrystalline TiO₂-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L^?1 As(III), 246 μg L^?1 As(V), 151 μg L^?1 MMA, and 202 μg L^?1 DMA was continuously passed through a TiO₂ filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L^?1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).