Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.     

Natural and anthropogenic methane sources in New England

We have recently completed a methane emissions inventory for the New England region. Methane emissions were calculated to be 0.91 Tg yr^-1, with wetlands and landfills dominating all other sources. Wetlands are estimated to produce 0.33 Tg CH₄ yr^-1, of which 74% come from Maine. Active landfills emit an estimated 0.28 Tg CH₄ yr^-1, 60% of which are generated from twelve landfills. Although uncertainty in the estimate is greater, emissions from closed landfills are on the same order of magnitude as active landfills and wetlands; 0.25 Tg CH₄ yr^-1. Sources of moderate magnitude include ruminant animals (0.05 Tg CH₄ yr^-1) and residential wood combustion (0.03 Tg CH₄ yr^-1). Motor vehicles, natural gas, and wastewater treatment make only minor contributions. New England is heavily forested and the soil uptake of atmospheric methane in upland forests, 0.06 Tg CH₄ yr^-1, decreases emissions from soils by about 18%. Although uncertainties remain, our estimates indicate that even in a highly urbanized region such as New England, natural sources of methane make the single greatest contribution to total emissions, with state totals varying between 8% (Massachusetts) and 92% (Maine). Because emissions from only a few large landfills dominate anthropogenic sources, mitigation strategies focused on these discrete point sources should result in significant improvements in regional air quality. Current federal regulations mandate landfill gas collection at only the largest sites. Expanding recovery efforts to moderately sized landfills through either voluntary compliance or further regulations offers the best opportunity to substantially reduce atmospheric methane in New England. In the short term, however, the large contribution from closed, poorly regulated landfills may make the attribution of air quality improvements difficult. Mitigation efforts toward these landfills should also be a priority.     

China's grazed temperate grasslands are a net source of atmospheric methane

A budget for the methane (CH₄) cycle in the Xilin River basin of Inner Mongolia is presented. The annual CH₄ budget in this region depends primarily on the sum of atmospheric CH₄ uptake by upland soils, emission from small wetlands, and emission from grazing ruminants (sheep, goats, and cattle). Flux rates for these processes were averaged over multiple years with differing summer rainfall. Although uplands constitute the vast majority of land area, they consume much less CH₄ per unit area than is emitted by wetlands and ruminants. Atmospheric CH₄ uptake by upland soils was ?3.3 and ?4.8 kg CH₄ ha^?1 y^?1 in grazed and ungrazed areas, respectively. Average CH₄ emission was 791.0 kg CH₄ ha^?1 y^?1 from wetlands and 8.6 kg CH₄ ha^?1 y^?1 from ruminants. The basin area-weighted average of all three processes was 6.8 kg CH₄ ha^?1 y^?1, indicating that ruminant production has converted this basin to a net source of atmospheric CH₄. The total CH₄ emission from the Xilin River basin was 7.29 Gg CH₄ y^?1. The current grazing intensity is about eightfold higher than that which would result in a net zero CH₄ flux. Since grazing intensity has increased throughout western China, it is likely that ruminant production has converted China's grazed temperate grasslands to a net source of atmospheric CH₄ overall.     

Methane emission from free-ranging sheep: a comparison of two measurement methods

Methane emissions from a flock of 14, 1-year old sheep grazing on a grass and legume pasture were measured using a micrometeorological mass-balance method and a sulphur hexaflouride (SF₆) tracer technique. The former measured the mean emission, over 45 min intervals, from all the sheep within a fenced 24 m×24 m enclosure, from the enrichment of methane (CH₄) in air as it passed over the sheep. The tracer technique measured emissions from a subset of 7 individual animals over 24 h periods from measurements of CH₄ and SF₆ concentrations in air exhaled by the sheep, and from the known rate of release of SF₆ from small permeation tubes placed in the animals’ rumens. Both methods gave highly similar results for 4 out of 5 days. When the species composition of dietary intake was steady during the last two days of measurement, the mean emission rate from the mass-balance method was 11.9±1.5 (SEM) g CH₄ sheep^-1 d^-1, while the rate from the tracer technique was 11.7±0.4 (SEM) g CH₄ sheep^-1 d^-1. These rates are for sheep with mean live mass of 27 kg, with a measured dry matter intake of 508 g sheep^-1 d^-1 and pasture dry matter digestibility of 69.5%. There was close agreement between these measurements and estimates from algorithms used to predict methane emissions from sheep for the Australian National Greenhouse Gas Inventory.     

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by ²¹⁰Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m^?2 yr^?1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m^?2 yr^?1. The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m^?2 yr^?1 for preindustrial and 11.7 μg m^?2 yr^?1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m^?2 yr^?1, which are lower than the modern sediment-based estimate of 11.7 μg m^?2 yr^?1, perhaps owing to inputs of dry-deposited Hg to the lakes.     

Trace gas variations at Cape Point,South Africa,during May 1997 following a regional biomass burning episode

During the continuous monitoring of atmospheric parameters at the station Cape Point (34°S, 18°E), a smoke plume originating from a controlled fire of 30-yr-old fynbos was observed on 6 May 1997. For this episode, which was associated with a nocturnal inversion and offshore airflow, atmospheric parameters (solar radiation and meteorological data) were considered and the levels of various trace gases compared with those measured at Cape Point in maritime air. Concentration maxima in the morning of 6 May for CO₂, CO, CH₄ and O₃ amounted to 370.3 ppm, 491 ppb, 1730 ppb and 47 ppb, respectively, whilst the mixing ratios of several halocarbons (F-11, F-12, F-113, CCl₄ and CH₃CCl₃) remained at background levels. In the case of CO, the maritime background level for this period was exceeded by a factor of 9.8. Differences in ozone levels of up to 5 ppb between air intakes at 4 and 30 m above the station (located at 230 m above sea level) indicated stratification of the air advected to Cape Point during the plume event. Aerosols within the smoke plume caused the signal of global solar radiation and UV–A to be attenuated from 52.4 to 13.0 mW cm⁻² and from 2.3 to 1.3 mW cm⁻², respectively, 5 h after the trace gases had reached their maxima. Emission ratios (ERs) calculated for CO and CH₄ relative to CO₂ mixing ratios amounted to 0.042 and 0.0040, respectively, representing one of the first results for fires involving fynbos. The CO ER is somewhat lower than those given in the literature for African savanna fires (average ER=0.048), whilst for CH₄ the ER falls within the range of ERs reported for the flaming (0.0030) and smouldering phases (0.0055) of savanna fires. Non-methane hydrocarbon (NMHC) data obtained from a grab sample collected during the plume event were compared to background levels. The highest ERs (ΔNMHC/ΔCH₄) have been obtained for the C₂–C₃ hydrocarbons (e.g. ethene at 229.3 ppt ppb⁻¹), whilst the C₄–C₇ hydrocarbons were characterised by the lowest ERs (e.g. n-hexane at 1.0 and n-pentane at 0.8 ppt ppb⁻¹).     

Air–water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast,Taiwan

Air–water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29 ± 0.59 ng m^?3 and 2.17 ± 1.19 ng L^?1 respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m^?2 d^?1 volatilization of phenanthrene during the rainy season with storm–water discharges raising dissolved phase concentration, to 67 ng m^?2 d^?1 absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air–water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m^?2 yr^?1 for pyrene to 50 μg m^?2 yr^?1 for phenanthrene and the absorption fluxes ranged from ?2.6 μg m^?2 yr^?1 for chrysene to ?3.5 μg m^?2 yr^?1 for fluoranthene.     

Methane emissions from lakes and floodplains in Pantanal,Brazil

To evaluate the tropical wetlands contribution to the methane (CH₄) burden better, field campaigns were performed during 2004 and 2005 near the Miranda River, in five sites inside the Brazilian Pantanal region. The CH₄ fluxes were determined using the static chamber technique. Environmental variables that may affect CH₄ emissions, as the water depth, the water and air temperatures were also measured. The overall average of the 320 individual CH₄ flux measurements made between March/2004 and March/2005 was 142±314 mg CH₄ m⁻² d⁻¹, which is a value near the ones observed in other tropical flooded regions. About 47% of the fluxes measurements presented nonlinear increases in the chamber concentrations, which were assumed to be linked to CH₄ losses through bubbles. The bubble flux represented about 90% of the total CH₄ losses in the measurements and ranged from 1 to 2187 mg CH₄ m⁻² d⁻¹ with an average of 292±410 mg CH₄ m⁻² d⁻¹ (median: 153 mg CH₄ m⁻² d⁻¹). The diffusive flux ranged from 1 to 124 mg CH₄ m⁻² d⁻¹, with an average of 10±17 mg CH₄ m⁻² d⁻¹ (median: 5 mg CH₄ m⁻² d⁻¹). The fluxes from lakes were smaller than those observed in the floodplains, where the flooding was more dependent on the seasonal cycle. The diffusive flux showed a slight, but not statistically significant seasonal variation, following the seasonal variation of the flooding of the Pantanal region. A rough estimative of the total annual CH₄ emission shows that the contribution of the Pantanal is about 3.3 Tg CH₄ yr⁻¹, which represents about 3.3% of the total CH₄ emissions estimated to be originated in wetlands ecosystems. It may be a conservative estimate, which may present a large interannual variation, since it was obtained during one of the lowest flood of the Pantanal in recent years.     

Methane emissions from an anaerobic swine lagoon

Gaseous methane (CH₄) emissions from a swine waste holding lagoon were determined periodically during the year. Micrometeorological techniques were used in order that emission rates from the lagoon were measured under ambient conditions with little disturbance to the natural environment. During the cold winter measurement period, CH₄ fluxes were linearly related to lagoon water temperature below 22°C (r=0.87). During warmer measurement periods, both water and air temperatures and windspeed affected emissions rates. In general, flux rates followed a diurnal pattern with greater fluxes during the day when both temperature and windspeed were greatest. Mathematical models using air and water temperature and windspeed factors could explain 47 to 75% of the variation in fluxes. Daily emission rates ranged from 1 to 500 kg CH₄ ha⁻¹ d⁻¹. The average flux for the year was 52.3 kg CH₄ ha⁻¹ d⁻¹ which corresponded to about 5.6 kg CH₄ animal⁻¹ yr⁻¹ from the primary lagoon.     

Historical changes in atmospheric nitrogen deposition to Cape Cod,Massachusetts, USA

We reconstructed the historical trends in atmospheric deposition of nitrogen to Cape Cod, Massachusetts, from 1910 to 1995 by compiling data from literature sources, and adjusting the data for geographical and methodological differences. The reconstructed data suggest that NO₃-N wet deposition to this region increased from a low of 0.9 kg N ha⁻¹ yr⁻¹ in 1925 to a high of approximately 4 kg N ha⁻¹ yr⁻¹ around 1980. The trend in NO₃-N deposition has remained since the early 1980s at around 3.6 kg N ha⁻¹ yr⁻¹. In contrast, NH₄-N wet deposition decreased from more than 4 kg N ha⁻¹ yr⁻¹ in the mid 1920s to about 1.5 kg N ha⁻¹ yr⁻¹ from the late-1940s until today. Emissions of NO_x-N in the Cape Cod airshed increased at a rate of 2.1 kg N ha⁻¹ per decade since 1910, a rate that is an order of magnitude higher than NO₃-N deposition. Estimates of NH₃ emissions to the northeast United States and Canada have decreased slightly throughout the century, but the decrease in reconstructed N-NH₄⁺ deposition rates does not parallel emissions estimates. The trend in reconstructed total nitrogen deposition suggests an overall increase through the century at a rate of 0.26 kg N ha⁻¹ per decade. This overall increase in deposition may expose coastal forests to rates of nitrogen addition that, if exceeded, could induce nitrogen saturation and increase nitrogen loads to adjoining estuaries.     

Biomass consumption and CO2, CO and main hydrocarbon gas emissions in an Amazonian forest clearing fire

Biomass consumption and CO₂, CO and hydrocarbon gas emissions in an Amazonian forest clearing fire are presented and discussed. The experiment was conducted in the arc of deforestation, near the city of Alta Floresta, state of Mato Grosso, Brazil. The average carbon content of dry biomass was 48% and the estimated average moisture content of fresh biomass was 42% on wet weight basis. The fresh biomass and the amount of carbon on the ground before burning were estimated as 528 t ha^?1 and 147 t ha^?1, respectively. The overall biomass consumption for the experiment was estimated as 23.9%. A series of experiment in the same region resulted in average efficiency of 40% for areas of same size and 50% for larger areas. The lower efficiency obtained in the burn reported here occurred possibly due to rain before the experiment. Excess mixing ratios were measured for CO₂, CO, CH₄, C₂–C₃ aliphatic hydrocarbons, and PM_2.5. Excess mixing ratios of CH₄ and C₂–C₃ hydrocarbons were linearly correlated with those of CO. The average emission factors of CO₂, CO, CH₄, NMHC, and PM_2.5 were 1,599, 111.3, 9.2, 5.6, and 4.8 g kg^?1 of burned dry biomass, respectively. One hectare of burned forest released about 117,000 kg of CO₂, 8100 kg of CO, 675 kg of CH₄, 407 kg of NMHC and 354 kg of PM_2.5.     

Definition of yearly emission factor of dust and greenhouse gases through continuous measurements in swine husbandry

The object of this study was to develop an accurate estimation method to evaluate the contribution of the various compartments of swine husbandry to dust and GHG (greenhouse gases, CO₂, CH₄ and N₂O) emission into the atmosphere during one year of observation.A weaning, a gestation, a farrowing and a fattening room in an intensive pig house were observed in three different periods (Autumn–Winter, Springtime and Summer, monitoring at least 60% of each period (20% at the beginning, in the middle and at the end) of each cycle).During monitoring, live weight, average live weight gain, number of animals and its variation, type of feed and feeding time were taken into account to evaluate their influence on PM₁₀, or the fraction of suspended particulate matter with an aerodynamic diameter less than or equal to 10 μm [Emission Inventory Guidebook, 2007. B1100 Particle Emissions from Animal Husbandry Activities. Available from: <http://reports.eea.europa.eu/EMEPCORINAIR5/en/B1100vs1.pdf> (accessed October 2008)] and to define GHG emission.The selected piggery had a ventilation control system using a free running impeller to monitor continuously real-time environmental and management parameters with an accuracy of 5%.PM₁₀ concentration was monitored by a sampler (Haz Dust EPAM 5000), either continuously or through traditional gravimetric technique, and the mean value of dust amount collected on the membranes was utilized as a correction factor to be applied to continuously collected data.PM₁₀ concentration amount incoming from inlets was removed from PM₁₀ emission calculation, to estimate the real contribution of pig house dust pollution into atmosphere.Mean yearly emission factor of PM₁₀ was measured in 2 g d^?1 LU^?1 for the weaning room, 0.09 g d^?1 LU^?1 for the farrowing room, 2.59 g d^?1 LU^?1 for the fattening room and 1.23 g d^?1 LU^?1 for the gestation room. The highest PM₁₀ concentration and emission per LU was recorded in the fattening compartment while the lowest value was recorded in the farrowing room.CO₂, CH₄ and N₂O concentrations were continuously measured in the exhaust ducts using an infrared photoacoustic detector IPD (Brüel & Kjaer, Multi-gas Monitor Type 1302, Multipoint Sampler and Doser Type 1303) sampling data every 15 min, for the 60% of the cycles.Yearly emission factor for CO₂ was measured in 5997 g d^?1 LU^?1 for the weaning room, 1278 g d^?1 LU^?1 for the farrowing room, 13,636 g d^?1 LU^?1 for the fattening room and 8851 g d^?1 LU^?1 for the gestation room.Yearly emission factor for CH₄ was measured in 24.57 g d^?1 LU^?1 for the weaning room, 4.68 g d^?1 LU^?1 for the farrowing room, 189.82 g d^?1 LU^?1 for the fattening room and 132.12 g d^?1 LU^?1 for the gestation room.Yearly emission factor for N₂O was measured in 3.62 g d^?1 LU^?1 for the weaning room, 0.66 g d^?1 LU^?1 for the farrowing room, 3.26 g d^?1 LU^?1 for the fattening room and 2.72 g d^?1 LU^?1 for the gestation room.     

Impact of permanent inundation on methane emissions from a Spartina alterniflora coastal salt marsh

To understand the effect of water level on CH₄ emissions from an invasive Spartina alterniflora coastal brackish marsh, we measured CH₄ emissions from intermittently and permanently (5 cm water depth) inundated mesocosms with or without N fertilizer added at a rate of 2.7 g N m^?2. Dissolved CH₄ concentrations in porewater and vertically-profiled sediment redox potential were measured, as were aboveground biomass and stem density of S. alterniflora. Mean CH₄ fluxes during the growing season in permanently inundated mesocosms without and with N fertilizer were 1.03 and 1.73 mg CH₄ m^?2 h^?1, respectively, which were significantly higher than in the intermittently inundated mesocosms. This response indicates that prolonged submergence of sediment, up to a water depth of 5 cm, stimulated CH₄ release. Inundation did not greatly affect aboveground biomass and stem density, but did significantly reduce redox potential in sediment, which in turn stimulated CH₄ production and increased the CH₄ concentration of porewater, resulting in higher CH₄ emission in the mesocosm. Our data showed that the stimulatory effect of shallow, permanent inundation on CH₄ emission in S. alterniflora marsh sediment was due primarily to an improved methanogenic environment rather than an increase in plant-derived substrates and/or the number of gas emission pathways through the plant’s aerenchymal system.     

Nitrous oxide emissions from mineral and organic soils of a Norway spruce stand in South–West Germany

Due to the high temporal and spatial variability of N₂O fluxes, estimates of N₂O emission from temperate forest ecosystems are still highly uncertain, particularly at larger scales. Although highest N₂O emissions with up to 7.0 kg N ha⁻¹ yr⁻¹ were mainly reported for soils affected by stagnant water, most of the reported gas flux measurements were performed at forest sites with well-aerated soils yielding mostly to low mean annual emission rates less than 1.0 kg N ha⁻¹ yr⁻¹. This study compares N₂O fluxes from upland (Cambisols) and temporally water-logged (Gleysols, Histosols) soils of the Central Black Forest (South-West Germany) over a period of 2 yr. Mean annual N₂O fluxes from investigated soils ranged between 0.2 and 3.9 kg N ha⁻¹ yr⁻¹. The fluxes showed a large variability between the different soil types. Emissions could be clearly ranked in the following order: Cambisols (0.26–0.75 kg N ha⁻¹ yr⁻¹)<Gleysols (1.37–2.68 kg N ha⁻¹ yr⁻¹)<Histosol (3.66–3.95 kg N ha⁻¹ yr⁻¹). Although the Cambisols cover two-thirds of the investigated area, only about half of the overall N₂O is emitted from this soil type. Therefore, regional or national N₂O fluxes from temperate forest soils are underestimated if soils characterised by intermediate aeration conditions are disregarded.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Spatial distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

Winter-grazing reduces methane uptake by soils of a typical semi-arid steppe in Inner Mongolia,China

Steppe ecosystems are regarded as an important sink of atmospheric methane (CH₄) and grazing is hypothesized to reduce CH₄ uptake. However, firm experimental evidence is required to prove this hypothesis. Using a fully automated, chamber-based measuring system, we conducted continuous high-frequency (at a 3-h interval) measurements of CH₄ uptake in a Leymus chinensis steppe, which is a typical grassland ecosystem in Inner Mongolia, China. Two management regimes were investigated: ungrazed since 1999 (UG99) and winter-grazed since 2001 (WG01). Measurements were carried out continuously during the periods of June–September 2004, May–September 2005 and March–June 2006. During all of these periods, significantly lower mean CH₄ uptake (±S.E.) at WG01 (28±0.7 μg C m⁻² h⁻¹) as compared to UG99 (56±1.0 μg C m⁻² h⁻¹) (p<0.01) was found. Total CH₄ uptake during the growing seasons (May–September) 2004 and 2005 at WG01 and UG99 was quantified as 1.15 and 2.15 kg C ha⁻¹, respectively. Annual rates of CH₄ uptake were approximately 1.91 (WG01) and 3.58 kg C ha⁻¹ (UG99), respectively. These results indicate that winter-grazing of steppe significantly reduced atmospheric CH₄ uptake by ca. 47%. The winter-grazing practice may have inhibited CH₄ uptake by (a) increasing the likelihood of physiological water stress for CH₄-consuming bacteria during dry periods, (b) decreasing gas diffusion into the soil and, (c) reducing the populations of CH₄ oxidizing bacteria. These three mechanisms could have collectively or independently facilitated the observed inhibitory effects. Our results suggest that grazing exerts a considerable negative impact on CH₄ uptake in semi-arid steppes at regional scales. Notwithstanding, further studies involving year-round, intensive measurements of CH₄ uptake are needed.     

Air pollutants in rural homes in Guizhou,China – Concentrations,speciation, and size distribution

Several types of fuels, including coal, fuel wood, and biogas, are commonly used for cooking and heating in Chinese rural households, resulting in indoor air pollution and causing severe health impacts. In this paper, we report a study monitoring multiple pollutants including PM₁₀, PM_2.5, CO, CO₂, and volatile organic compounds (VOCs) from fuel combustion at households in Guizhou province of China. The results showed that most pollutants exhibited large variability for different type of fuels except for CO₂. Among these fuels, wood combustion caused the most serious indoor air pollution, with the highest concentrations of particulate matters (218～417 μg m^?3 for PM₁₀ and 201～304 μg m^?3 for PM_2.5), and higher concentrations of CO (10.8 ± 0.8 mg m^?3) and TVOC (about 466.7 ± 337.9 μg m^?3). Coal combustion also resulted in higher concentrations of particulate matters (220～250 μg m^?3 for PM₁₀ and 170～200 μg m^?3 for PM_2.5), but different levels for CO (respectively 14.5 ± 3.7 mg m^?3 for combustion in brick stove and 5.5 ± 0.7 mg m^?3 for combustion in metal stove) and TVOC (170 mg m^?3 for combustion in brick stove and 700 mg m^?3 for combustion in metal stove). Biogas was the cleanest fuel, which brought about the similar levels of various pollutants with the indoor case of non-combustion, and worth being promoted in more areas. Analysis of the chemical profiles of PM_2.5 indicated that OC and EC were dominant components for all fuels, with the proportions of 30～48%. A high fraction of SO₄^2? (31～34%) was detected for coal combustion. The cumulative percentages of these chemical species were within the range of 0.7～1.3, which was acceptable for the assessment of mass balance.