Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

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.     

Simulation of global warming potential (GWP) from rice fields in the Tai-Lake region,China by coupling 1:50,000 soil database with DNDC model

Quantifying greenhouse gas (GHG) emissions from wetland ecosystems is a relatively new issue in global climate change studies. China has approximately 22% of the world's rice paddies and 38% of the world's rice production, which are crucial to accurately estimate the global warming potential (GWP) at regional scale. This paper reports an application of a biogeochemical model (DeNitrification and DeComposition or DNDC) for quantifying GWP from rice fields in the Tai-Lake region of China. For this application, DNDC is linked to a 1:50,000 soil database, which was derived from 1107 paddy soil profiles compiled during the Second National Soil Survey of China in the 1980–1990s. The simulated results show that the 2.34 Mha of paddy soil cultivated in rice–wheat rotation in the Tai-Lake region emitted about ?1.48 Tg C, 0.84 Tg N and 5.67 Tg C as CO₂, N₂O, and CH₄ respectively, with a cumulative GWP of 565 Tg CO₂ equivalent from 1982 to 2000. As for soil subgroups, the highest GWP (26,900 kg CO₂ equivalent ha^?1 yr^?1) was linked to gleyed paddy soils accounting for about 4.4% of the total area of paddy soils. The lowest GWP (5370 kg CO₂ equivalent ha^?1 yr^?1) was associated with submergenic paddy soils accounting for about 0.32% of the total area of paddy soils. The most common soil in the area was hydromorphic paddy soils, which accounted for about 53% of the total area of paddy soils with a GWP of 12,300 kg CO₂ equivalent ha^?1 yr^?1. On a regional basis, the annual averaged GWP in the polder, Tai-Lake plain, and alluvial plain soil regions was distinctly higher than that in the low mountainous and Hilly soil regions. As for administrative areas, the average annual GWP of counties in Shanghai city was high. Conversely, the average annual GWP of counties in Jiangsu province was low. The high variability in soil properties throughout the Tai-Lake region is important and affects the net greenhouse gas emissions. Therefore, the use of detailed soil data sets with high-resolution digital soil maps is essential to improve the accuracy of GWP estimates with process-based models at regional and national scales.     

Evaluation of the effect of long-range transport of air pollutants on coastal atmospheric monitoring sites in and around Taiwan

Long-range transport of pollution outflow from Asian mainland has been noticed and expected to play a significant role in Pacific background. Since 1993 the Taiwanese Environmental Protection Administration (TEPA) is conducting ground-based observations of various particulate and gaseous pollutants at 74 monitoring stations in Taiwan. One of these stations, Heng-Chun at the south coast of Taiwan can be considered as a background station with only negligible amounts of local pollution, and another one, Wan-Li at the north coast, predominantly receives air that has not passed over Taiwan, so that background air can be analysed by means of sectorisation. In this work, the sectorised 13-year time series of measurements of CO, SO₂, O₃, NO_x and PM₁₀, from the Wan-Li station are presen and compared to data from the Heng-Chun station and another TEPA background station off the coast of mainland China, Ma-Zu. The CO and O₃ measurements are also compared to data from the Yonaguni station, a Pacific island site, part of the Global Atmospheric Watch (GAW) network.The similarity of the sectorised data from the Wan-Li station with the data of the other station indicates that atmospheric measurements from the Wan-Li site can be used to make inferences about trends in western Pacific background air pollution and the effect of long-range transport of pollutants. The measurement time series from 1993 to 2006 do not indicate a significant trend in the monthly mean O₃ concentrations in accordance with other research about ozone in tropical latitudes. An increasing trend in CO concentrations of 2.8% per annum is observed between 1999 and 2006 for long-range transport to northern Taiwan, and a doubling of the SO₂ and NO_x concentrations observed at the Wan-Li and Heng-Chun sites within the period 2001–2006. SO₂ concentrations are found to quadruple at Ma-Zu within the same period. The data suggest that pollution from the Asian mainland enhances significantly the background air pollution over the Pacific.     

Carbon isotope analysis for source identification of atmospheric formaldehyde and acetaldehyde in Dinghushan Biosphere Reserve in South China

Formaldehyde and acetaldehyde are two most abundant carbonyls in ambient air. Biogenic emission has been proposed as a significant source other than anthropogenic emissions and atmospheric secondary formation. Here at a forest site in South China, the carbon isotopic compositions of formaldehyde and acetaldehyde emitted from leaves of three tree species (Litsea rotundifolia, Canarium album and Castanea henryi) were measured in comparison with the bulk carbon isotopic compositions of tree leaves. δ¹³C data of the emitted aldehydes (from ?31‰ to ?46‰) were quite different for tree species, which were all more depleted in ¹³C than the tree-leaf bulk δ¹³C values (from ?27‰ to ?32‰). Formaldehyde in ambient air at the forest site had δ¹³C values different from those of leaf-emitted formaldehyde, indicating other sources for ambient formaldehyde apart from direct emission from leaves, most probably the photooxidation of biogenic hydrocarbon like isoprene and monoterpene. The δ¹³C differences of acetaldehyde between ambient data and those of tree leaves emission were less than 1‰, implying direct biogenic emission as the dominant source.     

Evaluating inter-continental transport of fine aerosols:(2) Global health impact

In this second of two companion papers, we quantify for the first time the global impact on premature mortality of the inter-continental transport of fine aerosols (including sulfate, black carbon, organic carbon, and mineral dust) using the global modeling results of (Liu et al., 2009). Our objective is to estimate the number of premature mortalities in each of ten selected continental regions resulting from fine aerosols transported from foreign regions in approximately year 2000. Our simulated annual mean population-weighted (P-W) concentrations of total PM2.5 (aerosols with diameter less than 2.5 μm) are highest in East Asia (EA, 30 μg m^?3) and lowest in Australia (3.6 μg m^?3). Dust is the dominant component of PM2.5 transported between continents. We estimate global annual premature mortalities (for adults age 30 and up) due to inter-continental transport of PM2.5 to be nearly 380 thousand (K) in 2000. Approximately half of these deaths occur in the Indian subcontinent (IN), mostly due to aerosols transported from Africa and the Middle East (ME). Approximately 90K deaths globally are associated with exposure to foreign (i.e., originating outside a receptor region) non-dust PM2.5. More than half of the premature mortalities associated with foreign non-dust aerosols are due to aerosols originating from Europe (20K), ME (18K) and EA (15K); and nearly 60% of the 90K deaths occur in EA (21K), IN (19K) and Southeast Asia (16K). The lower and higher bounds of our estimated 95% confidence interval (considering uncertainties from the concentration–response relationship and simulated aerosol concentrations) are 18% and 240% of the estimated deaths, respectively, and could be larger if additional uncertainties were quantified. We find that in 2000 nearly 6.6K premature deaths in North America (NA) were associated with foreign PM2.5 exposure (5.5K from dust PM2.5). NA is least impacted by foreign PM2.5 compared to receptors on the Eurasian continent. However, the number of premature mortalities associated with foreign aerosols in NA (mostly occurring in the U.S.) is comparable to the reduction in premature mortalities expected to result from tightening the U.S. 8-h O₃ standard from 0.08 ppmv to 0.075 ppmv. International efforts to reduce inter-continental transport of fine aerosol pollution would substantially benefit public health on the Eurasian continent and would also benefit public health in the United States.     

Single particle mass spectrometry of oxalic acid in ambient aerosols in Shanghai: Mixing state and formation mechanism

Oxalic acid in individual aerosol particles was measured using single particle aerosol time-of-flight mass spectrometry (ATOFMS) in the summer of 2007 in Shanghai, China. Oxalate was found in 3.4% of total particles with diameters in the range of 0.2 – 2.0 μm. Size, chemical composition and hourly temporal counts of single particles that contained oxalic acid were measured. The predominant types of oxalate-containing particles were characterized to distinguish the primary and secondary sources of oxalic acid. Biomass burning was revealed as a major primary source of oxalic acid which contributed more than 20% of the oxalate-containing particles. Evidences for two different formation pathways of oxalic acid were observed in our experiment. The number fraction of oxalate-containing particles correlated with that of sulfate particles and the changes of air parcel backward trajectories, suggesting that in-cloud processing played important roles in oxalic acid formation. The diurnal patterns of dust and sea salt particle counts fitted well with the ambient relative humidity variation, suggesting that heterogeneous reactions occurring in hydrated/deliquesced aerosols also contributed to the production of oxalic acid.     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

Concentrations,seasonal variations,and transport of carbonaceous aerosols at a remote Mountainous region in western China

Carbonaceous aerosol concentrations were determined for total suspended particle samples collected from Muztagh Ata Mountain in western China from December 2003 to February 2006. Elemental carbon (EC) varied from 0.004 to 0.174 μg m^?3 (average = 0.055 μg m^?3) while organic carbon (OC) ranged from 0.12 to 2.17 μg m^?3 and carbonate carbon (CC) from below detection to 3.57 μg m^?3. Overall, EC was the least abundant fraction of carbonaceous species, and the EC concentrations approached those in some remote polar areas, possibly representing a regional background. Low EC and OC concentrations occurred in winter and spring while high CC in spring and summer was presumably due to dust from the Taklimakan desert, China. OC/EC ratios averaged 10.0, and strong correlations between OC and EC in spring–winter suggest their cycles are coupled, but lower correlations in summer–autumn suggest influences from biogenic OC emissions and secondary OC formation. Trajectory analyses indicate that air transported from outside of China brings ～0.05 μg m^?3 EC, ～0.42 μg m^?3 OC, and ～0.10 μg m^?3 CC to the site, with higher levels coming from inside China. The observed EC was within the range of loadings estimated from a glacial ice core, and implications of EC-induced warming for regional climate and glacial ice dynamics are discussed.