Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

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.     

Study on a new correlation between diffusion coefficient and temperature in porous building materials

The diffusion coefficient (D) and partition coefficient (K_ma) are the two important parameters used to predict the volatile organic compound (VOC) emission or sorption characteristics in porous building materials. D and K_ma may be strongly affected by temperature (T). In this study, we derived a new correlation between D and T based on the assumption that molecular diffusion is dominant, and evaluated this correlation using a series of existing experimental data. The modeling results using the new correlation agree well with the experimental data. The correlation would be useful for assessment of indoor air quality under different environmental (temperature) conditions.     

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.     

Observations of Atmospheric Nitrogen and Phosphorus Deposition During the Period of Algal Bloom Formation in Northern Lake Taihu,China

Cyanobacterial blooms in Lake Taihu occurred at the end of April 2007 and had crucial impacts on the livelihood of millions of people living there. Excessive nutrients may promote bloom formation. Atmospheric nitrogen (N) and phosphorus (P) deposition appears to play an important role in algal bloom formation. Bulk deposition and rain water samples were collected respectively from May 1 to November 30, 2007, the period of optimal algal growth, to measure the bulk atmospheric deposition rate, wet deposition rate, and dry deposition rate for total nitrogen (TN; i.e., all species of nitrogen), and total phosphorus (TP; i.e., all species of phosphorus), in northern Lake Taihu, China. The trends of the bulk atmospheric deposition rate for TN and the wet deposition rate for TN showed double peaks during the observation period and distinct influence with plum rains and typhoons. Meanwhile, monthly bulk atmospheric deposition rates for TP showed little influence of annual precipitation. However, excessive rain may lead to high atmospheric N and P deposition rates. In bulk deposition samples, the average percentage of total dissolved nitrogen accounting for TN was 91.2% and changed little with time. However, the average percentage of total dissolved phosphorus accounting for TP was 65.6% and changed substantially with time. Annual bulk atmospheric deposition rates of TN and TP during 2007 in Lake Taihu were estimated to be 2,976 and 84 kg km⁻² a⁻¹, respectively. The results showed decreases of 34.4% and 78.7%, respectively, compared to 2002–2003. Annual bulk deposition load of TN for Lake Taihu was estimated at 6,958 t a⁻¹ in 2007 including 4,642 t a⁻¹ of wet deposition, lower than the values obtained in 2002–2003. This may be due to measures taken to save energy and emission control regulations in the Yangtze River Delta. Nevertheless, high atmospheric N and P deposition loads helped support cyanobacterial blooms in northern Lake Taihu during summer and autumn, the period of favorable algal growth.     

长江三角洲城市间环境公平性研究

定义了环境公平性包括基于自然资源禀赋的环境公平性及基于经济产出的环境公平性。为表征基于自然资源禀赋的环境公平性,构造并计算了长江三角洲（简称长三角）各地环境压力指数。为表征经济产出的环境公平性,构造了环境基尼系数与绿色贡献系数。根据2004年环境经济发展水平及污染排放数据（COD与SO2排放量）,计算了长三角各地级市的环境压力与基于GDP的COD与SO2环境基尼系数与各地的绿色贡献系数。借助分层聚类分析,得出以下结论：（1）从基于自然资源禀赋的环境公平性上讲,上海面临的环境压力最高,江苏省城市较浙江省高;（2）从基于经济产出的环境公平性上讲,长三角地区基于GDP的COD、SO2环境基尼系数分别为017与013,相较全国,长三角实现了更高发展水平上的均衡;（3）在长三角内部比较,镇江、泰州等部分城市COD、SO2排放的生态效率仍需进一步提高。最后指出：在区域层面上合理分布区域环境压力,在比较中提高各地生态效率是推动长三角环境保护发展、促进长三角环境保护一体化的重要举措。     

Degradation of pentachlorobiphenyl by a sequential treatment using Pd coated iron and an aerobic bacterium (H1)

The reductive dechlorination and biodegradation of 2,2^′4,5,5^′-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2^′4,5,5^′-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2^′,4,5,5^′-pentachlorobiphenyl. In laboratory batch experiments, 2,2^′4,5,5^′-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2^′,4-trichlorobiphenyl (PCB#17), a reduction product from 2,2^′4,5,5^′-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.     

Endosulfan in China 1—gridded usage inventories

Background, aim, and scope  Endosulfan, an organochlorine pesticide (OCP), is genotoxic in mammalian cells and generally considered to be toxic and classified by the World Health Organization and the US Environmental Protection Agency as priority pollutants and a nominator for inclusion in a future iteration of the persistent organic pollutants treaty. Endosulfan is a currently used pesticide and still being used worldwide. The general trend of total global endosulfan use has increased continuously since the first year when this pesticide was applied. It is critical to create national endosulfan usage/emission inventories for China to carry out source–receptor relation analysis, risk assessment, and other research related to endosulfan in this country. Chinese inventories have been published for some OCPs, such as technical HCH and lindane, DDT, and chlordane; for endosulfan, however, there has not been any usage inventory available on any scales (national or provincial), although endosulfan has been widely used since 1994 in this country. This is the first part of the work. The goal of this paper is to quantify the historical production and usage of endosulfan in China and to compile gridded historical usage inventories of endosulfan for this country. Based on these usage inventories, emission and residue inventories will be created, which is the goal of the second part of the work. Materials and methods  Due to the lack of national production and usage information of endosulfan in China, a method to estimate the use of endosulfan was developed. First, information of crops on which endosulfan is applied and average endosulfan use and annual application frequencies of endosulfan on these crops were collected. Secondly, usage of endosulfan on each crop was estimated using the national cropland area for each province from Chinese government reports. Finally, with the help of GIS (geographic information system), the usage data of this insecticide was allocated to a grid system, with a 1/4° longitude by 1/6° latitude resolution, with a size for each grid cell of approximately 25 km by 25 km. Results and discussion  The use of endosulfan in agriculture in China started on cotton in 1994, and on wheat, tea, tobacco, apples, and other fruits in 1998. Endosulfan usage on cotton, wheat, tea, tobacco, and apples in China has been estimated to be approximately 25,700 t between 1994 and 2004. The province with the highest usage of endosulfan is Henan Province, with a total usage reaching 4,000 t, followed by the uses in Xinjiang Autonomous Region (3,200 t), Shandong Province (3,000 t), Hebei Province (2,100 t), and Anhui Province (1,900 t). Gridded usage inventories of endosulfan at a 1/4° longitude by 1/6° latitude resolution have been created, which indicate that the intensive endosulfan use was in the south of Hebei Province, west of Shandong Province, east of Henan Province, north of Anhui Province, east of Jiangsu Province, and some areas in Yunnan Province and Xinjiang Autonomous Region. General agreement has been found between the usage data from our estimation and the small amount of usage data published in China. Conclusions  This is the first national gridded endosulfan usage inventory produced for China. The annual applications of endosulfan from 1994 to 2004 in China were estimated based on the total areas of major crops, on which endosulfan was applied, and spatial distribution of the application was generated at provincial and prefecture levels. With the help of GIS, endosulfan usage based on prefecture was transferred to a 1/4° longitude by 1/6° latitude gridding system. The satisfaction of the inventories was supported by the consistence between the estimation of the annual usage and the reported annual production of endosulfan. Recommendations and perspectives  This gridded endosulfan usage inventory created in this study will be improved upon availability of new information of endosulfan. The usage inventories can be used to create gridded emission and residue inventories for this insecticide. It is believed that this work will pave the way for further endosulfan studies in China and beyond.     

Profile of Methane Concentrations in Soil and Atmosphere in Alpine Steppe Ecosystem on Tibetan Plateau

The methane concentration profile from -1.5m depth in soil to 32m height in air was measured in alpine steppe located in the permafrost area. Methane concentrations showed widely variations both in air and in soil during the study period. The mean concentrations in atmosphere were all higher than those in soil, and the highest methane concentration was found in air at the height of 16m with the lowest concentration occurring at the depth of 1.5m in soil. The variations of atmospheric methane concentrations did not show any clear pattern both temporally and spatially, although they exhibited a more steadystable state than those in soil. During the seasonal variations, the methane concentrations at different depths in soil were significantly correlated （R^2〉0.6） with each other comparing to the weak correlations （R^2〈0.2） between the atmospheric concentra- tions at different heights. Mean methane concentrations in soil significantly decreased with depth. This was the compositive influence of the decreasing production rates and the increasing methane oxidation rates, which was caused by the descent soil moisture with depth. Although the methane concentrations at all depths varied widely during the growing season, they showed very distinct temporal variations in the non-growing season. It was indicated from the literatures that methane oxidation rates were positively correlated with soil temperature. The higher methane concentrations in soil during the winter were determined by the lower methane oxidation rates with decreasing soil temperatures, whereas methane production rates had no reaction to the lower temperature. Relations between methane contribution and other environmental factors were not discussed in this paper for lacking of data, which impulse us to carry out further and more detailed studies in this unique area.