Establishment and Evaluation of a Method for Analyzing Atmospheric Volatile Organic Compounds

An automated cumulative sampling system and a method that combines a two-step cryo-concentrated system and gas chromatography/mass spectrometry （CCS-GC/MS） are introduced. The method is evaluated by a set of special experiments and the results are presented. The lowest measurement detection limit was expanded from 10^-6 nmol mol^-1 to 10^-12 nmol mol^-1 by using CCS-GC/MS instead of the simpler method of gas chromatography/mass spectrometry （GC/MS）, with the average responsible factor of 39 object compounds being 2.9 × 10^-12. When the volume of air sample reached 1000 cm^3, the lowest detection limit reached up to 7 × 10^-12-40 × 10^-12 nmol mol^-1. The CCS-GC/MS method can potentially identify all objective chemical species in an atmospheric sample, with an average 2.5 s bias error of retention time for 39 gas chromatography （GC） peaks. Within the range 0-400×10^-9 nmol mol^-1, the concentration of 39 kinds of objective compounds can be individually calculated very accurately by a standard curve [average r^2 （coefficient of determination） value of above 0.99]. The recovery efficiency was 88%-111%, with an average of 100.8% ±5.6%. The bias error of precision was 2%-14%, with an average of 6.6%.     

华东稻田CH4和N2O排放

稻田CH4和N2O排放的季节变化规律完全不同，两者的排放通量随土壤水分条件变化而互为消长，但它们的日变化形式则比较一致。晴天时的CH4和N2O排放日变化规律明显，主要表现为下午单峰模态，有时CH4排放夜间出现一个次峰。CH4和N2O排放总量因肥料类型而不同，堆肥加尿素处理比NH4HCO3处理少排放N2O 30%，多排放CH4 12%。     

三亚地区冬春季大气污染特征观测研究

为了研究海南省三亚地区冬春季大气污染状况,于2011年12月—2013年4月的冬春季节在三亚鹿回头村(监测点位于三亚市郊,三面临海,周围没有工业污染源)开展了大气主要污染物(NO_x、O₃、PM_2.5)的连续监测,利用观测数据对三亚地区冬春季大气污染变化特征进行分析.结果表明:三亚地区大气污染物浓度均低于国家一级标准的浓度值,NO、NO₂、NO_x、O₃、PM_2.5质量浓度的日平均值(平均值±标准差)分别为(2.1±2.2)、(5.2±3.4)、(7.3±3.8)、(59.8±28.4)和(17.5±14.3)μg·m^-3.在污染物的日变化方面,NO_x、PM_2.5呈现典型的双峰型,其峰值分别出现在08:00和17:00,峰谷在13:00;O₃的日变化为单峰型,峰值出现在13:00.通过后向轨迹分析发现,三亚地区大气污染物受局地源排放和外源输送的共同影响,来自陆地的气流易造成污染物的积累,而来自海上的气流则有利于污染物的清除.     

2013年元月我国中东部地区强霾污染成因分析

2013年元月,罕见强霾污染席卷我国中东部地区,引起社会各界高度关注．中国科学院“大气灰霾追因与控制”专项组,利用其建立的“中国气溶胶观测研究网”（CARE．China）对整个强霾污染过程进行了全程追踪观测,并对其成因进行了分析研究．本次强霾污染涉及我国整个中东部地区,污染最严重的京津冀地区共计发生5次强霾污染过程,其中两次超强过程发生在9—15日和25—31日,北京PM2．5小时浓度最高值分别达到680和530嵋m-。,石家庄和天津等重要城市强霾污染状况与北京相似．天气系统弱、强冷空气活动少和极其不利于污染物扩散的局地气象条件及地理位置,是造成本次强霾污染形成的外部条件;一次排放的气态污染物向颗粒态的快速转化,是本次强霾污染“爆发性”和“持续性”的内部促发因子,特别是大气中燃油排放为主的大量NOx促发了燃煤排放气态SO2向颗粒态硫酸盐的快速转化．通过NOx/SO2协同转化途径分析,发现气态污染物在细颗粒表面的非均相反应可改变大气颗粒物的粒径及化学组分,促使颗粒物中的二次无机盐（如硫酸盐和硝酸盐等）的比例逐渐增大,导致颗粒物吸湿性显著增强,从而对强霾污染形成起到了促进作用．     

Methane and nitrous oxide emissions from three paddy rice based cultivation systems in Southwest China

To understand methane (CH4) and nitrous oxide (N2O) emissions from permanently flooded rice paddy fields and to develop mitigation options, a field experiment was conducted in situ for two years (from late 2002 to early 2005) in three rice-based cultivation systems, which are a permanently flooded rice field cultivated with a single time and followed by a non-rice season (PF), a rice-wheat rotation system (RW) and a rice-rapeseed rotation system (RR) in a hilly area in Southwest China. The results showed that the total CH4 emissions from PF were 646.3±52.1 and 215.0±45.4 kg CH4 hm-2 during the rice-growing period and non-rice period, respectively. Both values were much lower than many previous reports from similar regions in Southwest China. The CH4 emissions in the rice-growing season were more intensive in PF, as compared to RW and RR. Only 33% of the total annual CH4 emission in PF occurred in the non-rice season, though the duration of this season is two times longer than the rice season. The annual mean N2O flux in PF was 4.5±0.6 kg N2O hm-2 yr-1. The N2O emission in the rice-growing season was also more intensive than in the non-rice season, with only 16% of the total annual emission occurring in the non-rice season. The amounts of N2O emission in PF were ignorable compared to the CH4 emission in terms of the global warming potential (GWP). Changing PF to RW or RR not only eliminated CH4 emissions in the non-rice season, but also substantially reduced the CH4 emission during the following rice-growing period (ca. 58%, P<0.05). However, this change in cultivation system substantially increased N2O emissions, especially in the non-rice season, by a factor of 3.7 to 4.5. On the 100-year horizon, the integrated GWP of total annual CH4 and N2O emissions satisfies PF>>RR≈RW. The GWP of PF is higher than that of RW and RR by a factor of 2.6 and 2.7, respectively. Of the total GWP of CH4 and N2O emissions, CH4 emission contributed to 93%, 65% and 59% in PF, RW and RR, respectively. These results suggest that changing PF to RW and RR can substantially reduce not only CH4 emission but also the total GWP of the CH4 and N2O emissions.     

On-line measurement of water-soluble ions in ambient particles

Combining the system of rapid collection of ambient particles and ion chromatography, the system of rapid collection of fine particles and ion chromatography (RCFP-IC) was established to automatically analyze on-line the concentrations of water-soluble ions in ambient particles. Here, the general scheme of RCFP-IC is described and its basic performance is tested. The detection limit of RCFP-IC for SO2? 4 , NO?3 , NO?2 , Cl? and F? is below 0.3 μg m?3. The collection efficiency of RCFP-IC increases rapidly with increasing sized particles. For particles larger than 300 nm, the collection efficiency approaches 100%. The precision of RCFP-IC is more than 90% over 28 repetitions. The response of RCFP-IC is very sensitive and no obvious cross-pollution is found during measurement. A comparison of RCFP-IC with an integrated filter measurement indicates that the measurement of RCFP-IC is comparable in both laboratory experiments and field observations. The results of the field experiment prove that RCFP-IC is an effective on-line monitoring system and is helpful in source apportionment and pollution episode monitoring.     

北京大气中可形成气溶胶的有机物——现状及变化规律的初步研究

北京大气中可形成气溶胶的有机污染物增加迅速,并有明显的季节变化、日变化和空间变化。其中含量最高增长也最快的是BTXE,1995～1998年增长率为20%/a,1998～1999年增长率突增为128%/a,但CFCs增长速率有所减慢。BTXE冬季出现峰值,夏季出现谷值,峰值比谷值高3～5倍;CFCs夏季出现明显峰值,但变化幅度比BTXE相对小。晴风天气与阴雾天气有相反的日变化形式,阴雾天大气的BTXE含量比晴风天的高2～3倍。北京城乡结合部的三、四环路地区污染物含量最高,天安门、中关村和石景山区大气污染程度相近。     

2013~2017年中国重点区域颗粒物质量浓度和化学成分变化趋势

对大气颗粒物浓度及其化学组分精准观测有助于探究大气霾污染的成因与来源解析,评价环境空气质量控制策略的合理性.文章基于CARE-China观测网中中国重点区域典型站点大气PM2.5膜采样和分不同粒径段颗粒物采样及化学成分数据,结合同期中国环境监测总站发布的环境空气质量数据,评估分析了中国2013~2017年《大气污染防治行动计划》实施期间,全国及重点区域大气颗粒物质量浓度的变化及其相应化学组成的演变.研究结果表明:(1)研究期内,中国环境空气颗粒物年平均浓度整体呈明显下降趋势,但仍有64%的城市PM2.5年平均浓度未达到中国现行标准(GB3095-2012).太行山东麓、汾渭平原和新疆乌昌等地区大气PM2.5浓度负荷依然较高,秋冬季重霾污染频发.(2)秋冬季重污染期间,颗粒物中硫酸盐和有机组分质量浓度下降明显.京津冀、珠三角、成渝和汾渭平原地区PM2.5中SO42-平均浓度分别下降了76%、12%、81%和38%;OM平均浓度分别下降70%、44%、48%和31%;NH4+平均浓度分别下降68%、1.6%、38%和25%. EC平均浓度在京津冀和成渝分别下降84%和20%,在珠三角和汾渭平原地区分别上升61%和11%;矿尘及未解析的化学成分(MI)平均浓度在京津冀、珠三角和汾渭平原地区下降了70%、24%和13%. PM2.5中化学成分的变化量,总体上与PM2.5质量浓度的下降量相一致.(3)相比2013年, 2015年京津冀、长三角、珠三角和成渝地区粗颗粒物中OM平均浓度下降46~57%,MI分别下降31~60%和39~73%,是颗粒物浓度下降的最主要因素. 2013~2015年,不同粒径段化学组分中,粗粒径段峰值降低显著,并且随着不同粒径段中颗粒物质量浓度的降低,其SO42-、NO3-和NH4+的细粒径段峰值从0.65~1.1μm转移到更细的0.43~0.65μm粒径段.     

不同土壤类型的热通量变化特征

利用2004—2007年中国科学院中国生态系统研究网络(CERN)生态站实测土壤热通量、辐射等资料,分析了不同土壤类型表层热通量的日变化和季节变化,以及不同土壤类型的热通量与总辐射、净辐射的关系。结果表明,由于导热率越大,热量传输就越快;热容量越小,热量传输也越快,造成土壤热通量的日较差和年较差较大,所以黄绵土和紫色土的表层热通量日较差最大(220～280 W.m-2),高寒草甸土和水稻土最小(55W.m-2);季节变化中土壤表层热通量的年较差变化范围在12～28W.m-2之间,灰漠土最大,为28W.m-2,热通量年较差从大到小依次为灰漠土、黄绵土、盐碱潮土、红壤土、紫色土、沼泽土、水稻土和高寒潮土,高寒潮土最小,为12W.m-2。不同土壤类型的热通量与总辐射、净辐射呈正相关关系,但不同土壤类型的土壤热通量在12:00(地方时)所占净辐射的比例各不相同,高寒草甸土最小,约为8%;黄绵土最大,为38%,多数土壤的热通量占净辐射的比例在15%～20%之间,这充分表明不同土壤类型表层热通量的传输存在很大差异。     

2007和2008年夏季北京奥运馆大气PM10与PM2.5质量浓度变化特征

为了监测北京奥运主场馆附近大气颗粒物的污染状况以及评估奥运污染源减排措施对北京大气颗粒物质量浓度变化的影响,利用颗粒物在线监测仪器TEOM于2007年和2008年夏季,在奥运主场馆附近的中国科学院遥感应用研究所办公楼楼顶对大气颗粒物PM10和PM2.5进行了连续同步观测。结果表明,2007年夏季监测点附近大气PM10与PM2.5质量浓度的平均值分别为153.9和71.2μg.m-3,而2008年夏季PM10与PM2.5质量浓度的平均值分别为85.2和52.8μg.m-3。与奥运前一年同时段相比,奥运时段大气PM10和PM2.5的质量浓度分别下降44.5%和25.1%。对比分析奥运前后的2次典型污染过程发现,空气相对湿度的增加和偏南气流输送的共同影响易造成大气颗粒物的累积增长,而降雨的湿清除作用和偏北气流则会使大气颗粒物浓度迅速降低。在相近的气象条件下,奥运前后的污染过程中,大气细粒子的日均增长速率分别为25.1和13.9μg.m-3.d-1,而大气粗粒子的日均增长速率分别为20.8和2.2μg.m-3.d-1,奥运时段污染累积过程中大气粗、细粒子的增长速率分别显著低于和略低于奥运前同时段污染过程中颗粒物的增长速率。污染源减排措施的实施是奥运期间大气颗粒物质量浓度降低的主要原因,从控制效果来看,奥运期间实施的污染源减排措施对大气粗粒子的控制效果明显好于大气细粒子。