Trends of Atmospheric CCl 3 F,CCl 2 F 2 and CCl 2 FCClF 2 in Shanghai (China)

Atmospheric concentrations of CCl 3 F (CFC-11), CCl 2 F 2 (CFC-12), and CCl 2 FCClF 2 (CFC-113) in troposphere in Shanghai, China (31°1N) have been routinely monitored by using gas chromatography with electron capture detector from November 1997 to December 2000. The observation shows that there is a slowly declining trend of the three compounds. On the other hand, a comparison has been drawn between the concentrations observed and the ones calculated by 2-box model on the basis of the global statistical data of CFCs production and emission. Our observation agrees with the calculations. It shows that production and emission of chlorofluorocarbons (CFCs) in China are still at a low level and gradually decreasing.     

Long-term trend in CHF2Cl (HCFC-22) from high spectral resolution infrared solar absorption measurements and comparison with in situ measurements

The average tropospheric volume mixing ratio of CHF₂Cl (HCFC-22) has been retrieved from a time series of high spectral resolution ground-based infrared solar absorption spectra recorded with the McMath Fourier transform spectrometer located at the U.S. National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude) for the time period October 1987–November 2002. The retrievals are based on fits to the well-isolated, unresolved 2ν₆ Q branch at 829.05 cm⁻¹ and the SFIT2 retrieval algorithm. The measured daily averages show a near linear rise per year in the mean tropospheric volume mixing ratio as a function of time with a best fit yielding an average increase rate of (5.66±0.15) parts per trillion (10⁻¹²) by volume per year, corresponding to (6.47±0.17)%yr⁻¹, 1 sigma, at the beginning of the time series. The tropospheric mixing ratios retrieved from the solar spectra have been compared with monthly average surface flask sampling measurements from the Climate Monitoring and Diagnostic Laboratory (CMDL) station at Niwot Ridge, Colorado (40.0°N, 105.5°W, 3013 m altitude), archived measurement from the same location, and early CMDL northern hemisphere Pacific cruise measurements. The average ratio of the retrieved tropospheric mixing ratio relative to the CMDL surface mixing ratio is 1.053 for the overlapping 1987 to 2002 time period. The retrieved mean tropospheric mixing ratio is consistent with the surface measurements within the errors estimated for the remote sensing observations.     

Retrieval of ozone profile from ground-based measurements with polarization: A synthetic study

We perform a retrieval based on optimal estimation theory to retrieve the vertical distribution of ozone from simulated spectra in the Huggins bands. The model atmosphere includes scattering by aerosol as well as Rayleigh scattering. The virtual instrument is ground-based and zenith-viewing. Using this algorithm, we show that it is possible to retrieve the ozone profile provided that the spectral resolution is at least 0.2 nm and the signal to noise ratio greater than 500. Our synthetic retrievals suggest that if we are able to measure the Stokes parameters Q, U and V with accuracy comparable to that of the intensity, the information contained in the measurements, and therefore the inversion, will improve. Furthermore, we find that the measurement of the full Stokes vector from the ground-based instrument will especially enhance the retrieval of tropospheric ozone. Utilizing concepts from information theory, our arguments are confirmed by increases in the degrees of freedom and the Shannon information content in the simulated measurements.     

Long-term evolution in the tropospheric concentration of chlorofluorocarbon 12 (CCl2F2) derived from high-spectral resolution infrared solar absorption spectra: retrieval and comparison with in situ surface measurements

The average tropospheric volume mixing ratios of chlorofluorocarbon 12 (CCl₂F₂) have been retrieved from high-spectral resolution ground-based infrared solar-absorption spectra recorded from March 1982 to October 2003 with the McMath Fourier transform spectrometer at the US National Solar Observatory facility on Kitt Peak in southern Arizona (31.9°N, 111.6°W, 2.09 km altitude). The retrievals are based on fits to the unresolved ν₈ band Q-branches near using the SFIT2 retrieval algorithm. The annual increase rate was equal to (16.88±1.37) parts per trillion (10^-12) by volume at the beginning of the time series, March 1982, or (4.77±0.04)%, 1 sigma, declining progressively to (2.49±1.24) parts per trillion, by volume at the end, October 2003, or (0.46±0.24)%, 1 sigma. Average tropospheric mixing ratios from the solar spectra have been compared with average surface flask and in situ sampling measurements from the Climate Monitoring and Diagnostics Laboratory (CMDL) station at Niwot Ridge, CO, (USA) (40.0°N, 105.5°W, 3013 m altitude). The average ratio and standard deviation of the monthly means of the retrieved tropospheric mixing ratios relative to the CMDL surface mixing ratios is (1.01±0.03) for the overlapping time period. Both datasets demonstrate the progressive impact of the Montreal protocol and its strengthening amendments on the trend of CCl₂F₂, though a tropospheric decrease has yet to be observed.     

对流层中的OH与HO2自由基的研究进展

OH与HO2自由基是大气中重要的氧化剂,研究它们的化学反应性质及对其进行实地测量,对深入理解大气氧化过程和了解区域乃至全球大气自净能力有重要意义.自工业革命以来,每年有数千万吨的自然和人为污染物进入对流层,这些物质会严重影响·OH的生成和消除,因此·OH的浓度可能在全球范围内发生大的变化.本文总结了国内外近年来有关·OH与HO2·的最新研究成果,目前比较一致的结论是由于人类活动的影响,全球·OH的浓度比工业革命前降低了.但是在一些污染地区,由于氮氧化合物对·OH的负反馈作用,一定程度上弥补了·OH的净损失.在最近20年中,·OH在对流层中的浓度基本稳定在106cm-3.本文还介绍了实验室研究方法及外场测量技术的进展,提出了尚待解决的一些问题.     

新型车载式激光雷达探测对流层气溶胶

介绍了中国科学院安光所自行研制的新型车载式激光雷达的结构和主要技术参数,给出了雷达数据的反演方法,并利用它对合肥地区对流层的大气气溶胶进行了探测。测量结果表明,该雷达具备昼夜连续观测对流层大气气溶胶的能力,可以很好地反映气溶胶粒子的时间与空间分布特征。     

车载式1 064 nm 和532 nm双波长米散射激光雷达

 新近研制的车载式双波长米散射激光雷达可用于1 064 nm 和532 nm两个波长对白天与夜晚对流层气溶胶消光系数垂直分布进行的探测。该激光雷达由激光发射单元、接收光学和后继光学单元、信号探测和采集单元以及系统运行控制单元组成，后继光路之间采用光纤导光、高低层分层探测等关键技术。该激光雷达使用1 064 nm和532 nm的两个波长，其单发脉冲能量分别为400和300 mJ，重复频率都为20 Hz，光束发散角小于0.5 mrad ；望远镜接收视场为1～3 mrad，滤光片的中心波长为1 064 nm和532 nm，带宽1 nm。分别使用R3236及H7680的PMT和VT120及Phillips777的放大器对两个波长的信号进行探测；对532 nm波长用3 A/D采集卡、1 064 nm波长用了光子计数卡。给出了双波长测量对流层气溶胶消光系数垂直分布的结果，该激光雷达可以探测10 ^-5～1之间的消光系数，探测高度可达10 km以上。     

紫外域激光雷达探测西安城区上空大气气溶胶时空剖面

开发了一套紫外域波长的米散射激光雷达系统,探测西安城区上空大气气溶胶污染物质的光学特性及时空变化.系统选用对人眼较为安全的355 nm波长激光作光源,采用高光谱分辨率光栅,并借助光阑,将接收到的主要大气回波信号谱线（米散射和瑞利散射光谱与白天太阳背景光）从空间分离,剔除大部分太阳背景噪音,提高系统的白天探测能力.通过对西安城区上空的气溶胶时空变化特性进行24 h连续观测,采用Klett方法反演得到气溶胶消光系数,首次测得西安城区不同时刻消光系数的高度分布剖面图以及24 h内气溶胶相对质量密度的时空变化特性.     

Long-term trends of tropospheric carbon monoxide and hydrogen cyanide from analysis of high resolution infrared solar spectra

Long-term trend and seasonal variation of the mean free tropospheric volume mixing ratios of carbon monoxide (CO) and hydrogen cyanide (HCN) have been derived from analysis of a time series of solar absorption spectra recorded from the US National Solar Observatory on Kitt Peak (31.9°N, 111.6°W, 2.09 km altitude) spanning almost three decades. The results of a fit to the CO 258 daily averages from May 1977 to April 2005 as a function of time with a model that assumes a sinusoidal seasonal cycle and a linear long-term trend with time yield a mean volume mixing ratio of 102±3) parts per billion (10^-9 per unit volume) below 10 km altitude, 1 sigma. The CO measurements show a seasonal cycle with a maximum in March and a minimum in September with an amplitude of (22.3±1.5)% relative to the mean. The best-fit corresponds to a long-term CO trend of , 1 sigma, relative to the mean. To quantify the possible impact of periods of intense fires, the CO measurements have been compared with the measurements of HCN, a well-documented emission product of biomass burning with a lifetime of ∼5 months. The best fit to the full HCN time series of 208 daily averages from May 1978 to April 2005 results in a mean volume mixing ratio of below 10 km altitude with a similar seasonal cycle, though with a lower relative amplitude than for CO. Although same-day enhancements up to a factor of 1.87 for HCN and 1.24 for CO were measured relative to values predicted by a fit to the time series that accounts for the seasonal cycles and trends of both molecules, excluding time periods of elevated fire emissions has no significant impact on the best-fit long-term free tropospheric CO and HCN trends. Our result of no long-term CO trend since the late 1970s suggests that the global average long-term decline reported from 1990 through 1995 measurements has not continued in the free troposphere. Similarly, a fit to the full time series of 208 HCN free tropospheric daily averages with the same model yields an average 2.09-10 km mixing ratio of 0.219 ppbv and a long-term trend of , 1 sigma, relative to the mean since 1978, also indicating no significant long-term trend above the lower mid-latitude continental US Kitt Peak station. The results for both molecules suggest the site was not significantly impacted by summer boreal fires during the time span of the measurements that in some years cause widespread pollution above northern higher latitude sites.     

天山北坡绿洲城市车流量与对流层NO2垂直柱浓度关系研究

为探讨天山北坡河谷绿洲城市车流量与对流层NO₂垂直柱浓度（VCD）的关系,基于各城市车流量状况,利用地基多轴差分光谱仪（Mini MAX-DOAS）在2018年-2019年天山北坡经济带上的综合性大城市乌鲁木齐、工业型中等城市石河子和工业型小城市阜康市中心区连续固定监测,并沿城市交通主干道进行车载移动监测,研究车流量对NO₂VCD的影响,对比分析山盆体系河谷绿洲城市与中东部发达城市污染严重原因的差异。结果表明：（1）天山北坡大中小城市的车流量日均值大城市乌鲁木齐（1 406辆/5 min）远大于中小城市,中等城市石河子（203辆/5 min）和小城市阜康（185辆/5 min）差异并不显著（p＞0.05）,而各类城市NO₂VCD整体差异显著（p＜0.05）,其日变化峰值有所差异,表现为乌鲁木齐（22.613×1015 molec·cm-2）＞阜康（17.758×1015 molec·cm-2）＞石河子（15.272×1015 molec·cm-2）,三类城市的车流量和NO₂VCD的日变化趋势一致,都呈现出“早晚高,中午低”的变化趋势;季节变化中三类城市的车流量和NO₂VCD均为：冬春季＞秋夏季;（2）虽然早晚各监测点的车流量有所差异,但三类城市的车流都集中在市中心附近;移动监测数据表明,NO₂VCD高值出现在车流较高的市区,并且在各城市风向稳定时,下风向浓度大于上风向;由于居住空间差异,人们在城市各功能区间的活动,车辆流向和NO₂VCD都集中于人流密集的商业区,说明车辆对NO₂VCD具有较大贡献;（3）2009年-2019年10年间天山北坡大中小城市经济生产总值增长率在200%以上,乌鲁木齐、石河子机动车增长率超过北京、上海等发达城市,城市快速发展,并处于河谷绿洲地带,地势南高北低,冬季逆温层深厚,静风天数较多,采暖期长达6个月,造成冬季污染严重。天山北坡城市除人为污染排放外,自然因素对污染物形成聚集作用。