塔克拉玛干沙漠黑碳气溶胶的特性及来源

长期监测并采集塔克拉玛干沙漠腹地的大气颗粒物及黑碳气溶胶样品.在塔克拉玛干沙漠腹地,沙尘气溶胶中的黑碳在PM10中的年平均含量高达1.14%,这说明在人迹罕至的塔克拉玛干沙漠地区,其上空的沙尘气溶胶也已经受到人为活动的影响.黑碳气溶胶具有明显的季节变化和日变化,冬季最高,平均达2261.7ngm-3,依次为冬季春季秋季夏季.黑碳气溶胶日变化特征与城市地区恰好相反,夜间高于白天,午夜0:00～2:00出现峰值,而在上午8:00～11:00出现低值.非沙尘暴期间黑碳对PM10的贡献是沙尘暴时期的11倍.塔里木盆地周边绿洲带人为活动,尤其是新疆南北部地区跨越春秋冬三季的居民采暖所产生的黑碳经由局地、区域或长途传输是塔克拉玛干沙漠腹地黑碳气溶胶的主要来源,也是沙漠黑碳气溶胶具有明显的季节特征和日变化的主要原因.随着沙尘气溶胶的长途传输,沙漠每年大约输出6.3×104吨黑碳气溶胶,这势必会对全球的气候与环境变化产生一定影响.     

环境及生物样品中黑碳的质谱分析技术研究进展

黑碳是由生物质及化石燃料燃烧产生的含碳颗粒,是除CO₂外对全球气候变暖贡献最大的辐射强迫因子。因此,黑碳对全球气候和环境系统具有重大影响。其次,黑碳超小(<100 nm)的粒径使其能够通过呼吸系统进入到人体内,其本身以及表面负载的有毒物质也会对人体健康产生严重危害。为了厘清黑碳对环境和人类健康的影响,研究人员已发展了多种针对黑碳颗粒的分析技术,其中质谱技术凭借出色的抗干扰能力和强大的定性定量分析性能成为研究黑碳环境效应和健康风险最有潜力的技术之一。该文综述了复杂介质中黑碳颗粒质谱分析技术的原理、技术特征和应用实例,并对未来黑碳的分析技术发展进行了展望。     

溶解态黑碳的环境过程研究

溶解态黑碳是黑碳连续体中可溶解于水的组分,是连接陆地土壤和海洋底泥两个主要黑碳库的关键纽带。溶解态黑碳也是天然可溶性有机质的重要组分,富含芳香微域结构和羧基、羟基、羰基等功能性官能团,具有较高的反应活性,可介导污染物在环境中的分配和转化过程。因此,研究溶解态黑碳的环境地球化学行为对研究全球碳循环以及污染物的环境归趋和效应都具有重要意义,已成为了相关领域的前沿和热点。本文综述了十余年以来溶解态黑碳在环境过程方面的研究进展,重点阐述了溶解态黑碳的定性、定量分析方法,在环境中的含量和空间分布、结构特征、环境转化过程,以及其对污染物吸附、氧化还原转化、光转化等环境行为的影响,并在此基础上对溶解态黑碳的未来研究方向进行了展望。     

NO2在黑碳表面的非均相反应

HONO是大气中OH自由基的重要来源,NO2在黑碳表面可反应生成HONO,因此NO2在黑碳表面的非均相反应引起了人们的关注。目前不同研究小组测量的摄取系数可相差7个数量级,选择不同的摄取系数去评估非均相反应的重要性将得到完全不同的结果。本文在深入分析NO2在黑碳表面反应机理的基础上,从反应体系、黑碳表面性质、反应条件等角度对不同小组测量的摄取系数存在差异的原因进行了分析,为模式中摄取系数的选取提供了依据。     

温度设置对热光法测定气溶胶中黑碳的影响

热光法中的无氧阶段最高温度(MT)和各温度阶梯的保持时间(HT)是测定大气气溶胶中黑碳的两个关键参数.该文采集了34个气溶胶样品(含20个大气样品和14个源排放样品),并设计了6个温度程序用以系统研究MT和HT对黑碳(BC)测定的影响.实验表明,提高MT的设置,会使BC测定值降低,最高温度为850℃时的BC值为550 ℃时的62%;而有机碳(OC)发生热解(碳化)与最高温度的关系没有固定的模式,这是由样品的化学成分不同造成的.增加保持时间,使BC的测定值下降约5%,使热解率下降10%.     

青藏高原雪冰样品中低含量水溶金属离子分析方法对比研究

从采自青藏高原阿汝和古里雅冰川的两支冰芯中选取31个样品,分别用三种仪器对比分析K^+、Na^+、Ca^2+、Mg^2+四种水溶金属离子,寻求最佳分析方案。分析结果对比发现,电感耦合等离子体发射光谱(ICP-OES)法在K+测量中存在困难,而离子色谱(IC)法和电感耦合等离子体质谱(ICP-MS)法均能够满足要求,且分析结果具有高度的一致性,四种离子的相关系数(R2)均在0.97以上,且并未出现ICP-MS法比IC法测量值明显偏高的现象。因此,除IC法外,ICP-MS法也是检测青藏高原雪冰样品中水溶金属离子的有效手段,其测定速度更快,且可以同时进行微、痕量元素检测,适用于大批量冰芯样品的快速分析。     

全球气候变化研究证据

全球气候和环境变化是国际上研究的热点问题,一般是提取与古气候相关的代用指标进行研究。从湖泊沉积物、树木年轮、冰芯、石笋、孢粉、海洋沉积物、珊瑚等方面,研究了国内近年来对过去近2000年来气候和环境变化的证据和方法。     

液相色谱-质谱法分析黑碳的分子标志物——苯多羧酸和硝基苯多羧酸

苯多羧酸法是定量检测黑碳和溶解态黑碳的重要分子标志物法,其中苯多羧酸和硝基苯多羧酸的分离和定量是关键环节。本文建立了苯多羧酸和硝基苯多羧酸的液相色谱-质谱分析方法,利用质谱的定性能力解决了部分苯多羧酸和硝基苯多羧酸化合物在缺乏标准品情况下的定性问题。用Phenomenex Synergi Polar RP分离柱,柱温为35 ℃,流动相为0.5%(体积分数)甲酸水溶液和甲醇,流速为0.5 mL/min,梯度洗脱,以电喷雾离子源负离子全扫描和选择扫描模式进行离子阱质谱检测,同时利用串联的二极管阵列检测器采集三维紫外光谱数据。在实际样品检测中,14个含3个及以上羧基的苯多羧酸和硝基苯多羧酸化合物获得良好分离。此方法简化并加快了苯多羧酸法定量黑碳和溶解态黑碳的分析过程,可满足环境样品中黑碳和溶解态黑碳的分析,促进了苯多羧酸法应用的普及。     

黑碳对大气环境的影响与控制

黑碳气溶胶是大气气溶胶的重要组成部分,主要是由富含碳的物质不完全燃烧产生的,比如化石原料和生物质原料燃烧等。黑碳气溶胶具有较为特殊的物理化学性质。黑碳气溶胶具有多孔性,粒径约在0．01-1μm。在化学成分上非常接近于石墨,在温度高于400％时才可以发生氧化。黑碳气溶胶对可见光和部分红外光谱有很强的吸收能力,它在大气中的各种化学和光化学反应、非均相反应以及气粒转化过程中起着重要作用。     

古里雅冰帽气候环境记录

古里雅冰帽极低的冰温和冻结到冰床等特征决定了该冰帽贮存了理想的气候环境记录。氧同位素、微粒含量、阴离子、阳离子等参数清楚的年际和季节循环特征,是该冰帽冰芯的高分辨率时间序列的准确断代的基础。冷期时稳定氧同位素值减少、微粒含量和各被测化学元素增加,而暖期时稳定氧同位素值增大、微粒含量和各被测化学元素减少的特征以及各种突发事件记录的合理解释将是系统恢复该冰帽所记录的各种气候环境的钥匙。古里雅冰芯记录表明,80年代中后期在这里发生的气候变暖是过去几十年最强烈的一次。     

Chemical signals of past climate and environment from polar ice cores and firn air

Chemical and isotopic records obtained from polar ice cores have provided some of the most iconic datasets in Earth system science. Here, I discuss how the different records are formed in the ice sheets, emphasising in particular the contrast between chemistry held in the snow/ice phase, and that which is trapped in air bubbles. Air diffusing slowly through the upper firn layers of the ice sheet can also be sampled in large volumes to give more recent historical information on atmospheric composition. The chemical and geophysical issues that have to be solved to interpret ice core data in terms of atmospheric composition and emission changes are also highlighted. Ice cores and firn air have provided particularly strong evidence about recent changes (last few decades to centuries), including otherwise inaccessible data on increases in compounds that are active as greenhouse gases or as agents of stratospheric depletion. On longer timescales (up to 800?000 years in Antarctica), ice cores reveal major changes in biogeochemical cycling, which acted as feedbacks on the very major changes in climate between glacial and interglacial periods.     

Laser ablation inductively coupled plasma mass spectrometry: a new tool for trace element analysis in ice cores

A new method for the detection of trace elements in polar ice cores using laser ablation with subsequent inductively coupled plasma mass spectrometry analysis is described. To enable direct analysis of frozen ice samples a special laser ablation chamber was constructed. Direct analysis reduces the risk of contamination. The defined removal of material from the ice surface by means of a laser beam leads to higher spatial resolution (300-1000 microm) in comparison to investigations with molten ice samples. This is helpful for the detection of element signatures in annual layers of ice cores. The method was applied to the successful determination of traces for the elements Mg, Al, Fe, Zn, Cd, Pb, some rare-earth elements (REE) and minor constituents such as Ca and Na in ice cores. These selected elements serve as tracer elements for certain sources and their element signatures detected in polar ice cores can give hints to climate changes in the past. We report results from measurements of frozen ice samples, the achievable signal intensities, standard deviations and calibration graphs as well as the first signal progression of 205Pb in an 8,000-year-old ice core sample from Greenland. In addition, the first picture of a crater on an ice surface burnt by an IR laser made by cryogenic scanning electron microscopy is presented.     

New application of a traditional analytical method – arsenic removal from water works sludge during iron(III) chloride coagulant production

A new method for the detection of trace elements in polar ice cores using laser ablation with subsequent inductively coupled plasma mass spectrometry analysis is described. To enable direct analysis of frozen ice samples a special laser ablation chamber was constructed. Direct analysis reduces the risk of contamination. The defined removal of material from the ice surface by means of a laser beam leads to higher spatial resolution (300– 1000 μm) in comparison to investigations with molten ice samples. This is helpful for the detection of element signatures in annual layers of ice cores. The method was applied to the successful determination of traces for the elements Mg, Al, Fe, Zn, Cd, Pb, some rare-earth elements (REE) and minor constituents such as Ca and Na in ice cores. These selected elements serve as tracer elements for certain sources and their element signatures detected in polar ice cores can give hints to climate changes in the past. We report results from measurements of frozen ice samples, the achievable signal intensities, standard deviations and calibration graphs as well as the first signal progression of ²⁰⁸Pb in an 8,000-year-old ice core sample from Greenland. In addition, the first picture of a crater on an ice surface burnt by an IR laser made by cryogenic scanning electron microscopy is presented.     

A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision delta13C measurements of atmospheric methane extracted from ice core samples

Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of delta13CH4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of approximately 200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 +/- 40 years) show a delta13C(VPDB) of -49.54 +/- 0.13 per thousand and Antarctic samples (1530 +/- 25 years) show a delta13C(VPDB) of -48.00 +/- 0.12 per thousand in good agreement with published data.     

Determination of trace amounts of heavy metals in arctic ice core samples using inductively coupled plasma mass spectrometry

Trace amounts of heavy metals in the ice cores from Canadian Arctic were analyzed using inductively coupled plasma mass spectrometry (ICP-MS). A custom made plastic device and ceramic knives were used to remove the contamination on the ice core surface. Ice cores could be broken into small sections (2-3 cm thick) after decontamination with the plastic device and ceramic knives. High-resolution depth profiles of various elements, i.e. As, Cd, Co, Cu, Ni, Pb, Zn and U, were thus attained. Concentrations in 518 ice core samples range from 0.1 (U) to 673.3 (Zn) pg g(-1).     

A new method based on low background instrumental neutron activation analysis for major,trace and ultra-trace element determination in atmospheric mineral dust from polar ice cores

Dust found in polar ice core samples present extremely low concentrations, in addition the availability of such samples is usually strictly limited. For these reasons the chemical and physical analysis of polar ice cores is an analytical challenge. In this work a new method based on low background instrumental neutron activation analysis (LB-INAA) for the multi-elemental characterization of the insoluble fraction of dust from polar ice cores is presented. Thanks to an accurate selection of the most proper materials and procedures it was possible to reach unprecedented analytical performances, suitable for ice core analyses. The method was applied to Antarctic ice core samples. Five samples of atmospheric dust (μg size) from ice sections of the Antarctic Talos Dome ice core were prepared and analyzed. A set of 37 elements was quantified, spanning from all the major elements (Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe) to trace ones, including 10 (La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu) of the 14 natural occurring lanthanides. The detection limits are in the range of 10⁻¹³–10⁻⁶ g, improving previous results of 1–3 orders of magnitude depending on the element; uncertainties lies between 4% and 60%.     

Suppressed ion chromatography methods for the routine determination of ultra low level anions and cations in ice cores.

The concentration of trace ionic species in snow and ice samples was determined using suppressed ion chromatography (IC) with conductivity detection and ultra-clean sample preparation techniques. Trace anion species were determined in a single 24-min run by combining sample preconcentration with gradient elution using Na2B4O7 eluent. The detection limits (ranging from 0.001 to 0.006 microM) are the lowest reported in the literature. Cation species were analysed by direct injection of 0.25 ml and isocratic elution with a H2SO4 eluent. The clean preparation techniques showed no evidence of a difference (Student's t-test) between Milli-Q water samples analysed directly and processed Milli-Q ice samples. These robust, ultra-clean IC methods were routinely applied to the analysis of large number of samples to produce a high-resolution trace ion ice core record from Law Dome, East Antarctica.