基于O2-O2吸收的非相干宽带腔增强吸收光谱浓度反演方法研究

针对传统非相干宽带腔增强吸收光谱浓度反演方法的定量结果易受镜片反射率标定误差的影响问题, 提出了一种基于测量大气O₂-O₂吸收的浓度反演方法. 该方法是将非相干宽带腔增强吸收光谱技术的光学增强腔等效成吸收光程不随波长变化的多次反射池, 首先根据测得的宽带腔增强大气吸收谱和参考谱计算出光学厚度, 并应用差分光学吸收光谱算法拟合修正后的气体吸收截面到光学厚度, 反演得到大气中O₂-O₂以及被测气体的柱浓度, 然后根据O₂-O₂在大气中的含量已知且相对稳定这一特性, 确定出等效多次反射池的吸收光程, 最后从被测气体的柱浓度中扣除吸收光程信息得到被测气体的浓度值. 以监测大气中NO₂实验为例, 应用该方法在454-487 nm波段反演得到了大气NO₂的浓度(1-30 ppbv范围内), 并将反演结果与传统浓度反演方法的结果进行了对比, 发现两者的不一致性在7%以内. 实验结果表明, 非相干宽带腔增强吸收光谱技术可以利用大气O₂-O₂的吸收来定量其他被测气体的浓度, 而且定量结果对镜片反射率的标定误差不敏感.     

基于量子相干控制吸收的准Λ型四能级原子局域化研究

提出了一种基于量子相干控制吸收的对准Λ型四能级原子进行二维局域化方案. 利用密度矩阵微扰理论, 得到了确定原子空间位置信息的筛选函数解析表达式. 在缀饰态表象中, 分析了在相干控制场作用下原子初始状态对原子局域的影响. 数值模拟了控制场参量对原子局域化结果的影响. 研究发现原子局域化结果与初始时刻在控制场作用下原子在下能态的布局、下能级间产生的极化密切相关; 不管探测场与耦合场是否满足电磁感应透明配置条件, 通过改变控制场中的行波场的振幅和探测场的失谐量, 均可实现高精度原子局域化, 在亚波长范围内测量到原子的概率达到100%.     

飞秒脉冲激光啁啾对4,4’-二(二正丁胺基)二苯乙烯的光限幅及动态双光子吸收的影响(英文)

通过采用预估矫正的时域有限差分方法(FDTD)数值求解Maxwell-Bloch方程,研究飞秒啁啾脉冲激光在4,4’-二(二正丁胺基)二苯乙烯(BDBAS)分子介质中的光限幅行为(OL)和动态双光子吸收(TPA)截面.计算表明啁啾率的符号和大小都对频谱演化和光限幅行为产生影响.啁啾率的符号决定频移的方向:正啁啾对应频谱蓝移,负啁啾对应频谱红移.随着啁啾率绝对值的增大,频移更加明显,光限幅窗口变窄,同时出射光强饱和值变大.有趣的是,当负啁啾降低到一定值(-0.025/fs2)时,出现自感应透明(SIT)现象.另外,动态双光子吸收截面在考虑啁啾效应的情况下减小.本研究提供了一种控制非线性光学吸收的方法.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

Spherical silica particles decorated with graphene oxide nanosheets as a new sorbent in inorganic trace analysis

Graphene oxide (GO) is a novel material with excellent adsorptive properties. However, the very small particles of GO can cause serious problems is solid-phase extraction (SPE) such as the high pressure in SPE system and the adsorbent loss through pores of frit. These problems can be overcome by covalently binding GO nanosheets to a support. In this paper, GO was covalently bonded to spherical silica by coupling the amino groups of spherical aminosilica and the carboxyl groups of GO (GO@SiO₂). The successful immobilization of GO nanosheets on the aminosilica was confirmed by scanning electron microscopy and X-ray photoelectron spectroscopy. The spherical particle covered by GO with crumpled silk wave-like carbon sheets are an ideal sorbent for SPE of metal ions. The wrinkled structure of the coating results in large surface area and a high extractive capacity. The adsorption bath experiment shows that Cu(II) and Pb(II) can be quantitatively adsorbed at pH 5.5 with maximum adsorption capacity of 6.0 and 13.6 mg g⁻¹, respectively. Such features of GO nanosheets as softness and flexibility allow achieving excellent contact with analyzed solution in flow-rate conditions. In consequence, the metal ions can be quantitatively preconcentrated from high volume of aqueous samples with excellent flow-rate. SPE column is very stable and several adsorption–elution cycles can be performed without any loss of adsorptive properties. The GO@SiO₂ was used for analysis of various water samples by flame atomic absorption spectrometry with excellent enrichment factors (200–250) and detection limits (0.084 and 0.27 ng mL⁻¹ for Cu(II) and Pb(II), respectively).     

The effect of boric acid on the vapour liquid equilibrium of aqueous potassium carbonate

Aqueous potassium carbonate has seen renewed interest as a viable solvent for pre and post combustion carbon capture and storage. However, slow reaction kinetics may require the addition of a rate promoter such as boric acid to improve efficiency. The vapour liquid equilibrium of 30 weight percent potassium carbonate with 0, 3 and 5 weight percent boric acid was investigated at 50 and 70 °C using a dynamic inert gas stripping method. By estimating the boric acid reactions an Electrolyte-NRTL model was able to fit this data and literature results very closely.     

Feasibility of high-resolution continuum source molecular absorption spectrometry in flame and furnace for sulphur determination in petroleum products

For the first time, high-resolution molecular absorption spectrometry with a high-intensity xenon lamp as radiation source has been applied for the determination of sulphur in crude oil and petroleum products. The samples were analysed as xylene solutions using vaporisation in acetylene-air flame or in an electrothermally heated graphite furnace. The sensitive rotational lines of the CS molecule, belonging to the ?ν = 0 vibrational sequence within the electronic transition X¹∑⁺ → A¹П, were applied. For graphite furnace molecular absorption spectrometry, the Pd + Mg organic modifier was selected. Strong interactions with Pd atoms enable easier decomposition of sulphur-containing compounds, likely through the temporal formation of Pd_xS_y molecules. At the 258.056 nm line, with the wavelength range covering central pixel ± 5 pixels and with application of interactive background correction, the detection limit was 14 ng in graphite furnace molecular absorption spectrometry and 18 mg kg⁻¹ in flame molecular absorption spectrometry. Meanwhile, application of 2-points background correction found a characteristic mass of 12 ng in graphite furnace molecular absorption spectrometry and a characteristic concentration of 104 mg kg⁻¹ in flame molecular absorption spectrometry.The range of application of the proposed methods turned out to be significantly limited by the properties of the sulphur compounds of interest. In the case of volatile sulphur compounds, which can be present in light petroleum products, severe difficulties were encountered. On the contrary, heavy oils and residues from distillation as well as crude oil could be analysed using both flame and graphite furnace vaporisation. The good accuracy of the proposed methods for these samples was confirmed by their mutual consistency and the results from analysis of reference samples (certified reference materials and home reference materials with sulphur content determined by X-ray fluorescence spectrometry).     

The hydrolytic effect of moisture and hygrothermal aging on poly(butylene succinate)/organo-montmorillonite nanocomposites

The study of hydrolysis on biodegradable poly(butylene succinate) (PBS) is essential to predict the materials properties in a humid environment. In this study, PBS nanocomposites were exposed to different conditions of relative humidity (RH) and temperature. The moisture uptake increased with organo-montmorillonite (OMMT) loading and the RH of the testing environment. The exposure of PBS and the nanocomposites to a humid environment caused changes in the mechanical properties. The hydrolytic degradation becomes more pronounced upon hygrothermal aging at high temperature, whereby premature failure occurred. PBS nanocomposites were found to exhibit a better hydrolytic stability than neat PBS. The degradation was evaluated through Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). A drastic reduction in the molecular weight of PBS has revealed the occurrence of degradation after exposure to moisture and heat. This has led to an alteration of the thermal behavior as investigated using differential scanning calorimetry (DSC).     

A rapid solid sampling method for determination of nickel and copper along human hair by ETAAS

A procedure for copper and nickel determination in scalp hair by solid sampling electrothermal atomic absorption spectrometric method was described. The hair samples (0.02 to 0.4 mg) were inserted directly on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the determination of copper and nickel by solid sampling atomic absorption spectrometry were investigated. After optimization of parameters, the average recoveries of copper in two different certified reference hair samples were 105.7 and 97.6%. The recoveries of nickel in the both certified reference hair samples were in 95.2 and 96.4%. The limits of detection (3σ, N = 10) for copper and nickel were 22 ng/g and 35 ng/g, respectively. Heterogenous distribution of analyte in microscale for segmental analysis could be determined which is important to know that analyte quantity and time of poisoning of a person was exposed. For this purpose, 0.5 cm of pieces were cut along one or a few close strands and analyzed by solid sampling. This process could not be performed by wet-digestion method because 50 mg of sample is needed each time. Finally, the method was applied for the determination of copper and nickel concentrations in the hairs of different persons.     

Determination of copper traces in water samples by flow injection-flame atomic absorption spectrometry using a novel solidified floating organic drop microextraction method

A simple, rapid and inexpensive solidified floating organic drop microextraction (SFODME) and flow injection flame atomic absorption spectrometric determination (FI-FAAS) method for copper were developed. 3-amino-7-dimethylamino-2-methylphenazine (Neutral red, NR) was used as the complexing agent. Several factors affecting the microextraction efficiency, such as, pH, NR and sodium dodecylbenzenesulfonate (SDBS) concentration, extraction time, stirring rate, and temperature were investigated and optimized. Under optimized experimental conditions an enrichment factor of 541 was obtained for 100 mL of sample solution. The calibration graph was linear in the range of 0.5–20.0 ng mL^{− 1} and the limit of detection (3 s) was 0.18 ng mL^{− 1}, the limit of quantification (10 s) was 0.58 ng mL^{− 1}. The relative standard deviation (RSD) for 10 replicate measurements of 10 ng mL^{− 1} copper was 2.7%. The developed method was successfully applied to the extraction and determination of copper in different certified reference materials (Estuarine water, Slew 3 and fortified water, TM 23.2) and real water samples and satisfactory results were obtained.