压缩真空态光场中二能级原子的简并双光子荧光谱

利用原子约化密度算符主方程的方法研究了多模压缩真空态光场中二能级原子的双光子荧光谱。我们发现存在一种Rabi振荡阈值,在阈值之下原子的简并双光子荧光谱呈现洛仑兹线型单峰结构。在阈值之上具有三峰结构。其三峰的线宽和峰高均呈现很强的相敏性,中峰线宽可小于热光场中的线宽,但大于真空场中双光子的自然线宽,两边峰的线宽随压缩光的强度增大而增宽,边峰到中峰的距离也依赖于压缩真空态光场的压缩特征。

叶绿体内多光子荧光谱及激子湮灭

实验表明,用波长为1.06μm的红外激光辐射植物叶片或叶色素提取液,在可见光区(480—520nm波段)有荧光发射.荧光发射光子能量比激发光子能量大.经分析判断,多光子荧光谱出自类胡萝卜素,这种现象为激发态离子相互作用引起的再吸收效应。

NO分子A^2Σ←X^2Π跃迁的激光双光子荧光激发谱

以Nd :YAG脉冲激光器泵浦的光学参量发生器 放大器 (OPG OPA)作激发光源 ,获得了 4 2 0～ 4 72nm波长范围内NO分子的双光子激光荧光激发谱 ,并利用此技术对NO分子的能级结构进行了实验研究 ,将所得谱线峰归属为NO(A2 Σ←X2 Π)的跃迁 ,荧光强度随激光强度的二次方变化关系表明此过程是一双光子激发过程。利用实验所得峰值波长计算了NO(A2 Σ)态的基振动频率ωe 和平衡位置的力常数k。通过对NO分子A2 Σ→X2 Π跃迁的荧光时间分辨光谱进行实验研究 ,得到 2 6 6Pa气压下A2 Σ(v′ =0 )态的能级寿命τ=5 3 76ns。测量荧光寿命随气压的变化 ,利用曲线拟合得到NOA2 Σ(v′=0 ,1)

Determination of Arsenic and Mercury in Soil by Microwave Digestion and Hidride GenerationAtomic Fluorescence Spectrometry

[Objective] The aim was to develop a rapid, simple method for determina- tion of arsenic and mercury in soil samples by atomic fluorescence spectrometry. [Method] The method for determination of As and Hg in soil by combined atomic fluorescence spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-80.0μg/L of As and 0-8.0 μg/L of Hg, and the detection limits of As and Hg was 0.036 μg/L and 0.015 μg/L, respectively. The precision for elevenfold determination of As at 40.0 ug/L level and Hg at 4.0μg/L level were 1.1% and 2.2%（RSD）, respectively. Recoveries of 103.0%-106.6% for As and 90.0%-95.0% for Hg were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of As and Hg in soil samples.

Distribution,fractionation,and contamination assessment of heavy metals in offshore surface sediments from western Xiamen Bay,China

Surface sediment samples were collected at 21 offshore sites in western Xiamen Bay, Southeast China. Total concentrations of Li, V, Cr, Co, Ni, Cu, Zn, St, Mn, Pb, Ba, Fe, and Ti were determined by inductively coupled plasma-optical emission spectrometry; Hg was determined by atomic fluorescence spectrometry. A modified BCR sequential extraction procedure was used to extract fractions of the above elements. Concentrations of Pb, Cr, and Hg at most sites met the primary standard criteria of Marine Sediment Quality except site S12 for Pb and S7 for Cr, while concentrations of Zn at 17 sites and Cu at seven sites exceeded the criteria. The mean concentration of Hg was three times higher than the background, with a possible source being the Jiulong River. Fe, Ti, Ba, Co, V, and Li dominated the residual phase, mainly from terrestrial input. Ni, Cr, Pb, and Hg in the non-residual phase varied largely between sites. Sr, Mn, Cu, and Zn were mainly in the non- residual fraction. Most sites showed considerable ecological risk; exceptions were site S7 （very high） and sites S10, S11, and S14 （moderate）. Cu showed moderate-to-high pollution and Pb exhibited no-to-low pollution, while other metals had a non-pollution status according to their ratios of secondary phase to primary phase （RSP）. Results of two assessment methods showed moderate pollution and a very high ecological risk for Cu, Zn, Ni, and Cr at site S7, which might be due to the local sewage treatment plant.

Determination of Trace Germanium in Marine Sediments by Hydride Generation-Atomic Fluorescence Spectrometry (HG-AFS)

A method for the analysis of trace germanium in marine sediments by HG-AFS has been investigated. The experimental conditions such as the acidity of reduction reaction, the amount of sodium boro-hydride, the carrier gas flow rate, etc., were tested and optimized by using a kind of orthogonal design. The detection limit of the presented method is 0.95 μg L -1 for germanium. The calibration curve shows a satisfactory line in the concentration range 0-320 μg L -1 Ge with a variation coefficient of ±2.1%.

Time-resolved two-photon excitation fluorescence spectroscopy and microscopy using a high repetition rate streak camera

We present a time-resolved two-photon excitation fluorescence spectroscopy and a simultaneous time- and spectrum- resolved multifocal multiphoton microscopy system that is based on a high repetition rate picosecond streak camera for providing time- and spectrum- resolved measurement and imaging in biomedicine. The performance of the system is tested and characterized by the fluorescence spectrum and lifetime analysis of several standard fluorescent dyes and their mixtures. Spectrum-resolved fluorescence lifetime images of fluorescence beads are obtained. Potential applications of the system include clinical diagnostics and cell biology etc.

Photoacoustic and Fluorescence Spectroscopy of Metallomesogens Containing Lanthanide Ions

Metallomesogens Ln（bta）3L2 （Ln^3＋： La^3＋, Eu^3＋, and Ho^3＋; bta： benzoyltrifluoroacetonate; L： Schiff base） were prepared. Photoacoustic （PA） spectroscopy was used to study physicochemical properties of the liquid crystalline metal complexes. In the region of ligand absorption, PA intensity increases for Eu（bta）3L2, La（bta）3L2, and Ho（bta）3L2, in that order. It is found that the PA intensity of the ligand bears a relation to the intramolecular energy transfer process. For the first time, phase transitions of Eu（bta）3L2 from glass state to smectic A （SmA） phase and SmA phase to isotropic liquid are monitored by PA and fluorescence （FL） spectroscopy from two aspects： nonradiative and radiative transitions. The results show that PA technique may serve as a new tool for investigating the spectral properties and phase transitions of liquid crystals containing metal ions.

Characterization and recycling of nickel- and chromium-contained pickling sludge generated in production of stainless steel

Pickling sludge generated during the neutralization of pickling wastewater with calcium hydroxide in stainless steel pickling process was characterized using X-ray fluorescence spectrometry, X-ray diffractometry, scanning electron microscopy, thermogravimetry and differential scanning calorimetry, etc. The major compositions of pickling sludge are CaF2, CaSO4, Me（OH）, （M： Fe, Cr, Ni）, and the content of CaF2 is high in the sludge. The melting point of pickling sludge is about 1350℃ and the viscosity is about 0.14 Pa.s at 1450 ℃, which are comparatively lower than those of normal refining slag. After heat treatment, the contents of sulfur and fluorine in the pickling sludge were reduced, confirming the thermal decomposition of sulfate in the sludge. Fluorine in the sludge is reduced by the gaseous SiF4 and A1F3 generated through the reactions of CaF2 with SiO2 and Al2O3. The preliminary results from the reduction test indicate that the sulfur content in the steel is not affected by the presence of sulfur in the sludge. The recovery of nickel is about 40%, and the chromium content changes marginally due to the protective atmosphere under the reduction condition of chromic oxide. The pickling sludge is a potential auxiliary material for the production of stainless steel.

Study on Atomic Fluorescence Spectrometry Excited by Synchrotron Radiation

A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.

Determination of Cadmium in TSP, PM10 in urban areas by hydride generation atomic fluorescence spectrometry

In this paper, two different diameter particles （TSP, PM10） were collected by TH-16A four-channels classification air sampler. The samples were treated by HNO3. Analysis of cadmium was carried out by hydride generation atomic fluorescence spectrometry （HG-AFS） method, and distribution proportions of elements in four phases were calculated. This method was based on the reaction of cadmium with 1.5% （m/v） KBH4 solution and 0.5% KOH（m/v） solution to form the hydride gas in medium of 2% （v/v） HCl. The detection limit for cadmium as low as 0.008μg/L was obtained. The lineally correlation coefficient was 0.99992. The relative standard deviation （n=5, C=1.00μg/L） was 3.26%. The proposed method was applied for the determination of cadmium in atmosphere aerosol samples and the recoveries in the range of 95-102.2% were obtained. This method was simple, rapid, less matrix interference and high sensitivity.

Theoretical Studies on Electronic Structures and Spectroscopy of Fluorescent Arylamino Fumaronitrile

A new series of fluorescent arylamino fumarinitrile derivatives was designed and optimized using density function theory at the B3LYP/6-31G^＊ level. Based on the optimized geometries, the electronic, fluorescent and 13C NMR spectra are calculated with INDO/CIS, CIS-ZINDO TD, and B3LYP/6-31G^＊ methods, respectively. Starting with the first of the series, the LUMO-HOMO energy gaps of the derivatives become wider and the fluorescent wavelengths and the main peaks in the electronic spectra are blue-shifted owing to the large steric effect of naphthyl rings. On the contrary, the energy gaps of the derivatives turn narrow, and the fluorescent wavelengths and the main peaks in the electronic spectra are red-shifted since hydroxyl groups improve the symmetry and extend the conjugation system. The chemical shifts of sp^2-C on the phenyl rings are moved upfield, while chemical shifts of carbon atoms on the cyano groups and those connected with the cyano groups are changed downfield in the presence of hydroxyl groups.

Simultaneous determination mercury species of Su-He-Xiang-Wan in rat tissues by HPLC-CVG-AFS

A simple and sensitive high performance liquid chromatography-chemical vapour generation-atom fluorescent spectrometry （HPLC-CVG-AFS） method was developed and validated for simultaneous determination mercury species in Su-He-Xiang-Wan （SHXW） and in tissues of rats, respectively. The species of mercury were separated by a Venusil MP-C 18 （5μm, 150 mm×4.6 ram） column with the optimized mobile phase containing 5% （w/v） acetonitrile, 0.01 mol/L L-cysteine and 0.06 moL/L ammonium acetate. The tissues of rats were freeze-dried after giving the medicine for 10 d, and then added into the solution containing 10% （w/v） HC1, 1% （w/v） sulfocarbamide and 0.15% （w/v） KC1 for increasing extraction rate. The resolutions of Hg2＋, MeHg and EtHg were 1.5 and 2.9, respectively. The detection limits of Hg2＋, MeHg and EtHg were 2.0, 1.0 and 0.9 ng/mL, respectively. The relative standard deviation （RSD） of inter- and intra-day precisions ranged from 1.56% to 2.86%. The recovery rates of three different adding level were 87%-101% （n=6）, and the RSDs were smaller than 8.2%. The results show that no MeHg and EtHg were detected in rat tissues. Only soluble mercury （Hg2＋） was determined for the mercury species of SHXW in rat tissues.

Occurrence and distribution of dissolved tellurium in Changjiang River estuary

With the implementation of the GEOTRACES program, the biogeochemical cycle and distribution of tellurium （Te） in marine environments are becoming increasing environmental concerns. In this study, the concentration of dissolved Te in the Changjiang （Yangtze） River estuary and nearby waters was determined in May 2009 by hydride-generation atomic fluorescence spectrometry to elucidate the abundance, dominant species, distribution, and relationship with environmental factors. Results show that： （1） dissolved Te was low owing to its low abundance in the Earth＇s crust, high insolubility in water, and strong affinity to particulate matter; （2） Te（IV） and Te（VI） predominated in surface water. Te（VI） was the dominant species in bottom water, and Te（IV） was the minor species; （3） Horizontally, resulting from low phytoplankton metabolism and the weak reduction from Te（VI） to Te（IV） in the shore, Te（IV） was concentrated in the central zone instead of the coastal region. However, Te（VI） was abundant near the mouth of the Changjiang River where the Changjiang water is diluted and in the area to the south where the Taiwan Warm Current invaded. In the adsorption-desorption process, Te（IV） was negatively related to suspended paniculate matter （SPM）, indicating that it was adsorbed by particulate matter. While for Te（VI）, the positive correlation with SPM suggested that it was desorbed from the solid phase. In the estuary, dissolved Te had a negative correlation to salinity. However, it deviated from the dilution line in high-salinity regions due to the invasion of the Taiwan Warm Current and the mineralization of organic matter. The relationship between Te（IV） and SPM nutrients indicated that it was more bioavailable and more related to phosphorus than to nitrogen. Progress in the field is slow and more research is needed to quantify the input of Te to the estuary and evaluate the biochemical role of organisms.

Laser-induced Fluorescence Excitation Spectrum of NiS in 15500-17200 cm^-1

The laser-induced fluorescence excitation spectrum of jet-cooled NiS molecule has been recorded in the energy range of 15500 17200 cm-1. Fifteen bands have been assigned as three transition progressions：[15.65]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）,[15.69]^3∑0^-（v′=0-4）-X^3∑0^-（v″=0）,and [15.81]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）.Spectroscopic constants for the three newly identified electronically excited states have been determined for the first time. In addition,the lifetimes for most observed vibronic bands have also been measured.

Preliminary Assessment of Total Mercury in Bulk Precipitation around Olkaria Area, Kenya

Geothermal power plants are receiving increasing attention as regards the mobilization of mercury （Hg） to the environment. Hg is a trace element that may be present in the geothermal fluid, but due to its volatility, it is transferred mainly into the vapor phase. Hence, it may be mostly discharged to the atmosphere with the non-condensable gases. Olkaria geothermal field hosts 3 geothermal power plants. In this area Hg deposition fluxes have not been studied. Concentrations and wet deposition fluxes of total mercury （T-Hg） were determined from April 2009 to May 2010 at 2 sites in this field. Event-based precipitation samples were collected using fabricated bulk precipitation samplers. Samples were treated according to trace metal protocol and analyzed by cold vapor atomic fluorescence spectrometry （CVAFS）. This paper thus reports the first ever determination of T-Hg concentrations and fluxes in precipitation. The T-Hg concentration in samples ranged from 0.002-0.0602 μg/L at the two sites, however, the volume-weighted mean concentration and wet deposition flux were 0.01974 and 0.02884μg.L^-1 and 0.0167-1.45 μg.m2 during the study period. The annual volume-weighted mean wet deposition fluxes of T-Hg for 2 sites were 13.74 and 19.83 μg.m-2.yr-1 with an average flux of 16.785μg.m-2.yr-1. Hg concentrations and the Hg fluxes in precipitation showed seasonal trends being lowest in the short-rains and highest in the long rains. The concentrations of T-Hg for the 2 sites is negatively correlated with the precipitation depth （r2 = 0.26 ＆ r2 = 0.0065）, suggesting that scavenging of particle-bound mercury from the atmosphere is an important mechanism contributing to mercury in rainwater. Mean Hg concentrations in precipitation at the study sites were comparable to the ranges reported for Canada and the USA by the Mercury Deposition Network （MDN）.

Determination of Hg in soil by ultrasonic slurry sampling hydride generation atomic fluorescence spectrometry

Ultrasonic aided slurry sampling hydride generation atomic fluorescence spectrometry （USS-HG-AFS） was developed for the determination of Hg in soil samples from a sewage-irrigated farm. 500 mg grounded soil was suspended in agar solution by an ultrasound water bath before the HG-AFS determination. The results for the reference material of soil （serial number GBW-07411） agreed satisfactorily with the certified values. Results obtained by the developed procedure compared well with those after traditional acid digestion of samples. The detection limit are 6.7ngL-1 for Hg respectively, with average relative standard deviation values of 6.4% for analysis of a series of soil samples of different origin. The recoveries of the anatytes varied in the range from 95 to 107%. This observation has stimulated interest in fast, accurate and sensitive analytical methods for determination of metals in soil.

Energy Transfer and Electron Transfer in Composite System of Carbon Quantum Dots/Rhodamine B Molecules

In this work, we investigated the energy transfer (EnT) and electron transfer (ET) processes as well as their relationship in the carbon quantum dots/rhodamine B (CQDs/RhB) including o-CQDs/Rh B and m-CQDs/RhB systems by using photoluminescence spectroscopy in combination with steady-state and transient absorption spectroscopy. We found that the ET process is negligible in the o-CQDs/RhB system with an EnT efficiency as high as 73.2%,while it becomes pronounced in the m-CQDs/RhB system whose EnT efficiency is lower than 33.5%. Such an interplay of En T and ET processes revealed in the prototypical composite system consisting of carbon quantum dots and dye molecules would provide helpful insights for applications of relevance to exciton quenching.

Determination of trace lead and mercury in airborne particles by hydride generation atomic fluorescence spectrometry

A new method for determination of trace lead and mercury by hydride generation atomic fluorescence spectrometry （HG-AFS） was established. Lead was determined in the medium of citric acid using potassium ferricyanide （K3Fe（CN）6） as oxidant. Ni enhanced the fluorescence signals in this system. Mercury was determined in the medium of nitric acid using mixture of thiourea and ascorbic acid as masking reagent, sodium dioctylsulphosuccinate （SDSS） as enhancing reagent. The working mechanism of the hydride generation of lead and mercury was discussed. Interferences of some coexisting ions were studied systematically and the determination conditions were optimized. Under the optimized conditions, the detection limits of the method were 0.31μg.L^-1 for lead and 0.023 μg·L^-1 for mercury, and the relative standard deviations based on eleven determinations of 5.00 μg·L^-1 standard of Pb and Hg, were 2.6% for Pb and 2.2 % for Hg. This method was applied to the analysis of lead and mercury in four different diameter airborne particles after microwave digestion. Results suggested heavy metal elements easily concentrated in smaller particles.

Laser-induced Fluorescence Spectroscopy of NiCl in 12900-15000 cm-1

Laser-induced fluorescence excitation spectra of jet-cooled NiC1 molecules were recorded in the energy range of 12900-15000 cm-1. Six vibronic bands with rotational structure have been observed and assigned to the [13.0]2II3/2（v＇=0-5）-X2II3/2（v＂=0） transition progression. The relevant rotational constants, significant isotopic shifts, and （equilibrium） molecular parameters have been determined. In addition, the lifetimes of the observed bands have also been measured.