Clustered and integrated fluorescence spectra from single atmospheric aerosol particles excited by a 263- and 351-nm laser at New Haven,CT, and Adelphi,MD

Fluorescence spectra from individual micron-sized atmospheric aerosol particles were measured by a Dual-wavelength-excitation Particle Fluorescence Spectrometer (DPFS). Particles were drawn into our laboratory at Adelphi, MD, an urban site in the Washington, DC, metroplex and within the Yale University campus at New Haven, CT. Two fluorescence spectra were obtained for every individual particle as it was moving through the DPFS system and excited sequentially by single laser pulses at 263 and 351 nm. There were around ten to a few hundred particles detected per second and up to a few million per day within the 1–10 μm particle size range. The majority of the particles have weak fluorescence, but 10–50% of the particles have fluorescence signals above the noise level at both sites at different time period. For the first time, these Ultra Violet laser-induced-fluorescence (UV-LIF) spectra from individual particles were integrated every 10 min, which forms a group of about a few thousand to a few tens of thousand particles, to provide the averaged background atmospheric fluorescence spectral profiles which may be helpful in the development of bioaerosol detection systems, particularly those systems based on integrated fluorescence from a group of aerosol particles, such as Light Detection And Rangeing (LIDAR) remotor biosensor and the point sensor based on collected particles on substrate. These integrated spectral profiles had small variations from time to time and were distinguishable from that of the bacterial simulant B. subtilis. Also for the first time, the individual spectra excited by a 351 nm laser were grouped using unstructured hierarchical cluster analysis, with parameters chosen so that spectra clustered into 8 main categories. They showed less spectral variations than that excited by a 263-nm laser. Over 98% of the spectra were able to be grouped into 8 clusters, and over 90% of the fluorescent particles were in clusters 3–5 with a fluorescence emission peak around 420–470 nm; these were mostly from biological and organic carbon-containing compounds. Integrated fluorescence spectral profiles and averaged spectra for each cluster show high similarity between New Haven, CT and Adelphi, MD.     

地基消光测量确定大气气溶胶模型

 分别取大陆型、海洋型、城市型和Junge谱分布气溶胶模型，用6S辐射传输算法计算出对应于太阳光度计测量时的各波段大气气溶胶光学厚度。将模式计算值与测量值进行比较，确定测量地区的大气气溶胶模型。将该方法用于2004年在北京地区测量的太阳光度计数据，结果显示该地区当日实际大气在几种气溶胶模型中较为符合城市型气溶胶模型。     

A k-distribution-based radiation code and its computational optimization for an atmospheric general circulation model

The gas absorption process scheme in the broadband radiative transfer code “mstrn8”, which is used to calculate atmospheric radiative transfer efficiently in a general circulation model, is improved. Three major improvements are made. The first is an update of the database of line absorption parameters and the continuum absorption model. The second is a change to the definition of the selection rule for gas absorption used to choose which absorption bands to include. The last is an upgrade of the optimization method used to decrease the number of quadrature points used for numerical integration in the correlated k-distribution approach, thereby realizing higher computational efficiency without losing accuracy. The new radiation package termed “mstrnX” computes radiation fluxes and heating rates with errors less than 0.6 W/m² and 0.3 K/day, respectively, through the troposphere and the lower stratosphere for any standard AFGL atmospheres. A serious cold bias problem of an atmospheric general circulation model using the ancestor code “mstrn8” is almost solved by the upgrade to “mstrnX”.     

Temperature measurements of high-temperature semi-transparent infrared material using multi-wavelength pyrometry

Temperature measurements inside semi-transparent materials are important in many fields. This study investigates the measurements of interior temperature distributions in a one-dimensional semi-transparent material using multi-wavelength pyrometry based on the Levenberg–Marquardt method (LMM). The investigated material is semi-transparent Zinc Sulfide (ZnS), an infrared-transmitting optical material operating at long wavelengths. The radiation properties of the one-dimensional semi-transparent ZnS plate, including the effective spectral–directional radiation intensity and the proportion of emitted radiation, are numerically discussed at different wavelengths (8.0–14.0 μm) and temperature distributions (400–800 K) to provide the basic data for the temperature inversion problem. Multi-wavelength pyrometry was combined with the Levenberg–Marquardt method to resolve the temperature distribution along the radiative transfer direction based on the line-of-sight spectral radiation intensities at multiple wavelengths in the optimized spectral range of (11.0–14.0 μm) for the semi-transparent ZnS plate. The analyses of the non-linear inverse problem show that with less than 5.0% noise, the inversion temperature results using the Levenberg–Marquardt method are satisfactory for linear or Gaussian temperature distributions in actual applications. The analysis provides valuable guidelines for applications using multi-wavelength pyrometry for temperature measurements of semi-transparent materials.     

Absolute line intensities measurements and calculations for the 5.7 and 3.6 μm bands of formaldehyde

The goal of this study is to achieve absolute line intensities for the strong 5.7 and 3.6 μm bands of formaldehyde and to generate, for both spectral regions, an accurate list of line positions and intensities. Both bands are now used for the infrared measurements of this molecule in the atmosphere. However, in the common access spectroscopic databases there exists, up to now, no line parameters for the 5.7 μm region, while, at 3.6 μm, the quality of the line parameters is quite unsatisfactory. High-resolution Fourier transform spectra were recorded for the whole 1600–3200 cm^?1 spectral range and for different path-length-pressure products conditions. Using these spectra, a large set of H₂CO individual line intensities was measured simultaneously in both the 5.7 and 3.6 μm spectral regions. From this set of experimental line strength which involve, at 5.7 μm the ν₂ band and, at 3.6 μm, the ν₁ and ν₅ bands together with nine dark bands, it has been possible to derive a consistent set of line intensity parameters for both the 5.7 and 3.6 μm spectral regions. These parameters were used to generate a line list in both regions. For this task, we used the line positions generated in [Margulés L, Perrin A, Janeckovà R, Bailleux S, Endres CP, Giesen TF, et al. Can J Phys, accepted] and [Perrin A, Valentin A, Daumont L, J Mol Struct 2006;780–782:28–42] for the 5.7 and 3.6 μm, respectively. The calculated band intensities derived for the 5.7 and 3.6 μm bands are in excellent agreement with the values achieved recently by medium resolution band intensity measurements. It has to be mentioned that intensities in the 3.6 μm achieved in this work are on the average about 28% stronger than those quoted in the HITRAN or GEISA databases. Finally, at 3.6 μm the quality of the intensities was significantly improved even on the relative scale, as compared to our previous study performed in 2006.     

Spectral properties of an UV fused silica within 0.8 to 5 µm at elevated temperatures

A thermal radiative inverse method was used to determine the high-temperature spectral properties of an ultraviolet fused silica from transmittance data for wavelengths from 0.8 to 5 µm. A developed FTIR system used to measure apparent transmittances of the fused silica sample has been designed and built. In order to reduce the system error caused by detector emission and stray radiation, a measurement strategy at high temperatures was proposed. For deriving spectral transport properties from experimental transmittances, the parameter identification principle was described. The results show that spectral properties are both wavelength dependent and temperature dependent. Spectral refractive indexes rise with increasing temperature and decrease with wavelength. Three absorption peaks of spectral absorptive indices respectively at about 1.4 µm, 2.22 µm and 2.75 µm shift toward the far infrared region and vary differently with increasing temperature. In addition, three absorption bands all become broader for temperatures from 20 °C to 900 °C.     

Conversion of ultraviolet and infrared to visible light in Er3+ and Dy3+ co-doped CsGd2F7

The CsGd₂F₇ crystal co-doped with 1 at% Er³⁺ and 0.2 at% Dy³⁺ ions was studied using the excitation of both synchrotron radiation and 355 nm laser. All the emission bands were assigned by using the Dieke diagram together with the conclusions from relaxation kinetics studies. The onset of the 4f–5d transition bands and the centers of charge transfer bands were also calculated for the lanthanide series CsLn₂F₇ and the results were used to assign the bands and peaks in the excitation spectra. The energy transfer and relaxation processes in CsGd₂F₇ were thoroughly analyzed. Quantum cutting downconversion of one vacuum ultraviolet to two visible photons was realized under 154 nm excitation. Upconverted green emission was observed under 980 nm excitation.     

Radiative transfer solutions for coupled atmosphere ocean systems using the matrix operator technique

Accurate radiative transfer models are the key tools for the understanding of radiative transfer processes in the atmosphere and ocean, and for the development of remote sensing algorithms. The widely used scalar approximation of radiative transfer can lead to errors in calculated top of atmosphere radiances. We show results with errors in the order of±8% for atmosphere ocean systems with case one waters. Variations in sea water salinity and temperature can lead to variations in the signal of similar magnitude. Therefore, we enhanced our scalar radiative transfer model MOMO, which is in use at Freie Universität Berlin, to treat these effects as accurately as possible. We describe our one-dimensional vector radiative transfer model for an atmosphere ocean system with a rough interface. We describe the matrix operator scheme and the bio-optical model for case one waters. We discuss some effects of neglecting polarization in radiative transfer calculations and effects of salinity changes for top of atmosphere radiances. Results are shown for the channels of the satellite instruments MERIS and OLCI from 412.5 nm to 900 nm.     

Radiation transfer in metallic powder beds used in laser processing

Two-dimensional radiation transfer in a powder layer backed with a substrate of the same material and normally irradiated with a narrow axially symmetric bell-like or the flat-top laser beam is numerically calculated. This corresponds to physical experiments with the powder layer of 50 μm thickness and the laser beam diameters 60–120 μm. The powder bed is treated as an equivalent homogeneous absorbing scattering medium, the radiative properties of which are estimated from the optical properties of the solid phase and the morphological parameters of the powder bed. The theoretical analysis shows that the absorptance of a semi-infinite powder bed of opaque particles is a universal function of the absorptivity of the solid phase being independent of the specific surface and the porosity. This is confirmed by literature experimental data. The radial transport of the radiative energy due to scattering of the incident laser beam in the powder layer can considerably reduce the deposited energy at the centre of the beam but the widening of the radial profile of the deposited energy is not pronounced. The fraction of laser energy deposited within the projection of the incident laser beam is evaluated. The efficiencies of laser heating the whole powder/substrate system and the substrate decrease with increasing the reflectivity of the material. More uniform heating of the powder layer can be attained at higher reflectivity.     

A neodymium fluid laser: Laser emission in circulating state

Differing from conventional liquid lasers, a novel concept of fluid laser was provided, which has attractively potential using in high average power lasers. The laser medium was prepared by dispersing Nd³⁺: phosphate glass micro-balls in organic match liquid. Its optical properties were investigated and the radiative transition rate was calculated by Judd–Ofelt theory. The experiment of laser oscillation in static state indicates that the heat exchanging has limited effect on refractive index of the fluid laser medium in a short time. In circulating state, a laser oscillation occurred at 1058.1 nm when pumped by two 808 nm diode lasers. The maximum output energy is 2.58 mJ with the absorbed pumping energy of 460 mJ. This study offers a new way in the exploration of high average power laser.     

Mid-infrared luminescence and energy transfer of Dy3+/Tm3+ doped fluorophosphate glass

This work reports the observation of emissions at 2.9 μm, 1.8 μm and 1.47 μm from Dy³⁺/Tm³⁺ codoped fluorophosphate glass upon excitation of a conventional 800 nm laser diode. Judd–Ofelt intensity parameters and radiative properties of Dy³⁺ ions in present glasses were calculated using the Judd–Ofelt theory. The mechanism and microparameters of energy transfer processes were investigated based on photoluminescence performance and lifetime measurements. The Dy³⁺/Tm³⁺ codoped fluorophosphate glass possessing advantageous spectroscopic characteristics as well as excellent thermal stability is a promising candidate for an efficient 2.9 μm laser.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Sensitivity of stratospheric ozone lidar measurements to a change in ozone absorption cross-sections

The effect of a change in ozone absorption cross-section data is evaluated for stratospheric ozone lidar measurements, which are regularly performed for the monitoring of the ozone layer. The change is analysed for the measurements based on both the elastic and Raman scattering of the laser light by the atmosphere. The latter technique is essentially used for measurements performed in the presence of volcanic aerosol layers in the stratosphere. The discrepancy in ozone number densities is evaluated for various ozone cross-section data sets, using an atmospheric model for the evaluation of ozone cross-section temperature dependence. Results show that the difference in both elastic and Raman DIAL retrievals is below 1.5% in absolute values from 10 to 30 km. Above 30 km, the difference, estimated for the elastic DIAL retrieval only, is maximum around 45 km, with largest differences reaching 1.8% in the tropics.     

基于MODTRAN模型使用被动傅里叶变换红外光谱技术对生物气溶胶的探测研究

利用MODTRAN模型在水平低仰角探测模式下,对生物气溶胶探测的问题进行了分析讨论.用傅里叶变换红外(FTIR)光谱技术对生物气溶胶进行探测研究.首先介绍了MODTRAN模型的大气模式和廓线,根据FTIR光谱技术对生物气溶胶的被动探测要求,利用辐射传输理论和最简单的三层模型,仿真计算得到大气背景和目标生物气溶胶之间的辐射亮度差?L,然后对?L进一步差值得到信号?2Lt,同时再结合光谱仪自身的噪声等效辐射亮度值,得到实际情况下的信号值?2Lt;最后根据探测条件和MODTRAN提供的大气模式,使用被动遥测红外光谱方法预测每种大气模式下生物气溶胶的探测限浓度.每种大气模式下探测限浓度的不同,是因为边界层温度、透过率和背景辐射亮度的不同所导致,同时还与生物气溶胶的吸收系数有关.研究表明,FTIR光谱被动遥测技术能够探测到生物气溶胶的存在,进一步说明探测生物气溶胶的可行性,也为生物气溶胶实际探测提供了一种方法.     

Broadband 2.84 μm luminescence properties and Judd–Ofelt analysis in Dy3+ doped ZrF4–BaF2–LaF3–AlF3–YF3 glass

2.84 μm luminescence with a bandwidth of 213 nm is obtained in Dy³⁺ doped (ZrF₄–BaF₂–LaF₃–AlF₃–YF₃) ZBLAY glass. Three intensity parameters and radiative properties have been determined from the absorption spectrum based on the Judd–Ofelt theory. The 2.84 μm emission characteristics and energy transfer mechanism upon excitation of a conventional 808 nm laser diode are investigated. The prepared Dy³⁺ doped ZBLAY glass possessing high predicted spontaneous transition probability (45.92 s^?1) along with large calculated emission cross section (1.17×10^?20 cm²) has potential applications in 2.8 μm laser.     

Investigation on Tm3+-doped silicate glass for 1.8 μm emission

A Tm³⁺-doped silicate glass (SiO₂–CaO–Na₂O–K₂O) with good thermal stability is prepared by the melt-quenching method. Intense 1.8 μm emission is obtained when pumped by an 808 nm laser diode. Based on the measured absorption spectra, radiative properties are predicted using Judd–Ofelt theory and Judd–Ofelt parameters Ω_λ (λ=2, 4, 6), as well as absorption and emission cross-sections are calculated and analyzed. The difference between the measured Tm³⁺:³F₄ lifetime and the calculated lifetime is also discussed. The emission property together with good thermal property indicates that Tm³⁺-doped silicate glass is a potential kind of laser glass for efficient 2 μm laser.     

Pump tuned wide tunable noncritically phase-matched ZnGeP2 narrow line width optical parametric oscillator

A line tunable singly resonant noncritically phase matched narrow band width ZnGeP₂ (ZGP) optical parametric oscillator pumped by the output idler radiation from a KTA OPO based on a 20 mm long KTA crystal pumped from a Q-switched Gaussian shaped Nd:YAG laser beam with a grating having grooves density 85 lines/mm has been demonstrated in the spectral ranges of 3–7 μm. The measured threshold of oscillation energy was 10 μJ. The conversion efficiency was 20.5% and slope efficiency of the ZGP OPO was 20% using a 23 mm long ZGP crystal at 26 mm cavity length. Line width of the generated infrared radiation from ZGP OPO was 37–60 nm.     

Measurements of the infrared absorption cross-sections of HCFC-141b (CH3CFCl2)

Detection of atmospheric trace gases by optical remote sensing techniques relies on the availability of molecular absorption spectra over a range of relevant temperatures. Absorption cross-sections of a pure vapour of the hydrochlorofluorocarbon HCFC-141b are reported at a resolution of 0.02 cm^?1 for a range of temperatures between 223 and 283 K and a spectral range of 570–3100 cm^?1. The integrated intensities of the nine main harmonic bands compare well with the data available from previous experimental studies and with theoretical calculations by ab initio and density functional theories.     

Mid- and long-wave infrared absorption cross sections for acetonitrile

Infrared absorption cross sections for acetonitrile (methyl cyanide; CH₃CN) have been determined in the 880–1700 cm^?1 spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical pathlength of 19.3 m. Spectra of acetonitrile/dry synthetic air mixtures were recorded at 0.015 cm^?1 resolution (calculated as the Bruker instrument resolution of 0.9/MOPD) at a number of temperatures between 203 and 297 K and pressures appropriate for atmospheric conditions. Intensities were calibrated using three composite acetonitrile spectra recorded at the Pacific Northwest National Laboratory. These absorption cross sections will provide an accurate basis for upper tropospheric/lower stratospheric retrievals of acetonitrile in the mid-infrared spectral region from ACE satellite data.     

2.7 μm fluorescence radiative dynamics and energy transfer between Er3+ and Tm3+ ions in fluoride glass under 800 nm and 980 nm excitation

A detailed study of the fluorescence radiative dynamics and energy transfer processes between Er and Tm ions in the Er³⁺/Tm³⁺ doped fluoride glass is reported. The fluorescence properties of 2.7 μm emission, other infrared and visible emissions are investigated under different selective laser excitations. Three Judd–Ofelt intensity parameters, energy transfer microparameters and efficiency have been determined and discussed. It is found that present Er³⁺/Tm³⁺ doped fluoride glass possesses large calculated emission cross section (8.98×10^–21 cm²) around 2.7 μm. The more suitable pumping scheme for laser applications at 2.7 μm laser is 980 nm excitation for Er³⁺/Tm³⁺ doped fluoride glass.