On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-muW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 mum, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.     

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.     

Nano filter from sintered rice husk silica membrane

A nano filter showing the Knudsen flow was demonstrated by a modification of a membrane constructed from rice husk silica. The membrane was prepared by pressing and sintering micron sized rice husk silica with 4 nm pores. The membrane showed a permeability of 5.2 x 10(-8) mol m(-1) sec(-1) Pa(-1) for H2 and ratios of gas permeability 2.1 and 3.2 for k(H2)/k(CH4) and k(H2)/k(CO2), respectively. When the membrane was treated by filtration of approximately 100 nm sized rice husk silica particles, the permeability decreased to 4.9 x 10(-8) mol m(-1) sec(-1) Pa(-1) and the ratios increased to 2.2 and 3.4. In the case of the membrane after treatments with the dispersion and chemical deposition of tetraethylorthosilicate (TEOS), the corresponding permeability and ratios of the membrane were 1.8 x 10(-8) mol m(-1) sec(-1) Pa(-1), and 2.9 and 4.5, respectively. From the change of the ratio of gas permeability for the membrane with modifications, it is suggested that approximately 100 nm sized rice husk silica particles pack the large pores among the micron sized rice husk silica particles while the chemical deposition of tetraethylorthosilicate (TEOS) reveals the gas flow through 4 nm pores in the rice husk silica by blocking large pores.     

Simultaneous in situ measurement of CO,H2O,and gas temperatures in a full-sized coal-fired power plant by near-infrared diode lasers

We present what is to our knowledge the first near-infrared diode-laser-based absorption spectrometer that is suitable for simultaneous in situ measurement of carbon monoxide, water vapor, and temperature in the combustion chamber (20-m diameter, 13-m path length) of a 600-MW lignite-fired power plant. A fiber-coupled distributed-feedback diode-laser module at 1.56 microm served for CO detection, and a Fabry-Perot diode laser at 813 nm was used to determine H2O concentrations and temperature from multiline water spectra. Despite severe light losses (transmission, <10(-8)) and strong background radiation we achieved a resolution of 1.9 x 10(-4) (1sigma) fractional absorption, equivalent to 200 parts in 10(6) by volume of CO (at 1450 K, 10(5) Pa) with 30-s averaging time.     

Development of a Tunable, Narrow-Linewidth, CW 2.066-mum Ho:YLF Laser for Remote Sensing of Atmospheric CO(2) and H(2)O

A smoothly tunable, narrow-linewidth, cw, 32-mW, 2.066-mum Ho:YLF laser was constructed and used for the first time in preliminary spectroscopic measurements of atmospheric CO(2) and H(2)O. The laser was constructed with a 4.5-mm-long, TE-cooled, codoped 5% Tm and 0.5% Ho yttrium lithium fluoride crystal (cut at Brewster's angle) pumped by an Ar(+)-pumped 500-mW Ti:sapphire laser operating at 792 nm. Intracavity etalons were used to reduce the laser linewidth to approximately 0.025 cm(-1) (0.75 GHz), and the laser wavelength was continuously and smoothly tunable over approximately 6 cm(-1) (180 GHz). The Ho:YLF laser was used to perform spectroscopic measurements on molecular CO(2) in a laboratory absorption cell and to measure the concentration of CO(2) and water vapor in the atmosphere with an initial accuracy of approximately 5-10%. The measurement uncertainty was found to be due to several noise sources, including the effect of asymmetric intensity of the laser modes within the laser linewidth, fluctuations caused by atmospheric turbulence and laser beam/target movement, and background spectral shifts.     

Micro-Raman densimeter for CO2 inclusions in mantle-derived minerals

We investigated the applicability of Raman microprobe spectroscopy for determining the density of CO2 in fluid inclusions in minerals of mantle-derived xenolith samples. A separation (delta) between two Raman bands of CO2 due to Fermi resonance can be a reliable densimeter for CO2 fluid. The relationship between the density of CO2 (g/cm3) and delta (cm-1) can be expressed as: d = -0.03238697 delta 3 + 10.08428 delta 2 - 1046.189 delta + 36163.67. This equation was obtained from the Raman data on CO2 fluid with densities from 0.1 to 1.21 g/cm3, including super critical fluids at 58-59 degrees C. The delta value was constant with increasing temperature from room temperature to 200 degrees C. This indicates that the Raman densimeter is not affected by a possible rise in temperature, an artifact induced by the high flux of the incident laser. The minimum size of measurable inclusions is 1 micron, and the precision in the determination of delta is 0.1 cm-1, corresponding to 0.02 g/cm3 for inclusions of 1 micron in size. The precision can be better for larger inclusions. The micro-Raman densimeter can determine the density of CO2 fluid inclusions over a wide range. In particular, densities of gas and mixtures of gas and liquid phases, which cannot be measured by microthermometry, can be determined.     

Degradation and by-product formation of diazinon in water during UV and UV/H(2)O(2) treatment

Kinetics and degradation products resulting from the application of UV and UV/H(2)O(2) to the US EPA Contaminant Candidate List pesticide diazinon were studied. Batch experiments were conducted with both monochromatic (low pressure [LP] UV 253.7 nm) and polychromatic (medium pressure [MP] UV 200-300 nm) UV sources alone or in the presence of up to 50 mg l(-1) H(2)O(2), in a quasi-collimated beam apparatus. Degradation of diazinon by both UV and UV/H(2)O(2) exhibited pseudo first order reaction kinetics, and quantum yield of 8.6 x 10(-2) and 5.8 x 10(-2) mol E(-1) for LP and MP lamps respectively. Photolysis studies under MP UV lamp showed 2-isopropyl-6-methyl-pyrimidin-4-ol (IMP) to be the main degradation product of diazinon at aqueous solution pH values of 4, 7 and 10. Trace levels up to 1.8 x 10(-3) microM of diazinon oxygen analogue diethyl 2-isopropyl-6-methylpyrimidin-4-yl phosphate (diazoxon) were detected only during the UV/H(2)O(2) reaction. Decay of both products was observed, as the UV/H(2)O(2) reaction prolonged, yet no mineralization was achieved over the UV fluence levels examined. Photolysis kinetics, quantum yield and UV/H(2)O(2) degradation of the reaction product IMP was determined using MP UV lamp at pH values of 4, 7 and 10.     

Photochemical mineralization of di-n-butyl phthalate with H2O2/Fe3+

This study evaluated the performance of photo-Fenton reaction initiated by the UV irradiation with H(2)O(2)/Fe(3+), denoted as UV/H(2)O(2)/Fe(3+), to decompose di-n-butyl phthalate (DBP) in the aqueous solution. The concentration of total organic carbon (TOC) was chosen as a mineralization index of the decomposition of DBP by the UV/H(2)O(2)/Fe(3+) process. A second-order kinetic model with respect to TOC was adequately adopted to represent the mineralization of DBP by the UV/H(2)O(2)/Fe(3+) process. The experimental results of this study suggested that the dosages with 4.74 x 10(-5) mol min(-1)L(-1) H(2)O(2) and initial Fe(3+) loading concentration of 4.50 x 10(-4) mol L(-1) in the solution at pH 3.0 with 120 microW cm(-2) UV (312 nm) provided the optimal operation conditions for the mineralization of DBP (5 mg L(-1)) yielding a 92.4% mineralization efficiency at 90 min reaction time.     

Laser-induced breakdown spectroscopy of gas mixtures of air, CO2, N2, and C3H8 for simultaneous C, H, O, and N measurement

Laser-induced breakdown spectroscopy (LIBS) was applied for simultaneous measurement of the elements C, H, N, and O in CO2-air, C3H8-CO2, and C3H8-N2 gas mixtures at atmospheric pressure. A single 7-mm-diameter aperture at the sample chamber was used for 1064-nm Nd:YAG laser irradiation and plasma signal output to an echelle spectrometer. Double-pulse laser bursts of approximately 8-ns pulse width (FWHM) and 250-ns interpulse separation were applied to increase the plasma signal. Calibration curves of the LIBS signal versus the partial pressure or the atomic abundance ratios were taken by dilution series in intervals that are relevant in the combustion of heptane (C7H16) near an equivalence ratio of 1.     

Intracavity CO laser photoacoustic trace gas detection: cyclic CH(4), H(2)O and CO(2) emission by cockroaches and scarab beetles

A liquid-nitrogen-cooled CO laser and an intracavity resonant photoacoustic cell are employed to monitor trace gases. The setup was designed to monitor trace gas emissions of biological samples on line. The arrangement offers the possibility to measure gases at the 10(9) by volume (ppbv) level (e.g., CH(4), H(2) O) and to detect rapid changes in trace gas emission. A detection limit of 1 ppbv for CH(4) in N(2) equivalent to a minimal detectable absorption of 3 × 10(-9) cm(-1) can be achieved. Because of the kinetic cooling effect we lowered the detection limit for CH(4) in air is decreased to 10 ppbv. We used the instrument in a first application to measure the CH(4) and H(2) O emission of individual cockroaches and scarab beetles. These emissions could be correlated with CO(2) emissions that were recorded simultaneously with an infrared gas analyzer. Characteristic breathing patterns of the insects could be observed; unexpectedly methane was also found to be released.     

Fe3O4 magnetic nanoparticles as peroxidase mimetics and their applications in H2O2 and glucose detection

Artificial enzyme mimetics are a current research interest because natural enzymes bear some serious disadvantages, such as their catalytic activity can be easily inhibited and they can be digested by proteases. A very recently study reported by Yan et al. has proven that Fe(3)O(4) magnetic nanoparticles (MNPs) exhibit an intrinsic enzyme mimetic activity similar to that found in natural peroxidases, though MNPs are usually thought to be biological and chemical inert (Gao, L. Z.; Zhuang, J.; Nie, L.; Zhang, J. B.; Zhang, Y.; Gu, N.; Wang, T. H.; Feng, J.; Yang, D. L.; Perrett, S.; Yan, X. Y. Nat. Nanotechnol. 2007, 2, 577-583). In the present work, we just make use of the novel properties of Fe(3)O(4) MNPs as peroxidase mimetics reported by Yan et al. to detect H(2)O(2). The Fe(3)O(4) MNPs were prepared via a coprecipitation method. The as-prepared Fe(3)O(4) MNPs were then used to catalyze the oxidation of a peroxidase substrate 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) by H(2)O(2) to the oxidized colored product (see eq 1) which provides a colorimetric detection of H(2)O(2). As low as 3 x 10(-6) mol/L H(2)O(2) could be detected with a linear range from 5 x 10(-6) to 1 x 10(-4) mol/L via our method. More importantly, a sensitive and selective method for glucose detection was developed using glucose oxidase (GOx) and the as-prepared Fe(3)O(4) MNPs. The detection platforms for H(2)O(2) and glucose developed in the present work not only further confirmed that the Fe(3)O(4) MNPs possess intrinsic peroxidase-like activity but also showed great potential applications in varieties of simple, robust, and easy-to-make analytical approaches in the future.     

Electron-transfer reactivity and enzymatic activity of hemoglobin in a SP Sephadex membrane

Hemoglobin can exhibit a direct electron-transfer reaction after being entrapped in a SP Sephadex membrane. A pair of stable and well-defined redox waves are obtained at a hemoglobin-SP sephadex modified pyrolytic graphite electrode. The anodic and cathodic peak potentials are located at -0.244 and -0.336 V (vs SCE), respectively. On the other hand, the peroxidase activity of the protein in the membrane is also greatly enhanced. The apparent Michaelis-Menten constant is calculated to be 1.9 mM, which shows a large catalytic activity of hemoglobin in the SP Sephadex membrane toward hydrogen peroxide (H2O2). According to the direct electron-transfer property and enhanced peroxidase activity of Hb in the membrane, a Hb/SP Sephadex membrane-based H2O2 biosensor is prepared, with a linear range approximately 5.0 x 10(-6) to 1.6 x 10(-4) mol/L.     

Raman line imaging for spatially and temporally resolved mole fraction measurements in internal combustion engines

An optical diagnostic system based on line imaging of Raman-scattered light has been developed to study the mixing processes in internal combustion engines. The system permits multipoint, single laser-shot measurements of CO(2), O(2), N(2), C(3)H(8), and H(2)O mole fractions with submillimeter spatial resolution. Selection of appropriate system hardware is discussed, as are subsequent data reduction and analysis procedures. Results are reported for data obtained at multiple crank angles and in two different engine flow fields. Measurements are made at 12 locations simultaneously, each location having measurement volume dimensions of 0.5 mm x 0.5 mm x 0.9 mm. The data are analyzed to obtain statistics of species mole fractions: mean, rms, histograms, and both spatial and cross-species covariance functions. The covariance functions are used to quantify the accuracy of the measured rms mole fraction fluctuations, to determine the integral length scales of the mixture inhomogeneities, and to quantify the cycle-to-cycle fluctuations in bulk mixture composition under well-mixed conditions.     

Analysis of heavy metal pollution in soil using transversely excited atmospheric CO2 laser-induced plasma by trapping the soil in microstructured holes on metal subtargets

A unique technique for direct analysis of soil samples utilizing a special advantage of a transversely excited atmospheric (TEA) CO(2) laser-induced plasma generated at atmospheric pressure on a metal target has been developed. In this technique, a metal subtarget, such as nickel plate, structured with intentional microholes on its surface, each with dimensions of around 100 microm in diameter and depth, was used to selectively trap small sized soil particles by immersing the metal plate subtarget into the polluted soil sample. The trapped small soil particles on the metal subtarget were irradiated by a TEA CO(2) laser (10.6 microm, 1.5 J, 200 ns) at atmospheric pressure under defocused condition with a spot size of 3 mm x 3 mm. This trapping and confining scheme substantially suppresses the blowing off effect; thus, the trapped soil particles can effectively be dissociated and atomized in the microstructured holes. Using this method of a microstructured metal plate subtarget, quantitative analysis was carried out on loam soil samples polluted by Pb. A linear calibration curve was obtained with a detection limit of approximately 50 mg/kg. Preliminary quantitative studies were carried out for a quartz sand sample containing Cr and Hg, resulting in linear calibration curves with detection limits of approximately 25 mg/kg and 10 mg/kg, respectively, at this stage. This technique is promising as a potential field screening tool for soil analysis.     

Detection of H2O and CO2 with distributed feedback diode lasers: measurement of broadening coefficients and assessment of the accuracy levels for volcanic monitoring

We reproduced the chemical-physical conditions of fumarolic emission at Phlaegrean Fields, Pozzuoli, Italy, and we measured the CO(2) and H(2)O concentrations using an absorption spectrometer based on two distributed feedback laser diodes at wavelengths of 1.578 and 1.393 mum. We discuss the accuracy levels of the different methods used. Furthermore, we measured the broadening coefficients for H(2)O (self-broadening, 28.2 +/- 0.6 MHz/Torr; CO(2) broadening, 6.0 +/- 0.4 MHz/Torr) and CO(2) (self-broadening, 3.2 +/- 0.1 MHz/Torr; H(2)O broadening, 4.0 +/- 0.1 MHz/Torr). Using the present data, we evaluated a minimum detectable variation of 9% for H(2)O and 1% for CO(2).     

Permeation of solvents through disk type rice husk silica membrane modified with alkyl silylation reagents

Rice husk silica (RHS) which was obtained with thermal treatment of rice husk has the size of approximately 10 micrometer with 4-5 nm pore. RHS can be mold to a disk type membrane. The membrane may have submicron pore originated from the space among the particles, and the nano pores of the rice husk silica (RHS pore). Even it is difficult to adjust the size of the pores, we can suggest that the membrane shows different permeability for the organic/inorganic solvents if the affinity between the surface of the pores and the permeating molecule is changed. In this study, we investigated the permeation of the typical solvents such as water, ethanol and toluene to the RHS membranes sintered at 1100 degrees C, 1150 degrees C and 1200 degrees C and modified with triethoxymethyl silane (CH3)Si(C2H5O)3, diethoxydiemethyl silane (CH3)2Si(C2H5O)2 and ethoxytriemethyl silane (CH3)3Si (C2H5O). The result showed that permeability of original membranes for water (e.g., 1100 degrees C, 2.87 x 10(-3) mol/m2 s Pa) was larger than ethanol (1100 degrees C, 5.51 x 10(-4) mol/m2 s Pa) and toluene (1100 degrees C, 3.09 x 10(-4) mol/m2 s Pa) at the sintering temperatures. For the silane modified membranes, the permeability for water decreased drastically while those for ethanol and toluene increased.     

Simultaneous determination of the (2)h/(1)h, (17)o/(16)o, and (18)o/(16)o isotope abundance ratios in water by means of laser spectrometry

We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative (2)H/(1)H, (17)O/(16)O, and (18)O/(16)O isotope abundance ratios in water. The method uses a narrow line width color center laser to record the direct absorption spectrum of low-pressure gas-phase water samples (presently 10 μL of liquid) in the 3-μm spectral region. It thus avoids the laborious chemical preparations of the sample that are required in the case of the conventional isotope ratio mass spectrometer measurement. The precision of the spectroscopic technique is shown to be 0.7‰ for δ(2)H and 0.5‰ for δ(17)O and δ(18)O (δ represents the relative deviation of a sample's isotope abundance ratio with respect to that of a calibration material), while the calibrated accuracy amounts to about 3 and 1‰, respectively, for water with an isotopic composition in the range of the Standard Light Antarctic Precipitation and Vienna Standard Mean Ocean Water international standards.     

Saturable absorber Co2+:MgAl2O4 crystal for Q switching of 1.34-microm Nd3+:YAlO 3 and 1.54-microm Er3+:glass Lasers

Saturable-absorber Q switching of a neodymium-doped YAlO(3) laser at 1.34 microm and an erbium-doped glass laser at 1.54 microm with a Co(2+):MgAl(2)O(4) crystal was demonstrated. Q-switched 1.34-microm pulses of 19-mJ energy and 60-ns duration and Q-switched 1.54-microm pulses of 2.7-mJ energy and 75-ns width were obtained. The ground-state absorption cross sections of the Co(2+):MgAl(2)O(4) crystal were estimated to be (2.8 +/- 0.4) x 10(-19) and (3.5 +/- 0.6) x 10(-19) cm(2) at 1.34 and 1.54 microm, respectively. The (4)T(1)((4)F)-->(4)A(2) relaxation time of the Co(2+) ion in the MgAl(2)O(4) crystal was measured to be approximately 350 ns.     

Conversion of O(2) into CO(2) for High-Precision Oxygen Isotope Measurements

An improved procedure of (18)O/(16)O ratio measurements by means of oxygen conversion to CO(2) is developed, which allows one to obtain the true δ(18)O values with a precision of ±0.05‰ in oxygen samples down to 7 μmol. The isotopic exchange between quartz glass and oxygen gas was measured in the temperature range of 600-900 °C, and it was found to be less than 0.2%.     

卤化银光纤式CO2激光手术刀

卤化银多晶光纤「ＡｇＣｌｘＢｒ（１－ｘ），０≤ｘ≤１」是一种性能优良的中红外传能光纤。光纤原料采用高真空熔炼、氯气气氛下区域融熔和高真厂长发瓿内单昌生长等特殊工艺方法提纯，光纤用热挤压法成型。已制成的直径Φ１．０（ｍｍ）光纤Ｌ＝１．６４（ｍ）输出ＣＯ２激光功率〉２０（Ｗ），损耗０．３￣０．５ｄＢ／ｍ，Ｆｏｒｕｒｉｅｒ红外光谱（ＦＴＩＲ）测量结果显示，光纤在４￣１６μｍ波段内有良好的透过率，用光纤制