A double-beam UV-laser differential absorption method for monitoring tropospheric trace gases

A method is described which uses the differential absorption of a narrow-band tunable ultra-violet laser for integrated measurements of tropospheric trace gas concentrations over a path length of 12.8 km, at near ground level. A XeCl excimer laser serves as a reference beam to compensate for turbulence-induced intensity losses. After suitable statistical averaging the method is capable of detecting differential absorptions as low as 10^-4, enabling the simultaneous detection of SO₂, CH₂O and of OH radicals around 308 nm.     

A study of OH radicals in an atmospheric AC discharge plasma using near infrared diode laser cavity ringdown spectroscopy combined with optical emission spectroscopy

Simultaneous measurements of absolute concentrations of H₂O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×10¹⁵ molecule cm^-3. Ringdown measurements of the H₂O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, , to be 4.8 ×10^-3, where N_OH and are the number densities of OH and H₂O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10^-9  cm^-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×10¹³ molecule cm^-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications.     

Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments

Intracavity absorption spectroscopy with a broadband Er³⁺-doped fiber laser is applied for the measurements of several molecular species revealing quantitative information about the gas concentration, temperature and chemical reactions in flames. The spectral range of measurements extends from 6200 cm⁻¹ to 6550 cm⁻¹ with the proper choice of the fiber length and by moving an intracavity lens. With a pulsed laser applied in this experiment, the sensitivity to absorption corresponds to an effective absorption path length of 3 km assuming the cavity is completely filled with the sample. For a cw laser, the effective absorption path length is estimated to be 50 km. Absorption spectra of various molecules such as CO₂, CO, H₂O, H₂S, C₂H₂ and OH were recorded separately in the cell and/or in low-pressure methane and propane flames. The presented measurements demonstrate simultaneous in situ detection of three molecular products of chemical reactions at different flame locations. Variation of the relative strengths of OH absorption lines with the temperature enables the estimation of the local flame temperature. The sensitivity of this laser does not depend on the broadband cavity losses and it can be used for in situ measurements of absorption spectra in hostile environments such as contaminated samples, flames or combustion engines. The presented technique can be applied for various diagnostic purposes, such as in environmental, combustion and plasma research, in medicine and in the determination of stable isotope ratios.     

Measurement of tropospheric O3, SO2 and aerosol from a volcanic emission event using new multi-wavelength differential-absorption lidar techniques

We present measurements of tropospheric O₃, SO₂ and aerosol from a volcanic emission event using new multi-wavelength differential absorption lidar (DIAL) techniques that enable us to remove the mutual effects between O₃ and SO₂ from the raw measurements. The aerosol extinction coefficient is retrieved directly from the lidar return signal at the “off” wavelength and is used to estimate aerosol effects on O₃ and SO₂measurements. Null error, statistical error, and absorption cross-section error are also analyzed. The O₃ and SO₂ concentrations at height between 1000 m and 2000 m for a volcanic event on September 10, 2001 were about 20 ppb and 10–35 ppb, respectively, with an error less than 10 ppb. The measured SO₂ concentration was much higher than the normal SO₂ background value (∼1 ppb) in the troposphere. We also measured O₃ concentrations from 13 December 2000 to 06 January 2001 and investigated O₃ diurnal variation during a 24-hour period on November 24, 2000. A high O₃ concentration of about 250 ppb was observed in late December 2000. PACS 42.68.Wt; 42.68.Kh; 42.68.Jg     

Characterization of uranium(VI) sorption by organobentonite

The U(VI) sorption on the bentonite modified by hexadecyltrimethylammonium bromide (HDTMA) was studied in the concentration range: 0.0001-0.001 mol/dm³ in the aqueous phase and in the pH range: 3-10. The experiments concerning the pH influence on the molar absorption coefficient c_b of U(VI) in the bentonite phase showed that the species: UO₂²⁺, UO₂(OH)⁺, UO₂(OH)₂ UO₂(OH)₃⁻, UO₂(OH)₄²⁻, (UO₂)₃(OH)₅⁺, (UO₂)₃(OH)₇⁻, present in the aqueous phase, are responsible for uranium sorption. Their sorption parameters K were determined and it is evident that for higher concentrations of HDTMA⁺ cations in the bentonite phase, i.e. for b96-b157 bentonite, the presence of anionic species: UO₂(OH)₃⁻, UO₂(OH)₄²⁻, and (UO₂)₃(OH)₇⁻ in the aqueous phase results in the increase of U(VI) molar absorption coefficient c_b in the sorbent phase.     

Photonic sensing of the atmosphere by absorption spectroscopy

Chemically reactive atmospheric species play a crucial role in tropospheric processes which affect regional air quality and global climate change. Contrary to long-lived species such as greenhouse gases, interference-free accurate and precise concentration assessments of strongly reactive short-lived species represent a real challenge. In this paper, we report on the recent progress in spectroscopic instrumental developments for monitoring of OH, NO₃, HONO and NO₂ by using modern photonic sources (Quantum Cascade Laser, distributed feedback diode laser, light emitting diode) in conjunction with high-sensitivity spectroscopic measurement techniques such as multi-pass cell based long optical path length absorption spectroscopy, wavelength-modulation enhanced off-axis integrated cavity output spectroscopy, Faraday rotation spectroscopy, incoherent broadband cavity enhanced absorption spectroscopy. The main techniques available for routine atmospheric measurements of OH, NO₃ and HONO are overviewed, in comparison with the emerging modern photonic spectroscopy techniques.     

The reaction of CH3 + O2: experimental determination of the rate coefficients for the product channels at high temperatures

The reaction of methyl radicals (CH₃) with molecular oxygen (O₂) has been investigated in high-temperature shock tube experiments. The overall rate coefficient, k₁ = k_1a + k_1b, and individual rate coefficients for the two high-temperature product channels, (1a) producing CH₃O + O and (1b) producing CH₂O + OH, were determined using ultra-lean mixtures of CH₃I and O₂ in Ar/He. Narrow-linewidth UV laser absorption at 306.7 nm was used to measure OH concentrations, for which the normalized rise time is sensitive to the overall rate coefficient k₁ but relatively insensitive to the branching ratio of the individual channels and to secondary reactions. Atomic resonance absorption spectroscopy measurements of O-atoms were used for a direct measurement of channel (1a). Through the combination of measurements using the two different diagnostics, rate coefficient expressions for both channels were determined. Over the temperature range 1590–2430 K, k_1a = 6.08 × 10⁷T^1.54 exp (−14005/T) cm³ mol⁻¹ s⁻¹ and k_1b = 68.6 T^2.86 exp (−4916/T) cm³ mol⁻¹ s⁻¹. The overall rate coefficient is in close agreement with a recent ab initio calculation and one other shock tube study, while comparison of k_1a and k_1b to these and other experimental studies yields mixed results. In contrast to one recent experimental study, reaction (1b) is found to be the dominant channel over the entire experimental temperature range.     

Determination of the OH radical in atmospheric pressure dielectric barrier discharge plasmas using near infrared cavity ring-down spectroscopy

The hydroxyl radical (OH) plays an important role in combustion systems, atmospheric chemistry and the removal of air pollutants by non-thermal plasmas. The present work reports the determination of the hydroxyl radicals in atmospheric dielectric barrier discharge plasmas via near infrared continuous wave cavity ring-down spectroscopy. The P-branches of OH X²Π_i (ν' = 2 ←ν^′′ = 0) bands were used for its number density measurements. The minimum measurable absorption coefficient is about 3 × 10^-8 cm^-1 in DBD plasmas. At certain experimental conditions (a.c. frequency of 70 kHz, 6700 ppm H₂O in He, 1 atm), when the peak-to-peak discharge voltage varied from 6 kV to 10.4 kV, the determined OH radical concentration increased from (2.1 ± 0.1) × 10¹³ molecules cm^-3 to (3.7 ± 0.1) × 10¹³ molecules cm^-3. The plasma gas temperature, derived from the Boltzmann plots of OH rotational population distributions, ranged from 312 ± 10 K to 363 ± 10 K when the discharge voltage was raised in the above range. The influences of O₂ and N₂ addition on the production of OH radicals have been also investigated.     

Synthesis and characterization of Zn(O,OH)S and AgInS2 layers to be used in thin film solar cells

In this paper AgInS₂ and Zn(O,OH)S thin films were synthesized and characterized. AgInS₂ layers were grown by co-evaporation from metal precursors in a two-step process, and, Zn(O,OH)S thin films were deposited from chemical bath containing thiourea, zinc acetate, sodium citrate and ammonia. X-ray diffraction measurements indicated that AgInS₂ thin films grown with chalcopyrite structure, and the as-grown Zn(O,OH)S thin films were polycrystalline. It was also found that the AgInS₂ films presented p-type conductivity, a high absorption coefficient (greater than 10⁴ cm⁻¹) and energy band-gap E_g of about 1.95 eV, Zn(O,OH),S thin films presented E_g of about 3.89 eV. Morphological analysis showed that under this synthesis conditions Zn(O,OH),S thin films coated uniformly the absorber layer. Additionally, the Zn(O,OH)S kinetic growth on AgInS₂ layer was studied also. Finally, the results suggest that these layers possibly could be used in one-junction solar cells and/or as top cell in a tandem solar cell.     

Interpretation of NO2 absorption in twilight sky spectra

A multiple scattering model has been developed to calculate nitrogen dioxide (NO₂) absorption in the light from the zenith sky during twilight. Model studies show that this absorption is not very sensitive to the atmospheric temperature profile or to tropospheric NO₂.The model was used to interpret some ground-based measurements of NO₂ sky absorption. Values for the total stratospheric column amount vary from 2 to 12×10¹⁵moleccm^-2, and the mean altitude of the stratospheric concentration profile is around 35 km. These observations are in broad agreement with those of other workers.     

Shock tube measurements of ignition delay times and OH time-histories in dimethyl ether oxidation

Ignition delay times and OH concentration time-histories were measured in DME/O₂/Ar mixtures behind reflected shock waves. Initial reflected shock conditions covered temperatures (T₅) from 1175 to 1900 K, pressures (P₅) from 1.6 to 6.6 bar, and equivalence ratios (?) from 0.5 to 3.0. Ignition delay times were measured by collecting OH^∗ emission near 307 nm, while OH time-histories were measured using laser absorption of the R₁(5) line of the A-X(0,0) transition at 306.7 nm. The ignition delay times extended the available experimental database of DME to a greater range of equivalence ratios and pressures. Measured ignition delay times were compared to simulations based on DME oxidation mechanisms by Fischer et al. [7] and Zhao et al. [9]. Both mechanisms predict the magnitude of ignition delay times well. OH time-histories were also compared to simulations based on both mechanisms. Despite predicting ignition delay times well, neither mechanism agrees with the measured OH time-histories. OH Sensitivity analysis was applied and the reactions DME ↔ CH₃O + CH₃ and H + O₂ ↔ OH + O were found to be most important. Previous measurements of DME ↔ CH₃O + CH₃ are not available above 1220 K, so the rate was directly measured in this work using the OH diagnostic. The rate expression k[1/s] =  1.61 × 10⁷⁹T^−18.4 exp(−58600/T), valid at pressures near 1.5 bar, was inferred based on previous pyrolysis measurements and the current study. This rate accurately describes a broad range of experimental work at temperatures from 680 to 1750 K, but is most accurate near the temperature range of the study, 1350-1750 K. When this rate is used in both the Fischer et al. and Zhao et al. mechanisms, agreement between measured OH and the model predictions is significantly improved at all temperatures.     

Accurate wavenumbers of the AΣ → XΠ (0, 0) and (1, 0) bands of OH and OD

The important A²Σ → X²Π (0, 0) absorption band of OH has been remeasured from spectra obtained by flash photolysis of H₂O₂ vapor. Accurate wavenumber measurements using thorium standards show that the previous rotational line measurements are about 0.1 cm^-1 too large. Measurements are also given for the (1, 0) band of OH and the (0, 0) and (1, 0) bands of OD.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

SF6 ground-based infrared solar absorption measurements: long-term trend, pollution events, and a search for SF5CF3 absorption

Infrared solar spectra recorded with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak (31.9°N latitude, 111.6°W, altitude), southwest of Tucson, Arizona, have been analyzed to retrieve average SF₆ tropospheric mixing ratios over a two-decade time span. The analysis is based primarily on spectral fits to absorption by the intense, unresolved ν₃ band Q branch at . A best fit to measurements recorded with SF₆ near typical background concentrations yields a SF₆ increase in the average tropospheric mixing ratio from (10⁻¹² per unit volume) in March 1982 to in March 2002. The long-term increase by a factor of 3.34 over the time span is consistent with the rapid growth of surface mixing ratios measured in situ at Northern Hemisphere remote stations, though the infrared measurements show a large scatter. Average tropospheric mixing ratio enhancements above background by 2-3 orders of magnitude have been identified in spectra recorded on 5 days between November 1988 and April 1997. These spectra were individually analyzed in an attempt to detect the strongest 8- band of SF₅CF₃, a molecule recently identified with an atmospheric growth that has closely paralleled the rise in SF₆ during the past three decades. Absorption by the strongest SF₅CF₃ band was predicted to be above the noise level in the Kitt Peak spectrum with the highest average mean tropospheric SF₆ mixing ratio, assuming the reported atmospheric SF₅CF₃/SF₆ ratio and a room temperature absorption cross sections reported for the SF₅CF₃ 903-cm⁻¹ band. An upper limit of 8×10¹⁵ for the SF₅CF₃ total column was estimated for this case. We hypothesize that the highly elevated SF₆ levels above Kitt Peak resulted from a local release experiment rather than production via electrochemical fluoridation of intermediate products, the proposed source of atmospheric SF₅CF₃. The absence of the SF₅CF₃ feature in the spectra with elevated SF₆ is consistent with the absence of SF₅CF₃ reported in a pure SF₆ sample.     

High-resolution spectroscopy of SO2 using a frequency-doubled,continuous-wave dye laser

The SO₂ molecule is of considerable interest in the context of atmospheric pollution, and in many laser monitoring techniques the ultraviolet absorption band at 300 nm is used to determine SO₂ concentrations in the atmosphere. Recent laboratory experiments with a resolution of 2 × 10^-3 nm showed that variations could occur in absorption cross-section measurements made with different laser bandwidths due to unresolved fine structure. We have investigated absorption spectra with a line width of 3 × 10^-6 nm, using a frequency-doubled continuous-wave dye laser, and have confirmed the existence of fine structure in the absorption even when collisionally broadened with an atmosphere of nitrogen. These measurements provide a data base from which valid absorption cross sections may be calculated for all monitoring laser bandwidths. We estimate the pressure broadening coefficient for nitrogen in this wavelength region as 83 ± 38 kHz Pa^-1 (11 ± 5 MHz torr^-1). The temperature dependence of the absorption cross-section was also investigated.     

Electron concentration dependence of exciton localization and freeze-out at local potential fluctuations in InN films

InN films with electron concentration ranging from n～10¹⁷ to 10²⁰ cm^?3 grown by metal–organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE) were investigated by variable-temperature photoluminescence and absorption measurements. The energy positions of absorption edge as well as photoluminescence peak of these InN samples with electron concentration above 10¹⁸ cm^?3 show a distinct S-shape temperature dependence. With a model of potential fluctuations caused by electron-impurity interactions, the behavior can be quantitatively explained in terms of exciton freeze-out in local potential minima at sufficiently low temperatures, followed by thermal redistribution of the localized excitons when the band gap shrinks with increasing temperature. The exciton localization energy σ _loc is found to follow the n ^5/12 power relation, which testifies to the observed strong localization effects in InN with high electron concentrations.     

Absorption line strengths of <Superscript>15</Superscript>NH<Subscript>3</Subscript> in the near infrared spectral region

We present initial results of an investigation of the near infrared absorption spectrum of ¹⁵NH₃ between 6468 and 6692 cm⁻¹. A widely tunable external cavity diode laser is used in a direct absorption setup to determine the line positions and line strengths of several lines in that spectral range. Line data measurements on a ¹⁴NH₃ sample are used for validation of the setup by comparison of the results with available literature data. The presented overview measurements on absorption lines of ¹⁵NH₃ have been performed to serve as a starting point for candidate line selection for prospective isotopic ratio measurements of ¹⁴NH₃ and ¹⁵NH₃.     

Multi-decade measurements of the long-term trends of atmospheric species by high-spectral-resolution infrared solar absorption spectroscopy

Solar absorption spectra were recorded for the first time in 5 years with the McMath Fourier transform spectrometer at the US National Solar Observatory on Kitt Peak in southern Arizona, USA (31.91°N latitude, 111.61°W longitude, 2.09 km altitude). The solar absorption spectra cover 750-1300 and 1850-5000 cm⁻¹ and were recorded on 20 days during March-June 2009. The measurements mark the continuation of a long-term record of atmospheric chemical composition measurements that have been used to quantify seasonal cycles and long-term trends of both tropospheric and stratospheric species from observations that began in 1977. Fits to the measured spectra have been performed, and they indicate the spectra obtained since return to operational status are nearly free of channeling and the instrument line shape function is well reproduced taking into account the measurement parameters. We report updated time series measurements of total columns for six atmospheric species and their analysis for seasonal cycles and long-term trends. As an example, the time series fit shows a decrease in the annual increase rate in Montreal-Protocol-regulated chlorofluorocarbon CCl₂F₂ from 1.51±0.38% yr⁻¹ at the beginning of the time span to −1.54±1.28% yr⁻¹ at the end of the time span, 1 sigma, and hence provides evidence for the impact of those regulations on the trend.     

Two-wavelength and power-balanced oscillation of a CO2 laser for application to differential absorption measurements

A new technique of alternate two-wavelength oscillation of a CO₂ laser is discussed for application to various differential absorption spectroscopic measurements. Power-balanced, two-adjacent branch oscillation using a single CO₂ laser was achieved by modulating the angle of a mirror inside the laser cavity and adjusting automatically the cavity length. The two-wavelength modulation frequency was extended up to about 1.2 kHz. Line tuning and power modulation characteristics were studied. The laser was used in long-path differential absorption measurements of ethylene air pollution molecules to demonstrate the capability of this power-balanced, two-wavelength oscillation method. The minimum detectable absorption was nearly 1×10^–3 in a short-path cell experiment and 3×10^–3 in a long-path experiment.     

1+1′ resonant multiphoton ionisation of OH radicals via the A2Σ+ state: insights from direct comparison with A-X laser-induced fluorescence detection

A 1+1′ resonance-enhanced multiphoton ionisation (REMPI) scheme for OH X²Π radicals is characterised for a broad range of intermediate A²Σ⁺ (v = 1, J, F_i) levels. The intensities of OH A-X (1,0) transitions detected by subsequent fixed-frequency VUV ionisation are compared with those obtained by near simultaneous laser-induced fluorescence (LIF) measurements. The ratios of the 1+1′ REMPI to LIF signals are used to derive enhancement factors which reflect the VUV absorption to the OH A³Π, 3d, v = 0 Rydberg state and/or the fast autoionisation process that yields OH⁺ ions. The determination of the enhancement factors permits 1+1′ REMPI to be utilised as a quantitative state-specific probe of OH X²Π radicals.