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Line-shape models such as the Hartmann-Tran (HT) profile have adjustable high-order parameters that are usually determined by fits to experimental spectra. As an alternative approach, we demonstrate that fitting the HT profile to theoretical spectra provides high-order line-shape parameters for O2 transitions that are consistent with experimentally determined values. To this end, normalized absorption spectra of air-broadened O2 lines were computed without adjustable parameters using requantized classical molecular dynamics simulations (rCMDS). These theoretical calculations were made at a pressure of 203 kPa and for values of the Doppler width that cover near-Doppler-limited to collisional-broadened pressure conditions. Hartmann-Tran (HT) line profiles with adjustable line-shape parameters were then simultaneously fit to the set of rCMDS-calculated spectra in a global multispectrum analysis. The retrieved high-order line-shape parameters (i.e. the speed dependence of the line broadening and the Dicke narrowing coefficient) were subsequently used as fixed HT parameters in the analysis of seven air-broadened O2 lines of the a 1 Δ g ← X 3 Σ g − ( 0 , 0 ) band. The spectra were measured over a fifteen-fold range of total gas pressure at high spectral resolution and signal-to-noise ratio with a frequency-stabilized cavity ring-down spectroscopy system. We show that these predicted parameters enable all the measured lines to be fit to within 1%, which is much better than best fits of the Voigt line profile to the measured spectra. This approach opens the route for predicting high-order line-shape parameters from first-principles calculations and for their inclusion in spectroscopic databases. Furthermore, the temperature dependences of the broadening coefficient and its speed dependent component for air-broadened O2 lines were also calculated using rCMDS.

Various spectroscopic data for absorption lines due to the magnetic dipole transitions of the a 1 Δ g − X 3 Σ g − ( 0 − 0 ) band of O2 centered at 1.27 µm are tested by comparison with high-resolution ground-based atmospheric measurements recorded by Fourier Transform Spectrometers at Park Falls and Caltech (USA). This band is of importance for atmospheric remote sensing since it will be used (together with the O2 A-band near 760 nm) by the passive short wave infrared spectrometer onboard the MicroCarb satellite mission (i.e. this band includes the B4 band of MicroCarb, from about 7800 cm−1 to 7912 cm−1) for the determination of surface pressure and atmospheric aerosols. Spectroscopic data of the HITRAN2016 and GEISA2015 databases as well as those from recent laboratory studies are here used in a radiative transfer code to simulate atmospheric transmissions under the conditions of the measurements. Comparisons are made for different solar zenith angles and for the whole B4 spectral range considered by MicroCarb. Spectroscopic data of water vapor are also tested by considering both relatively dry and humid atmospheric conditions. Averaging the “calculated-observed” residuals over numerous recordings made for close values of the solar zenith angle and humidity enables reduction of the uncertainties due to the radiometric noise of the instrument and to the imperfect description of the atmospheric state. This enables the detection of systematic differences in the spectral residuals caused by small changes in spectroscopic data. The results show that the spectroscopic parameters in the HITRAN2016 and GEISA2015 databases lead to large residuals while data of two recent laboratory studies, obtained from spectra measured with the cavity ring-down spectroscopy technique using the speed-dependent Nelkin-Ghatak profile lead to much better agreement with atmospheric measurements. Significant residuals are noted for water vapor absorption lines simulated using parameters provided by both the HITRAN and GEISA databases.

Main text At the highest metrological level, ammonia gas standards are commonly prepared gravimetrically as Primary Standard Mixtures or using a dynamic standard. This international key comparison addressed the measurement of the amount fraction ammonia in nitrogen, to support calibration and measurement services for mainly environmental applications. The nominal amount fraction was 14 μmol mol-1. The results in this Track C key comparison on the composition of biogas are generally good. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

In this article we describe a high-precision laboratory measurement targeting the R(6) manifold of the 2ν3 band of 12CH4. Accurate physical models of this absorption spectrum will be required by the Franco-German, Methane Remote Sensing LIDAR (MERLIN) space mission for retrievals of atmospheric methane. The analysis uses the Hartmann-Tran profile for modeling line shape and also includes line-mixing effects. To this end, six high-resolution and high signal-to-noise absorption spectra of air-broadened methane were recorded using a frequency-stabilized cavity ring-down spectroscopy apparatus. Sample conditions corresponded to room temperature and spanned total sample pressures of 40 hPa – 1013 hPa with methane molar fractions between 1 μmol mol−1 and 12 μmol mol−1. All spectroscopic model parameters were simultaneously adjusted in a multispectrum nonlinear least-squares fit to the six measured spectra. Comparison of the fitted model to the measured spectra reveals the ability to calculate the room-temperature, methane absorption coefficient to better than 0.1% at the on-line position of the MERLIN mission. This is the first time that such fidelity has been reached in modeling methane absorption in the investigated spectral region, fulfilling the accuracy requirements of the MERLIN mission. We also found excellent agreement when comparing the present results with measurements obtained over different pressure conditions and using other laboratory techniques. Finally, we also evaluated the impact of these new spectral parameters on atmospheric transmissions spectra calculations.

Accurate and spectroscopic measurements of molecular transition frequencies are increasingly being employed in a variety of rigorous tests of physics, including the validity of quantum electrodynamics, the proton–electron mass ratio, and the dipole moment of the electron. Near-infrared molecular transitions may also underpin secondary frequency standards for length metrology and provide convenient wavelength standards for telecommunication and spectroscopy. To report progress in this field, we describe measurements of near-infrared Doppler-broadened carbon dioxide line positions. Our experiment uses cavity ring-down spectroscopy in the linear domain and provides an accurate International System of Units (SI)-traceable frequency axis via active locking of the probe laser and ring-down cavity to a Cs-clock-referenced optical frequency comb. The approach has several key attributes: the ability to rapidly scan the probe laser while maintaining a phase lock to the optical frequency comb, continuously tunable spectrum frequency axes that are not limited by the cavity mode spacing, and high signal-to-noise-ratio spectra resulting in stationary statistics amenable to long-term averaging. This performance is achieved by phase locking a single-mode probe laser to the optical frequency comb, coherent electro-optical phase modulation for rapid cavity mode-to-mode shifting of the probe laser, and sub-kilohertz-level frequency stabilization of the ring-down cavity relative to the probe laser. We report vacuum transition frequencies of five transitions in the ( 30012 ) ← ( 00001 ) vibrational band of 12 C 16 O 2 near 1.57 µm and achieve combined standard uncertainties as low as 212 Hz, corresponding to a relative combined standard uncertainty near 10 − 12 .

As part of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of the National Institute of Standards and Technology (NIST) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone amount-of-substance fraction range of 0 nmol/mol to 500 nmol/mol. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol−1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

As part of the on-going key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of Singapore maintained by the National Metrology Centre, A*STAR (NMC, A*STAR) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM), via a transfer standard maintained by the National Institute of Standards and Technology (NIST). The instruments have been compared over a nominal ozone amount-of-substance fraction range of 0 nmol/mol to 500 nmol/mol. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Remote sensing applications require accurate, precise, and traceable measurement science to meet demanding mission goals. Advances in laboratory spectroscopy and molecular line shapes have impressively reduced the uncertainty in satellite, aircraft, and ground-based field campaigns. This has enabled observation of spatially and temporally resolved trends of species such as CO 2 . However, the ambitious requirements of modern remote sensing missions place great demands on laboratory measurements and require state-of-the-art measurement science. Here we present some recent advances in frequency stabilized cavity ring-down spectroscopy (FS-CRDS) measurements of molecular line intensities of carbon dioxide, carbon monoxide, and water. These results are compared to existing spectroscopic databases and reveal that refinements are necessary to meet the accuracy targets for both ground-based and satellite-based remote sensing missions. These results are also compared to ab initio calculations, which may provide a route to directly link molecular absorptions measurements to the SI, without using calibrated gas reference mixtures or artifact standards.

The noble gases, namely neon, argon, krypton and xenon, have many uses including in incandescent and gas discharge lighting, in plasma televisions, shielding gas in welding, in lasers for surgery and semiconductors, and in magnetic resonance imaging (MRI) of the lungs. When incorporating these noble gases in industries, especially the medical field, it is important to know accurately the composition of the noble gas mixture. Therefore, there is a need for accurate gas standards that can be used to determine the noble gas amount-of-substance fraction in the appropriate mixture application. A recent comparison of mixtures containing four noble gases in a helium balance showed mixed results among National Metrology Institutes. Significant differences, 0.7 to 3.8% relative, were seen in the analytical amount-of-substance assignments versus the gravimetric value of the noble gases in the comparison mixture when using "binary standards", i.e. neon in helium, argon in helium and krypton in helium, as applied by the National Institute of Standards and Technology. Post-comparison studies showed that when all four noble gases were included in the standards, the agreement between analytical and gravimetric values was within 0.05% relative. Further research revealed that different carrier gases (hydrogen, helium and nitrogen) resulted in varying differences between the analytical and gravimetric values assignments. This paper will discuss the findings of these analytical comparisons. Graphical abstract ᅟ.

High-resolution absorption spectra of the a 1 ∆ g ←X 3 Σ g − O 2 band measured using cavity ring-down spectroscopy were fitted using the Voigt and speed-dependent Voigt line shapes. We found that the speed-dependent Voigt line shape was better able to model the measured absorption coefficients than the Voigt line shape. Total columns of O 2 were retrieved from ground-based high-resolution absorption spectra from four Total Carbon Column Observing Network (TCCON) sites using both Voigt and speed-dependent Voigt line shapes to calculate absorption coefficients. A lower O 2 concentration was retrieved with the speed-dependent Voigt line shape, with the difference increasing as a function of solar zenith angle. CO 2 total columns were also retrieved from the same spectra using a Voigt line shape and speed-dependent Voigt with line mixing. The column-averaged dry-air mole fraction of CO 2 (XCO 2 ) was calculated using the CO 2 and O 2 columns retrieved with both line shapes from measurements made over a one-year period at the four sites and compared. The inclusion of speed dependence reduces the airmass dependence of XCO 2 . The TCCON empirical airmass correction factor for XCO 2 derived from a year of measurements from TCCON sites at Darwin, Lamont, and Park Falls for XCO 2 improved from −0.0071±0.0057 to −0.0012±0.0054 when speed dependence was included. XCO 2 retrieved with the Voigt and speed-dependent Voigt line shapes was compared to aircraft profiles measured at 13 TCCON sites. The bias between the TCCON measurements and the integrated aircraft profile measurements was reduced from 0.9897±0.0005 to 1.0041±0.0005 for XCO 2 retrieved with the Voigt and speed-dependent Voigt line shapes respectively. These results suggest that speed dependence should be included in the forward model when fitting near-infrared CO 2 and O 2 spectra to improve the accuracy of XCO 2 measurements.

We report the cavity ring-down spectroscopy of 14C, 13C and 12C isotopologues of CO2 in the near- and mid-infrared, measurements which yielded accurate transition intensities, mole fraction determinations, and isotope ratios.

We report a dual-wavelength rapid-scanning spectrometer with ≤ 1%o measurement reproducibility for 13C/12C isotope ratios in air. Initial evaluations of accuracy were performed using gas samples with known δ 13C.

We present a complex-valued electric field model for experimentally observed cavity transmission in coherent cavity-enhanced (CE) multiplexed spectroscopy (i.e., dual-comb spectroscopy, DCS). The transmission model for CE-DCS differs from that previously derived for Fourier-transform CE direct frequency comb spectroscopy [Foltynowicz et al., Appl. Phys. B 110, 163-175 (2013)] by the treatment of the local oscillator which, in the case of CE-DCS, does not interact with the enhancement cavity. Validation is performed by measurements of complex-valued near-infrared spectra of CO and CO$_2$ by an electro-optic frequency comb coherently coupled to an enhancement cavity of finesse $F=19600$. Following validation, we measure the $30012\leftarrow00001$ $^{12}$C$^{16}$O$_2$ vibrational band origin with a combined standard uncertainty of 770 kHz (fractional uncertainty of $4\times10^{-9}$)., 36 pages, 8 figures, 1 table, 95 references

We present new high accuracy measurements of the (30012)←(00001) CO 2 band near 1575 nm recorded with a frequency-agile, rapid scanning cavity ring-down spectrometer. The resulting spectra were fit with the partially correlated, quadratic-speed-dependent Nelkin-Ghatak profile with line mixing. Significant differences were observed between the fitted line shape parameters and those found in existing databases, which are based upon more simplistic line profiles. Absolute transition frequencies, which were referenced to an optical frequency comb, are given, as well as the other line shape parameters needed to model this line profile. These high accuracy measurements should allow for improved atmospheric retrievals of greenhouse gas concentrations by current and future remote sensing missions.

We present a cavity ring-down spectrometer which was developed for near-infrared measurements of laser absorption by atmospheric greenhouse gases. This system has several important attributes that make it possible to conduct broad spectral surveys and to determine line-by-line parameters with wide dynamic range, and high spectral resolution, sensitivity and accuracy. We demonstrate a noise-equivalent absorption coefficient of 4×10 −12 cm −1 Hz −1/2 and a signal-to-noise ratio of 1.5×10 6 :1 in an absorption spectrum of carbon monoxide. We also present high-resolution measurements of trace methane in air spanning more than 1.2 THz and having a frequency axing with an uncertainty less than 100 kHz. Finally, we discuss how this system enables stringent tests of advanced line shape models. To illustrate, we measured an air-broadened carbon dioxide transition over a wide pressure range and analyzed these data with a multi-spectrum fit of the partially correlated, quadratic speed-dependent Nelkin–Ghatak profile. We obtained a quality-of-fit parameter in the multispectrum fit equal to 36,000, thus quantifying small-but-measurable limitations of the model profile. This analysis showed that the line shape depends upon collisional narrowing, speed dependent effects and partial correlations between velocity- and phase-changing collisions.

The absorption spectrum of ethane was measured by frequency-stabilized cavity ring-down spectroscopy over the wave number range 5950–5967 cm−1. Spectra are reported for both pure ethane acquired at pressures near 3 Pa and mixtures of ethane in air at pressures ranging from 666 Pa to 101.3 kPa. Absorption cross sections are reported with a spectrum sampling period of 109 MHz and frequency resolution of 200 kHz. Atmospheric pressure cross sections agree fairly well with existing cross sections determined by FTS in nitrogen, but there are significant variations in cross sections at lower pressures. Source identification of fugitive methane emissions using spectroscopic measurements of the atmospheric ethane-to-methane ratio is also discussed.

We present measurements of approximately 70 isolated, self-broadened, water vapor lines which are assigned to the (1,0,1)–(0,0,0), (0,0,2)–(0,0,0), (1,2,0)–(0,0,0), and (2,0,0)–(0,0,0) vibrational bands and which occur in the transparency window region from 7710 cm−1 to 7920 cm−1. We acquired absorption spectra on room-temperature, water samples over the pressure range 150–800 Pa with the frequency-stabilized cavity ring-down spectroscopy technique. In order to optimize measurement accuracy, we integrated mK-level temperature control and SI-traceable pressure measurements into our cavity ring-down spectroscopy measurements. This technique yielded relative uncertainties of 0.04% and 0.20% in sample density and measured line intensity, respectively. We also referenced our spectrum frequency axes to a Cs clock, which provided vacuum line positions with a combined standard uncertainty of 3 MHz. Comparison of our measured intensities, positions and self-broadening parameters with literature values reveals that the present work substantially reduces uncertainty in these line parameters. For the (1,0,1)–(0,0,0) vibrational band, the measured line intensities agree at the 1%-level with published ab initio calculations. Our spectra exhibited signal-to-noise ratios up to ≈20,000:1 to enable stringent tests of theoretical line profiles through multispectrum least-squares data analysis. We show that the partially correlated, quadratic-speed-dependent Nelkin–Ghatak profile gives a quality of fit that is commensurate with the high spectrum signal-to-noise ratio, and unlike most other profiles considered here, reproduces the measured line shapes without systematic residuals over the entire pressure range. Our results confirm that mechanisms of (1) collisional narrowing, (2) speed-dependent effects and (3) partial correlation between velocity-changing and dephasing collisions, contribute to the self-broadened line shape of isolated water vapor transitions.

We present a new cavity ring-down spectroscopy system which was developed for variable-temperature absorption measurements (220–290 K) of atmospheric gases. This laser spectrometer was developed in the framework of the NASA Orbiting Carbon Observatory-2 project to improve our understanding of line shape parameters for carbon dioxide and oxygen. The apparatus consists of a monolithic, fixed-mirror ring-down cavity within a temperature-regulated enclosure, which is interrogated by a tunable, single-frequency diode laser. We experimentally characterize and model the dependence of the spectrum detuning axis at each setpoint temperature, and show that absolute frequencies are stable to within 200 kHz over several hours, corresponding to temperature stabilities better than 1 mK. We measure the R16e (30013-0001) 12C16O2 transition and carry out multi-spectrum analyses using two line profiles incorporating speed-dependent (quadratic approximation) and Dicke narrowing (hard collision assumption) effects. The resulting broadening coefficient and temperature exponent are in excellent agreement (0.05% level) with previous high-resolution Fourier-transform spectroscopy measurements, and the speed dependent broadening parameter is within 3% of the theoretical value.

International audience; High signal-to-noise ratio spectra of the (3-0) band P(1) and P(17) lines of CO broadened by He, Ar, Kr and SF6 were measured with a frequency-stabilized cavity ring-down spectroscopy system. For each collision-partner and both lines, multiple spectra were measured over pressures spanning nearly three decades up to 130 kPa. These data were analyzed with a multispectrum fitting procedure. Line shapes were modeled using the Hartmann-Tran (HT) profile with first-order line mixing as well as several other simplified profiles. The results show that for all considered collision partners (with the exception of SF6), the HT profile captures the measured line shapes with maximum absolute residuals that are within 0.1% of the peak absorption. In the case of SF6, which is the heaviest perturber investigated here, the maximum residuals for the HT profile are twice as large as for the other collision partners.

Electro-optic frequency combs were generated using a train of frequency chirped waveforms. These combs had up to 10,000 teeth with a spacing as narrow as 200 kHz which enabled Doppler and sub-Doppler spectroscopy of 39K.

We present line shape parameters and intensities of air-broadened CO (3 α 0) and (4 α1) band transitions using frequency-stabilized cavity ringdown spectroscopy at room temperature. Measurements are compared to ab initio calculations.

Reported here is the optical detection of radiocarbon below contemporary levels using cavity ring-down spectroscopy in the linear absorption regime. Petrogenic and biogenic samples of CO 2 are readily distinguished by repeated optical measurements.

We extend the tunable bandwidth of electro-optic frequency comb spectroscopy to >2 THz around λ = 1.6 μm using an external cavity diode laser and report precision spectroscopy of CO2, H2O, and N2O.

We present our first-generation cavity ring-down spectrometer for the optical trace-detection of radiocarbon (14C) as well as define an absolute 14C scale based on ab initio 14C16O2 intensities and linear absorption principles.

Near-IR dual frequency combs generated from waveform driven electro-optic phase modulators (EOMs) are used for high resolution studies in low pressure cells and for remote sensing from natural targets (Boulder Flatirons). Arbitrary waveform generators (with up to 20 GHz of bandwidth) enable amplitude (AM), phase (PM) and harmonic (HM) modulation control of dual parallel phase modulators to generate tailored frequency combs for sensing requirements.

A photoacoustic spectrometer operating near 2.0 μm has been developed for high precision measurements of the 13CO 2 /12CO 2 isotope ratio. The instrument performance and effects of water vapor on the photoacoustic signal are discussed.

We have developed a portable photoacoustic spectrometer that offers routine, precise and accurate measurements of the molar concentration of atmospheric carbon. The temperature-controlled spectrometer continuously samples dried atmospheric air and employs an intensity-modulated distributed feedback laser and fiber amplifier operating near 1.57 µm. For measurements of carbon dioxide in air, we demonstrate a measurement precision (60-s averaging time) of 0.15 µmol mol−1 and achieve a standard uncertainty of 0.8 µmol mol−1 by calibrating the analyzer response in terms of certified gas mixtures. We also investigate how water vapor affects the photoacoustic signal by promoting collisional relaxation of the carbon dioxide.

We demonstrate a heterodyne-detected cavity ring-down spectroscopy (CRDS) method that allows for a noise-equivalent absorption coefficient of 6 × 10−14 cm−1 Hz−1/2, the lowest which has been reported in a CRDS measurement. It is shown that heterodyne-detected CRDS also reaches the quantum noise limit at reasonable optical powers. In addition to offering ultra-high sensitivity, this technique provides high frequency agility over a range of 2 THz in the near-infrared, which allows entire absorption bands to be recorded in minutes. As a demonstration experiment, high resolution spectra of a near-infrared carbon dioxide band have been recorded.

An optical frequency comb generated with an electro-optic phase modulator and a chirped radiofrequency waveform is used to perform saturation and pump-probe spectroscopy on the $D_1$ and $D_2$ transitions of atomic potassium. With a comb tooth spacing of 200 kHz and an optical bandwidth of 2 GHz the hyperfine transitions can be simultaneously observed. Interferograms are recorded in as little as 5 $\mu$s (a timescale corresponding to the inverse of the comb tooth spacing). Importantly, the sub-Doppler features can be measured as long as the laser carrier frequency lies within the Doppler profile, thus removing the need for slow scanning or a priori knowledge of the frequencies of the sub-Doppler features. Sub-Doppler optical frequency comb spectroscopy has the potential to dramatically reduce acquisition times and allow for rapid and accurate assignment of complex molecular and atomic spectra which are presently intractable., Comment: 11 pages (including Supplementary Material), 4 figures

We present the global research landscape which aims to deliver a measurement infrastructure to underpin atmospheric observations of key greenhouse gases governing changes in the Earth’s climate. These measurements present a significant challenge to the metrological community, analytical laboratories and major producers of reference materials. The review focuses on the progress made in the Gas Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM-GAWG) in establishing the primary realisation of the amount-of-substance fraction for carbon dioxide, methane and nitrous oxide in an air matrix. It also focuses on the importance of providing traceable measurements of isotopic composition of these components for commutability of reference materials and for isotope ratio measurements for greenhouse gas source attribution. The review examines the developments in the Global Atmosphere Watch (GAW) Programme of the World Meteorological Organisation (WMO) for providing the framework for the development and implementation of integrated greenhouse gas observations, which is vital for understanding the global carbon cycle and the role greenhouse gases play in climate change. The developments in analytical techniques are also discussed which have shaped the direction of the metrology required to meet the evolving and future needs of stakeholders.

Isotope dilution-cold-vapor-inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has become the primary standard for measurement of gaseous elemental mercury (GEM) mass concentration. However, quantitative mass spectrometry is challenging for several reasons including (1) the need for isotopic spiking with a standard reference material, (2) the requirement for bias-free passive sampling protocols, (3) the need for stable mass spectrometry interface design, and (4) the time and cost involved for gas sampling, sample processing, and instrument calibration. Here, we introduce a high-resolution laser absorption spectroscopy method that eliminates the need for sample-specific calibration standards or detailed analysis of sample treatment losses. This technique involves a tunable, single-frequency laser absorption spectrometer that measures isotopically resolved spectra of elemental mercury (Hg) spectra of 6 (1)S(0) ← 6 (3)P(1) intercombination transition near λ = 253.7 nm. Measured spectra are accurately modeled from first-principles using the Beer–Lambert law and Voigt line profiles combined with literature values for line positions, line shape parameters, and the spontaneous emission Einstein coefficient to obtain GEM mass concentration values. We present application of this method for the measurement of the equilibrium concentration of mercury vapor near room temperature. Three closed systems are considered: two-phase mixtures of liquid Hg and its vapor and binary two-phase mixtures of Hg–air and Hg–N(2) near atmospheric pressure. Within the experimental relative standard uncertainty, 0.9–1.5% congruent values of the equilibrium Hg vapor concentration are obtained for the Hg-only, Hg–air, Hg–N(2) systems, in confirmation with thermodynamic predictions. We also discuss detection limits and the potential of the present technique to serve as an absolute primary standard for measurements of gas-phase mercury concentration and isotopic composition.

[1] The vapor pressure of hexagonal (Ih) water ice was measured over the temperature range 175 K to 253.4 K and referenced to the value at the triple point of water. This experiment combined a highly accurate humidity generation system containing an ice-coated saturator (millikelvin-level temperature control) to provide humidified streams of nitrogen to a cavity-enhanced laser absorption spectrometer. The measured ice vapor pressures had relative standard uncertainties ranging from 0.4% to 0.7% over the entire temperature range. We demonstrate that these measurements validate thermodynamic correlations for ice vapor pressure based on integration of the Clapeyron equation. Moreover, they also indicate that some commonly used vapor pressure correlations are inaccurate and should be avoided.

Absolute transition frequencies were measured for a series of transitions in the (30013)←(00001) near-infrared 12C16O2 band. These measurements were referenced to a cesium atomic clock through the use of an optical frequency comb. Combined standard uncertainties as low as 18 kHz (6×10−7 cm−1) were achieved. Importantly, deviations as large as 5 MHz were observed relative to the HITRAN 2008 database. These measurements were then included in a global fit of 416 CO2 mid-infrared and near-infrared measurements each of which was absolute. The resulting spectroscopic parameters provide a series of secondary frequency standards with kHz-level uncertainties across a wide frequency range and should significantly improve spectroscopic retrieval algorithms for space-based measurements of atmospheric CO2.

Primary gas standards, gas chromatography, and frequency-stabilized cavity ring-down spectroscopy measurements have been used to assess the effect of variations in the argon mixing ratio on the CO2 mixing ratios reported by commercial cavity ring-down spectroscopy sensors. Supporting calculations demonstrate that the use of argon-free, synthetic air standards can lead to a bias of ≈0.7 μmol mol−1 at atmospheric concentration levels of CO2 as a result of pressure-broadening effects. This bias is an order of magnitude greater than the precision of the best commercial sensors and significantly exceeds the World Meteorological Organization's target compatibility goal.

The optical properties of atmospheric aerosols vary widely, being dependent upon particle composition, morphology, and mixing state. This diversity and complexity of aerosols motivates measurement techniques that can discriminate and quantify a variety of single- and multicomponent aerosols that are both internally and externally mixed. Here, we present a new combination of techniques to directly measure the mass-specific extinction and absorption cross sections of laboratory-generated aerosols that are relevant to atmospheric studies. Our approach employs a tandem differential mobility analyzer, an aerosol particle mass analyzer, cavity ring-down and photoacoustic spectrometers, and a condensation particle counter. This suite of instruments enables measurement of aerosol particle size, mass, extinction and absorption coefficients, and aerosol number density, respectively. Taken together, these observables yield the mass-specific extinction and absorption cross sections without the need to model particle morphology or account for sample collection artifacts. Here we demonstrate the technique in a set of case studies which involve complete separation of aerosol by charge, separation of an external mixture by mass, and discrimination between particle types by effective density and single-scattering albedo.

We present ultrasensitive measurements of molecular absorption using frequency-agile rapid scanning, cavity ring-down spectroscopy with an external-cavity diode laser. A microwave source that drives an electro-optic phase modulator with a bandwidth of 20 GHz generates pairs of sidebands on the probe laser. The optical cavity provides for high sensitivity and filters the carrier and all but a single, selected sideband. Absorption spectra were acquired by stepping the tunable sideband from mode-to-mode of the ring-down cavity at a rate that was limited only by the cavity decay time. This approach allows for scanning rates of 8 kHz per cavity resonance, a minimum detectable absorption coefficient of 1.7 × 10−11 cm−1 after only 20 ms of averaging, and a noise-equivalent absorption coefficient of 1.7 × 10−12 cm−1 Hz−1/2. By comparison with cavity-enhanced laser absorption spectrometers reported in the literature, the present system is, to the best of our knowledge, among the most sensitive and has by far the highest spectrum scanning rate.

Retrievals of atmospheric composition from near-infrared measurements require measurements of airmass to better than the desired precision of the composition. The oxygen bands are obvious choices to quantify airmass since the mixing ratio of oxygen is fixed over the full range of atmospheric conditions. The OCO-2 mission is currently retrieving carbon dioxide concentration using the oxygen A-band for airmass normalization. The 0.25% accuracy desired for the carbon dioxide concentration has pushed the required state-of-the-art for oxygen spectroscopy. To measure O2 A-band cross-sections with such accuracy through the full range of atmospheric pressure requires a sophisticated line-shape model (Rautian or Speed-Dependent Voigt) with line mixing (LM) and collision induced absorption (CIA). Models of each of these phenomena exist, however, this work presents an integrated self-consistent model developed to ensure the best accuracy. It is also important to consider multiple sources of spectroscopic data for such a study in order to improve the dynamic range of the model and to minimize effects of instrumentation and associated systematic errors. The techniques of Fourier Transform Spectroscopy (FTS) and Cavity Ring-Down Spectroscopy (CRDS) allow complimentary information for such an analysis. We utilize multispectrum fitting software to generate a comprehensive new database with improved accuracy based on these datasets. The extensive information will be made available as a multi-dimensional cross-section (ABSCO) table and the parameterization will be offered for inclusion in the HITRANonline database.