Optical cavity spectroscopy using heterodyne detection with optical feedback laser frequency locking.

We demonstrate an accurate high sensitivity method for cavity spectroscopy. We measure the frequency intervals of transverse electromagnetic modes relative to a fundamental mode in a high finesse optical resonator, and attribute their mode numbers unambiguously. A laser is frequency locked to a fundamental T E M 00 cavity mode by optical feedback, and phase modulation is used to obtain frequency side bands, which may come to resonance with other transverse cavity modes as the radio-frequency of the modulation is tuned. At these resonances, transmission of the side bands is sensitively detected by heterodyning with the carrier. We also analyze the transverse spatial profile of the heterodyne signal for identification of mode numbers. The adjustment of the Gaussian cavity model to the measured frequency intervals yields values of cavity length, mirror radius of curvature, and mirror ellipticity, with high precision to the ppm level.

Continuous Endogenous Exhaled CO Monitoring by Laser Spectrometer in Human EVLP Before Lung Transplantation.

Endogenous production of carbon monoxide (CO) is affected by inflammatory phenomena and ischemia-reperfusion injury. Precise measurement of exhaled endogenous CO (eCO) is possible thanks to a laser spectrometer (ProCeas® from AP2E company). We assessed eCO levels of human lung grafts during the normothermic Ex-Vivo Lung Perfusion (EVLP). ProCeas® was connected in bypass to the ventilation circuit. The surgical team took the decision to transplant the lungs without knowing eCO values. We compared eCO between accepted and rejected grafts. EVLP parameters and recipient outcomes were also compared with eCO values. Over 7 months, eCO was analyzed in 21 consecutive EVLP grafts. Two pairs of lungs were rejected by the surgical team. In these two cases, there was a tendency for higher eCO values (0.358 ± 0.52 ppm) compared to transplanted lungs (0.240 ± 0.76 ppm). During the EVLP procedure, eCO was correlated with glucose consumption and lactate production. However, there was no association of eCO neither with edema formation nor with the PO2/FiO2 ratio per EVLP. Regarding post-operative data, every patient transplanted with grafts exhaling high eCO levels (>0.235 ppm) during EVLP presented a Primary Graft Dysfunction score of 3 within the 72 h post-transplantation. There was also a tendency for a longer stay in ICU for recipients with grafts exhaling high eCO levels during EVLP. eCO can be continuously monitored during EVLP. It could serve as an additional and early marker in the evaluation of the lung grafts providing relevant information for post-operative resuscitation care.

Comb coherence-transfer and cavity ring-down saturation spectroscopy around 1.65 µm: kHz-accurate frequencies of transitions in the 2ν3 band of 12CH4.

Comb Coherence Transfer (CCT) uses a feed-forward frequency correction to transfer the optical phase of a frequency comb to the beam of a free-running diode laser. This allows the amplification of a selected comb tooth by 50 dB while adding agile and accurate frequency tuning. In the present work, SI-traceable frequency calibration and comb tooth narrowing down to 20 kHz is additionally provided by comb frequency locking to an ultrastable optical frequency reference distributed from Paris to Grenoble through the RENATER optical fiber network [Lisdat et al., Nat. Commun., 2016, 7, 12443]. We apply this CCT broadly tunable source for saturated cavity ring-down spectroscopy of ro-vibrational R0 to R10 multiplets in the 2ν3 band of 12CH4 (from 6015 to 6115 cm-1). Indeed, efficient cavity injection with large intra-cavity power build-up induces saturation of the ro-vibrational transitions at low pressure and Doppler-free Lamb dips are observed with high signal/noise. kHz-accurate transition frequencies are derived improving by three orders of magnitude previous values from spectra in the Doppler regime, which are strongly affected by line blending. While previous saturation spectroscopy investigations addressed specific 2ν3 multiplets (R6 or R9), the CCT approach allowed for a rapid coverage of the entire R0-R10 series. Measured transition frequencies are compared with experimental and theoretical line lists available in the literature.

Privacy and uniqueness of neighborhoods in social networks.

The ability to share social network data at the level of individual connections is beneficial to science: not only for reproducing results, but also for researchers who may wish to use it for purposes not foreseen by the data releaser. Sharing such data, however, can lead to serious privacy issues, because individuals could be re-identified, not only based on possible nodes' attributes, but also from the structure of the network around them. The risk associated with re-identification can be measured and it is more serious in some networks than in others. While various optimization algorithms have been proposed to anonymize networks, there is still only a limited theoretical understanding of which network features are important for the privacy problem. Using network models and real data, we show that the average degree of networks is a crucial parameter for the severity of re-identification risk from nodes' neighborhoods. Dense networks are more at risk, and, apart from a small band of average degree values, either almost all nodes are uniquely re-identifiable or they are all safe. Our results allow researchers to assess the privacy risk based on a small number of network statistics which are available even before the data is collected. As a rule-of-thumb, the privacy risks are high if the average degree is above 10. Guided by these results, we explore sampling of edges as a strategy to mitigate the re-identification risk of nodes. This approach can be implemented during the data collection phase, and its effect on various network measures can be estimated and corrected using sampling theory. The new understanding of the uniqueness of neighborhoods in networks presented in this work can support the development of privacy-aware ways of designing network data collection procedures, anonymization methods, and sharing network data.

Monitoring of endogenous nitric oxide exhaled by pig lungs during ex-vivo lung perfusion.

In the context of organ shortage for transplantation, new criteria for better organ evaluation should be investigated. Ex-vivo lung perfusion (EVLP) allows extra-corporal lung re-conditioning and evaluation, under controlled parameters of the organ reperfusion and mechanical ventilation. This work reports on the interest of exhaled gas analysis during the EVLP procedure. After a 1 h cold ischemia, the endogenous gas production by an isolated lung of nitric oxide and carbon monoxide is simultaneously monitored in real time. The exhaled gas is analysed with two very sensitive and selective laser spectrometers developed upon the technique of optical-feedback cavity-enhanced absorption spectroscopy. Exhaled gas concentration measured for an ex-vivo lung is compared to the corresponding production by the whole living pig, measured before euthanasia. On-line measurements of the fraction of nitric oxide in exhaled gas (FENO) in isolated lungs are reported here for the first time, allowing to resolve the respiratory cycles. In this study, performed on 9 animals, FENO by isolated lungs range from 3.3 to 10.6 ppb with a median value of 4.4 ppb. Pairing ex-vivo lung and pig measurements allows to demonstrate a systematic increase of FENO in the ex-vivo lung as compared to the living animal, by a factor of 3 ± 1.2. Measurements of the fraction of carbon monoxide in exhaled gas (FECO) confirm levels recorded during previous studies driven to evaluate FECO as a potential marker of ischemia reperfusion injuries. FECO production by ex-vivo lungs ranges from 0.31 to 2.3 ppm with a median value of 0.8 ppm. As expected, these FECO values are lower than the production by the corresponding whole pig body, by a factor of 6.9 ± 2.7.

High inhaled oxygen concentration quadruples exhaled CO in healthy volunteers monitored by a highly sensitive laser spectrometer.

Carbon monoxide (CO) monitoring in human breath is the focus of many investigations as CO could possibly be used as a marker of various diseases. Detecting CO in human breath remains a challenge because low concentrations (

Feed-forward comb-assisted coherence transfer to a widely tunable DFB diode laser.

The transfer of phase coherence from an ultrastable master laser to a distributed feedback diode laser, using an optical comb as a transfer oscillator, is obtained via a new scheme allowing continuous scanning across the whole tuning range of the slave laser together with absolute frequency determination. This is accomplished without phase lock loops, through a robust high-bandwidth feed-forward control acting directly on the slave laser output radiation. The correction is obtained by means of a dual-parallel Mach-Zehnder interferometer used as an optical single-sideband modulator. Coherence transfer across a master-slave frequency gap of 14 THz yields an ∼10 kHz linewidth providing high injection efficiency of an optical cavity with finesse 250 000. This allows demonstrating a cavity ring-down absorption spectrum of low-pressure ambient air over a 300 GHz spectral window.

Sub-Ocean: Subsea Dissolved Methane Measurements Using an Embedded Laser Spectrometer Technology.

We present a novel instrument, the Sub-Ocean probe, allowing in situ and continuous measurements of dissolved methane in seawater. It relies on an optical feedback cavity enhanced absorption technique designed for trace gas measurements and coupled to a patent-pending sample extraction method. The considerable advantage of the instrument compared with existing ones lies in its fast response time of the order of 30 s, that makes this probe ideal for fast and continuous 3D-mapping of dissolved methane in water. It could work up to 40 MPa of external pressure, and it provides a large dynamic range, from subnmol of CH4 per liter of seawater to mmol L-1. In this work, we present laboratory calibration of the instrument, intercomparison with standard method and field results on methane detection. The good agreement with the headspace equilibration technique followed by gas-chromatography analysis supports the utility and accuracy of the instrument. A continuous 620-m depth vertical profile in the Mediterranean Sea was obtained within only 10 min, and it indicates background dissolved CH4 values between 1 and 2 nmol L-1 below the pycnocline, similar to previous observations conducted in different ocean settings. It also reveals a methane maximum at around 6 m of depth, that may reflect local production from bacterial transformation of dissolved organic matter.

Nitric Oxide Analysis Down to ppt Levels by Optical-Feedback Cavity-Enhanced Absorption Spectroscopy.

Monitoring nitric oxide at the trace level is required in a large range of applications. We report on a trace gas analyzer optimized for nitric oxide measurements by Optical Feedback Cavity Enhanced Absorption Spectroscopy with an interband cascade laser at 5.3 µm. The short response time of the instrument allows for reaching the level of 50 ppt in only 180 ms. Its stability enables averaging up to 12 min to reach a detection limit of 0.9 ppt. Absolute concentration calibration requires to account for the optical saturation effect that results from the intense absorption line intensity addressed here, in the mid infrared region, in contrast to instruments that are operating in the near infrared region.

Feed-forward coherent link from a comb to a diode laser: Application to widely tunable cavity ring-down spectroscopy.

We apply a feed-forward frequency control scheme to establish a phase-coherent link from an optical frequency comb to a distributed feedback (DFB) diode laser: This allows us to exploit the full laser tuning range (up to 1 THz) with the linewidth and frequency accuracy of the comb modes. The approach relies on the combination of an RF single-sideband modulator (SSM) and of an electro-optical SSM, providing a correction bandwidth in excess of 10 MHz and a comb-referenced RF-driven agile tuning over several GHz. As a demonstration, we obtain a 0.3 THz cavity ring-down scan of the low-pressure methane absorption spectrum. The spectral resolution is 100 kHz, limited by the self-referenced comb, starting from a DFB diode linewidth of 3 MHz. To illustrate the spectral resolution, we obtain saturation dips for the 2ν3 R(6) methane multiplet at µbar pressure. Repeated measurements of the Lamb-dip positions provide a statistical uncertainty in the kHz range.

Laser spectroscopy for breath analysis: towards clinical implementation.

Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.

Exhaled carbon monoxide is correlated with ischemia reperfusion injuries during ex vivo lung perfusion in pigs.

Measurement of exhaled carbon monoxide (eCO) might help in the selection of lung grafts during ex vivo lung perfusion (EVLP) since its endogenous production is increased under ischemia reperfusion. The objective of this study was to measure eCO variations depending on the extent of lung ischemia reperfusion injuries. Using a porcine model and a laser spectrometer instrument, eCO was measured during EVLP. eCO was compared after 30 min (D0) or 24 h (D1) of cold ischemia. The ability of eCO to distinguish lungs deemed suitable for transplantation was evaluated. Six lungs were studied at D0 and compared to six lungs studied at D1. eCO was systematically higher on D1 (1.35 ± 0.26 ppmv versus 0.95 ± 0.31 ppmv, p = 0.01). The best threshold concentration for eCO to select lungs was 0.86 ppmv (area under the receiver operating characteristic curve: 0.65 [95% confidence interval: 0.34-0.97], p = 0.40). These results show that eCO varies during EVLP. The interpretation of this variation and the role of eCO as a biomarker of ischemia reperfusion injuries during EVLP should be tested in further clinical studies.

Paleoclimate. Enhanced tropical methane production in response to iceberg discharge in the North Atlantic.

The causal mechanisms responsible for the abrupt climate changes of the Last Glacial Period remain unclear. One major difficulty is dating ice-rafted debris deposits associated with Heinrich events: Extensive iceberg influxes into the North Atlantic Ocean linked to global impacts on climate and biogeochemistry. In a new ice core record of atmospheric methane with ultrahigh temporal resolution, we find abrupt methane increases within Heinrich stadials 1, 2, 4, and 5 that, uniquely, have no counterparts in Greenland temperature proxies. Using a heuristic model of tropical rainfall distribution, we propose that Hudson Strait Heinrich events caused rainfall intensification over Southern Hemisphere land areas, thereby producing excess methane in tropical wetlands. Our findings suggest that the climatic impacts of Heinrich events persisted for 740 to 1520 years.

Communication: Saturated CO2 absorption near 1.6 µm for kilohertz-accuracy transition frequencies.

Doppler-free saturated-absorption Lamb dips were measured on weak rovibrational lines of (12)C(16)O2 between 6189 and 6215 cm(-1) at sub-Pa pressures using optical feedback frequency stabilized cavity ring-down spectroscopy. By referencing the laser source to an optical frequency comb, transition frequencies for ten lines of the 30013←00001 band P-branch and two lines of the 31113←01101 hot band R-branch were determined with an accuracy of a few parts in 10(11). Involving rotational quantum numbers up to 42, the data were used for improving the upper level spectroscopic constants. These results provide a highly accurate reference frequency grid over the spectral interval from 1599 to 1616 nm.

Optical phase cloning by an integrated dual-parallel Mach-Zehnder modulator.

The use of a dual-parallel Mach-Zehnder modulator in a feed-forward configuration is shown to serve the purpose of cloning the optical phase of a master oscillator on a distributed-feed-back (DFB) slave laser exhibiting a multi-MHz-wide frequency noise spectrum. A residual phase error of 113 mrad is obtained together with an extremely high control bandwidth of hundreds of megahertz and a gigahertz-level capture and tuning range. Besides offering a dramatic improvement over feedback loops, this approach is susceptible of hybrid integration in a cost-effective compact device benefiting from the wide tunability of DFB lasers.

Optical feedback frequency stabilized cavity ring-down spectroscopy.

We introduce optical feedback frequency stabilized cavity ring-down spectroscopy (OFFS-CRDS), a near-shot-noise-limited technique that combines kilohertz resolution with an absorption detection sensitivity of 5×10(-13) cm(-1) Hz(-1/2). Its distributed feedback laser source is stabilized to a highly stable V-shaped reference cavity by optical feedback and fine-tuned by means of single-sideband modulation. The stability of this narrow laser is transferred to a ring-down (RD) cavity using a new fibered Pound-Drever-Hall (PDH) locking scheme without a dedicated electro-optic phase modulator, yielding several hundred RD events per second. We demonstrate continuous coverage of more than 7 nm with a baseline noise of 5×10(-12) cm(-1) and a dynamic range spanning six decades. With its resonant intracavity light intensity on the order of 1 kW/cm2, the spectrometer was used for observing a Lamb dip in a transition of carbon dioxide involving four vibrational quanta. Saturating such a weak transition at 160 µW input power, OFFS-CRDS paves the way to Doppler-free molecular overtone spectroscopy for precision measurements of hyperfine structures and pressure shifts.

Optical feedback stabilized laser tuned by single-sideband modulation.

We report a subkilohertz-linewidth distributed-feedback diode laser that is optical-feedback locked to a highly stable V-shaped cavity with drift rates below 20 Hz/s. This source is continuously tunable over 1 THz around 1590 nm by selecting a cavity mode and using an innovative single-sideband modulation scheme, which allows for frequency shifting over up to 40 GHz with millihertz accuracy. This robust setup achieves high performance without advanced vibration isolation and will be a powerful tool for metrological applications, in particular a redetermination of the Boltzmann constant by molecular spectroscopy.

Frequency comb based spectrometer for in situ and real time measurements of IO, BrO, NO2, and H2CO at pptv and ppqv levels.

We report an instrument designed for trace gas measurement of highly reactive halogenated radicals, such as bromine oxide and iodine oxide, as well as for nitrogen dioxide and formaldehyde. This compact and robust spectrometer relies on an alternated injection of a frequency-doubled femtosecond radiation at 338 and 436 nm into two parallel high-finesse cavities, for measuring BrO + H(2)CO, and IO + NO(2), respectively. The transmission of the broadband radiation through the cavity is analyzed with a high resolution, compact spectrograph consisting of an echelle grating and a high sensitivity CCD camera. The transportable instrument fits on a breadboard 120 × 60 cm size and is suitable for in situ and real time measurements of these species. A field campaign at the Marine Boundary Layer in Roscoff (in the northwest of France, 48.7°N, 4.0°W) during June 2011 illustrates the outstanding performance of the instrument, which reaches a bandwidth normalized minimum absorption coefficient of 1.3 × 10(-11) cm(-1) Hz(-1/2) per spectral element, and provides detection levels as low as 20 parts per quadrillion of IO in 5 min of acquisition.

High-speed off-axis Cavity Ring-Down Spectroscopy with a re-entrant configuration for spectral resolution enhancement.

Monitoring of changing samples by Cavity Ring-Down Spectroscopy (CRDS) is possible using fast frequency scans of the laser and/or the cavity resonance. Mode-matched cavity excitation improves performance of fast CRDS but data-points result separated by the cavity Free Spectral Range (FSR): low pressure samples demand long cavities. We demonstrate fast CRDS with off-axis injection of a "re-entrant" resonator yielding FSR/N data-points separation. Our N = 4 short-cavity setup is found to perform well compared with other fast-CRDS implementations. Interestingly, the intrinsic chirped ringing affecting ring-down signals in mode-matched fast-CRDS disappear with off-axis injection. This is due to a fine splitting of the re-entrant-cavity degenerate groups of modes by astigmatism.