Off-axis Integrated Cavity Output Spectroscopy Research Articles

Large, sustained soil CO2 efflux but rapid recovery of CH4 oxidation in post-harvest and post-fire stands in a mixedwood boreal forest

The net effect of forest disturbances, such as fires and harvesting, on soil greenhouse gas fluxes is determined by their impacts on both biological and physical factors, as well as the temporal dynamics of these effects post-disturbance. Although harvesting and fire may have distinct effects on soil carbon (C) dynamics, the temporal patterns in soil CO2 and CH4 fluxes and the potential differences between types of disturbances, remain poorly characterized in boreal forests. In this study, we measured soil CO2 and CH4 fluxes using a off-axis integrated cavity output spectroscopy system in snow-free seasons over two years in post-harvest and post-fire chronosequence sites within a mixedwood boreal forest in northwestern Ontario, Canada. Soil CO2 efflux showed a post-disturbance peak, with differing dynamics depending on the disturbance type: post-harvest stands exhibited a nearly tenfold increase (from ∼1 to ∼11 μmol CO2.m-2.s−1) from 1 to 9–10 years post-disturbance, followed by a steep decline; post-fire stands showed a more gradual increase, peaking at ∼6–7.2 μmol CO2.m-2.s−1 after ∼12–15 years. The youngest post-harvest stands were net sources of CH4,whereas post-fire stands were never net CH4 sources. In both disturbance types, the strength of the CH4 sink increased with stand age, approaching ∼2.4 nmol.m-2.s−1 by 15 years post-disturbance. Volumetric water content, bulk density, litter depth, and pH were significant predictors of CO2 fluxes; for CH4 fluxes, litter depth, pH, and the interaction of VWC and soil temperature were significant predictors in both disturbance types, with EC also showing a relationship in post-harvest stands. Our findings indicate that while soil CH4 oxidation rapidly recovers following disturbance, both post-harvest and post-fire stands show a multi-decade release of soil CO2 that is too large to be offset by C gains over this period.

Simultaneous measurement of multi-component gases from pyrolysis of hydrocarbon fuels using absorption spectroscopy

Endothermic hydrocarbon fuel is cracked into small hydrocarbons at high temperatures. Quantitative analysis of the pyrolysis product’s component concentration is of great significance for the analysis of engine combustion regenerative cooling technology and combustion efficiency. Off-axis integrated cavity output spectroscopy technique was adopted in laser absorption spectroscopy. Using the near-infrared spectroscopic properties of methane and ethylene, the component concentrations of methane and ethylene at different temperatures and cracking times were measured. In addition, a high temperature kerosene pyrolysis spectrum measurement system was built, and a concentration measurement error of not more than 3.2 % was achieved. Pyrolysis experiment shows that at low temperatures and short heating times, the concentration of the components that crack methane and ethylene is low. Ethylene is the first to crack as the temperature rises, and it accounts for a relativity large proportion of the mixture. Other gases crack out with the increase of the cracking time. The component concentration of ethylene is basically stable at approximately 12 %.

Dual-path coupling V-shaped structure off-axis integrated cavity output spectroscopy (V-OA-ICOS) for water vapor stable isotope detection at 3.66 μm

Residual cavity mode noise and weak output signal are the main factors that restrict the detection performance of off-axis integrated cavity output spectroscopy (OA-ICOS). In order to overcome the above drawbacks, a novel V-shaped off-axis integrated cavity output spectroscopy (V-OA-ICOS) device was demonstrated, and the dual-path coupling method was further proposed. The dual-path coupling V-OA-ICOS device can not only suppress the residual cavity mode noise but also enhance the intensity of the output signal. The V-shaped resonator cavity ensures a more uniform and square-shaped spot pattern distribution on the surface of the highly reflective mirrors, significantly reducing spots overlap. The dual-path coupling method can re-couple the laser reflected by the front cavity mirror, thereby increasing the total energy and mode density of the cavity. The spectrum of water vapor stable isotopes HD16O and H216O at 3.66 μm was measured to illustrate the performance of the presented approach, the dual-path coupling V-OA-ICOS increases the signal-to-noise ratio (SNR) by a factor ∼ 2.1 compared to single path V-OA-ICOS and the signal intensity by a factor of ∼ 2. The δD variation was obtained by measuring the outdoor water vapor isotope using this device for three consecutive days. The variation range of δD is −220‰ ∼ −120‰. This work proposes a new cavity structure and optical re-coupling method, which offers a novel approach to enhance the performance of OA-ICOS devices.

Precipitation fuels dissolved greenhouse gas (CO2, CH4, N2O) dynamics in a peatland-dominated headwater stream: results from a continuous monitoring setup

Stream ecosystems are actively involved in the biogeochemical cycling of carbon (C) and nitrogen (N) from terrestrial and aquatic sources. Streams hydrologically connected to peatland soils are suggested to receive significant quantities of particulate, dissolved, and gaseous C and N species, which directly enhance losses of greenhouse gases (GHGs), i.e., carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O), and fuel in-stream GHG production. However, riverine GHG concentrations and emissions are highly dynamic due to temporally and spatially variable hydrological, meteorological, and biogeochemical conditions. In this study, we present a complete GHG monitoring system in a peatland stream, which can continuously measure dissolved GHG concentrations and allows to infer gaseous fluxes between the stream and the atmosphere and discuss the results from March 31 to August 25 at variable hydrological conditions during a cool spring and warm summer period. Stream water was continuously pumped into a water-air equilibration chamber, with the equilibrated and actively dried gas phase being measured with two GHG analyzers for CO2 and N2O and CH4 based on Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) and Non-Dispersive Infra-Red (NDIR) spectroscopy, respectively. GHG measurements were performed continuously with only shorter measurement interruptions, mostly following a regular maintenance program. The results showed strong dynamics of GHGs with hourly mean concentrations up to 9959.1, 1478.6, and 9.9 parts per million (ppm) and emissions up to 313.89, 1.17, and 0.40 mg C or N m−2h−1 for CO2, CH4, and N2O, respectively. Significantly higher GHG concentrations and emissions were observed shortly after intense precipitation events at increasing stream water levels, contributing 59% to the total GHG budget of 762.2 g m−2 CO2-equivalents (CO2-eq). The GHG data indicated a constantly strong terrestrial signal from peatland pore waters, with high concentrations of dissolved GHGs being flushed into the stream water after precipitation. During drier periods, CO2 and CH4 dynamics were strongly influenced by in-stream metabolism. Continuous and high-frequency GHG data are needed to assess short- and long-term dynamics in stream ecosystems and for improved source partitioning between in-situ and ex-situ production.

Re-injection off-axis integrated cavity output spectroscopy for the simultaneous detection of N2O, H2O and CO with a mid-infrared QCL laser.

Off-axis integrated cavity output spectroscopy (OA-ICOS) has attracted much interest because it potentially allows highly sensitive field measurements with robust optical alignment. In this paper, a novel instrument that employs a high-finesse optical cavity as an absorption cell has been developed for sensitive measurements of multi-component gases N2O, H2O and CO in the atmosphere based on a mid-infrared quantum cascade laser (QCL) and OA-ICOS. In order to improve the energy utilization and increase the signal-to-noise ratio (SNR) of the signal, a new type of optical path structure of the laser re-injection method is adopted. Furthermore, the system performance can be effectively improved by using a new intervention method of injecting radio frequency (RF) white noise into a laser driver to suppress cavity mode noise and combining the wavelength modulation method (WMS). We compared the sensitivity of the second harmonic signal demodulation between the re-injection method and the standard OA-ICOS, and the SNR increased by 2.68 times compared to the latter. Analysis of the spectral measurements with Allan variance indicates that within an integration time of 1 s, the measurement accuracy of N2O, H2O, and CO is 6.71 ppb, 13.945 ppm, and 1.81 ppb, respectively, and within an integration time of 820 s, the measurement accuracy of N2O, H2O, and CO can be further improved to 1.26 ppb, 2.089 ppm, and 172 ppt, respectively. Our approach represents an underlying analytical method that provides guidelines for monitoring of representative gases in the atmosphere, industrial processes, emergency safety, etc.

Measurement of Carbon Isotopes in Methane Based on Off-Axis Integrated Cavity Output Spectroscopy Technology with Booster Optical Amplifier

Measurement of Carbon Isotopes in Methane Based on Off-Axis Integrated Cavity Output Spectroscopy Technology with Booster Optical Amplifier

Designing a Long Optical Path Direct-Injection-Integrated Cavity for Laser Absorption Spectroscopy

Trace gas measurement has a wide range of applications needed in industrial, medical, and environmental protection. With the evolution of time, the demand for real-time, sensitivity, and accuracy of gas detection has been increasingly heightened. Off-axis integrated cavity output spectroscopy (OA-ICOS) is an effective method for the high-sensitivity detection of trace gases. It uses an integrated cavity with two highly reflective mirrors to provide a long optical path, which guarantees its high sensitivity. However, as the reflectivity of the mirrors increases, the intensity of the output light decreases, and the signal-to-noise ratio decreases. This contradiction makes it difficult to achieve a long optical path and a high signal-to-noise ratio together. To combat this issue, this paper proposes a type of integrated cavity using a direct-injection method. This structure, under equivalent mirror conditions, can maintain an effective absorption optical path very close to the original off-axis integrated cavity while increasing the output light intensity hundreds of times. This enhancement increases the sensitivity of OA-ICOS.

Wavelength modulation enhanced off-axis integrated cavity output spectroscopy for OH radical measurement at 2.8 µm

Wavelength modulation enhanced off-axis integrated cavity output spectroscopy for OH radical measurement at 2.8 µm

Simultaneous detection of CO2/CH4 based on off-axis integrated cavity output spectroscopy and time-division-multiplexing-based wavelength modulation spectroscopy

A highly sensitive dual gases detection system was established for detecting the concentrations of carbon dioxide (CO2) and methane (CH4) simultaneously based on off-axis integrated cavity output spectroscopy (OA-ICOS) technology. Two Distributed Feedback (DFB) lasers with central wavelengths of 1580 nm and 1653 nm were used as the light sources of the system. A time-division-multiplexing-based wavelength modulation spectroscopy (WMS) method was used to scan the current of lasers for improving the signal-to-noise ratio of the system and getting the optimal modulation amplitudes of CO2 and CH4 simultaneously. In addition, the cavity mode noise was suppressed by radio frequency (RF) white noise loading and laser current to further improve the measurement accuracy. Allan deviation analysis indicates that measurement precision of 0.483 ppm for CO2 and 1.37 ppb for CH4 was achieved by averaging up to 993 s and 1093 s respectively. This compact and high-precision measurement system is suitable for measuring atmospheric greenhouse gases.

Simultaneous detection of CH4 and CO2 through dual modulation off-axis integrated cavity output spectroscopy

This study established a novel method for the simultaneous detection of two-component gases. Radio frequency (RF) white noise disturbance laser current and wavelength modulation were simultaneously used to improve the off-axis integrated cavity output spectroscopy technique, and a high-precision dual modulation OA-ICOS (RF-WM-OA-ICOS) system was established. The two laser beams were coupled into one laser beam that was applied incident to the cavity of RF-WM-OA-ICOS system. The second harmonic signals of CH4 and CO2 gas simultaneously appeared in the rising or falling edge of a triangular wave. This method was used to measure CH4 and CO2 with different concentrations. The results indicated that the proposed system has high stability and can accurately and simultaneously measure the concentrations of CH4 and CO2, with an optimal integration time of 220 s. The minimum detection limit was 10 ppb for CH4 and 1.5 ppm for CO2. The corresponding noise equivalent absorption sensitivity values were calculated as 2.67 × 10−13 cm−1⋅Hz−1/2 and 5.18 × 10−11 cm−1⋅Hz−1/2, respectively. The proposed dual-component gas simultaneous detection method can also be used for high-precision simultaneous detection of other gases. Therefore, this study may serve as a reference for developing portable multicomponent gas analyzers.

On-line measurement of atmospheric oxygen by an open-path OA-ICOS based sensor with high accuracy at ambient pressure

In this paper, a compact optical oxygen (O2) sensor system was demonstrated based on off-axis integrated cavity output spectroscopy (OA-ICOS). Light from a distributed feedback laser near 761 nm was coupled into an open-path F-P cavity by off-axis configuration. To address the challenges of changing field environments for open-path configuration, the influence of pressure on the sensor system was studied. A linewidth enhancement factor (δ) was proposed to measure the ambient pressure and a pressure correction method was developed to improve the measurement accuracy. A minimum detection limit of 0.0038% was obtained for an optimum averaging time of 20 s under 760 Torr. Indoor and outdoor O2 concentration measurements were conducted and the sensing applicability of the sensors system at ambient pressure was verified. The demonstrated sensor system allows operation without a vacuum pump and a pressure controller combine with the self-developed laser driver and digital lock-in amplifier, which has advantages of reduced size, low power consumption, low cost and has wide application prospect for O2 sensing in field environments.

Measurement of 24-h continuous human CH4 release in a whole room indirect calorimeter.

We describe the technology and validation of a new whole room indirect calorimeter (WRIC) methodology to quantify volume of methane (VCH4) released from the human body over 24 h concurrently with the assessment of energy expenditure and substrate utilization. The new system extends the assessment of energy metabolism by adding CH4, a downstream product of microbiome fermentation that could contribute to energy balance. Our new system consists of an established WRIC combined with the addition of off-axis integrated-cavity output spectroscopy (OA-ICOS) to measure CH4 concentration ([CH4]). Development, validation, and reliability of the system included environmental experiments to measure the stability of the atmospheric [CH4], infusing CH4 into the WRIC and human cross-validation studies comparing [CH4] quantified by OA-ICOS and mid-infrared dual-comb spectroscopy (MIR DCS).Our infusion data indicated that the system measured 24-h [CH4] and VCH4 with high sensitivity, reliability, and validity. Cross-validation studies showed good agreement between OA-ICOS and MIR DCS technologies (r = 0.979, P < 0.0001). Human data revealed 24-h VCH4 was highly variable between subjects and within/between days. Finally, our method to quantify VCH4 released by breath or colon suggested that over 50% of the CH4 was eliminated through the breath. The method allows, for the first time, measurement of 24-h VCH4 (in kcal) and therefore the measurement of the proportion of human energy intake fermented to CH4 by the gut microbiome and released via breath or from the intestine; also, it allows us to track the effects of dietary, probiotic, bacterial, and fecal microbiota transplantation on VCH4.NEW & NOTEWORTHY This is the first time that continuous assessment of CH4 is reported in parallel with measurements of O2 consumption and CO2 production inside a whole room indirect calorimeter in humans and over 24 h. We provide a detailed description of the whole system and its parts. We carried out studies of reliability and validity of the whole system and its parts. CH4 is released in humans during daily activities.

Wavelength Modulation Off-axis Integrated Cavity Output Spectroscopy for High-sensitivity Detection of OH Radicals in Mid-infrared

Wavelength Modulation Off-axis Integrated Cavity Output Spectroscopy for High-sensitivity Detection of OH Radicals in Mid-infrared

Near-infrared detection and line intensity measurements of H2S with ECDL source based off-axis integrated cavity output spectroscopy

Hydrogen sulphide (H2S) is an extremely hazardous gas which leads to poisoning at higher concentration. Here, we demonstrate the trace detection and line intensity measurement of H2S by means of efficient and indigenously developed off–axis integrated cavity output spectroscopy (OA-ICOS) technique coupled with an external cavity diode laser operating in near-infrared spectral region. Trace detection of H2S was made with OA-ICOS absorbance spectra of ro-vibrational line (51, 5 → 61, 6 & 50, 5 → 60, 6) centered at ∼ 6344 cm−1 of ν1 + ν2 + ν3 band. A ∼ 600 ppbv limit of detection was achieved for an averaging time of 350 s with Allan deviation analysis. Additionally, line intensities of several degenerate R branch transitions of ν1 + ν2 + ν3 band including 51, 5 → 61, 6 & 50, 5 → 60, 6 transition was experimentally measured with OA-ICOS. The study will be valuable in aiding the spectroscopic databases of H2S and have potential application in extracting molecular concentrations in the planet’s atmospheres.

Methane emissions from forested closed landfill sites: Variations between tree species and landfill management practices

Trees in natural and managed environments can act as conduits for the transportation of methane (CH4) from below ground to the atmosphere, bypassing oxidation in aerobic surface soils. Tree stem emissions from landfill sites exhibit large temporal and spatial variability in temperate environments and can account for approximately 40% of the total surface CH4 flux. Emission variability was further investigated in this study by measuring CH4 and CO2 fluxes from landfill sites with different management strategies and varying tree species over a 7-month period. Stem and soil measurements were obtained using flux chambers and an off-axis integrated cavity output spectroscopy analyser. Analysis showed average stem and soil CH4 emissions varied significantly (p < 0.01) between landfills with different management practices. On average, tree stem CH4 fluxes from sites with no clay cap but gas extraction, clay cap and gas extraction, and no clay cap and no gas extraction were 1.4 ± 0.4 μg m−2 h−1, 47.2 ± 19.0 μg m−2 h−1, and 111.9 ± 165.1 μg m−2 h−1, respectively. There was no difference in stem CH4 fluxes between species at each site, suggesting environmental conditions (waterlogging) and site age had a greater influence on both stem and soil fluxes. These results highlight the importance of management practices, and the resultant environmental conditions, in determining CH4 emissions from historic landfill sites.

First use of triply labelled water analysis for energy expenditure measurements in mice

The doubly labelled water (DLW) method is widely used to determine energy expenditure. In this work, we demonstrate the addition of the third stable isotope, 17O, to turn it into triply labelled water (TLW), using the three isotopes measurement of optical spectrometry. We performed TLW (2H, 18O and17O) measurements for the analysis of the CO2 production (rCO2) of mice on different diets for the first time. Triply highly enriched water was injected into mice, and the isotope enrichments of the distilled blood samples of one initial and two finals were measured by an off-axis integrated cavity output spectroscopy instrument. We evaluated the impact of different calculation protocols and the values of evaporative water loss fraction. We found that the dilution space and turnover rates of 17O and 18O were equal for the same mice group, and that values of rCO2 calculated based on 18O–2H, or on 17O–2H agreed very well. This increases the reliability and redundancy of the measurements and it lowers the uncertainty in the calculated rCO2 to 3% when taking the average of two DLW methods. However, the TLW method overestimated the rCO2 compared to the indirect calorimetry measurements that we also performed, much more for the mice on a high-fat diet than for low-fat. We hypothesize an extra loss or exchange mechanism with a high fractionation for 2H to explain this difference.

Methane emissions from trees planted on a closed landfill site.

Trees have morphological adaptations that allow methane (CH4) generated below ground to bypass oxidation in aerobic surface soils. This natural phenomenon however has not been measured in a landfill context where planted trees may alter the composition and magnitude of CH4 fluxes from the surface. To address this research gap, we measured tree stem and soil greenhouse gas (GHG) emissions (CH4 and CO2) from a closed UK landfill and comparable natural site, using an off-axis integrated cavity output spectroscopy analyser and flux chambers. Analyses showed average CH4 stem fluxes from the landfill and non-landfill sites were 31.8 ± 24.4 µg m–2 h–1 and –0.3 ± 0.2 µg m–2 h–1, respectively. The landfill site showed seasonal patterns in CH4 and CO2 stem emissions, but no significant patterns were observed in CH4 and CO2 fluxes at different stem heights or between tree species. Tree stem emissions accounted for 39% of the total CH4 surface flux (7% of the CO2); a previously unknown contribution that should be included in future carbon assessments.

Recent advances and applications of off‐axis integrated cavity output spectroscopy

AbstractThe off‐axis integrated cavity output spectroscopy (OA‐ICOS) represents a suitable solution in many applications with a simple structure and high sensitivity. The off‐axis configuration allows the continuous spectrum output without cavity mode structure when a continuous wave laser is used while preserving the optical resonator's ability to enhance the optical path by tens of thousands of times. This review summarizes the recent advances and applications of OA‐ICOS in recent decades. The evolutionary process and basic principle of OA‐ICOS are introduced. Various approaches for improving the technical performance and enabling simultaneous multigas measurement are reported. Finally, the various field applications of OA‐ICOS technology and the potential development directions are discussed.

Stable isotope variations of dew under three different climates

As a supplementary or the only water source in dry regions, dew plays a critical role in the survival of organisms. The new hydrological tracer 17O-excess, with almost sole dependence on relative humidity, provides a new way to distinguish the evaporation processes and reconstruct the paleoclimate. Up to now, there is no published daily dew isotope record on δ2H, δ18O, δ17O, d-excess, and 17O-excess. Here, we collected daily dew between July 2014 and April 2018 from three distinct climatic regions (i.e., Gobabeb in the central Namib Desert with desert climate, Nice in France with Mediterranean climate, and Indianapolis in the central United States with humid continental climate). The δ2H, δ18O, and δ17O of dew were simultaneously analyzed using a Triple Water Vapor Isotope Analyzer based on Off-Axis Integrated Cavity Output Spectroscopy technique, and then d-excess and 17O-excess were calculated. This report presents daily dew isotope dataset under three climatic regions. It is useful for researchers to use it as a reference when studying global dew dynamics and dew formation mechanisms.

Accuracy and Practical Considerations for Doubly Labeled Water Analysis in Nutrition Studies Using a Laser-Based Isotope Instrument (Off-Axis Integrated Cavity Output Spectroscopy)

BackgroundGiven the utility of the doubly labeled water (DLW) method for determination of energy expenditure, additional techniques for isotope analysis of the samples are welcome. Laser-based instruments are one such new analytical tool, but their accuracy and feasibility for DLW studies are grossly understudied. ObjectivesWe assessed the accuracy of laser-based isotope ratio measurements as part of the DLW method for estimation of carbon dioxide production rate (rCO2) and total energy expenditure (TEE), in between-group comparison study designs. MethodsUrine samples from a previous study were analyzed with a laser-based instrument [off-axis integrated cavity output spectroscopy (OA-ICOS)]. In that study, participants consumed a high-, moderate-, or low-carbohydrate diet for 20 wk; urine samples were obtained in weeks 18–20 before and after a 2H- and 18O-enriched water dose. Isotope ratios (δ2H and δ18O), rCO2, and TEE calculated by standard methods were compared to results previously obtained with the standard technique of isotope ratio mass spectrometry (IRMS). Bias, SD, and bias ± 1.96SD bands between IRMS and OA-ICOS were computed. ResultsThe between OA-ICOS and IRMS rCO2 and TEE trends were equivalent (within 1.2% and 4.1%, respectively), in spite of the differences in measured δ18O values at high enrichment levels. The OA-ICOS δ18O values displayed an increasing offset from the IRMS results as the 18O enrichment increased (mean ± SD 4.6–5.7‰ ± 2‰ offset at the time point with highest 18O enrichment, ∼135‰), whereas the hydrogen isotope ratio (δ2H) differed only slightly between the methods (mean offset −4.9‰ for all time points). The between-diet differences in TEE from the previous study were recapitulated with a smaller subset of participants and time points. ConclusionsOA-ICOS analysis is an accurate and feasible technique for the DLW method. Given the δ18O offset observed at high enrichment, validation of each OA-ICOS instrumental setup against established methods (e.g., IRMS) is recommended.