An injection method for measuring the carbon isotope content of soil carbon dioxide and soil respiration with a tunable diode laser absorption spectrometer

Abstract. Tunable diode laser absorption spectrometry (TDLAS) is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C) of carbon dioxide (CO2) in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site), providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35‰ for δ13C, but after fixing several problems the isotope precision improved to 0.2‰ (over the last several months). The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional) seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.

Variations in the isotopic composition (δ13C, δD) of methane produced within a landfill site near Mainz, Germany, were studied using a newly developed tunable diode laser absorption spectrometer (TDLAS) method. Additional data on the mixing ratios of CO2, O2, N2, CH4 itself and δ13C of the CO2 in the landfill gas were also acquired. Samples taken from several branches of the landfill biogas collection system had methane isotopic compositions in the range δ13C = −62.3 to −55.3‰ VPDB (n = 23) and δD = −327 to −287‰ VSMOW (n = 23). Although the variability of the stable isotope ratios is small, several significant correlations were found between these and the other measured parameters, which provide insight into the microbiological processes occurring within the landfill. Several samples showed evidence of admixture of atmospheric air which occurs when the pumping rate in the collection branch exceeds the local methane production rate. A fraction of the atmospheric oxygen is consumed during the passage through the landfill and CO2 is produced in addition to the CO2 associated with methanogenesis. The consumption of oxygen is correlated with the δ13C and δD of CH4 and the δ13C of CO2. The correlation is consistent with partial bacterial oxidation of CH4 resulting in the progressive enrichment of the remaining CH4 (α(δ13C) = 1.008 ± 0.003 and α(δD) = 1.044 ± 0.020) and in the formation of very depleted CO2. For samples showing no evidence of oxidation, there was a negative correlation between δD and δ13C(CH4)(r = −0.86, n = 14) and between δ13C(CO2) and δ13C(CH4) (r = −0.95, n = 14), which we interpret as originating from slightly varying contributions from the two methanogenic pathways CO2 reduction and acetate fermentation.

Considerable research has recently been devoted to understanding biogeochemical processes under winter snow cover, leading to enhanced appreciation of the importance of many winter ecological processes. In this study, a comprehensive investigation of the stable carbon isotope composition (δ13C) of CO2 within a high-elevation subalpine forest snowpack was conducted. Our goals were to study the δ13C of biological soil respiration under snow in winter, and to assess the relative importance of diffusion and advection (ventilation by wind) for gas transport within snow. In agreement with other studies, we found evidence of an active microbial community under a roughly 1-m deep snowpack during winter and into spring as it melted. Under-snow CO2 mole fractions were observed up to 3,500 μmol mol−1, and δ13C of CO2 varied from ~−22 to ~−8‰. The δ13C of soil respiration calculated from mixing relationships was −26 to −24‰, and although it varied in time, it was generally close to that of the bulk organic horizon (−26.0‰). Subnivean CO2 and δ13C were quite dynamic in response to changes in soil temperature, liquid water availability, and wind events. No clear biologically-induced isotopic changes were observed during periods when microbial activity and root/rhizosphere activity were expected to vary, although such changes cannot be eliminated. There was clear evidence of isotopic enrichment associated with diffusive transport as predicted by theory, but simple diffusive enrichment (4.4‰) was not observed. Instead, ventilation of the snowpack by sustained wind events in the forest canopy led to changes in the diffusively-enriched gas profile. The isotopic influence of diffusion on gases in the snowpack and litter was greatest at greater depths, due to the decreased relative contribution of advection at depth. There were highly significant correlations between the apparent isotopic content of respiration from the soil with wind speed and pressure. In summary, physical factors influencing gas transport substantially modified and potentially obscured biological factors in their effects on δ13C of CO2 within this subalpine forest snowpack.

Large impacts of small methane fluxes on carbon isotope values of soil respiration

Abstract. A method was devised for analysing small discrete gas samples (50 mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from < 0.1 to > 20 000 ppm and δ13C–CO2 values from −100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples h−1, with 13 h−1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C–CO2 levels varying from −27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C–CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.

We developed an experimental method for precise determination of carbon stable isotope ratio (δ13C) of soil-respired CO2 under natural condition. We devised a flask sampling system optimized for collecting soil-respired CO2 to minimize the measurement artifacts related to pressure anomaly. The δ13C of soil-respired CO2 was estimated from relationship between change rates of the CO2 mole fraction and the δ13C of the CO2 in a closed chamber at the soil surface by using two end-member simple mixing model. We tested the influence of CO2 enrichment in the soil-chamber headspace on the estimates of the δ13C of soil respired CO2 by using high-precision measurements of CO2 mole fraction and δ13C. To our results, the estimates of the δ13C of soil respired CO2 was rather insusceptible to the influence of the CO2 enrichment in the chamber as compared with the soil CO2 efflux. Improvement of analytical precision of δ13C is preferred approach to reduce the error in the estimates of δ13C of soil respired CO2. On the other hand, extending the sampling range of CO2 mole fraction in the chamber can be cost-effective means for the error-reduction practically.

Abstract. Recent studies have examined temporal fluctuations in the amount and carbon isotope content (δ13C) of CO2 produced by the respiration of roots and soil organisms. These changes have been correlated with diel cycles of environmental forcing (e.g., sunlight and soil temperature) and with synoptic-scale atmospheric motion (e.g., rain events and pressure-induced ventilation). We used an extensive suite of measurements to examine soil respiration over 2 months in a subalpine forest in Colorado, USA (the Niwot Ridge AmeriFlux forest). Observations included automated measurements of CO2 and δ13C of CO2 in the soil efflux, the soil gas profile, and forest air. There was strong diel variability in soil efflux but no diel change in the δ13C of the soil efflux (δR) or the CO2 produced by biological activity in the soil (δJ). Following rain, soil efflux increased significantly, but δR and δJ did not change. Temporal variation in the δ13C of the soil efflux was unrelated to measured environmental variables, and we failed to find an explanation for this unexpected result. Measurements of the δ13C of the soil efflux with chambers agreed closely with independent observations of the isotopic composition of soil CO2 production derived from soil gas well measurements. Deeper in the soil profile and at the soil surface, results confirmed established theory regarding diffusive soil gas transport and isotopic fractionation. Deviation from best-fit diffusion model results at the shallower depths illuminated a pump-induced ventilation artifact that should be anticipated and avoided in future studies. There was no evidence of natural pressure-induced ventilation of the deep soil. However, higher variability in δ13C of the soil efflux relative to δ13C of production derived from soil profile measurements was likely caused by transient pressure-induced transport with small horizontal length scales.

Abstract. The carbon isotopic composition (δ13C) of CO2 efflux (δ13Cefflux) from soil is generally interpreted to represent the actual isotopic composition of the respiratory source (δ13CRs). However, soils contain a large CO2 pool in air-filled pores. This pool receives CO2 from belowground respiration and exchanges CO2 with the atmosphere (via diffusion and advection) and the soil liquid phase (via dissolution). Natural or artificial modification of δ13C of atmospheric CO2 (δ13Catm) or δ13CRs causes isotopic disequilibria in the soil-atmosphere system. Such disequilibria generate divergence of δ13Cefflux from δ13CRs (termed "disequilibrium effect"). Here, we use a soil CO2 transport model and data from a 13CO2/12CO2 tracer experiment to quantify the disequilibrium between δ13Cefflux and δ13CRs in ecosystem respiration. The model accounted for diffusion of CO2 in soil air, advection of soil air, dissolution of CO2 in soil water, and belowground and aboveground respiration of both 12CO2 and 13CO2 isotopologues. The tracer data were obtained in a grassland ecosystem exposed to a δ13Catm of −46.9 ‰ during daytime for 2 weeks. Nighttime δ13Cefflux from the ecosystem was estimated with three independent methods: a laboratory-based cuvette system, in-situ steady-state open chambers, and in-situ closed chambers. Earlier work has shown that the δ13Cefflux measurements of the laboratory-based and steady-state systems were consistent, and likely reflected δ13CRs. Conversely, the δ13Cefflux measured using the closed chamber technique differed from these by −11.2 ‰. Most of this disequilibrium effect (9.5 ‰) was predicted by the CO2 transport model. Isotopic disequilibria in the soil-chamber system were introduced by changing δ13Catm in the chamber headspace at the onset of the measurements. When dissolution was excluded, the simulated disequilibrium effect was only 3.6 ‰. Dissolution delayed the isotopic equilibration between soil CO2 and the atmosphere, as the storage capacity for labelled CO2 in water-filled soil pores was 18 times that of soil air. These mechanisms are potentially relevant for many studies of δ13CRs in soils and ecosystems, including FACE experiments and chamber studies in natural conditions. Isotopic disequilibria in the soil-atmosphere system may result from temporal variation in δ13CRs or diurnal changes in the mole fraction and δ13C of atmospheric CO2. Dissolution effects are most important under alkaline conditions.

Tunable diode laser absorption spectrometers (TDLAS) are versatile devices with a wide range of applications. In particular, they can be used to detect methane using an analyzer that operates with an infrared band (1.6 – 1.7 μm) laser beam configured in an open path architecture. This setup is suitable for nonhomogeneous airflow coming from coal mine ventilation shafts. TDLAS devices are compact, robust, easy to install, and require minimal maintenance.Methane emissions from the coal mining sector in Poland account for approximately 0.5 million tons of methane per year and are significant contributors to the continental budget of this gas. Most of the emissions occur through the ventilation shafts, where the methane content can vary from 0.05% to 0.7%.During June 2023, a TDLAS analyzer (Unisearch, LasIR) was installed at a selected ventilation shaft air diffuser. The device operated for one month, recording the methane concentration in the ventilated air with a temporal resolution of 1 second. In addition to TDLAS, two other instruments were used to determine methane content: an ICOS analyzer (LGR/ABB, mGGA-918) and a pellistor sensor (EMAG, DCH). The ICOS analyzer was used to cross calibrate the TDLAS instrument across a wide range of methane concentrations. The pellistor sensor is a popular type of sensor used in coal mines for safety reasons. Typically, methane emissions are determined through gas chromatographic analyses conducted using periodically collected samples (e.g., once a month). However, methane content in ventilated air can vary on shorter timescales of hours, days, and weeks. Additionally, pellistor sensors are less precise, and the uncertainty of a single measurement cannot be better than 0.1%. In contrast, TDLAS analyzers can be commonly used by coal mine operators for methane reporting, as their precision is usually better than 0.01%.The presentation will address the challenges associated with using TDLAS for methane emission calculations and highlight its advantages over other commonly used techniques. It will also provide insights into interpreting pellistor sensor readings for quantifying methane emissions and assessing associated uncertainties. Finally, the presentation will discuss the benefits of deploying TDLAS techniques in the coal mining industry, both in the short term and as a potential long-term solution of the reporting of CH4 release. This research was funded by and performed in collaboration with UNEP's International Methane Emissions Observatory. The results presented here are part of the findings from a series of three measurement campaigns performed in Poland’s Upper Silesia coal basin.

Soil respiration is the largest flux of carbon (C) from terrestrial ecosystems to the atmosphere. Here, we tested the hypothesis that photosynthesis affects the diurnal pattern of grassland soil-respired CO(2) and its C isotope composition (delta(13)C(SR)). A combined shading and pulse-labelling experiment was carried out in a mountain grassland. delta(13)C(SR) was monitored at a high time resolution with a tunable diode laser absorption spectrometer. In unlabelled plots a diurnal pattern of delta(13)C(SR) was observed, which was not explained by soil temperature, moisture or flux rates and contained a component that was also independent of assimilate supply. In labelled plots delta(13)C(SR) reflected a rapid transfer and respiratory use of freshly plant-assimilated C and a diurnal shift in the predominant respiratory C source from recent (i.e. at least 1 d old) to fresh (i.e. photoassimilates produced on the same day). We conclude that in grasslands the plant-derived substrates used for soil respiratory processes vary during the day, and that photosynthesis provides an important and immediate C source. These findings indicate a tight coupling in the plant-soil system and the importance of plant metabolism for soil CO(2) fluxes.

• Photosynthetic carbon (C) isotope discrimination (Δ(Α)) labels photosynthates (δ(A) ) and atmospheric CO(2) (δ(a)) with variable C isotope compositions during fluctuating environmental conditions. In this context, the C isotope composition of respired CO(2) within ecosystems is often hypothesized to vary temporally with Δ(Α). • We investigated the relationship between Δ(Α) and the C isotope signals from stem (δ(W)), soil (δ(S)) and ecosystem (δ(E)) respired CO(2) to environmental fluctuations, using novel tuneable diode laser absorption spectrometer instrumentation in a mature maritime pine forest. • Broad seasonal changes in Δ(Α) were reflected in δ(W,) δ(S) and δ(E). However, respired CO(2) signals had smaller short-term variations than Δ(A) and were offset and delayed by 2-10 d, indicating fractionation and isotopic mixing in a large C pool. Variations in δ(S) did not follow Δ(A) at all times, especially during rainy periods and when there is a strong demand for C allocation above ground. • It is likely that future isotope-enabled vegetation models will need to develop transfer functions that can account for these phenomena in order to interpret and predict the isotopic impact of biosphere gas exchange on the C isotope composition of atmospheric CO(2).

Abstract. Nitrous oxide (N2O) fluxes measured using the eddy-covariance method capture the spatial and temporal heterogeneity of N2O emissions. Most closed-path trace-gas analyzers for eddy-covariance measurements have large-volume, multi-pass absorption cells that necessitate high flow rates for ample frequency response, thus requiring high-power sample pumps. Other sampling system components, including rain caps, filters, dryers, and tubing, can also degrade system frequency response. This field trial tested the performance of a closed-path eddy-covariance system for N2O flux measurements with improvements to use less power while maintaining the frequency response. The new system consists of a thermoelectrically cooled tunable diode laser absorption spectrometer configured to measure both N2O and carbon dioxide (CO2). The system features a relatively small, single-pass sample cell (200 mL) that provides good frequency response with a lower-powered pump ( ∼ 250 W). A new filterless intake removes particulates from the sample air stream with no additional mixing volume that could degrade frequency response. A single-tube dryer removes water vapour from the sample to avoid the need for density or spectroscopic corrections, while maintaining frequency response. This eddy-covariance system was collocated with a previous tunable diode laser absorption spectrometer model to compare N2O and CO2 flux measurements for two full growing seasons (May 2015 to October 2016) in a fertilized cornfield in Southern Ontario, Canada. Both spectrometers were placed outdoors at the base of the sampling tower, demonstrating ruggedness for a range of environmental conditions (minimum to maximum daily temperature range: −26.1 to 31.6 °C). The new system rarely required maintenance. An in situ frequency-response test demonstrated that the cutoff frequency of the new system was better than the old system (3.5 Hz compared to 2.30 Hz) and similar to that of a closed-path CO2 eddy-covariance system (4.05 Hz), using shorter tubing and no dryer, that was also collocated at the site. Values of the N2O fluxes were similar between the two spectrometer systems (slope = 1.01, r2 = 0.96); CO2 fluxes as measured by the short-tubed eddy-covariance system and the two spectrometer systems correlated well (slope = 1.03, r2 = 0.998). The new lower-powered tunable diode laser absorption spectrometer configuration with the filterless intake and single-tube dryer showed promise for deployment in remote areas.

Abstract. Three approaches for determining the stable isotopic composition (δ13C and δ18O) of soil CO efflux were compared. A new technique employed mini-towers, constructed of open-topped piping, that were placed on the soil surface to collect soil-emitted CO2. Samples were collected along a vertical gradient and analyzed for CO2 concentration and isotopic composition. These data were then used to produce Keeling plots to determine the δ18O and δ13C of CO2 emitted from the soil. These results were then compared to the δ18O and δ13C of soil-respired CO2 measured with two other techniques: (1) flux chambers and (2) estimation from the application of the diffusional fractionation factor to measured values of below ground soil CO2 and to CO2 in equilibrium with soil water δ18O. Mini-tower δ18O Keeling plots were linear and highly significant (0.81< r 2 > 0.96), in contrast to chamber δ18O Keeling plots, which showed significant curvature, necessitating the use of a mass balance to calculate the δ18O of respired CO2. In the chambers, the values determined for the δ18O of soil respired CO2 approached the value of CO2 in equilibrium with surficial soil water, and the results were significantly δ18O enriched relative to the mini-tower results and the δ18O of soil CO2 efflux determined from soil CO2. There were close agreements between the three methods for the determination of the δ13C of soil efflux CO2. Results suggest that the mini-towers can be effectively used in the field for determining the δ18O and the δ13C of soil-respired CO2.

An intercomparison was made between eddy covariance flux measurements of ammonia by a quantum cascade laser absorption spectrometer (QCLAS) and a lead-salt tunable diode laser absorption spectrometer (TDLAS). The measurements took place in September 2004 and again in April 2005 over a managed grassland site in Southern Scotland, U.K. These were also compared with a flux estimate derived from an "Ammonia Measurement by ANnular Denuder with online Analysis" (AMANDA), using the aerodynamic gradient method (AGM). The concentration and flux measurements from the QCLAS correlated well with those of the TDLAS and the AGM systems when emissions were high, following slurry application to the field. Both the QCLAS and TDLAS, however, underestimated the flux when compared with the AMANDA system, by 64%. A flux loss of 41% due to chemical reaction of ammonia in the QCLAS (and 37% in the TDLAS) sample tube walls was identified and characterized using laboratory tests but did not fully accountforthis difference. Recognizing these uncertainties, the agreement between the systems was nevertheless very close (R2 = 0.95 between the QCLAS and the TDLAS; R2 = 0.84 between the QCLAS and the AMANDA) demonstrating the suitability of the laser absorption methods for quantifying the temporal dynamics of ammonia fluxes.

Introduction to a <i>Virtual Special Issue</i>: probing the carbon cycle with ¹³C