Off-axis Integrated Cavity Output Spectrometer Research Articles

The influence of dissolved organic matter on the marine production of carbonyl sulfide (OCS) and carbon disulfide (CS<sub>2</sub>) in the Peruvian upwelling

Abstract. Oceanic emissions of the climate-relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2) are a major source to their atmospheric budget. Their current and future emission estimates are still uncertain due to incomplete process understanding and therefore inexact quantification across different biogeochemical regimes. Here we present the first concurrent measurements of both gases together with related fractions of the dissolved organic matter (DOM) pool, i.e., solid-phase extractable dissolved organic sulfur (DOSSPE, n=24, 0.16±0.04 µmol L−1), chromophoric (CDOM, n=76, 0.152±0.03), and fluorescent dissolved organic matter (FDOM, n=35), from the Peruvian upwelling region (Guayaquil, Ecuador to Antofagasta, Chile, October 2015). OCS was measured continuously with an equilibrator connected to an off-axis integrated cavity output spectrometer at the surface (29.8±19.8 pmol L−1) and at four profiles ranging down to 136 m. CS2 was measured at the surface (n=143, 17.8±9.0 pmol L−1) and below, ranging down to 1000 m (24 profiles). These observations were used to estimate in situ production rates and identify their drivers. We find different limiting factors of marine photoproduction: while OCS production is limited by the humic-like DOM fraction that can act as a photosensitizer, high CS2 production coincides with high DOSSPE concentration. Quantifying OCS photoproduction using a specific humic-like FDOM component as proxy, together with an updated parameterization for dark production, improves agreement with observations in a 1-D biogeochemical model. Our results will help to better predict oceanic concentrations and emissions of both gases on regional and, potentially, global scales.

STABLE ISOTOPE (δ13C, δ18O) ANALYSIS OF SULFIDE-BEARING CARBONATE SAMPLES USING LASER ABSORPTION SPECTROMETRY

Hydrothermally altered country rocks surrounding hydrothermal ore deposits are commonly characterized by altered δ 18 O and δ 13 C values relative to distal, unaltered rocks. Stable isotopes have been recognized as a powerful tool to complement traditional geochemical and geophysical approaches during mineral exploration, particularly in carbonate replacement and Carlin-type deposits. However, wall-rock alteration and carbonate veining during ore formation is often accompanied by the precipitation of sulfide minerals, complicating stable isotope analysis. The classic phosphoric acid extraction technique for carbonate minerals results in the release of additional H 2 S gas, interfering with isotope ratio mass spectrometry (IRMS), and laser absorption spectrometry (LAS) analysis of CO 2 . Here we present the first results from a novel off-axis integrated cavity output spectrometer (OA-ICOS) instrument, capable of determining the stable isotope composition ( δ 13 C, δ 18 O) of mixed CO 2 -H 2 S gas evolved from carbonate-sulfide mixtures. Instrument calibration was performed by analyzing in-house and commercially available CaCO 3 stable isotope reference materials. Analyses of mixed CO 2 -H 2 S tank gas and sulfide-spiked stable isotope reference materials containing up to 40 wt % chalcopyrite and sphalerite demonstrate that the method outlined here is capable of effectively analyzing previously problematic high sulfide samples. The analytical capabilities, together with the robust nature of the OA-ICOS instrument, may be of direct practical use for mineral exploration in carbonate-hosted hydrothermal systems including ore deposits.

Real Time Measurement of Concentration and δ13C-CH4 in Water

A new, high temporal and spatial resolution, in-situ method for the fast and precise determination of methane (CH4) concentration and its δ13C isotope value (δ13C-CH4) in water was developed. Methane is extracted from water by the application of a vacuum to a membrane gas/liquid exchange module and analysed by a portable cavity ring-down spectroscopy (CRDS) analyser (Picarro® G2201-i). The system was calibrated for concentration and δ13C of CH4 using synthetic water standards. Reference samples were analysed with gas chromatography (GC) and mass spectroscopy (GC-C-IRMS) via the headspace method. All results show good correlations for CH4 concentration (R2 = 0.994) and a measuring accuracy of 0.002ppm (CH4 concentration) and 0.6‰ (δ13C-CH4). Calculated response times τ were averaged, resulting in 13.5 s. This allows much faster analyses compared to previously published methods. This method was successfully tested in a field campaign at Lake Stechlin (Germany), which has a pronounced CH4 peak at the thermocline in summer. Hypolimnic CH4 concentrations up to 0.6μmol/l indicate microbial methanogenesis in the well-oxygenated upper 10 m of the water column. Simultaneous measurements by the CRDS-membrane system (M-CRDS), a membrane combined with off-axis integrated cavity output spectrometer system (M-ICOS) and gas chromatography (GC) show similar results. 24-hour measurements were performed at the depth of maximum CH4 concentration and indicate short-term variations of 0.2μmol/l (CH4 concentration) and 7‰ (δ13C-CH4) within 24hours. The M-CRDS provides a high temporal and spatial data resolution for accurate detection, mapping and quantification of CH4 distribution in aquatic systems.

Continuous measurements of greenhouse gases and atmospheric oxygen at the Namib Desert Atmospheric Observatory

Abstract. A new coastal background site has been established for observations of greenhouse gases (GHGs) in the central Namib Desert at Gobabeb, Namibia. The location of the site was chosen to provide observations for a data-poor region in the global sampling network for GHGs. Semi-automated continuous measurements of carbon dioxide, methane, nitrous oxide, carbon monoxide, atmospheric oxygen, and basic meteorology are made at a height of 21 m a.g.l., 50 km from the coast at the northern border of the Namib Sand Sea. Atmospheric oxygen is measured with a differential fuel cell analyzer (DFCA). Carbon dioxide and methane are measured with an early-model cavity ring-down spectrometer (CRDS); nitrous oxide and carbon monoxide are measured with an off-axis integrated cavity output spectrometer (OA-ICOS). Instrument-specific water corrections are employed for both the CRDS and OA-ICOS instruments in lieu of drying. The performance and measurement uncertainties are discussed in detail. As the station is located in a remote desert environment, there are some particular challenges, namely fine dust, high diurnal temperature variability, and minimal infrastructure. The gas handling system and calibration scheme were tailored to best fit the conditions of the site. The CRDS and DFCA provide data of acceptable quality when base requirements for operation are met, specifically adequate temperature control in the laboratory and regular supply of electricity. In the case of the OA-ICOS instrument, performance is significantly improved through the implementation of a drift correction through frequent measurements of a reference cylinder.

In situ measurement of dissolved methane and carbon dioxide in freshwater ecosystems by off-axis integrated cavity output spectroscopy.

A novel low-cost method for the combined, real-time, and in situ determination of dissolved methane and carbon dioxide concentrations in freshwater ecosystems was designed and developed. This method is based on the continuous sampling of water from a freshwater ecosystem to a gas/liquid exchange membrane. Dissolved gas is transferred through the membrane to a continuous flow of high purity nitrogen, which is then measured by an off-axis integrated cavity output spectrometer (OA-ICOS). This method, called M-ICOS, was carefully tested in a laboratory and was subsequently applied to four lakes in Mexico and Alaska with contrasting climates, ecologies, and morphologies. The M-ICOS method allowed for the determination of dissolved methane and carbon dioxide concentrations with a frequency of 1 Hz and with a method detection limit of 2.76 × 10(-10) mol L(-1) for methane and 1.5 × 10(-7) mol L(-1) for carbon dioxide. These detection limits are below saturated concentrations with respect to the atmosphere and significantly lower than the minimum concentrations previously reported in lakes. The method is easily operable by a single person from a small boat, and the small size of the suction probe allows the determination of dissolved gases with a minimized impact on shallow freshwater ecosystems.

Methane fluxes measured by eddy covariance and static chamber techniques at a temperate forest in central Ontario, Canada

Abstract. Methane flux measurements were carried out at a temperate forest (Haliburton Forest and Wildlife Reserve) in central Ontario (45°17´11´´ N, 78°32´19´´ W) from June to October 2011. Continuous measurements were made by an off-axis integrated cavity output spectrometer that measures methane (CH4) at 10 Hz sampling rates. Fluxes were calculated from the gas measurements in conjunction with wind data collected by a 3-D sonic anemometer using the eddy covariance (EC) method. Observed methane fluxes showed net uptake of CH4 over the measurement period with an average uptake flux (±standard deviation of the mean) of −2.7 ± 0.13 nmol m−2 s−1. Methane fluxes showed a seasonal progression with average rates of uptake increasing from June through September and remaining high in October. This pattern was consistent with a decreasing trend in soil moisture content at the monthly timescale. On the diurnal timescale, there was evidence of increased uptake during the day, when the mid-canopy wind speed was at a maximum. These patterns suggest that substrate supply of CH4 to methanotrophs, and in certain cases hypoxic soil conditions supporting methanogenesis in low-slope areas, drives the observed variability in fluxes. A network of soil static chambers used at the tower site showed reasonable agreement with the seasonal trend and overall magnitude of the eddy covariance flux measurements. This suggests that soil-level microbial processes, and not abiological leaf-level CH4 production, drive overall CH4 dynamics in temperate forest ecosystems such as Haliburton Forest.

Field intercomparison of two optical analyzers for CH<sub>4</sub> eddy covariance flux measurements

Abstract. Fast response optical analyzers based on laser absorption spectroscopy are the preferred tools to measure field-scale mixing ratios and fluxes of a range of trace gases. Several state-of-the-art instruments have become commercially available and are gaining in popularity. This paper aims for a critical field evaluation and intercomparison of two compact, cryogen-free and fast response instruments: a quantum cascade laser based absorption spectrometer from Aerodyne Research, Inc., and an off-axis integrated cavity output spectrometer from Los Gatos Research, Inc. In this paper, both analyzers are characterized with respect to precision, accuracy, response time and also their sensitivity to water vapour. The instruments were tested in a field campaign to assess their behaviour under various meteorological conditions. The instrument's suitability for eddy covariance flux measurements was evaluated by applying an artificial flux of CH4 generated above a managed grassland with otherwise very low methane exchange. This allowed an independent verification of the flux measurements accuracy, including the overall eddy covariance setup and data treatment. The retrieved fluxes were in good agreement with the known artificial emission flux, which is more than satisfactory, given that the analyzers were attached to separate sonic anemometers placed on individual eddy towers with different data acquisition systems but similar data treatment that are specific to the best practice used by the involved research teams.

Simultaneous 13C/12C and 18O/16O isotope ratio measurements on CO2 based on off-axis integrated cavity output spectroscopy

A prototype off-axis integrated cavity output spectrometer (OA-ICOS) utilizing two identical cavities together with a near-infrared (1.63 μm) external cavity tunable diode laser is described. The two-cavity design—one for a reference gas and one for a sample gas—takes advantage of classical double-beam infrared spectrometer characteristics in reducing uncertainties due to laser scan or power instabilities and major temperature variations by a factor of three or better compared with a single-cavity scheme. This is the first OA-ICOS instrument designed to determine 13C/12C and 18O/16O ratios from CO2 rotation/vibration fine structure in three different combination bands. Preliminary results indicate that at 0.8 Hz a precision of 3.3 and 2.8 \\permil\\ is obtained for δ13C and δ18O, respectively, over a period of 10 h and a pure CO2 gas sample at 26 hPa. By averaging 100 spectra over a subset of the data, we achieved a precision of 1.6 and 0.8 \\permil\\ for δ13C and δ18O, respectively.