scholarly journals Versatile soil gas concentration and isotope monitoring: optimization and integration of novel soil gas probes with online trace gas detection

2022 ◽  
Vol 19 (1) ◽  
pp. 165-185
Author(s):  
Juliana Gil-Loaiza ◽  
Joseph R. Roscioli ◽  
Joanne H. Shorter ◽  
Till H. M. Volkmann ◽  
Wei-Ren Ng ◽  
...  

Abstract. Gas concentrations and isotopic signatures can unveil microbial metabolisms and their responses to environmental changes in soil. Currently, few methods measure in situ soil trace gases such as the products of nitrogen and carbon cycling or volatile organic compounds (VOCs) that constrain microbial biochemical processes like nitrification, methanogenesis, respiration, and microbial communication. Versatile trace gas sampling systems that integrate soil probes with sensitive trace gas analyzers could fill this gap with in situ soil gas measurements that resolve spatial (centimeters) and temporal (minutes) patterns. We developed a system that integrates new porous and hydrophobic sintered polytetrafluoroethylene (sPTFE) diffusive soil gas probes that non-disruptively collect soil gas samples with a transfer system to direct gas from multiple probes to one or more central gas analyzer(s) such as laser and mass spectrometers. Here, we demonstrate the feasibility and versatility of this automated multiprobe system for soil gas measurements of isotopic ratios of nitrous oxide (δ18O, δ15N, and the 15N site preference of N2O), methane, carbon dioxide (δ13C), and VOCs. First, we used an inert silica matrix to challenge probe measurements under controlled gas conditions. By changing and controlling system flow parameters, including the probe flow rate, we optimized recovery of representative soil gas samples while reducing sampling artifacts on subsurface concentrations. Second, we used this system to provide a real-time window into the impact of environmental manipulation of irrigation and soil redox conditions on in situ N2O and VOC concentrations. Moreover, to reveal the dynamics in the stable isotope ratios of N2O (i.e., 14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O), we developed a new high-precision laser spectrometer with a reduced sample volume demand. Our integrated system – a tunable infrared laser direct absorption spectrometry (TILDAS) in parallel with Vocus proton transfer reaction mass spectrometry (PTR-MS), in line with sPTFE soil gas probes – successfully quantified isotopic signatures for N2O, CO2, and VOCs in real time as responses to changes in the dry–wetting cycle and redox conditions. Broadening the collection of trace gases that can be monitored in the subsurface is critical for monitoring biogeochemical cycles, ecosystem health, and management practices at scales relevant to the soil system.

2020 ◽  
Author(s):  
Juliana Gil-Loaiza ◽  
Joseph R. Roscioli ◽  
Joanne H. Shorter ◽  
Till H. M. Volkmann ◽  
Wei-Ren Ng ◽  
...  

Abstract. Gas concentrations and isotopic signatures can unveil microbial metabolisms and their responses to environmental changes in soil. Currently, few methods measure soil trace gases such as the products of nitrogen and carbon cycling, or volatile organic compounds (VOCs), that could constrain microbial biochemical processes like nitrification, methanogenesis, respiration, and microbial communication. Versatile trace gas sampling systems that integrate soil probes with sensitive trace gas analyzers could fill this gap with measurements resolving spatial (centimeter scale) and temporal (minutes) variations in concentrations and isotopic signatures of in situ soil gases. We developed a system that integrates new 15 cm long sintered PTFE diffusive soil gas probes with various infrared spectrometers and a VOC mass spectrometer. The system is based on porous and hydrophobic soil probes that non-disruptively collect and transport gas from multiple probes to one or more central gas analyzers. Here, we demonstrate the feasibility and versatility of an automated multi-probe system for soil gas measurements of isotopic ratios of nitrous oxide (δ18O, δ15N, and the 15N site-preference of N2O), methane, carbon dioxide (δ13C), and VOCs. First, we used an inert silica matrix to challenge probe measurements under controlled gas conditions. By changing and controlling system flow parameters, including probe flow rate, we optimized recovery of representative soil gas samples while reducing sampling artifacts on subsurface concentrations. Second, we forced environmental manipulations in soil-filled columns to demonstrate real-time detection of subsurface gas dynamics in response to irrigation and soil redox conditions. In addition, we developed a new laser spectrometer to recover isotope ratios for 14N14N16O (δ446), 14N15N16O (δ456), 15N14N16O (δ546), and 14N14N18O (δ448) with high precision and low concentration dependence. We captured temporal subsurface gas pulses in CO2, N2O, and VOCs. This demonstrated the potential for diffusive-based probes to couple to trace gas sensors for soil health and fertility studies, and to inform high-throughput meta-omics, leading to the development of a suite of powerful new tools for soil analysis.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Joseph R. Roscioli ◽  
Laura K. Meredith ◽  
Joanne H. Shorter ◽  
Juliana Gil-Loaiza ◽  
Till H. M. Volkmann

AbstractSoil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N2O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N2O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.


2020 ◽  
Vol 61 (6) ◽  
Author(s):  
C E Schrank ◽  
K Gioseffi ◽  
T Blach ◽  
O Gaede ◽  
A Hawley ◽  
...  

Abstract We present a review of a unique non-destructive method for the real-time monitoring of phase transformations and nano-pore evolution in dehydrating rocks: transmission small- and wide-angle synchrotron X-ray scattering (SAXS/WAXS). It is shown how SAXS/WAXS can be applied to investigating rock samples dehydrated in a purpose-built loading cell that allows the coeval application of high temperature, axial confinement, and fluid pressure or flow to the specimen. Because synchrotron sources deliver extremely bright monochromatic X-rays across a wide energy spectrum, they enable the in situ examination of confined rock samples with thicknesses of ≤ 1 mm at a time resolution of order seconds. Hence, fast kinetics with reaction completion times of about hundreds of seconds can be tracked. With beam sizes of order tens to hundreds of micrometres, it is possible to monitor multiple interrogation points in a sample with a lateral extent of a few centimetres, thus resolving potential lateral spatial effects during dehydration and enlarging sample statistics significantly. Therefore, the SAXS/WAXS method offers the opportunity to acquire data on a striking range of length scales: for rock samples with thicknesses of ≤ 10-3 m and widths of 10-2 m, a lateral interrogation-point spacing of ≥ 10-5 m can be achieved. Within each irradiated interrogation-point volume, information concerning pores with sizes between 10-9 and 10-7 m and the crystal lattice on the scale of 10-10 m is acquired in real time. This article presents a summary of the physical principles underpinning transmission X-ray scattering with the aim of providing a guide for the design and interpretation of time-resolved SAXS/WAXS experiments. It is elucidated (1) when and how SAXS data can be used to analyse total porosity, internal surface area, and pore-size distributions in rocks on length scales from ∼1 to 300 nm; (2) how WAXS can be employed to track lattice transformations in situ; and (3) which limitations and complicating factors should be considered during experimental design, data analysis, and interpretation. To illustrate the key capabilities of the SAXS/WAXS method, we present a series of dehydration experiments on a well-studied natural gypsum rock: Volterra alabaster. Our results demonstrate that SAXS/WAXS is excellently suited for the in situ tracking of dehydration kinetics and the associated evolution of nano-pores. The phase transformation from gypsum to bassanite is correlated directly with nano-void growth on length scales between 1 and 11 nm for the first time. A comparison of the SAXS/WAXS kinetic results with literature data emphasises the need for future dehydration experiments on rock specimens because of the impact of rock fabric and the generally heterogeneous and transient nature of dehydration reactions in nature. It is anticipated that the SAXS/WAXS method combined with in situ loading cells will constitute an invaluable tool in the ongoing quest for understanding dehydration and other mineral replacement reactions in rocks quantitatively.


2021 ◽  
Author(s):  
Pieternel F. Levelt ◽  
Deborah C. Stein Zweers ◽  
Ilse Aben ◽  
Maite Bauwens ◽  
Tobias Borsdorff ◽  
...  

Abstract. The aim of this paper is two-fold: to provide guidance on how to best interpret TROPOMI trace gas retrievals and to highlight how TROPOMI trace gas data can be used to understand event-based impacts on air quality from regional to city-scales around the globe. For this study, we present the observed changes in the atmospheric column amounts of five trace gases (NO2, SO2, CO, HCHO and CHOCHO) detected by the Sentinel-5P TROPOMI instrument, driven by reductions of anthropogenic emissions due to COVID-19 lockdown measures in 2020. We report clear COVID-19-related decreases in NO2 concentrations on all continents. For megacities, reductions in column amounts of tropospheric NO2 range between 14 % and 63 %. For China and India supported by NO2 observations, where the primary source of anthropogenic SO2 is coal-fired power generation, we were able to detect sector-specific emission changes using the SO2 data. For HCHO and CHOCHO, we consistently observe anthropogenic changes in two-week averaged column amounts over China and India during the early phases of the lockdown periods. That these variations over such a short time scale are detectable from space, is due to the high resolution and improved sensitivity of the TROPOMI instrument. For CO, we observe a small reduction over China which is in concert with the other trace gas reductions observed during lockdown, however large, interannual differences prevent firm conclusions from being drawn. The joint analysis of COVID-19 lockdown-driven reductions in satellite observed trace gas column amounts, using the latest operational and scientific retrieval techniques for five species concomitantly is unprecedented. However, the meteorologically and seasonally driven variability of the five trace gases does not allow for drawing fully quantitative conclusions on the reduction of anthropogenic emissions based on TROPOMI observations alone. We anticipate that in future, the combined use of inverse modelling techniques with the high spatial resolution data from S5P/TROPOMI for all observed trace gases presented here, will yield a significantly improved sector-specific, space-based analysis of the impact of COVID-19 lockdown measures as compared to other existing satellite observations. Such analyses will further enhance the scientific impact and societal relevance of the TROPOMI mission.


2021 ◽  
Author(s):  
Zoe Davis ◽  
Debora Griffin ◽  
Yue Jia ◽  
Susann Tegtmeier ◽  
Mallory Loria ◽  
...  

<p>A recent method uses satellite measurements to estimate lifetimes and emissions of trace-gases from point sources (Fioletov et al., 2015). Emissions are retrieved by fitting measured vertical column densities (VCDs) of trace-gases to a three-dimensional function of the wind speed and spatial coordinates. In this study, a plume model generated “synthetic” satellite observations of prescribed emissions to examine the accuracy of the retrieved emissions. The Lagrangian transport and dispersion model FLEXPART (v10.0) modelled the plume from a point source over a multi-day simulation period at a resolution much higher than current satellite observations. The study aims to determine how various assumptions in the retrieval method and local meteorological conditions affect the accuracy and precision of emissions. These assumptions include that the use of a vertical mean of the wind profile is representative of the transport of the plume’s vertical column. In the retrieval method, the VCDs’ pixel locations are rotated around the source based on wind direction so that all plumes have a common wind direction. Retrievals using a vertical mean wind for rotation will be compared to retrievals using VCDs determined by rotating each altitude of the vertical profile of trace-gas using the respective wind-direction. The impact of local meteorological factors on the two approaches will be presented, including atmospheric mixing, vertical wind shear, and boundary layer height. The study aims to suggest which altitude(s) of the vertical profile of winds results in the most accurate retrievals given the local meteorological conditions. The study will also examine the impact on retrieval accuracy due to satellite resolution, trace-gas lifetime, plume source altitude, number of overpasses, and random and systematic errors. Sensitivity studies repeated using a second, “line-density”, retrieval method will also be presented (Adams et al., 2019; Goldberg et al., 2019).</p>


Ocean Science ◽  
2017 ◽  
Vol 13 (3) ◽  
pp. 379-410 ◽  
Author(s):  
Burkard Baschek ◽  
Friedhelm Schroeder ◽  
Holger Brix ◽  
Rolf Riethmüller ◽  
Thomas H. Badewien ◽  
...  

Abstract. The Coastal Observing System for Northern and Arctic Seas (COSYNA) was established in order to better understand the complex interdisciplinary processes of northern seas and the Arctic coasts in a changing environment. Particular focus is given to the German Bight in the North Sea as a prime example of a heavily used coastal area, and Svalbard as an example of an Arctic coast that is under strong pressure due to global change.The COSYNA automated observing and modelling system is designed to monitor real-time conditions and provide short-term forecasts, data, and data products to help assess the impact of anthropogenically induced change. Observations are carried out by combining satellite and radar remote sensing with various in situ platforms. Novel sensors, instruments, and algorithms are developed to further improve the understanding of the interdisciplinary interactions between physics, biogeochemistry, and the ecology of coastal seas. New modelling and data assimilation techniques are used to integrate observations and models in a quasi-operational system providing descriptions and forecasts of key hydrographic variables. Data and data products are publicly available free of charge and in real time. They are used by multiple interest groups in science, agencies, politics, industry, and the public.


2020 ◽  
Author(s):  
Marianna Linz ◽  
Benjamin Birner ◽  
Alan Plumb ◽  
Edwin Gerber ◽  
Florian Haenel ◽  
...  

<p>Age of air is an idealized tracer often used as a measure of the stratospheric circulation. We will show how to quantitatively relate age to the diabatic circulation and the adiabatic mixing. As it is an idealized tracer, age cannot be measured itself and must be inferred from other tracers. Typically, the two primary trace gases used are sulfur hexafluoride and carbon dioxide. Other tracers have a compact relationship with age, however, and can also be used to calculate age. We will discuss a range of tracer measurements from both satellites and in situ, including sulfur hexafluoride, carbon dioxide, nitrous oxide, methane, and the ratio of argon to nitrogen. We will compare the age derived from these different species, including different calculation methods and caveats, and compare with modeled ideal age and trace gas concentrations. We conclude by showing the strength of the diabatic circulation and the adiabatic mixing calculated from these trace gas calculations.</p>


2020 ◽  
Author(s):  
Hans-Christoph Lachnitt ◽  
Peter Hoor ◽  
Daniel Kunkel ◽  
Stafan Hofmann ◽  
Martina Bramberger ◽  
...  

<p>The tropopause acts as a transport barrier between the upper troposphere and the lower stratosphere. Non-conservative (i.e. PV changing) processes are required to overcome this barrier. Orographically generated gravity waves (i.e. mountain waves) can potentially lead to cross-isentropic fluxes of trace gases via the generation of turbulence. Thus they may alter the isentropic gradient of these trace species across the tropopause.<br>The specific goal of this study is to identify cross-isentropic mixing processes at the tropopause based on the distribution of trace gases (i.e. tracer-tracer correlations). Based on airborne in-situ trace gas measurements of CO and N<sub>2</sub>O during the DEEPWAVE (Deep Propagating Gravity Wave Experiment) campaign in July 2014 we identified mixing regions above the Southern Alps during periods of gravity wave activity. These in-situ data show that the composition of the air above the Southern Alps change from the upstream to the leeward side of the mountains indicating cross isentropic mixing of trace gases in the region of gravity wave activity.<br>We complement our analysis of the measurement data with high resolution operational analysis data from the ECMWF (European Centre for Medium-Range Weather Forecasts). Furthermore, using potential vorticity and stability parameters.<br>Using 3D wind fields, data form Graphical Turbulence Guidance (GTG) system and in-situ measurements of the vertical wind we identify occurrence of turbulence in the region of mixing events. Using wavelet analysis, we could identify the spatial and temporal scales of local trace gas fluxes. We also give estimates of cross-isentropic flux, i.e. we want to quantify the mixing in terms of exchange.</p>


2004 ◽  
Vol 4 (5) ◽  
pp. 1427-1442 ◽  
Author(s):  
P. Hoor ◽  
C. Gurk ◽  
D. Brunner ◽  
M. I. Hegglin ◽  
H. Wernli ◽  
...  

Abstract. We present airborne in-situ trace gas measurements which were performed on eight campaigns between November 2001 and July 2003 during the SPURT-project (SPURenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region). The measurements on a quasi regular basis allowed an overview of the seasonal variations of the trace gas distribution in the tropopause region over Europe from 35°-75°N to investigate the influence of transport and mixing across the extratropical tropopause on the lowermost stratosphere. From the correlation of CO and O3 irreversible mixing of tropospheric air into the lowermost stratosphere is identified. The CO distribution indicates that transport and subsequent mixing of tropospheric air across the extratropical tropopause predominantly affects a layer, which closely follows the shape of the local tropopause. In addition, the seasonal cycle of CO2 illustrates the strong coupling of that layer to the extratropical troposphere. Both, horizontal gradients of CO on isentropes as well as the CO-O3-distribution in the lowermost stratosphere reveal that the influence of quasi-horizontal transport and subsequent mixing weakens with distance from the local tropopause. The mixing layer extends to about 25 K in potential temperature above the local tropopause exhibiting only a weak seasonality. However, at large distances from the tropopause a significant influence of tropospheric air is still evident. The relation between N2O and CO2 indicates that a significant contribution of air originating from the tropical tropopause contributes to the background air in the extratropical lowermost stratosphere.


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