scholarly journals Calibration and Field Testing of Cavity Ring-Down Laser Spectrometers Measuring CH<sub>4</sub>, CO<sub>2</sub>, and δ<sup>13</sup>CH<sub>4</sub> Deployed on Towers in the Marcellus Shale Region

2017 ◽  
Author(s):  
Natasha L. Miles ◽  
Douglas K. Martins ◽  
Scott J. Richardson ◽  
Christopher W. Rella ◽  
Caleb Arata ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Natural Gas ◽  
Mole Fraction ◽  
Isotopic Ratio ◽  
Marcellus Shale ◽  
Isotopic Ratios ◽  
Study Region ◽  
Field Calibration ◽  
Cavity Ring Down

Abstract. Four in-situ cavity ring-down spectrometers (G2132-i, Picarro, Inc.) measuring methane dry mole fraction (CH4), carbon dioxide dry mole fraction (CO2) and the isotopic ratio of methane (δ13CH4) were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. The calibration of the continuous isotopic methane analyzers used in this study required both a linear calibration and a mole fraction correction, and a correction for cross-interference from ethane. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications, and characterize their performance in the field for the period January–December 2016. Prior to deployment, each analyzer was calibrated using high methane mole fraction air bottles with various isotopic ratios, from biogenic to thermogenic source values, diluted in zero air. Furthermore, at each tower location, three field calibration tanks were employed, from ambient to high mole fractions, with various isotopic ratios. By testing multiple calibration schemes, we determined an optimized field calibration method. A method to correct for cross interference from ethane is also described. Using an independent field tank for evaluation, the standard deviation of 4-hour means of the isotopic ratio of methane difference from the known value was found to be 0.26 ‰ δ13CH4. Following improvements in the field calibration tank sampling scheme, the standard deviation of 4-hour means was 0.11 ‰, well within the target compatibility of 0.2 ‰. Round robin style testing using tanks with near ambient isotopic ratios indicated mean errors of −0.14 to 0.03 ‰ for each of the analyzers. Flask to in-situ comparisons showed mean differences over the year of 0.02 and 0.08 ‰, for the East and South towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median enhancements of isotopic ratio measured at three of the towers, compared to the background tower, were −0.15 to 0.12 ‰ with standard deviations of the 10-min isotopic ratio enhancements of 0.8 ‰. In terms of source attribution, analyzer compatibility of 0.2 ‰ δ13CH4 affords the ability to distinguish a 50 ppb CH4 peak from a biogenic source from one originating from a thermogenic source. Using a Keeling plot approach for the non-afternoon data at a tower in the center of the study region, we determined the source isotopic signature to be −31.2 ‰, consistent with a deep-layer Marcellus natural gas source.

scholarly journals Calibration and field testing of cavity ring-down laser spectrometers measuring CH<sub>4</sub>, CO<sub>2</sub>, and <i>δ</i><sup>13</sup>CH<sub>4</sub> deployed on towers in the Marcellus Shale region

2018 ◽  
Vol 11 (3) ◽  
pp. 1273-1295 ◽  
Author(s):  
Natasha L. Miles ◽  
Douglas K. Martins ◽  
Scott J. Richardson ◽  
Christopher W. Rella ◽  
Caleb Arata ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Natural Gas ◽  
Mole Fraction ◽  
Isotopic Ratio ◽  
Marcellus Shale ◽  
Isotopic Ratios ◽  
Study Region ◽  
Wide Range ◽  
Cavity Ring Down

Abstract. Four in situ cavity ring-down spectrometers (G2132-i, Picarro, Inc.) measuring methane dry mole fraction (CH4), carbon dioxide dry mole fraction (CO2), and the isotopic ratio of methane (δ13CH4) were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications and characterize their performance in the field for the period January–December 2016. Prior to deployment, each analyzer was tested using bottles with various isotopic ratios, from biogenic to thermogenic source values, which were diluted to varying degrees in zero air, and an initial calibration was performed. Furthermore, at each tower location, three field tanks were employed, from ambient to high mole fractions, with various isotopic ratios. Two of these tanks were used to adjust the calibration of the analyzers on a daily basis. We also corrected for the cross-interference from ethane on the isotopic ratio of methane. Using an independent field tank for evaluation, the standard deviation of 4 h means of the isotopic ratio of methane difference from the known value was found to be 0.26 ‰ δ13CH4. Following improvements in the field tank testing scheme, the standard deviation of 4 h means was 0.11 ‰, well within the target compatibility of 0.2 ‰. Round-robin style testing using tanks with near-ambient isotopic ratios indicated mean errors of −0.14 to 0.03 ‰ for each of the analyzers. Flask to in situ comparisons showed mean differences over the year of 0.02 and 0.08 ‰, for the east and south towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median differences of the isotopic ratio measured at three of the towers, compared to the background tower, were &amp;minus0.15 to 0.12 ‰ with standard deviations of the 10 min isotopic ratio differences of 0.8 ‰. In terms of source attribution, analyzer compatibility of 0.2 ‰ δ13CH4 affords the ability to distinguish a 50 ppb CH4 peak from a biogenic source (at −60 ‰, for example) from one originating from a thermogenic source (−35 ‰), with the exact value dependent upon the source isotopic ratios. Using a Keeling plot approach for the non-afternoon data at a tower in the center of the study region, we determined the source isotopic signature to be −31.2 ± 1.9 ‰, within the wide range of values consistent with a deep-layer Marcellus natural gas source.

scholarly journals Using ship-borne observations of methane isotopic ratio in the Arctic Ocean to understand methane sources in the Arctic

2019 ◽  
Author(s):  
Antoine Berchet ◽  
Isabelle Pison ◽  
Patrick M. Crill ◽  
Brett Thornton ◽  
Philippe Bousquet ◽  
...  
Keyword(s):  
Arctic Ocean ◽  
Large Scale ◽  
Transport Model ◽  
Isotopic Ratio ◽  
The Arctic ◽  
Isotopic Ratios ◽  
Air Masses ◽  
Remote Areas ◽  
The Arctic Ocean

Abstract. Due to the large variety and heterogeneity of sources in remote areas hard to document, the Arctic regional methane budget remain very uncertain. In situ campaigns provide valuable data sets to reduce these uncertainties. Here we analyse data from the SWERUS-C3 campaign, on-board the icebreaker Oden, that took place during summer 2014 in the Arctic Ocean along the Northern Siberian and Alaskan shores. Total concentrations of methane, as well as isotopic ratios were measured continuously during this campaign for 35 days in July and August 2014. Using a chemistry-transport model, we link observed concentrations and isotopic ratios to regional emissions and hemispheric transport structures. A simple inversion system helped constraining source signatures from wetlands in Siberia and Alaska and oceanic sources, as well as the isotopic composition of lower stratosphere air masses. The variation in the signature of low stratosphere air masses, due to strongly fractionating chemical reactions in the stratosphere, was suggested to explain a large share of the observed variability in isotopic ratios. These points at required efforts to better simulate large scale transport and chemistry patterns to use isotopic data in remote areas. It is found that constant and homogeneous source signatures for each type of emission in the region (mostly wetlands and oil and gas industry) is not compatible with the strong synoptic isotopic signal observed in the Arctic. A regional gradient in source signatures is highlighted between Siberian and Alaskan wetlands, the later ones having a lighter signatures than the first ones. Arctic continental shelf sources are suggested to be a mixture of methane from a dominant thermogenic origin and a secondary biogenic one, consistent with previous in-situ isotopic analysis of seepage along the Siberian shores.

An Evaluation of Calibration Techniques for In Situ Carbon Dioxide Measurements Using a Programmable Portable Trace-Gas Measuring System

2009 ◽  
Vol 26 (2) ◽  
pp. 291-316 ◽  
Author(s):  
Sean P. Burns ◽  
Anthony C. Delany ◽  
Jielun Sun ◽  
Britton B. Stephens ◽  
Steven P. Oncley ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Measurement System ◽  
Co2 Concentration ◽  
Calibration Method ◽  
Measuring System ◽  
Trace Gas ◽  
Field Calibration ◽  
Gas Measurement ◽  
Calibration Techniques

Abstract The construction and deployment of a portable trace-gas measurement system (TGaMS) is described. The air-collection system (dubbed HYDRA) collects air samples from 18 different locations and was connected to either one or two LI-COR LI-7000 gas analyzers to measure CO2. An in situ “field calibration” method, that uses four calibration gases with an uncertainty on the order of ±0.1 μmol mol−1 relative to the WMO CO2 mole fraction scale, revealed CO2 output from the LI-7000 had a slightly nonlinear relationship relative to the CO2 concentration of the calibration gases. The sensitivity of the field-calibrated CO2 to different forms of the field-calibration equation is investigated. To evaluate TGaMS performance, CO2 from collocated inlets, portable gas cylinders, and nearby independent CO2 instruments are compared. Results are as follows: 1) CO2 measurements from HYDRA multiple inlets are feasible with a reproducibility of ±0.4 μmol mol−1 (based on the standard deviation of the CO2 difference between collocated inlets when HYDRA was operating with two LI-7000s); 2) CO2 differences among the various field-calibration equations were on the order of ±0.3 μmol mol−1; and 3) comparison of midday hourly CO2 measurements at 30 m AGL between TGaMS and an independent high-accuracy CO2 measurement system (within 300 m of TGaMS) had a median difference and standard deviation of 0.04 ± 0.81 μmol mol−1 over two months.

Improved in situ Li isotopic ratio analysis of silicates by optimizing signal intensity, isotopic ratio stability and intensity matching using ns-LA-MC-ICP-MS

2017 ◽  
Vol 32 (4) ◽  
pp. 834-842 ◽  
Author(s):  
Jie Lin ◽  
Yongsheng Liu ◽  
Xirun Tong ◽  
Lvyun Zhu ◽  
Wen Zhang ◽  
...  
Keyword(s):  
Signal Intensity ◽  
Isotopic Ratio ◽  
Silicate Glasses ◽  
Isotopic Ratios ◽  
Ratio Analysis ◽  
Icp Ms

How to get accurate and precise in situ Li isotopic ratios of silicate glasses on a ns-LA-MC-ICP-MS (Neptune Plus).

scholarly journals Air-Sea Interactions over Eddies in the Brazil-Malvinas Confluence

2021 ◽  
Vol 13 (7) ◽  
pp. 1335
Author(s):  
Ronald Souza ◽  
Luciano Pezzi ◽  
Sebastiaan Swart ◽  
Fabrício Oliveira ◽  
Marcelo Santini
Keyword(s):  
Latent Heat ◽  
Large Scale ◽  
Surface Wind ◽  
Heat Fluxes ◽  
Lower Atmosphere ◽  
Meteorological Variables ◽  
Global Ocean ◽  
Study Region ◽  
Cold Core

The Brazil–Malvinas Confluence (BMC) is one of the most dynamical regions of the global ocean. Its variability is dominated by the mesoscale, mainly expressed by the presence of meanders and eddies, which are understood to be local regulators of air-sea interaction processes. The objective of this work is to study the local modulation of air-sea interaction variables by the presence of either a warm (ED1) and a cold core (ED2) eddy, present in the BMC, during September to November 2013. The translation and lifespans of both eddies were determined using satellite-derived sea level anomaly (SLA) data. Time series of satellite-derived surface wind data, as well as these and other meteorological variables, retrieved from ERA5 reanalysis at the eddies’ successive positions in time, allowed us to investigate the temporal modulation of the lower atmosphere by the eddies’ presence along their translation and lifespan. The reanalysis data indicate a mean increase of 78% in sensible and 55% in latent heat fluxes along the warm eddy trajectory in comparison to the surrounding ocean of the study region. Over the cold core eddy, on the other hand, we noticed a mean reduction of 49% and 25% in sensible and latent heat fluxes, respectively, compared to the adjacent ocean. Additionally, a field campaign observed both eddies and the lower atmosphere from ship-borne observations before, during and after crossing both eddies in the study region during October 2013. The presence of the eddies was imprinted on several surface meteorological variables depending on the sea surface temperature (SST) in the eddy cores. In situ oceanographic and meteorological data, together with high frequency micrometeorological data, were also used here to demonstrate that the local, rather than the large scale forcing of the eddies on the atmosphere above, is, as expected, the principal driver of air-sea interaction when transient atmospheric systems are stable (not actively varying) in the study region. We also make use of the in situ data to show the differences (biases) between bulk heat flux estimates (used on atmospheric reanalysis products) and eddy covariance measurements (taken as “sea truth”) of both sensible and latent heat fluxes. The findings demonstrate the importance of short-term changes (minutes to hours) in both the atmosphere and the ocean in contributing to these biases. We conclude by emphasizing the importance of the mesoscale oceanographic structures in the BMC on impacting local air-sea heat fluxes and the marine atmospheric boundary layer stability, especially under large scale, high-pressure atmospheric conditions.

Composition of Mixtures of Natural Gas Components Determined by Raman Spectrometry

1980 ◽  
Vol 34 (4) ◽  
pp. 411-414 ◽  
Author(s):  
Dwain E. Diller ◽  
Ren Fang Chang
Keyword(s):  
Natural Gas ◽  
Mole Fraction ◽  
Gas Mixtures ◽  
Spectrometric Method ◽  
Gas Mixture ◽  
Raman Intensity ◽  
Raman Spectrometry ◽  
Intensity Measurements ◽  
Hydrocarbon Gas ◽  
Related Line

The feasibility of using Raman spectrometry for determining the composition of mixtures of natural gas components was examined. Raman intensity measurements were carried out on eight, gravimetrically prepared, binary gas mixtures containing methane, nitrogen, and isobutane at ambient temperature and at pressures to 0.8 MPa. The repeatability of the molar intensity ratio, ( I2/ y2)/( I1/ y1), where y1 is the concentration of component 1 in the mixture, and I1 is the intensity of the related line in the mixture spectrum, was examined. The compositions of two gravimetrically prepared methane-nitrogen-isobutane gas mixtures were determined spectrometrically with an estimated precision of about 0.001 in the mole fraction. Typical differences from the gravimetric concentrations were less than 0.002 in the mole fraction. The Raman spectrum of a gravimetrically prepared, eight component, hydrocarbon gas mixture was obtained to show that the Raman spectrometric method has potential for being applicable to natural gas type mixtures.

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