Standard Gas Mixtures Research Articles

Influence of on-site sampling conditions on the representativeness of the sample for the analysis of trace VOCs in raw renewable gases.

In the context of the energy transition and in order to fully manage the integration of renewable and/or low-carbon gases into the gas mix, these new renewable gases need to be characterized, including volatile organic compounds (VOCs) at trace levels that may have an impact on different stages of the gas chain event at low concentrations. This study focuses on sampling because it is the first step in any method for analyzing trace VOCs and its careful execution is essential to ensure reliable results even if the on-site conditions can be variable, such as the external temperature. The stabilization time, the effect of external temperature, and the impact of using an intermediate sample cylinder prior to transfer to tubes were hence studied in the laboratory using a standard gas mixture representative of renewable gases. The latter was also studied using a real sample. To perform this study, VOCs were sampled in Tenax® TA tubes and then analyzed by thermal desorption hyphenated to comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry. The results showed that 45min were required to stabilize the sampling system and that external temperature had little influence, limited to the heaviest compounds. Finally, the use of a cylinder to temporarily collect gas prior to transfer to tubes led to a loss of compounds, particularly when the cylinder was stored before the transfer.

On novel front-end electronics for the ATLAS BI RPC upgrade at HL-LHC developed in SiGe BiCMOS technology with a high-resolution rad-hard Time-To-Digital converter embedded

The High Luminosity phase of LHC will require a huge improvement on the ATLAS detector in terms of performance, being the entire apparatus operated in much harsher conditions. The BI project is one of the ATLAS Phase-2 approved upgrades, ensuring the demands coming from the physics for the next 20 years. In this framework, a novel dedicated Front-End electronics has been developed, which exploits a BJT-based preamplifier, a fast discriminator and a high resolution (¡ 100 ps) Time-To-Digital converter in SiGe BiCMOS technology, to vastly enhance the detector rate capability. This front-end electronics is integrated for the first time within the detector Faraday cage, largely reducing the effects of spurious noise and allowing a minimum effective charge threshold on the induced signal of 1-2 fC. The integration of the front-end electronics directly within the detector Faraday cage is also permitted by the low power consumption of 15 mW/ch. The RPC coupled with this novel front-end electronics represents a new generation of large area timing detectors, granting a record time resolution of 350 ps on a single gas gap of 1 mm with 1.2 mm electrodes thickness and operated with the ATLAS standard gas mixture. The effect of the extremely low threshold has also an impact on the gas mixture, enabling the usage of eco-friendly gas mixtures which would not be usable elsewise. The latest performance of this newly developed front-end electronics along with the results achieved with RPC detector coupled with it will be shown.

Value assignment and uncertainty evaluation for certified reference gas mixtures

AbstractThe procedures used to assign values to certified reference gas mixtures and to evaluate their associated uncertainties, which are described in ISO 6143, and that were variously improved by Guenther and Possolo (Anal Bioanal Chem 399:489–500, 2011. 10.1007/s00216-010-4379-z), are further enhanced by the following developments: (i) evaluating and propagating uncertainty contributions derived from comparisons with historical reference gas mixtures of similar nominal composition; (ii) recognizing and quantifying mutual inconsistency (dark uncertainty) between primary standard gas mixtures used for calibration; (iii) employing Bayesian procedures for calibration, value assignment, and uncertainty evaluations; and (iv) employing state-of-the-art methods of meta-analysis to combine cylinder-specific measurement results. These developments are illustrated in examples of certification of two gas mixture Standard Reference Materials developed by the National Institute of Standards and Technology (NIST, USA). These examples serve only to demonstrate the methods described in this contribution and do not replace any official measurement results delivered in the certificates of any reference materials developed by NIST.

Method Validation of Gas Chromatography and Stability Study for Analysis of Standard Gas Mixtures of Carbon Dioxide in Nitrogen Matrix

Method Validation of Gas Chromatography and Stability Study for Analysis of Standard Gas Mixtures of Carbon Dioxide in Nitrogen Matrix

Vacuum partial pressure measurement using low-budget dual comb system

Dual-comb spectroscopy is a powerful tool for gas sensing but its expensive cost is limiting its practical application in many fields. In terms of this issue, we present a low-cost and effective dual-comb generation method without complicated feedback lock electronics and nonlinear optics. The proposed dual combs are seeded with the same CW laser, and modulated by electric-optic modulators driven by a pair of pulse trains with slightly different repetition rates of 200 MHz and 200.25 MHz to generate tooth resolved spectrum. A pair of vacuum partial pressure measurements were performed to demonstrate its feasibility and ability. In the experiment, the built dual-comb apparatus is applied to analyze two standard gas mixtures containing carbon monoxide and carbon dioxide respectively. The relative deviations of measurement results against their certified values for carbon monoxide and carbon dioxide are both below 2%. Furthermore, by averaging a set of measurement results at different wavenumbers, the deviation could further be reduced, indicating that the proposed manner is capable of enabling gas partial pressure measurement with good accuracy and low cost.

Ecological transition for the gas mixtures of the MRPC cosmic ray telescopes of the EEE Project

The Extreme Energy Events (EEE) Collaboration is fully involved in an ecological transition. The use of the standard gas mixture, C2H2F4 + SF6, has stopped in favor of an alternative green mixture based on C3H2F4 with the addition of He or CO2.The choise of these new mixtures is motivated by the significant lower Global Warming Potential (GWP) to reduce the emission of gases potentially contributing to the greenhouse effect.The EEE experiment consists of 61 muon telescopes based on Multigap Resistive Plate Chambers (MRPCs), each telescope composed of 3 chambers filled with gas.Several EEE detectors are today completely fluxed with the new ecological mixture. This contribution will report recent results about the telescope performance obtained from studies with the eco-friendly alternative mixture carried out in the last years.

Operation of a low resistivity glass MRPC at high rate using ecological gas

The Multigap Resistive Plate Chamber (MRPC) is a gaseous detector that has low building costs and excellent timing performances. It is usually operated using a mixture of C2F4H2 and SF6, which have very high Global Warming Potential (GWP) values (1430 and 23,900 respectively). The ecological HFO-1234ze (C3F4H2), GWP <7, was investigated if it could be a viable alternative to the standard gas mixture. In this work, we present the performances of an MRPC with 10 gaps of 235μm width, built using 0.5 mm thick plates of low resistive glass. This detector was also operated using the standard gas mixture for comparison. At low particle rate, this detector reaches an efficiency of 98% and a time resolution of around 70 ps for the two mixtures of gases. We observed no degradation of its performances when a limited size of its active area is exposed to particle rates up to 63 kHz/cm2.

On a new environment-friendly gas mixture for Resistive Plate Chambers

The standard gas mixture for the Resistive Plate Chambers (RPC), composed of C2H2F4/i-C4H10/SF6, allows the detector operation in avalanche mode, as required by the high-luminosity collider experiments. The gas density, the low total charge delivered inside the gas and the comfortable avalanche-streamer separation guarantee high detection efficiency, rate capability and slow detector aging. The standard RPC gas mixture is mostly based on Hydrofluorocarbons, HFCs, extensively used in the refrigeration industry. The Hydrofluorocarbons are now considered to be non-eco-friendly gases for their high Global Warming Potential (GWP). The SF6 has the largest GWP, 22900, but, due to its low concentration, it contributes only with few tens of units to the total value. The major contribution comes from the main standard gas mixture component, the C2H2F4 (GWP ≈ 1300). These gases are not recommended for industrial uses anymore, thus their availability will be increasingly difficult over time and the search for an alternative gas mixture with low-GWP is then of absolute priority within the RPC community. We report the performance of the RPC working with new environment-friendly gases which could replace the standard mixture. In this work the standard mixture main component, the C2H2F4, is replaced by a proper mixture of CO2 (GWP = 1) and Tetrafluoropropene (C3H2F4, GWP≈6). The other high-GWP component, the SF6, is replaced by a molecule, the Chloro-Trifluoropropene (C3H2ClF3, GWP ≈ 5) never tested in RPC detectors. The mixtures studied have a total GWP ≈ 10. We report, for several eco-gas mixtures, the detection efficiency, streamer probability, electronic and ionic charge as a function of the high voltage. Moreover, the timing properties are studied and the detector time resolution is measured. We also focus the attention on a new category of signals having intermediate properties between avalanche and streamer, called ”transition events”. This category is negligible for the standard gas mixture but relevant for HFO/CO2-based gas mixtures. We show a direct comparison between SF6 and C3H2ClF3 to study in depth the possibility to replace the SF6.

MATOQ: a Monte Carlo simulation of electron transport in environmental-friendly gas mixtures for Resistive Plate Chambers

The increasing interest in environmental-friendly gas mixtures for gaseous particle detectors, especially tetrafluoropropene-based gas mixtures for Resistive Plate Chambers (RPCs), has prompted in recent years the need for simulating electron transport coefficients and reaction rates in these mixtures. MATOQ is a Monte Carlo simulation program that calculates electron transport parameters, specifically designed for studying and optimizing environmental-friendly gas mixtures for RPCs. Unlike other existing codes, MATOQ allows for the simulation of electron avalanches by including the effect of space charge electric field, which can significantly impact the avalanche evolution in gaseous detectors such as RPCs. After the validation of the MATOQ simulation in the temporal and spatial growth configurations, we present the electron transport coefficients and the reaction rates in tetrafluoropropene-based gas mixtures, which may represent a valid alternative to the standard gas mixtures currently used for RPCs.

Studies on RPC detectors operated with environmentally friendly gas mixtures in LHC-like conditions

Resistive Plate Chambers (RPC) are gasesous detectors employed at CERN LHC experiments thanks to their trigger performance, timing capabilities and contained production costs. High Pressure Laminate RPCs are operated with a three-component gas mixture, made of 90–95% of C_2H_2F_4, around 5% of i-C_4H_{10} and 0.3% of SF_6. Due to the presence of leaks at detector level and to the greenhouse characteristics of C_2H_2F_4 and SF_6, RPCs in ATLAS and CMS were accounting for about 87% of CO_2 equivalent emissions during LHC Run 2. To address this, several alternative gases were studied, including R-1234ze as a possible substitute for R-134a. Furthermore, the addition of some amount of CO_2 into the RPCs gas mixture was explored as a possible short-to-medium term solution to lower the total greenhouse gas emissions and reduce the usage of C_2H_2F_4. A dedicated data taking campaign was performed at the Gamma Irradiation Facility at CERN, where RPCs detectors performance were studied with muon beam and gamma background. The detectors were operated with the addition of 30% and 40% and 50% of CO_2 to the standard gas mixture, together with an increased fraction of SF_6. Two different amounts of i-C4H10 were also evaluated to assess compatibility with the CMS and ATLAS requirements. Results from these beam tests with the above-mentioned gas mixtures are reported in this work.

A mid‐infrared laser absorption sensor for calibration‐free measurement of nitric oxide in laminar premixed methane/ammonia cofired flames

AbstractAn interband cascade laser (ICL)‐based absorption sensor was developed for calibration‐free and high‐fidelity measurement of nitric oxide (NO) in laminar premixed methane/ammonia cofired flames using a combination of a micro‐probe and a low‐pressure, high‐temperature gas cell. The developed sensor, which has been shown to be particularly suitable for kinetic studies of ammonia combustion, used a tunable, continuous, narrow‐linewidth, free‐space ICL operating at ~5.2 μm to target the optimal NO transition centered at 1900.07 cm−1. A direct absorption spectroscopy technique with a reduced line model was implemented for calibration‐free measurements. Comprehensive experiments were first conducted to evaluate the sensor performance against the standard gas mixture at varied pressure from 20 to 101 kPa at 393 K, showing a relative difference of ≤2.5% and a measurement uncertainty of ≤2.0%. Such a sensor shows a minimum detection limit of ~2 ppm at the integration time of 1 s. The sensor was then applied for investigating the NO formation in ammonia‐methane cofiring flames with various ammonia blending ratios; the acquired experimental data was further used as benchmark data for evaluation of literature chemical mechanisms for ammonia combustion. The developed sensor system was demonstrated to be capable of providing quantitative and spatially resolved measurement of NO in ammonia‐methane cofired flames.

A two-staged adsorption/thermal desorption GC/MS online system for monitoring volatile organic compounds.

Real-time online monitoring of volatile organic compounds (VOCs) in ambient air is crucial for timely and effective human health protection. Here, we developed an innovative, automated two-staged adsorption/thermal desorption gas chromatography/mass spectrometry (GC/MS) system for real-time online monitoring of 117 regulated volatile organic compounds (VOCs). This system comprised a sampling unit, water management trap, two-staged adsorption/thermal desorption unit, thermoelectric coolers (TECs), and a commercial GC/MS system. By implementing a micro-purge-and-trap (MP & T) step and a two-staged adsorption/thermal desorption unit, the presence of interfering substances was effectively minimized. The utilization of a heart-cutting GC, combined with a single MS detector, facilitated the precise separation and detection of 117 C2-C12 VOCs, while circumventing the identification and coelution challenges commonly associated with traditional GC-FID or GC-FID/MS methods. The performance of our newly developed online system was meticulously optimized and evaluated using standard gas mixtures. Under optimal conditions, we achieved impressive results, with R2 values ≥ 0.9946 for the standard linear curves of all 117 VOCs, demonstrating a precision (RSD) ranging from 0.2% to 6.4%. When applied in the field monitoring, the concentration drifts for 10 ppbv standard gas mixtures were 0.01-5.64% within 24h. Our study developed a system for online monitoring of 117 atmospheric VOCs with relatively high accuracy and robustness.

Measurements of fluoride production in Resistive Plate Chambers

Resistive Plate Chambers (RPCs) are operated with a gas mixture made of C2H2F4, SF6 and iC4H10. It is well known that under the effect of a high electric field and radiation, the C2H2F4 molecule breaks into several compounds and free fluoride ions, which can accumulate under gas recirculation and could be harmful for the long-term detector operation. Furthermore, if High Pressure Laminate (HPL) electrodes are employed, the gas mixture is humidified and, in presence of water, the free fluoride ions become hydrofluoric acid (HF), a very reactive compound. The F− production depends on several factors such as radiation rate, gas flow, detector current and gas mixture. In this study we developed and tested two different set-ups for the F− concentration measurements by using an Ion Selective Electrode (ISE) station. The measurement on the F− production were performed on 2 mm gas gap bakelite RPC detector irradiated at the CERN Gamma Irradiation Facility (GIF++) with different absorption factors. Several gas mixtures were tested to understand how the formation of HF is affected. The F− production of the standard gas mixture was compared with the one of the standard gas mixture with the addition of 30% CO2 at several gamma rates. Different concentrations of SF6 were also investigated to understand if and how the SF6 could affect the F− production. Finally, two gas mixtures containing HFO1234ze, C2H2F4 and He or CO2 were used to study the RPC F− production in presence of the HFO1234ze, which is less stable in atmosphere with respect to the C2H2F4.

Studies on RPC detectors operated with environmentally friendly gas mixtures in LHC-like conditions

Resistive Plate Chambers (RPC) are gaseous detectors employed at CERN LHC experiments thanks to their trigger performance, timing capabilities and contained production costs. High Pressure Laminate RPCs are operated with a three-component gas mixture, made of 90%–95% of C2H2F4, around 5% of i-C4H10 and 0.3% of SF6. Due to the presence of leaks at detector level and to the greenhouse characteristics of C2H2F4 and SF6, RPCs in ATLAS and CMS were accounting for about 87% of CO2 equivalent emissions during LHC Run 2. The addition of some amount of CO2 into the RPCs gas mixture was explored as a possible short-to-medium term solution to lower the total greenhouse gases emissions and reduce the usage of C2H2F4. A dedicated data taking campaign was performed at the Gamma Irradiation Facility at CERN, where RPCs detectors performance were studied with muon beam and gamma background. The detectors were operated with the addition of 30% and 40% of CO2 to the standard gas mixture, together with an increased fraction of SF6. In addition, the performance with two different amount of i-C4H10 were evaluated in order to assess the compatibility of the gas mixture with the CMS and ATLAS requirements. Results on the muon beam performance of RPCs operated with the aforementioned gas mixtures are reported in this work.

Performance studies of RPC detectors operated with C2H2F4 and CO2 gas mixtures

Resistive Plate Chambers detectors are largely employed at the CERN LHC experiments thanks to their excellent trigger performances and contained costs. They are operated with a gas mixture made of 90%–95% of C2H2F4, that provides a high number of ion–electron pairs, about 5% of i-C4H10, that ensures the suppression of photon-feedback effects, and 0.3% of SF6, used as an electron quencher to further operate the detector in streamer-free mode. C2H2F4is known to be a Greenhouse gas, with a global warming potential (GWP) of 1430. CERN has identified several strategies to reduce the consumption of greenhouse gas emissions from particle detectors at LHC experiments. One research line is focused on the study of alternatives to C2H2F4. In this context, a conservative approach for the next years of LHC operation could be to focus on reducing the GWP of the RPC gas mixture by only adding CO2 and not using new gases, whose effects on detector long-term operation have to be studied. The RPC performance with standard gas mixture with the addition of 30%–50% of CO2 (and SF6 concentration between 0.3 and 0.9%) were studied both in laboratory set-up and at the CERN Gamma Irradiation Facility in presence of muon beam and gamma background radiation. Encouraging results were obtained showing that the addition of CO2 to the standard gas mixture can represent a mid-term solution to reduce emissions and lower operational costs by keeping stable detector performance and safe long-term operation.

Intercomparison of in situ measurements of ambient NH3: instrument performance and application under field conditions

Abstract. Ammonia (NH3) in the atmosphere affects both the environment and human health. It is therefore increasingly recognised by policy makers as an important air pollutant that needs to be mitigated, though it still remains unregulated in many countries. In order to understand the effectiveness of abatement strategies, routine NH3 monitoring is required. Current reference protocols, first developed in the 1990s, use daily samplers with offline analysis; however, there have been a number of technologies developed since, which may be applicable for high time resolution routine monitoring of NH3 at ambient concentrations. The following study is a comprehensive field intercomparison held over an intensively managed grassland in southeastern Scotland using currently available methods that are reported to be suitable for routine monitoring of ambient NH3. In total, 13 instruments took part in the field study, including commercially available technologies, research prototype instruments, and legacy instruments. Assessments of the instruments' precision at low concentrations (&lt; 10 ppb) and at elevated concentrations (maximum reported concentration of 282 ppb) were undertaken. At elevated concentrations, all instruments performed well and with precision (r2 &gt; 0.75). At concentrations below 10 ppb, however, precision decreased, and instruments fell into two distinct groups, with duplicate instruments split across the two groups. It was found that duplicate instruments performed differently as a result of differences in instrument setup, inlet design, and operation of the instrument. New metrological standards were used to evaluate the accuracy in determining absolute concentrations in the field. A calibration-free CRDS optical gas standard (OGS, PTB, DE) served as an instrumental reference standard, and instrument operation was assessed against metrological calibration gases from (i) a permeation system (ReGaS1, METAS, CH) and (ii) primary standard gas mixtures (PSMs) prepared by gravimetry (NPL, UK). This study suggests that, although the OGS gives good performance with respect to sensitivity and linearity against the reference gas standards, this in itself is not enough for the OGS to be a field reference standard, because in field applications, a closed path spectrometer has limitations due to losses to surfaces in sampling NH3, which are not currently taken into account by the OGS. Overall, the instruments compared with the metrological standards performed well, but not every instrument could be compared to the reference gas standards due to incompatible inlet designs and limitations in the gas flow rates of the standards. This work provides evidence that, although NH3 instrumentation have greatly progressed in measurement precision, there is still further work required to quantify the accuracy of these systems under field conditions. It is the recommendation of this study that the use of instruments for routine monitoring of NH3 needs to be set out in standard operating protocols for inlet setup, calibration, and routine maintenance in order for datasets to be comparable.

Selection of gas standards, gas chromatography column and adsorbents for the measurement of very volatile organic compounds (C1–C6) in indoor air

The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve Carbosieve™ SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.

Enhanced dilution step and gravimetric preparation uncertainty for low-amount fraction standard gas mixtures using a newly developed automatic weighing system for a mini cylinder

The gravimetric method is widely used to prepare standard gas mixtures in gas cylinders. Several dilution steps are required to prepare a low-amount fraction gas mixture, such as at μmol mol−1 level, using the gravimetric method. We have developed a new automatic weighing system (AWS) that is applicable to a mini cylinder (100 mL or less) to reduce the number of dilution steps. The developed mini-AWS is operated by an automatic cylinder exchange mechanism that is similar to the existing AWS. However, the minimum measurable mass was decreased to measure a small amount of target gas; therefore, the gas mixture can be prepared directly at the μmol mol−1 scale. This study evaluated the fundamental performance of the developed mini-AWS, and we gravimetrically prepared several gas mixtures of nominal 100 μmol mol−1 carbon monoxide (CO) in nitrogen (N2). The uncertainties of prepared gas mixtures were consistent within 0.1% of the relative expanded uncertainty. They were then compared to the standard gas mixture, which was gravimetrically prepared using the existing AWS. The compared results agreed within their expanded uncertainties (k = 2).

Deep eutectic solvents-based headspace single-drop microextraction for the chromatographic determination of phenols and aliphatic alcohols in atmospheric air

In this work, the possibility for gas chromatography determination of volatile organic compounds in atmospheric air with preliminary microextraction into single drop of a deep eutectic solvent is presented for the first time. Highly toxic compounds (phenol, o-cresol) and aliphatic alcohols (methanol, n-butanol, n-pentanol) were selected as analytes for which low MPCs in the atmospheric air were established. A eutectic mixture of natural, environmentally friendly substances menthol and thymol was used as an extractant. The resulting eutectic solvent forms a stable drop that allows the rapid extraction of analytes from the gas phase. 30 min of sampling is enough to achieve sensitivity at the level of maximum permissible concentrations of these analytes in atmospheric air. At the same time, the volatility of the components of the eutectic compound themselves made it possible to introduce this solvent directly into the gas chromatograph without dilution. The developed procedure was used to analyze real air samples and standard gas mixtures. The limits of detection for analytes were in the range 0.001–0.01 mg L−1. The RSD for all analytes was <5 %. This sample preparation method can be easily and efficiently combined with subsequent chromatographic detection.

Adaptive Air Quality Sensing using Machine Learning

Abstract: Air pollution is a worldwide problem having impacts on both local and global scales. According to the World Health Organization (WHO), air pollution causes 7 million deaths every year, with 4.2 million attributed to exposure to outdoor air pollution. Compared to the reference methods defined in the Air Quality Directive, the use of low-cost air quality sensors for monitoring ambient air pollution would reduce air pollution monitoring costs and would also allow larger spatial coverage especially in remote areas where monitoring with traditional facilities is uneasy. Theses multi-sensors were either calibrated against standard gas mixtures or using artificial neural network under field conditions. The later method resulted in mixed results either satisfactory for short periods or generally weak for longer data series. This project mainly focuses on the adaptive calibration of the low-cost sensors using the trained machine learning model. The performances of several field calibration methods for low-cost sensors, including linear/multi linear regression and supervised learning techniques will be compared. A cluster of ozone, nitrogen dioxide, nitrogen monoxide, carbon monoxide and carbon dioxide sensors will be operated. Subsequently, the accuracy of the predicted values will be evaluated for about a period. These predicted values are fed through the training model and the model will run accordingly and it will adapt all the error situations. This will be useful to the automobile industry in the current situation for smoke emission control and also for many refinery industries in which low-cost sensors can be used with the following modelling for the higher accuracy. This would reduce the cost and also yields more accuracy beyond the varying situation. Keywords: 1) Low-Cost Sensors (LCS) 2) Internet of Things (IoT)