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Novel traceable analytical methods and reference gas standards were developed for the detection of trace-level ammonia in biogas and biomethane. This work focused on an ammonia amount fraction at an upper limit level of 10 mg m–3 (corresponding to approximately 14 μmol mol–1) specified in EN 16723-1:2016. The application of spectroscopic analytical methods, such as Fourier transform infrared spectroscopy, cavity ring-down spectroscopy, and optical feedback cavity-enhanced absorption spectroscopy, was investigated. These techniques all exhibited the necessary ammonia sensitivity at the required 14 μmol mol–1 amount fraction. A 29-month stability study of reference gas mixtures of 10 μmol mol–1 ammonia in methane and synthetic biogas is also reported.

This Feature highlights the role of metrology, the science of measurement, in maintaining the infrastructure we all rely on for accurate chemical measurements. In particular, the recent change to the definition of the mole, the unit of chemistry, is explained.

The precise measurement of the amount fraction of atmospheric nitrous oxide (N2O) is required to understand global emission trends. Analysis of the site-specific stable isotopic composition of N2O provides a means to differentiate emission sources. The availability of accurate reference materials of known N2O amount fractions and isotopic composition is critical for achieving these goals. We present the development of nitrous oxide gas reference materials for underpinning measurements of atmospheric composition and isotope ratio. Uncertainties target the World Metrological Organisation Global Atmosphere Watch (WMO-GAW) compatibility goal of 0.1 nmol mol−1 and extended compatibility goal of 0.3 nmol mol−1, for atmospheric N2O measurements in an amount fraction range of 325–335 nmol mol−1. We also demonstrate the stability of amount fraction and isotope ratio of these reference materials and present a characterisation study of the cavity ring-down spectrometer used for analysis of the reference materials.

This report describes work to evaluate the performance of different commercial and proprietary cylinder treatments in improving the stability of ammonia reference materials in high pressure cylinders. Gas mixtures of 100 µmol/mol and 10 µmol/mol ammonia in nitrogen were prepared gravimetrically at both NPL and VSL. Comparative measurements at each amount-of-substance fraction were used to assess which passivation technique minimised the loss of ammonia upon preparation. The results indicate little difference between the commercial treatments, except at lower amount-of-substance fractions (10 μmol/mol). The variation observed in performance might be explained by the different abilities of the various treatments to prevent the adsorption of ammonia molecules on the internal surfaces of the cylinder, although the role of residual water on the cylinder surface in reacting with ammonia is unclear.

The effect of rounding when presenting the uncertainties associated with bespoke gas certified reference materials has been investigated. This has been examined in the context of wanting to provide the customer with as close a match as possible to what was originally contracted whilst needing to comply with the minimum uncertainties allowed by internationally agreed calibration and measurement capabilities under the International Committee for Weights and Measures’ Mutual Recognition Arrangement or other scopes of accreditation. The effect of rounding has, in relative terms, been shown to be large in some cases and this has prompted an investigation into improved methods to express more precisely values presented on certificates accompanying bespoke gas certified reference materials. This has included a new proposal to present relative, instead of absolute, uncertainties on certificates thereby matching exactly customer requirements. This Practitioner’s Report also demonstrates how considerations of customer and quality system requirements should be properly balanced and how internal review of technical procedures leads to continuous improvement.

One way of obtaining isotope ratios, traceable to the International System of Units, is the gravimetric isotope mixtures method. Adapting this method to carbon dioxide is challenging since measuring all twelve isotopologues at once with a gas mass spectrometer is currently not possible. The calculation of the mass bias correction factors is no straightforward task due to the fact that the isotopic equilibrium has to be considered. This publication demonstrates a potential way of adapting this method to carbon dioxide while considering isotope equilibrium. We also show how we prepared binary blends from enriched/depleted carbon dioxide parent gases and how equilibrating the different gases by heating affects the measurements. Furthermore, we reveal mathematical limitations of our approach when the gases are not in isotope equilibrium and which issues occur due to measurement limitations. In a simulation, using authentic data, we asses our approach in terms of achievable uncertainties and discuss further improvements, like using atomic spectroscopy methods.

Information on the isotopic composition of nitrous oxide (NWithin the project Metrology for Stable Isotope Reference Standards (SIRS), seven pure NThe established NA set of seven N

Main text CCQM-K3.2019 was a repeat of the key comparison CCQM-K3 on the composition of automotive exhaust gases. New in CCQM-K3.2019 was the addition of the amount fraction oxygen to the programme. The key comparison reference values were obtained independently, using static gravimetry and appropriate corrections from purity analysis. The key comparison results show equivalence between the measurement standards maintained by the participating national metrology institutes. The demonstrated equivalence can be used to underpin services related to automotive exhaust gases as well as generically through the flexible scheme ("track A"). To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

This research builds upon two early efforts to explore robot trading strategies within the double auction market: (1) Gode and Sunder's Zero Intelligence robots, a simple, loss-avoiding, random, persistent, liquidity-providing strategy that produced, in double auction markets, high efficiency of allocation and market price convergence (within-period) towards the predictions of competitive theory; and (2) an entirely parasitic version of Todd Kaplan's Snipers, a simple, loss-avoiding, deterministic, liquidity-removing strategy. The original version of Kaplan's Snipers achieved the highest profit in an early tournament (the Santa Fe Double Auction Tournament) in part by accepting others’ orders when there was an excellent price, a low bid-ask spread, or time was running out. As we increase the proportion of snipers in a market, we find that sniping is not generally superior to the ZI strategy and that the snipers’ parasitic and end-of-period behaviors eventually cause extreme price variance and divergence from competitive equilibrium, lower market efficiencies, and rising Gini coefficients of inequality. Our results contrast with earlier claims by Gode and Sunder and others that double auction market efficiency and convergence to competitive equilibria are market properties relatively insensitive to agent strategies. Instead, we find a need to consider agent strategy in explaining how our market outcomes differ from those previously obtained either by Gode and Sunder or by Kaplan's successful tournament entry. Specifically, the interaction of parasitic sniper strategies creates a trading constraint: snipers will never trade with each other. These strategy-induced trading constraints force the standard market efficiency metric lower as the sniper population rises.

We have shown that an exchange dilution preparation method reduces the impact of surface adsorption of the target component in high-pressure gas mixtures used for underpinning measurements of amount-of-substance fraction. Gas mixtures are diluted in the same cylinder by releasing an aliquot of the parent mixture. Additional matrix gas is then added to the cylinder. This differs from conventional methods where dilutions are achieved by transferring the parent mixture to another cylinder, which then stores the final reference material. The benefit of this revolutionary approach is that losses due to adsorption to the walls of the cylinder and the valve are reduced as the parent mixture pacifies the surface with only a negligible relative change in amount-of-substance fraction. This development allows for preparation of gas reference materials with unprecedented uncertainties beyond the existing state of the art. It has significant implications for the preparation of high accuracy gas reference materials which underpin a broad range of requirements, particularly in atmospheric monitoring of carbon dioxide, where understanding the adsorption effects is the major obstacle to advancing the measurement science. It has the potential to remove the reliance on proprietary surface pretreatments as the method provides an in situ and consistent alternative.

Emergent behavior in repeated collective decisions of minimally intelligent agents -- who at each step in time invoke majority rule to choose between a status quo and a random challenge -- can manifest through the long-term stationary probability distributions of a Markov Chain. We use this known technique to compare two kinds of voting agendas: a zero-intelligence agenda that chooses the challenger uniformly at random, and a minimally-intelligent agenda that chooses the challenger from the union of the status quo and the set of winning challengers. We use Google Co-Lab's GPU accelerated computing environment to compute stationary distributions for some simple examples from spatial-voting and budget-allocation scenarios. We find that the voting model using the zero-intelligence agenda converges more slowly, but in some cases to better outcomes.

The precise measurement of the amount fraction of atmospheric nitrous oxide (N2O) is required to understand global emission trends. Analysis of the site-specific stable isotopic composition of N2O provides a means to differentiate emission sources. The availability of accurate reference materials of known N2O amount fractions and isotopic composition is critical for achieving these goals. We present the development of nitrous oxide gas reference materials for underpinning measurements of atmospheric composition and isotope ratio. Uncertainties target the World Metrological Organisation Global Atmosphere Watch (WMO-GAW) compatibility goal of 0.1 nmol mol−1 and extended compatibility goal of 0.3 nmol mol−1, for atmospheric N2O measurements in an amount fraction range of 325–335 nmol mol−1. We also demonstrate the stability of amount fraction and isotope ratio of these reference materials and present a characterisation study of the cavity ring down spectrometer used for analysis of the reference materials.

Impurities in carbon dioxide can affect several aspects of the carbon capture and storage process, including storage capacity, rock erosion, accuracy of flow meters, and toxicity of potential leaks. There is an industry need for guidance on performing purity analysis before carbon dioxide is transported and stored. This paper reviews selected reports that specifically provide threshold amount fraction limits for impurities in carbon dioxide for the purpose of transport and storage, with rationales for these limits. A carbon dioxide purity specification is provided (including threshold amount fractions of impurities) on the basis of the findings, as well as recommendations on further work required to develop a suitable gas metrology infrastructure to support these measurements including primary reference materials, sampling methods, and instruments for performing purity analysis. These recommendations provide important guidance to operators and gas analysis laboratories for performing quality assurance.

Main text The CCQM-K10.2018 comparison aimed to evaluate the capabilities of national metrology institutes (NMIs) to prepare and/or value assign primary reference mixtures containing benzene, toluene, ethylbenzene, p-xylene, m-xylene and o-xylene (subsequently referred to as BTEX) in nitrogen. This key comparison was separated into two parallel studies. The first study, deemed the "gravimetric study", evaluated the level of compatibility of BTEX standards provided by NMIs. Seven participating laboratories each submitted one standard at nominal 5 nmol mol-1 BTEX in nitrogen. Comparison measurements were performed by the National Institute of Standards and Technology (NIST) from July to October 2018. The second study, deemed the "comparative study", compared the capabilities of NMIs to measure the amount fractions of BTEX in a mixture provided by NIST. NIST prepared one standard at nominal 5 nmol mol-1 BTEX in nitrogen, which was measured consecutively by three participating laboratories. The participants' measurements took place from August 2018 to March 2019. The comparison protocol adopted for CCQM-K10.2018 was more challenging than for the original comparison, CCQM-K10 in 2001, and the results provide an extended evaluation of the level of compatibility of BTEX in nitrogen standards. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Main text CCQM-K118 was an international key comparison on natural gas composition with two types of gases, i.e., a low calorific hydrogen-enriched natural gas and a high calorific LNG type of gas. There were 14 participating laboratories. The traveling standards (i.e., 14 mixtures each) were obtained from an external source and checked for homogeneity and stability before and after the participants' measurements at the two coordinating laboratories. The data evaluation was performed using a consensus value and a laboratory effect model. The results of the participants were benchmarked against a key comparison reference value computed from the largest consistent subset (LCS) of the submitted results, adjusted for the differences between the travelling standards. For the first time in a key comparison in gas analysis, the model included a term to account for excess variability in the LCS. Most of the participants reported one or a few (slightly) discrepant results. Partly this is due to the heterogeneity and heteroscedasticity of the datasets. In all, the results in this key comparison demonstrate the good comparability of the national measurement standards for natural gas composition maintained by the participating NMIs. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA). To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The purity analysis of zero air is a significant contributor to the uncertainty in preparing reference materials of high impact greenhouse gases, limiting progress toward coherent and comparable measurements required to assess climate trends. We have produced a commutable synthetic zero air reference material with an oxygen, nitrogen, and argon matrix closely matching atmospheric composition. This is the critical step in preventing systematic biases from pressure broadening effects when using these reference materials to calibrate instruments based on optical spectroscopy. The amount fractions of carbon dioxide, methane, and carbon monoxide, which are present as minor impurities in the zero air reference material, have been accurately quantified using a novel dilution device that can generate gas mixtures of these components at trace amount fractions. These developments will have a significant impact on advancing the state of the art in high accuracy reference materials and for baseline calibration of spectroscopic instrumentation.

Monoterpenes play an important role in atmospheric chemistry due to their large anthropogenic and biogenic emission sources and high chemical reactivity. As a consequence, measurements are required to assess how changes in emissions of monoterpenes impact air quality. Accurate and comparable measurements of monoterpenes in indoor and outdoor environments require gaseous primary reference materials (PRMs) that are traceable to the international system of units (SI). PRMs of monoterpenes are challenging to produce due to the high chemical reactivity and low vapour pressures of monoterpenes and also their propensity to convert into other compounds, including other terpenes. In this paper, the long-term stability of gravimetrically prepared static monoterpene PRMs produced in differently passivated cylinders, including sampling canisters, was assessed. We demonstrate that static PRMs of multiple monoterpenes can be prepared and used as a suitable long-term standard. For the first time the effect of cylinder pressure and decanting from one cylinder to another on the chemical composition and amount fraction of monoterpenes was also studied. Gravimetrically prepared PRMs of limonene in high pressure cylinders were compared to a novel portable dynamic reference gas generator based on dilution of pure limonene vapour emitted from a permeation tube.

Metrological traceability is the property of a measurement result whereby it can be related to a stated reference through a documented unbroken chain of calibrations, each contributing to the measurement uncertainty. The stated reference can be the International System of Units, and more specifically a realisation of a primary standard with its value and uncertainty expressed in SI units, which offers many benefits such as long term stability and the ability to reproduce the standard within its stated uncertainty at any time. Alternatively, measurements can be made traceable to an empirical scale, an approach that has evolved for practical reasons to meet the needs of certain measurement communities. We explore the benefits and drawbacks of these two measurements systems as they have evolved for greenhouse gas measurements at background levels and outline the advantages of using elements from each to secure a more robust measurement infrastructure. In particular, this work examines the importance of compatibility, the accuracy of measurement results and the benefits of comparisons with independent primary standards.

This work was supported by Innovate UK [Project No: 101830]. Formaldehyde is an intermediate of the steam methane reforming process for hydrogen production. According to International Standard ISO 14687-2 the amount fraction level of formaldehyde present in hydrogen supplied to fuel cell electric vehicles (FCEV) must not exceed 10 nmol mol−1. The development of formaldehyde standards in hydrogen is crucial to validate the analytical results and ensure measurement reliability for the FCEV industry. NPL demonstrated that these standards can be gravimetrically prepared and validated at 10 μmol mol−1 with a shelf-life of 8 weeks (stability uncertainty

We have shown that the amount fraction of carbon dioxide in a nitrogen or synthetic air matrix stored in cylinders increases as the pressure of the gas mixture reduces, while the amount fraction of methane remains unchanged. Our measurements show the initial amount fraction of carbon dioxide to be lower than the gravimetric value after preparation, which we attribute to the adsorption of a proportion of the molecules to active sites on the internal surface of the cylinder and the valve. As the mixture is consumed, the pressure in the cylinder reduces and the amount fraction of the component is observed to increase. The effect is less pronounced in the presence of water vapor. More dramatic effects have been observed for hydrogen chloride. These findings have significant implications for the preparation of high accuracy gaseous reference materials with unprecedented uncertainties which underpin a broad range of requirements, in particular atmospheric monitoring of high impact greenhouse gases.

A fixed volume case of sequential standard addition calibration (S-SAC) for the value assignment of impurities in zero gas is described. A mathematical description of this technique has been derived and has been shown to exhibit a similar systematic bias during the extrapolation process to that seen for other S-SAC cases. The use of S-SAC in the gas phase has demonstrated that variation in the sample volume for S-SAC in the liquid phase is not the generalised cause of the bias experienced during extrapolation. Instead it is the variation in the volume of the original sample with respect to the overall volume of the mixture following the addition of standard. In addition, the requirement to perform a bias correction on the extrapolated values has been discussed and best practice solutions for correction proposed.

Measurements of volatile organic compounds (VOCs) have been ongoing for decades to track growth rates and assist in curbing emissions of these compounds into the atmosphere. To accurately establish mole fraction trends and assess the role of these gas-phase compounds in atmospheric chemistry it is essential to have good calibration standards. A necessity and precursor to accurate VOC gas standards are the gas cylinders and the internal wall treatments that aid in maintaining the stability of the mixtures over long periods of time, measured in years. This paper will discuss the stability of VOC gas mixtures in different types of gas cylinders and internal wall treatments. Stability data will be given for 85 VOCs studied in gas mixtures by National Metrology Institutes and other agency laboratories. This evaluation of cylinder treatment materials is the outcome of an activity of the VOC Expert Group within the framework of the World Meteorological Organization (WMO) Global Atmospheric Watch (GAW) program.

International audience; A detailed review and analysis of literature values for the absorption cross-section of ozone at room temperature at the mercury-line wavelength (253.65 nm, air) is reported. Data from fourteen independent sets of measurements spanning the years 1959-2016 were considered. The present analysis is based upon a revised assessment of all Type A and Type B uncertainty components for each previously reported cross-section. A consensus value for the absorption cross-section of 1.1329(35) × 10 −17 cm 2 molecule −1 is recommended based on statistical analysis of the weighted data. This new cross-section value is 1.23% lower and its uncertainty sixfold smaller than the uncertainty of the conventionally accepted reference value reported by Hearn (1961 Proc. Phys. Soc. 78 932-40).

Main text At the highest metrological level, ammonia gas standards are commonly prepared gravimetrically as Primary Standard Mixtures or using a dynamic standard. This international key comparison addressed the measurement of the amount fraction ammonia in nitrogen, to support calibration and measurement services for mainly environmental applications. The nominal amount fraction was 14 μmol mol-1. The results in this Track C key comparison on the composition of biogas are generally good. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

An international comparison was coordinated by the National Physical Laboratory to assess the analytical capabilities of laboratories for measuring ten selected volatile organic compounds. These were chosen to represent a wide range of non-methane hydrocarbons, terpenes and oxygenated hydrocarbons, which pose a significant risk to public health from their presence in indoor environments from emissions by building and consumer materials. The components were loaded onto sorbent tubes and distributed to twenty-four participating laboratories for analysis. It was found that laboratories predominantly reported analytical results that were greater than the reference value, however the majority of results were closer to the reference value when compared to the previous comparison carried out in 2010.

At the highest metrological level, biogas standards are commonly prepared gravimetrically as PSMs (primary standard mixtures). This international key comparison addresses the composition of biogas, to support calibration and measurement services for this renewable energy gas. The mixtures contain nitrogen, carbon dioxide, methane, ethane, propane, hydrogen and oxygen and represent the composition of biogas from landfills. The results in this Track C key comparison on the composition of biogas are generally good. Some of the datasets, especially that of oxygen, showed substantial extra dispersion, that could not be explained by the stated uncertainties. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The measurement of trace amounts of water in process gases is of paramount importance to a number of manufacturing processes. Water is considered to be one of the most difficult impurities to remove from gas supply systems and there is strong evidence that the presence of water contamination in semiconductor gases has a measurable impact on the quality and performance of devices. Consequently, semiconductor manufacturers are constantly reducing target levels of water in purge and process gases. As the purity of gases improves, the problem of quantifying contamination and ensuring that the gases are within specification at the point of use becomes more challenging. There are several established techniques for detecting trace water vapour in process gases. These include instruments based on the chilled mirror principle which measures the dew-point of the gas and the quartz crystal adsorption principle which measures the adsorption of water vapour into a crystal with a hygroscopic coating. Most recently, spectroscopic instruments such as those employing cavity ring-down spectroscopy (CRDS) have become available. The calibration of such instruments is a difficult exercise because of the very limited availability of accurate water vapour standards. This CCQM pilot study aims to assess the analytical capabilities of laboratories for measuring the composition of 10 μmol mol−1 water vapour in nitrogen. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Monoterpenes play an important role in atmospheric chemistry due to their large anthropogenic and biogenic emission sources and high chemical reactivity. As a consequence, measurements are required to assess how changes in emissions of monoterpenes impact air quality. Accurate and comparable measurements of monoterpenes in indoor and outdoor environments require gaseous primary reference materials (PRMs) that are traceable to the international system of units (SI). PRMs of monoterpenes are challenging to produce due to the high chemical reactivity and low vapour pressures of monoterpenes and also their propensity to convert into other compounds, including other terpenes. In this paper, the long-term stability of gravimetrically prepared static monoterpene PRMs produced in differently passivated cylinders, including sampling canisters, was assessed. We demonstrate that static PRMs of multiple monoterpenes can be prepared and used as a suitable long-term standard. For the first time the effect of cylinder pressure and decanting from one cylinder to another on the chemical composition and amount fraction of monoterpenes was also studied. Gravimetrically prepared PRMs of limonene in high pressure cylinders were compared to a novel portable dynamic reference gas generator based on dilution of pure limonene vapour emitted from a permeation tube.

This paper considers how decisions on internationally recommended datasets are made and implemented and, further, how the ownership of these decisions comes about. Examples are given of conventionally agreed data and values where the responsibility is clear and comes about through official designation or by common usage and practice over long time periods. The example of the dataset describing the mass concentration of mercury in air at saturation is discussed in detail. This is a case where there are now several competing datasets that are in disagreement with each other, some with historical authority and some more recent but, arguably, with more robust metrological traceability to the SI. Further, it is elaborated that there is no body charged with the responsibility to make a decision on an international recommendation for such a dataset. This has led to the situation where several competing datasets are in use simultaneously. Close parallels are drawn with the current debate over changes to the ozone absorption cross section, which has equal importance to the measurement of ozone amount fraction in air and to subsequent compliance with air quality legislation. It is noted that in the case of the ozone cross section there is already a committee appointed to deliberate over any change. We make the proposal that a similar committee, under the auspices of IUPAC or the CIPM's CCQM (if it adopted a reference data function) could be formed to perform a similar role for the mass concentration of mercury in air at saturation.

The first practical comparison of the characteristics of Ag|AgCl electrodes prepared at different National Metrology Institutes (NMIs) has been carried out as a pilot study organised by the Consultative Committee for Amount of Substance (CCQM). Each NMI prepared at least three Ag|AgCl electrodes representative of those employed in their primary pH calibration facilities. The electrodes were sent to a coordinating laboratory where comparative measurements of their potential difference to a de facto reference, slope as a function of chloride ion concentration and electrochemical impedance were made. Electrodes from most NMIs were highly repeatable and consistent within the typical rejection criteria applied during production. An analysis of the electrode slopes in a phosphate buffer containing different concentrations of NaCl revealed the influence of variances in the Ag|AgCl electrodes between NMIs on the certified pH value of the buffer solution. The difference between NMIs is consistent with submitted values in CCQM-K9, although biases were smaller in the analysis here, suggesting the presence of other unknown contributions to the uncertainty such as cell design. The smaller biases observed in this work may also reflect improvements in the Ag|AgCl electrodes since CCQM-K9 was performed. Electrochemical impedance spectroscopy suggests a similar microstructure for electrodes prepared by most NMIs.

Ag|AgCl reference electrodes have been prepared by anodising silver under constant potential in an aqueous electrolyte containing the chloride salt of three different alkali metals. These have been compared to Ag|AgCl reference electrodes anodised in hydrogen chloride that are conventionally used. Our research reveals that the size of the alkali metal cation has an influence on the Ag|AgCl electrode microstructure, with smaller cations resulting in a more porous material and improved electrode stability. This research has positive implications for improving the performance of Ag|AgCl reference electrodes for pH measurement.

Biogas is a renewable energy source with many different production pathways and various excellent opportunities to use, for example as vehicle fuel (biomethane). Reliable analytical methodologies for assessing the quality of the gas are critical to ensure that the gas can technically and safely be used. An essential part of any procedure aiming to determine the quality is the sampling and the transfer to the laboratory. One of the greatest challenges is then to ensure that the composition of the sample collected does not change between the time of sampling and the analysis. The choice of the sampling vessel to be used must be made only after fully assessing its short-term stability. In this paper, the results from short-term stability studies in different vessels (cylinders, bags and sorbents) are presented for siloxanes, BTEX, halogenated hydrocarbons and sulfur compounds. Storage of dry gas at high pressure (> 6 MPa) appears to be a good alternative however it is currently challenging to find an optimal treatment of the cylinders for all species to be assessed in biogas/biomethane. At lower pressure, adsorption effects on the inner surface of the cylinders have been observed. The use of bags and sorbent tubes also shows limitation. No existing sorbent tubes are sufficiently universal as to trap all possible impurities and high boiling compounds may adsorbed on the inner surface of the bags walls. Moreover, the presence of water when storing biogas most certainly impacts the storage stability of compounds in most vessels. Using at least two sampling methods for a given compound and comparing results will allow taking into account the eventual effects of water vapour, and adsorption on the inner surface of the vessels.of vessels and adsorbents for the short-term storage of biogas/biomethane for the determination of impurities - Siloxanes, sulfur compounds, halogenated hydrocarbons, BTEX

The requirement for evaluating high performance barrier layers with water vapor transmission rates (WVTR) far below 10−3 g/m2 d has been sparked by the growing application of flexible and organic electronics. While several highly sensitive WVTR-measurement techniques are described in the literature, their accuracy and comparability has not yet been tested. There is an absence of direct comparison of these methods. With a growing body of literature referring to different coating and barrier technologies (often under different testing conditions), it is extremely difficult to gather a coherent picture both of the performance of the materials studied and the permeation measurement methods used. In order to clarify these points we report on independent WVTR measurements of the same batch of a high performance barrier film under two sets of conditions in several laboratories with different state-of the-art methods. These methods also include several calcium test set-ups. The results showed that, while some differences are present, there is a remarkable level of agreement between the measurement methods even prior to harmonization.

We report the preparation and validation of the first fully synthetic gaseous reference standards of CO2 and CH4 in a whole air matrix with an isotopic distribution matching that is in the ambient atmosphere. The mixtures are accurately representative of the ambient atmosphere and were prepared gravimetrically. The isotopic distribution of the CO2 was matched to the abundance in the ambient atmosphere by blending (12)C-enriched CO2 with (13)C-enriched CO2 in order to avoid measurement biases introduced by measurement instrumentation detecting only certain isotopologues. The reference standards developed here have been compared with standards developed by the National Institute of Standards and Technology and standards from the WMO scale. They demonstrate excellent comparability.

We have developed a unique dynamic dilution system for generating high accuracy reference standards of reactive gases at concentrations which are unstable in high pressure cylinders. It uses state of the art ‘Molbloc’ flow elements and is capable of generating adjustable reference standards with an estimated relative expanded uncertainty lower than 1%. This is a significant development, improving the accuracy of primary reference gas mixtures used to provide and disseminate traceability for measurements of many key gaseous air pollutants.

We provide a dataset for our research article “Profitability, Efficiency and Inequality in Double Auction Markets with Snipers” [1]. This dataset [2] includes configuration files, raw output data, and replications of calculated metrics for our robot-populated market simulations. The raw data is subdivided into a hierarchy of folders corresponding to simulation treatment variables, in a 2 × 2 × 21 design for 84 treatments in total. Treatments variables include: (i) robot population ordering, either “primary” or “reverse”; (ii) two market schedules of agent's values and costs: equal-expected-profit “market 1” and unequal-expected-profit “market 2”; (iii) 21 robot populations identified by the number of Sniper Bots (0–20) on each side of the market. Each treatment directory contains a simulator input file and outputs for 10,000 periods of market data. The outputs include all acceptable buy and sell orders, all trades, profits for each agent, and market metrics such as efficiency-of-allocation, Gini coefficient, and price statistics. An additional public copy in Google Cloud is available for database query by users of Google BigQuery.The market simulator software is a private product created by Paul Brewer at Economic and Financial Technology Consulting LLC. Free open source modules are available for tech-savvy users at GitHub, NPM, and Docker Hub repositories and are sufficient to repeat the simulations. An easier-to-use paid market simulation product will eventually be available online from Econ1.Net. We provide instructions for repeating individual simulations using the free open source simulator and the free container tool Docker. Keywords: Markets, Double auction, Competitive equilibrium, Efficiency, Inequality, Numerical experiments, Simulations