Air pollution monitoring: Development of ammonia (NH₃) dynamic reference gas mixtures at nmol/mol levels for improving the lack of traceability of measurements

The measurement of ammonia (NH3) in ambient air is a sensitive and priority topic due to its harmful effects on human health and ecosystems. NH3 emissions have continuously increased over the last century in Europe, because of intensive livestock practices and enhanced use of nitrogen-based fertilizers. European air quality monitoring networks monitor atmospheric NH3 amount fractions. However, the lack of stable reference gas mixtures (RGMs) at atmospheric amount fractions to calibrate NH3 analyzers is a common issue of the networks, which results in data that are not accurate, traceable and, thus, geographically comparable. In order to cover this lack, LNE developed, in close collaboration with the company 2M PROCESS, a gas reference generator to generate dynamically NH3 RGMs in air. The method is based on gas permeation and further dynamic dilution to obtain an amount fraction range between 1 and 400 nmol/mol. The calibration of the elements of the generator against LNE primary standards ensures the traceability of the RGMs to the international system of units. Furthermore, the highly accurate flow and oven temperature measurements of the reference generator, together with the associated calibration procedure defined by LNE, guarantee relative expanded uncertainties of the calibration of the NH3 analyzer calibrations lower than 2 % (coverage factor = 2). This result is very satisfactory considering the low NH3 amount fraction levels (1 to 400 nmol/mol) and the phenomena of adsorption and desorption, especially in the presence of traces of water on the surfaces in contact. A bilateral comparison was organized between METAS and LNE, consisting on the calibration of a PICARRO G2103 gas analyzer by both national metrology institutes (NMI). The results highlighted the good agreement between the NH3 reference generators developed by the two institutes and allowed to validate both LNE’s reference generator and calibration procedure. The development of the NH3 reference generator has already raised great interest within the French air quality monitoring networks (AASQA). Since the end of 2020, LNE calibrated several NH3 analyzers of the networks. These requests shows the interest of the AASQA in the development of this new gas reference generator to guarantee the traceability of measurements carried out on the French territory.

MULTIPARAMETRIC RECOGNITION OF ORGANIC VAPORS BY USING A GAS SENSOR BASED ON A NANOSTRUCTURED TIN DIOXIDE FILM

Исследовано влияние паров органических веществ (изопропанола, этанола и ацетона) различной концентрации на отклик сенсоров газа на основе наноструктурированных пленок диоксида олова, синтезированных золь-гель методом. Экспериментально установлено, что напуск газовых проб, содержащих пары органических веществ, приводит к увеличению проводимости наноструктурированных пленок диоксида олова. В области высоких концентраций (более 50% от насыщенного пара) концентрационная зависимость проводимости имеет тенденцию к насыщению. Показана возможность распознавания сорта примесного газа с помощью статистической обработки отклика только одного сенсора при различных концентрациях анализируемой пробы. Определено положение поверхностного донорного уровня примесного газа относительно акцепторного уровня кислорода и теплота десорбции частиц исследуемых газов. Предложен новый метод мультипараметрического распознавания газовых смесей, основанный на использование в качестве признаков классификации физико-химических параметров анализируемых газов, не зависящих от их концентрации. Установлено, что предложенный метод мультипараметрического распознавания газовых смесей имеет более высокую надежность по сравнению со стандартными методами, основанными на анализе отклика сенсоров газа. The influence of organic vapors (isopropanol, ethanol, and acetone) with different concentrations in air on a response gas sensor based on nanostructured tin dioxide films synthesized by the sol-gel method was studied. It was found experimentally that inject of the gas mixtures containing organic vapors into measure chamber results to an increase of the conductivity of nanostructured tin dioxide films. In the area of high concentrations (more than 50% of saturated vapor), the concentration dependence of conductivity trends to saturation. The recognizing possibility of species gas admixture by using statistical processing of response only single sensor at different analyzed gas mixture concentrations is validated. The surface donor level of gas-reducing relative to acceptor level oxygen and desorption heat of gas particle were determined. A new method based multiparametric recognition gas mixtures is proposed based on using concentration-independent physical and chemical parameters of analyzed gases as classification properties. It is shown that proposed multiparametric recognition method has higher reliability in comparison with standard methods based on the analysis gas sensor response.