Carlo Tiebe

A metrological approach to improve accuracy and reliability of ammonia measurements in ambient air

The environmental impacts of ammonia (NH3) in ambient air have become more evident in the recent decades, leading to intensifying research in this field. A number of novel analytical techniques and monitoring instruments have been developed, and the quality and availability of reference gas mixtures used for the calibration of measuring instruments has also increased significantly. However, recent inter-comparison measurements show significant discrepancies, indicating that the majority of the newly developed devices and reference materials require further thorough validation. There is a clear need for more intensive metrological research focusing on quality assurance, intercomparability and validations. MetNH3 (Metrology for ammonia in ambient air) is a three-year project within the framework of the European Metrology Research Programme (EMRP), which aims to bring metrological traceability to ambient ammonia measurements in the 0.5–500 nmol mol−1 amount fraction range. This is addressed by working in three areas: (1) improving accuracy and stability of static and dynamic reference gas mixtures, (2) developing an optical transfer standard and (3) establishing the link between high-accuracy metrological standards and field measurements. In this article we describe the concept, aims and first results of the project.

Geographical provenience differentiation and adulteration detection of cumin by means of electronic sensing systems and SPME-GC-MS in combination with different chemometric approaches

The detection of the aroma and flavour volatile compounds of spices is key in product quality control. Accordingly, it is necessary to develop new electronic sensing systems for food adulteration control and authenticity assessment for protecting customers health. In this work, the capability of the E-nose and VE-tongue in combination with SPME-GC-MS to correctly discriminate between several cumin samples of different geographical origins and to detect their adulteration, by using unsupervised and supervised chemometric tools, was evaluated. Regarding the aroma profile, eleven volatile compounds were characterized by SPME-GC-MS; all of them were found in cumin powder while only eight are found in cumin seeds. The main volatile compounds detected were β-pinene, m-cymene, γ-terpinene, cuminaldehyde and cuminic alcohol, in different proportions depending on the cumin sample form (seed or powder). In summary, the results obtained are sufficiently encouraging as a starting point for the development of new electronic sensing systems with more improvement in the reliability of the sensors performance as well as chemometric tools in order to deal with a complex dataset.

Electronic Noses for the Quality Control of Spices

Abstract Spices are parts of plants, which are added to foodstuffs due to their natural flavoring. Their flavor is usually stimulated by a great number of volatile organic compounds. As natural products, the quality varies due to origin, seasons as well as processing and requires quality control. In addition to established methods, such as sensory and chemical analysis, electronic nose analysis has been developed to characterize various quality parameters of spices. Electronic noses are deployed for the discrimination between different types, provenience, and quality of spices. Furthermore, aroma intensity, aging effects, and mold infestation have been investigated. Electronic noses are used to characterize the impact of processing spices by milling or irradiation. Spice mixtures have been investigated in order to detect adulterations. In most cases, the deployment of electronic noses is performed in combination with other methods for reference such as sensory or chemical analysis.

Measurement uncertainty of coulometric trace humidity sensors

Abstract Especially trace amounts of water vapour in gases can be reliably determined by coulometric trace humidity sensors. The principle of these sensors is based on water vapour absorption in a hygroscopic layer and its subsequent electrolytic decomposition. The calibration of sensors was performed in the humidity range, expressed as frost point temperature, from − 30 ° C-30\hspace{0.1667em}^\circ \mathrm{C} to − 80 ° C-80\hspace{0.1667em}^\circ \mathrm{C}. This range is equivalent to volume fractions smaller than 376 µL·L−1. Generated humidity was measured with coulometric sensors and a chilled dew point hygrometer that was used as reference. An empirical non-linear function was found between sensor signal and measured reference humidity. This function consists of two parameters with a measurement uncertainty. Both calibration parameters were checked by means of one-way analysis of variance. It showed that gas specific function can be used for humidity measurement in nitrogen, hydrogen, dinitrogen monoxide, compressed and synthetic air. It is possible to determine trace humidity in all tested gases with an expanded uncertainty less than 2.1 K (coverage factor k = 2k=2) regarding frost point temperature.

P4.02 - Novel sensor for long-term monitoring of ammonia in gas phase

Because ammonia and its reaction products can cause considerable damage to human health and ecosystems, there is a need for reliably operating and reversibly interacting sensor materials to monitor traces of gaseous ammonia in ambient air, which at best can be used on-site for in-the-field measurements. Herein, the development of a sensor material for gaseous ammonia in the lower ppm to ppb range using optical fluorescence as transduction mechanism is presented. A fluorescent dye, which shows reversible fluorescence enhancement in the presence of ammonia is incorporated into a polymer matrix, the latter to ensure the accumulation of ammonia. The sensor material is integrated into a prototype of a miniaturized sensor device, facilitating long-term operation. To calibrate the optical sensor system a gas standard generator, producing standard gas mixtures, is used, leading to a sensitivity down to lower ppm concentrations of ammonia.

Determination of safranal concentration in saffron samples by means of VE-Tongue, SPME-GC-MS, UV-Vis Spectrophotometry and multivariate analysis

An experimental investigation has been carried out to characterize and discriminate seven saffron samples and to verify their declared geographical origin using a voltammetric electronic tongue (VE-tongue). The ability of multivariable analysis methods such as Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA) to classify the saffron samples according to their geographical origin have been investigated. A good discrimination has reached using PCA and HCA in the VE-tongue characterization case. Furthermore, cross validation and Partial Least Square (PLS) techniques were applied in order to build suitable management and prediction models for the determination of safranal concentration in saffron samples based on SPME-GC-MS and UV-Vis Spectrophotometry. The obtained results reveals that some relationships were established between the VE-tongue signal, SPME-GC-MS and UV-Vis spectrophotometry methods to predict safranal concentration levels in saffron samples by using the PLS model. In the light of these results, we can say that the proposed electronic system offer a fast, simple and efficient tool to recognize the declared geographical origin of the saffron samples.