Biogenic volatile organic compounds (BVOCs; e.g. terpenes) are highly reactive compounds typically present at sub-parts-per-billion mole fractions in the air. Due to this, their measurements are challenging and they may suffer losses during sampling, storage and analyses. Even though online measurements of BVOCs are becoming more common, the use of sorbent tubes is expected to continue because they offer greater spatial coverage compared to online measurements, and no infrastructure (e.g. electricity, housing/shelter with stable temperature and humidity, sampling lines) is required for sampling. In this study, the performance of an offline technique for the measurement of BVOCs based on sorbent tube sampling was evaluated. Tested compounds included eight monoterpenes, five sesquiterpenes and five oxygenated BVOCs, which are generally either directly emitted (1,8-cineol, linalool, bornyl acetate) or oxidation products (nopinone and 4-acetyl-1-methylcyclohexene). Two sorbent materials (Tenax TA and Carbopack B) and four tube materials (stainless steel (SS), SilcoNert 1000, glass and glass-coated SS) were used. The laboratory evaluations determined the storage stability, breakthrough volumes, suitable tube materials, recovery from ozone scrubbers and particulate filters, and sampling efficiency. In addition, an intercomparison between two laboratories was conducted. No multibed configurations were tested. Of the sorbent materials Tenax TA showed acceptable results for these BVOCs, while with Carbopack B losses and increases in some compounds were detected. Studied compounds were found to be stable in Tenax TA tubes for at least 1 month at −20 and at +20 ^∘C. Breakthrough tests indicated that α- and β-pinene have clearly lower breakthrough volumes in the Tenax TA tubes used (4–7 and 8–26 L, respectively) than other terpenes (> 160 L). SS, SilcoNert 1000 and glass were all shown to be suitable tube materials. Results from Tenax TA sorbent tube sampling agreed with online sampling for most compounds. Heated SS tubes, sodium thiosulfate filters and $\mathrm{KI}/\mathrm{Cu}$ traps were found to be suitable ozone scrubbers for the studied BVOCs. Tested particle filters had a greater impact on limonene (relative difference < +7 %) than on α- and β-pinene (relative difference ±2 %). The laboratory intercomparison of α- and β-pinene measurements showed that in general, measured values by the two laboratories were in good agreement with Tenax TA.

The measurement of ammonia (NH₃) in ambient air is a sensitive and priority topic due to its impact on ecosystems. NH₃ emissions have continuously increased over the last century in Europe because of intensive livestock practices and the enhanced use of nitrogen-based fertilizers. European air quality monitoring networks monitor atmospheric NH₃ amount-of-substance fractions. However, the lack of stable reference gas mixtures (RGMs) of atmospheric amount-of-substance fractions of ammonia to calibrate NH₃ analyzers is a common issue of the networks, which results in data that are not accurate, traceable, or, thus, geographically comparable. In order to cover this lack, LNE (Laboratoire National de Métrologie et d'Essais) developed, in close collaboration with the company 2M PROCESS, a gas reference generator to dynamically generate NH₃ RGMs in air. The method is based on gas permeation and a further dynamic dilution to obtain an amount-of-substance fractions ranging between 1 and 400 nmol mol⁻¹ (also well known as ppb or parts per billion; 1 ppb (NH₃) to ≈ 0.7 µg m⁻³) to cover the amount-of-substance fractions of ammonia measured in ambient air (emissions) and the operating range of the NH₃ analyzers used by the monitoring networks. The calibration of the elements of the generator against the 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 analyzers that are lower than 2 % (coverage factor = 2). This result is very satisfactory, considering the low NH₃ amount-of-substance fraction levels (1 to 400 nmol mol⁻¹) and the phenomena of adsorption and desorption, especially in the presence of traces of water on contact surfaces. A bilateral comparison was organized between METAS (Swiss Federal Institute of Metrology) and LNE, which consisted of the calibration of a Picarro G2103 gas analyzer by both national metrology institutes (NMIs). The results highlighted the good agreement between the NH₃ reference generators developed by the two institutes and allowed the validation of both LNE's reference generator and calibration procedure. Since the end of 2020, LNE has calibrated several NH₃ analyzers from the French air quality monitoring networks (Associations Agréées de Surveillance de la Qualité de l'Air – AASQA) using the newly developed SI-traceable RGMs. The enhanced number of calibrations provided may increase the comparability, accuracy, and traceability of the NH₃ measurements carried out on French territory.

Sensor networks, which are increasingly being used in a broad range of applications, constitute a measurement paradigm involving ensembles of sensors measuring possibly different quantities at a discrete sample of spatial locations and temporal points outside the laboratory. If sensor networks are to be considered as true metrology systems and the measurement results derived from them used for decision-making, such as in a regulatory context, it is important that the results are accompanied by reliable statements of measurement uncertainty. This paper gives a preview of some of the work undertaken within the European-funded ‘Fundamental principles of sensor network metrology (FunSNM)’ project to address the challenges of measurement uncertainty evaluation in some real-world sensor network applications. The applications demonstrate that sensor networks possess features related to the nature of the measured quantities, to the nature of the measurement model, and to the nature of the measured data. These features make conventional methods of measurement uncertainty evaluation, and established guidelines for measurement uncertainty evaluation difficult to apply. An overview of some of the modelling tools used to address the challenges of measurement uncertainty evaluation in those applications is given.

Nitrogen dioxide (NO${}_2$) is a major tropospheric air pollutant. Its concentration in the atmosphere is most frequently monitored indirectly by chemiluminescence detection or using direct light absorption in the visible range. Both techniques are subject to known biases from other trace gases (including water vapor), making accurate measurements at low concentration very challenging. Selective measurements of NO${}_2$ in the mid-infrared have been proposed as a promising alternative, but field deployments and comparisons with established techniques remain sparse. Here, we describe the development and validation of a quantum cascade laser-based spectrometer (QCLAS). It relies on a custom-made astigmatic multipass absorption cell and a recently developed low heat dissipation laser driving and a FPGA based data acquisition approach. We demonstrate a sub-pptv precision (1 $\sigma$) for NO${}_2$ after 150 s integration time. The instrument performance in terms of long-term stability, linearity and field operation capability was assessed in the laboratory and during a two-week inter-comparison campaign at a suburban air pollution monitoring station. Four NO${}_2$ instruments corresponding to three different detection techniques (chemiluminescence detection (CLD), cavity-attenuated phase shift (CAPS) spectroscopy and QCLAS) were deployed after calibrating them with three different referencing methods: gas-phase titration of NO, dynamic high-concentration cylinder dilution and permeation. These measurements show that QCLAS is an attractive alternative for high-precision NO${}_2$ monitoring. Used in dual-laser configuration, its capabilities can be extended to NO, thus allowing for unambiguous quantification of nitrogen oxides (NO${}_x$), which are of key importance in air quality assessments.

Volatile organic compounds (VOCs) have a large impact on the oxidising capacity of the troposphere and are major precursors of tropospheric ozone and secondary atmospheric aerosols. Accurate measurements and data comparability of VOCs among monitoring networks are essential to assessing the trends of these secondary air pollutants. Metrological traceability of the measurements to the International System of Units (SI traceability) contributes to both measurement consistency and data comparability. Accurate, stable and SI-traceable reference gas mixtures (RGMs) and working standards are needed to achieve SI traceability through an unbroken chain of calibrations of the analytical instruments used to monitor VOCs. However, for many oxygenated VOCs (OVOCs), such RGMs and working standards are not available at an atmospheric amount of substance fraction levels (< 10 nmol mol⁻¹). Here, we present the protocols developed to transfer SI traceability to the field by producing two types of SI-traceable working standards for selected OVOCs. These working standards, based on RGMs diluted dynamically with dry nitrogen and on certified spiked whole-air samples, were then assessed using a thermal desorber–gas chromatograph–flame ionisation detector (TD–GC–FID) and proton transfer reaction–time of flight–mass spectrometer (PTR–ToF–MS) as analytical methods. For that purpose, we calibrated five analytical instruments using in-house calibration standards and treated the new SI-traceable working standards as samples. Due to analytical limitations, the assessment was only possible for acetaldehyde, acetone, methanol and methyl ethyl ketone (MEK). Relative differences between assigned and measured values were used to assess the working standards based on the dilution of RGMs. The relative differences were within the measurement uncertainty for acetone, MEK, methanol and acetaldehyde at an amount of substance fractions around 10 nmol mol⁻¹. For the working standards based on certified spiked whole-air samples in pressurised cylinders, results showed a good agreement among the laboratories (i.e. differences within the measurement expanded uncertainty (U) ranging between 0.5 and 3.3 nmol mol⁻¹) and with the certified amount of substance fraction for acetaldehyde (15.7 nmol mol⁻¹ ± 3.6 (U) nmol mol⁻¹), acetone (17 nmol mol⁻¹ ± 1.5 (U) nmol mol⁻¹) and MEK (12.3 nmol mol⁻¹ ± 2.3 (U) nmol mol⁻¹). Despite the promising results for the working standards based on the dilution of RGMs and on certified spiked whole-air samples filled into pressurised cylinders, the assessment must be considered with care due to the large measurement uncertainty, particularly for methanol. Active collaboration among the metrological, meteorological and atmospheric chemistry monitoring communities is needed to tackle the challenges of OVOC monitoring, such as the lack of stable and SI-traceable calibration standards (i.e. RGMs and working standards). Besides this collaboration, other research applications, such as modelling and remote sensing, may benefit from the transfer of SI traceability to monitoring stations.

The effects of climate change on plants are particularly pronounced in the Arctic region. Warming relaxes the temperature and nutrients boundaries that limit tundra plant growth. Increased resource availability under future climate conditions may induce a shift from a conservative economic strategy to an acquisitive one. Following the leaf economics spectrum that hypothesizes a strategy gradient between survival, plant size and costs for the photosynthetic leaf area, light absorption of tundra plants may increase. We investigated climate change effects on light absorptance and the relationship between light absorptance (fraction of absorbed photosynthetically active radiation, FAPAR) and structural and nutritional leaf traits, performing a soil warming and surface soil fertilization experiment on two deciduous tundra shrub species. Our results show that fertilization and warming combined increase light absorptance in Arctic shrubs and that FAPAR is correlated with leaf nutrients but not with structural leaf traits. This indicates an economic strategy shift of shrubs from conservative to acquisitive induced by warming and fertilization combined. We found species‐specific differences: FAPAR was influenced by warming alone in Betula nana but not in Salix pulchra, and FAPAR was correlated with leaf phosphorus in B. nana but not in S. pulchra. We attribute this to water limitation of B. nana that generally grows in drier areas within the study site compared to S. pulchra. We conclude that FAPAR is a measure that opens up more possibilities to estimate nutritional leaf traits and nutrient cycles, plant economic strategies, and ecological feedbacks of the tundra ecosystem on broader scales.