Electrochemical ozone sensors : A miniaturised alternative for ozone measurements in laboratory experiments and air-quality monitoring

Ozone (O3) measurements are a critical component of air quality management and many atmospheric chemistry laboratory experiments. Conventional ozone monitoring devices based on UV absorption are relatively cumbersome and expensive, and have a relative high power consumption that limits their use to fixed sites. In this study electrochemical O3 sensors (OXB421, Alphasense) were used in a miniaturised O3 measurement device combined with LabJack and Labview data acquisition (DAQ). The device required a power supply of 5 V direct current (VDC) with a total power consumption of approximately 5 W. Total weight was less than 0.5 kg, low enough for portable in situ field deployment. The electrochemical O3 sensors produced a voltage signal positively proportional to O3 concentrations over the range of 5 ppb–10 ppm. There was excellent agreement between the performances of two O3 sensors with a good linear coefficient (R2 = 0.9995). The influences of relative humidity (RH) and gas sample flow rate on sensor calibrations and sensitivities have been investigated separately. Coincident calibration curves indicate that sensor performances were almost identical even at different RHs and flow rates after a re-zeroing process to offset the sensor baseline drifts. Rapid RH changes (∼20%/min) generate significant and instant changes in sensor signal, and the sensors consistently take up to 40 min to recover their original values after such a rapid RH change. In contrast, slow RH changes (∼0.1%/min) had little effect on sensor response. To test the performance of the miniaturised O3 device for real-world applications, the O3 sensors were employed for (i) laboratory experiments to measure O3 loss by seawater uptake and (ii) air quality monitoring over an 18-day period. It was found that ozone uptake by seawater was linear to the volume of linoleic acid on a sea surface microlayer and the calculated uptake coefficients based on sensor measurements were close to those from previous studies. For the 18-day period of air quality monitoring the corrected data from the O3 sensor was in a good agreement with those obtained by reference UV O3 analyser with an r2 of 0.83 (n = 8502). The novelty of this study is that the electrochemical O3 sensor was comprehensively investigated in O3 measurements in both laboratory and ambient air quality monitoring and it can to be a miniaturised alternative for conventional O3 monitoring devices due to its low cost, low power-consumption, portable and simple-conduction properties

Simplified speciation and atmospheric volatile organic compound emission rates from non-aerosol personal care products

Volatile organic compounds (VOCs) emitted from personal care products (PCPs) can affect indoor air quality and outdoor air quality when ventilated. In this paper, we determine a set of simplified VOC species profiles and emission rates for a range of non-aerosol PCPs. These have been constructed from individual vapor analysis from 36 products available in the UK, using equilibrium headspace analysis with selected-ion flow-tube mass spectrometry (SIFT-MS). A simplified speciation profile is created based on the observations, comprising four alcohols, two cyclic volatile siloxanes, and monoterpenes (grouped as limonene). Estimates are made for individual unit-of-activity VOC emissions for dose-usage of shampoos, shower gel, conditioner, liquid foundation, and moisturizer. We use these values as inputs to the INdoor air Detailed Chemical Model (INDCM) and compare results against real-world case-study experimental data. Activity-based emissions are then scaled based on plausible usage patterns to estimate the potential scale of annual per-person emissions for each product type (eg, 2 g limonene person−1 yr−1 from shower gels). Annual emissions from non-aerosol PCPs for the UK are then calculated (decamethylcyclopentasiloxane 0.25 ktonne yr−1 and limonene 0.15 ktonne yr−1) and these compared with the UK National Atmospheric Emissions Inventory estimates for non-aerosol cosmetics and toiletries

Halocarbons associated with Arctic sea ice

Short-lived halocarbons were measured in Arctic sea-ice brine, seawater and air above the Greenland and Norwegian seas (∼81°N, 2 to 5°E) in mid-summer, from a melting ice floe at the edge of the ice pack. In the ice floe, concentrations of C2H5I, 2-C3H7I and CH2Br2 showed significant enhancement in the sea ice brine, of average factors of 1.7, 1.4 and 2.5 times respectively, compared to the water underneath and after normalising to brine volume. Concentrations of mono-iodocarbons in air are the highest ever reported, and our calculations suggest increased fluxes of halocarbons to the atmosphere may result from their sea-ice enhancement. Some halocarbons were also measured in ice of the sub-Arctic in Hudson Bay (∼55°N, 77°W) in early spring, ice that was thicker, colder and less porous than the Arctic ice in summer, and in which the halocarbons were concentrated to values over 10 times larger than in the Arctic ice when normalised to brine volume. Concentrations in the Arctic ice were similar to those in Antarctic sea ice that was similarly warm and porous. As climate warms and Arctic sea ice becomes more like that of the Antarctic, our results lead us to expect the production of iodocarbons and so of reactive iodine gases to increase

Estimating person-to-person variability in VOC emissions from personal care products used during showering

Abstract An increasing fraction of volatile organic compounds (VOC) emissions come from the domestic use of solvents, contained within myriad commonplace consumer products. Emission rates are often poorly characterized and depend significantly on individual behavior and specific product formulation and usage. Time-concentration profiles of volatile organic compounds (VOCs) arising from the use of a representative selection of personal care products (PCPs) during showering are generated, and person-to-person variability in emissions calculated. A panel of 18 participants used a standardized set of products, dosages, and application times during showering in a controlled indoor bathroom setting. Proton transfer mass spectrometry was used to measure the in-room VOC evolution of limonene (representing the sum of monoterpenes), benzyl alcohol, and ethanol. The release of VOCs had reproducible patterns between users, but noticeable variations in absolute peak concentrations, despite identical amounts of material being used. The amounts of VOC emitted to air for one showering activity were as follows: limonene (1.77 mg ± 42, benzyl alcohol (1.07 mg ± 41, and ethanol (0.33 mg ± 78. Real-world emissions to air were between 1.3 and 11 times lower than bottom-up estimates based on dynamic headspace measurements of product emissions rates, likely a result of PCPs being washed away before VOC evaporation could occur

Does green mean clean? Volatile organic emissions from regular versus green cleaning products

Cleaning products emit a range of volatile organic compounds (VOCs), including some which are hazardous or can undergo chemical transformations to generate harmful secondary pollutants. In recent years, “green” cleaners have become increasingly popular, with an implicit assumption that these are better for our health and/or the environment. However, there is no strong evidence to suggest that they are better for indoor air quality compared to regular products. In this study, the VOC composition of 10 regular and 13 green cleaners was examined by headspace analysis. Monoterpenes were the most prevalent VOCs, with average total monoterpene concentrations of 8.6 and 25.0 mg L-1 for regular and green cleaners, respectively. Speciated monoterpene emissions were applied to a detailed chemical model to investigate the indoor air chemistry following a typical cleaning event. Green cleaners generally emitted more monoterpenes than regular cleaners, resulting in larger increases in harmful secondary pollutant concentrations following use, such as formaldehyde (up to 7%) and PAN species (up to 6%). However, emissions of the most reactive monoterpenes (a-terpinene, terpinolene and a-phellandrene), were observed more frequently from regular cleaners, resulting in a disproportionately large impact on the concentrations of radical species and secondary pollutants that were formed after cleaning occurred

Evaluation of a low-cost optical particle counter (Alphasense OPC-N2) for ambient air monitoring

A fast-growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high-density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision need to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments shows some limitations for measuring mass concentrations of PM1, PM2.5 and PM10. The OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (>85%) and a calibration factor was developed based upon °-Köhler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33% of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20%). Inter-unit precision for the 14 OPC-N2 sensors of 22±13% for PM10 mass concentrations was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are (i) correctly calibrated and (ii) corrected for ambient RH. The level of precision demonstrated between multiple OPC-N2s suggests that they would be suitable devices for applications where the spatial variability in particle concentration was to be determined

Evaluation of a low-cost optical particle counter (Alphasense OPC-N2) for ambient air monitoring

A fast growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision needs to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments demonstrated reasonable agreement for the measured mass concentrations of PM1, PM2.5 and PM10. However, the OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (> 85 %) and a calibration factor was developed based upon κ-Kohler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33 % of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20 %). Reasonable inter-unit precision for the 14 OPC-N2 sensors was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are i) correctly calibrated and ii) corrected for ambient RH. The reasonable level of precision demonstrated between multiple OPC-N2 suggests that they would be suitable device for applications where the spatial variability in particle concentration was to be determined

The impacts of water vapour and co-pollutants on the performance of electrochemical gas sensors used for air quality monitoring

The analytical performance of low cost air pollution sensors under real-world conditions is a key factor that will influence their future uses and adoption. In this study five different electrochemical gas sensors (O3, SO2, CO, NO, NO2) are tested for their performance when challenged with cross interferences of water vapour and other gaseous co-pollutants. These experiments were conducted under both controlled laboratory conditions and during ambient air monitoring in urban background air at a site in York, UK. Signal outputs for O3, SO2 and CO showed a positive linear dependence on relative humidity (RH). The output for the NO sensor showed a negative correlation. The output for the NO2 sensor showed no trend with RH. Potential co-pollutants (O3, SO2, CO, NO2, NO and CO2) were introduced under controlled conditions using gas standards and delivered to each sensor in series along with variable RH. A matrix of cross-interference sensitivities were established which could be used to correct sensor signals. Interference-corrected sensor responses were compared against reference observations over an 18-day period. Once cross interferences had been removed the corrected 5 min averaging data for O3, CO, NO and NO2 sensors showed good agreement with the reference techniques with r2 values of 0.89, 0.76, 0.72, and 0.69, respectively. The SO2 sensor could not be evaluated in ambient air since ambient SO2 was below the sensor limit of detection

The impacts of water vapour and co-pollutants on the performance of electrochemical gas sensors used for air quality monitoring

The analytical performance of low cost air pollution sensors under real-world conditions is a key factor that will influence their future uses and adoption. In this study five different electrochemical gas sensors (O3, SO2, CO, NO, NO2) are tested for their performance when challenged with cross interferences of water vapour and other gaseous co-pollutants. These experiments were conducted under both controlled laboratory conditions and during ambient air monitoring in urban background air at a site in York, UK. Signal outputs for O3, SO2 and CO showed a positive linear dependence on relative humidity (RH). The output for the NO sensor showed a negative correlation. The output for the NO2 sensor showed no trend with RH. Potential co-pollutants (O3, SO2, CO, NO2, NO and CO2) were introduced under controlled conditions using gas standards and delivered to each sensor in series along with variable RH. A matrix of cross-interference sensitivities were established which could be used to correct sensor signals. Interference-corrected sensor responses were compared against reference observations over an 18-day period. Once cross interferences had been removed the corrected 5 min averaging data for O3, CO, NO and NO2 sensors showed good agreement with the reference techniques with r2 values of 0.89, 0.76, 0.72, and 0.69, respectively. The SO2 sensor could not be evaluated in ambient air since ambient SO2 was below the sensor limit of detection