Electrochemical sensors applied to pollution monitoring: Measurement error and gas ratio bias — A volcano plume case study

https://doi.org/10.1016/j.jvolgeores.2014.02.023Get rights and content

Highlights

  • Quantification of electrochemical sensor response to fluctuating gas concentrations

  • Finite sensor response time causes hysteresis scatter and bias in derived gas ratio.

  • Effect demonstrated in volcanic plume and reproduced by sensor response model

  • Integrating sensor output across plume episodes can yield more accurate gas ratios.

  • Multi-Gas ratios from sensors with mismatched response times may need revisiting.

Abstract

There is an increasing scientific interest in the use of miniature electrochemical sensors to detect and quantify atmospheric trace gases. This has led to the development of ‘Multi-Gas’ systems applied to measurements of both volcanic gas emissions, and urban air pollution. However, such measurements are subject to uncertainties introduced by sensor response time, a critical issue that has received limited attention to date. Here, a detailed analysis of output from an electrochemical SO2 sensor and two H2S sensors (contrasting in their time responses and cross-sensitivities) demonstrates how instrument errors arise under the conditions of rapidly fluctuating (by dilution) gas abundances, leading to scatter and importantly bias in the reported gas ratios. In a case study at Miyakejima volcano (Japan), electrochemical sensors were deployed at both the crater-rim and downwind locations, thereby exposed to rapidly fluctuating and smoothly varying plume gas concentrations, respectively. Discrepancies in the H2S/SO2 gas mixing ratios derived from these measurements are attributed to the sensors' differing time responses to SO2 and H2S under fluctuating plume conditions, with errors magnified by the need to correct for SO2 interference in the H2S readings. Development of a sensor response model that reproduces sensor t90 behaviour (the time required to reach 90% of the final signal following a step change in gas abundance) during calibration enabled this measurement error to be simulated numerically. The sensor response times were characterised as SO2 sensor (t90 ~ 13 s), H2S sensor without interference (t90 ~ 11 s), and H2S sensor with interference (t90 ~ 20 s to H2S and ~ 32 s to SO2). We show that a method involving data integration between periods of episodic plume exposure identifiable in the sensor output yields a less biased H2S/SO2 ratio estimate than that derived from standard analysis approaches. For the Miyakejima crater-rim dataset this method yields highly correlated H2S and SO2 abundances (R2 > 0.99) and the improved crater-rim data analysis combined with downwind measurements yields H2S/SO2 = 0.11 ± 0.01. Our analysis has significant implications for the reliance that can be placed on ‘Multi-Gas’-derived gas ratios, whether for volcanological or other purposes, in the absence of consideration of the complexities of sensor response times.

Introduction

The commercial development of low-cost, lightweight electrochemical gas sensors (e.g. as manufactured by Alphasense, CityTech, Membrapor), with low power requirements, brings new opportunities within environmental science for in-situ monitoring of atmospheric gases. The incorporation of electrochemical sensors into ‘Multi-Gas’ systems used for volcano monitoring has enabled a range of gases (including H2S, SO2, CO, H2, HCl) to be characterised in volcanic plumes (e.g. see Roberts et al., 2012 and references therein). Temporal variations in volcanic gas composition (as identified from gas ratios) can be used to infer changes in subsurface processes and inform long-term volcano hazard monitoring (e.g. Shinohara et al., 2008, Aiuppa et al., 2009). Measurements of volcanic gas emissions also inform the assessment of downwind plume impacts on the atmosphere and ecosystems. Recently, similar miniature electrochemical sensors have also been deployed in networks to characterise urban pollution (Hasenfratz et al., 2012, Li et al., 2012, Mead et al., 2013), using both fixed stations and mobile sensors (e.g. carried by cyclists, pedestrians and on urban tramways).

A challenge in both urban and volcanic environments is to quantify gas abundance from the sensor current or voltage output. The sensor is exposed to complex mixtures of gases whose abundances may fluctuate rapidly, due to close proximity to the pollution source(s), in-homogenous dilution by turbulent eddies or local wind field variations affecting exposure of the sensor. The sensor itself has a finite response time, typically 10–30 s to reach 90% of signal (see Manufacturer's datasheets (Alphasense.com) and Roberts et al., 2012, Mead et al., 2013). In such a period, gas exposure to a volcanic plume at a given location may vary substantially as dictated by the source dynamics and changing wind field. Physical limitations to the time-response of electrochemical sensing devices include the rate of diffusion of species within the sensor, which can be compounded by absorption and desorption of gases from surfaces within the instrument, e.g. for HCl (Roberts et al., 2012). For miniature electrochemical sensors (~ cm, < 10–20 g), a relatively fast (10–30 s) response time has been achieved through novel sensor design minimising distances between the electrodes, electrolyte and gas diffusion barrier, resulting in very small, low cost and low power sensing devices. Where weight and power requirements allow, electrochemical detector sensitivity can be improved and time-responses reduced to just a few seconds by using portable (~ 2 kg) instruments (Interscan, Inc.) e.g. as deployed by Kelly et al. (2013) for in-situ measurements of H2S and SO2 alongside a UV ozone spectrometer in Redoubt volcano plume.

Determining the measurement uncertainties under complex, heterogeneous plume conditions is non-trivial if gas fluctuations occur on similar timescales to the sensor response, and particularly where cross-sensitivities also need to be subtracted in post-processing: the sensor output is a function of its time-dependent response(s) to its recent exposure to (multiple) gases whose abundances may rapidly fluctuate with time. In other words, gas ratios computed for an unvarying source will show variations (artefacts) related to the exposure time histories and sensor responses. This can be a particular issue where sensors are exposed to intermittent ‘puffs’ of volcanic plume, and if attempts are made to identify rapid fluctuations in source composition. Such measurement errors have not been considered in detail to date in volcanic gas ratios reported from Multi-Gas systems. Here, careful analysis of H2S and SO2 electrochemical sensor measurements of the plume of Miyakejima volcano (Japan), at both crater-rim and downwind locations (where gas abundances fluctuate to contrasting extents), are used to identify these sources of error. The focus is how finite (and contrasting) response times of the sensors can act to introduce measurement uncertainties and bias in the reported gas ratios (e.g. H2S/SO2) under rapidly fluctuating gas concentrations (particularly in cases where interferences are subtracted in data post-processing). Sensor response modelling and a forward ‘instrument model’ are developed to illustrate Multi-Gas instrument behaviour. Improved data analysis approaches are discussed, including sensor response modelling (Roberts et al., 2012) and an integrated data analysis method. The aim is to highlight a source of inaccuracy in Multi-Gas monitoring of volcano emissions and their reported gas ratios (e.g. H2S/SO2, CO2/SO2), and to outline methods for improved quantitative characterisation of complex fluctuating plume environments (e.g. volcanic and urban) by electrochemical sensors.

Section snippets

Electrochemical sensing of pollutant gases

An overview of the use of miniature electrochemical sensors to monitor volcanic plume gases (SO2, H2S, HCl, CO, H2) and urban pollution (CO, NO, NO2) is given by Roberts et al. (2012) and Mead et al. (2013), the former also detailing use of electrochemical sensors within in-situ (Multi-Gas) monitoring systems in volcanology (e.g. Aiuppa et al., 2005a; Shinohara, 2005, Witt et al., 2008b). Issues concerning the application of electrochemical and other miniature sensors to environmental

Materials and methods

The ‘Multi-Gas’ instrument used in this study incorporates Alphasense electrochemical sensors, SO2-AF, H2S-A1, and NO2-A1, as described by Roberts et al. (2012). Gas is drawn over the sensors by a miniature pump, a filter (hepa-vent) prevents particles > 0.3 μm entering the instrument and each sensor also includes its own dust filter. Minimal use of tubing limits potential adsorption of gases within the instrument. Calibrations were performed in October 2007, shortly after the fieldwork, exposing

Discrepancies in H2S/SO2 gas ratios detected at Miyakejima volcano

The 1 Hz electrochemical sensor measurements of SO2 and H2S in Miyakejima volcano plume, as detected both downwind and in the near-source (crater-rim) plume, are illustrated in Fig. 1 as scatter plots of H2S versus SO2 mixing ratios in the downwind and crater-rim plume. H2S is derived from either the NO2-A1 sensor (with no interference), or the H2S-A1 sensor (where the interference from SO2 has been subtracted). Robust regression is used to determine H2S/SO2, which yields very similar gradient

Implications for Multi-Gas volcano monitoring, and wider electrochemical sensor applications

Through detailed investigation of Multi-Gas measurements at Miyakejima volcano, this study has shown how errors can manifest in the determination of gas ratios from in-situ sensors with non-identical response times, when sensors are exposed to fluctuating plume gas concentrations (e.g. at the crater-rim), and particularly when interferences need to be subtracted in the data analysis. A key question is to what extent this source of measurement error may influence reported volcanic gas ratios

Conclusions

There is a growing interest in the use of electrochemical sensors within environmental science as a low-cost, low-power and highly portable gas measurement technique to detect and characterise sources of and exposure to pollution. Such sensors are commonly deployed alongside other in-situ detectors (e.g. infra-red sensors for CO2, H2O) for characterisation of gas mixtures such as volcanic emissions. Here we show how the non-instantaneous time response of electrochemical sensors can lead to

Acknowledgements

We are particularly grateful to Darryl Dawson of Alphasense Ltd who provided sensor calibrations and measurement advice. TJR acknowledges a NERC studentship (2006-9) during which the instrument was deployed, and further funding from LABEX VOLTAIRE (VOLatils – Terre Atmosphère Interactions – Ressources et Environnement) ANR-10-LABX-100-01 (2011-20). TJR is grateful to C.F. Braban, P.T. Griffiths, R.A. Freshwater, R.A. Cox and R.L. Jones for advice during instrument development, and we thank E.

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