Emissions of Intermediate-Volatility and Semi-Volatile Organic Compounds from Domestic Fuels Used in Delhi, India
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Atmos. Chem. Phys., 21, 2407–2426, 2021 https://doi.org/10.5194/acp-21-2407-2021 © Author(s) 2021. This work is distributed under the Creative Commons Attribution 4.0 License. Emissions of intermediate-volatility and semi-volatile organic compounds from domestic fuels used in Delhi, India Gareth J. Stewart1, Beth S. Nelson1, W. Joe F. Acton2,a, Adam R. Vaughan1, Naomi J. Farren1, James R. Hopkins1,3, Martyn W. Ward1, Stefan J. Swift1, Rahul Arya4, Arnab Mondal4, Ritu Jangirh4, Sakshi Ahlawat4, Lokesh Yadav4, Sudhir K. Sharma4, Siti S. M. Yunus5, C. Nicholas Hewitt2, Eiko Nemitz6, Neil Mullinger6, Ranu Gadi7, Lokesh K. Sahu8, Nidhi Tripathi8, Andrew R. Rickard1,3, James D. Lee1,3, Tuhin K. Mandal4, and Jacqueline F. Hamilton1 1Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UK 2Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK 3National Centre for Atmospheric Science, University of York, York, YO10 5DD, UK 4CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi, Delhi 110012, India 5School of Water, Energy and Environment, Cranfield University, Cranfield, MK43 0AL, UK 6UK Centre for Ecology and Hydrology, Bush Estate, Penicuik, EH26 0QB, UK 7Indira Gandhi Delhi Technical University for Women, Kashmiri Gate, New Delhi, Delhi 110006, India 8Physical Research Laboratory (PRL), Ahmedabad 380009, India anow at: School of Geography, Earth and Environmental Sciences, University of Birmingham, B15 2TT, Birmingham, UK Correspondence: Jacqueline F. Hamilton ([email protected]) Received: 17 August 2020 – Discussion started: 25 August 2020 Revised: 2 December 2020 – Accepted: 22 December 2020 – Published: 18 February 2021 Abstract. Biomass burning emits significant quantities of The method was analysed for suitability to make quantitative intermediate-volatility and semi-volatile organic compounds measurements of I/SVOCs using SPE discs. Analysis of SPE (I/SVOCs) in a complex mixture, probably containing many discs indicated phenolic and furanic compounds were impor- thousands of chemical species. These components are sig- tant for gas-phase I/SVOC emissions and levoglucosan to the nificantly more toxic and have poorly understood chemistry aerosol phase. Gas- and particle-phase emission factors for compared to volatile organic compounds routinely quantified 21 polycyclic aromatic hydrocarbons (PAHs) were derived, in ambient air; however, analysis of I/SVOCs presents a dif- including 16 compounds listed by the US EPA as priority ficult analytical challenge. pollutants. Gas-phase emissions were dominated by smaller The gases and particles emitted during the test combus- PAHs. The new emission factors were measured (mg kg−1) tion of a range of domestic solid fuels collected from across for PAHs from combustion of cow dung cake (615), munic- Delhi were sampled and analysed. Organic aerosol was col- ipal solid waste (1022), crop residue (747), sawdust (1236), lected onto Teflon (PTFE) filters, and residual low-volatility fuelwood (247), charcoal (151) and liquefied petroleum gas gases were adsorbed to the surface of solid-phase extraction (56). (SPE) discs. A new method relying on accelerated solvent ex- The results of this study indicate that cow dung cake and traction (ASE) coupled to comprehensive two-dimensional municipal solid waste burning are likely to be significant gas chromatography with time-of-flight mass spectrometry PAH sources, and further study is required to quantify their (GC × GC–ToF-MS) was developed. This highly sensitive impact alongside emissions from fuelwood burning. and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be de- tected. A total of 15 %–100 % of gas-phase emissions and 7 %–100 % of particle-phase emissions were characterised. Published by Copernicus Publications on behalf of the European Geosciences Union. 2408 G. J. Stewart et al.: Emissions of I/SVOCs from domestic fuel combustion in India 1 Introduction The reason for this is because of the exponential growth of potential isomers with carbon number, which results in Biomass burning is one of the most important global sources a large number of coeluting peaks (Goldstein and Galbally, of trace gases and particles to the atmosphere (Simoneit, 2007). The high resolution of two-dimensional gas chro- 2002; Chen et al., 2017; Andreae, 2019), with residen- matography (GC × GC) has been demonstrated as an ideal tial solid-fuel combustion and wildfires emitting significant technique to overcome this issue when analysing complex quantities of organic matter (Streets et al., 2003; Barboni organic samples in both gas (Lewis et al., 2000; Stewart et et al., 2010; Chen et al., 2017; Liu et al., 2017; Kiely et al., 2021a) and particle phases (Hamilton et al., 2004; Lyu al., 2019). Emissions of volatile organic compounds (VOCs) et al., 2019). The application of GC × GC to biomass burn- and particulate matter (PM) from biomass burning are of in- ing emissions has shown hundreds of gaseous I/SVOCs us- terest due to their detrimental impact on air quality. VOCs ing adsorption–thermal-desorption cartridges (Hatch et al., react to form ozone and secondary organic aerosol (SOA). 2015) or solid-phase extraction (SPE) discs (Hatch et al., Intermediate-volatility and semi-volatile organic compounds 2018). GC × GC has also been used to analyse the parti- (I/SVOCs) are also a significant emission from biomass burn- cle phase with samples collected onto PTFE or quartz fil- ing (Stockwell et al., 2015; Koss et al., 2018). I/SVOCs are ters (Hatch et al., 2018; Jen et al., 2019), with the latter an important class of air pollutant due to their contribution study quantifying 149 organic compounds which accounted to aerosol formation (Bruns et al., 2016; Lu et al., 2018). for 4 %–37 % of the total mass of organic carbon. The pro- I/SVOC emissions are poorly, if at all, represented in regional cess used by Hatch et al. (2018) demonstrated high recov- inventories and chemical transport models. Consequently, eries of non-polar species from PTFE filters, with lower re- their impacts to air quality in developing regions, where coveries from SPE discs. This study highlighted the need for solid-fuel combustion is a dominant fuel source, are not well further evaluation of samples collected onto PTFE filters and understood. Recent studies have shown that the inclusion of SPE discs, ideally improving the method to remove undesir- I/SVOCs leads to better agreement between modelled and able steps such as trimethylsilylation derivatisation, the use measured values (Ots et al., 2016; Woody et al., 2016; Jathar of pyridine and centrifuging, which led to high evaporative et al., 2017; Murphy et al., 2017). Global I/SVOC emissions losses. The need to develop improved sampling and measure- to the atmosphere from biomass burning were estimated to ment techniques for I/SVOCs has also been highlighted. This be ∼ 54 Tg yr−1 from 2005–2008 (Hodzic et al., 2016), with is because these species often do not transmit quantitatively I/SVOCs contributing in the range 8–15.5 Tg yr−1 to SOA through the inlet and tubing when measured using online gas- (Cubison et al., 2011; Hodzic et al., 2016). phase techniques (Pagonis et al., 2017). SOA formation from biomass burning emissions is poorly Residential combustion, agricultural crop residue burning understood globally. Important factors include the formation and open municipal solid waste burning in the developing of less volatile products from the oxidation of non-methane world are large, poorly characterised pollution sources with volatile organic compounds (NMVOCs) which partition into the potential to have a significant impact on local and re- the aerosol phase, heterogeneous oxidation of aerosol phase gional air quality, impacting human health (Venkataraman et organics, and plume dilution followed by evaporation and al., 2005; Jain et al., 2014; Wiedinmyer et al., 2014). Haz- further gas-phase oxidation (Lim et al., 2019). Ahern et ardous indoor air pollution from combustion of solid fuels al. (2019) showed that for burning of biomass needles, bio- has been shown to be the most important factor from a range genic VOCs were the dominant class of SOA precursor. This of 67 environmental and lifestyle risk factors causing disease study also found that for wire grass, furans were the most im- in South Asia (Lim et al., 2012). Despite this, nearly 76 % portant SOA precursor. Bruns et al. (2016) showed that SOA of rural Indian households depend on solid biomass for their formation from combustion of beech fuelwood was domi- cooking needs (Gordon et al., 2018), using biofuels such as nated by 22 compounds, with phenol, naphthalene and ben- fuelwood, cow dung cake and crop residue. Combustion of- zene contributing up to 80 % of the observed SOA. SOA for- ten takes place indoors, without efficient emission controls, mation from biomass burning has been shown to be signifi- which significantly increases the mean household concentra- cant in laboratory studies, with SOA yields from the burning tion of pollutants, particularly particulate matter with a diam- of western US fuels reported to be 24 ± 4 % after 6 h and eter less than 2.5 µm (PM2:5). The health effects from this are 56 ± 9 % after 4 d (Lim et al., 2019). However, the effect of significant, with an estimated 3.8 million premature deaths atmospheric ageing on I/SVOCs still remains poorly under- globally due to inefficient indoor combustion from cooking stood (Liu et al., 2017; Decker et al., 2019; Sengupta et al., (WHO, 2018). 2020). Few detailed studies examining the composition of Better understanding of the quantity and composition of I/SVOC emissions from solid-fuel combustion sources from I/SVOCs from biomass burning is needed to evaluate their South Asia have been conducted. Sheesley et al. (2003) used impact on the atmosphere. This is a difficult analytical task, solvent extraction followed by GC–MS to produce emission which is not well suited to conventional analysis with gas factors and examine molecular markers from combustion of chromatography coupled to mass spectrometry (GC–MS).