Molecular composition of particulate matter emissions from dung and brushwood burning household cookstoves in Haryana, India

Emissions of airborne particles from biomass burning are a significant source of black carbon (BC) and brown carbon (BrC) in rural areas of developing countries where biomass is the predominant energy source for cooking and heating. This study explores the molecular composition of organic aerosols from household cooking emissions with a focus on identifying fuel-specific compounds and BrC chromophores. Traditional meals were prepared by a local cook with dung and brushwood-fueled cookstoves in a village in Palwal district, Haryana, India. Cooking was done in a village kitchen while controlling for variables including stove type, fuel moisture, and meal. Fine particulate matter (PM_2.5) emissions were collected on filters, and then analyzed via nanospray desorption electrospray ionization–high-resolution mass spectrometry (nano-DESI-HRMS) and high-performance liquid chromatography–photodiode array–high-resolution mass spectrometry (HPLC-PDA-HRMS) techniques. The nano-DESI-HRMS analysis provided an inventory of numerous compounds present in the particle phase. Although several compounds observed in this study have been previously characterized using gas chromatography methods a majority of the species in the nano-DESI spectra were newly observed biomass burning compounds. Both the stove (<i>chulha</i> or <i>angithi</i>) and the fuel (brushwood or dung) affected the composition of organic aerosols. The geometric mean of the PM_2.5 emission factor and the observed molecular complexity increased in the following order: brushwood–<i>chulha </i>(7.3 ± 1.8 g kg⁻¹ dry fuel, 93 compounds), dung–<i>chulha</i> (21.1 ± 4.2 g kg⁻¹ dry fuel, 212 compounds), and dung–<i>angithi</i> (29.8 ± 11.5 g kg⁻¹ dry fuel, 262 compounds). The mass-normalized absorption coefficient (MAC_bulk) for the organic-solvent extractable material for brushwood PM_2.5 was 3.7 ± 1.5 and 1.9 ± 0.8 m² g⁻¹ at 360 and 405 nm, respectively, which was approximately a factor of two higher than that for dung PM_2.5. The HPLC-PDA-HRMS analysis showed that, regardless of fuel type, the main chromophores were C_<i>x</i>H_<i>y</i>O_<i>z</i> lignin fragments. The main chromophores accounting for the higher MAC_bulk values of brushwood PM_2.5 were C₈H₁₀O₃ (tentatively assigned to syringol), nitrophenols C₈H₉NO₄, and C₁₀H₁₀O₃ (tentatively assigned to methoxycinnamic acid)