Morphology, molecular structure, and stable carbon isotopic composition of black carbon (BC) in urban topsoils

Abstract

Urban soils contain significant amounts of black carbon (BC) from biomass and fossil fuel combustion and regard to be a pool of BC. BC in urban soils has multiple effects on environmental processes in urban system, such as global climate change, air quality, and public health. Urban topsoil samples (0–10 cm) were collected from Anshan, Liaoning Province, northeast China, which is one of the most important old steel industrial bases in China. The BC in urban topsoils was extracted using the density method. Their chemical composition, morphology, molecular structure, and stable carbon isotopic composition were examined using elemental analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and stable carbon isotope (δ¹³C). Elemental analysis shows that carbon content in the BC of studied soils ranged from 64.5 to 78.4%, with the average more than 70%. The O/C atomic ratio of BC is on average 0.18. The BC particle displays different morphology, including porous spherical, irregular porous fragmentary, and blocky shapes. The porous spherical BC particles has atomic molar O/C ratio determined by SEM-EDS ranging from 0.04 to 0.37. XRD indicates that BC exists in mainly combining with mineral phases hematite (Fe₂O₃), kaolinite (Al₂Si₂O₅(OH)₄), quartz (SiO₂), and calcite (CaCO₃). The FTIR spectra of BC particles show major bands at approximately 3400 cm⁻¹ (O–H), 2920 cm⁻¹ (C = H), 1600 cm⁻¹ (C = C), 1230 cm⁻¹ (C = O), and 1070 cm⁻¹ (C = O). The stable carbon isotope (δ¹³C) of BC ranges from −24.48 to −23.18‰ with the average of −23.79 ± 0.39‰. The concentration of BC in the industrial area is significantly (p < 0.05) higher than that in the roadside area. The BC of industrial area is characterized by porous spherical structure, suggesting that they are mainly derived from fossil fuel combustion. Results indicated that a combination of atomic O/C ratio, porous structure, and stable carbon isotopic (δ¹³C) of BC could reflect effectively the origin of BC in urban topsoils. It could conclude that BC in Anshan urban topsoil was mainly from fossil fuel combustion.