Chemical fractionation, bioavailability, and health risks of heavy metals in fine particulate matter at a site in the Indo-Gangetic Plain, India

In the present study, the distribution and chemical fractionation of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in PM_2.5 collected at Sikandarpur in Agra from September 2015 to February 2016 were carried out to evaluate their mobility potential, environmental, and human health risk through inhalation. Sequential extraction procedure was applied to partition the heavy metals into four fractions (soluble and exchangeable fraction (F1); carbonates, oxides, and reducible fraction (F2); bound to organic matter, oxidizable, and sulphidic fraction (F3); and residual fraction (F4)) in PM_2.5 samples. The metals in each fraction were analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Daily PM_2.5 concentration ranged between 13 and 238 μg m^-3 during the study period. For more than 92% of the days, the mass concentrations were greater than the National Ambient Air Quality Standard (NAAQS) set at 60 μg m^-3. The total mass concentration of the eight metals was 3.3 μg m^-3 that accounted for 2.5% of the PM_2.5 mass concentration and followed the order Fe > Zn > Cu > Mn > Pb > Ni > Cd > Cr in dominance. The carcinogenic metals (Cd, Cr, Ni, and Pb) comprised 10% of the total metal determined. Almost all the metals had the highest proportion in the residual fraction (F4) except Ni, which had the highest proportion in the reducible fraction (F2). Chemical fractionation and contamination factor (CF) showed that Pb and Ni are readily mobilized and more bioavailable. Risk assessment code (RAC) showed that Cd, Cu, Mn, Ni, Pb, and Zn had medium environmental risk, while Cr and Fe had low risk. When the bioavailable (F1 + F2) concentrations were applied to calculate non-carcinogenic and carcinogenic risk, the results showed that the value of hazard index (HI) for toxic metals was 1.7 for both children and adults through inhalation. The integrated carcinogenic risk was 1.8 × 10^-6 for children and 7.3 × 10^-6 for adults, with both values being higher than the precautionary criterion (1 × 10^-6). Enrichment factor (EF) calculations showed that Cd, Pb, Zn, and Ni were enriched being contributed by anthropogenic activities carried out in the industrial sectors of the city.