The bioavailability and human health risks of As, Pb, Ni, Co, Cr and Cd in fine particulate matter (PM) at an urban site on a National highway in Agra, India were investigated. Inductively coupled plasma-optical emission spectrometer was used for metal analysis in sequentially extracted samples to ascertain the highly mobile, reducible, bioavailable and immobile fractions of the metals. Cancer risk resulting from inhalation, dermal and ingestion exposure to each metal in these fractions was calculated according to US EPA models. The average mass concentration of PM was 87.16 ± 62.51 μg/m. Cr, Ni and Pb were the most abundant metals. The results showed that Pb and Cr were higher in the mobile fraction. Cd and Co had high bioavailability. Ingestion is the major exposure pathway for all heavy metals except Cr to infants, children and adults followed by inhalation and dermal contact. The cumulative risk for Cr(VI) due to dermal and inhalation routes exceed the maximum acceptable limit for children of age 1-7 years, 8-15 years and adults when total concentration is considered, but the estimated risks are within the acceptable limit when the bioavailable, water soluble and mobile fraction are taken into account. Hence the study shows that children and adults living in the vicinity of this site are more susceptible, hence more attention should be paid to protect them from pollution hazards. The study indicates the importance of metal speciation in assessing associated human health risks.
Aerosol samples in the dual-phase (gaseous and particulate) were collected simultaneously for the first time in Agra at a rural and a traffic dominated site during post-monsoon and winter seasons to investigate the gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs). The samples were collected using a high volume sampler on quartz micro-fiber filter papers and polyurethane foam plugs for particulate and gas phases respectively. The samples were extracted in a mixture of DCM and n-hexane. 16 priority PAHs and two nitro-PAHs were analyzed using gas chromatograph-mass spectrometry. The total concentration of PAHs (gas + particulate) was 4015 and 624 ng m at the traffic and rural sites respectively. Two and three ring PAHs were dominant in the gas phase while four, five and six ring PAHs were abundant in the particle phase. A statistically significant correlation (r = 0.69-0.98, p < 0.001) for log Kvs. was obtained for individual PAHs at both sites where slopes varied between -2.83 and -0.04 at the traffic site and from -3.15 to -0.06 at the rural site. Regression statistics of Clausius-Clapeyron plots suggest that the concentration of highly volatile PAHs in the atmosphere is influenced by temperature. The gas-particle partitioning coefficient K in its logarithmic form correlated with 1/T (r = 0.5-0.95, p < 0.001) and a positive slope for individual PAHs was found. In health risk assessment DbA was found to be the most carcinogenic and mutagenic as compared to other PAHs followed by BaP. 1-NPyr had a larger contribution to BaP-TEQ than 3-NFla.
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