Using functionalized asphaltenes as effective adsorbents for the removal of chromium and lead metal ions from aqueous solution.

For the first time, functionalized asphaltene has been designed, synthesized, and used for the removal of heavy metals from the water. Asphaltene was separated from the crude oil with the addition of n-alkanes. Asphaltene having a complex chemical structure including multilayered and clustered aromatic fused rings bearing aliphatic chains. Asphaltene also contains heteroatoms like N, S, and O atoms along with Ni and V as prominent trace metals. On functionalization of asphaltene with nitric acid, the aliphatic chains and some of the naphthenic rings broke down and developed -COOH, -CO, C-O, and other oxygen functional groups which are playing key roles as surface-active agents in the removal of the heavy metals via chemisorption. The study was conducted using different parameters such as dose, time, pH, and concentration. The adsorption efficiency for this material at pH 4 is excellent for the removal of chromium and lead. The Langmuir, Freundlich and Temkin adsorption isotherm models as well as Lagergren pseudo second-order kinetic model were investigated. The positive enthalpies ΔHs confirm that the adsorption process is endothermic and the negative free energies ΔGs confirm the spontaneity of the process. The good efficiency of the adsorption implies the efficacy in the removal of the heavy metal ions, as well as the good efficiency in desorption, which implies the excellent recovery of the adsorbent. The effective reusability of this adsorbent makes it applicable for industrial water treatment from contaminants.

Temporal and spatial variations of PM2.5 organic and elemental carbon in Central India.

This study describes spatiotemporal patterns from October 2015 to September 2016 for PM2.5 mass and carbon measurements in rural (Kosmarra), urban (Raipur), and industrial (Bhilai) environments, in Chhattisgarh, Central India. Twenty-four-hour samples were acquired once every other week at the rural and industrial sites. Twelve-hour daytime and nighttime samples were acquired either a once a week or once every other week at the urban site. Each site was equipped with two portable, battery-powered, miniVol air samplers with PM2.5 inlets. Annual average PM2.5 mass concentrations were 71.8 ± 27 µg m-3 at the rural site, 133 ± 51 µg m-3 at the urban site, and 244.5 ± 63.3 µg m-3 at the industrial site, ~ 2-6 times higher than the Indian Annual National Ambient Air Quality Standard of 40 µg m-3. Average monthly nighttime PM2.5 and carbon concentrations at the urban site were consistently higher than those of daytime from November 2015 to April 2016, when temperatures were low. Annual average total carbon (TC = OC + EC) at the urban (46.8 ± 23.8 µg m-3) and industrial (98.0 ± 17.2 µg m-3) sites also exceeded the Indian PM2.5 NAAQS. TC accounted for 30-40% of PM2.5 mass. Annual average OC ranged from 17.8 ± 6.1 µg m-3 at the rural site to 64 ± 9.4 µg m-3 at the industrial site, with EC ranging from 4.51 ± 2.2 to 34.01 ± 7.8 µg m-3. The average OC/EC ratio at the industrial site (1.88) was 18% lower than that at the urban site and 52% lower than that at the rural site. OC was attributed to 43.0% of secondary organic carbon (SOC) at the rural site, twice that estimated for the urban and industrial sites. Mortality burden estimates for PM2.5 EC are 4416 and 6196 excess deaths at the urban and industrial sites, respectively, during 2015-2016.

Chemical fractionation of particulate-bound metal(loid)s to evaluate their bioavailability, sources and associated cancer risk in India.

Eleven potentially toxic metal(loid)s (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), proven source markers of mineral based coal-fired industrial emissions and vehicular exhausts, were analysed using the four steps sequential extraction method to evaluate metal(loid)s concentration, in total and fractions of bioavailable and non-bioavailable for fine (PM2.5) and coarse (PM10-2.5) particulate modes. A total of 26-day-wise samples with three replications (total number of samples = 78) were collected in January-December 2019 for each PM10 and PM2.5 at an urban-residential site in India. In both the coarse and fine particulate modes, Pb and Cr have respectively shown the highest and lowest total concentrations of the measured metal(loid)s, indicating the presence of coal-fired power plants and heavy vehicular activities near to study area. In addition, Mn has shown highest bioavailable fraction for both coarse and fine particulate modes. More than 50 % of metal(loid)s concentration, in total to a bioavailable fraction (BAF) were observed in case of As, Cd, Cr, Co, Mn, Ni, and Pb of PM2.5. Mn and Zn have shown similar behaviour in the case of coarse particulate mode. Source apportionment of metal(loid)s bioavailable fractions using positive matrix factorization (PMF 5.0) has found three significant sources: crustal and natural dust (30.04 and 39 %), road traffic (49.57 and 20 %), and industrial emission (20.39 and 41 %) for coarse and fine particulate mode, respectively. Cancer risk through the inhalation pathway was high in total concentration but lower in BAF concentration in both age groups (children and adults).

Household solid fuel burning emission characterization and activity levels in India.

Emission factors (EFs) of PM2.5, carbon fractions, major ionic (K+, Ca2+, NH4+, SO42-, NO3- and Cl-) and elemental (Al, Cr, Cu and Fe) species from combustion of commonly used household solid fuel were determined in 10 different states in India during cooking practices. The study involved sampling during actual household cooking involving use of a variety of fuels including coal balls (CB), fuel wood (FW), dung cakes (DC), crop residues (CR), mixed fuels (MF: dung cakes + fuel woods). Species-wise highest EFs (g·kg-1) were: 34.16 ±â€¯10.1 for PM2.5 (CB), 14.18 ±â€¯5.8 for OC (CB), 2.33 ±â€¯1.4 for EC (DC), 1.03 ±â€¯0.2 for K+ (CR), 2.21 ±â€¯0.6 NH4+ (DC), 0.61 ±â€¯0.2 for NO3- (CB), 0.59 ±â€¯0.1 for SO42- (CB), 0.69 ±â€¯0.1 for Cl- (CR) among the fuels. Higher OC EFs for CB could be attributed to higher moisture content (>13%) in coal-powder that is used to handmade coal balls. It is observed that, in general, OC3 and EC1 were the dominant thermally evolved carbon mass fractions. The study averaged MCE values were in the range 0.93-0.98, which could be attributed to higher variability in flaming and smoldering episodes during the combustion of selected fuels. Sum of ionic EFs for emissions from DC, CR and MF were found to be higher than those observed for FW and CB. The K+/EC and Cl-/EC (~1) ratios could be better indicators of CR fuels to differentiate it from FW, whereas NH4+/EC (~1) is suitable to indicate DC. Average annual emission estimates of PM2.5 (2.00 ±â€¯0.53 Tg·yr-1), OC (0.86 ±â€¯0.23 Tg·yr-1) and EC (0.11 ±â€¯0.02 Tg·yr-1) for tested fuels are evaluated to be contributing 27, 15 and 4% of total PM2.5, OC and EC, respectively, toward annual emission budget from different anthropogenic activities in India.

Coarse particle (PM10-2.5) source profiles for emissions from domestic cooking and industrial process in Central India.

To develop coarse particle (PM10-2.5, 2.5 to 10µm) chemical source profiles, real-world source sampling from four domestic cooking and seven industrial processing facilities were carried out in "Raipur-Bhilai" of Central India. Collected samples were analysed for 32 chemical species including 21 elements (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, S, Sb, Se, V, and Zn) by atomic absorption spectrophotometry (AAS), 8 water-soluble ions (Na+, K+, Mg2+, Ca2+, Cl-, F-, NO3-, and SO42-) by ion chromatography, ammonium (NH4+) by spectrophotometry, and carbonaceous fractions (OC and EC) by thermal/optical transmittance. The carbonaceous fractions were most abundant fraction in household fuel and municipal solid waste combustion emissions while elemental species were more abundant in industrial emissions. Most of the elemental species were enriched in PM2.5 (<2.5µm) size fraction as compared to the PM10-2.5 fraction. Abundant Ca (13-28%) was found in steel-rolling mill (SRM) and cement production industry (CPI) emissions, with abundant Fe (14-32%) in ferro-manganese (FEMNI), steel production industry (SPI), and electric-arc welding emissions. High coefficients of divergence (COD) values (0.46 to 0.88) among the profiles indicate their differences. These region-specific source profiles are more relevant to source apportionment studies in India than profiles measured elsewhere.