Profile of atmospheric particulate PAHs near busy roadway in tropical megacity, India.

Objective: This study focuses on the profile of ambient particulate polycyclic aromatic hydrocarbons (PAHs), their seasonal distribution, source identification and human health risk assessment due to inhalation exposure of ambient PAHs in Delhi, India.Materials and Methods: Two sampling sites were chosen, one at roadway (MH) and other at urban background (JNU) site in Delhi. Determination of PAHs was carried with the help of HPLC with UV detector. Principal component analysis and Molecular diagnostic ratios were used for the source apportionment of PAHs. Health risks associated with inhalation of particulate PAHs were assessed using benzo(a)pyrene equivalent concentration and incremental lifetime cancer risk (ILCR) approach.Results: The results showed that the average mass concentration of Σ16 PAHs near roadway (67.8 ± 40.2 ng m-3) is significantly higher than urban background site (56 ± 30 ng m-3). Moreover, source apportionment study indicated that major PAH-emission sources in Delhi NCR are traffic and coal combustion. ILCR values at both the sites fall in the range of 10-2-10-4 that corresponds to the priority risk level (10-3) and higher than the acceptable risk level (10-6).conclusions: The high PAHs concentration at MH site was due to it's nearness to busy traffic area. Thus, the spatial variations in PAHs were influenced by local emission sources. The high PAHs level during the winter season can be due to their higher emissions from local heating sources, shift of gas/particle partitioning toward the particulate phase at low temperature and reduced photochemical degradation of some PAHs in winter. The low level of PAHs in monsoon season can be attributed to their wet scavenging and higher percentage in vapor phase. PCA showed that the emissions from vehicles predominate at MH site; whereas, coal combustion and traffic both are the significant PAHs sources at JNU site. Health risk assessment revealed that the highest exposure risks occur at busy traffic site, thereby indicating a significantly higher health risk to the population of Delhi.

Elucidating the distribution and sources of street dust bound PAHs in Durgapur, India: A probabilistic health risk assessment study by Monte-Carlo simulation.

Spatial and seasonal distribution of PAHs, source identification, and their associated carcinogenic health risk was investigated in street dust of Durgapur, India. Street dust is an important indicator to detect the quality of the environment as well as the sources of pollutants. The obtained results showed fluctuation in PAHs concentrations from 2317 ± 402 ng/g to 5491 ± 2379 ng/g along with the sampling sites. Seasonal variation revealed higher PAHs concentrations in the winter season (5401 ± 993 ng/g) with the maximum presence of 4-ring PAHs. Two-way analysis of variance (ANOVA) exposed that the sites, seasons and site-season interactions were vividly affected by dissimilar PAHs. The PAHs source identification was investigated by principal component analysis (PCA), positive matrix factorization (PMF), diagnostic ratios, and they revealed pyrogenic, diesel, gasoline, wood and coal combustion to be the key sources of the PAHs in street dust. Obtained results from incremental lifetime cancer risk (ILCR) model exhibited the carcinogenic risk for children ranged from 2.4E-06 to 3.8E-06 while 2.1E-06 to 3.4E-06 for adults which were above the baseline value 1.0E-06. The Monte Carlo simulation model identified cumulative cancer risk of sixteen PAHs in 50th percentile were 2.8 and 1.7 times more while in 95th percentile, the values were 8.8 and 7.8 times higher than the acceptable value of 1E-06 for child and adult respectively.

Profile of polycyclic aromatic hydrocarbons in digested sewage sludge.

One of the methods of sludge disposal in cities is its use as an amendment in adjoining agricultural soil. Contaminants in sludge can, however, nullify the benefits. Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent organic pollutants, if present, can pose health risks by virtue of their carcinogenic potential and persistence in soil. The present study deals with profile analysis of PAHs in digested sewage sludge of a megacity, Delhi. Mean concentration of the sum of 16 PAHs in the sludge from 5 sewage treatment plants (STPs) was 20.67 ± 4.14 mg/kg, dry weight (dw). Carcinogenic PAHs represented ∼47% of the total PAHs. Benzo[g,h,i]perylene recorded the highest mean concentration followed by dibenzo[a,h]anthracene. Low molecular weight PAHs and high molecular weight PAHs contributed 19% and 81% to total PAHs content respectively. Principal component analysis identified the major sources of PAHs in sludge as coal and natural gas combustion. Wood combustion, oil and oil derivatives are the other identified sources. The observed PAH levels in sludge from selected STPs of Delhi were found to violate the limit values proposed by the European Union and the US legislation for application in agriculture.

Health risk assessment of organochlorine pesticide exposure through dietary intake of vegetables grown in the periurban sites of Delhi, India.

The study investigated the levels of organochlorine pesticides (OCPs) in different types of vegetables grown in periurban area of National Capital Region (NCR), India. Vegetable sampling was carried out in winter and summer season of 2012. A total of 20 different OCPs were determined using gas chromatography (GC) assembled with electron capture detector (ECD). Obtained results showed that average levels of ∑(20)OCP ranged from 83.8 ± 25.5 ng g(-1) in smooth gourd to 222.4 ± 90.0 ng g(-1) in cauliflower. The mean concentrations of different OCPs were observed in order of ∑HCH > ∑CHLs > drins > ∑endosulfan > ∑DDT in all vegetables except in brinjal and smooth gourd. Most of the OCP residues recorded in vegetable samples exceeded the maximum residue levels (MRLs) set by international and national regulatory agencies. Health risk assessment suggests that daily dietary OCP exposure via vegetable consumption was higher for children (mean value 4.25E-05) than adults (mean value 2.19E-05). The hazard quotient (HQ) and lifetime cancer risk (LCR) estimated from dietary exposure of these vegetables were above the acceptable limit and can be considered as a serious concern for Delhi population.

Persistence, variance and toxic levels of organochlorine pesticides in fluvial sediments and the role of black carbon in their retention.

The present study assesses the persistence and variation of organochlorine pesticides (OCPs) and their regulation by total organic carbon (TOC) and black carbon (BC) in freshwater sediment. Sediment samples from the Yamuna River, a major tributary of the Ganges (one of the most populated and intensively used rivers in Asia), had high levels of Σ20OCPs (21.41 to 139.95 ng g(-1)). ß-Hexachlorocyclohexane (ß-HCH) was the most predominant component. ΣHCH and Σdichloro-diphenyl-trichloroethane (DDT) constituted ~86% of Σ20OCPs. Isomer ratios indicated fresh usage of lindane, DDT and technical-grade HCH. Toxicological comparison with freshwater sediment quality guidelines showed γ-HCH and DDT at high levels of concern. ß-HCH, α-HCH, endrin, heptachlor epoxide, dichloro-diphenyl-dichloroethane (DDD), dichloro-diphenyl-dichloroethylene and chlordane were above some of the guideline levels. TOC and BC had mean concentrations of 1.37 ± 0.51% and 0.46 ± 0.23 mg g(-1), respectively. BC constituted 1.25 to 10.56% of TOC. We observed low to moderate correlations of BC with isomers of HCH, p,p'-DDT and methoxychlor while of TOC with Σ20OCPs, γ-HCH, endosulfan sulfate and methoxychlor. Principal component analysis enabled correlating and clustering of various OCPs, BC and TOC. OCP distribution was related with pH, electrical conductivity, soil moisture and finer fractions of sediment. OCPs with similarity in properties that determine their interactions with carbonaceous components of sediment clustered together. A number of factors may, thus, be involved in the regulation of interactive forces between BC and OCPs. BC in this study may be more important than TOC in the retention of some OCPs into fluvial sediments, thereby reducing their bioavailability. The finding is probably the first of its kind to report and emphasises the role of BC in the persistence of OCPs in fluvial sediments.

Accumulation and risks of polycyclic aromatic hydrocarbons and trace metals in tropical urban soils.

The study deals with the combined contribution of polycyclic aromatic hydrocarbons (PAHs) and metals to health risk in Delhi soils. Surface soils (0-5 cm) collected from three different land-use regions (industrial, flood-plain and a reference site) in Delhi, India over a period of 1 year were characterized with respect to 16 US Environmental Protection Agency priority PAHs and five trace metals (Zn, Fe, Ni, Cr and Cd). Mean annual ∑16PAH concentrations at the industrial and flood-plain sites (10,893.2 ± 2826.4 and 3075.4 ± 948.7 µg/kg, respectively) were ~15 and ~4 times, respectively, higher than reference levels. Significant spatial and seasonal variations were observed for PAHs. Toxicity potentials of industrial and flood-plain soils were ~88 and ~8 times higher than reference levels. Trace metal concentrations in soils also showed marked dependencies on nearness to sources and seasonal effects. Correlation analysis, PAH diagnostic ratios and principal component analysis (PCA) led to the identification of sources such as coal and wood combustion, vehicular and industrial emissions, and atmospheric transport. Metal enrichment in soil and the degree of soil contamination were investigated using enrichment factors and index of geoaccumulation, respectively. Health risk assessment (incremental lifetime cancer risk and hazard index) showed that floodplain soils have potential high risk due to PAHs while industrial soils have potential risks due to both PAHs and Cr.

Risk assessment of inhalation exposure to polycyclic aromatic hydrocarbons in school children.

Polycyclic aromatic hydrocarbons (PAHs) associated with the inhalable fraction of particulate matter were determined for 1 year (2009-2010) at a school site located in proximity of industrial and heavy traffic roads in Delhi, India. PM10 (aerodynamic diameter ≤10 µm) levels were ∼11.6 times the World Health Organization standard. Vehicular (59.5%) and coal combustion (40.5%) sources accounted for the high levels of PAHs (range 38.1-217.3 ng m(-3)) with four- and five-ring PAHs having ∼80 % contribution. Total PAHs were dominated by carcinogenic species (∼75%) and B[a]P equivalent concentrations indicated highest exposure risks during winter. Extremely high daily inhalation exposure of PAHs was observed during winter (439.43 ng day(-1)) followed by monsoon (232.59 ng day(-1)) and summer (171.08 ng day(-1)). Daily inhalation exposure of PAHs to school children during a day exhibited the trend school hours > commuting to school > resting period in all the seasons. Vehicular source contributions to daily PAH levels were significantly correlated (r = 0.94, p < 0.001) with the daily inhalation exposure level of school children. A conservative estimate of ∼11 excess cancer cases in children during childhood due to inhalation exposure of PAHs has been made for Delhi.

Profile of PAHs in the inhalable particulate fraction: source apportionment and associated health risks in a tropical megacity.

The present study proposed to investigate the atmospheric distribution, sources, and inhalation health risks of polycyclic aromatic hydrocarbons (PAHs) in a tropical megacity (Delhi, India). To this end, 16 US EPA priority PAHs were measured in the inhalable fraction of atmospheric particles (PM(10); aerodynamic diameter, ≤ 10 µm) collected weekly at three residential areas in Delhi from December 2008 to November 2009. Mean annual 24 h PM(10) levels at the sites (166.5-192.3 µg m(-3)) were eight to ten times the WHO limit. Weekday/weekend effects on PM(10) and associated PAHs were investigated. Σ(16)PAH concentrations (sum of 16 PAHs analyzed; overall annual mean, 105.3 ng m(-3); overall range, 10.5-511.9 ng m(-3)) observed were at least an order of magnitude greater than values reported from European and US cities. Spatial variations in PAHs were influenced by nearness to traffic and thermal power plants while seasonal variation trends showed highest concentrations in winter. Associations between Σ(16)PAHs and various meteorological parameters were investigated. The overall PAH profile was dominated by combustion-derived large-ring species (85-87 %) that were essentially local in origin. Carcinogenic PAHs contributed 58-62 % to Σ(16)PAH loads at the sites. Molecular diagnostic ratios were used for preliminary assessment of PAH sources. Principal component analysis coupled with multiple linear regression-identified vehicular emissions as the predominant source (62-83 %), followed by coal combustion (18-19 %), residential fuel use (19 %), and industrial emissions (16 %). Spatio-temporal variations and time-evolution of source contributions were studied. Inhalation cancer risk assessment showed that a maximum of 39,780 excess cancer cases might occur due to lifetime inhalation exposure to the analyzed PAH concentrations.

Health risk assessment of polycyclic aromatic hydrocarbons and heavy metals via dietary intake of vegetables grown in the vicinity of thermal power plants.

Six different vegetables grown in the vicinity of three thermal power plants and a background site in Delhi, India were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) and 7 heavy metals (Cd, Cu, Cr, Ni, Zn, Fe and Mn). Annual mean concentrations of PAHs and all metals were found to be significantly higher (ANOVA, p<0.001) at power plant sites as compared to the background site. Higher abundances of coal tracer PAHs such as Phen, Anth, Flan, Pyr and Chry in power plant vegetables suggested possible impacts of coal combustion emissions. Higher ratios of polluted sample-to-background sample of vegetables were found especially for Cr, Cd, Ni and Zn. Spinach and radish showed greater accumulation of PAHs and metals on a mass basis at the power plant sites while vegetables belonging to the gourd family showed highest relative enrichment. Power plant samples showed 184-475% greater metal pollution index (MPI) values as compared to the background location while health risk indices (HRI) for Cd and Ni exceeded the safe limit for most vegetables. Incremental lifetime cancer risk (ILCR) assessment showed that up to 58 excess cancer cases are likely in Delhi for lifetime ingestion exposure to PAHs at their observed concentrations.

Metallic species in ambient particulate matter at rural and urban location of Delhi.

In the present study 14 metallic species (six crustal and eight trace metals) were quantified in the suspended particulate matter (SPM) at a rural and urban location of Delhi, India. Particulate matter was collected on glass fiber filters for a period of one year (from September 2003 to August 2004). Rank sum test revealed that the TSP concentration at the urban site was significantly (P=0.47) higher as compared to the rural site. Urban site showed highest SPM concentration during winter while rural site during summer. Enrichment factor (EF) and coefficient of variation (CV) were calculated to assess the variability of elemental concentration data. Trace metals viz. Pb, Cd, Cu and Zn were observed to be highly enriched at both the sites, but EF for Zn and Cu was 2-3 times higher at the urban site as compared to the rural site. Trace and crustal metal concentration displayed less variability at the urban site. In the urban area, metals were mainly found to come from construction and industrial activities in surrounding. At the rural site, re-suspended and wind-blown dust appeared to be the source of observed elemental concentration.

Pattern, sources and toxic potential of PAHs in the agricultural soils of Delhi, India.

Surface soil (0-5 cm) from various agricultural sites in Delhi was analyzed to discern the contents of 16 priority polycyclic aromatic hydrocarbons (PAHs). Reference and deuterated standards were used for identification and quantification of PAHs by high performance liquid chromatography (HPLC) with UV detection. summation operator(16)PAHs ranged from 830 to 3880 microg kg(-1) (dry wt.) with an arithmetic mean of 1910+/-1020 microg kg(-1) summation operator(16)PAHs values at the urban sites were 2-5 times higher as compared to the rural sites. In general, low molecular weight PAHs were predominant. Total organic carbon (TOC) was found to be significantly correlated with summation operator(16)PAHs. Isomer pair ratios and Principal component analysis (PCA) suggested biomass and fossil fuel combustion as the main sources of PAHs. The toxic equivalency factors (TEFs) were used to estimate benzo[a]pyrene-equivalent concentration (B[a]P(eq)). Therewith, PAH content of urban agricultural soil was found to have more carcinogenic potential.

Impact of CNG implementation on PAHs concentration in the ambient air of Delhi: a comparative assessment of pre- and post-CNG scenario.

The use of alternative fuel is considered to be an effective measure to improve the urban air quality. Concerned over deteriorating air quality in Delhi, the Delhi government initiated different measures including stringent emission norms, improved fuel quality and above all introduction of cleaner fuel-CNG in public transport system. The entire city bus fleet was converted to CNG mode by 2002. The present study reports the comparative assessment of the status of air quality with respect to PM(10) and PAH before and after the introduction of CNG in public transport system in Delhi. The study has been carried out for two different time periods: first in the year 1998 and second in the year 2004. Following the total conversion of public transport system to CNG in 2002, Post-CNG data indicate a sharp reduction of 51-74% in the PM(10) concentration and 58-68% in the TPAH concentration as compared to the Pre-CNG data.

Assessment of PAHs in soil around the International Airport in Delhi, India.

Present study was undertaken to determine the level of PAH contamination due to jet turbine exhaust in the peripheral soil of the International Airport in Delhi, India. Densely populated residential areas surrounding the airport come directly under both the landing and take-off flight paths. Twelve priority polycyclic aromatic hydrocarbons (PAHs) were analyzed in the <2 mm surface soil fraction. Identification and quantification of PAHs was done by high performance liquid chromatography (HPLC). The sum of 12 PAHs ranged from 2.39 microg g(-1) to 7.53 microg g(-1) with a mean concentration of 4.43+/-1.45 microg g(-1). PAH levels observed in the present study were found to be higher as compared to most of the literature values. Among the three sampling sites selected around the International Airport, the site near landing point revealed maximum concentration of PAHs, while minimum concentration was observed at the site near take-off point. Predominance of pyrene was observed in the airport soil. Factor analysis and isomer pair ratios suggest pyrogenic origin of PAHs in the study area.

Spatial and temporal variation of BTEX in the urban atmosphere of Delhi, India.

Benzene, toluene, ethylbenzene and xylene (BTEX) form an important group of aromatic Volatile Organic Compounds (VOCs) because of their role in the tropospheric chemistry and the risk posed by them to human health. Concentrations of BTEX were determined at different sampling points in the ambient air of Delhi in order to investigate their temporal and spatial distributions. Significant positive correlation coefficient (p<0.01) was found between inter-species concentrations at all the sampling locations. Inter-species ratio and Pearson's correlations indicate that gasoline vehicular exhaust could be the major source of BTEX in Delhi. The inter-species ratios exhibit clear seasonal variations indicating differential reactivity of the VOC species in different seasons. Xylenes were found the largest contributor to the ozone formation followed by toluene.

Temporal variability of benzene concentration in the ambient air of Delhi: a comparative assessment of pre- and post-CNG periods.

CNG (compressed natural gas) was fully implemented in public transport system in Delhi in December 2002. The study assesses the benzene concentration trends at two busy traffic intersections and a background site in Delhi, India. Monitoring was done for two different time periods viz; in the year 2001-2002 (pre-CNG) and two winter months (January and February) of the year 2007 (post-CNG) to assess the impact of various policy measures adopted by the government of Delhi to improve the air quality in the city. Annual average benzene concentration for the pre-CNG period was found to be 86.47+/-53.24 microg m(-3). Average benzene concentrations for the winter months (January-February) of pre- and post-CNG periods were 116.32+/-51.65 microg m(-3) and 187.49+/-22.50 microg m(-3), respectively. Enhanced values could be solely attributed to the increase in the vehicular population from 3.5 million in the year 2001-2002 to approximately 5.1 millions in the year 2007.

Visibility impairing aerosols in the urban atmosphere of Delhi.

To study the visual air quality of Delhi, size fractionated aerosols - coarse and fine fractions of PM10 - were collected and analysed for SO4(-2), NO(-3), NH4+ and EC at three sites with different background activities. The analysed species constitute a smaller portion of coarse fraction (39%) but a larger portion of fine fraction (69%). The sampling was performed from June 2003 to November 2003 which covers monsoon and post monsoon seasons. Aerosol data was used to describe the spatial variation of Visibility Range as a function of chemical composition of visibility impairing aerosols. During the study period, visibility was found to be poor varying between 4.7 and 13 km with an average value of 9.4 km. It is observed that visibility impairment was more due to carbonaceous aerosol followed by sulphate.

PAHs contamination in bank sediment of the Yamuna river, Delhi, India.

This study was performed to elucidate the distribution, concentration trend and possible sources of PAHs in bank sediment of river Yamuna in Delhi, India. The levels of 16 priority polycyclic aromatic hydrocarbons (PAHs) were analyzed during pre-monsoon, monsoon and post-monsoon seasons in the sediment fraction < 53 microm. Reference standards and internal standards were used for identification and quantification of PAHs by HPLC. The sum of 16 PAH compounds ranged from 4.50 to 23.53 microg/g with a mean concentration of 10.15 +/- 4.32 microg/g (dry wt.). Among 5 sites studied, the site, Income Tax Office (ITO) was found to be the hotspot attaining highest concentration. Predominance of 2-4 ring PAHs suggests a relatively recent local sources of PAHs in the study area. Moreover, molecular indices based source apportionment also illustrates pyrogenic source fingerprint of PAHs. No significant temporal trend was observed.

Profile of PAH in the exhaust of gasoline driven vehicles in Delhi.

A preliminary study to determine the profile of PAHs in the exhaust of gasoline vehicles in Delhi was conducted. Three different types of vehicles (cars, autorickshaws and scooters) were selected with different age groups for sampling purpose. The concentration of Total PAHs (Sigma12PAHs) was found to be 27.27 +/- 2.27, 28.61 +/- 3.70 and 29.81 +/- 3.57 mg/g in the exhaust of cars, auto- rickshaws (three wheelers) and two wheelers, respectively. The levels of PAHs were found to be high in scooter exhaust as compared to that of cars and autorickshaws. The total PAHs concentration in the present study was found to be higher as compared to other studies. Such a high concentration could be attributed to different parameters like the age of the vehicles, driving conditions, the fuel quality and the emission standards.

Profile of PAHs in the diesel vehicle exhaust in Delhi.

A preliminary study to determine the profile of PAHs in the exhaust of diesel vehicles plying on Delhi roads was conducted. Two different types of diesel vehicles (buses and trucks) with different age groups were selected for sampling purpose. The concentration of Total PAHs (sigma12 PAHs) was found to be 50.76 +/- 6.62 and 57.72 +/- 4.15 mg/g in the exhaust of buses and trucks, respectively. The levels of PAHs were found to be high in trucks as compared to that of buses. The total PAHs concentration in the present study was found to be higher as compared to other studies. Such a high concentration could be attributed to different parameters like the age of the vehicles, driving conditions, the fuel quality and the emission standards.

Spatial and temporal variation of heavy metals in atmospheric aerosol of Delhi.

The levels of Suspended Particulate Matter (SPM) and heavy metals viz. Pb, Cd, Cr, Ni and Fe were measured. Aerosol samples from four different locations in Delhi were collected by High-volume samplers for a period of one year from July 1997 June 1998. Metal concentration was determined by Atomic Absorption Spectrometry. The annual average concentration of SPM in Delhi was found to be 416.34 +/- 223 microg m(-3). The atmospheric aerosol samples were highly enriched with elements viz. Pb and Cd, which originate from various human activities like transportation and industrial processes. Principal Component Analysis (PCA) showed vehicular traffic and industrial emission as the major contributors of metals. The annual average concentration of Pb did not exceed the national standard of 0.75 microg m(-3).