Pesticides in the hydrogeo-environment: a review of contaminant prevalence, source and mobilisation in India.

Chemical pesticides in the hydrogeological system are a global concern as they pose a severe threat to humans and other organisms. In agriculture, around 4.12 million tonnes of pesticides were used globally in 2018, which is 50% more than in the 1990s. Various pesticides detected in the hydrogeological system of India since the 1990s have been documented and reviewed to understand the prevalence, source, history and degradation pathways. This review contributes to a better understanding of existing pesticide pollution and the state of hydrogeological resource deterioration. Small to excess levels of pesticide residues were detected in groundwater, surface water, soil, and sediments. Pesticides that were most commonly and predominantly found in the hydrogeological system were HCHs, DDTs, endosulfan, heptachlor, drins (aldrin, dieldrin, endrin), chlordane etc. ß and γ-HCH isomers among HCHs, whereas p,p'-DDT and p,p'-DDE among the DDTs were detected most prevalently. In many regions, pesticide residue levels in water have exceeded the maximum residue limits of WHO and BIS, while those in soils and sediments have exceeded the threshold effect level and probable effect level. Higher pesticide residues were detected in the water resources of rural agricultural areas compared to peri-urban or urban areas. A positive correlation of pesticide residues between water resources and soil has been observed in some regions, suggesting a similar contamination source. Diagnostic ratios of pesticides reveal their source, history and degradation pathways. Diagnostic ratios observed in various studies conducted in India suggest historical as well as recent use of banned pesticides. Strengthening current policies and regulations, monitoring pesticide use, changes in pesticide application practices, awareness among farmers, and the use of prominent removal techniques are necessary to tackle pesticide contamination in India.

Assessment of toxicity and potential health risk from persistent pesticides and heavy metals along the Delhi stretch of river Yamuna.

The present study aims at the assessment of environmental quality of the most polluted stretch of river Yamuna along the megacity of Delhi. The study was conducted in order to examine toxicity and health hazards associated with persistent pollutants present in the fluvial ecosystem. Eighty four sediment and 56 vegetable samples from same locations were collected from the Delhi segment of river Yamuna flood plain in order to examine 20 organochlorine pesticides (OCPs) and 9 heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn). Both the organic and inorganic groups of persistent toxic substances were monitored and analysed for the extent of eco-toxicological as well as dietary health risks posed to the local population. Eco-toxicological assessment was done based on sediment quality guidelines, enrichment factor, geo-accumulation index, degree of contamination and Pollution Load Index. The dietary-risk was assessed with the help of translocation factors (TF) of these pollutants in vegetables. Carcinogenic and non-carcinogenic health risks from consumption of vegetables were also investigated. The level of concern for heavy metals was greater than that of OCPs as per the sediment quality guidelines. DDT, Cd, Pb and Zn had maximum concentrations corresponding to level 3 of concern, while Cr and Ni reached up to the highest i.e., 4th level of concern. Sediment samples were found to be enriched and contaminated significantly with Cd and moderately with Pb, as represented respectively by enrichment factors and contamination factors (CF). CF for metals lied in order Zn > Cd > CrNi > PbCu. Pollution load index was highest at the location lying on the exit point of Yamuna in Delhi. TF values greater than 1 were observed in majority of samples analysed for Ni, Cr, Cu and Zn. Spinach topped among vegetables in terms of metal contamination. Cd, Ni and Pb accumulated more in the roots, as against Mn, Zn, Cu and Cr which had higher accumulation in the shoots. Translocation factors were substantially high in vegetables for most of the OCPs, clearly indicating bioaccumulation and potential health risk to the consumers. Health risk to humans was assessed for non-carcinogenic and carcinogenic potentials from ingestion of vegetables. Hazard Quotient (HQ) > 1 due to radish (roots and leaves) and cauliflower consumption in children indicated non-carcinogenic risk. Hazard Index (HI) beyond 1 for all the vegetables (except onion leaves) confirmed substantial cumulative risk. Lifetime cancer risk (LCR) revealed moderate (spinach, radish, beet root and cauliflower) to low (all the others) levels of carcinogenic risk to humans. Cancer risks from γ-HCH, ß- HCH, Hept, Hept Ep, Ald, p,p'-DDT, and Cr exposure through the food chain could be well established.

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.

Chemical speciation of respirable suspended particulate matter during a major firework festival in India.

Ambient respirable particles (PM ≤ 10 µm, denoted by PM(10)) were characterized with respect to 20 elements, 16 polycyclic aromatic hydrocarbons (PAHs), elemental and organic carbon (EC and OC) during a major firework event-the "Diwali" festival in Delhi, India. The event recorded extremely high 24-h PM(10) levels (317.2-616.8 µg m(-3), 6-12 times the WHO standard) and massive loadings of Ba (16.8 µg m(-3), mean value), K (46.8 µg m(-3)), Mg (21.3 µg m(-3)), Al (38.4 µg m(-3)) and EC (40.5 µg m(-3)). Elemental concentrations as high as these have not been reported previously for any firework episode. Concentrations of Ba, K, Sr, Mg, Na, S, Al, Cl, Mn, Ca and EC were higher by factors of 264, 18, 15, 5.8, 5, 4, 3.2, 3, 2.7, 1.6 and 4.3, respectively, on Diwali as compared to background values. It was estimated that firework aerosol contributed 23-33% to ambient PM(10) on Diwali. OC levels peaked in the post-Diwali samples, perhaps owing to secondary transformation processes. Atmospheric PAHs were not sourced from fireworks; instead, they correlated well with changes in traffic patterns indicating their primary source in vehicular emissions. Overall, the pollutant cocktail generated by the Diwali fireworks could be best represented with Ba, K and Sr as tracers. It was also found that chronic exposure to Diwali pollution is likely to cause at least a 2% increase in non-carcinogenic hazard index (HI) associated with Al, Mn and Ba in the exposed population.