Occurrence, spatial distribution and ecological risk assessment of Organophosphate Esters in surface water and sediments from the Ravi River and its tributaries.

Organophosphate esters (OPEs) are widely used as substitutes for brominated flame retardants and characterized as emerging contaminants. Due to their toxicity and persistent nature, OPEs are becoming a matter of greater concern worldwide. However, information about the pollution profile of OPEs and associated ecological risks is still scarce in environmental matrices of the South Asian region, particularly Pakistan. Hence, the current study was conducted to investigate the occurrence, spatial distribution patterns, ecological risks and riverine flux of 10 organophosphate esters in surface water and sediments of Ravi River and its four tributaries. The concentrations of ∑10OPEs were in the range of 19.2 - 105 ng/L, with the dominance of chlorinated-OPEs (51 %) in surface water, whereas in case of sediments, the ∑10OPEs concentrations ranged from 20.7 to 149 ng/g dw, with high abundance of non - chlorinated alkyl-OPEs, which contributed about 56 % to total OPE concentration. The correlation analysis signified a strong positive relation of OPEs with TOC (p < 0.05, R = 0.76) in sediments; and in addition to this, field-based LogKoc values were estimated to be higher than predicted LogKoc. Moreover, a significantly positive correlation (p < 0.05, R = 0.88) was observed between LogKoc and LogKow, implying that hydrophobicity plays a significant role in OPE distribution in different environmental matrices. The global comparison revealed that contamination status of OPEs in the present study was comparatively lower than other regional findings, furthermore, principal component analysis suggested vehicular emissions, industrial discharges, household supplies and atmospheric deposition as main sources of OPEs occurrence in current study region. Furthermore, the riverine flux of ∑10OPEs was estimated to be 0.68 tons/yr and the ecological risk assessment indicated that all OPEs, except EHDPP and TCrP, showed negligible or insignificant ecological risks for aquatic organisms.

Distribution, bioaccumulation, and health risk assessment of organochlorines across the riverine ecosystem of Punjab Province, Pakistan.

This study was designed to assess the distribution of organochlorines (OCs) in fish species, their spatio-temporal variations, bioaccumulation potential, and associated human health risks via dietary intake. The levels of twenty-three organochlorine pesticides (OCPs) and thirty-five polychlorinated biphenyls (PCBs) were analyzed in six fish species collected from the riverine ecosystem of Punjab Province, Pakistan. The results indicated that the mean levels of Σ23OCPs were 74.1 ng/g ww and 184 ng/g ww, and for Σ35PCBs the levels were 38.8 ng/g ww and 74.8 ng/g ww in herbivorous and carnivorous fish species, respectively. The most abundant contaminants in all fish species were DDTs (65%) and HCHs (14%) among OCPs and heavier PCB congeners (62%) among PCBs. As for dioxin-like PCBs, the WHO toxic equivalency values (ng TEQ/g ww) were in the range of 0.21 (Cyprinus Carpio) to 2.38 (Rita Rita), exceeding the maximum allowable limit of 0.004 ng TEQ/g, ww by the European Commission. Spatio-temporal analysis indicated relatively higher OC levels in winter season with elevated concentrations in fish samples from industrial zone. The bioconcentration factor (L/kg) values ranged from 723 to 2773 for PCBs and 315 to 923 for OCPs in all fish species, with higher levels were reported in carnivorous species. The human health risk assessment at both 50th and 95th percentiles revealed the absence of any significant non-carcinogenic risk as calculated HR was less than 1. However, the critical carcinogenic risk was found to be associated for most of the contaminants, signifying the dietary exposure to OCPs and PCBs might pose the public health concern.

Organochlorines in the riverine ecosystem of Punjab province, Pakistan: contamination status, seasonal variation, source apportionment, and ecological risk assessment.

The aim of the present study was to determine the occurrence, spatio-temporal variations, source apportioning, and ecological risk assessment of selected PCBs and OCPs in surface water and sediments collected riverine environment of Punjab province, Pakistan. The concentration of ΣOCPs (water: 64-455 ng/L; sediments: 117-616 ng/g) and ΣPCBs (water: 2-132 ng/L; sediments: 3.27-200 ng/g) was found comparatively higher than the levels reported from other parts of the world. The higher concentrations of DDTs and HCHs were detected in both studied matrices, whereas among PCBs, CB-28, 49 and CB-37, 82 were dominant in water and sediments, respectively. The isomeric ratios including α-HCH/γ-HCH, (DDE + DDD) / DDTs, and α /ß-endosulfan reflected the recent use of lindane, technical DDT, and endosulfan in the study area. The WHO-TEQ values of DL-PCBs ranged from 3.6 × 10-6 to 0.115 ng/L and 8.7 × 10-6 to 0.157 ng/g in surface water and sediments in both seasons, respectively. The spatial variation analysis revealed that the sites in the industrial and agricultural zones were highly contaminated. The OCPs and PCBs fluxes to downstream areas were estimated to be 12.4 tons/year and 1.9 tons/year, respectively. The significant ecological risks were estimated to be posed by OCPs and PCBs, as their levels in 67% and 62% of surface water and sediment samples were exceeding the threshold limits, highlighting effects to ecological integrities.