Population exposure to emerging perfluoroalkyl acids (PFAAs) via drinking water resources: Application of multivariate statistics and risk assessment models.

This study assessed the occurrence, origins, and potential risks of emerging perfluoroalkyl acids (PFAAs) for the first time in drinking water resources of Khyber Pakhtunkhwa, Pakistan. In total, 13 perfluoroalkyl carboxylic acids (PFCAs) with carbon (C) chains C4-C18 and 4 perfluoroalkyl sulfonates (PFSAs) with C chains C4-C10 were tested in both surface and ground drinking water samples using a high-performance liquid chromatography system (HPLC) equipped with an Agilent 6460 Triple Quadrupole liquid chromatography-mass spectrometry (LC-MS) system. The concentrations of ∑PFCAs, ∑PFSAs, and ∑PFAAs in drinking water ranged from 1.46 to 72.85, 0.30-8.03, and 1.76-80.88 ng/L, respectively. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) were the dominant analytes in surface water followed by ground water, while the concentration of perfluorobutane sulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), and perfluorododecanoic acid (PFDoDA) were greater than long-chain PFOA and PFOS. The correlation statistics, which showed a strong correlation (p < 0.05) between the PFAA analytes, potentially indicated the fate of PFAAs in the area's drinking water sources, whereas the hierarchical cluster analysis (HCA) and principal component analysis (PCA) statistics identified industrial, domestic, agricultural, and commercial applications as potential point and non-point sources of PFAA contamination in the area. From risk perspectives, the overall PFAA toxicity in water resources was within the ecological health risk thresholds, where for the human population the hazard quotient (HQ) values of individual PFAAs were < 1, indicating no risk from the drinking water sources; however, the hazard index (HI) from the ∑PFAAs should not be underestimated, as it may significantly result in potential chronic toxicity to exposed adults, followed by children.

Heavy metals in five commonly consumed fish species from River Swat, Pakistan, and their implications for human health using multiple risk assessment approaches.

This study analyzed the levels of heavy metals bioaccumulation in commonly consumed riverine fish species, including G. cavia, T. macrolepis, G. gotyla, S. plagiostomus, and M. armatus from River Swat in Pakistan, and quantify their potential risk to children and adults in general and fisherfolk communities using multiple pollution and risk assessment approaches. The highest metal detected by inductive coupled plasma mass spectrometry (ICP-MS) was Zn, which ranged from 49.61 to 116.83 mg/kg, followed by Fe (19.25-101.33 mg/kg) > Mn (5.25-40.35 mg/kg) > Cr (3.05-14.59 mg/kg) > Ni (4.26-11.80 mg/kg) > Al (1.59-12.25 mg/kg) > Cu (1.24-8.59 mg/kg) > Pb (0.29-1.95 mg/kg) > Co (0.08-0.46 mg/kg) > Cd (0.01-0.29 mg/kg), demonstrating consistent fluctuation with the safe recommendations of global regulatory bodies. The average bioaccumulation factor (BAF) values in the examined fish species were high (BAF > 5000) for Pb, Zn, Mn, Cu, Cr, Ni, and Cd, bioaccumulate (1000 > BAF < 5000) for Co, and probable accumulative (BAF <1000) for Fe, and Al, while the overall ∑heavy metals pollution index (MPI) values were greater than one (MPI > 1) indicating sever heavy metals toxicity in G. cavia, followed by S. plagiostomus, M. armatus, G. gotyla, and T. macrolepis. The multivariate Pearson's correlation analysis identified the correlation coefficients between heavy metal pairs (NiCr, CuCr, PbCr, AlCo, CuNi, and PbNi), the hierarchical cluster analysis (CA) determined the origin by categorizing heavy metal accumulation into Cluster-A, Cluster-B, and Cluster-C, and the principal component analysis (PCA) discerned nearby weathering, mining, industrial, municipal, and agricultural activities as the potential sources of heavy metals bioaccumulation in riverine fish. As per human risk perspective, S.plagiostomus contributed significantly to the estimated daily intake (EDI) of heavy metals, followed by G.cavia > M.armatus > G.gotyla > T.macrolepis in dependent children and adults of the fisherfolk followed by the general population. The non-carcinogenic target hazard quotient (THQ) and hazard index (HI) values for heavy metal intake through fish exposure were < 1, while the carcinogenic risk (CR) for individual metal intake and the total carcinogenic risk (TCR) for cumulative Cr, Cd, and Pb intake were within the risk threshold of 10-6-10-4, suggesting an acceptable to high non-carcinogenic and carcinogenic risk for both children and adults in the fisherfolk, followed by the general population.

Heavy metal pollution in the soil of a riverine basin: distribution, source, and potential hazards.

Soil pollution with heavy metals (HMs) has become a world environmental problem. This study focuses on surface soil contamination with Cr, Mn, Co, Ni, Cu, Zn, Cd, Hg, Pb, Fe, and Al, their sources, and potential hazards along the basin of River Swat, Pakistan. The average concentrations (mg/kg) of HMs were the most abundant for Al (24,730.19) followed by Fe (22,419.41) > Mn (386.78) > Zn (57.75) > Cr (38.07) > Ni (32.46) > Cu (23.43) > Pb (19.59) > Co (10.77) > Cd (3.18) > Hg (0.12). The concentrations of Cr and Mn in 5.45% each, Co in 10.90%, Zn in 27.27%, Cu in 36.36%, Ni in 41.81%, and Hg in 92.72% of the total soil samples exceeded their respective background values. The geostatistical approaches determined the distribution patterns of HM pollution along the basin, whereas the statistics of principal component analysis exposed the likely sources of HM contamination in the area. Pollution indices evaluated the overall HM distribution and pollution status in the area. Contamination factor showed a high degree of HM contamination in 82% of the total sampling sites, while the geo-accumulation index designated low to moderate contamination with Cr, Mn, Co, Ni, Cu, Zn, Hg, and Pb, and moderate to extreme contamination with Cd, Fe, and Al. The trend of ecological toxicity showed potential ups and downs along with the sites from low to considerable hazard (< 95 < PEHI < 190), whereas the human carcinogenic hazard was within the USEPA acceptable limits (1 × 10-7-1 × 10-4), but the non-carcinogenic hazard was higher than the threshold (HI > 1) for children because they are more exposed than adults.

Evaluation of toxicological risk of foodstuffs contaminated with heavy metals in Swat, Pakistan.

This study aimed to assess the concentrations of heavy metals such as cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb) and zinc (Zn) in the available foodstuffs (crops, milk and water), their bioaccumulation in human body and potential human health risks in Swat valley, northern Pakistan. Heavy metal concentrations in foodstuffs and human blood (adults (18-above) and children (1-12 years)) were analyzed using atomic absorption spectrometer. The results revealed high level of Mn in foodstuffs followed by Cr>Cu>Zn>Ni>Cd>Pb, which significantly increased the levels of heavy metals in the adult׳s blood as compared to that of children in the order of Cr>Zn>Mn>Ni>Pb>Cu>Cd. Principal component analysis showed that selected foodstuffs were the possible sources of metal contamination in human blood, while correlation analysis revealed that the concentrations of Cr, Cu, Mn, Ni, Pb and Zn in foodstuffs significantly correlated with that in human blood. Moreover, risk assessments for individual metals via foodstuffs were found within safe limits, except for Cd (HQ>1); Whereas, for aggregate multiple metals the risk was calculated as 3.97E+00 (HI>1), in which water and milk were perceived as the greater contributors (81 percent) to HI; while fruits, grains and vegetables contributed 5 percent each, and pulses 4 percent.