Polycyclic Aromatic Hydrocarbons (PAHs) iIn the Diep And Plankenburg Rivers and potential remediation using charred Vitis vinifera (GRAPE) leaf litter

Abstract

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in freshwater systems may aggravate the water crisis currently being experienced in the Western Cape province of South Africa. However, there is dearth of data on the levels of PAHs, necessary for effective assessment of water quality as well as remediation strategies. This study therefore assessed levels of PAHs in two important freshwater systems in the Western Cape Province, South Africa. The potential of grape leaf litter for PAH abatement was also investigated. A solid-phase extraction - gas chromatography - flame ionisation detection (SPE-GC-FID) method was developed to simultaneously determine the 16 United States Environmental Protection Agency (US EPA) priority PAHs in environmental samples. Levels of 16 US EPA priority PAHs were assessed in water, sediment and plants from seven selected sites on the Diep and Plankenburg Rivers. Seasonal variations of some water quality parameters and PAHs levels in water and sediment samples were determined from the selected sites. Activated carbons produced from Vitis vinifera (grape) leaf litter were utilised for PAH-remediation. The SPE-GC-FID method developed for the 16 US EPA priority PAHs determination gave acceptable linearity (R2 > 0.999). Instrument detection limits ranged between 0.02 and 0.04 µg/mL and instrument quantification limits of between 0.06 and 0.13 µg/mL. Recovery studies were also acceptable (70.35 - 100.83%) with the exception of naphthalene that had lower recoveries. The average ∑16 PAHs detected in water samples at a given site, over a one-year period ranged from 73.90 to187.11 µg/L. The highest PAHs levels were detected in water samples from industrial areas of both rivers; chrysene (Chy) followed by benzo[a]anthracene (BaA) were the most abundant PAHs detected in water samples. Higher PAHs levels were detected in sediment samples relative to water samples; the average ∑16 PAHs detected in sediment samples at a given site, over a one-year period ranged from 6.048 to 39.656 µg/g. PAHs levels were also highest in sediment samples from industrial areas of the two rivers; benzo[b]fluoranthene (BbF) followed by benzo[k]fluoranthene (BkF) were the most abundant PAHs detected in sediment samples. The average ∑16 PAHs detected in plant samples [Phragmites australis (common reed) and Eichhornia crassipes (water hyacinth)] at a given site, ranged between 62.11 and 226.72 µg/g. Highest levels of PAHs were therefore detected in plant samples, suggesting possible bioaccumulation of PAHs in plant tissues. The bioaccumulation of PAHs by the plants also indicates the phytoremediation potential of these plants for PAHs remediation. The levels of PAHs measured in water and sediment samples were subjected to probabilistic risk assessment to predict the possibility of regulatory values being exceeded. The average percentage exceedence of 63.26 and 42.81 were obtained for PAHs in water samples of the Diep and Plankenburg Rivers respectively, while the corresponding average percentage exceedence obtained for sediment samples were 63.71 and 77.20. Vitis vinifera (grape) leaf litter showed enormous prospect as precursor for activated carbon. The yield of activated carbons obtained from grape leaf litter ranged from 44.65 to 58.40% and the Brunauer-Emmett-Teller (BET) surface area of up to 616.60 m2/g was obtained for activated carbons. The estimated adsorption capacities of the ZnCl2 and H3PO4 activated carbons for phenanthrene removal from aqueous solutions were 94.12 and 89.13 mg/g respectively. The environmental samples analysed were heavily contaminated with the 16 US EPA priority PAHs and the probabilistic risk assessment suggested risks of the carcinogenic PAHs at the levels measured in the environment. Vitis vinifera leaf litter, showed enormous potential as renewable precursor for activated carbon production, capable of removing varied contaminants from wastewater.