Determination of selected persistent organic pollutants in wastewater from landfill leachates, using an amperometric biosensor

Landfill leachates that contain persistent organic pollutants (POPs) are a big threat to groundwater systems and are projected to have hazardous effects in the long term if proper management strategies of the landfills are not put in place by those responsible. Monitoring the levels of POPs in landfill leachates is very crucial. This work presents an amperometric biosensor for determination of selected POPs in landfill leachates. The biosensor is based on kinetic inhibition of horseradish peroxidase (HRP). The enzyme was immobilised by electrostatic attachment on a polyaniline-modified Pt electrode surface. Selected POPs inhibited HRP enzyme activity and the decrease in the enzyme activity was used to determine these environmental pollutants. Selected polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and polychlorinated biphenyls (PCBs) were the analytes of choice because they are commonly found in South Africa water systems. Limits of detection for the amperometric biosensor were established as 0.014, 0.018, 0.022, 0.016 and 0.019 μg l−1 for BDE-100, PBB-1, PCB-1, PCB-28 and PCB-101, respectively. The HRP biosensor system gave different linear ranges for; BDE-100 (0.424–25.8 μg l−1), PBB-1 (0.862–13.4 μg l−1), PCB-1 (0.930–18.1 μg l−1), PCB-28 (0.730–15.7 μg l−1) and PCB-101 (0.930–27.1 μg l−1). Inhibition studies on HRP biosensor response toward the reduction of H2O2 in the absence and presence of the selected POPs were carried out to investigate the inhibition kinetics and its mechanism. The results obtained indicated that the inhibition mechanism was competitive for PBDEs and non-competitive for biphenyls (PCBs and PBBs). The application of the biosensor was tested on wastewater samples obtained from landfill leachate for determination of selected POPs. The leachate samples were found to contain PCB-28 (0.28 ± 0.03 μg l−1) and PCB-101 (0.31 ± 0.02 μg l−1). The samples were also analysed by GC–MS as a cross-check method and the two sets of results were in close agreement.