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

Abstract 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 H 2 O 2 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.

[1]  F. Hernández,et al.  GC-MS/MS multi-residue method for the determination of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in human breast tissues. , 2009, Journal of separation science.

[2]  Xiu‐Ping Yan,et al.  Multiwalled carbon nanotubes coated fibers for solid-phase microextraction of polybrominated diphenyl ethers in water and milk samples before gas chromatography with electron-capture detection. , 2006, Journal of chromatography. A.

[3]  R. Sariri,et al.  Inhibition of horseradish peroxidase activity by thiol type inhibitors , 2006 .

[4]  J. Tadeo,et al.  Determination of polybrominated diphenyl ethers in human hair by gas chromatography-mass spectrometry. , 2009, Talanta.

[5]  R. Samperi,et al.  Liquid chromatography-negative ion atmospheric pressure photoionization tandem mass spectrometry for the determination of brominated flame retardants in environmental water and industrial effluents. , 2009, Journal of chromatography. A.

[6]  Yongyao Xia,et al.  Direct electrochemistry and bioelectrocatalysis of hemoglobin immobilized on carbon black. , 2007, Bioelectrochemistry.

[7]  W. Xing,et al.  Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon , 2004 .

[8]  B D Malhotra,et al.  Recent advances in polyaniline based biosensors. , 2011, Biosensors & bioelectronics.

[9]  José M. Pingarrón,et al.  Reactivities of organic phase biosensors. 2. The amperometric behaviour of horseradish peroxidase immobilised on a platinum electrode modified with an electrosynthetic polyaniline film , 1997 .

[10]  G. Palleschi,et al.  Enzyme inhibition-based biosensors for food safety and environmental monitoring. , 2006, Biosensors & bioelectronics.

[11]  Songqin Liu,et al.  Renewable reagentless hydrogen peroxide sensor based on direct electron transfer of horseradish peroxidase immobilized on colloidal gold-modified electrode. , 2002, Analytical biochemistry.

[12]  Joseph Owino,et al.  Electrochemical detection of glyphosate herbicide using horseradish peroxidase immobilized on sulfonated polymer matrix. , 2009, Bioelectrochemistry.

[13]  Sigbritt Karlsson,et al.  Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE). , 2009, Talanta.

[14]  C. Samara,et al.  Persistent organic pollutants (POPs) in the sewage treatment plant of Thessaloniki, northern Greece: occurrence and removal. , 2004, Water research.

[15]  Martin M. F. Choi,et al.  On-line monitoring of methanol in n-hexane by an organic-phase alcohol biosensor. , 2007, Biosensors & bioelectronics.

[16]  S. Ai,et al.  A novel hydrogen peroxide biosensor based on horseradish peroxidase immobilized on gold nanoparticles-silk fibroin modified glassy carbon electrode and direct electrochemistry of horseradish peroxidase , 2009 .

[17]  Peng Wang,et al.  Inhibition of benzoic acid on the polyaniline–polyphenol oxidase biosensor , 2010 .

[18]  Damià Barceló,et al.  Biosensors as useful tools for environmental analysis and monitoring , 2006, Analytical and bioanalytical chemistry.

[19]  Zhousheng Yang,et al.  An Amperometric Horseradish Peroxidase Inhibition Biosensor for the Determination of Phenylhydrazine , 2008, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[20]  Booncharoen Wongkittisuksa,et al.  Semi disposable reactor biosensors for detecting carbamate pesticides in water. , 2005, Biosensors & bioelectronics.

[21]  K. Khajeh,et al.  Inhibition of horseradish peroxidase by thiol type inhibitors: Mercaptoethanol and mercaptoacetic acid , 2006 .

[22]  Shi-Wen Huang,et al.  Hydrogen peroxide biosensor based on the bioelectrocatalysis of horseradish peroxidase incorporated in a new hydrogel film , 2007 .

[23]  Juan C. Vidal,et al.  A Modulated Tyrosinase Enzyme‐Based Biosensor for Application to the Detection of Dichlorvos and Atrazine Pesticides , 2008 .

[24]  A. Vonderheide A review of the challenges in the chemical analysis of the polybrominated diphenyl ethers , 2009 .

[25]  B. Gómara,et al.  A simple and fast method for the simultaneous determination of polychlorinated biphenyls and polybrominated diphenyl ethers in small volumes of human serum. , 2007, Journal of chromatography. A.

[26]  Ana María L. Zatón,et al.  Horseradish peroxidase inhibition by thiouracils , 1995, FEBS letters.

[27]  S. Cosnier,et al.  A biosensor as warning device for the detection of cyanide, chlorophenols, atrazine and carbamate pesticides , 1995 .

[28]  Lucas Franco Ferreira,et al.  Amperometric biosensing of carbamate and organophosphate pesticides utilizing screen-printed tyrosinase-modified electrodes. , 2007, Analytica chimica acta.

[29]  Martin M. F. Choi,et al.  An organic-phase optical phenol biosensor coupling enzymatic oxidation with chemical reduction. , 2004, The Analyst.

[30]  P. Nomngongo,et al.  Determination of Selected Heavy Metals Using Amperometric Horseradish Peroxidase (HRP) Inhibition Biosensor , 2011 .