Analysis of selected organic pollutants in water using various concentration techniques

Abstract

Among persistent organic pollutants, chlorobenzenes are some of the most frequently encountered compounds in aqueous systems. These compounds can enter the environment via natural and anthropogenic sources, and are ubiquitous due to their extensive use over the past several decades. Several chlorobenzene compounds, once in the environment, can biologically accumulate, and are reputed to be carcinogens and extremely hazardous to health. Several chlorobenzenes are listed as priority pollutants by the United States Environmental Protection Agency. Excessive exposure to these compounds affects the central nervous system, irritates skin and upper respiratory tract, hardens skin and leads to haematological disorders including anaemia. In spite of these harmful effects, chlorobenzenes are still used widely as process solvents and raw materials in the manufacture of pesticides, chlorinated phenols, lubricants, disinfectants, pigments and dyes. In the light of the above, it is imperative to monitor the levels of chlorinated benzenes in all types of surface waters, using low-cost but sensitive methods of preconcentration and detection. In this study, a simple and relatively cheap preconcentration method using direct immersion solid phase microextraction (DI-SPME) followed by gas chromatography equipped with a flame ionisation detector (GC-FID) was developed for the analysis of 7 chlorinated benzenes in dam water. Experimental parameters affecting the extraction efficiency of the selected chlorobenzenes, such as fibre type, sample size, rate of agitation, salting-out effect and extraction time, were optimised and applied to the Grootdraai Dam water samples. The optimised method comprises the use of a 100 µm polydimethylsiloxane (PDMS) fibre coating; 5 ml sample size; 700 revolutions per minute rate of agitation and an extraction time of 30 minutes. The calibration curves were linear with correlation coefficients ranging from 0.9957–0.9995 for a concentration range of 1–100 ng/ml. The respective limits of detection and quantification for each analyte was as follows: 1,3-dichlorobenzene, 0.02 and 0.2 ng/ml; 1,4-dichlorobenzene, 0.04 and 0.4 ng/ml; 1,2-dichlorobenzene, 0.02 and 0.2 ng/ml; 1,2,4-trichlorobenzene, 0.3 and 2.7 ng/ml; 1,2,4,5-tetrachlorobenzene, 0.09 and 0.9 ng/ml; 1,2,3,4-tetrachlorobenzene, 0.07 and 0.7 ng/ml; pentachlorobenzene, 0.07 and 0.7 ng/ml. Recoveries ranged from 83.6–107.2% with relative standard deviation of less than 9%, indicating that the method has good precision, is reliable and free of matrix interferences. Water samples collected from the Grootdraai Dam were analysed using the optimised conditions to assess the potential of the method for trace level screening and quantification of chlorobenzenes. The method proved to be efficient, as 1,3 dichlorobenzene, 1,4-dichlorobenzene and pentachlorobenzene were detected at concentrations of 0.4 ng/ml, 1.7 ng/ml and 1.4 ng/ml, respectively.