RESUMO
Anionic surfactants (AS) are becoming a major emerging contaminant of waters due to their widespread use in household and industrial products. The standard chloroform method for analysis of AS in water relies on chloroform extraction of a methylene blue active substance (MBAS), which contains ion pairs between methylene blue (MB) molecules (positively charged) and AS. Due to the poor extractability of chloroform, the procedure is complicated, time-consuming, and subject to anionic interferences. A mixture of methyl isobutyl ketone (MIBK)-1,2-dichloroethane (DCE) at a 3:1 ratio of MIBK:DCE proved to be a robust solvent for AS extraction for a wide range of samples under various chemical conditions. The objectives of this research were to set the washing protocol to eliminate the anionic interferences in the MIBK-DCE extraction and to develop a new simplified analytical method for AS analysis using the MIBK-DCE (3:1) extractant. The suitability of the proposed MIBK-DCE method was validated based on quality control and assurance criteria, such as selectivity, accuracy, precision, method detection limit (MDL), limit of quantification (LOQ), and sensitivity. Various water samples, such as freshwater, wastewater, and seawater, were used for the method development and validation. Interferences by inorganic and organic anions were evident in the reference chloroform method but were eliminated in the MIBK-DCE procedure with a two-step process that consisted of washing with a carbonate/bicarbonate solution at pH 9.2 and a mixture of silver sulfate (Ag2SO4) and potassium alum (AlK(SO4)2). The simplified MIBK-DCE method for sodium dodecyl sulfate (SDS) analysis consisted of (i) sample pre-treatment, (ii) MIBK-DCE extraction, (iii) washing and filtration, and (iv) absorbance measurement. The MIBK-DCE method was accurate, precise, selective, and sensitive for AS analysis and showed MDL of 0.0001 mg/L, LOQ of 0.0005 mg/L, relative standard deviation (RSD) of 0.1%, and recovery of 99.0%. All these criteria were superior to those of the chloroform method. Sensitivity analysis showed highly significant correlations in AS analyses between the MIBK-DCE and chloroform methods for domestic wastewater, industrial wastewater, and seawater. The MIBK-DCE method is simple, rapid, robust, reproducible, and convenient, when compared to the chloroform method. Results demonstrate that the simplified MIBK-DCE method can be employed for AS analysis in a wide range of environmental waters including seawater.
RESUMO
Anionic surfactants (AS) are detrimental aquatic pollutants due to their well-characterized toxicity to aquatic organisms. The concentration of AS in aquatic environments is increasing because of their extensive use in many industries and households. The standard reference method for AS analysis is to determine a methylene blue active substance (MBAS) complex formed between AS and the methylene blue (MB) cation by using chloroform. However, chloroform has a low AS extraction efficiency and other limiting properties, such as a high density and volatility, which make the conventional AS analytical method time-consuming and labor-intensive. In an effort to replace the use of chloroform, this study was carried out to screen novel solvents for their ability to extract AS in water samples. Criteria were based on AS extraction efficiency, physicochemical properties, and the stability of the solvent under different environmental conditions. Organic solvents, such as methyl isobutyl ketone (MIBK), 1,2-dichloroethane (DCE), dichloromethane, benzene, and n-hexane, were assessed. In extraction of the anionic surfactant sodium dodecyl sulfate (SDS), the mixture of MIBK-DCE (3:1) proved to be an optimum solvent as an alternative to chloroform. It not only enhanced SDS extractability but also improved properties, such as having a lower volatility, a lower density than water, and a quicker phase separation. Among solvents screened, no one single solvent in SDS extraction could meet such criteria. The performance of the MIBK-DCE (3:1) mixture in SDS extraction was stable, irrespective of pH and ionic strength of the SDS solution, washing process, and presence of cations. Anionic interference from halogen and polyatomic and organic anions in SDS extraction by MIBK-DCE (3:1) existed only at an elevated concentration, which is not occurring in the natural aquatic environment. Results demonstrated that a MIBK-DCE (3:1) mixture solvent could be used in AS analysis for a wide range of aquatic samples and it could be the basis for the development of a new analytical method to replace conventional chloroform.
