Considerations on ultra-trace analysis of phthalates in drinking water

Abstract

Stir bar sorptive extraction with liquid desorption followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD/LVI-GC–MS), had been applied for the determination of ultra-traces of seven-phthalates (dimethyl phthalate, diethyl phthalate, di- n-butyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate) in drinking water samples, which are included in the priority lists set by several international regulatory organizations. Instrumental calibration under the selected-ion monitoring mode acquisition (LVI-GC–MS(SIM)), experimental parameters that could affect the SBSE-LD efficiency, as well as, the control of the contamination profile are fully discussed. Throughout systematic assays on 30 mL water samples spiked at the 0.40 μg/L level, it had been established that stir bars coated with 47 μL of polydimethylsiloxane, an equilibrium time of 60 min (1000 rpm) and methanol as back extraction solvent, allowed the best analytical performance to monitor phthalates in water matrices. From the data obtained, good accuracy and a remarkable reproducibility (< 14.8%) were attained, providing experimental recovery data in agreement with the theoretical equilibrium described by the octanol–water partition coefficients ( K PDMS/W≈ K O/W), with the exception of bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate, for which lower yields were measured. Additionally, a remarkable linear dynamic range between 25 and 2000 ng/L ( r 2 > 0.99 ) and low detection limits (3–40 ng/L) were also achieved for the seven-phthalates studied. The application of the present method to monitor phthalates in tap and bottled mineral water samples, allowed convenient selectivity and high sensitivity up to 1.0 μg/L level, using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low sample volume requirement to monitor phthalates in drinking water matrices at the ultra-trace level, in compliance with international regulatory directives on water quality.