Determination of naphthenic acids in produced water by using microchip electrophoresis with integrated contactless...

This study reports for the first time the use of a microchip electrophoresis (ME) device with integrated capacitively coupled contactless conductivity detection (C⁴D) to analyze naphthenic acids in produced water. A mixture containing 9-anthracenecarboxylic, 1-naphthoic, and benzoic acids was separated and detected using a running buffer composed of 10 mmol L^-1 carbonate buffer (pH = 10.2). The separation was achieved within ca. 140 s with baseline resolution greater than 2 and efficiency values ranging from 1.9 × 10⁵ to 2.4 × 10⁵ plates m^-1. The developed methodology provided linear correlation with determination coefficients greater than 0.992 for the concentration ranges between 50 and 250 µmol L^-1 for benzoic and 9-anthracenecarboxylic acids, and between 50 and 200 µmol L^-1 for 1-naphthoic acid. The achieved limit of detection values varied between 4.7 and 7.7 µmol L^-1. The proposed methodology revealed satisfactory repeatability with RSD values for a sequence of eight injections between 5.5 and 7.7% for peak areas and lower than 1% for migration times. In addition, inter-day precision was evaluated for sixteen injections (a sequence of four injections performed during four days), and the RSD values were lower than 11.5 and 4.9% for peak areas and migration time, respectively. Five produced water samples were analyzed, and it was possible to detect and quantify 9-anthracenecarboxylic acid. The concentrations ranged from 1.05 to 2.24 mmol L^-1 with recovery values between 90.8 and 96.0%. ME-C⁴D demonstrated satisfactory analytical performance for determining naphthenic acids in produced water for the first time, which is useful for petroleum or oil industry investigation.