Electromembrane Extraction of Naphthenic Acids in Produced Water Followed by Ultra-High-Resolution Mass Spectrometry Analysis.

Naphthenic acids comprise one of the most toxic compounds of the produced water released from offshore oil platforms. Therefore, developing and applying faster, simpler, and more efficient analytical methods for analyzing naphthenic acids are urgently needed. Electromembrane extraction (EME) uses the electrokinetic migration of target ions through a porous membrane. Herein, the EME method was applied to extract naphthenic acids from produced water. The EME method was optimized, and the optimal conditions encompassed decanol as the organic solvent, the sample with pH 10.0, 5 min of extraction at 200 V, and the ratio 4:1 (borate buffer/matrix, v/v). Electrochemical impedance spectroscopy confirmed charged species' migration from produced water through the EME. Subsequently, all extracts were analyzed by ultra-high-resolution mass spectrometry. The EME efficiency was assessed by comparing the extraction results to the liquid-liquid extraction (LLE) method results. Analytical results showed good linearity for both solvent and matrix curves (R2 > 0.98). Low detection limits ranged from 0.10 to 0.13 µg mL-1 and quantification limits from 0.36 to 0.45 µg mL-1. Precision and accuracy values ranged from -13.3% to 16.5%. These values fit the proposed method, demonstrating that the EME was more efficient than LLE in naphthenic acid extraction. The EME method preferably extracted aromatic compounds with double-bond equivalence from 6 to 8. The EME coupled with ultra-high-resolution mass spectrometry was demonstrated as a promising analytical approach to naphthenic acid extraction as an efficient and more environmentally friendly alternative to conventional extraction methods.

Polypyrrole monolithic extraction phase: From conventional to miniaturized sample preparation techniques.

Monolithic polymers are described as continuous and highly porous materials. They have been gaining popularity as an effective extracting phase for some sample preparation methods, due to their variety of functionalities, such as wide pH range tolerance, good permeability, and its ability to allow changes into their surface. Polypyrrole represents an interesting alternative for the modification in extraction phases due to its well related ability to perform multiple interactions, such as acid-base, π - π, ion exchange, interactions with hydrophobic affinities or polar functional groups. Among the different sample preparation techniques, solid-phase extraction (SPE) is one of the most popular and used; a miniaturized version of SPE is the disposable pipette extraction (DPX). DPX is a recent miniaturized extraction technique that usually employing silica-based sorbents inside a pipette tip (5 or 1 mL). The present study proposes the development of a monolithic extraction phase composed by styrene divinylbenzene (1:1) modified with polypyrrole for SPE and DPX techniques. The efficiency of the material was evaluated in face of the extraction of different samples and analytes, triazine herbicides in water and dexamethasone in synthetic synovial liquid by conventional and miniaturized solid-phase extraction techniques. The extractions performed by SPE and DPX presented absolute recovery values ranging from 74.8 to 105.0%, inter-day precision ranging from 0.6 to 14.0%, and limit of quantification of 0.5 and 5.0 ng.mL-1, respectively. The DPX miniaturized method exhibited results equivalent to the methods reported in the literature for extraction of dexamethasone in synovial fluid samples. Moreover, this technique proved to be quicker and cheaper than SPE, and produced fewer residual volumes, supporting the preference for green chemistry. Monolithic polymers modified with polypyrrole presented to be a feasible alternative extraction phase for miniaturized sample preparation techniques.