On-line sample processing involving microextraction techniques as a front-end to atomic spectrometric detection for trace metal assays: A review

• Role of flow injection in automation of microextraction techniques for metal assays.
• On-line coupling of liquid phase microextraction (LPME) to atomic spectrometry.
• Critical evaluation of on-line single drop and dispersive LPME.
• On-line coupling of micro-solid phase extraction (μSPE) to atomic spectrometry.
• Critical appraisal of magnetic/carbon nanoparticles and biomass for on-line μSPE.

Within the last decade, liquid-phase microextraction (LPME) and micro-solid phase extraction (μSPE) approaches have emerged as substitutes for conventional sample processing procedures for trace metal assays within the framework of green chemistry. This review surveys the progress of the state of the art in simplification and automation of microextraction approaches by harnessing to the various generations of flow injection (FI) as a front end to atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS) or inductively coupled plasma atomic emission spectrometry or mass spectrometry (ICP-AES/MS). It highlights the evolution of flow injection analysis and related techniques as vehicles for appropriate sample presentation to the detector and expedient on-line matrix separation and pre-concentration of trace levels of metals in troublesome matrices. Rather than being comprehensive this review is aimed at outlining the pros and cons via representative examples of recent attempts in automating green sample preparation procedures in an FI or sequential injection (SI) mode capitalizing on single-drop microextraction, dispersive liquid-phase microextraction and advanced sorptive materials including carbon and metal oxide nanoparticles, ion imprinted polymers, superparamagnetic nanomaterials and biological/biomass sorbents. Current challenges in the field are identified and the synergetic combination of flow analysis, nanotechnology and metal-tagged biomolecule detection is envisaged.

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