Sample pretreatment is one of the most crucial and error-prone steps of an analytical procedure; it consents to improve selectivity and sensitivity by sample clean-up and pre-concentration. Nowadays, the arousing interest in greener and sustainable analytical chemistry has increased the development of microextraction techniques as alternative sample preparation procedures. In this review, we aimed to show two different categorizations of the most used micro-solid-phase extraction (μSPE) techniques. In essence, the first one concerns the solid-phase extraction (SPE) sorbent selection and structure: normal-phase, reversed-phase, ion-exchange, mixed-mode, molecular imprinted polymer, and special techniques (e.g., doped cartridges for specific analytes). The second is a grouping of the commercially available μSPE products in categories and sub-categories. We present every device and technology into the classifications paying attention to their historical development and the actual state of the art. So, this study aims to provide the state-of-the-art of μSPE techniques, highlighting their advantages, disadvantages, and possible future developments in sample pretreatment.

The solid‐phase microextraction (SPME), invented by Pawliszyn in 1989, today has a renewed and growing use and interest in the scientific community with fourteen techniques currently available on the market. The miniaturization of traditional sample preparation devices fulfills the new request of an environmental friendly analytical chemistry. The recent upswing of these solid‐phase microextraction technologies has brought new availability and range of robotic automation. The microextraction solutions propose today on the market can cover a wide variety of analytical fields and applications. This review reports on the state‐of‐the‐art innovative solid‐phase microextraction techniques, especially those used for chromatographic separation and mass‐spectrometric detection, given the recent improvements in availability and range of automation techniques. The progressively implemented solid‐phase microextraction techniques and related automated commercially available devices are classified and described to offer a valuable tool to summarize their potential combinations to face all the laboratories requirements in terms of analytical applications, robustness, sensitivity, and throughput.

Sample pretreatment is the first and the most important step of an analytical procedure. In routine analysis, liquid–liquid microextraction (LLE) is the most widely used sample pre-treatment technique, whose goal is to isolate the target analytes, provide enrichment, with cleanup to lower the chemical noise, and enhance the signal. The use of extensive volumes of hazardous organic solvents and production of large amounts of waste make LLE procedures unsuitable for modern, highly automated laboratories, expensive, and environmentally unfriendly. In the past two decades, liquid-phase microextraction (LPME) was introduced to overcome these drawbacks. Thanks to the need of only a few microliters of extraction solvent, LPME techniques have been widely adopted by the scientific community. The aim of this review is to report on the state-of-the-art LPME techniques used in gas and liquid chromatography. Attention was paid to the classification of the LPME operating modes, to the historical contextualization of LPME applications, and to the advantages of microextraction in methods respecting the value of green analytical chemistry. Technical aspects such as description of methodology selected in method development for routine use, specific variants of LPME developed for complex matrices, derivatization, and enrichment techniques are also discussed.

In the last decade, the development and adoption of greener and sustainable microextraction techniques have been proved to be an effective alternative to classical sample preparation procedures. In this review, 10 commercially available solid-phase microextraction systems are presented, with special attention to the appraisal of their analytical, bioanalytical, and environmental engineering. This review provides an overview of the challenges and achievements in the application of fully automated miniaturized sample preparation methods in analytical laboratories. Both theoretical and practical aspects of these environment-friendly preparation approaches are discussed. The application of chemometrics in method development is also discussed. We are convinced that green analytical chemistry will be really useful in the years ahead. The application of cheap, fast, automated, “clever”, and environmentally safe procedures to environmental, clinical, and food analysis will improve significantly the quality of the analytical data.

The aim of this study is to validate an integrated air monitoring approach for assessing airborne formaldehyde (FA) in the workplace. An active sampling by silica gel impregnated with 2,4-dinitrophenylhydrazine, a passive solid phase microextraction technique using O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine as on-fiber derivatization reagent, an electrochemical direct-reading monitor, and an enzyme-based badge were evaluated and tested over a range of 0.020-5.12 ppm, using dynamically generated FA air concentrations. Simple linear regression analysis showed the four methods were suitable for evaluating airborne FA. Personal and area samplings in 12 anatomy pathology departments showed that the international occupational exposure limits in the GESTIS database were frequently exceeded. This monitoring approach would allow a fast, easy-to-use, and economical evaluation of both current work practices and eventual changes made to reduce FA vapor concentrations.