Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y

Fuel ether oxygenates are incorporated into gasoline as alternatives to lead, aiming to increase the oxygen content of the fuel and enhance its octane rating. While they offer benefits, concerns about their impact on human health and the environment have led to numerous studies. Methyl tert‑butyl ether (MTBE) has been banned in the United States since 2003 due to its carcinogenic properties. Despite this, global production and use of fuel oxygenates continue to rise. The two other commonly used fuel oxygenates are ethyl tert‑butyl ether (ETBE) and tert‑butyl formate (TBF) [1,2].

Overall, there are various techniques and sorbents used for the removal of toxic materials from different matrices. It is worth mentioning that each method for the removal of toxic materials comes with its own set of strengths and limitations. In this same regard, given the adverse effects on human health and the environment, various methods have been developed for sampling and analyzing fuel ether oxygenates. However, a crucial aspect in the determination of these compounds lies in the sample preparation step, due to complicated matrices of the real environmental and biological samples [3], [4], [5], [6]. The sampling and preconcentration of ether oxygenates in real samples encounter certain limitations, particularly when dealing with biological samples that contain proteins, salts, acids, bases, and various other compounds. These components can contribute to increased matrix interference effects on the target compounds. On the other hand, fuel oxygenates demonstrate higher water solubility, lower Henry's law constants, and lower sorption constants, compared to other contaminants associated with fuels, making their separation and perconcentration more challenging [7], [8], [9].

To address the limitations of the conventional sample preparation strategies, several successful microextraction techniques have been utilized for the extraction and precontraction of fuel ether oxygenates. However, there have been limited studies assessing these compounds in biological matrices [8,10]. Needle trap device (NTD) is a highly effective and robust microextraction method that, up to now, has not been utilized for studying these specific compounds. It is crucial to highlight that the selection of an appropriate sorbent plays a vital role in the overall success of NTD sampling strategy [11].

As the demand for materials with superior selectivity in sample preconcentration continues to rise, molecularly imprinted polymers (MIPs) have emerged as a solution to meet this need. In contrast to conventional extraction materials, MIPs offer numerous advantages such as excellent mechanical and chemical stability, remarkable selectivity, cost-effectiveness, straightforward synthesis, and reversible binding of analytes [12], [13], [14]. Moreover, surface imprinted polymers possess considerable high surface areas, which enhances their potential binding capacity. Indeed, MIP surfaces are a specific type of material created through a process called molecular imprinting. This technique involves the creation of cavities or binding sites within a polymer matrix that are complementary in shape and chemical functionality to a specific target molecule. These cavities are formed by polymerizing monomers around the target molecule, which is then removed, leaving behind specific recognition sites [15,16].

In urine of humans exposed to fuel ether oxygenates by inhalation, a part of fuel ether oxygenates is excreted unchanged with urine. Urine is a commonly used matrix for biomonitoring studies because it can provide information on recent exposure to chemicals. The selection of urine samples for detecting fuel ether oxygenates allows researchers to assess exposure levels, evaluate potential health risks, and monitor the effectiveness of exposure reduction strategies in populations exposed to these compounds [17,18]. This research aims to develop a novel microextraction sorbent by using MIP surface-modified Zeolite Y to prepare a new NTD for the sampling of fuel oxygenates in urine samples. The surface-modified Zeolite Y is anticipated to exhibit exceptional characteristics, including a high surface area, uniform pore size, excellent chemical and thermal stability, and exceptional selectivity [19], [20], [21]. To the best of our knowledge, this is the first report regarding the preparation of NTDs utilizing a MIP surface-modified Zeolite Y. The NTD was employed for the sampling of MTBE, ETBE, and TBF in urine samples, followed by gas chromatography-flame ionization detection (GC-FID) analysis. Of note, the use of chromatographic techniques can significantly boost the analytical capabilities, resulting in more precise and dependable outcomes in various fields [22], [23], [24]. A response surface methodology was also applied to optimize the experimental variables in this process.

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