A fast and straightforward reversed-phase dispersive liquid–liquid microextraction (RP-DLLME) using a deep eutectic solvent (DES) procedure to determine free tryptophan in vegetable oils was developed. The influence of eight variables affecting the RP-DLLME efficiency has been studied by a multivariate approach. A Plackett–Burman design for screening the most influential variables followed by a central composite response surface methodology led to an optimum RP-DLLME setup for a 1 g oil sample: 9 mL hexane as the diluting solvent, vortex extraction with 0.45 mL of DES (choline chloride–urea) at 40 °C, without addition of salt, and centrifugation at 6000 rpm for 4.0 min. The reconstituted extract was directly injected into a high-performance liquid chromatography (HPLC) system working in the diode array mode. At the studied concentration levels, the obtained method detection limits (MDL) was 11 mg/kg, linearity in matrix-matched standards was R2 ≥ 0.997, relative standard deviations (RSD) was 7.8%, and average recovery was 93%. The combined use of the recently developed DES -based RP-DLLME and HPLC provides an innovative, efficient, cost-effective, and more sustainable method for the extraction and quantification of free tryptophan in oily food matrices. The method was employed to analyze cold-pressed oils from nine vegetables (Brazil nut, almond, cashew, hazelnut, peanut, pumpkin, sesame, sunflower, and walnut) for the first time. The results showed that free tryptophan was present in the range of 11–38 mg/100 g. This article is important for its contributions to the field of food analysis, and for its development of a new and efficient method for the determination of free tryptophan in complex matrices, which has the potential to be applied to other analytes and sample types.
The occurrence and distribution of yttrium and rare earth elements (REYs), along with major elements and heavy metal(loid)s (HMs) in coal fly ash (CFA) from five coal-fired power plants (CFPPs), were analyzed, and the REY-associated ecological and health risks were assessed. The individual REYs in CFA were abundant in the following order: Ce > La > Nd > Y > Pr > Gd > Sm > Dy > Er > Yb > Eu > Ho > Tb > Tm > Lu. The total REY content ranged from 135 to 362 mg/kg, averaging 302 mg/kg. The mean light-to-heavy REY ratio was 4.1, indicating prevalent light REY enrichment in CFA. Significantly positive correlations between the REYs suggested that they coexist and share similar origins in CFA. REYs were estimated to pose low to moderate ecological risks, with risk index (RI) values ranging from 66 to 245. The hazard index (HI) and target cancer risk (TCR) of REYs from CFA, estimated to be higher for children (HIc = 0.15, TCRc = 8.4 × 10−16) than for adults (HIa = 0.017, TCRa = 3.6 × 10−16), were well below the safety limits (HI = 1, TCR = 1.0 × 10−6). However, the danger to human health posed by HMs in the same CFA samples (HIc = 5.74, TCRc = 2.6 × 10−4, TCRa = 1.1 × 10−4) exceeded the safe thresholds (excl. HIa = 0.63). The mean RI and HI attributed to REYs in CFA were 14% and 2.6%, respectively, of the total risks that include HMs.
A core-shell amino-functionalized glycidyl methacrylate magnetic molecularly imprinted polymer (MIP) was synthesized by the suspension polymerization/surface imprinting method and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), mercury porosimetry, nitrogen gas adsorption–desorption, and elemental analysis. This MIP was used as the sorbent in dispersive solid-phase microextraction (DSPME) of aniline from textile wastewater prior to high-performance liquid chromatography-mass spectrometry (HPLC-MS) measurements. Since aniline is toxic and a probable human carcinogen, its determination in water is of great significance. This is a challenging task because aniline is usually present at trace levels. The effects of different DSPME variables on the preconcentration efficiency have been studied by using the Plackett–Burman screening design of experiments (DoE) followed by response surface methodology optimization using the Box-Behnken design. Thus, DoE enabled the investigation of several variables simultaneously. Under optimized conditions, aniline was effectively and selectively separated by a small amount of the DSPME sorbent and detected in real textile wastewater samples. The method detection limit of 1 ng mL−1 was attained, with good method linearity and acceptable recovery and precision. The results showed that the studied MIP could be a reliable DSPME sorbent for efficiently analyzing trace aniline in real wastewater samples.
Organic UV filters are substances widely used as active ingredients in cosmetic products for protection against solar radiation. The frequent application of sunscreens containing multiple UV filters has led to their extensive release into the aquatic environment, posing adverse effects on aquatic organisms. There is a reason for concern about their presence in the environment due to their persistence and potential bioaccumulation in organisms, as well as their negative impact on the endocrine systems of humans and animals. Low concentrations of UV filters in natural waters make their detection challenging, thus requiring the selection of appropriate sample preparation techniques for analysis. This work aims to optimize solid-phase extraction for the analysis of selected UV filters in water. Organic UV filters commonly used as active ingredients in sunscreens were selected for analysis. High-performance liquid chromatography coupled with tandem mass spectrometry was used to identify and quantify the analytes. Five factors that are most significant for the efficiency of solid-phase extraction (sample volume and pH-value, salt concentration in the sample, eluent type and volume) were optimized. The optimized sample preparation technique enabled the examination of fiveselected UV filters with high extraction yields (75%–112%) and an enrichment factor of 150, allowing for trace-level analysis of these chemicals in water.