Separations, Volume 9, Issue 3 (March 2022) – 28 articles

The wastewater reuse is an important measure to face water shortage, thus improving the resilience of agricultural production chains. However, treated wastewater can contain residual organic micropollutants residues that may result in crop contamination. Among edible crops, olive is the most important agricultural product in the Mediterranean region. Methods to assess the contamination of organic micropollutants such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in olives are poorly investigated. Given the complexity of olives, this study focused on the development and validation of a method for the simultaneous extraction of PAHs and PCBs from olives, and subsequent analysis by gas chromatography coupled with mass spectrometry detection. Extraction was optimized through a QuEChERS protocol, studying the effect of the extraction solvent (CH₂Cl₂, cyclohexane, CH₃CN) and of the dispersive-solid phase extraction (d-SPE) sorbent (octadecyl silica, Florisil, primary secondary amine, Z-Sep) on the recovery of micropollutants. The best recoveries (94–122%, relative standard deviations below 5%) were obtained using CH₃CN/H₂O and a double purification step with Z-Sep and Florisil. The method developed for PAHs and PCBs, which showed good intra-day (<2.7%) and inter-day (<2.9%) precision and low matrix effect (|ME| < 14%), was applied to the analysis of olives grown by irrigation with reclaimed wastewaters. Full article

Many gluten-free products are deficient in amino acids, especially in essential amino acids (EAA). Therefore, the incorporation of additives rich in free amino acids (FAA) into gluten-free products can be a promising strategy to alleviate certain symptoms of celiac disease associated with EAA deficiencies. This study aimed to evaluate the effect of the incorporation of broccoli leaf powder (BLP) into gluten-free mini sponge cakes (GFS) on the profile of FFA. BLP replaced an equivalent amount (2.5%, 5%, 7.5%; w/w) of corn and potato starches in GFS formulation, resulting in B1-B3 formulations. The first step was the selection of the most efficient method for extraction of FAA. Extraction based on 50% methanol (method 1) was compared to extraction by 25% of acetonitrile in 0.1 M hydrochloric acid (method 2). In total, 26 and 14 FAA were found in BLP after extraction using methods 1 and 2, respectively. Moreover, considering the total content of FAA, method 1 was more efficient, reaching a 14-fold higher concentration of FFA in BLP compared to method 2. The incorporation of BLP resulted in a significant increase in FAA, irrespective of the applied extraction method. The total concentrations of NEAA and EAA increased significantly in B3 compared to control GFS. In summary, this study showed that 50% methanol was more efficient for the extraction of FFA from plant and bakery matrices. Moreover, BLP was found as a good source of FFA, including EAA, and the obtained experimental GFS could be considered a promising product for individuals on a gluten-free diet. Full article

Cuticular waxes can be used in high-value applications, including cosmetics, foods and nutraceuticals, among the others. The extraction process determines their quality and purity that are of particular interest when biocompatibility, biodegradability, flavor and fragrance are the main features required for the final formulations. This study demonstrated that supercritical fluid extraction coupled with fractional separation can represent a suitable alternative to isolate cuticular waxes from vegetable matter that preserve their natural properties and composition, without contamination of organic solvent residues. Operating in this way, cuticular waxes can be considered as a fingerprint of the vegetable matter, where C₂₇, C₂₉ and C₃₁ are the most abundant compounds that characterize the material; the differences are mainly due to their relative proportions and the presence of hydrocarbon compounds possessing other functional groups, such as alcohols, aldehydes or acids. Therefore, selectivity of supercritical fluid extraction towards non-polar or slightly polar compounds opens the way for a possible industrial approach to produce extracts that do not require further purification steps. Full article

Rice crops are especially vulnerable to arsenic exposure compared to other cereal crops because flooding growing conditions facilitates its uptake. Besides, there are still many unknown questions about arsenic’s mode of action in rice. Here, we apply two untargeted approaches using liquid chromatography coupled to mass spectrometry (LC-MS) to unravel the effects on rice lipidome and metabolome in the early stages of growth. The exposure is evaluated through two different treatments, watering with arsenic-contaminated water and soil containing arsenic. The combination of regions of interest (ROI) and multivariate curve resolution (MCR) strategies in the ROIMCR data analyses workflow is proposed and complemented with other multivariate analyses such as partial least square discriminant analysis (PLS-DA) for the identification of potential markers of arsenic exposure and toxicity effects. The results of this study showed that rice metabolome (and lipidome) in root tissues seemed to be more affected by the watering and soil treatment. In contrast, aerial tissues alterations were accentuated by the arsenic dose, rather than with the watering and soil treatment itself. Up to a hundred lipids and 40 metabolites were significantly altered due to arsenic exposure. Major metabolic alterations were found in glycerophospholipids, glycerolipids, and amino acid-related pathways. Full article

Pesticides are chemicals used in agriculture to prevent insects, fungi, weeds, and other pests, from damaging crops. In addition, some types of pesticides are used after harvest as sprout suppressant agents help keeping the quality parameters of crops during storage. Nonetheless, its presence, even at trace levels, in food products is becoming a big challenge regarding human health. The current work aimed to develop and validate a sensitive and high-throughput analytical approach, based on a state-of-the-art microextraction technique—µQuEChERS, combined with ultra-high performance liquid chromatography equipped with a photodiode array detection system (UHPLC-PDA) to quantify isopropyl-N-(3-chlorophenyl) carbamate (chlorpropham), commonly used as efficient sprout suppressant stored potatoes, in raw and cooked potatoes cultivated in different geographical regions of Madeira Island (Portugal). Good results were obtained in terms of figures of the merit of the method, with correlation coefficients (R²) higher than 0.999 and recoveries between 94.5% to 125%. Method limit of detection (LOD) and limit of quantification (LOQ) were 0.14 μg/Kg and 0.43 μg/Kg, respectively, which are much lower than the accepted and legislated requirements by the European Union, which is 20 μg/Kg for chlorpropham. The concentration of chlorpropham in raw potatoes is significantly higher when compared to cooked samples, which revealed that the thermic treatment during cooking had a significant effect on its degradation. A significant decrease (90%, on average) was observed on chlorpropham levels. Full article

Morus spp. leaves (MSLs) show various beneficial effects in the treatment of metabolic-related diseases, which have created a growing interest in MSL development as dietary supplements and functional foods. The illustration of chemical compositions and screening of high-quality MSL resources are therefore necessary for further application. This study developed a new UHPLC-ESI-QTOF-MS/MS strategy of in-source collision-induced dissociation (IS-CID) and target collision-cell CID (TCC-CID) to quickly capture analogues with consistent skeleton, and combined global natural product social molecular networking (GNPS) to efficiently annotate bioactive phytochemicals in MSLs. For the results, 49 bioactive ingredients, including quercetin-type flavonoids, kaempferol-type flavonoids, chlorogenic acid isomers, 1-deoxynojirimycin, γ-aminobutyric acid, amino acids, and unsaturated fatty acids, were systematically identified in MSLs for the first time. Quantification for the typical components was simultaneously carried out in MSLs of 90 Morus resources collected from different locations. Partial least squares discriminant analysis (PLS-DA) indicated that quercetin-3-O-(6″-O-malonyl)-glucoside, rutin, kaempferol-3-O-(6″-O-malonyl)-glucoside, kaempferol-3-O-rutinoside, and chlorogenic acid showed high variable importance in the project (VIP > 1) that were significant constituents for the differences between MSL species. Then, high-quality MSLs were comprehensively screened in multiple Morus cultivars based on the criteria importance through intercriteria correlation (CRITIC) method. This study presented an efficient strategy to annotate bioactive compounds, revealed the difference of bioactive components in MSLs, and provided important information for the high-value production of Morus cultivars in food and supplement fields. Full article

One of the plants used in Indonesian traditional medicine, namely, Patiwala (Lantana camara), is traditionally used to treat some diseases, including itching, wounds, ulcers, swelling, eczema, tetanus, malaria, tumors, rheumatism, and headaches. This study aimed to characterize the compound nonpolar fraction of Patiwala leaf capable of scavenging free radicals. The characterization of compound was carried out using the Ultra-Performance Liquid Chromatography–tandem Mass Spectrometry (UPLC-MS/MS) with positive ion method, while the antioxidant testing was carried out using the radical DPPH (2,2-diphenyl-1-picrylhidrazyl) and FRAP (ferric reducing antioxidant power) methods. The results showed that the nonpolar fraction of the methanol extract of L. camara leaves was very strong toward DPPH radicals (IC₅₀ 34.65 ± 1.26 μg/mL and 40.23 ± 0.18 μg/mL), and FRAP radical (IC₅₀ 4.93 ± 0.22 μg/mL and 12.79 ± 0.09 μg/mL). Nineteen compounds identified by UPLC-MS/MS method were Resveratrol dimer, iso-humolones, oleuropein glucoside, quercetin-3-O-glycoside, myricetin, oleuropein, 12-deoxy-16-hydroxy-phorbol, aloeresin A, humulones, ursolic acid, viniferin, Epicatechin, oleanolic acid, 5-hydroxy-3′,4′,7-trimerthoxy-flavanone, Apigenin-6,8-di-C-β-D-glucoside, procyanidin A2, caffeoyl-O-hexoside, tansihnone IIA, and phillyrin. The methanolic extract of L. camara leaves can be developed as a source of antioxidants from natural ingredients. Full article

A novel hydrocyclone sand washer featured by connecting a cylindrical hydrocyclone and a conical-cylindric hydrocyclone in series was developed to improve the poor grading performance in current machine-made sand processing technology. The former hydroycyclone with a flat bottom was designed to enhance the centrifugal intensity, thereby achieving the pre-grading of fine and coarse particles and ensuring the discharge of most fine mud particles from the overflow pipe. The latter hydrocyclone was designed to achieve the secondary fine separation and therefore reduce the content of fine particles in the underflow product. Firstly, the flow field inside the consecutive hydrocyclones was simulated using an RSM and VOF model. The DPM model was introduced to trace the particle motion trajectory and validate the feasibility of hydrocyclone separation. Then, the experimental study was performed using the control variable method, and the effects of the first-section overflow pipe diameter, the feeding rate, and the mud–sand mixing ratio on the desliming performance were examined. Results show that the content of particles with a diameter of below 75 μm in the second-section underflow drops significantly after the separation in the hydrocyclone sand washer. When the first-section overflow pipe diameter, the feeding rate, and the mud–sand mixing ratio are set to 34 mm, 60 kg/h and 1:1, respectively, the desliming rate of the novel hydrocyclone sand washer can reach 94.31% and the loss rate of quartz sand is only 1.28%. Full article

Copper ions bind to biomolecules (e.g., peptides and proteins) playing an essential role in many biological and physiological pathways in the human body. The resulting complexes may contribute to the initiation of neurodegenerative diseases, cancer, and bacterial and viral diseases, or act as therapeutics. Some compounds can chemically damage biological macromolecules and initiate the development of pathogenic states. Conversely, a number of these compounds may have antibacterial, antiviral, and even anticancer properties. One of the most significant current discussions in Cu biochemistry relates to the mechanisms of the positive and negative actions of Cu ions based on the generation of reactive oxygen species, including radicals that can interact with DNA molecules. This review aims to analyze various peptide–copper complexes and the mechanism of their action. Full article

Crosslinkers are indispensable constituents for the preparation of SPE materials with ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) among the most prominent representatives. A crosslinker that has not yet been used for the preparation of SPE sorbents is 3,3’-(hexane-1,6-diyl)bis(1-vinylimidazolium) bromide [C₆-bis-VIM] [Br]. In this study, we synthesized differently crosslinked vinylimidazole polymers with EGDMA, DVB and [C₆-bis-VIM] [Br] and evaluated their extraction efficiencies towards phenolic acids. Dispersive SPE experiments performed with the [C₆-bis-VIM] [Br] crosslinked polymers exhibited significantly higher extraction recoveries for the majority of analytes. Due to these promising results, the [C₆-bis-VIM] [Br] crosslinked polymer was optimized in terms of the monomer to crosslinker ratio and an efficient dispersive SPE protocol was developed, with maximum recoveries ranging from 84.1–92.5% and RSD values ˂ 1%. The developed extraction procedure was also applied to cartridges resulting in recoveries between 97.2 and 98.5%, which were on average 5% higher than with the commercial anion exchange sorbent Oasis^® MAX. Furthermore, the sorbent was regenerated showing a good reusability for the majority of analytes. In conclusion, this study clearly highlights the yet untapped potential of the crosslinker, [C₆-bis-VIM] [Br], with respect to the synthesis of efficient anion exchange polymers for SPE. Full article

This study investigated the influence of four different methods of cooking (charcoal grilling, electric barbecue grilling, superheated-steam roasting and infrared grilling) on the volatile profile of lamb meat patties. The study included the patties of the oyster cut muscle of lambs cooked using charcoal grilling, electric barbecue grilling, infrared grilling and superheated-steam roasting methods. The principal component analysis (PCA) of electric nose data showed a total variance of 73.71%. The e-nose values showed differentiation of the volatiles released from the lamb meat patties. Data of PCA of e-nose and GC-MS revealed good separation between groups. Significance (p < 0.05) was found for the flavour profile values of charcoal-grilled and superheated-steam-roasted samples while the lowest significance was observed between infrared- and electric-barbecue-grilled samples. Saltiness and sourness were higher in superheated-steam-roasted patties than charcoal-grilled samples through e-tongue. The main volatile compound found in all the lamb patties was 2,3-octanedione with a content of 20.43 µg/g–27.83 µg/g. 1-hexanol was highest at 34.74 µg/g in the charcoal-grilled samples while 2,3-octanedione was highest at 35.83 µg/g in superheated-steam-roasted patties. Full article

Alternaria toxins (ATs) are frequently found contaminants in foodstuffs (e.g., alternariol), often reaching high concentrations (e.g., tenuazonic acid). They can spoil a wide variety of food categories (e.g., cereals, vegetables, seeds and drinks) and storage at fridge temperatures does not prevent the growth of Alternaria fungi. Therefore, reliable and validated analytical methods are needed to protect human health and to ensure a transparent and fair trade. This paper describes new technical features that improved a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the analysis of ATs in tomato, wheat and sunflower seeds. This analytical method should be simple to implement in different laboratories across the EU and thus be an attractive candidate for standardisation. The major element for improvement was the use of isotopically labelled internal standards, only recently commercially available, thereby reducing the sample handling and improving the accuracy of the results. In addition, the sample extraction and the solid-phase extraction (SPE) enrichment/clean-up were fine-tuned, whereas a more suitable analytical column (XSelect HSS T3) with improved selectivity was also employed. Overall, this method shows adequate precision (repeatability < 5.7% RSD; intermediate precision < 7.0% RSD) and trueness (recoveries ranging from 74% to 112%). The limits of quantification in wheat (the most analytically demanding matrix) vary between 0.19 and 1.40 µg/kg. These figures were deemed satisfactory by the European Committee for Standardization (CEN) and have formed the basis for a subsequent interlaboratory validation study. The corresponding standard was published by CEN in 2021. Full article

Anthracyclines are a group of antineoplastic compounds used to treat acute leukemia and other cancers, and they are excreted after consumption by patients. These chemicals are often found in sewage at very low concentration levels. For this reason, the development of sensitive analytical methodologies capable of determining them at low concentrations is of prime importance. A simple, fast and sensitive analytical method using fabric phase sorptive extraction (FPSE) followed by ultra-high performance liquid chromatography with fluorescence detection (UHPLC-FD) has been developed and validated for the extraction of anthracyclines from sewage samples. FPSE is a green, cheap, simple, selective and rapid sample preparation technique. The different parameters that affect the performance of the FPSE process, including extraction time, eluting solvent, elution time and pH, were optimized. The developed method showed satisfactory reproducibility, with intraday and interday RSD values lower than 15% for all the compounds and limits of detection between 0.1–0.15 µg·L⁻¹. The unique combination of sample preparation by this micro-extraction technique with fluorescence detector have resulted in the satisfactory extraction of highly polar anthracyclines, without any noticeable matrix effect, a very common shortcoming of exhaustive sample preparation technique such as solid phase extraction (SPE) and mass spectrometry. Full article

One-hundred and seven different volatile compounds were identified in the samples of Arctostaphylos uva-ursi collected from nine locations in Spain. This plant is commonly brewed and used as tea. Volatile compounds profile was detected using solid-phase microextraction gas chromatography-mass spectrometry. The most interesting compounds detected from an antioxidant capacity point of view were esters, phenols, and aromatics compounds. All samples were discriminated by principal component analysis. The insolation and altitude of harvest areas, and latent structures were considered for interpretation of results. Discriminant analysis was applied to control the type and concentration of metabolites and determine the best plant antioxidant profiles of volatile compounds from plant origin. Moreover, a heatmap displayed correlations between detected compounds. The discriminant analysis led to 20 quality markers being identified for the analysed plants. The strongest antioxidant capacity was obtained in the samples from Pina de Montalgrao and Loarre (collected in September) for ORAC (33.11 ± 0.61 g Trolox/g sample) and DPPH (IC₅₀ = 711 ± 12 µg/g) methods, respectively. The plant with the highest total phenolic content was Loarre collected in September (171.9 ± 19.4 mg GAE/g DW) and November (177.1 ± 11.0 mg GAE/g DW). Full article

Mine waste can constitute an environmental hazard, especially when poorly managed. Environmental assessment is essential for estimating potential threats and optimizing mine waste management. This study evaluated the potential environmental risk of sulfidic mine waste samples originating from the Neves Corvo Mine, Portugal, and the closed Freiberg mining district, Germany. Metal(loid)s in the waste samples were partitioned into seven operationally defined fractions using the Zeien and Brummer sequential extraction scheme. The results showed similar partitioning patterns for the elements in the waste rock and tailing samples from Neves Corvo Mine; most metal(loid)s showed lower mobility, as they were mainly residual-bound. On the contrary, the Freiberg tailing sample had considerably elevated (24–37%) mobile fractions of Zn, Co, Cd, and Mn. The majority of Fe (83–96%) in all samples was retained in the residual fractions, while Ca was highly mobile. Overall, Pb was the most mobile toxic element in the three samples. A large portion of Pb (32–57%) was predominantly found in the most mobilizable fractions of the studied waste samples. This study revealed that the three mine wastes have contamination potential for Pb and Zn, which can be easily released into the environment from these waste sources. Full article

Chestnut (Castanea sativa Mill.), a valuable fruit crop, is cultivated in small areas in Romania, mostly in the west, where the moderate continental climate has a slight Mediterranean influence. This work aims to investigate the bioactive characteristics (total polyphenols, total flavonoids and antioxidant activity), individual polyphenolic composition, phytochemical and nutritional HRMS screening profiles, sugar and mineral composition of six sweet chestnut cultivars, namely ‘Marsol’, ‘Maraval’, ‘Bournette’, ‘Précoce Migoule’ and ‘Marissard’ grown at Fruit Growing Research—Extension Station (SCDP) Vâlcea, in Northern Oltenia, Romania. Fruit samples were collected in two consecutive years, in order to study the impact of genetic variability between cultivars and the influence of the different climatic conditions corresponding to different cultivation years. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) allow the discrimination between the sweet chestnut fruits harvested in different years and different sweet chestnut cultivars. Analytical investigations revealed that sweet chestnut cultivars grown in Romania show similar bioactive, phytochemical and nutritional composition to cultivars grown in the large European chestnut-producing countries, indicating the high adaptation potential of the chestnut in the temperate continental zone with small Mediterranean influences characteristic of the southwestern area of Romania. Full article

In an effort to combat the risks associated with traditional tobacco products, tobacco product innovation has been redirected towards reducing the consumer’s potential exposure to harmful or potentially harmful constituents (HPHCs). Among these innovations are modern oral nicotine products (MONPs). This product class aims to deliver nicotine while limiting the consumer’s potential toxicant exposure. This body of work sought to investigate the potential for select HPHC exposure (tobacco-specific nitrosamines, carbonyls, benzo[a]pyrene, nitrite, and metals) from MONPs and to compare it to that from traditional tobacco products. This work expands on previously published studies both in terms of diversity of products assessed and analytes tested. In total, twenty-one unique MONPs were assessed and compared to four traditional tobacco products. We found that there was a difference in the potential exposure based on the MONP filler—plant material vs. granulate/powder. Typically, the HPHC levels observed in plant-based MONPs were higher than those observed for granulate/powder products, most notably within the metals analysis, for which the levels were occasionally greater than those seen in traditional smokeless tobacco products. Generally, the overall HPHC levels observed in MONP were at or below those levels observed in traditional tobacco products. Full article

In this study, zeolite molecular sieve SAPO-34/polydimethylsiloxane (PDMS) mixed matrix membranes (MMMs) were prepared to recover propane. n-Octyltrichlorosilane (OTCS) was introduced to improve compatibility between SAPO-34 and PDMS, and enhance the separation performance of the MMMs. Physicochemical properties of the MMMs were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and water contact angle (WCA). Results showed that, after modification, alkyl chains were successfully grafted onto SAPO-34 without changing its crystal structure, particles in the MMMs were evenly distributed in the base film, and the hydrophobicity of the MMMs was enhanced. Moreover, the effects of SAPO-34 filling content, operating pressure, and feed gas concentration on the separation performance was explored. This indicated that the modification with OTCS effectively enhanced the separation performance of SAPO-34/PDMS MMMs. When the filling content of modified SAPO-34 was 15%, the maximal separation factor of 22.1 was achieved, and the corresponding propane permeation rate was 101 GPU. Full article

Wastewater reuse is essential for sustainable water management. However, it requires tertiary treatment within the plant to ensure suitable water quality. This project aims to investigate the comparative performance of conventional tertiary treatment (sand filtration) against membrane filtration technology to demonstrate the viability of membrane treatment for wastewater reuse. Sand filtration along with two membrane filtrations, Nano Filtration (NF) and Reverse Osmosis (RO), were tested for their efficiency in removing the target pollutants: chromium, phosphate, and UV-254 from secondary effluent. Standard medium-sized laboratory setups were used. Synthetic secondary effluent was used for comparison among the different treatment processes. The synthetic effluent was compared to the real wastewater to demonstrate the reliability of using synthetic effluent. Evaluation of the role of time and pressure on the treatment efficiency was also examined. Based on the experimental results, RO had the highest removal efficiency for all pollutants with more than 90% removal. The experimental results also showed that synthetic wastewater was reliable in representing the treatability of real wastewater. Time did not seem to have an impact on the quality of filtration. Moreover, as pressure increased there was a slight increase in the efficiency. This trend was observed in all pollutants except UV-254. ANOVA showed different results of the effect of pressure on the removal efficiency in both RO and NF as well as time in NF. Full article

The development of advanced feed spacers under different working conditions can enhance the performance of the reverse osmosis (RO) desalination process. The 3D-printed experimental results on triply periodic minimal surfaces (TPMS)-based spacers in previous literature indicate that the spacers have higher permeation flux of water compared to those of the common commercial spacers. In this paper, a hybrid modeling approach is developed and applied to predict and evaluate the performance of TPMS-based spacers. The effect of feed channels’ height and porosity on the performance of spacers in brackish water RO (BWRO) process is studied by using a high-throughput approach. The predicted pressure drop by new simulations using the TPMS-based spacers (≈0.09–0.27 bar) from inlet to outlet in a typical two-stage BWRO system is reduced by more than 89% than that of using the commercial spacer (≈2.57 bar). Using the designed advanced spacers, the average permeation flux of water increases more than 8.6% compared to that of the commercial one. With the increase in feed channel height and porosity, the performance of spacers is gradually improved. TPMS-based spacers have significant industrial application prospects. Full article

A simple and green ultra-high-performance micellar liquid chromatography (MLC) method was developed here, comparing Tween 20 and Tween 40 for the first time as the only mobile phase modifiers with a C18 column. Its application to the separation of nine hydroxycinnamic acid (HCA) derivatives (cinnamic, caffeic, ferulic, sinapic, o-, m-, p-coumaric, 3,4-dihydroxyhydrocinnamic, and chlorogenic acids) was made, due to their importance as antioxidants in a variety of natural beverages such as wine and coffee. The optimal conditions of 45 °C temperature (T), 1% surfactant in the mobile phase, and pH control with 2.5 mM sulfuric acid were determined and used to elucidate the analytical figures of merit. Although the effect of these conditions was insignificant between the two surfactants, the nine-component HCA mixture was separated faster—in about 15 min—and with less peak tailing using Tween 20 than with Tween 40. The linearity of the Van’t Hoff (lnk versus 1/T) plots was evident for Tween 20, indicating a single retention mechanism—but less so for Tween 40. The equilibrium constants of the analytes with the micelles and the stationary phase were calculated. The developed method was successfully used to analyze organic red wine, spiked organic red wine, and green coffee diet pills. The percent recoveries of the nine HCA compounds spiked in the organic red wine ranged from 90% to 107%. The green coffee extract diet pills showed the presence of a significant amount of chlorogenic acid. Full article

The production of bioethanol fuels using extractive fermentation increases the efficiency of the bioconversion reaction by reducing the toxic product inhibition. The choice of appropriate solvents to remove the bioethanol product without inhibiting the fermentation is important to enable industrial scale application. This work applies computer-aided molecular design technologies to systematically screen a wide variety of candidate solvents to enhance the separation, also considering the microorganisms that perform the fermentation. The performance of the candidates was evaluated using a rigorous process simulator for extractive fermentation, assisted by functional group-contribution (QSPR/QSAR) models for the prediction of various solvent properties, including toxicity and life cycle impacts. The solvent designs generated through this approach can provide powerful insights on the kind of molecular structures and functionalities that satisfy the process objectives and constraints, as well the desired sustainability features. Full article

A novel rapid and cost-effective pre-processing method for the simultaneous determination of pyrethroid pesticides in vegetables has been developed and validated. The process of pesticide extraction was carried out by the QuEChERS (quick, easy, cheap, effective, rugged and safe) method combined with filtration by filter paper, and cleanup was carried out by the multi-plug-filtration-cleanup (m-PFC) method with no centrifuge program during the whole process. The pre-processing method is optimized for gas chromatography (GC). The process is convenient and time saving, requiring just a few seconds per sample. The recovery rate (70–120%), limit of detection (0.0001–0.007 mg/kg), precision (0.2–9.3%) and accuracy for each analyte were determined in 10 representative vegetables with good results. Finally, the feasibility of the developed method was further confirmed by the successful determination of pyrethroid-pesticide residues in pyrethroid-containing practical samples within the processing method coupled with thin-layer chromatography and a colloidal-gold test strip. Full article

Aflatoxin M1(AFM1), a major metabolite of Aflatoxin B1(AFB1), has been identified as a potential contaminant in dairy products. Because of its possible carcinogenicity, the legislation limits as set by Commission Regulation (EC) No. 1881/2006 are very strict, namely 0.050 μg kg⁻¹ in milk and 0.025 μg kg⁻¹ in infant formulas. To meet these requirements, a sensitive and accurate method was developed, employing liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Ιmmunoaffinity columns (R-Biopharm) were used for sample purification and preconcentration of the analyte of interest. The quantification of AFM1 was conducted using fortified milk samples, while Aflatoxin B2 (AFB2) was used as an internal standard (IS). The method was validated in terms of linearity, precision, trueness, limits of detection and quantification and uncertainty. The performance criteria for the method were evaluated based on European Commission Regulation (EC) No. 401/2006 and its most recent amendment, as well as the suggested criteria for revision by the EU Reference Laboratory for Mycotoxins and Plant Toxins. The recovery was in the range of 77.9–81.0% for all fortification levels (0.025–0.050–0.075 μg kg⁻¹), with RSD_R values (Relative Standard Deviation of intermediate precision) ranging from 6.1% to 12%. The method’s detection and quantification limits were 0.0027 μg kg⁻¹ and 0.0089 μg kg⁻¹, respectively. The occurrence of AFM1 was investigated in 40 samples of different animal origin (cow, goat and sheep milk) provided by Greek producers. Full article

Most commercially available lithium ion battery systems and some of their possible successors, such as lithium (metal)-sulfur batteries, rely on liquid organic electrolytes. Since the electrolyte is in contact with both the negative and the positive electrode, its electrochemical stability window is of high interest. Monitoring the electrolyte decomposition occurring at these electrodes is key to understand the influence of chemical and electrochemical reactions on cell performance and to evaluate aging mechanisms. In the context of lithium-sulfur batteries, information about the analysis of soluble species in the electrolytes—besides the well-known lithium polysulfides—is scarcely available. Here, the irreversible decomposition reactions of typically ether-based electrolytes will be addressed. Gas chromatography in combination with mass spectrometric detection is able to deliver information about volatile organic compounds. Furthermore, it is already used to investigate similar samples, such as electrolytes from other battery types, including lithium ion batteries. The method transfer from these reports and from model experiments with non-target analyses are promising tools to generate knowledge about the system and to build up suitable strategies for lithium-sulfur cell analyses. In the presented work, the aim is to identify aging products emerging in electrolytes regained from cells with sulfur-based cathodes. Higher-molecular polymerization products of ether-based electrolytes used in lithium-sulfur batteries are identified. Furthermore, the reactivity of the lithium polysulfides with carbonate-based solvents is investigated in a worst-case scenario and carbonate sulfur cross-compounds identified for target analyses. None of the target molecules are found in carbonate-based electrolytes regained from operative lithium-titanium sulfide cells, thus hinting at a new aging mechanism in these systems. Full article

This review explores the potential of separating and recycling rare earth elements (REEs) from different energy conversion systems, such as wind turbines, electric vehicles batteries, or lighting devices. The REEs include 17 elements (with global production of 242 kilometric tons in 2020) that can be found abundantly in nature. However, they are expensive and complicated to extract and separate with many environmental challenges. The overall demand for REEs is continuously growing (with a 10% yearly increase) and it is quite clear that recycling has to be developed as a supply strategy in addition to conventional mining. However, the success of both mining and recycling depends on appropriate separation and processing technologies. The overall REE recycling situation today is very weak (only 2% of REEs are recovered by recycling processes compared with 90% for iron and steel). The biggest recycling potentials rely on the sectors of lamp phosphors (17%), permanent magnets (7%), and NiMH batteries (10%) mainly at the end-of-life stage of the products. The profitability of rare earth recycling mostly depends on the prices of the elements to accommodate the processing costs. Therefore, end-of-life REE recycling should focus on the most valuable and critical REEs. Thus, the relevant processes, feed, and economic viability warrant the detailed review as reported here. Full article

A new open-chain ether-linked polymer has been prepared via nucleophilic aromatic substitution reaction on a C-F bond of 1,4-dibromo-2,5-difluorobenzene by using 2,2-bis(4-hydroxyphenyl) hexafluoropropane (bisphenol AF or BAF). The new polymer (PE-AF) has shown a good solubility in non-polar solvents, good thermal stability (up to 300 °C) and random surface morphology. Tailoring these properties has been achieved by utilizing the post-modification synthetic methodology on the bromo-sites of the polymer backbone via the application of an Ullmann coupling reaction with aniline to form the polymer (PE-Sec-NHPh). The successful synthesis of the polymers has been confirmed by elemental analysis, infrared spectroscopy (IR), ¹H- and ¹³C-NMR and ¹³C CP-MAS solid state. Upon incorporation of the aniline linker, the nitrogen content increased when compared with the parent polymer chain, and thus PE-Sec-NHPh revealed a higher thermal stability up to 350 °C and a more uniformly aggregated morphology (spherical particles ca. 0.3–0.1 µm). A further evaluation has been conducted on the polymers by measuring their surface tendency toward carbon dioxide capture. Interestingly, despite their non-porous nature, the polymers demonstrated a reasonable amount of gas capture that reached 90.0 and 41.0 mg/g for PE-Sec-NHPh and PE-AF, respectively. Furthermore, the calculated CO₂ binding affinities of the polymers are consistent with data reported previously in the literature. Full article