Separations, Volume 9, Issue 6 (June 2022) – 22 articles

The study aims to treat artificial wastewater contaminated with copper (II) ions by reverse osmosis using (SEPA CF042 Membrane Test Skid-TFC BW30XFR). Several concentrations of feedstock were prepared. Different operating pressure, temperature, and flow rate were applied. The effect of these operating conditions on both the amount of Cu (II) removal and the permeate flux was monitored. The results of the study revealed that both the permeate flux and Cu (II) removal amount were directly proportional to the operating pressure and feed temperature but inversely proportional to the feed concentration. In contrast, the feed flow rate showed a negligible effect on the permeate flux and Cu (II) removal amount. The temperature correction factor (TCF) of the membrane was calculated and was found to be directly proportional to the feed temperature but inversely proportional to the applied pressure. It was seen that the concentration and flow rate of that feed did not affect the temperature correction factor. Mathematical models have been developed based on these experimental data for both permeate flux and the Cu (II) removal. It was noted that the permeate flux model matched the experimental data, while the Cu (II) removal model did not show a perfect match. In addition to the above, the research highlights for subsequent studies the possibility of a deep link between experimental work and mathematical models. Full article

A review of the investigations devoted to the solvent extraction processes of metal ions with a chelating ligand thenoyltrifluoroacetone (HTTA) is presented herein. It seems that this molecule has been preferred in the field for more than half a century, and that it is used very often as an extractant for almost all metals. The main objective of the present review is also to provide an overview of the synergistic solvent extraction of lanthanoids, particularly with the use of a β-diketone−neutral mixture. Based on the previous published results in the open literature, the extraction efficiency has been examined in detail and discussed further mainly in terms of the corresponding equilibrium constants among other outlined, so-important parameters. Major conclusions on the role of ligating groups of extractants towards the mechanism, an improved extraction enhancement, and selectivity are additionally provided. The fact that ionic liquids (ILs) appear to be replacing volatile diluents in the field of the liquid–liquid extraction of metals, again with the participation of this β-diketone, is not surprising. As is well known, a very efficient and simple way to determine the stoichiometry of the extracted species in the organic phase is by the simple use of the slope analysis method; however, it is sometimes difficult to perform, either because it somehow requests good solubility of the ligand or because obtained slopes are quite often far from integer values in ILs. Full article

Recycling waste concrete has become a large problem in developing countries. The aim of this work is to provide guidance for screening concrete particles and improving screening efficiency. First, the elastoplastic collision model is established for calculating the coefficient of restitution for concrete particles with different compressive strengths. Then, a bar circular vibrating screen is applied to simulate the screening process of concrete particles by using the discrete element method (DEM). The optimal vibrating parameters, which contain amplitude, frequency and inclination angles, is analyzed for the representative concrete particles containing C15, C45 and C80 by comparing the screening efficiency. The results show that the optimal screening parameters of amplitude and frequency is smaller with the increase in the compressive strength of the concrete particles. Appropriately, the large inclination angle is suitable for screening fine concrete particles with a gap vibrating screen. This work should be helpful for the screening process of concrete waste particles and provides a theoretical basis and simulation case for screening and recycling other particles, such as sand, stone, iron ore and copper ore. In the screening processes of construction wastes, the optimal screening parameters can be selected quickly by calculating the coefficient of restitution and adopting the DEM simulation. Full article

The study aimed to evaluate the antioxidant potential of sprout and seed extracts from three species of plants, namely Glycine max (GMsp-sprouts, GMsd-seeds), Anethum graveolens (AGsp-sprouts, AGsd-seeds) and Pimpinella anisum (PAsp-sprouts, PAsd-seeds), which are widely accepted by consumers and have various applications in food flavoring, and also in natural medical treatments in the pharmaceutical industries. These plants are rich in valuable compounds that show a remarkable antioxidant power and are associated with many health benefits. Ethanol extracts were obtained by ultrasound-assisted extraction and they were comparatively evaluated for their in vitro antioxidant properties. The extracts were characterized by HPTLC, HPLC-DAD, total phenol content (TPC), total flavonoid content (TFC) analysis and antioxidant activities with different assays, such as total antioxidant capacity (TAC), 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) radical cation decolorization assay (ABTS), 1,1-diphenyl 1-2-picryl-hydrazyl (DPPH) and iron binding ability of chelators. Our results showed that the sprout and seed extracts of the studied plants exhibited a high content of phytochemicals and promising antioxidant properties. The highest polyphenols content was detected for AGsd (53.02 ± 0.57 mg/g DW), PAsd (48.75 ± 0.34 mg/g DW) and the highest flavonoids content for PAsp (26.84 ± 0.57 mg/g DW). Moreover, the presence of valuable compounds was demonstrated by using HPTLC, FT-IR and HPLC-DAD techniques. In order to have a better understanding of the relationship between the biological properties and the electronic structure, a molecular modelling study of genistein was also conducted. Our approach to the comparative assessment of these three plant species was based on a priori knowledge from literature data; however, this study demonstrated that these plant extracts of seeds and also sprouts are excellent sources of natural antioxidants. Significant additional differences that were found in the phytochemical composition could be exploited in future research for pharmaceutical purposes. Full article

Wastewater treatment for indirect potable reuse (IPR) is a possible approach to address water scarcity. In this study, a novel membrane bioreactor–membrane distillation (MBR-MD) system was evaluated to determine the environmental impacts of treatment compared to an existing IPR facility (“Baseline”). Physical and empirical models were used to obtain operational data for both systems and inform a life cycle inventory. Life cycle assessment (LCA) was used to compare the environmental impacts of each system. Results showed an average 53.7% reduction in environmental impacts for the MBR-MD system when waste heat is used to operate MD; however, without waste heat, the environmental impacts of MBR-MD are significantly higher, with average impacts ranging from 218% to 1400% greater than the Baseline, depending on the proportion of waste heat used. The results of this study demonstrate the effectiveness of the novel MBR-MD system for IPR and the reduced environmental impacts when waste heat is available to power MD. Full article

This paper describes the isosteric enthalpy through narrow pores at low levels of coverage through adsorption of CO₂, CH₄, and H₂ on pores in natural chabazite exchanged with aqueous solutions of Na⁺, Mg²⁺, and Ca²⁺ salts at different concentrations, and with variable time and temperature of treatment. Experimental data of CO₂, CH₄, and H₂ adsorption were treated by the Freundlich and Langmuir equations. Complementarily, the degree of interaction of these gases with these zeolites was evaluated by the evolution of isosteric enthalpy of adsorption. The exchange with Mg²⁺ and Na+ favors an increase in the adsorption capacity for CO₂. while that of Ca²⁺ and Mg²⁺ favor adsorption through to H₂ and CH₄. These cations occupy sites in strategic positions S4 and S4’, which are located in the channels and nanocavities of these zeolites. The presence of Ca²⁺ and Mg²⁺ at S4 and S4′ sites causes increased adsorption into the nanocavities and on the external area of the ion-exchanged zeolites. Depending on the conditions of the exchange treatment, Ca²⁺ and Mg²⁺, and Na+ were found to be most favorable, well distributed, and accessible for CO₂, CH₄, and H₂ adsorption. Full article

High potential toxic element (PTE) concentrations in soils that exceed local regulatory threshold values have been reported in non-polluted mountainous areas worldwide. However, there have been few studies that have comprehensively investigated the contribution of natural factors including the parental material, pedogenesis processes and physiochemical properties of soils on the distribution of PTEs in these soils. Therefore, in this study, we studied the distribution of 13 PTEs in sloping farmland soils collected from a mountainous watershed in Guizhou Province, Southwest China. The contributions of natural influencing factors were analyzed using a geostatistical analysis and a geographic detector method. All of the PTEs were unevenly distributed, especially Sb, and the average contents of V, Cr, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl, Pb and Hg were 57.15, 36.20, 4.61, 12.61, 13.36, 63.50, 11.94, 0.78, 0.37, 6.44, 0.48, 27.42 and 0.36mg/kg, respectively. The proportion of samples with Cd, Hg and As exceeding the screening value of the soil pollution risk of agricultural land in China was 46.7%, 5.9% and 4.4%, respectively. Except for Cd and Pb, the q values of the PTEs calculated from the geographical detector were above 0.05, indicating that altitude changes, which affect the pedogenesis process, have a great impact on the spatial distribution. Stratigraphic factors contributed greatly to the distribution of Co, Ni and Cu, which indicates their similarity in parental material. The combined effect of clay content, topographic factors and agricultural land types had the strongest explanatory power for V, Cr, Mo and Pb. The distributions of As, Sb, Tl and Hg are strongly associated with a potential source of mercury ore, and their accumulation is also enhanced by the adsorption on soil clay. Agricultural As also contributes to its distribution. Full article

The extensive use of pesticides represents a risk to human health. Consequently, legal frameworks have been established to ensure food safety, including control programs for pesticide residues. In this context, the performance of analytical methods acquires special relevance. Such methods are expected to be able to determine the largest number of compounds at trace concentration levels in complex food matrices, which represents a great analytical challenge. Technical advances in mass spectrometry (MS) have led to the development of more efficient analytical methods for the determination of pesticides. This review provides an overview of current analytical strategies applied in pesticide analysis, with a special focus on MS methods. Current targeted MS methods allow the simultaneous determination of hundreds of pesticides, whereas non-targeted MS methods are now applicable to the identification of pesticide metabolites and transformation products. New trends in pesticide analysis are also presented, including approaches for the simultaneous determination of pesticide residues and other food contaminants (i.e., mega-methods), or the recent application of techniques such as ion mobility–mass spectrometry (IM–MS) for this purpose. Full article

The analytical GREEnness metric (AGREE) tool is widely used as a reliable greenness assessment method for chromatographic analyses. The AGREE tool has the ability to determine the greenness of analytical methods in terms of both quality and quantity, whereas other commonly used methods assess the greenness either quantitatively or qualitatively. Greenness profiles of six chromatographic methods for simultaneous estimations of serotonin, dopamine, acetylcholine, GABA and glutamate were assessed using AGREE and NEMI tools as a case study. The AGREE assessment tool proved to be user-friendly, and provides a full profile of assessment, hence it can be described as the tool of choice for the assessment of LC-MS chromatographic methods. For optimum application, the weights of 4 of the 12 assessment criteria were set high (weight of four) due to their importance, namely criteria number 7 (waste), number 8 (analysis thruput/number of analytes per run), number 11 (toxicity) and number 12 (operator’s safety). Setting proper weights of the assessment criteria contributed significantly to the discrimination of greenness of the compared methods. The selected greenest method for the analysis of the proposed quinary mixture showed an AGREE tool pictogram with a 0.66 score. Additionally, the selected method allows simultaneous estimation of seven constituents in total. It offers high sensitivity, allowing detection of acetylcholine, serotonin and glutamate at levels as low as 2 pg, and dopamine, norepinephrine, GABA and glycine at levels as low as 10 pg, and finally offers fast analysis where all components can be analyzed within 5 min. Full article

Stability as a function of mobile phase pH is an important consideration when selecting a chromatographic column. While the pH stability of reversed-phase columns is widely studied, there are relatively few reports of the stability of hydrophilic interaction chromatography (HILIC) columns. We evaluated the stability of silica and ethylene-bridged hybrid HILIC columns when used with mobile phases containing basic buffers. The predominant mode of column degradation observed in our studies was a decrease in efficiency due to voiding, resulting from the hydrolysis of the silica particles. Associated with this were increases in tailing factors. Retention factor changes were also noted but were smaller than the efficiency losses. The dependence of the rate of efficiency decrease on the key variables of temperature, mobile phase pH and water content were studied for an unbonded silica column. The effect of the acetonitrile concentration on the pH of the mixed aqueous/acetonitrile mobile phases was also investigated. Using conditions found to cause a 50% decrease in efficiency after approximately five hours of exposure to the basic solution, we evaluated eight different commercially available HILIC columns containing silica or ethylene-bridged hybrid particles. The results show large differences between the stability of the silica and ethylene-bridged hybrid particle stationary phases, with the latter exhibiting greater stability. Full article

For non-bovine milks, information regarding bioactive lipids is fragmented, unreliable or unavailable. The purpose of the current study was to analyse bioactive lipids in the milk of dairy animals using modern analytical methods to achieve the most reliable results. Bioactive lipids in human milk were also analysed and used as a reference. A suite of modern analytical methods was employed, namely High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS), Gas Chromatography (GC) and Nuclear Magnetic Resonance (NMR). The total lipid content was determined, and phospholipid, fatty acid, neutral glycosphingolipids and ganglioside (GM3 and GD3) levels were measured. Lipid classes in selected milks were reliably characterised for the first time, including gangliosides in deer, camel and sheep; cerebrosides in deer, camel and buffalo; plasmalogens in deer, buffalo and goat and phospholipids in deer. Our study demonstrated the advantage of utilising a range of analytical techniques in order to characterise a diverse set of bioactive lipids. Full article

Educational and research laboratories often produce relatively small amounts of highly diverse organic wastes. Treating waste can contribute significantly to the cost of running laboratories. This study introduced a simple and economical waste management system such that readily available used chromatography-grade inorganic materials, such as silica and alumina (basic and acidic), are utilized to treat remnant dye solutions and solution wastes from educational and small research laboratories. To recycle the adsorbents, they were heated to 600 °C, where the adsorbates were combusted. The results showed that acidic alumina is an effective adsorbent material for azo dyes and anionic dyes/stains, as well as textile dyes, with a 98 to 100% removal efficiency. Furthermore, alumina and silica possess excellent regeneration properties, where the dye removal efficiency of the materials was retained after regeneration at 600 °C. The adsorption properties of the materials were compared with those of aliginite and activated biomass from coffee grounds. Kinetic and thermodynamic studies of the sorption processes on the different materials were carried out. Overall, the inorganic materials used were efficient at removing contaminating remnant organic dyes stemming from educational and small research laboratories. Full article

Urine citrate analysis is relevant in the screening and monitoring of patients with calcium nephrolithiasis. A sensitive, fast, easy, and low-maintenance ion chromatographic (IC) method with conductivity detection for the analysis of urine citrate is developed and validated. Its application on true samples is also reported. Sample urine is diluted with a water solution containing internal standard (IS) before the chromatographic assay. The isocratic chromatographic run time is twenty-five minutes, using sodium hydroxide aqueous solution as the mobile phase. The method is fully validated as a quantitative method to objectively demonstrate its applicability for the intended use. The analytical response is linear in the 0.08–10.4 mmol/L concentration range. Precision and accuracy studies carried out on spiked urine and internal quality control samples reveal an imprecision CV% lower than 11% and an accuracy between 85 and 103%. The stability of citrate in urine samples is also evaluated. An easy, rapid, and low-maintenance, cost-effective IC method for urinary citrate determination is developed and validated. Internal standardization improves reliability and precision. The method has been currently used in our laboratory over recent years to analyze more than 1000 samples per year. Full article

In this experiment, the Box–Behnken design (BBD) of the response surface methodology (RSM) was used to optimize the ultrasound-assisted extraction variables (liquid-to-solid ratio, extraction temperature, and time) to obtain the maximum yield of physcion from the methanol extract of S. occidentalis (aerial parts). The analysis of physcion in the extracts obtained by using the optimized extraction condition was carried out in a gradient system by the HPLC-UV method with 0.5% formic acid in ultra-pure water (Solvent A) and acetonitrile (Solvent B) in different ratios as the mobile phase. The optimal extraction conditions for the maximum physcion extraction were found as: a liquid-to-solid ratio of 20.16 mL/g, extraction temperature of 52.2 °C, and extraction time of 46.6 min. Under these optimal ultrasonic extraction conditions, the experimental yield (% w/w of the dried extract) of the physcion was found to be 2.43%, which agreed closely with the predicted value (2.41). The experimental value was consistent with the value predicted by the RSM model, thus validating the fitness of the employed model and the success of the RSM in optimizing the extraction conditions. In future, this optimized ultrasonic extraction condition can be used in the maximum extraction of physcion from marketed herbal supplements containing S. occidentalis as well as other Senna species. Full article

The main branch of vitamin D₃ metabolism involves several hydroxylation reactions to obtain mono-, di- and trihydroxylated metabolites, including the circulating and active forms—25(OH)D₃ and 1,25(OH)₂D₃, respectively. However, most clinical trials strictly target the determination of 25(OH)D₃ to offer a view of the metabolic status of vitamin D₃. Due to the growing interest in expanding this restricted view, we have developed a method for measuring vitamin D₃ metabolism by determination of vitamin D₃, 25(OH)D₃, 24,25(OH)₂D₃, 1,25(OH)₂D₃ and 1,24,25(OH)₃D₃ in human plasma. The method was based on SPE–LC–MS/MS with a large volume injection of human plasma (240 µL). Detection of di- and trihydroxymetabolites, found at the picogram per milliliter level, was attained by the combined action of high preconcentration and clean-up effects. The method allows obtaining information about ratios such as the known vitamin D metabolite ratio (24,25(OH)₂D₃/25(OH)D₃), which can provide complementary views of vitamin D₃ metabolic status. The method was applied to a cohort of obese patients and a reference cohort of healthy volunteers to find metabolic correlations between target analytes as well as differences as a function of vitamin D levels within and between cohorts. Full article

A method for quantifying the anthocyanins in grapes was firstly developed by ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOFMS) combined with quantitative analysis of multi-components by single marker (QAMS). A total of 10 main anthocyanins were analyzed by using peonidin 3-O-glucoside as the reference standard. The accuracy of this method was evaluated by an established and validated external standard quantification method with 10 reference compounds. The standard method difference (SMDs) of the quantification results between QAMS and the external standard methodwasless than 15%. Furthermore, the QAMS method was used to analyzefour batches of grapes and the data was compared with those obtained using the external standard method. No significant difference wasobtained in the results obtained by both methods. These results indicated that the QAMS method could accurately determine the anthocyanins in grapes. This method can provide a basis to address the absence of reference standards for analyzing anthocyanins in other foods. Full article

The study provides a review of various applications of biomass-derived biochars, waste-derived biochars, and modified biochars as adsorbent materials for removing dyestuff from process effluents. Processing significant amounts of dye effluent discharges into receiving waters can supply major benefits to countries which are affected by the water crisis and anticipated future stress in many areas in the world. When compared to most conventional adsorbents, biochars can provide an economically attractive solution. In comparison to many other textile effluent treatment processes, adsorption technology provides an economic, easily managed, and highly effective treatment option. Several tabulated data values are provided that summarize the main characteristics of various biochar adsorbents according to their ability to remove dyestuffs from wastewaters. Full article

Phytochemical characterization of the ethyl acetate fraction of Saussurea hypoleuca root extract resulted in the isolation of oleic acid (1) and luteolin (2), which were isolated for the first time from Saussurea hypoleuca root. A heavy metal analysis of the root powder performed using atomic absorption spectroscopy showed that the contents of iron, cadmium, lead, zinc, nickel, and copper were within the certified limits according to the WHO guidelines. Differential scanning calorimetry (DSC) revealed its crystalline and amorphous nature; meanwhile, standardization of the root with UHPLC revealed the presence of 14.79 ± 0.015 µg/mL of luteolin. Both the total methanol extract and the ethyl acetate fraction of the plant root held significant anthelmintic activity. Oleic acid and luteolin exhibited potent antioxidant activity, evidenced by their IC₅₀ values, which were equal to 47.0 and 119.8 µg/mL, respectively, in a 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging assay. In silico studies showed that luteolin exerted the highest fitting within the binding sites of NADPH oxidase (Nox). For myeloperoxidase (MP), oleic acid revealed the best fitting in its active sites. The results of ADMET (absorption, distribution, metabolism, excretion, and toxicity) and TOPKAT (toxicity prediction) protocols revealed acceptable pharmacodynamic and pharmacokinetic characteristics, in addition to reasonable toxicity characteristics for both compounds. Thus, they can be incorporated into pharmaceutical dosage forms to combat oxidative stress. Full article

In this study, the steam distillation process of volatile oil from Angelicaesinensis Radix was optimized according to the concept of quality-by-design. A homemade glass volatile oil extractor was used to achieve better cooling of the volatile oil. First, the soaking time, distillation time, and liquid–material ratio were identified as potential critical process parameters by consulting the literature. Then, the three parameters were investigated by single factor experiments. The volatile oil yield increased with the extension in the distillation time, and first increased and then decreased with the increase in soaking time and liquid–material ratio. The results confirmed that soaking time, distillation time, and liquid–material ratio were all critical process parameters. The kinetics models of volatile oil distillation from Angelicaesinensis Radix were established. The diffusion model of spherical particle was found to be the best model and indicated that the major resistance of mass transfer was the diffusion of volatile oil from the inside to the surface of the medicinal herb. Furthermore, the Box–Behnken experimental design was used to study the relationship between the three parameters and volatile oil yield. A second-order polynomial model was established, with R2 exceeding 0.99. The design space of the volatile oil yield was calculated by a probability-based method. In the verification experiments, the average volatile oil yield reached 0.711%. The results showed that the model was accurate and the design space was reliable. In this study, 21 chemical constituents of volatile oil from Angelicaesinensis Radix were identified by gas chromatograph-mass spectrometer(GC-MS), accounting for 99.4% of the total volatile oil. It was found that the content of Z-ligustilide was the highest, accounting for 85.4%. Full article

In this study, Italian industrial hemp (Cannabis sativa L.) intended for food use was isotopically characterized for the first time. The stable isotope ratios of five bioelements were analyzed in different parts of the plant (i.e., roots, stems, inflorescences, and seeds) sampled in eight different regions of Italy, and in five hemp seed oils. The values of δ²H, δ¹³C, δ¹⁸O, and δ³⁴S differed according to the latitude and, therefore, to the geographical origin of the samples and the climate conditions of plant growth, while the δ¹⁵N values allowed us to distinguish between crops grown under conventional and organic fertilization. The findings from this preliminary study corroborate the reliability of using light stable isotope ratios to characterize hemp and its derived food products and contribute to the creation of a first isotopic database for this plant, paving the way for future studies on authentication, traceability, and verification of organic labeling. Full article

In many countries, thiabendazole is used as a fungicide to prevent the decay of food and to lengthen storage periods. However, in Korea, thiabendazole is unauthorised and does not have standards or specifications for use as a food additive. In this study, a simple analytical method was developed and validated using the HPLC–PDA method to detect thiabendazole in foods frequently consumed in South Korea. The calibration curve was obtained using samples of solid and liquid foods containing banana and citrus fruits containing concentrations in the range of 0.31–20.00 μg/mL with a satisfactory coefficient of determination (R²) of 0.999. The limit of detection (LOD) values for the solid and liquid food samples were 0.009 and 0.017 μg/mL, respectively, and the limit of quantification (LOQ) values were 0.028 and 0.052 μg/mL. The intra-day and inter-day precision values were less than 1.33% (relative standard deviation), and the recoveries of thiabendazole from spiked solid and liquid food samples ranged from 93.61 to 98.08% at concentration levels of 2.5, 5, and 10 μg/mL. In addition, the expanded uncertainties of the measu-rements ranged from 0.57 to 3.12%. These results showed that the developed method was appropriate for the quantitative analysis of thiabendazole in solid and liquid foods containing banana and citrus fruits. Full article

Although the Republic of Croatia is a relatively small country geographically, it can boast numerous scientists who have left indelible marks in various scientific fields. However, this paper is exclusively about chromatography as one of the most important analytical techniques of our time. The development of chromatography in the Republic of Croatia and the role that three institutions have played in it—the Faculty of Chemical Engineering and Technology of the University of Zagreb, the Croatian Society of Chemical Engineers, and the Central European Group for Separation Sciences—will be briefly discussed. Full article