A closer look at how the dispersive liquid–liquid microextraction method works. Investigation of the effect of solvent mixture composition on the quality and stability of the cloudy state

The dispersive liquid–liquid microextraction (DLLME) is one of the most popular miniaturized extraction procedures. In this paper, the degree of dispersion and dispersion stability were studied with the aim to assess the correlations of these parameters with efficiency for the selected analytical application. The dependence between the degree of dispersion (cloudy state quality) and its stability obtained by various emulsification procedures, such as solvent-assisted emulsification (using various dispersive solvents) and mechanical emulsification (using auxiliary energies), is investigated and discussed. It was found out that the degree of dispersion depends on the type of emulsification procedure and decreases in the series: solvent-assisted (SA-) = ultrasound-assisted (UA-) > air-assisted (AA-) > vortex-assisted (VA-) emulsification. The emulsion stability depends on the degree of dispersion and there were 1810 and 2070 s for the most effective emulsification procedures, such us solvent-assisted and ultrasound-assisted emulsification, respectively. A comparison between the sensitivity of the analytical methods (using spectrophotometric determination of the anionic surfactants) and the degree of dispersion have been made. The sensitivity of the methods was ranked as follows: DLLME > UA-LLME > VA-LLME > AA-LLME

End-of-life management of single-use baby diapers: Analysis of technical, health and environment aspects

Single-use baby diapers belongs to an important group of products used in the parenting journey because of their high performance and convenience. Single-use baby diapers are normally thrown away after one-time use, resulting in a waste management problem. The goal of this paper was to better understand main environmental concerns of different types of diapers and address how to reduce them, with a special consideration of waste management strategies and user behaviour practices. Furthermore, health and environmental hazards potentially associated with materials included in diapers, or substances formed from diapers during the waste treatment stage, are also analysed (e.g., phthalates, pesticides, dioxins, pesticides). Three main types of baby diapers have been analysed: single-use baby diapers, reusable baby diapers, and biodegradable single-use diapers. Each type of diaper comes with technical characteristics and environmental concerns and challenges, which are discussed in this paper to support the development of measures for the safe(r) and sustainable design, use and end of life management of baby diapers.Justyna Płotka-Wasylka is grateful for the finantial support by the National Science Centre, Poland within the grant project (No.: 2020/37/B/ST4/02886)

Deep eutectic solvent-based shaking-assisted extraction for determination of bioactive compounds from Norway spruce roots

Polyphenolic compounds play an essential role in plant growth, reproduction, and defense mechanisms against pathogens and environmental stresses. Extracting these compounds is the initial step in assessing phytochemical changes, where the choice of extraction method significantly influences the extracted analytes. However, due to environmental factors, analyzing numerous samples is necessary for statistically significant results, often leading to the use of harmful organic solvents for extraction. Therefore, in this study, a novel DES-based shaking-assisted extraction procedure for the separation of polyphenolic compounds from plant samples followed by LC-ESI-QTOF-MS analysis was developed. The DES was prepared from choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and fructose (Fru) as the hydrogen bond donor (HBD) at various molar ratios with the addition of 30% water to reduce viscosity. Several experimental variables affecting extraction efficiency were studied and optimized using one-variable-at-a-time (OVAT) and confirmed by response surface design (RS). Nearly the same experimental conditions were obtained using both optimization methods and were set as follows: 30 mg of sample, 300 mg of ChCl:Fru 1:2 DES containing 30% w/w of water, 500 rpm shaking speed, 30 min extraction time, 10°C extraction temperature. The results were compared with those obtained using conventional solvents, such as ethanol, methanol and water, whereby the DES-based shaking-assisted extraction method showed a higher efficiency than the classical procedures. The greenness of the developed method was compared with the greenness of existing procedures for the extraction of polyphenolic substances from solid plant samples using the complementary green analytical procedure index (ComplexGAPI) approach, while the results for the developed method were better or comparable to the existing ones. In addition, the practicability of the developed procedure was evaluated by application of the blue applicability grade index (BAGI) metric. The developed procedure was applied to the determination of spruce root samples with satisfactory results and has the potential for use in the analysis of similar plant samples

New Carvone-Based Deep Eutectic Solvents for Siloxanes Capture from Biogas

During biogas combustion, siloxanes form deposits of SiO2 on engine components, thus shortening the lifespan of the installation. Therefore, the development of new methods for the purification of biogas is receiving increasing attention. One of the most effective methods is physical absorption with the use of appropriate solvents. According to the principles of green engineering, solvents should be biodegradable, non-toxic, and have a high absorption capacity. Deep eutectic solvents (DES) possess such characteristics. In the literature, due to the very large number of DES combinations, conductor-like screening models for real solvents (COSMO-RS), based on the comparison of siloxane activity coefficient of 90 DESs of various types, were studied. DESs, which have the highest affinity to siloxanes, were synthesized. The most important physicochemical properties of DESs were carefully studied. In order to explain of the mechanism of DES formation, and the interaction between DES and siloxanes, the theoretical studies based on σ-profiles, and experimental studies including the 1H NMR, 13C NMR, and FT-IR spectra, were applied. The obtained results indicated that the new DESs, which were composed of carvone and carboxylic acids, were characterized by the highest affinity to siloxanes. It was shown that the hydrogen bonds between the active ketone group (=O) and the carboxyl group (-COOH) determined the formation of stable DESs with a melting point much lower than those of the individual components. On the other hand, non-bonded interactions mainly determined the effective capture of siloxanes with DES

Absorptive Desulfurization of Model Biogas Stream Using Choline Chloride-Based Deep Eutectic Solvents

The paper presents a synthesis of deep eutectic solvents (DESs) based on choline chloride (ChCl) as hydrogen bond acceptor and phenol (Ph), glycol ethylene (EG), and levulinic acid (Lev) as hydrogen bond donors in 1:2 molar ratio. DESs were successfully used as absorption solvents for removal of dimethyl disulfide (DMDS) from model biogas steam. Several parameters affecting the absorption capacity and absorption rate have been optimized including kinds of DES, temperature, the volume of absorbent, model biogas flow rate, and initial concentration of DMDS. Furthermore, reusability and regeneration of DESs by means of adsorption and nitrogen barbotage followed by the mechanism of absorptive desulfurization by means of density functional theory (DFT) as well as FT-IR analysis were investigated. Experimental results indicate that the most promising DES for biogas purification is ChCl:Ph, due to high absorption capacity, relatively long absorption rate, and easy regeneration. The research on the absorption mechanism revealed that van der Waal interaction is the main driving force for DMDS removal from model biogas

Silica Gel Impregnated by Deep Eutectic Solvents for Adsorptive Removal of BTEX from Gas Streams

The paper presents the preparation of new adsorbents based on silica gel (SiO2) impregnated with deep eutectic solvents (DESs) to increase benzene, toluene, ethylbenzene, and p-xylene (BTEX) adsorption efficiency from gas streams. The DESs were synthesized by means of choline chloride, tetrapropylammonium bromide, levulinic acid, lactic acid, and phenol. The physico-chemical properties of new sorbent materials, including surface morphology and structures, as well as porosity, were studied by means of thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller analysis. The effect of DESs type, flow rate, and initial concentration of BTEX were also investigated followed by regeneration and reusability of adsorbents. The results indicate that SiO2 impregnated with tetrapropylammonium bromide and lactic acid in a 1:2 molar ratio have great potential for the removal of BTEX from gas streams. Its adsorption capacity was higher than the pure SiO2 and other developed SiO2-DES adsorbents. This result can be explained by the specific interaction between DESs and BTEX, i.e., hydrogen bonds interaction

Dezodoryzacja modelowego strumienia biogazu z użyciem nowej niejonowej cieczy eutektycznej

The paper presents new non-ionic deep eutectic solvent (DES) composed of natural and non-toxic components i.e. guaiacol, camphor and levulinic acid in 1:1:3 molar ratio as a promising absorbent for removal of selected volatile organic compounds (VOCs) including dichloromethane, toluene, hexamethyldisiloxane and propionaldehyde from model biogas. The affinity of DES for VOCs was determined as vapour-liquid coefficients and the results were compared with several well-known DESs based on quaternary ammonium salt as well as n-hexadecane and water. For new DES, the absorption process was carried out under dynamic conditions. The results indicate that non-ionic DES has high affinity and capacity for VOCs being comparable to n-hexadecane. In addition, absorbed VOCs could be easily desorbed from DES using activated carbon and absorbent could be re-use minimum five times without significant loss of absorption capacity.W pracy przedstawiono nową niejonową ciecz eutektyczną (DES) złożoną z naturalnych i nietoksycznych składników tj. gwajakol, kamfora i kwas lewulinowy w stosunku molowym 1:1:3, jako obiecujący absorbent do usuwania wybranych lotnych związków organicznych w tym dichlorometanu, toluenu, heksametylodisiloksanu oraz aldehydu propionowego. W celu określenia powinowactwa DES do LZO, wyznaczono współczynniki podziału ciecz–para. Uzyskane wyniki porównano z popularnymi DES zawierającymi w strukturze czwartorzędową sól amoniową, a także z n-heksadekanem oraz wodą. Dla nowej DES, proces absorpcji przeprowadzono również w warunkach dynamicznych. Wyniki wykazały, że nowa niejonowa DES charakteryzuje się dużym powinowactwem do wybranych LZO oraz dużą pojemnością sorpcyjną, a parametry te są porównywalne do n-heksadekanu. Dodatkowo, zaabsorbowane LZO mogą być łatwo desorbowane przy użyciu węgla aktywnego. Dzięki temu, absorbent w postaci DES może być użyty minimum pięć razy bez znaczącego zmniejszenia pojemności sorpcyjne

Purification of model biogas from toluene using deep eutectic solvents

Biogas from landfills and wastewater treatment facilities typically contain a wide range of volatile organic compounds (VOCs), that can cause severe operational problems when biogas is used as fuel. Among the contaminants commonly occur aromatic compounds, i.e. benzene, ethylbenzene, toluene and xylenes (BTEX). In order to remove BTEX from biogas, different processes can be used. A promising process for VOCs removal is their absorption in deep eutectic solvents (DES). In this work, three DES: ([ChCl] U TEG [choline chloride]:urea:tetraethylene glycol (1:2:2), [ChCl] U [choline chloride]:urea (1:2), [ChCl] DEG [choline chloride]:diethylene glycol (1:2)) and water were tested to toluene absorption in concentration of 2000 ppm v/v in nitrogen stream. The results demonstrated the high absorption capacity of toluene using DES based on glycols

Efficient Extraction of Fermentation Inhibitors by Means of Green Hydrophobic Deep Eutectic Solvents

The methods for hydrogen yield efficiency improvements, the gaseous stream purification in gaseous biofuels generation, and the biomass pretreatment are considered as the main trends in research devoted to gaseous biofuel production. The environmental aspect related to the liquid stream purification arises. Moreover, the management of post-fermentation broth with the application of various biorefining techniques gains importance. Chemical compounds occurring in the exhausted liquid phase after biomass pretreatment and subsequent dark and photo fermentation processes are considered as value-added by products. The most valuable are furfural (FF), 5-hydroxymethylfurfural (HMF), and levulinic acid (LA). Enriching their solutions can be carried with the application of liquid–liquid extraction with the use of a suitable solvent. In these studies, hydrophobic deep eutectic solvents (DESs) were tested as extractants. The screening of 56 DESs was carried out using the Conductor-like Screening Model for Real Solvents (COSMO-RS). DESs which exposed the highest inhibitory effect on fermentation and negligible water solubility were prepared. The LA, FF, and HMF were analyzed using FT-IR and NMR spectroscopy. In addition, the basic physicochemical properties of DES were carefully studied. In the second part of the paper, deep eutectic solvents were used for the extraction of FF, LA, and HMF from post-fermentation broth (PFB). The main extraction parameters, i.e., temperature, pH, and DES: PFB volume ratio (VDES:VPFB), were optimized by means of a Box–Behnken design model. Two approaches have been proposed for extraction process. In the first approach, DES was used as a solvent. In the second, one of the DES components was added to the sample, and DES was generated in situ. To enhance the post-fermentation broth management, optimization of the parameters promoting HMF, FF, and LA extraction was carried under real conditions. Moreover, the antimicrobial effect of the extraction of FF, HMF, and LA was investigated to define the possibility of simultaneous separation of microbial parts and denatured peptides via precipitation

Dimethyl ether (DME) as potential environmental friendly fuel

In recent years, there has been a growing interest in replacing petroleum fuels with so-called second generation environmental friendly fuels. Compared to traditional petroleum fuels dimethyl ether (DME) could be used as a clean high-efficiency compression ignition fuel with reduced particulate matter (PM), sulfur oxides (SOx), hydrocarbons (HC), carbon monoxide (CO) as well as combustion noise. Compared to some of the other leading alternative fuel candidates i.e., methane, methanol, ethanol, compressed natural gas, DME appears to have the largest potential impact on society including well-to-wheel greenhouse gas emissions, non-petroleum feedstocks, well-to-wheel efficiencies, fuel versatility, infrastructure, availability, economics, and safety and should be considered as the fuel of choice for eliminating the dependency on petroleum. This paper reviews the properties and the DME combustion effects on environmental and they were compared to diesel characteristic as well as the effect of blending DME with liquefied petroleum gas (LPG), conventional diesel fuel and biodiesel were discussed