An efficient deep eutectic magnetic nano gel for rapid ultrasound-assisted dispersive µ-solid phase extraction of residue of tetracyclines in food samples.

In the present study, a magnetic nano gel as the sorbent which is the combination of octatonic acid: cumarin as eutectic solvent and Fe3O4@SiO2 was introduced as the sorbent in ultrasound-assisted dispersive µ-solid phase extraction process coupled with high performance liquid chromatography with photo diode array detector for simultaneous separation and determination of tetracyclines residues in food samples. FT-IR, SEM, VSM were used for the characterization of the synthetized magnetic nano gel. Under obtained optimum conditions, the obtained linear ranges were 1.5-500 (µg L-1), 2.5-750 (µg L-1), 2-750 (µg L-1), and 2.5-500 (µg L-1) for tetracycline, oxytetracycline, chlortetracycline, and doxycycline, respectively. Moreover, the below level of quantification (BLQ) (based on S/N = 3) of 0.47 µg L-1, 0.11 µg L-1, 0.85 µg L-1, 0.66 µg L-1, 0.81 µg L-1 and the limit of quantification (based on S/N = 10) of 1.61, 2.74, 2.23 (µg L-1), and 2.66 were achieved for tetracycline, oxytetracycline, chlortetracycline, and doxycycline, respectively. The intra-day and inter-day precision (%) of the procedure were less than 3.2 and 3.8, respectively. The recoveries over 95% confirmed high sufficiency of the proposed method for application in complex matrices such as honey, milk, and egg. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-023-05798-w.

Heavy metal pollution levels and health risk assessment of dust storms in Jazmurian region, Iran.

The Jazmurian basin in Iran is an area affected by climate change and desertification where aerosols and dust storms are common. The aim of this work was to determine the human and ecological risks from atmospheric particles during dust storms in different cities in the Jazmurian basin. For this purpose, the dust samples were collected from Jiroft, Roodbar Jonoob, Ghaleh Ganj, Kahnooj and Iranshahr cities, which are located around the Jazmurian playa in southeast of Iran. Satellite-based Moderate Resolution Imaging Spectroradiometer (MODIS) aerosol products and the Aerosol Optical Depth (AOD) were used to detect aerosol loading in the atmosphere. Moreover, the trace element composition of the collected particles was determined and used to evaluate human and ecological impact assessment using US EPA human health risk assessment and ReCiPe 2016 endpoint hierarchist impact assessment method incorporated in the OpenLCA 1.10.3 software. The human health risk assessment of the particles revealed high non-carcinogenic risks for children from exposure to nickel and manganese and carcinogenic risks in both adults and children due to hexavalent chromium, arsenic and cobalt during dust storm events. Terrestrial ecotoxicity was found to have the largest ecological impact on ecosystems with copper, nickel and zinc exhibiting the largest contributions.

The MIL100(Fe)/BaTi0.85Zr0.15O3 nanocomposite with the photocatalytic capability for study of tetracycline photodegradation kinetics.

The visible light-active nanocomposite with the photocatalytic capability was facile one-pot solvothermal method successfully synthesized. X-ray diffraction (XRD), Thermogravimetry and Derivative Thermogravimetry (TG-DTG), Scanning Electron Microscopy with Energy Dispersive X-ray Analysis (SEM-EDX), Diffuse Reflectance Spectroscopy (UV-Vis DRS), and Fourier Transform Infra-Red (FT-IR) analysis were employed to characterize the synthetized BaTi0.85Zr0.15O3, MIL-100(Fe), and the MIL-100(Fe)/BaTi0.85Zr0.15O3 samples. As a result of the Scherrer equations, the size of grains for MIL-100(Fe), BaTi0.85Zr0.15O3, and MIL-100(Fe)/BaTi0.85Zr0.15O3 was estimated to be 40.81, 12.00, and 22.70 nm, respectively. MIL-100(Fe), BaTi0.85Zr0.15O3, and MIL-100(Fe)/BaTi0.85Zr0.15O3 samples showed bandgap values of 1.77, 3.02, and 2.56 determined from their absorption edge wavelengths. In the photodegraded solutions, chemical oxygen demand (COD) data and tetracycline (TC) absorbencies were used to obtain the rate constants of 0.032 min-1 and 0.030 min-1, respectively. This corresponds to t1/2-values of 27.7 min and 21.7 min, respectively, for the degradation and mineralization of TC molecules during photodegradation process.

Heterogeneous adsorbent based on CeZrO2 nanoparticles doped magnetic graphene oxide used for vortex assisted magnetic dispersive solid phase extraction of erythromycin in chicken.

A simple, fast, and efficient method of vortex assisted magnetic dispersive solid phase extraction for separation and pre-concentration of erythromycin in chicken samples prior to high LC-UV determination has been developed. The novel heterogeneous CeZrO2 nanoparticles doped magnetic graphene oxide, for use as an efficient nanosorbent, was synthetised and applied for the adsorption of erythromycin. The synthetised nanosorbent was characterised using both Fourier-transform infra-red (FT-IR) and energy dispersive X-Ray (EDX) spectroscopy together with field emission scanning electron microscopy-EDX. To obtain the best extraction condition and maximum extraction efficiency of erythromycin, the effect of important parameters including pH, amount of sorbent, vortexing time, ionic strength, sample volume, and desorption conditions were investigated. At optimum conditions, a linear range of 0.25-300 µg kg-1, LOD (S/N = 3) of 0.079 µg kg-1, and LOQ (S/N = 10) of 0.270 µg kg-1 were obtained. The precision of the method was established as having an RSD (%) at 100 µg kg-1 of erythromycin for seven replicates of 2.6% and 3.2% for the intra-day and the inter-day, respectively. Recoveries over 94.0% confirmed a high capability of the proposed method for separation and determination of erythromycin residues in chicken being one of the most important animal products.

An efficient 3D adsorbent foam based on graphene oxide/AgO nanoparticles for rapid vortex-assisted floating solid phase extraction of bisphenol A in canned food products.

In this study, a three-dimensional adsorbent was developed based on graphene oxide/AgO nanoparticles over interconnected nickel foam (GO/AgO@Ni foam) for rapid and efficient vortex assisted floating solid phase extraction of bisphenol A in canned food products prior to high performance liquid chromatography with a fluorescence detector. The analytical techniques scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared (FT-IR) were used for characterization of the synthetized GO/AgO@Ni foam. The effect of proficiency factors including pH, foam size, vortexing time, salt addition, sample volume, desorption type and volume, and desorption time on the extraction efficiency of bisphenol A were explored through the matrix match method. Under the above experimental conditions, the figures of merit of the method were acquired as LODs (S/N = 3) of 0.18-0.84 µg kg-1, LOQs of 0.61-2.81 µg kg-1 (S/N = 10), linear ranges of 0.5-500 µg kg-1, and enrichment factors of 235.5-244.9. The inter-day precision values (RSD%, n = 7) of 2.5-3.6 and the intra-day precision (%) of (5 days and seven replicates for each day) 2.8-3.8 were achieved for bisphenol A at a concentration of 50 µg kg-1. The relative recoveries of 94.0% to 99.6% were obtained for the canned food samples.

Development of a rapid efficient solid-phase microextraction: An overhead rotating flat surface sorbent based 3-D graphene oxide/ lanthanum nanoparticles @ Ni foam for separation and determination of sulfonamides in animal-based food products.

In this study, an overhead rotating flat surface sorbent based solid-phase microextraction was developed as a rapid and efficient method for simultaneous separation and determination of sulfonamides in animal based-food products. 3D graphene oxide/ lanthanum nanoparticles @ Ni foam was introduced as a novel selective sorbent. SEM-EDX and FT-IR techniques were applied for characterization of the sorbent. At optimum conditions, the linear ranges of 0.4-700.0 (µg L-1), 0.3-900.0 (µg L-1), and 0.25-500 (µg L-1) and the enrichment factors of 606.8, 604.3, 608.9 were obtained for SDZ, SMX, and SMZ, respectively. The LOD (S/N = 3) of 0.14, 0.11, 0.08 (µg L-1) were achieved for SDZ, SMX, and SMZ, respectively. The intra-day and inter-day precision (%) (five days, n = 7) for the concentration of 100 µg L-1 were less than 4.3 and 3.8, respectively. The recoveries over 90.0 % revealed high capability of the method for utilization in complex matrixes.

Selective and highly efficient removal of uranium from radioactive effluents by activated carbon functionalized with 2-aminobenzoic acid as a new sorbent.

The purpose of this study was modification of activated carbon (AC) to prepare a new selective sorbent for removal of uranium ion. The modification was performed by introducing carboxyl groups onto AC using ammonium persulfate (APS) in sulfuric acid solution followed by functionalization with 2-aminobenzoic acid (ABA) as a selective ligand for U (VI) ion (UO22+) adsorption. The characterization of the synthetized sorbent (AC-ABA) was carried out through several methods including potentiometry, scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction and FT-IR to confirm successful functionalization of the sorbent surface with oxygen and amine groups. The sorption of U (VI) on the unmodified AC and AC-ABA was investigated as a function of contact time, sorbent content, initial uranium concentration, solution pH, and temperature using batch sorption technique. In addition, the effect of various parameters on the U (VI) sorption capacity was optimized by the response surface methodology as a potent experimental design method. The results indicated that sorption of U (VI) under the optimal conditions was significantly improved onto AC-ABA compared to AC. Kinetic studies displayed that the sorption process reached equilibrium after 100 min and followed the pseudo-second-order rate equation. The isothermal data fitted better with the Langmuir model than the Freundlich model. The maximum sorption capacity of AC-ABA for U(VI) was obtained to be 194.2 mg g-1 by the Langmuir model under optimum conditions, which demonstrates the sorption capacity has been improved by the modification process. The thermodynamic parameters (ΔH, ΔS and ΔG) indicated that sorption of uranium onto AC-ABA was an endothermic and spontaneous process. The sorption studies on radioactive effluents of the nuclear fuel plant represented high selectivity of AC-ABA for removal of uranium in the presence of other metal ions, and the selectivity coefficients significantly improved after modification of the sorbent. Application of AC-ABA for treatment of industrial effluents containing heavy and radioactive metal ions show high potential and capability of the proposed method.

Efficient removal and recovery of uranium from industrial radioactive wastewaters using functionalized activated carbon powder derived from zirconium carbide process waste.

Development of efficient sorbents for selective removing and recovery of uranium from radioactive wastewaters is highly important in nuclear fuel industries from the standpoint of resource sustainability and environmental safety issues. In this study, carbon powder waste was modified by various chemical activating agents under atmosphere of nitrogen gas at 725 °C to prepare an efficient sorbent for removal and recovery of uranium ions from radioactive wastewaters of nuclear fuel conversion facility. Activation of the carbon powder with KOH, among different activators, provided maximum porosity and surface area. The activated samples were modified by reacting with ammonium persulfate in sulfuric acid solution to generate surface functional groups. The synthetized sorbents were characterized with FT-IR, XRD, BET, and SEM-EDS techniques. The effects of solution pH, contact time, initial uranium concentration, and temperature on the sorption capacity of the sorbent with respect to U(VI) from wastewater were investigated by batch method, followed by optimizing the effect of influential parameters by experimental design using central composite design. The sorption of UO22+ ions on the sorbents follows the Langmuir isotherm and pseudo-second-order kinetic models. Maximum sorption capacity for U(VI) was 192.31 mg g-1 of the modified sorbent at 35 °C. Thermodynamic data showed that sorption of U(VI) on the sorbent was through endothermic and spontaneous processes. The sorption studies on radioactive effluents of the nuclear industry demonstrated that the modified sorbent had a favorable selectivity for uranium removal in the presence of several other metal ions.

Sonodecoration of magnetic phosphonated-functionalized sporopollenin as a novel green nanocomposite for stir bar sorptive dispersive microextraction of melamine in milk and milk-based food products.

The novel green magnetic phosphonated-functionalized sporopollenin nanocomposite (MPSP-nanocomposite) was synthetized and used for stir bar sorptive dispersive microextraction (SBSDME) of melamine in milk and milk-based food products. TEM, SEM-EDX, FT-IR, VSM techniques were applied for characterization of MPSP-nanocomposite. The influential parameters including pH, extraction time, stirring rate, elution solvent type and volume, sample volume, desorption time, and ionic strength were studied and at optimum conditions, the linear range of 1-500 (µg L-1), the LOD (S/N = 3) of 0.30 (µg L-1), and the LOQ (S/N = 10) of 0.95 (µg L-1) were achieved. The intra-day precision values (RSD (%), n = 7) of 3.5% for the melamine concentration of 25 (µg L-1). The relative recoveries of 95.8% to 99.6% were acquired for the real samples which confirmed that the proposed method could be successfully utilized in complex matrixes with high matrix effects.

Ultrasonication-facilitated synthesis of functionalized graphene oxide for ultrasound-assisted magnetic dispersive solid-phase extraction of amoxicillin, ampicillin, and penicillin G.

A simplistic approach is presented for the synthesis of ultrasonically fabricated graphene oxide functionalized with polyaniline and N-[3-(Trimethoxysilyl)propyl]ethylenediamine. The synthesized nanocomposite was then employed for the facile, green, ultrasound-assisted, magnetic dispersive solid-phase extraction of amoxicillin, ampicillin, and penicillin G in milk samples and infant formula prior to high-performance liquid chromatography-ultraviolet determination. The designed nanocomposites were comprehensively characterized using field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. In order to achieve the best extraction efficiencies, the influential parameters including pH, amount of magnetic sorbent, type and volume of elution solvent, extraction time, sample volume, and desorption time were assessed. At the optimum conditions, linear ranges of 2.5-1000 (µg L-1) for ampicillin and penicillin G and a linear range of 2.5-750 (µg L-1) were obtained for amoxicillin at optimum conditions. Moreover, the limits of detection (S/N = 3) of 0.5, 0.8, and 0.9 (µg L-1) were obtained for amoxicillin, ampicillin, and penicillin G, respectively. The precision (relative standard deviations (%)) values of 3.1, 2.6, and 2.5 at the concentration of 50 µg L-1 for seven replicates were obtained for ampicillin, amoxicillin, and penicillin G, respectively. The efficiencies of ≤ 96% and relative standard deviations of less than 3.1% were also obtained thereby confirming the high potential of the synthesized nanocomposites for simultaneous preconcentration and separation of the ß-lactam antibiotics in complex matrixes. Graphical Abstract.

Pollution and contamination assessment of heavy metals in the sediments of Jazmurian playa in southeast Iran.

Jazmurian playa was an ephemeral lake with a large catchment in southeast Iran, which dried up over the last 10 years as a result of prolonged drought. As the lake was recipient of incoming industrial water with trace metals deposited to the sediment, the dust is the cause of environmental concern of the region and requires evaluation and better management. The aim of this study was to evaluate the environmental and ecological pollution of Jazmurian playa. Hence, 24 collected surface sedimentary samples were analyzed with ICP-OES. The environmental pollution indices including degree of contamination (Cd), geoaccumulation index (Igeo), enrichment factor (EF), pollution load index (PLI) and potential ecological risk (PER) were determined. The study revealed moderately to strongly pollution levels of Pb, Ni and Al, while Dy, Pb, Y, Yb, Sm, Te, U, Cu, Mn, Sc represented moderate pollution. The EF values indicated four sites were highly enriched with Dy, Pb and Ni. The PER results showed high risk for four sites and considerable risk for others. Cluster analysis illustrated interconnection between the contaminants and the sites with major pollution at six sites. Obviously, climate change has considerable complex environmental impacts through transformation of local water and sediment pollution problem.

Green ultrasound assisted magnetic nanofluid-based liquid phase microextraction coupled with gas chromatography-mass spectrometry for determination of permethrin, deltamethrin, and cypermethrin residues.

Ultrasound-assisted magnetic nanofluid-based liquid-phase microextraction was coupled to GC-MS in a method for simultaneous determination of the pyrethroid insecticides permethrin, deltamethrin, and cypermethrin. A highly efficient extraction solvent called "magnetic nanofluid (MNF)" is introduced for preconcentration of pyrethroids. The MNF consists of magnetic multiwalled carbon nanotubes (MMWCNTs) and deep eutectic solvent. Following microextraction, the MNF was detached by an external magnet from the medium without the need for centrifugation. 2-Pyridinecarboxamide, choline chloride, and anhydrous ferric chloride were used for the synthesis of the deep eutectic solvent. The effects of pH value, volume of MNF, sonication time, sample volume, and ionic strength, type and amount of back extraction solvent were investigated. Under optimum conditions of MNF volume of 50 µL, time of 5 min, 100 µL acetone as back extraction solvent, NaCl concentration of 1 mol.L-1 and sample volume of 30 mL, the detection limits are 2.8, 2.7 and 2.0 ng·mL-1 for permethrin, deltamethrin and cypermethrin, respectively. The linear response ranges are between 0.01 and 250 ng·mL-1, and relative standard deviations (for n = 7) are 3.5, 3.2 and 2.8%. The method was successfully applied to the determination of trace levels of permethrin, deltamethrin and cypermethrin in (spiked) milk samples. Graphical abstract Schematic representation of ultrasound assisted magnetic nanofluid-based liquid phase microextraction separation/preconcentration of permethrin, deltametrin, and cypermethrin residues in milk using GC-MS.

Centrifuge-less deep eutectic solvent based magnetic nanofluid-linked air-agitated liquid-liquid microextraction coupled with electrothermal atomic absorption spectrometry for simultaneous determination of cadmium, lead, copper, and arsenic in food samples and non-alcoholic beverages.

In this research, the novel environmentally-friendly analytical method, Centrifuge-less deep eutectic solvent based magnetic nanofluid-linked air-agitated liquid-liquid microextraction (CL-DES-MNF-AALLME) coupled with ETAAS was proposed for simultaneous preconcentration of heavy metals of lead, arsenic, cadmium, and copper. In CL-DES-MNF-AALLME, the extraction solvent is novel magnetic nanofluid consists of DES based magnetic multiwall carbon nanotubes which can easily be separated from the media with no need to centrifugation. The detection limits of 4.2, 3, 3.5 and 3.6 ng L-1 were acquired for cadmium, lead, copper, and arsenic respectively. The proper closeness of enrichment factors in the range of 635-644.5 to preconcentration factor (640), confirm the quantitatively of the proposed extraction method with relative standard deviation of 2.5-3.1(%) (n = 7). The potential of the CL-DES-MNF-AALLME was considered in walnut, rice, tomato paste, spinach, orange juice, black tea, and water samples which showed high capability of the proposed method for application in the complex matrixes.

Efficient removal of crystal violet from aqueous solutions with Centaurea stem as a novel biodegradable bioadsorbent using response surface methodology and simulated annealing: Kinetic, isotherm and thermodynamic studies.

The novel green bioadsorbent, Centaurea stem, was utilized for crystal violet removal from aqueous solutions. SEM and FT-IR were used for characterization of Centaurea stem. The effects of the pH, time, temperature, bioadsorbent amount, and initial dye concentration were investigated. Response surface methodology was used to depict the experimental design and the optimized data of pH 12.57, time 19.661, temperature 38.94 °C, amount of bioadsorbent 12.218 mg, and initial dye concentration 36.62 mg L-1 were achieved. Moreover, artificial neural network (ANN) and simulated annealing (SA) were applied for prediction and optimization of the process respectively. The SA acquired optimum conditions of 10.114, 7.892 min, 25.127 °C, 64.405 mg L-1, 14.54 mg for pH, time, temperature, initial dye concentration, and bioadsorbent amount, respectively which were more close to the experimental results and indicated higher ability of SA-ANN in prediction and optimization of the process. The adsorption isotherms confirm the experimental data were appropriately fitted to the Langmuir model with high adsorption capacity of 476.190 mg g-1. The thermodynamic parameters were evaluated. The positive ΔH° and ΔS° values described endothermic nature of adsorption. The adsorption of crystal violet followed the pseudo-second order kinetic model.