Solid-phase Extraction Efficiency Research Articles

One-step hot-press synthesis of amino functionalized Zr-based metal organic framework for determination and speciation of trace inorganic arsenic species in water samples with EDXRF spectrometry

Herein, amino functionalized Zr-based metal organic framework (UiO-66-NH2) on carbon cloth substrate was synthesized by using one-step hot-pressing method and the product (UiO-NH2@CC) was evaluated as a new solid phase extraction (SPE) material for determination and speciation of inorganic arsenic species (As(V) and As(III)) in water samples through energy dispersive X-ray fluorescence (EDXRF) spectrometry. SPE efficiency of UiO-NH2@CC was examined in batch and continuous adsorption (pre-concentration) processes and combination of either batch or continuous pre-concentration process with EDXRF spectrometry proposed analytical method, offering remarkable benefits (i.e., user-friendly, no elution procedure, environmentally friendly and cost-effective, etc.). Batch adsorption studies indicated that As(V) could be selectively adsorbed by UiO-NH2@CC at pH 2 and better represented by Freundlich isotherm model in 60 min of equilibrium time. Continuous adsorption studies at pH 2 demonstrated a drop in As(V) adsorption efficiency of UiO-NH2@CC for sample loading volume above 30 mL with increasing flow rate from 0.3 to 1.0 mL/min and initial As(V) concentration from 20 to 100 µg/L. By considering fortification experiments on real water samples at two levels (5 and 50 µg/L) of As(V) species, both batch and continuous pre-concentration steps coupled with EDXRF spectrometry, with LOD values of 0.790 and 0.220 µg/L, respectively, indicated good recoveries in the range of 87(±11)–104(±7) with no statistically significant differences. Finally, the continuous pre-concentration step followed by EDXRF measurement, as a representative analytical method, was of successful applicability to the speciation of As(III) and As(V) in real water samples with notable advantages (i.e., effortless, economical, practical and reproducible, etc.).

Determination of fluoroquinolones residues in bean sprouts using covalent organic framework based solid-phase extraction coupled with UHPLC-MS/MS

A solid-phase extraction (SPE) method using three-dimensional covalent organic framework (COFs) coupled with ultra-high performance liquid chromatography-mass spectrometry was developed for the detection of 13 fluoroquinolones (FQs) in bean sprout samples. Critical extraction parameters influencing SPE efficiency were optimized and matrix-matched standard curves were used to eliminate matrix effects and validate the proposed method. The analytical method proved to have good linearity in the concentration range of 1.0–100 μg L–1 with correlation coefficients of r≥0.9995. The limits of detection were 0.10–0.45 μg kg–1, whereas the limits of quantification were 0.34–1.51 μg kg–1. The recoveries ranged from 92.7 % to 105 % with satisfactory precision (< 4.82 %). The COFs-packed SPE cartridge maintained recovery efficiency for the target FQs over five reuse cycles. The adsorption selectivity was mainly attributed to π–π interactions, hydrogen bonding, and electrostatic attraction between FQs and the adsorbent. Analysis of actual samples revealed the presence of enrofloxacin, ciprofloxacin, and norfloxacin in three batches of bean sprout samples. These results highlight the importance of monitoring antibiotics residues in bean sprouts.

Preparation of magnetic coconut clothing biochar for extracting neonicotinoid insecticides from environmental water samples

In this study, the magnetic coconut clothing biochar hybrid materials were successfully prepared by in-situ method. The obtained magnetic biochar was characterized in detail by using series of analytical techniques. The results showed that the magnetic hybrid materials presented alveolate network structures with abundant large pores and good magnetic separation ability with Fe3O4 nanoparticles obviously attached on the surface of biochar. The magnetic biochar hybrid materials were used as adsorbents during magnetic solid-phase extraction process for extracting neonicotinoid insecticides from environmental water samples. The adsorption and desorption parameters (adsorption time, elution condition, sample volume, sample pH) affecting magnetic solid-phase extraction efficiency were carefully investigated. Under the optimum conditions (adsorption for 15 min, 5 % formic acid-acetonitrile as elution condition, 50 mL of sample volume, 15 mg of magnetic biochar, pH at 5.0), the magnetic solid-phase extraction process based on magnetic coconut clothing biochar hybrid materials coupled with high performance liquid chromatography tandem mass spectrometry for enriching and detecting neonicotinoid insecticides in environmental water samples was established. The good linear relationship in the range of 0.5–200 ng mL−1 with correlation coefficients greater than 0.9989 and the lower limits of detection (0.0017–0.0069 ng·mL−1) were obtained. The recovery in the spiked water samples was in the range of 68.6 %-104.0 % with relative standard deviation from 0.4 % to 9.3 %. These results demonstrated that the established method was highly sensitive, convenient and repeatable for directly analyzing trace neonicotinoid insecticides in environmental water samples. More importantly, the novel biochar from coconut clothing was introduced into sample pretreatment to enrich trace organic pollutants.

Enhancing solid-phase extraction of tetracyclines with a hybrid biochar sorbent: A comparative study of chlorella and bamboo biochars

Biochar, a sustainable sorbent derived from pyrolyzed biomass, has garnered attention for its efficacy in solid-phase extraction (SPE) of antibiotics, with a particular focus on tetracyclines (TCs). Despite its recognized potential, the intricate separation mechanisms operative in biochar-based SPE systems have not been fully deciphered. This investigation contrasts chlorella biochar against commercial bamboo biochar, harnessing an array of analytical methodologies-microstructure characterization, adsorption thermodynamics, competitive adsorption kinetics, H+ back titration, and selectivity adsorption studies-complemented by a Box-Behnken design for the optimization of chlorella/bamboo-SPE and subsequent application in the analysis of animal-derived foodstuffs. The study unveils that a hybrid sorbent, integrating nitrogen-doped microporous chlorella biochar with mesoporous bamboo biochar in a 95/5 mass ratio, markedly diminishes irreversible adsorption while enhancing selectivity, surpassing the performance of single biochar SPE systems. The elucidated separation mechanisms implicate a partition model, propelled by oxygen-rich functional groups on chlorella biochar and the rapid adsorption kinetics of bamboo biochar, all orchestrated by electrostatic interactions within the mixed biochar framework. Moreover, the synergy of mixed biochar-SPE with high-performance liquid chromatography (HPLC) demonstrates exceptional proficiency in detecting TCs in animal viscera, evidenced by recovery rates spanning 80.80 % to 106.98 % and RSDs ranging from 0.24 % to 14.69 %. In essence, this research not only sheds light on the multifaceted factors influencing SPE efficiency but also propels the use of biochar towards new horizons in environmental monitoring and food safety assurance.

Molecularly imprinted beads based on modified cellulose hydrogel:A novel solid phase extraction filler for specific adsorption of camptothecin

Traditional solid phase extraction (SPE) suffers from a lack of specific adsorption. To overcome this problem, a combination of adsorption method and molecular imprinting technology by polydopamine modification was proposed to realize specific recognition of target compounds in SPE, which is of great significance to improve the separation efficiency of SPE. Cellulose hydrogel beads were prepared by dual cross-linking curing method and modified with polydopamine to make them hydrophilic and biocompatible. Subsequently, cellulose hydrogel-based molecularly imprinted beads (MIBs) were synthesized by surface molecular imprinting technology and used as novel column fillers in SPE to achieve efficient adsorption (34.16 mg·g−1) with specific selectivity towards camptothecin (CPT) in 120 min. The simulation and NMR analysis revealed that recognition mechanism of MIBs involved hydrogen bond interactions and Van der Waals effect. The MIBs were successful used in separating CPT from Camptotheca acuminata fruits, exhibiting impressive adsorption capacity (1.19 mg·g−1) and efficient recovery of CPT (81.54 %). Thus, an environmentally friendly column filler for SPE was developed, offering a promising avenue for utilizing cellulose-based materials in the selective separation of natural products.

Enhancing Solid-Phase Extraction of Tamoxifen and Its Metabolites from Human Plasma Using MOF-Integrated Polyacrylonitrile Composites: A Study on CuBTC and ZIF-8 Efficacy.

This study investigates electrospun fibers of metal-organic frameworks (MOFs), particularly CuBTC and ZIF-8, in polyacrylonitrile (PAN) for the solid-phase extraction (SPE) of Tamoxifen (TAM) and its metabolites (NDTAM, ENDO, and 4OHT) from human blood plasma. The focus is on the isolation, pre-concentration, and extraction of the analytes, aiming to provide a more accessible and affordable breast cancer patient-monitoring technology. The unique physicochemical properties of MOFs, such as high porosity and surface area, combined with PAN's stability and low density, are leveraged to improve SPE efficiency. The study meticulously examines the interactions of these MOFs with the analytes under various conditions, including elution solvents and protein precipitators. Results reveal that ZIF-8/PAN composites outperform CuBTC/PAN and PAN alone, especially when methanol is used as the protein precipitator. This superior performance is attributed to the physicochemical compatibility between the analytes' properties, like solubility and polarity, and the MOFs' structural features, including pore flexibility, active site availability, surface polarity, and surface area. The findings underscore MOFs' potential in SPE applications and provide valuable insights into the selectivity and sensitivity of different MOFs towards specific analytes, advancing more efficient targeted extraction methods in biomedical analysis.

Progress in the application of novel nano-materials to the safety analysis of agricultural products

The quality and safety of agricultural products are strongly related to human livelihood. Thus, the government and consumers have recently paid increased attention to the quality and safety of agricultural products. The development of efficient, rapid, and sensitive analytical methods for detecting pesticides, veterinary drugs, heavy metals, mycotoxins, and environmental pollutants in agricultural products is of great significance. Owing to the complexity of many sample matrices and the low concentration of pollutants in a typical sample, appropriate sample pretreatment steps are necessary to enrich pollutants in agricultural products. Solid-phase extraction (SPE) is the most widely used sample pretreatment technology; in this technique, the adsorbent generally determines the selectivity and efficiency of the extraction process. An increasing number of novel materials have been used as SPE adsorbents. The extraction efficiency, extraction selectivity, and analytical throughput of SPE could be greatly improved by combining these novel materials with various extraction modes (e. g., solid-phase microextraction, dispersed SPE, and magnetic SPE (MSPE)) during sample preparation. Because of their large specific surface area and high affinity toward target analytes, nanomaterials are often used as SPE adsorbents, thereby greatly improving the selectivity and sensitivity of the analytical technology. More importantly, these materials have become a priority area of research on preconcentration technologies for trace compounds in agricultural products. This paper summarizes the adsorption characteristics of several new nanomaterials, including magnetic materials, carbon-based materials, metal nanomaterials (MNs), metal oxide nanomaterials (MONs), metal organic frameworks (MOFs), and covalent organic frameworks (COFs). These nanomaterials present numerous advantages, such as large specific surface areas, high adsorption capacities, and tailorable structural designs. MSPE employs magnetic materials as sorbents to afford fast dispersion and efficient recycling when applied to complex sample matrices under an external magnetic field. The use of MSPE can avoid several typical problems associated with SPE such as poor adsorbent packing and high pressure, thereby greatly simplifying the pretreatment process and providing a high flux for sample analysis. Carbon-based materials are powdered or bulk nonmetallic solid materials with carbon as the main component; carbon and nitrogen materials, mesoporous carbon, carbon nanotubes, and graphene are some examples of these materials. These materials provide large specific surface areas, abundant pore structures, good thermal stability, high mechanical strength and adsorption capacity, and controllable morphology. Pure and modified carbon nanomaterials have been successfully used to purify target analytes from agricultural products. Given their unique physical and chemical properties, MNs and MONs have attracted significant interest for use in sample preparation. MNs and MONs with excellent thermal and mechanical stabilities show good resistance to a wide pH range and diverse organic solvents, which is crucial in adsorbent-based extraction methods. The surface of these materials can be easily modified with various ligands to improve their selectivity. MOFs and COFs present many advantages such as large specific surface areas, high porosity, adjustable pore performance, and good thermal stability. Several methods that employ novel adsorbent materials to analyze pollutants in a variety of agricultural products, such as chromatography, spectroscopy, mass spectrometry, and other detection technologies, have been established. This paper also reviews the application of adsorbent materials in the analysis of agricultural product quality and safety, and discusses the future development trends of these sorbents in sample preparation for the safety analysis of agricultural products.

Comparative evaluation of SPE methods for biotoxicity assessment of water and wastewater: Linkage between chemical extracting efficiency and biotoxicity outcome

Biotoxicity assessment results of environmental waters largely depend on the sample extraction protocols that enrich pollutants to meet the effect-trigger thresholds of bioassays. However, more chemical mixture does not necessarily translate to higher combined biotoxicity. Thus, there is a need to establish the link between chemical extracting efficiency and biotoxicity outcome to standardize extraction methods for biotoxicity assessment of environmental waters. This study compares the performance of five different extraction phases in solid phase extraction (SPE), namely HLB, HLB+Coconut, C18 cartridge, C18 disk and Strata-X, and evaluated their chemical extracting efficiencies and biotoxicity outcomes. We quantitatively assessed cytotoxicity, acute toxicity, genotoxicity, estrogenic activity, and neurotoxicity of the extracts using in vitro bioassays and characterized the chemical extracting efficiencies of the SPE methods through chemical recoveries of 23 model compounds with different polarities and total organic carbon. Using Pareto ranking, we identified HLB+Coconut as the optimal SPE method, which exhibited the highest level of water sample biotoxicity and recovered the most chemicals in water samples. We found that the biotoxicity outcomes of the extracted water samples significantly and positively correlated with the chemical extracting efficiencies of the SPE methods. Moreover, we observed synchronous changing patterns in biotoxicity outcome and chemical extracting efficiencies in response to increasing sample volumes per cartridge (SVPC) during SPE. Our findings underscore that higher chemical extracting efficiency of SPE corresponds to higher biotoxicity outcome of environmental water samples, providing a scientific basis for standardization of SPE methods for adequate assessment of biotoxicities of environmental waters.

Miniaturized matrix solid-phase dispersion and solid-phase clear-up combined with capillary electrophoresis for efficient determination of trace bioactive components in complicated sample matrix: Take Wubi Shanyao Pill as an example.

Accurate quantitative analysis of trace analytes in a complicated matrix is a challenge in modern analytical chemistry. An appropriate analytical method is considered to be one of the most common gaps during the whole process. In this study, a green and efficient strategy based on miniaturized matrix solid-phase dispersion and solid-phase extraction combined with capillary electrophoresis was first proposed for extracting, purifying and determining target analytes from complicated matrix, using Wubi Shanyao Pill as an example. In detail, 60mg of samples were dispersed on MCM-48 to obtain high yields of analytes, then the extract was purified with a solid-phase extraction cartridge. Finally, four analytes in the purified sample solution were determined by capillary electrophoresis. The parameters affecting the extraction efficiency of matrix solid-phase dispersion, purification efficiency of solid-phase extraction and separation effect of capillary electrophoresis were investigated. Under the optimized conditions, all analytes demonstrated satisfactory linearity (R2 >0.9983). What's more, the superior green potential of the developed method for the determination of complex samples was confirmed by the Analytical GREEnness Metric Approach. The established method was successfully applied in the accurate determination of target analytes in Wubi Shanyao Pill and thus provided reliable, sensitive, and efficient strategy support for its quality control.

An Imine-Based Porous 3D Covalent Organic Polymer as a New Sorbent for the Solid-Phase Extraction of Amphenicols from Water Sample.

In this paper, an imine-based porous 3D covalent organic polymer (COP) was synthesized via solvothermal condensation. The structure of the 3D COP was fully characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and powder X-ray diffractometry, thermogravimetric analysis, and Brunauer-Emmer-Teller (BET) nitrogen adsorption. This porous 3D COP was used as a new sorbent for the solid-phase extraction (SPE) of amphenicol drugs, including chloramphenicol (CAP), thiamphenicol (TAP), and florfenicol (FF) in aqueous solution. Factors were investigated for their effects on the SPE efficiency, including the types and volume of eluent, washing speed, pH, and salinity of water. Under the optimized conditions, this method gave a wide linear range (0.1-200 ng/mL) with a high correlation coefficient value (R2 > 0.99), low limits of detection (LODs, 0.01-0.03 ng/mL), and low limits of quantification (LOQs, 0.04-0.10 ng/mL). The recoveries ranged from 83.98% to 110.7% with RSDs ≤ 7.02%. The good enrichment performance for this porous 3D COP might contribute to the hydrophobic and π-π interactions, the size-matching effect, hydrogen bonding, and the good chemical stability of 3D COP. This 3D COP-SPE method provides a promising approach to selectively extract trace amounts of CAP, TAP, and FF in environmental water samples in ng quantities.

Determination of polyfluoroalkyl substances in cosmetic products using dispersed liquid-liquid extraction coupled with UHPLC-MS/MS.

Human exposure to polyfluoroalkyl substances (PFASs) via cosmetics has been of increasing concern due to the tremendous detrimental health impacts of PFASs. Developing an effective method for extracting and determining PFASs in cosmetics is crucial in accurately assessing their corresponding human exposure risk. Herein, this study developed a new sample pre-treatment method to address the challenges posed by the variety and complexity of cosmetic matrices. Seventeen PFASs in cosmetic products, including 9 perfluoro carboxylic acids and 8 perfluorosulfonic acids, were simultaneously determined using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The whole pre-treatment process can be divided into three steps. In step 1, cosmetics with diverse matrix types can be effectively dispersed during extraction by using saturated sodium chloride-acetonitrile and saturated sodium chloride-tetrahydrofuran as extraction solvents. In step 2, the pre-purification step employs a potassium ferrocyanide-zinc acetate co-precipitant to remove high molecular weight interferents from the extraction solution, thereby enhancing the efficiency of solid-phase extraction (SPE). In step 3, WAX-SPE is utilized to further eliminate interferents from the extraction solution while concentrating the analytes, meeting the trace analysis requirements for PFASs in cosmetics. The method detection limits were 0.09-0.26 ng g-1. The recoveries ranged from 70.1% to 114.7%, with relative standard deviations in the range of 2.0-19.1%. The method was applied to cosmetic samples in the Guangzhou market, and the total concentration of PFASs ranged from 0 to 10.8 ng g-1. This method has strong anti-interference ability, good applicability, high sensitivity, and good reproducibility, making it suitable for the analysis and detection of perfluorinated acids in cosmetic samples. It provides technical support for cosmetics safety regulation.

Recovery of Metals from Electronic Waste-Printed Circuit Boards by Ionic Liquids, DESs and Organophosphorous-Based Acid Extraction.

The extraction of metals from waste printed circuit boards (WPCBs) with ionic liquids (ILs), Deep Eutectic Solvents (DESs) and organophosphorous-based acid (Cyanex 272) has been presented. The study was undertaken to assess the effectiveness of the application of the new leaching liquids, and the new method of extraction of metals from the leachate and the solid phase with or without the leaching process. Solvent extraction from the liquid leachate phase has been studied in detail with popular ILs, such as tetraoctylphosphonium bromide, {[P8,8,8,8][Br] and tributyltetradecylphosphonium chloride, [P4,4,4,14][Cl] using Aqueous Biphasic Systems (ABS) method. Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate, [P6,6,6,14][Cyanex272], ([P6,6,6,14][BTMPP]), trihexyltetradecylphosphonium thiocyanate, [P6,6,6,14][SCN], methyltrioctylammonium chloride (Aliquat 336), as well as bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272) were also used in the extraction of metals from the leachate. Two DESs (1) {choline chloride + lactic acid, 1:2} and (2) {choline chloride + malonic acid, 1:1} were used in the extraction of metals from the solid phase. The extraction behavior of metals with DESs was compared with that performed with three new bi-functional ILs: didecyldimethylammonium salicylate, [N10,10,1,1][Sal], didecyldimethylammonium bis(2-ethylhexyl) phosphate, [N10,10,1,1][D2EHPA], and didecyldimethylammonium bis(2,4,4-trimethylpentyl) phosphinate, [N10,10,1,1][Cyanex272]. The [P6,6,6,14][Cyanex272]/toluene and (Cyanex 272 + diethyl phosphite ester) mixtures exhibited a high extraction efficiency of about 50–90% for different metal ions from the leachate. High extraction efficiency of about 90–100 wt% with the ABS method using the mixture {[P8,8,8,8][Br], or [P4,4,4,14][Cl] + NaCl + H2O2 + post-leaching liquid phase} was obtained. The DES 2 revealed the efficiency of copper extraction, ECu = 15.8 wt% and silver, EAg = 20.1 wt% at pH = 5 from the solid phase after the thermal pre-treatment and acid leaching. The solid phase extraction efficiency after thermal pre-treatment only was (ECu = 9.6 wt% and EAg = 14.2 wt%). The use of new bi-functional ILs did not improve the efficiency of the extraction of metal ions from the solid phase. Process factors such as solvent concentration, extraction additives, stripping and leaching methods, temperature, pH and liquid/solid as well as organic/water ratios were under control. For all the systems, the selectivity and distribution ratios were described. The proposed extraction processes can represent alternative paths in new technologies for recovering metals from electronic secondary waste.

Selective solid-phase extraction of atrazine from agricultural environmental water samples using high permeability nanoporous carbon derived from melamine-based polybenzoxazine followed by HPLC-UV

ABSTRACT For the first time, a highly permeable nanoporous carbon derived from melamine-based polybenzoxazine (NPC-PBZ-m) was used as the solid-phase extraction sorbent for trace analysis of atrazine (ATZ) herbicide in environmental water samples as a pre-treatment to enhance detection for high-performance liquid chromatography. Extraction performance was investigated using an agricultural field matrix-water sample. The parameters affecting the solid-phase extraction efficiency were carefully investigated. The optimisation conditions were determined as 200.0 mg of sorbent with an adsorption flow rate of 10.0 mL min−1, an elution flow rate of 1.0 mL min−1, and an elution volume of 3.0 mL. Moreover, it was not necessary to adjust the pH of the sample. Under these optimised extraction conditions, good linearity between 5.00 and 30.0 µg L−1 was achieved along with a limit of detection (LOD) of 1.25 µg L−1 and a limit of quantification (LOQ) of 3.79 µg L−1. Furthermore, the reusability of the NPC-PBZ-m column was found up to 8 cycles making it a new cost-effective material for herbicide enrichment. Finally, this developed method was successfully applied to analyse ATZ in water samples from rice fields, fish farms, and natural canal water, with 98–117% relative recoveries. These results indicate that NPC-PBZ-m with our proposed method is feasible and demonstrates its potential application as an effective adsorbent for herbicide enrichment.

Preparation of flower-like molybdenum disulfide for solid-phase extraction of N-nitrosoamines in environmental water samples.

In this paper, a flower-like molybdenum disulfide material was prepared by hydrothermal method and was first used as adsorbents in the solid-phase extraction process for enriching N-nitrosoamines. Molybdenum disulfide exhibited three-dimensional petal-like microspheres with about 500nm in diameter. The relevant analyte extraction and elution parameters (sample volumes, solution pH, washing solvents, elution solvents, and elution volumes) were optimized to improve the solid-phase extraction efficiency. The solid-phase extraction process coupled with high-performance liquid chromatography-tandem mass spectrometry for determining N-nitrosoamines in environmental water samples was established. The limits of detection were in the range of 0.01-0.05ng/mL. The satisfactory recoveries (68.9-106.1%) were obtained at three different spiked concentrations (2, 5, and 8ng/mL) in water samples, and the relative standard deviations were between 1.96 and 8.38%. This proposed method not only showed high sensitivity and good reusability but also provided a new adsorbent for enriching trace N-nitrosoamines in environmental water samples.

Effect of operating variables on the separation of radiostrontium from aqueous matrices with ion-selective solid-phase extraction systems

Radiostrontium (r-Sr: 90Sr) is one of the primary fission products in nuclear power plants and generates liquid radioactive waste when intermixed to the aqueous matrix. Therefore, separation or preconcentration of r-Sr from the aqueous matrices is necessary for environmental monitoring or nuclear forensics. The solid-phase extraction (SPE) approach is prevalently used for r-Sr isolation and to design matrix-specific methods, while generalized SPE-assisted operating protocols are not proposed by far. In the current work, four different SPEs, namely AnaLig Sr-01, Eichrom Sr, Triskem TK100, and Eichrom DGA, were evaluated for selective separation of Sr from aqueous matrices. Operating variables, e.g., solution acidity, washing solvent, eluent-type or volume, loading or elution flow-rate, were varied to optimize the SPEs performance. The objective was to ascertain the operating variables for maximum Sr-separation yield from aqueous environmental samples with the SPEs mentioned above. In addition, the Sr-separation efficiency of SPEs was evaluated by calculating the separation factor (SFSr/M) between Sr and interfering elements to r-Sr (M = Ca, Mg, Ba, or Y), and the Sr-retention capacity of the SPEs was determined. Finally, the optimized operating variables for the evaluated SPEs were used to construct protocols for r-Sr separation from aqueous matrices. Real 90Sr contaminated aqueous samples from the Chernobyl nuclear power plant cooling pond were treated by those protocols, and the results are validated comparing with the IAEA-recommended classical protocol. All the SPEs were able to isolate Sr at varying extents from matrices at the optimum conditions, even at much higher contents of interfering elements. Eichrom Sr or AnaLig Sr-01 showed better Sr-retention capability among the SPEs, while Triskem TK100 showed superiority over other SPEs regarding Sr-selectivity.

Determination of seven phenoxy acid herbicides in water by dispersive solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on cationic metal-organic framework mixed matrix membrane

离子型金属有机骨架材料(iMOFs)对离子型化合物具有良好的选择吸附性,利用水热法合成了一种金属有机骨架材料MIL-101-NH2,以聚偏二氟乙烯(PVDF)为交联剂将其制备成混合基质膜(MMM),然后用三氟甲烷磺酸甲酯进行季胺基功能化改性,最终得到阳离子型金属有机骨架膜材料MIL-101-$NMe_{3}^{+}$-PVDF MMM,采用分散固相萃取方式富集水中的苯氧羧酸类除草剂,建立了一种基于阳离子型MOF混合基质膜的分散固相萃取-超高效液相色谱-串联质谱(UPLC-MS/MS)测定水体中7种苯氧羧酸类除草剂的分析方法。通过傅里叶变换红外光谱和扫描电子显微镜对制备的混合基质膜进行表征,结果表明季胺基功能化改性是成功的,得到了阳离子型MOF膜。对影响萃取效果的主要因素(吸附剂用量、水样pH值、萃取时间、洗脱剂种类、洗脱剂体积及洗脱时间)进行了优化,确定了最佳萃取条件。以0.01%(v/v)甲酸水溶液和乙腈作为流动相进行梯度洗脱,目标化合物在ACQUITY UPLC BEH C18色谱柱(100 mm×2.1 mm, 1.7 μm)上分离,在电喷雾电离源、负离子模式下进行多反应监测(MRM),外标法定量。结果表明,7种苯氧羧酸类除草剂在各自范围内线性关系良好,线性相关系数均大于0.997,方法的检出限(LOD)和定量限(LOQ)分别为0.00010~0.00090 μg/L和0.00033~0.00300 μg/L。在0.005、0.05和0.2 μg/L 3个加标水平下进行加标回收率试验,7种待测物的平均回收率为80%~102%,日内、日间相对标准偏差分别为1.4%~9.4%和4.2%~12.6%。该方法操作简单、快速,灵敏度高,适用于环境水体中7种苯氧羧酸类除草剂的检测。

Evaluation of the phenyl-bonded silica-based sorbent for pre-concentration of the booster antifouling biocides Zinc Pyrithione, Zineb and Ziram using solid-phase extraction technique and Inductively Coupled Plasma Mass Spectrometry

A robust method of solid-phase extraction technique with use of the phenyl-bonded silica-based sorbent (Si-PH sorbent) for pre-concentration of three booster antifouling biocides: zinc pyrithione, Zineb and Ziram in ultrapure water fortified and estuarine water sample was evaluated for zinc determination by collision cell technology-inductively coupled plasma-mass spectrometry (CCT-ICP-MS). Decontamination process to remove metals and prevent (trans-) metallization of the Si-PH sorbent with 20 mL of nitric acid 0.006 mol L-1 was performed. This proposed solid-phase extraction efficiency of three booster antifouling biocides by the phenyl-bonded silica-based sorbent (Si-PH sorbent) was evaluated in 40 mL of ultrapure water fortified sample (40 μg L-1 of the zinc biocides). The adsorption of zinc pyrithione, Zineb and Ziram were 94.2 ± 0.1%, 85.13 ± 0.04% and 93.35 ± 0.09%, respectively. The limit of detection and limit of quantification values obtained were 0.66 μg L-1 and 2.19 μg L-1, respectively. Good recoveries of zinc pyrithione (85 ± 2%), Zineb (89 ± 5%) and Ziram (111 ± 2%) in the elution step for booster antifouling biocides from the fortified estuarine water were obtained.

Preparation of magnetic flower-like molybdenum disulfide hybrid materials for the extraction of organophosphorus pesticides from environmental water samples

In this study, the magnetic flower-like molybdenum disulfide hybrid materials (Fe3O4/MoS2) were successfully synthesized by in-situ fabrication method and utilized in the magnetic solid-phase extraction of organophosphorus pesticides. Fe3O4 nanoparticles with different loading amounts of MoS2 were evaluated and detail characterized. The results showed that MoS2 played a key role with rapid and high adsorption capacity towards organophosphorus pesticides. The higher extraction efficiency and good magnetic performance were obtained with loading amount of 200 mg MoS2. Fe3O4 was attached on the surface of MoS2 with flower-like shape (500 nm in diameter). The parameters (amounts of adsorbents, adsorption time, solution pH, elution solvents and sample volumes) affecting magnetic solid-phase extraction efficiency were optimized. Under the optimum conditions, magnetic solid-phase extraction coupled with high liquid chromatography-tandem mass spectrometry for analyzing organophosphorus pesticides in environmental water samples was established. All the analytes exhibited good recoveries spiked at three different concentration levels (10, 20, 50 ng/mL) in water samples. The relative standard deviations were between 1.4% and 6.8%. The developed method showed high sensitivity and good potential use of this convenient and high efficient method for determining organophosphorus pesticides. More importantly, this study can provide a new magnetic adsorbent with extremely fast mass transfer rate for other potential trace contaminants.

Physicochemical characteristics of the active fractions of polyphenols from Arctic macrophytes

Brown algae of the Fucaceae family, collected in the western segment of the Arctic, contain a large number of polyphenolic compounds—phlorotannins—with a unique chemical nature, macromolecular structure, and physicochemical properties, exhibiting bioactive properties. The peculiarity of the biopolymers’ properties and structure, which are an element of fundamental scientific research of the cycle, structure—functional nature—properties, determines the priority of the directions of use of polyphenols as effective biologically active pharmaceutical preparations. This work aims to develop methods for selective extraction of phlorotannins from the Arctic brown alga Fucus vesiculosus, characterization of physicochemical properties, and biological activity of these compounds. The efficiency of solid-phase extraction (SPE) on a hydrophobic sorbent with grafted hexadecyl groups was shown for fractionation of the polyphenolic extract: active fractions were obtained, characterized by a high content of polyphenols (yield of polyphenols up to 98% relative to the content of these components in algae) with mass-average molecular weights of 21.4–35.8 kDa and oligomeric components in the mass range 374–994 Da. The IR spectra of the fractions were characterized, and the tendency of phlorotannins to form aggregates at high concentrations of the extract was shown. During hydrodynamic studies, a strong polyelectrolyte swelling of polyphenols (PP) was noted. The obtained polyphenolic fractions differ in physicochemical characteristics (acid-base and redox properties) and antioxidant activity.

Microwave-assisted synthesis of magnetic surface molecular imprinted polymer for adsorption and solid phase extraction of 4-nitrophenol in wastewater

A novel sorbent based on surface molecularly imprinted polymers (MIPs) was prepared for efficient adsorption and extraction of 4-nitrophenol (4-NP) from water. Microwave-assisted surface imprinting technology was employed to synthesize the surface molecularly imprinted polymer of Fe3O4@SiO2@PNP-SMIP with the γ-ureidopropyltrimethoxysilane as functional monomer, 4-NP as template molecule and Fe3O4@SiO2 as support material. It was characterized by Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and Brunner–Emmet–Teller (BET). The results indicated that Fe3O4@SiO2@PNP-SMIP can effectively adsorb and extract PNP. The adsorption capacity of this polymer for 4-NP can reach 134.23 mg·g−1, in comparison with 64.07 mg·g−1 of the corresponding non-imprinted polymer. The adsorption process could be well described with pseudo second order kinetic model (R2 = 0.9900–0.9936) and the Langmuir model. The solid phase extraction efficiency of the Fe3O4@SiO2@PNP-SMIP to 4-NP could reach 99% underthecondition of the initial 4-NP concentration of 6.5 μg·mL−1, pH of 7 and the eluent of 2 mL mixed solvent of methanol/acetic acid (5:1, v/v). And the selective SPE efficiency attained 99.2% in the presence of multiple structural analogues of 4-NP. These results demonstrate that Fe3O4@SiO2@PNP-SMIP could be employed for separation and detection of 4-NP from water samples.