Guoqiang Xiang

Poly(ionic liquid) immobilized magnetic nanoparticles as new adsorbent for extraction and enrichment of organophosphorus pesticides from tea drinks

New poly(ionic liquid) immobilized magnetic nanoparticles (PIL-MNPs) were synthesized via co-polymerization of 1-vinyl-3-hexylimidazolium-based ionic liquid and vinyl-modified magnetic particles and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and magnetic measurements. The PIL-MNPs were utilized as adsorbent phases in magnetic solid-phase extraction (MSPE). The extraction and enrichment efficiency were evaluated by using four organophosphorus pesticides (parathion, fenthion, phoxim and temephos) as test analytes. Various parameters, such as amount of adsorbent, adsorption time, desorption solvent and time, and ionic strength were investigated. The proposed method showed good linearity for the analytes in the concentration range of 1-200μgL(-1) with a correlation coefficient (R)>0.9963. Low limit of detection of 0.01μgL(-1) and high enrichment factors ranging from 84 to 161 were achieved. The proposed method has been successfully used to determine organophosphorus pesticides from three tea drink samples with satisfactory recovery of 81.4-112.6% and RSDs of 4.5-11.3%. The PIL-MNP adsorbent can be reused for 20 times without a noticeable decrease in extraction efficiency.

Cloud point extraction combined with electrothermal atomic absorption spectrometry for the speciation of antimony(III) and antimony(V) in food packaging materials.

A simple, sensitive method for the speciation of inorganic antimony by cloud point extraction combined with electrothermal atomic absorption spectrometry (ETAAS) is presented and evaluated. The method based on the fact that formation of a hydrophobic complex of antimony(III) with ammonium pyrrolidine dithiocarbamate (APDC) at pH 5.0 and subsequently the hydrophobic complex enter into surfactant-rich phase, whereas antimony(V) remained in aqueous solutions. Antimony(III) in surfactant-rich phase was analyzed by ETAAS after dilution by 0.2 mL nitric acid in methanol (0.1M), and antimony(V) was calculated by subtracting antimony(III) from the total antimony after reducing antimony(V) to antimony(III) by l-cysteine. The main factors affecting the cloud point extraction, such as pH, concentration of APDC and Triton X-114, equilibrium temperature and incubation time, sample volume were investigated in detail. Under the optimum conditions, the detection limit (3 sigma) of the proposed method was 0.02 ng mL(-1) for antimony(III), and the relative standard deviation was 7.8% (c=1.0 ng mL(-1), n=7). The proposed method was successfully applied to speciation of inorganic antimony in the leaching solutions of different food packaging materials with satisfactory results.

Selective cloud point extraction for the determination of cadmium in food samples by flame atomic absorption spectrometry

A new cloud point extraction (CPE) procedure for preconcentration of cadmium prior to the determination by flame atomic absorption spectrometry (FAAS) was developed. The method is based on the fact that cadmium could form hydrophobic ion-associated complex in the presence of iodide and methyl green (MG), and the hydrophobic ion-associated complex could be extracted into surfactant-rich phase. The main factors affecting CPE procedure, such as pH, concentration of KI, MG and surfactant, equilibrium temperature and incubation time, sample volume were investigated. Potential interference from co-existing ions was largely eliminated as most of co-existing ions can not form extractable ion-associated complex with iodide and MG. Under the optimum conditions, the limit of detection (3σ) and limit of quantity (10σ) were 0.90ngmL(-1) and 3.0ngmL(-1) for cadmium, respectively, and relative standard deviation was 4.2% (c=50ngmL(-1), n=7). The proposed method was successfully applied to determination of cadmium in the certified reference rice sample (GBW08510) and food samples with satisfactory results.

Determination of trace copper in food samples by flame atomic absorption spectrometry after solid phase extraction on modified soybean hull

Soybean hull was chemically modified with citric acid and used as a solid phase extraction adsorbent for the determination of trace amounts of Cu(2+) in food samples by flame absorption spectrometry (FAAS). The effect of pH, sample flow rate and volume, elution flow rate and volume and co-existing ions on the recovery of the analyte were investigated. The results showed that Cu(2+) could be adsorbed on the modified soybean hull at pH 8.0 and eluted by 2.0 mL of 1.0 mol L(-1) HCl. Under the optimized conditions, the adsorption capacity of modified soybean hull was found to be 18.0 mg g(-1) for Cu(2+). The detection limit of the proposed method was 0.8 ng mL(-1) for Cu(2+) with an enrichment factor of 18. The analytical result for the certified reference tea sample (GBW07605) was in a good agreement with the certified value. The proposed method has also been successfully applied to the determination of trace Cu(2+) in dried sweet potato, lake water and milk powder, the recovery of Cu(2+) for spiked samples was between 91% and 109.6%.

Thiol-Modified Magnetic Silica Sorbent for the Determination of Trace Mercury in Environmental Water Samples Coupled with Cold Vapor Atomic Absorption Spectrometry

Core-shell magnetic silica has been prepared and then chemically modified with thiol groups. It was used for magnetic solid phase extraction (MSPE) of trace Hg2+ from environmental samples, followed by its determination by cold vapor atomic absorption spectrometry (CV-AAS). The parameters for MSPE procedure, such as pH, elution conditions, ultrasonic time, and effects of co-existing ions were investigated. The results showed that Hg2+ ions are adsorbed on the thiol-modified magnetic silica at pH 6.0 after a 10-min ultrasonic treatment and were quantitatively eluted with 5.0 mL thiourea (2%, m/v) in nitric acid solution (0.1 M) after a 2-min ultrasonic treatment. Under the optimized experimental conditions, the adsorption capacity of the new sorbent was 101.0 mg g−1 for Hg2+. The detection limit of the proposed method was 0.06 n g mL−1 for Hg2+ and the enrichment factor was 16.6. The analytical data obtained from a certified reference water sample (GBW00809) were in good agreement with the certified value. The method has also been successfully applied to the determination of trace Hg2+ in rain water, well water and treated water from a sewage treatment plant. The recovery of Hg2+ from spiked samples was between 96.0% and 110.0%.

Macrocyclic polyamine‐functionalized silica as a solid‐phase extraction material coupled with ionic liquid dispersive liquid–liquid extraction for the enrichment of polycyclic aromatic hydrocarbons

In this study, silica modified with a 30-membered macrocyclic polyamine was synthesized and first used as an adsorbent material in SPE. The SPE was further combined with ionic liquid (IL) dispersive liquid-liquid microextraction (DLLME). Five polycyclic aromatic hydrocarbons were employed as model analytes to evaluate the extraction procedure and were determined by HPLC combined with UV/Vis detection. Acetone was used as the elution solvent in SPE as well as the dispersive solvent in DLLME. The enrichment of analytes was achieved using the 1,3-dibutylimidazolium bis[(trifluoromethyl)sulfonyl]imide IL/acetone/water system. Experimental conditions for the overall macrocycle-SPE-IL-DLLME method, such as the amount of adsorbent, sample solution volume, sample solution pH, type of elution solvent as well as addition of salt, were studied and optimized. The developed method could be successfully applied to the analysis of four real water samples. The macrocyclic polyamine offered higher extraction efficiency for analytes compared with commercially available C18 cartridge, and the developed method provided higher enrichment factors (2768-5409) for model analytes compared with the single DLLME. Good linearity with the correlation coefficients ranging from 0.9983 to 0.9999 and LODs as low as 0.002 μg/L were obtained in the proposed method.

Dicationic polymeric ionic-liquid-based magnetic material as an adsorbent for the magnetic solid-phase extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons

Magnetic particles modified with a dicationic polymeric ionic liquid are described as a new adsorbent in magnetic solid-phase extraction. They were obtained through the copolymerization of a 1,8-di(3-vinylimidazolium)octane-based ionic liquid with vinyl-modified SiO2 @Fe3 O4 , and were characterized by FTIR spectroscopy, X-ray diffraction, and vibrating sample magnetometry. The modified magnetic particles are effective in the extraction of organophosphate pesticides and polycyclic aromatic hydrocarbons. Also, they can provide different extraction performance for the selected analytes including fenitrothion, parathion, fenthion, phoxim, phenanthrene, and fluoranthene, where the extraction efficiency is found to be in agreement with the hydrophobicity of analytes. Various factors influencing the extraction efficiency, such as, the amount of adsorbent, extraction, and desorption time, and type and volume of the desorption solvent, were optimized. Under the optimized conditions, a good linearity ranging from 1-100 μg/L is obtained for all analytes, except for parathion (2-200 μg/L), where the correlation coefficients varied from 0.9960 to 0.9998. The limits of detection are 0.2-0.8 μg/L, and intraday and interday relative standard deviations are 1.7-7.4% (n = 5) and 3.8-8.0% (n = 3), respectively. The magnetic solid-phase extraction combined with high-performance liquid chromatography can be applied for the detection of trace targets in real water samples with satisfactory relative recoveries and relative standard deviations.

Determination of the acid values of edible oils via FTIR spectroscopy based on the OH stretching band

A new method for determining the acid values (AVs) of edible oils based on the OH stretching band was developed. The oil sample was diluted with carbon tetrachloride and was placed in a quartz cuvette with a thickness of 1cm to record the FTIR spectrum. The peak at 3535cm(-1), which corresponds to the OH stretch of the carboxyl group in free fatty acids, together with the peak valley at 3508cm(-1) and the spectral data in the range of 3340-3390cm(-1) were used to determine the AV of the edible oil. The excellent linear relationship between the AVs measured in this work and those measured using a titration method, with a correlation coefficient (R) of 0.9929, indicates that the present procedure can be applied as an alternative to the classic method for determining the AVs of edible oils.

Immobilization of lead in soil influenced by soluble phosphate and calcium: lead speciation evidence.

We investigated the effect of soluble Ca on the speciation of Pb in phosphate-amended soils. A calcareous soil was amended in sequence with soluble phosphate (0 and 299 mg kg P), calcium nitrate (0, 200, and 400 mg kg Ca), and/or lead nitrate (0 and 1000 mg kg Pb) and incubated for 50 d. Extractable Ca was relatively similar across all samples, with a minor reduction in Ca release for treatments amended with P possibly from the formation of Ca-phosphate minerals. Olsen-P extractability from P-added treatments was highest in the non-Pb-amended soils and was about 40% lower when Pb was added as a result of Pb-phosphate formation. In the absence of P, diethylene triamine pentaacetic acid (DTPA)-Pb extractability increased with increasing Ca amendment; however, in the P-amended treatments, DTPA-Pb decreased with increasing Ca addition. X-ray absorption spectroscopy results of the Pb spiked soils indicate that adsorbed Pb is the primary phase (up to 92%) in non-P-amended soils with minor distribution to hydrocerussite and Pb-phosphate phases. In the P-amended treatments, Pb speciation shifted to Pb-phosphate [chloropyromorphite and Pb(PO)] (42-48%) and adsorbed Pb (44-50%). As Ca concentration increased in the P-amended soils, Pb-phosphate speciation moved from combined chloropyromorphite and Pb(PO) (0 mg kg Ca) to exclusively chloropyromorphite. The study demonstrates that soluble Ca enhances Pb immobilization with P amendments.

Lead retention in a calcareous soil influenced by calcium and phosphate amendments

Phosphate amendments in calcareous lead (Pb)-contaminated soils to immobilize Pb may be hindered due to competition of Pb with calcium (Ca) that may inhibit the retention of Pb as a precipitation mechanism. This study explored the retention of Pb in a calcareous soil spiked and aged with 500 mg kg(-1) Pb(2+) and amended with H2PO4(-). In addition, Ca(2+) was added immediately or three days before or after phosphate, after which ryegrass (Lolium perenne) was planted. Diethylene triamine pentaacetic acid (DTPA)-extractable Pb of the soils in which Ca was added immediately after phosphate was lower than those only amended with phosphate or when Ca was added three days before or after phosphate. The addition of Ca immediately after phosphate resulted in the greatest reduction of ammonia acetate-exchangeable Ca concentration, Olsen-P concentration, and carbonate phase Pb. Higher plant biomass yields were observed for the simultaneous P and Ca treatment. The results of the study demonstrate that co-added Ca and P may help reduce Pb availability by forming fresh Ca-P sorbent phases to retain Pb through an adsorption-substitution mechanism, which may play an important role in the sequestration of Pb in calcareous soils with soluble phosphate in addition to the mechanism of the direct precipitation as pyromorphite.