Coconut shell biochar application in liquid-solid microextraction of triazine herbicides from multi-media environmental samples.

A rapid, fast, widely applicable liquid-solid microextraction and purification method of triazine herbicides (TRZHs) in muti-media samples using salting-out assisted liquid-liquid extraction (SALLE) combined with self-assembled monolithic spin columns-solid phase micro extraction (MSC-SPME) was developed. Environmentally friendly coconut shell biochar (CSB) was used as the adsorbents of MSC-SPME. Ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was the separation and determination method. The adsorption kinetics and isotherms were investigated to indicate the interaction between CSB and TRZHs. Several parameters influencing the liquid-solid microextraction efficiency, such as sample pH, salting-out solution volume and pH, sample loading speed, elution speed, elution ratio and volume of eluent were systematically investigated with the aid of orthogonal design. The whole extraction process was operated within 10 min. Under the optimum extraction and determination conditions, good linearities for three TRZHs were obtained in a range of 0.10-200.00 ng mL-1, with linear coefficients (R2) greater than 0.999. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 6.99-11.00 ng L-1 and 23.33-36.68 ng L-1, respectively. The recoveries of the three TRZHs in multi-media environmental samples were ranged from 69.00% to 124.72%, with relative standard deviations (RSDs) lower than 0.43%. This SALLE-MSC-SPME-UPLC-MS/MS method was successfully applied to the determination of TRZHs in environmental and food samples and exhibited the advantages of high efficiency and sensitivity, low cost, and environmental friendliness. Compared with the methods published before, CSB-MSC was green, rapid, easy-operated, and reduced the whole cost of the experiment; SALLE combined MSC-SPME eliminated the matrix references effectively; what's more, the SALLE-MSC-SPME-UPLC-MS/MS method could be applied to various sample without complicated sample pretreatment procedure.

Self-synthesized TiO2 nanoparticles-pH-mediated dispersive solid phase extraction coupled with high performance liquid chromatography for the determination of quinolones in biological matrices.

A simple and efficient pH-mediated dispersive solid phase extraction (dSPE) based on terbium doped titanium dioxide nanoparticles (TiO2-Tb NPs) combined with high performance liquid chromatography (HPLC) has been firstly developed for the determination of quinolones (QNs) in various biological samples. The adsorption kinetics and isotherms were investigated to indicate that the kinetic and equilibrium adsorption were well-described by pseudo-second order kinetic and Henry, Langmuir isotherm model, respectively. The parameters influencing the extraction performance were systematically investigated. The QNs are transferred into TiO2-Tb NPs in the first step at pH = 6.0 and eluted into acidic aqueous phase at pH = 2.5 in the second step. Under the optimum extraction and determination conditions, a linearity range with the coefficient of determination (R2) from 0.9977 to 0.9991 were obtained in a range of 10-10,000 ng mL-1. The limits of detection (LODs) based on a signal-to-noise ratio of 3 were 3.3 ng mL-1. The recoveries of the three QNs in human urine, rabbit plasma and serum samples ranged from 69.3% to 117.6%, with standard deviations ranging from 2.4% to 9.9%. Therefore, this pH-mediated dSPE-HPLC method exhibited the advantages of remarkable sensitivity, ease of operation, rapidity, low cost and environmental friendliness.

Salting-out assisted liquid-liquid extraction combined with gas chromatography-mass spectrometry for the determination of pyrethroid insecticides in high salinity and biological samples.

A salting-out assisted liquid-liquid extraction (SALLE) combined with gas chromatography-mass spectrometry (GC-MS) method was developed for the determination of four pyrethroid insecticides (PYRs) in high salinity and biological samples. Several parameters including sample pH, salting-out solution volume and salting-out solution pH influencing the extraction efficiency were systematically investigated with the aid of orthogonal design. The optimal extraction conditions of SALLE were: 4mL of salting-out solution with pH=4 and the sample pH=3. Under the optimum extraction and determination conditions, good responses for four PYRs were obtained in a range of 5-5000ng/mL, with linear coefficients greater than 0.998. The recoveries of the four PYRs ranged from 74% to 110%, with standard deviations ranging from 1.8% to 9.8%. The limits of detection based on a signal-to-noise ratio of 3 were between 1.5-60.6ng/mL. The method was applied to the determination of PYRs in urine, seawater and wastewater samples with a satisfactory result. The results demonstrated that this SALLE-GC-MS method was successfully applied to determine PYRs in high salinity and biological samples. SALLE avoided the need for the elimination of salinity and protein in the sample matrix, as well as clean-up of the extractant. Most of all, no centrifugation or any special apparatus are required, make this a promising method for rapid sample preparation procedure.

Dual-cloud point extraction coupled to high performance liquid chromatography for simultaneous determination of trace sulfonamide antimicrobials in urine and water samples.

Dual-cloud point extraction (dCPE) was successfully developed for simultaneous extraction of trace sulfonamides (SAs) including sulfamerazine (SMZ), sulfadoxin (SDX), sulfathiazole (STZ) in urine and water samples. Several parameters affecting the extraction were optimized, such as sample pH, concentration of Triton X-114, extraction temperature and time, centrifugation rate and time, back-extraction solution pH, back-extraction temperature and time, back-extraction centrifugation rate and time. High performance liquid chromatography (HPLC) was applied for the SAs analysis. Under the optimum extraction and detection conditions, successful separation of the SAs was achieved within 9min, and excellent analytical performances were attained. Good linear relationships (R2≥0.9990) between peak area and concentration for SMZ and STZ were optimized from 0.02 to 10µg/mL, for SDX from 0.01 to 10µg/mL. Detection limits of 3.0-6.2ng/mL were achieved. Satisfactory recoveries ranging from 85 to 108% were determined with urine, lake and tap water spiked at 0.2, 0.5 and 1µg/mL, respectively, with relative standard deviations (RSDs, n=6) of 1.5-7.7%. This method was demonstrated to be convenient, rapid, cost-effective and environmentally benign, and could be used as an alternative tool to existing methods for analysing trace residues of SAs in urine and water samples.

Graphene oxide-based microspheres for the dispersive solid-phase extraction of non-steroidal estrogens from water samples.

A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method based on the dispersive solid-phase extraction (dSPE) combined with high performance liquid chromatography (HPLC) was developed for the determination of non-steroidal estrogens in water samples. In this study, graphene oxide-based silica microspheres (SiO2@GO) were used as dSPE material for the preconcentration of analytes. HPLC was used for the separation and detection. This was the first time that the synthesized SiO2@GO microspheres were used as stationary phases for the off-line preconcentration of the non-steroidal estrogens in dSPE. dSPE parameters, such as sample pH, volume and type of eluent were optimized. Application of the developed method to analyze spiked lake, reservoir and tap water samples resulted in good recoveries values ranging from 70 to 106% with relative standard deviation values lower than 7.0% in all cases. Limits of detection were in the range of 0.2-6.1 µg/L. The combined data obtained in this study recommended that the proposed method is very fast, simple, repeatable and accurate for the detection of non-steroidal estrogens. Furthermore, the SiO2@GO microspheres application could potentially be expanded to extract and pre-concentrate other compounds in various matrices.

Isolation and characterization of Pseudomonas sp. strain capable of degrading diethylstilbestrol.

Since diethylstilbestrol (DES) interrupts endocrine systems and generates reproductive abnormalities in both wildlife and human beings, methods to remove DES from the environments are urgently recommended. In this study, bacterial strain J51 was isolated and tested to effectively degrade DES. J51 was identified as Pseudomonas sp. based on its nucleotide sequence of 16S rRNA. The quinoprotein alcohol dehydrogenase and isocitrate lyase were identified to be involved in DES degradation by MALDI-TOF-TOF MS/MS analysis. In the presence of 40 mg/l DES, increase of the genes encoding quinoprotein alcohol dehydrogenase and isocitrate lyase in both RNA and protein levels was determined. The HPLC/MS analysis showed that DES was hydrolyzed to a major degrading metabolite DES-4-semiquinone. It was the first time to demonstrate the characteristics of DES degradation by specific bacterial strain and the higher degradation efficiency indicated the potential application of Pseudomonas sp. strain J51 in the treatment of DES-contaminated freshwater and seawater environments.

Molecularly imprinted matrix solid-phase dispersion coupled to micellar electrokinetic chromatography for simultaneous determination of triazines in soil, fruit, and vegetable samples.

A simple and sensitive method for the simultaneous determination of four triazines from soil, strawberry, and tomato samples was developed by selective molecularly imprinted matrix solid-phase dispersion (MI-MSPD) coupled to micellar electrokinetic chromatography (MEKC). Using atrazine as template, the synthesized molecularly imprinted polymers (MIPs) were employed as the dispersion sorbent of MSPD to successfully extract atrazine and its analogs of simazine, ametryn, and propazine from the three different real samples, while matrix interferences were effectively eliminated simultaneously under the optimum extraction conditions. Excellent separation was achieved within 7 min by using an optimized buffer system composed of 30 mmol/L ammonium acetate, 20 mmol/L SDS, and 15% ACN at pH 9.45, obtained by orthogonal design. Good linearity was obtained in a range of 0.5-25 µg/g with the correlation coefficients R(2) ≥0.9991 except for strawberry sample within 1-25 µg/g, and limits of detection were between 12.9-31.5 ng/g in all the three samples. The average recoveries of the four triazines at three different spiked levels were ranged from 53.5 to 98.4% with the relative standard deviations of 1.28-4.89%. This method was proved convenient, costeffective, and environmental benign and could be used as an alternative tool to the existing methods for analyzing the residues of triazines in soil, fruit, and vegetable samples.

Isolation and characterization of sulfonamide-degrading bacteria Escherichia sp. HS21 and Acinetobacter sp. HS51.

With the intensive application of sulfonamides in aquaculture and animal husbandry and the increase of sulfonamides discharged into the environments, there is an increasing need to find a way to remediate sulfonamide-contaminated environments. Two bacterial strains capable of degrading sulfonamides, HS21 and HS51, were isolated from marine environments. HS21 and HS51 were identified as members of Escherichia sp. and Acinetobacter sp., respectively, based on 16S rRNA gene sequencing. Degradation of each sulfonamide by Escherichia sp. HS21 and Acinetobacter sp. HS51 was characterized using capillary electrophoresis. About 66 or 72% of sulfapyridine and 45 or 67% of sulfathiazole contained in the media was degraded by Escherichia sp. HS21 or Acinetobacter sp. HS51, respectively, after incubation for 2 days. The supernatant from culture of Escherichia sp. HS21 or Acinetobacter sp. HS51 grown in sulfapyridine or sulfathiazole contained media had much attenuated cytotoxicity against HeLa cells. These results suggest that Escherichia sp. HS21 and Acinetobacter sp. HS51 are new bacterial resources for biodegrading sulfonamides and indicate the potential of isolated strains for the bioremediation of sulfonamide-polluted environments.

Isolation and characterization of Pseudomonas sp. DX7 capable of degrading sulfadoxine.

Given that the intensive application of sulfonamides in aquaculture, animal husbandry and malaria treatment has lead to an increase in sulfonamide discharge into the environment, there is an increasing need to find a way to remediate sulfonamide-contaminated sites. The bacterial strain DX7 was isolated from a marine environment and is capable of degrading sulfadoxine. DX7 was identified as a Pseudomonas sp. based on 16S rRNA gene sequencing. Approximately 30% of sulfadoxine was degraded after Pseudomonas sp. DX7 was inoculated into mineral salt plus tryptone media containing 10 mg l(-1) sulfadoxine for 2 days. The degradation efficiency under different environmental conditions was characterized using HPLC. The optimal temperature and pH for sulfadoxine biodegradation were around 30°C and 6.0, respectively. The optimal concentrations of sulfadoxine and tryptone for sulfadoxine biodegradation were determined to be approximately 30 mg l(-1) and between 2.0 and 8.0 g l(-1), respectively. Cytotoxicity analysis indicated that the metabolites of sulfadoxine generated by Pseudomonas sp. DX7 showed significantly reduced cytotoxicity to Hela cells. These results suggest that Pseudomonas sp. DX7 is a new bacterial resource for degrading sulfadoxine and indicate the potential of the isolated strain in the bioremediation of sulfadoxine-contaminated environments.