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 selfassembled 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 SALLEMSC-SPME-UPLC-MS/MS method could be applied to various sample without complicated sample pretreatment procedure.

Automated summary

A rapid and efficient method of liquid-solid microextraction and purification 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 microextraction (MSC-SPME) was developed. Coconut shell biochar (CSB) was used as the adsorbents of MSC-SPME. The method exhibited high efficiency and sensitivity, low cost, and environmental friendliness, and could be applied to various samples without complicated pretreatment. The developed method could accurately determine TRZHs in environmental and food samples, with good linearities, low LODs and LOQs, and satisfactory recoveries.