Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Key Laboratory of Integrated Pest Management in Crops, Ministry of Agriculture, Beijing 100193, China.
J Chromatogr A. 2012 Feb 10;1224:51-60. doi: 10.1016/j.chroma.2011.12.044. Epub 2011 Dec 20.
The manuscript concerns the development and validation of a novel and sensitive multi-residue method for simultaneous enantiomeric analysis of 8 triazole fungicides (tetraconazole, fenbuconazole, epoxiconazole, diniconazole, hexaconazole, triadimefon, paclobutrazol, and myclobutanil) in soil and water using chiral liquid chromatography coupled with tandem mass spectrometry. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralcel OD-RH (150 mm × 4.6 mm) column, under isocratic conditions using a mixture of ACN-2 mM ammonium acetate in water (55/45, v/v) as the mobile phase at 0.45 mL/min flow rate. The effects of three cellulose-based columns and three amylose-based columns on the separation were also investigated. The QuEChERS (acronym for quick, easy, cheap, effective, rugged and safe) method and solid-phase extraction (SPE) were used for the extraction and clean-up of the soil and water samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were undertaken. Under optimal conditions, the mean recoveries for all sixteen enantiomers from the soil samples were 76.4-108.1% with 2.6-12.0% intra-day relative standard deviations (RSD) and 4.2-14.1% inter-day RSD at 5, 25 and 50 μg/kg levels; the mean enantiomer recoveries from the water samples were 81.2-106.5% with 2.1-11.5% intra-day RSD and 3.4-13.6% inter-day RSD at 0.25, 0.5 and 2.5 μg/L levels. Coefficients of determination R2 ≥ 0.9989 were achieved for all studied analytes in the soil and water matrix calibration curves within the range of 1.0-125 μg/L. The limits of detection (LOD) (S/N=3) for all enantiomers in the soil and water were less than 1.0 μg/kg or μg/L, whereas the limit of quantification (LOQ) (S/N=10) did not exceed 3.0 μg/kg or μg/L. The results of the method validation confirm that this proposed method is convenient and reliable for the enantioselective determination of the enantiomers of triazole fungicides in soil and water.
本文涉及一种新型、灵敏的多残留方法的开发和验证，用于使用手性液相色谱串联质谱法同时对土壤和水中的 8 种三唑类杀菌剂（四唑、苯醚甲环唑、环氧氯丙烷、烯唑醇、己唑醇、三唑酮、戊唑醇和腈菌唑）进行对映体分析。分离和测定是在反相色谱上进行的，使用纤维素手性固定相，Chiralcel OD-RH（150mm×4.6mm）柱，在等度条件下，流动相为 ACN-2mM 乙酸铵在水中（55/45，v/v），流速为 0.45mL/min。还研究了三种纤维素基柱和三种直链淀粉基柱对分离的影响。QuEChERS（快速、简便、廉价、有效、坚固和安全的缩写）方法和固相萃取（SPE）分别用于土壤和水样的提取和净化。进行了基质效应、线性、精密度、准确度和稳定性等参数的研究。在最佳条件下，从土壤样品中获得的所有 16 种对映体的平均回收率为 76.4-108.1%，日内相对标准偏差（RSD）为 2.6-12.0%，5、25 和 50μg/kg 水平的日间 RSD 为 4.2-14.1%；从水样中获得的平均对映体回收率为 81.2-106.5%，日内 RSD 为 2.1-11.5%，0.25、0.5 和 2.5μg/L 水平的日间 RSD 为 3.4-13.6%。在所研究的土壤和水基质校准曲线的范围内为 1.0-125μg/L，所有分析物的决定系数 R2均大于 0.9989。所有对映体在土壤和水中的检出限（LOD）（S/N=3）均小于 1.0μg/kg 或μg/L，而定量限（LOQ）（S/N=10）均不超过 3.0μg/kg 或μg/L。方法验证的结果证实，该方法方便可靠，可用于土壤和水中三唑类杀菌剂对映体的选择性测定。
