Comparison of gas and high performance liquid chromatography with selective detection for determination of triazine herbicides and their degradation products extracted ultrasonically from soil

GC and HPLC with selective detectors were compared for simultaneous determination of triazine herbicides simazine, atrazine, propazine, terbuthylazine, cyanazine, ametryn, prometryn, and atraton, and of their dealkylated degradation products in soil. The compounds were ultrasonically extracted from spiked agricultural soil samples (organic matter content < 5%) with a 2:1 acetone:n‐hexane mixture. High efficiency of GC capillary column and high selectivity of the thermionic sensitive detector (TSD) and ion trap detector (ITD) made it possible to directly analyse uncleaned soil extracts and determine all 12 compounds in one run. In reversed‐phase HPLC with diode‐array detector (DAD), the co‐elution of soil matrix components interfered with the determination of methylthiotriazines and terbuthylazine. The recovery of triazine compounds, determined by GC‐TSD, from a silty sand soil (organic matter content 1.82%, pH 6.22) spiked at levels of 15–600 ng g^–1, were 70–90% (RSD 9–19%), except for deisopropylatraton (38%). GC‐TSD analysis with detection limits of 5–15 ng g^–1 for chloro‐ and methylthiotriazines and 30 ng g^–1 for methoxytriazines was more sensitive than GC‐MS(ITD). GC analysis with electron capture detection was sensitive for some chlorotriazines, but a reliable compound quantification in complex chromatograms of uncleaned soil of extracts was not possible. For all compounds save didealkylatrazine, HPLC‐DAD was at least two times less sensitive than GC‐TSD. Soil/sediment organic matter, clay and silt content, and pH were identified as matrix characteristics which might affect ultrasonic extraction recovery of a particular compound.     

Simultaneous HPLC determination of phenylurea herbicides and their corresponding anilines in water after on-line preconcentration

On-line preconcentration on a short C₁₈ column, prior to HPLC with UV and electrochemical detection, has been used for determination of some phenylurea herbicides and their possible degradation products, substituted anilines, in water samples. With electrochemical detection the detection limit at a signal-to-noise ratio of 3 was 5 ppt for 4-chloroaniline and 4-bromoaniline and 7 ppt for 3,4-dichloroaniline; with UV detection the detection limit was ca 300 ppt for all analytes.     

Analysis of phenylurea and propanil herbicides by solid-phase microextraction and liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection

This study examines the application of solid-phase microextraction coupled with high performance liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection (SPME-HPLC-PIF-FD) for the determination of four phenylurea herbicides (monolinuron, diuron, linuron and neburon) and propanil in groundwater. Direct immersion (DI) SPME was applied using a 60 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber for the extraction of the pesticides from groundwater samples. An AQUASIL C₁₈ column (150 mm × 4.6 mm i.d., 5 μm) was used for separation and determination in HPLC. The method was evaluated with respect to the limits of detection (LODs) and the limits of quantification (LOQs) according to IUPAC. The limits of detection varied between 0.019 μg L⁻¹ and 0.034 μg L⁻¹. Limits of quantification ranged between 0.051 μg L⁻¹ and 0.088 μg L⁻¹. These values meet the recommended limits for individual pesticides in groundwater (0.1 μg L⁻¹) established by the EU. Recoveries ranged between 86% and 105% and relative standard deviation values between 2% and 8%.     

Analysis of the plant growth regulator chlormequat in soil and water by means of liquid chromatography–tandem mass spectrometry,pressurised liquid extraction,and solid-phase extraction

We present a new, precise and accurate method for quantitative analysis of chlormequat in soil and aqueous matrices. The method, which is based on LC–MS/MS, pressurised liquid extraction and solid-phase extraction, is eminently suitable for studying the fate of chlormequat in the soil environment. The limit of detection is 0.003–0.008 μg/L for rainwater, surface water and groundwater and 0.07–0.4 μg/kg for soil. In water samples amended to 0.04 μg/L, precision is better than 10%. The residual content of chlormequat in three agricultural topsoils analysed 4 months after its application was 23–55 μg/kg (12–23% of the amount applied). No trace of chlormequat was detected in groundwater from 66 water supply wells located in rural areas treated with chlormequat.     

On the low-lying excited states of sym-triazine-based herbicides.

We report a joint computational and luminescence study on the low-lying excited states of sym-triazines, namely, 1,3,5-triazine (1) and the ubiquitous herbicides atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (2)] and ametryn [6-methylthio-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (3)]. Geometrical structures, energetics, and transition and state properties of I and 2 were computed at the TD-DFT, CASSCF, and CASPT2 levels of theory. The fluorescence and phosphorescence emission spectra, lifetimes, and fluorescence quantum yields were measured for the three compounds, and from these, the energies of the lowest excited states and their corresponding radiative rates were determined. The predictions from CASPT2 calculations are in good agreement with the experimental results obtained from the luminescence studies and allow the interpretation of different absorption and emission features.     

Ion-trap versus quadrupole for analysis of quaternary ammonium herbicides by LC-MS

Summary An ion-trap mass spectrometer for determination of quaternary ammonium herbicides in water samples is evaluated. Implementation of the method previously optimized in a quadrupole mass spectrometer (VG Platform II) in an ion-trap (LCQ) required modifications to the sample inlet of the electrospray source. Quality parameters were established and detection limits, after trace enrichment, range 5–50 ng L⁻¹. Good reproducibilities (day-to-day and run-to-run) <12% were obtained. The method was applied to analysis of spiked samples and the results were comparable with those determined using a quadrupole mass spectrometer.     

拓展浓度加和模型预测三种三嗪类除草剂混合物的时间依赖毒性

浓度加和(CA)模型是评估与预测化学混合物毒性效应的常用模型之一,已广泛应用于药物组合与农药混配等多个混合物体系. 然而,CA不能用于包含不同时间具有不同效应组分的混合物体系,需要拓展. 以具有不同时间依赖毒性特征的三种三嗪类除草剂即嗪草酮(MET)、西草净(SIM)和环嗪酮(HEX)为混合物组分,以直接均分射线法(EquRay)构建它们的二元混合物,以青海弧菌Q67为受试生物,在6个不同时间(即0.25,2,4,8,12和16 h)下测定各混合物组分及其二元混合物暴露于Q67时的发光抑制毒性,分析与归纳抑制毒性随时间的变化规律. 结果表明,三种除草剂对发光菌Q67的发光抑制毒性具有不同的时间变化规律：MET的毒性随时间延长有明显增大的趋势,SIM的毒性在不同时间没有显著性变化,而HEX随着时间的延长毒性开始有所增加,而后变化很小;二元混合物毒性的时间变化规律与混合物组分有关,MET与HEX的二元混合物体系的毒性随暴露时间的延长而逐步增加,MET-SIM体系开始有所下降而后缓慢增加,而SIM-HEX体系的毒性在不同时间差异不明显;应用拓展后的CA模型分析所有二元混合物在不同时间点的毒性变化,表明都是加和的,没有协同或拮抗作用.     

具有药物活性的离子液体

离子液体阴阳离子的可设计性使其具有可控溶解性、独特表面活性、高热稳定性、增强的生物利用率和生物活性,这些特点使离子液体在消除同质多晶现象、改变药物传输模式及可包含传统药物组分等方面具有优势,成为当前离子液体研究领域的热点之一。本文对离子液体在医药领域的应用做了全面的阐述,主要介绍了近十年来离子液体在活性药物组分、抗菌剂及除草剂方面的成果,探讨了当前存在的问题及研究方向,并对其应用做了展望。     

气相色谱-质谱法测定茶叶中29种酸性除草剂的残留量

建立了茶叶中29种酸性除草剂残留量的气相色谱-质谱测定与确证方法。采用乙腈超声振荡提取试样中29种酸性除草剂,石墨化炭黑固相萃取柱净化,三甲基硅烷化重氮甲烷衍生化,再经弗罗里硅土固相萃取柱净化,用气相色谱-质谱法选择离子监测方式测定,外标法定量,根据离子丰度比确证。在加标水平为0.01,0.05,0.1 mg/kg时,29种目标物的加标回收率为57.1%～120.4%,相对标准偏差(RSD)为4.3%～20.9%;方法的检出限在0.002～0.005 mg/kg之间。该方法准确、灵敏、快速,可满足国际上对茶叶中29种酸性除草剂残留的检测需要。     

毛细管电泳-激光诱导荧光法测定草甘膦、草胺膦及氨甲基膦酸

建立了一种快速、有效的毛细管电泳分离-激光诱导荧光检测有机磷除草剂草甘膦、草胺膦和草甘膦的代谢物氨甲基膦酸的方法。将荧光衍生试剂5-(4, 6-二氯三嗪基)氨基荧光素(DTAF)成功用于衍生上述3种化合物。最佳衍生条件: DTAF的浓度为1.0 μmol/L,以50 mmol/L硼酸(pH 9.5)作为缓冲溶液,在30 ℃下反应40 min。以pH 9.5的30 mmol/L硼酸缓冲溶液(含15 mmol/L Brij-35)作为电泳背景电解质,3种衍生物得到基线分离。在优化的条件下,草甘膦、草胺膦、氨甲基膦酸的检出限分别为3.21、6.14和1.99 ng/kg。将该方法应用于环境水样和土壤中除草剂及代谢物的测定,回收率为91.3%～106.0%。该方法准确、灵敏,可满足环境样品中有机磷农药及其代谢物残留的检测要求。