Rapid determination of polar pesticides and plant growth regulators in fruits and vegetables by liquid chromatography/tandem mass spectrometry

ABSTRACT

A simple high-throughput liquid chromatography/tandem mass spectrometry (LC-MS/MS) multiresidue analysis method was developed for the simultaneous determination of polar pesticides, plant growth regulators and other polar compounds. These included amitrole, chlormequat, mepiquat, cyromazine, ETU, PTU, perchlorate, and daminozide using a mixed-mode column. A 10 g test portion was shaken with acidified methanol for 10 min. After centrifugation, the sample extract was injected and analyzed within 11 min by LC-MS-MS. This column eliminated the need for derivatization or the use of ion paring reagent. Two MS-MS transitions were monitored in the method for each target compound to achieve true positive identification. Eight isotopically-labeled internal standards corresponding to each analyte were used to correct for matrix suppression effect and/or instrument signal drift. The average recovery for all analytes at 20, 40, and 250 ng/g (n = 6) ranged from 73–136%, with a relative standard deviation of ≤ 20%.     

Fate of atrazine in a soil under different agronomic management practices

Agricultural management affects the movement of atrazine in soil and leaching to groundwater. The objective of this study was to determine atrazine adsorption in a soil after 20 years of atrazine application under agronomic management practices differing in tillage practice (conventional and zero tillage), residue management (with and without residue retention) and crop rotation (wheat-maize rotation and maize monoculture). Atrazine sorption was determined using batch and column experiments. In the batch experiment, the highest distribution coefficient K_d (1.1 L kg^?1) at 0–10 cm soil depth was observed under zero tillage, crop rotation and residue retention (conservation agriculture). The key factor in adsorption was soil organic matter content and type. This was confirmed in the column experiment, in which the highest K_d values were observed in treatments with residue retention, under either zero or conventional tillage (0.81 and 0.68 L kg^?1, respectively). Under zero tillage, the fact that there was no soil movement helped to increase the K_d. The increased soil organic matter content with conservation agriculture may be more important than preferential flow due to higher pore connectivity in the same system. The soil's capacity to adsorb 2-hydroxyatrazine (HA), an important atrazine metabolite, was more important than its capacity to adsorb atrazine, and was similar under all four management practices (K_d ranged from 30 to 40 L kg^?1). The HA adsorption was attributed to the type and amount of clay in the soil, which is unaffected by agronomic management. Soils under conservation agriculture had higher atrazine retention potential than soils under conventional tillage, the system that predominates in the study area.     

水中草甘膦和氨甲基膦酸的柱前衍生-液相色谱方法研究

建立柱前衍生-液相色谱-荧光检测法同时测定水中草甘膦和氨甲基膦酸的方法。水样经芴甲氧羰酰氯衍生化后取上清液进样,采用ODS C18柱,以水(5 mmol/L乙酸铵)-乙腈作为流动相进行梯度洗脱,采用荧光检测器进行检测。实验通过加入柠檬酸三钠,解决了实际水样中金属阳离子的干扰问题。草甘膦和氨甲基膦酸在一定范围内线性良好(r=0.997 3~0.999 0),回收率为92.2%~102%,相对标准偏差为4.3%~8.5%,方法检出限为1.29μg/L和1.84μg/L。     

毛细管柱气相色谱法测定工业废气和废水中N,N-二甲基甲酰胺

采用HP-INNOWAX毛细管柱、气相色谱氢火焰离子化检测器测定工业废气和废水中的N,N-二甲基甲酰胺,可能共存的丙酮、乙醇和乙酰丙酮均对测试无干扰.方法在0.939 mg/L～75.1 mg/L范围内线性良好,对工业废水、无组织排放工业废气和有组织排放工业废气中N,N-二甲基甲酰胺的检出限分别为0.47 mg/L、0.16 mg/m3和0.31 mg/m3,标准溶液平行测定的RSD为1.9％ ～2.2％,废水样品加标回收率为94％～ 97％.     

深厚砂砾石地层帷幕灌浆质量检测与评价技术

灌浆是基础处理常用且有效的方法。采用有效的检测方法查明基础灌浆缺陷的位置,以便及时进行技术处理,是工程建设的一个重要的课题。本文就目前工程界常用的砂砾石层帷幕灌浆的检测与评价方法进行了系统地分析、比较,总结得出适合于深厚砂砾石层防渗帷幕灌浆质量检测与评价的方法。     

高效生物吸附剂处理含铬废水

将菌株(R32)和复合菌群(Fh01)2种生物吸附剂与活性污泥进行复合使用,观察了柱式生物曝气法对高浓度含铬模拟水样和含铬电镀废水的生物吸附效果.结果表明,这2种吸附剂性能稳定,对进水pH值适应范围广,当pH值为1.0～7.0时,R32对50.0mg/L铬的去除率达71%～86%;当pH值为1.0～5.0时,Fh01对铬的去除率均在60%以上.R32对铬浓度、进水速度、处理时间等因素均具有较好的适应性.而Fh01对低浓度含铬废水的处理效率高,当总Cr浓度为5.0～20.0mg/L时,对铬的去除率达100%.R32和Fh01串联曝气处理效果理想,吸附2h后,对总Cr,Cu2+,CODCr浓度分别为78.3,2.29,45.0mg/L的电镀废水的去除率分别高达94.0%,99.2%,74.5%.     

应用大型原状土柱渗漏计测定冬小麦-夏玉米轮作期硝态氮淋失

从 1998— 2 0 0 0年 ,利用土壤溶液提取器和大型原状土柱渗漏装置 (面积 0 18m2 ,2m深 )田间观测了北京地区冬小麦 夏玉米轮作期间的NO-3 N淋失 .设置对照和常量氮肥水平两个处理 .土柱渗出液的NO-3 N平均浓度 ,对照处理为 35 0mg L ,常量施氮土柱为 5 5 6mg L ;NO-3 N淋失通量 ,对照处理为 1 3g (m2 ·a) ,常量施氮土柱为 2 0g (m2 ·a) ;氮肥表观淋失百分数分别为 10 %、0 86 %和 0 5 4%,受年降雨变化的影响非常明显 .常量氮肥施用条件下 0— 2 0 0cm土壤提取液和土柱底部渗出液的NO-3 N浓度 ,都超过饮用水卫生标准 10mg L ,因此 ,常量施氮水平引起的硝态氮对浅层地下水的污染不容忽视 .     

不同磷处理对污染土壤中有效态铅及磷迁移的影响

为了研究不同含磷化合物对污染土壤中铅有效性的影响及其在土壤剖面中的迁移状况,对3种不同性质的含磷化合物按含量为2500、5000 mg·kg-1进行了土柱试验.结果表明,对铅污染土壤施入磷酸氢钙(SSP)、磷矿粉(PR)及羟基磷灰石(HA)能显著降低土壤表层CaCl2(0.01 mol·L-1)提取态铅的含量,且有效铅的含量随磷施入含量的增加而显著降低.在施磷270 d后,施入含量为5000 mg·kg-1的磷酸氢钙(SSP5)、磷矿粉(PR5)及羟基磷灰石(HA5)处理土壤有效铅的含量分别比对照降低了86.6%、81.1%和89.7%.对不同深度土壤有效磷和全磷含量分析表明,土壤中施入不同溶解性质的磷显著增加了土壤表层(0～10 cm)的有效磷(Olsen-p)及全磷的含量,土壤中有效磷及全磷的含量随着土柱深度的增加而显著降低.除了SSP5处理外,上述不同磷处理对于大于50 cm深度的土壤中的有效磷和全磷变化没有显著影响,而所有处理对于大于70 cm深度的土壤中有效磷和全磷含量没有显著影响.这表明在铅污染土壤中施入不同性质的磷能显著降低土壤中CaCl2(0.01 mol·L-1)提取态铅的含量,而土壤中施入的磷在土壤垂直剖面的迁移却很少,即使是易溶性的磷酸氢钙(SSP)也不会造成大于70cm深度的土壤剖面中磷含量的显著性差异,其原因可能与土壤胶体对磷的强力吸附有关.     

生物样品中甲磺基多氯联苯的测定及手性拆分

建立了一种生物样品中甲磺基多氯联苯(MeSO2-PCBs)及其手性对映体的分析测定方法.本方法利用索氏抽提对鱼肉组织进行提取,抽提液依次经凝胶渗透色谱柱、氧化铝硅胶复合柱和弗罗里硅土柱进行净化和分离,气相色谱-质谱联用仪进行分析.10个流程空白中,所有目标化合物都低于仪器检出限;17种MeSO2-PCBs在5个空白加标中的平均回收率在77.2%—98.2%之间;样品平行样中目标化合物含量相对标准偏差均小于15%;方法检测限为0.3—20.0 pg.g-1湿重.采用Cyclosil-B手性柱拆分5种MeSO2-PCBs手性对映体,分离度在0.671—2.543之间.     

城市水样中首次检出痕量硝基多环芳烃（NO2—PAH）

本文利用还原衍生化高分辨ＧＣ－ＥＣＤ法，采用双柱定性首次在城市地表水样中检出环境潜在致癌物－硝基多环芳烃（ＮＯ２－ＰＡＨ），结果表明，在不同的水样中共检出包括动物致癌物２－硝基萘在内的八种ＮＯ２－ＰＡＨ。河水和饮用水中均有ｐｐｔ级ＮＯ２－ＰＡＨ存在，其中溶解度较大的两环硝基多环芳烃的含量高于三环以上的。饮用水中ＮＯ２－ＰＡＨ的浓度低于与其相邻的河水中相应硝基多环芳烃的含量，经煮沸处理后，饮用水中Ｎ