望虞河西岸九里河中四种除草剂的污染现状

基于气相色谱-质谱联用(GC-MS)法结合固相萃取(SPE)前处理技术,建立了水中4种除草剂氯草定、阿特拉津、乙草胺和异丙甲草胺残留的分析方法,于2018年春(4、5月)、秋(9、10月)和冬(1、3月)季对太湖流域望虞河西岸九里河水体中4种除草剂的污染现状进行调查分析。结果表明,4种除草剂的加标回收率为71. 2%～108%,RSD均10%,方法检出限为3. 5～6. 0 ng/L。九里河水体中氯草定、阿特拉津、乙草胺和异丙甲草胺4种除草剂质量浓度分别为未检出～0. 025 7,0. 019 1～1. 19,未检出～0. 026 0和未检出～0. 094 3μg/L。4种除草剂中阿特拉津最高值接近《地表水环境质量标准》(GB 3838—2002)限值,其他3种其值较低,氯草定首次在太湖流域水体中检出。     

Pressurized liquid extraction of six tetracyclines from agricultural soils

Veterinary antibiotics used in agriculture can be introduced into the environment through land application of animal manure, accumulating in soils and groundwaters and posing a significant risk to human health and animal well-being. As the analysis of tetracyclines in soil is challenging due to their strong interaction with soil minerals and organic carbon, the objective of this study was to develop a reliable and reproducible method for quantitative analysis of chlortetracycline and oxytetracycline, and their respective metabolites in soils. A method based on pressurized liquid extraction (PLE) with in-cell clean-up was developed for the extraction of chlortetracycline and oxytetracycline and four likely metabolites from a set of four soils. Optimized conditions included a cell size of 22?mL, soil loading of 5?g, pH of 8.0, methanol:water ratio of 3:1, 50?°C, and two cycles. Soil extracts were analysed by high-performance liquid chromatography (HPLC) coupled with ion trap mass spectrometry (MS). Recoveries of seven tetracyclines from soil ranged from 41% to 110%. The limits of detection for tetracyclines were 0.08–0.3 µg g^?1 soil, and intra- and inter-day variation ranged from 0.12–0.34%. The proposed PLE method is suitable for quantification of tetracyclines in agricultural soils at typical concentrations expected in contaminated environments.     

高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调p H值至7.0左右,过固相萃取小柱进行富集,用14 m L甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/m L)和58.0%~107.8%(加标水平50 ng/m L),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

高效液相色谱-二极管阵列检测器测定邻苯二甲酸酯色谱条件优化

采用高效液相色谱-二极管阵列检测器对6种PAEs类物质进行测定,并对梯度洗脱条件、流速、检测波长等影响化合物色谱响应的关键参数进行优化。综合考虑样品测试效率、分析精度、实际样品中存在杂质干扰等因素,确定以乙腈-水为流动相进行梯度洗脱,洗脱0~11 min流动相乙腈-水梯度比例为50∶50,11 min后流动相调整为100%乙腈,各化合物均能完全分离;色谱分析流速为0.8 m L/min;PAEs的最佳吸收波长为225 nm。在优化的色谱条件下,6种PAEs的线性良好,相关系数均大于0.999 8,仪器检出限为0.08~0.12 mg/L,保留时间、峰面积的相对标准偏差分别为0.02%~0.60%、0.13%~0.86%。方法灵敏度较高,适合土壤等邻苯二甲酸酯含量较高基质样品的快速分析。     

全二维气相色谱-飞行时间质谱法分离复杂体系中7种指示剂 多氯联苯

采用全二维气相色谱-飞行时间质谱法(GC×GC TOF-MS)分析了混标样品Aroclor 1260、Aroclor 1254、Aroclor 1242中的多氯联苯(PCBs)单体,考察了在复杂体系下对7种PCBs指示剂的分离能力。结果表明,与优化柱系统的分离效果相比,136种单体的混标样品中共分离出121种单体,7种指示剂经一维和二维的保留时间及质谱定性,在121种单体的2D斑点图中清晰可辨。全二维对于复杂体系的PCBs和指示剂的分离表明其强大的分离能力和对于检测复杂体系中指示剂的分辨能力,对该类物质的定性和定量检测具有重要意义。     

ASE-气相色谱法测定油田区土壤中多种石油烃

采用气相色谱法测定油田区土壤中C_(10)～C_(40)的石油烃,通过优化加速溶剂萃取的条件,使方法在62 mg/L～3 100 mg/L范围内线性良好,方法检出限为4.8 mg/kg。用该方法测定石油区短期、中期、长期油井污染土壤样品,5次测定结果的RSD为1.3%～5.2%,加标回收率为84.8%～98.5%,有证标准样品测定结果在可信区间内。     

基于ACF-AMDF的气井环空液面回波特征提取方法

为了精确有效地提取声波法检测气井环空液位的回波周期，在分析环空中测试波的传播特征及基音周期检测的基础上，提出1种基于检测信号短时自相关函数(ACF)及平均幅度差函数(AMDF)的液面回波周期提取方法；利用自主搭建的室内模拟实验系统开展了不同初始环空压力下环空液位检测实验；对检测信号进行中心削波处理并计算ACF/AMDF，提取出液面回波周期并与理论计算值对比分析；同时分析了现场环空液位检测信号，提取其回波周期。研究结果表明:提出的新方法能有效地用于提取环空液面回波周期；室内实验中，该方法最大误差绝对值为1.54%；该方法能够有效抑制液面回波信号中的随机噪声及接箍反射波等，处理后的信号曲线在回波周期处峰值更加突出、集中，而在其他位置更加平滑，提高了对液面回波周期特征的辨识能力。     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

气相色谱-串联质谱法测定沉积物中多环芳烃

采用ASE法提取沉积物中16种多环芳烃,以固相萃取法净化提取液,用气相色谱-串联质谱法测定。通过优化测定条件,使方法在5.00μg/L~1 600μg/L范围内线性良好,方法检出限为0.15μg/kg~0.66μg/kg。空白石英砂的加标回收率为61.9%~121%,7次测定结果的RSD为2.6%~11.1%。     

钻屑法测定煤层H_2S含量

为了测定煤层硫化氢(H2S)含量,防治矿井H2S涌出,提出一种通过钻屑法测定煤层H2S含量的方法。在未受采动影响的新鲜煤壁,采用钻屑法取样,通过测定煤样H2S解吸量、取样过程损失量和H2S残存量确定煤层H2S含量。根据溶于水中H2S的p H值和色谱分析解吸气体中H2S体积分数,确定H2S解吸量;根据煤样解吸规律和气样H2S体积分数,确定H2S损失量;根据色谱分析残存气体中H2S体积分数,确定其残存量。用此方法,对山西某矿H2S涌出煤层进行现场和实验室测定。研究表明,该矿H2S含量为(4.465~6.701)×10-3m3/t。钻屑法测定煤层H2S含量是可行的,可以为矿井H2S治理提供基础数据。