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。     

钻孔间距对水力压裂促抽煤层瓦斯的影响

针对定量确定合理钻孔间距困难问题，基于损伤力学和多场耦合理论，建立了水力压裂和瓦斯抽采的煤层流固耦合模型，包括和水运移场、应力场以及孔隙度、渗透率演化方程，并采用Comsol联合Matlab求解，研究了不同钻孔间距时压裂和抽采过程中煤层弹模、损伤值、渗透率、瓦斯压力、抽采量和压裂贯通时间的变化规律。结果表明:耦合模型可较准确地模拟煤层水力压裂和瓦斯抽采过程；压裂贯通时间与钻孔间距呈指数增长关系；在马堡煤矿，当钻孔间距为4~8 m时，压裂损伤区在抽采孔贯通，渗透率呈“n”型曲线，瓦斯抽采后，瓦斯压力迅速下降，抽采有效区随间距的增加而增大；当钻孔间距为9~12 m时，压裂损伤区未贯通，煤层渗透率呈“m”型曲线，抽采有效区随间距的增加而减小，与间距4~8 m相比，瓦斯抽采量较小。     

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。     

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。     

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%。     

水环境中26种类固醇激素的分析方法研究

建立了固相萃取-超高效液相-串联质谱法同时测定水环境中26种类固醇激素的分析方法。明确了取样体积为500 m L,Cleanert PEP为富集柱,乙酸乙酯为洗脱剂,甲醇为溶剂进行提取操作。选择了正离子模式,以0. 1%甲酸/甲醇-水为流动相,负离子模式以0. 1%氨水/乙腈-水为流动相,试样经AcquityTMUPLC BEH C18色谱柱分离后,选用质谱检测模式进行定性、定量分析。通过方法验证,26种类固醇激素的方法检出限为0. 3～1. 5 ng/L,测定下限为1. 2～6. 0 ng/L,代表性样品测定结果的相对标准偏差为2. 6%～13. 7%(n=6),加标回收率为71. 2%～121%。该方法操作便捷,灵敏度高,精密度和准确度良好,可适用于水环境中多种痕量、超痕量类固醇激素的定性定量分析。     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

An LC-MS/MS method for creatine and creatinine analysis in paraquat-intoxicated patients

Abstract

A sudden increase in serum creatinine after paraquat intoxication has been reported in several clinical studies. However, this dramatic change of creatinine may be possibly due to an interconversion of creatine-creatinine in relation to paraquat toxicity. In order to investigate the creatine-creatinine relationship, a liquid chromatography tandem mass spectrometry in combination with electrospray ionization was developed and validated for simultaneous determination of creatine and creatinine in the serum. The chromatographic separation was achieved on a Gemini® C₆-Phenyl column with a gradient elution consisting of 0.1% formic acid in ultrapure water and methanol as the mobile phase. The method yielded suitable levels of specificity and selectivity, and calibration curves of creatine and creatinine in serum were linear over the concentration range of 0.5–200?µg mL^?1. The limit of quantification of both compounds was 0.5?µg mL^?1, and the method was accurate within the recovery range of 96.23–102.75%, indicating the robustness of the method. The method was successfully applied to toxicological samples from paraquat-intoxicated patients, and the concentrations of creatine and creatinine were quantified. High creatine concentrations in serum samples were observed which may lead to high serum creatinine despite normal kidney function as creatine is converted to creatinine in proportion to its concentration.     

Analysis of metabolic changes in Trichoderma asperellum TJ01 at different fermentation time-points by LC-QQQ-MS

Trichoderma spp. are among the most widely recognized biocontrol fungi used to inhibit pathogens and promote plant growth. These functions are related to primary and secondary metabolites. This study investigated the different metabolites in Trichoderma asperellum TJ01 cultured for 24 and 72?h using liquid chromatography with triple-quadrupole mass spectrometry. Compared to the 24?h culture of T. asperellum TJ01, the 72?h culture with amino acid metabolism tended to decrease while sugar and lipid metabolisms tended to increase. Furthermore, the 72?h culture had a higher proportion of upregulated flavonoids, in combination with a higher proportion of downregulated alkaloids, and equal proportions of upregulated and downregulated polyphenols and hormones. This study also identified a few valuable medicinal substances such as trigonelline and 5-hydroxytryptophan in T. asperellum TJ01 fermentation cultures.     

电感耦合等离子体质谱法测定地表水中铊的研究

本研究建立了电感耦合等离子体质谱法(ICP-MS)测定地表水中铊的方法。对仪器工作条件进行了优化,用在线内标校正基体效应的干扰,重点考察了样品测定介质、酸度、共存元素干扰等因素对测定结果的影响。在最佳实验条件下,该方法的检出限可达0.003μg/L,线性相关系数不小于0.999 9,加标回收率为93%~110%。与传统的原子吸收法相比,该方法不需要富集等繁琐的前处理过程,具有检出限低、快速、精密度和准确度高等优点。