水中藻类代谢异味物质检测前处理方法研究

III
苏州科技学院硕士学位论文
目录
目录
摘要 .............................................................................................................. Ⅰ Abstract ...................................................................................................... Ⅱ 第一章 绪论 ................................................................................................ 1
I
Master Dissertation of Suzhou University of Science and Technology

Abstract
Abstract
At present ， eutrophication of lakes is becoming more and more serious ． Blooming algae consume dissolved oxygen in water ， release some taste and odor metabolites ． Off-flavor problems caused by algae-producing odorous compounds have been of the focuses in drinking water industry and aquacultu re ． Therefore ， research on the problem between taste and odor metabolites and its analysis has great significance ． The studies of this paper focus on the determination methods of 2-methylisoborneol (2-MIB) 、 geosmin(GSM) 、 β - cyclocitral and β -ionone in water which includes the four parts below ： 1. In the second part, a novel method was developed for the pre-concentration and determination of 2- MIB 、 GSM 、 β -cyclocitral and β -ionone in water by ultrasound-assisted dispersive liquid-liquid microextraction(DLLME) coupled with capillary gas chromatography with mass spectrometry (GC/MS). Parameters affecting extraction efficiency were investigated and optimized. Under optimum conditions, linearity of the method was observed for all target analytes in the r ange from 0.05 to 20μg/L with the correlations (R 2 ) ranging from 0.9979 to 0.9998. The LODs (S/N=3) were estimated to be in the range from 0.01 to 0.03 μg/L. The relative standard deviations were between 4.7% and 12.4% ( n =6). As high as 176 to 465 fold enrichment factors were achieved. The advantage of the DLLME technique is simple and fast with high recovery and enrichment factor. 2. In the third part, application of SPE-GC/MS on the determination of 2-MIB 、 GSM 、 β - cyclocitral and β -ionone in water samples was studies. Extraction conditions and GC/MS conditions were optimized by experiments. Under optimized conditions, linearity of the method was observed for all target analytes in the r ange from 0.05 to 20μg/L, with the correlations (R 2 ) ranging from 0.9962 to 0.9998. The LODs were estimated to be in the range from 0.005 to 0.01 μg/L. The relative standard deviations were between 5.04% and 12.7% ( n=6). 3. In the forth part, A method was developed for the determination of 2-MIB 、 GSM 、 β - cyclocitral and β -ionone in water with SPME and GC/MS.
苏州科技学院硕士学位论文
水中藻类代谢异味物质检测 前处理方法研究
硕士研究生：付 杰 指 导 教 师：张占恩教授 学 科 专 业：环境工程
苏州科技学院环境科学与工程学院 二○一二年 六月
Master Dissertation of Suzhou University of Science and Technology
Research on the pretreatment technologies of determining odorous compounds metabolized by algaes
Master Candidate: Fu Jie Supervisor: Prof. Zhang Zhanen Major: Environmental Engineering
II
Master Dissertation of Suzhou University of Science and Technology
Abstract
Under the most optimum conditions, linearity varied from 1 to 1000μg/L with the correlations (R 2 ) ranging from 0.9978 to 0.9999. The LODs based on a signal-to-noise ratio (S/N) of 3, varied from 0.2 to 0.8 ng/L. The relative standard deviations were between 2.97% and 7.93% ( n =6). 4. In the last part ， to find the best method from 3 kinds of pretreatment technologies which analysised for 4 sorts of Odorous compounds. Key words ： GC/MS ， Dispersive liquid – liquid microextraction (DLLME), Solid-Phase Extraction(SPE), Solid-phase microextraction(SPME), 2-methylisoborneol ， Geosmin ， β -cyclocitral ， β -ionone ， Odorous compounds
（保密论文在解密后遵守此规定） 论文作者签名： 指导教师签名： 日期： 日期： 年 年 月 月 日 日
苏州科技学院硕士论文
摘要
摘要
目前，由于生活和农业污水排入湖泊，致使其富营养化愈来愈严重，导 致水中藻类的大量繁殖；藻类的过量繁殖不仅会减少水中的溶解氧，同时还 会产生大量的异味代谢物质，引起水体的发臭恶心等，而这些异味是水产养 殖和饮用水长期关注焦点。 因此对于藻类代谢产物异味物质的监测方法的研 究具有重要的意义。 本课题以土臭素和 2- 甲基异莰醇、β - 环柠檬醛、β - 紫罗兰酮为研究对象， 研究了其在水中含量的测定方法。本课题主要包括以下四方面内容： 1. 建立了超声辅助分散液液微萃取与气相色谱质谱联用检测水中二甲 基异莰醇、土臭素、β - 环柠檬醛和 β - 紫罗兰酮的方法。对影响萃取富集效率 的因素进行了优化，在最佳测定条件下， 4 种物质在 0.05~20 μg/L 范围内呈 良 好 的 线 性 关 系 ， 相 关 系 数 R2 在 0.9979~0.9998 之 间 ， 最 低 检 出 限 在 0.01~0.03 μg/ L(S/N=3) ，相对标准偏差 RSD（ n=6 ）在 4.7%~12.4% 之间 , 富 集倍数在 176~465 之间。此方法具有操作简单、快速和成本低等特点。 2. 应用固相萃取 (SPE) 与气相色谱质谱 (GC/MS) 联用技术， 建立了测定 环境水样中土臭素和 2- 甲基异莰醇、β - 环柠檬醛、β - 紫罗兰酮的分析方法。 在最优化条件下，4 种异味物质在 0.05~20 μg/L 范围内呈良好的线性关系，相 关系数 R2 在 0.9962~0.9998 之间，最低检出限在 0.005~0.01μg/ L 之间。 3. 采用固相微萃取 (SPME) 与气相色谱质谱 (GC/MS) 联用技术，建立了 测定水中土臭素和 2- 甲基异莰醇、β - 环柠檬醛、β - 紫罗兰酮的分析方法。 对影响萃取富集效率的因素进行了优化， 4 种异味物质在 1~1000ng/L 范围 内呈良好的线性关系，相关系数 R2 在 0.9978~0.9999 之间，最低检出限在 0.2~0.8ng/L 之间 , 六次重复实验 RSD 在 2.97%-7.93% 之间，重现性良好。 4. 依据三种前处理方法对 4 种异味物质的分析结果，选出最佳的前处理 方法。 关键词： 气相色谱质谱，分散液液微萃取 (DLLME) ，固相萃取 (SPE) ，固相 微萃取（ SPME ） ，土臭素， 2- 甲基异莰醇，β - 环柠檬醛，β - 紫罗兰酮，异 味物质