地表水中和海水中醛酮类化合物的测定
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摘要
本文主要分为四部分对水体中的醛酮类化合物进行了研究:
第一部分提出了醛类化合物的危害,来源。综述了近年来国内外醛酮类化合物的分析方法。重点论述了使用2,4-二硝基苯肼(2,4-Dinitrophenylhydrazine, DNPH)为衍生试剂,利用气相或液相色谱法来测定醛酮类化合物的方法。
第二部分研究了选用DNPH为衍生化试剂,利用HPLC-UV研究了测定地表水中多种醛酮类化合物的分析方法,进行了条件实验,并成功的应用于青岛三个饮用水源地的测定。结果发现:
1.使用3mL2,4-二硝基苯肼在pH=3的条件下,40℃反应1h衍生效率最高。甲醛的加标回收率可达到99.9%。三氯乙醛的回收率为70.4%。用二氯甲烷做萃取剂,甲醛腙、乙醛腙、丙烯醛腙及三氯乙醛腙的回收率在83~109%之间。
2.当使用液相色谱进行分析时,三元梯度即A泵(Φ水=100%)40%、B泵(Φ甲醇=100%)50%、C泵(Φ乙腈=100%)10%以线性梯度15min变化到A泵(Φ水=100%)20%、B泵(Φ甲醇=100%)60%、C泵(Φ乙腈=100%)20% ,较二元梯度具有更好的分离效果。四种醛类化合物均能达到基线分离,而且谱图中的杂质峰亦减少。
3.通过对空白实验的考察发现,由于醛类化合物广泛存在于大气中,因此无法避免空白中的目标化合物。通过计算可知,空白中甲醛的含量在2.0μg/L左右,远远小于《地表水环境质量标准》中甲醛标准限值。因此可以通过扣除的方法解决。
4.对青岛棘洪滩水库、崂山水库、移风坝三个典型的饮用水源地采样调查发现,均有甲醛检出,但远低于《地表水环境质量标准》特定项目标准限值。崂山水库甲醛的检出量更远低于检出限。其余醛类化合物均未检出。加标
The thesis investigates aldehydes and ketones in surface water and sea water by four aspects as follows.
In the first part, we discourses the hazards and principle source of aldehydes and ketones. Simultaneity,we also discusses some analytical methods of aldehydes and ketones during recent years at home and abroad. However, we lay heavy stress on 2,4-Dinitrophenylhydrazine(DNPH) derivatization and analysis by using of HPLC and GC.
In the second, the optional conditions for derivative reaction and HPLC separation of aldehydes and ketones in surface water based on DNPH derivatization are described, including quantity of DNPH, temperature, time, pH, extraction efficiency and so on. The method has been successfully used to determinate aldehydes and ketones in drink water of Qingdao. The results are as follows:
1. The derivatization efficiency was the best while adding 3mL DNPH, reacting 1h in 40℃and adjusting pH=3. The recovery of formaldehyde reached 99.9%. The recovery of trichloroaldehyde was 70.4%. When formaldehyde-DNPH, acetaldehyde-DNPH, acrolein-DNPH and trichloroaldehyde-DNPH were extracted by methylene dichloride, the recovery for DNPH derivatives of these four aldehydes were in the range of 83%~109%.
2. The separation efficiency for DNPH derivatives of aldehydes in ternary system {Pump A(Φwater=100%)40%, Pump B(Φmethanol=100%)50%, Pump C(Φacetonitrile=100%)10% changing in linear gradient way in 15min to Pump
第一部分提出了醛类化合物的危害,来源。综述了近年来国内外醛酮类化合物的分析方法。重点论述了使用2,4-二硝基苯肼(2,4-Dinitrophenylhydrazine, DNPH)为衍生试剂,利用气相或液相色谱法来测定醛酮类化合物的方法。
第二部分研究了选用DNPH为衍生化试剂,利用HPLC-UV研究了测定地表水中多种醛酮类化合物的分析方法,进行了条件实验,并成功的应用于青岛三个饮用水源地的测定。结果发现:
1.使用3mL2,4-二硝基苯肼在pH=3的条件下,40℃反应1h衍生效率最高。甲醛的加标回收率可达到99.9%。三氯乙醛的回收率为70.4%。用二氯甲烷做萃取剂,甲醛腙、乙醛腙、丙烯醛腙及三氯乙醛腙的回收率在83~109%之间。
2.当使用液相色谱进行分析时,三元梯度即A泵(Φ水=100%)40%、B泵(Φ甲醇=100%)50%、C泵(Φ乙腈=100%)10%以线性梯度15min变化到A泵(Φ水=100%)20%、B泵(Φ甲醇=100%)60%、C泵(Φ乙腈=100%)20% ,较二元梯度具有更好的分离效果。四种醛类化合物均能达到基线分离,而且谱图中的杂质峰亦减少。
3.通过对空白实验的考察发现,由于醛类化合物广泛存在于大气中,因此无法避免空白中的目标化合物。通过计算可知,空白中甲醛的含量在2.0μg/L左右,远远小于《地表水环境质量标准》中甲醛标准限值。因此可以通过扣除的方法解决。
4.对青岛棘洪滩水库、崂山水库、移风坝三个典型的饮用水源地采样调查发现,均有甲醛检出,但远低于《地表水环境质量标准》特定项目标准限值。崂山水库甲醛的检出量更远低于检出限。其余醛类化合物均未检出。加标
The thesis investigates aldehydes and ketones in surface water and sea water by four aspects as follows.
In the first part, we discourses the hazards and principle source of aldehydes and ketones. Simultaneity,we also discusses some analytical methods of aldehydes and ketones during recent years at home and abroad. However, we lay heavy stress on 2,4-Dinitrophenylhydrazine(DNPH) derivatization and analysis by using of HPLC and GC.
In the second, the optional conditions for derivative reaction and HPLC separation of aldehydes and ketones in surface water based on DNPH derivatization are described, including quantity of DNPH, temperature, time, pH, extraction efficiency and so on. The method has been successfully used to determinate aldehydes and ketones in drink water of Qingdao. The results are as follows:
1. The derivatization efficiency was the best while adding 3mL DNPH, reacting 1h in 40℃and adjusting pH=3. The recovery of formaldehyde reached 99.9%. The recovery of trichloroaldehyde was 70.4%. When formaldehyde-DNPH, acetaldehyde-DNPH, acrolein-DNPH and trichloroaldehyde-DNPH were extracted by methylene dichloride, the recovery for DNPH derivatives of these four aldehydes were in the range of 83%~109%.
2. The separation efficiency for DNPH derivatives of aldehydes in ternary system {Pump A(Φwater=100%)40%, Pump B(Φmethanol=100%)50%, Pump C(Φacetonitrile=100%)10% changing in linear gradient way in 15min to Pump
引文
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