Date of Award

11-2017

Document Type

Thesis

Degree Name

Master of Science in Chemistry

Department

Chemistry

First Advisor

Syed Salman Ashraf

Second Advisor

Soleiman Hisaindee

Third Advisor

Mohamed Abdul Rauf

Abstract

Organic pollutants, especially those found in water bodies; pose a direct threat to various aquatic organisms as well as humans. A variety of different remediation approaches, including chemical and biological methods have been developed for the degradation of these organic pollutants. However, comparative mechanistic studies of pollutant degradation by these different systems are almost non-existent. In this study, the degradation of two emerging pollutants an antibiotic pollutant, Sulfamethoxazole (SMX) and a model thiazole pollutant, Thioflavin T (ThT), was carried out using advanced oxidation process (AOP), using UV+H2O2 or a peroxidase enzyme system. Optimization conditions for Sulfamethoxazole degradation by peroxidase enzyme showed an absolute requirement for a redox mediator (Hydroxybenzotriazole) as well as low pH for pollutant degradation. The other conditions for the efficient degradation were as follows: the concentration of hydrogen peroxide, peroxidase enzyme and SMX needed were 56 μM, 78 nM and 5 ppm respectively. The degradation of both pollutants was followed using UV-Vis spectrophotometry and liquid chromatography-mass spectroscopy (LC-MS), and the products formed were identified using tandem liquid chromatography-mass spectrometry-mass spectrometry (LC-MS-MS). The results showed that the two remediation approaches UV+H2O2 and peroxidases produced different sets of intermediates suggesting that different degradation schemes were operating in the two systems (AOP vs. Peroxidase enzyme system). Phytotoxicity studies carried out using Lactuca sativa (lettuce) showed different levels of detoxification of the pollutants by the two different remediation approaches. This is the first time that a detailed comparative study showing in detail the intermediates generated in chemical and biological remediation methods has been presented. Furthermore, the results show that different remediation systems have very different degradation schemes and result in products having different toxicities.

Arabic Abstract


ﻣﻘﺎرﻧﺔ ﺗﺤﻠﻞ اﻟﻤﻠﻮﺛﺎت اﻟﻌﻀﻮﯾﺔ اﻟﻨﺎﺷﺌﺔ ﺑﺎﺳﺘﺨﺪام اﻟﻌﺎﻣﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ واﻟﻌﺎﻣﻞ اﻻﻧﺰﯾﻤﻲ

اﻟﻤﻠﻮﺛﺎت اﻟﻌﻀﻮﯾﺔ ﻻﺳﯿﻤﺎ ﺗﻠﻚ اﻟﻤﺘﻮاﺟﺪة ﻓﻲ اﻟﻤﯿﺎه ﻟﮭﺎ ﺗﺄﺛﯿﺮ ﻣﺒﺎﺷﺮ ﻋﻠﻰ اﻟﺤﯿﺎه اﻟﺒﺤﺮﯾﺔ وﻋﻠﻰ اﻻﻧﺴﺎن اﯾﻀﺎ. ﻣﻦ أﻧﻮاع اﺳﺎﻟﯿﺐ اﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺴﺘﺨﺪﻣﺔ ﻓﻲ ﺗﺤﻠﯿﻞ  اﻟﻤﻠﻮﺛﺎت اﻟﻌﻀﻮﯾﺔ ھﻲ اﺳﺘﺨﺪام اﻟﻌﺎﻣﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ و اﻟﻌﺎﻣﻞ اﻷﺣﯿﺎﺋﻲ. و ﻟﻜﻦ اﻟﺪراﺳﺎت اﻟﻤﯿﻜﺎﻧﯿﻜﯿﺔ اﻟﺘﻲ ﺗﻘﺎرن ﻣﺎ ﺑﯿﻦ ﺗﺤﻠﻞ ھﺬه اﻟﻤﻠﻮﺛﺎت اﻟﻌﻀﻮﯾﺔ ﺑﻮاﺳﻄﺔ ھﺬه اﻟﻨﻈﻢ اﻟﻤﺨﺘﻠﻔﺔ ﺗﻜﺎد ﺗﻜﻮن ﻣﻌﺪوﻣﺔ. ﻓﻲ ھﺬه اﻟﺪراﺳﺔ، ﺗﻢ إﺟﺮاء ﺗﺤﻠﻞ ﻟﻤﻀﺎد ﺣﯿﻮي ﺳﻠﻔﺎﻣﯿﺜﻮﻛﺴﺎزول وﻣﻠﻮث ﺛﯿﺎزوﻟﻲ وھﻮ ﺛﯿﻮﻓﻼﻓﯿﻦ ﻋﻦ طﺮﯾﻖ ﻋﻤﻠﯿﺎت اﻷﻛﺴﺪة اﻟﻤﺘﻘﺪﻣﺔ  و ﻧﻈﺎم اﻻﻧﺰﯾﻢ اﻟﺒﯿﺮوﻛﺴﯿﺪاز. واﻟﻈﺮوف اﻷﻣﺜﻞ ﻟﺘﺤﻠﻞ اﻟﺴﻠﻔﺎﻣﯿﺜﻮﻛﺴﺎزول ﻋﻦ طﺮﯾﻖ اﻧﺰﯾﻢ اﻟﺒﯿﺮوﻛﺴﯿﺪاز أن ﺗﺘﻄﻠﺐ وﺳﯿﻂ اﻷﻛﺴﺪة اﻟﮭﯿﺪروﻛﺴﻲ ﺑﻨﺰوﺗﺮﯾﺎزول و وﺳﻂ ﺣﻤﻀﻲ. واﯾﻀﺎ، ﻛﺎﻧﺖ ﺑﻌﺾ اﻟﻈﺮوف اﻟﻤﺜﻠﻰ اﻷﺧﺮى ﻋﻠﻰ اﻟﻨﺤﻮ اﻟﺘﺎﻟﻲ ﺗﺮﻛﯿﺰ ﺑﯿﺮوﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ 0.056 ﻣﯿﻜﺮو ﻣﻮﻟﺮ و ﺗﺮﻛﯿﺰ اﻧﺰﯾﻢ اﻟﺒﯿﺮوﻛﺴﯿﺪاز 78 ﻧﺎﻧﻮ ﻣﻮﻟﺮ ﺗﺮﻛﯿﺰ اﻟﺴﻠﻔﺎﻣﯿﺜﻮﻛﺴﺎزول 5 أﺟﺰاء ﻟﻜﻞ ﻣﻠﯿﻮن. واﻟﻈﺮوف اﻷﻣﺜﻞ ﻟﺘﺤﻠﻞ ﺛﯿﻮﻓﻼﻓﯿﻦ ﻋﻦ طﺮﯾﻖ اﻧﺰﯾﻢ اﻟﺒﯿﺮوﻛﺴﯿﺪاز أﻧﮭﺎ ﻻ ﺗﺘﻄﻠﺐ وﺳﯿﻂ اﻷﻛﺴﺪة اﻟﮭﯿﺪروﻛﺴﻲ ﺑﻨﺰوﺗﺮﯾﺎزول. واﯾﻀﺎ، ﻛﺎﻧﺖ ﺑﻌﺾ اﻟﻈﺮوف اﻟﻤﺜﻠﻰ اﻷﺧﺮى ﻋﻠﻰ اﻟﻨﺤﻮ اﻟﺘﺎﻟﻲ ﺗﺮﻛﯿﺰ ﺑﯿﺮوﻛﺴﯿﺪ اﻟﮭﯿﺪروﺟﯿﻦ 1 ﻣﯿﻠﻲ ﻣﻮﻟﺮ و ﺗﺮﻛﯿﺰ اﻧﺰﯾﻢ اﻟﺒﯿﺮوﻛﺴﯿﺪاز 10 ﻧﺎﻧﻮ ﻣﻮﻟﺮ ﺗﺮﻛﯿﺰ ﺛﯿﻮﻓﻼﻓﯿﻦ 25 أﺟﺰاء ﻟﻜﻞ ﻣﻠﯿﻮن. وﺑﻌﺪ ذﻟﻚ ﺗﻢ ﺗﺤﻠﯿﻞ اﻟﻌﯿﻨﺎت وﻧﺘﺎﺋﺠﮭﺎ ﺑﺴﺘﺨﺪام ﺗﻘﻨﯿﺔ الـ HPLCوالـLC-MS-MS. وأظﮭﺮت اﻟﻨﺘﺎﺋﺞ أن ﻧﮭﺠﻲ اﻟﻌﺎﻟﺠﺔ أﻧﺘﺠﺖ ﻣﺠﻤﻮﻋﺎت ﻣﺨﺘﻠﻔﺔ ﻣﻦ اﻟﻮﺳﺎﺋﻂ. ﻣﻤﺎ ﯾﺸﯿﺮ اﻟﻰ ان ﻧﮭﺠﻲ اﻟﻤﻌﺎﻟﺠﺔ ﯾﻌﻤﻠﻮن ﺑﻄﺮق ﻣﺨﺘﻠﻔﺔ. وﻗﺪ ﺗﻢ ﻋﻤﻞ دراﺳﺎت ﻟﻠﺘﺴﻤﻢ اﻟﻨﺒﺎﺗﻲ ﻋﻠﻰ اﻟﻤﻠﻮﺛﺎت، ﺑﺎﺳﺘﺨﺪام ﺑﺬوراﻟﺨﺲ و ﻗﺪ أظﮭﺮت اﻟﻨﺘﺎﺋﺞ ﻣﺴﺘﻮﯾﺎت ﻣﺨﺘﻠﻔﺔ ﻣﻦ إزاﻟﺔ اﻟﺴﻤﻮم ﻟﻜﻞ ﻣﻦ اﻟﻤﻠﻮﺛﺎت. ھﺬه ھﻲ اﻟﻤﺮة اﻷوﻟﻰ اﻟﺘﻲ ﺗﻢ ﻓﯿﮭﺎ ﻋﺮض دراﺳﺔ آﻟﯿﺔ ﻣﻘﺎرﻧﺔ ﺗﺒﯿﻦ ﺑﺎﻟﺘﻔﺼﯿﻞ اﻟﻮﺳﻄﺎء اﻟﻤﺘﻮﻟﺪة ﻓﻲ طﺮق اﻟﻤﻌﺎﻟﺠﺔ اﻟﻜﯿﻤﯿﺎﺋﯿﺔ واﻟﺒﯿﻮﻟﻮﺟﯿﺔ. وﻋﻼوة ﻋﻠﻰ ذﻟﻚ، ﺗﺒﯿﻦ اﻟﻨﺘﺎﺋﺞ أن ﻧﻈﻢ اﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺨﺘﻠﻔﺔ ﻟﺪﯾﮭﺎ ﻣﺨﻄﻄﺎت ﺗﺤﻠﻞ ﻣﺨﺘﻠﻔﺔ ﺟﺪا وﺗﺆدي إﻟﻰ ﻣﻨﺘﺠﺎت ﻟﮭﺎ درﺟﺎت ﻣﺨﺘﻠﻔﺔ ﻣﻦ السمية.

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