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GRADUATE UNIVERSITY SCIENCE AND TECHNOLOGY
QUAN CAM THUY
ANALATYCAL STUDY OF INTERMEDIATE PRODUCTS
FORMED DURING THE TREATMENT OF PARACETAMOL
BY UV/NaClO
Research field: Analatycal Chemistry
Code: 62.44.01.18
SUMMARY OF DOCTORAL THESIS
HA NOI - 2018
MINISTRY OF EDUCATION AND
TRAINING
VIETNAM ACADEMY
OF SCIENCE AND TECHNOLOGY
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This study was completed at: Vietnam Academy of Science and Technology
Advisor: Assoc. prof. Le Truong Giang
Reviewer 1:
Reviewer 2:
Reviewer 3:
The thesis is presented to doctoral dissertation council, meeting at the Academy
of Science and Technology - Vietnam Academy of Science and Technology and
at ... hours ... day ... month ... year ...
You can find the thesis at:
- Library of the Academy of Science and Technology
- National Library of Vietnam
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PREFACE
1. The urgency of the thesis
All activities in human life and production produce waste. Waste exists in solid, liquid
and gaseous form. In addition to inorganic and organic pollutants ... there are many
microorganisms in the water such as bacteria, viruses such as cholera, dysentery, typhoid, etc.
Therefore, disinfection of water is an indispensable process in water treatment technology.
Water disinfection is the process of eliminating potentially pathogenic microbes, which are
the necessary barrier and ultimately prevent human exposure to pathogenic microbes,
including viruses, bacteria, and protozoa. The basis of chemical disinfection is to use stronger
oxidizers to oxidize the yeast of microbial cells and destroy them. Commonly used chemicals
are: chlorine halides, bromine; chlorine dioxide; the hypoclorite and its salts; ozone, etc.
Highly effective chemical disinfection methods should be used extensively with many
different scales.
Chlorine is a strong oxidizer, in any form, pure or compound, chlorine acts to water
will generate hypochlorous acid (HOCl), a highly potent antiseptic. On the other hand,
Chlorine has the advantage of being able to maintain a small concentration in water for
relatively long periods of time to ensure resilience against water supply and storage.
Therefore, chlorine is still used most often for disinfection. Recently, many methods of
disinfection have been studied to replace chlorine, such as ozone, UV, bromine, etc. But there
is no alternative to chlorine. The current trend is to combine chlorine with other methods such
as UV irradiation to increase the effectiveness of disinfection and reduce the amount of
chlorine needed. One of commonly used method recently is UV / HOCl / ClO-.
However, the presence of chlorine in water can also lead to the formation of organic
chlorine compounds, which are responsible for cancer. Natural organic substances such as
humic acid, dissolved organic acids, amino acids and industrial organic pollutants are always
present in natural water. These organic compounds are often complex and can react with
chlorine to form hazardous compounds such as chloroform and trihalomethanes (THMs)
which including trichloromethane, dibromochoromethane, bromodichloromethane, etc. These
compounds Chlorophyll, especially in the human body, will cause damage to the liver and
kidney and has been demonstrated to be linked to the cause of cancer.
Under the influence of light, especially ultraviolet light, can lead to the dissociation of
HClO and ClO- ions that form free radicals. These free radicals can oxidize organic matters
and form various byproducts. The transformation of new contaminated organic compounds
and their by-products into the process is a new research trend in the field of analysis in the
world as well as in Vietnam.
2. Research objectives
Study on the transformation and identification of Paracetamol byproducts by UV /
HClO / ClO- in various environmental conditions.
3. Main research contents of the thesis
- Study on the degradation of Paracetamol by UV, Chlorination and UV/HOCl/ClO-.
- Study on factors affecting the degradation of Paracetamol by UV irradiation-only,
UV/NaClO oxidation.
- Study the optimum conditions to determine the by-products of oxidation by LC-MS/MS.
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CHAPTER 1: OVERVIEW
1.1. Pharmaceutical pollution in water environment
1.2. Residual PRC in water environment
1.3. Advanced oxidation processes applied in water treatment
1.4. Theoretical background of photosynthesis method
1.5. Method of analyzing micropollutants in water
1.6. Situation of research in domestic and foreign
CHAPTER 2: EXPERIMENTAL PROCEDURE AND METHODOLOGY
2.1. Equipments and Chemicals
2.2. Methodology
2.3. Experimental method
2.4. Experimental procedures
2.4.1. Degradation of PRC by UV, UV/NaClO, UV/H2O2
Prepare 2 liter of NaClO100μM solution (or 100mM H2O2), transfer to the reactor,
stir, adjust pH = 7, add 2.0ml PRC 10μM solution, add to the reactor, then 254nm UV light
for 20 minutes, the samples were taken over time starting from the UV lamp irradiance. Each
time a 1.0ml sample was taken into the vial with 0.2ml Na2S2O3 2mM (ratio
[NaClO]/[Na2S2O3] = 2-3), UV/H2O2 system using Na2SO3 2mM with the ratio
[NaClO]/[Na2SO3] = 2). PRC concentrations over time were monitored by HPLC.
NaClO concentrations were determined by optical method with DPD reagent.
H2O2 concentration was determined by optical method with TiCl4 reagent.
2.4.2. The experiments determine the role of free radicals
Determination of • OH free radical concentration:
The competitive dynamic reaction between the two compounds is PRC and NB as follows:
Prepare 2 liters of NaClO100μM solution, transfer to reactor, stir, adjust pH = 7, add 2.0ml of
PRC 10mM, 2.0ml of C6H5NO2 2mM solution to the reactor, UV irradiance 254nm for 30
minutes, the samples were taken over time, starting from UV irradiance. Each time a 1.0ml
sample is taken into the vial with 0.2ml Na2S2O3 2mM (ratio [NaClO]/[Na2S2O3] = 2-3). The
concentration of PRC, NB over time is monitored by HPLC
Determination of Cl of free radicals:
The competitive dynamics between the three compounds PRC, NB and BA are as follows:
Prepare 2 liters of NaClO 100 μM solution, transfer to reactor, stir, adjust pH = 7, add 2.0 ml
PRC 10mM, 2.0 ml C6H5NO2 2mM solution, 2 ml C6H5COOH 2mM solution to the reactor,
then UV irradiance 254nm for 30 minutes, the samples were taken over time starting from the
UV irradiance. Each time a 1.0ml sample is taken into the vial with 0.2ml Na2S2O3 2mM (the
ratio [NaClO]/[Na2S2O3] = 2-3). PRC, NB, BA concentrations over time were monitored by
HPLC.
2.4.3. Experiment to determine the by-product of the degradation of PRC by UV,
UV/NaClO
Prepare 2 liters of 500 mL NaClO solution, transfer to the reactor, stir, adjust pH = 7,
add 20.0 mL of PRC 10mM solution, add to the reactor, then irradiance 254nm for 20
minutes, The sample is taken over time. Each time a 0.5ml sample of the vial is available with
0.3ml Na2S2O3 2mM ([NaClO]/[Na2S2O3] = 2-3) is obtained prior to LC-MS/MS
measurement. White Blank (B) is added to a separate vial of distilled water and Na2S2O3.
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CHAPTER 3: RESULTS AND DISCUSSION
3.1. Research on the presence and distribution of pharmaceutical residues in surface
water in some rivers and lakes in Hanoi
3.1.1. Quantitative pharmaceutical residue on LC-MS/MS equipment
In this study we focus on the investigation of the concentration of 9 drugs, especially
nonsteroidal anti-inflammatory drugs and some typical antibiotics widely used in Vietnam
and in the world.
3.1.2. Residual quantities of pharmaceuticals in the rivers and lakes of Hanoi
The results showed that: TMP, TC and TRA were not detected in any sample, it means
that the concentration was below the detection threshold of the method. CAR, DIC are drugs
with low excretion rate but the concentration is still high, especially in the sample of Lu river
water corresponding to 1003ng/L and 1020ng/L.
Notably, IBU and PRC were detected at high alarming levels, corresponding to a
maximum concentration of 4161ng/L and 3925ng/L and were present in all samples. IBU was
most commonly used in the non-steroidal anti-inflammatory drug group, 220 tonnes in France
in 2006 (Haguenoer et al), and was found in four wastewater treatment plants in Spain, with a
concentration of 3.73 to 603μg/L (Santos et al., 2009). For paracetamol, according to the
Ministry of Health, paracetamol is the market leader in the Vietnamese pharmaceutical market
with more than 2,000 registered monotherapies and other combinations. This is a popular
analgesic and is offered over-the-counter. Therefore, the detection of paracetamol at high
concentrations in the samples is appropriate. Large PRC concentrations are also consistent
with previous releases, such as river waters in Australia, Africa and the Aire River in the UK
at concentrations of 7150ng/L, 3000ng/L and 4300ng/L.
3.1.3. Changes in the content of pharmaceutical residues in the river in Hanoi
Comparison of results between time intervals indicates that the content of substances may be
depended on climatic and weather conditions. Research has shown that the effectiveness of
the LC/MS-MS analysis method opens up new directions for analyzing a variety of sample
objects, particularly water samples that are not too complex.
3.2. Influencing factors to PRC degradation by UV irradiation-only and UV/NaClO
3.2.1. Comparison of different advanced oxidation process on PRC degradation
The oxidation methods used to study the degradation of PRC include: Chlorination,
UV irradiation-only, UV/H2O2 and UV/NaClO. The experiments were performed with a
concentration of [PRC] = 10 μM, pH = 6.5 [NaClO] = 100 μM, [H2O2] = 100 μM.
Table 3.1: PRC degradation by different AOPs
Experiment
conditions
[PRC]
µM
pH
[H2O2]
µM
[NaClO]
µM
kobs(s-1)
Para/UV
10
6,59
2,23 E-04
Para/UV/H2O2
10
6,65
100
3,71 E-04
Para/NaClO
10
6,38
100
5,25E-04
Para/NaClO/UV
10
6,45
100
2,36E-03
Only 10%, 20%, and 26% PRC were decomposed by direct UV photosynthesis, H2O2/UV and
chlorinated with NaClO after 20 minutes of reaction, confirming that the relative PRC
chemically stable for these oxidation processes.