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15CHEMICAL SCIENCES
APPLYING AOPS FOR ANTIBIOTICS EXCSTRACTION FROM WASTEWATER
Kyrii S.
Assistant, The Department of The Technology of Inorganic Substances, Water Purification and General Chemical Technology, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute "
Krimets G.
Assistant professor, PhD., The Department of The Technology of Inorganic Substances,
Water Purification and General Chemical Technology, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute"
Kosogina I.
Assistant professor, PhD., The Department of The Technology of Inorganic Substances,
Water Purification and General Chemical Technology, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute"
Astrelin I.
Professor, Doctor of Technical Sciences, The Department of The Technology of Inorganic Substances, Water Purification and General Chemical Technology, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute"
Fedorenko O.
Student, The Department of The Technology of Inorganic Substances, Water Purification and General Chemical Technology, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute"
Abstract
This paper presents a study of sulbactam degradation by Advanced oxidation processes. It was investigated the efficiency of usage O3/UV for removal of sulbactam with different concentrations 200 mg/l and 20 mg/l at different values рН in the range of 3 - 12. It was found that in an alkaline environment, the oxidation process takes place much faster, maximum deletion is observed at рН 8,87. The reduction of the COD was 100% -through the method: UV/O3, and about 80% of the UV for 2 hours of oxidative action. The sulbactam degradation mechanism in the alkaline and an acidic medium is proposed.
Keywords: wastewater, antibiotics, sulbactam, АОРs, water treatment
1. Introduction
Among all pharmaceuticals that can cause environmental pollution through antibiotics take an important place because of their getting into sewage as a result of incomplete assimilation by organisms. The presence of antibiotics in the aquatic environment is increasing concern around the world due to their toxic effects on hydrobionts, incomplete expansion and subsequent entry into water supply systems. So, studies conducted in Ukraine [1] showed that drinking water supplied to the population remains trace concentrations of pharmaceuticals, including antibiotics, sex hormones, sedative and anticonvulsants, painkillers, as well as many others that are given only on doctors prescription.
There are varied ways of getting such pharmaceuticals into the water. In particular, due to the fact that people take medications, some part of them are digested by the human organism, and those part that have not been digested (this is approximately 70% of the consumed medications) excreted naturally, without changing its chemical composition and accordingly falls into the sewage systems. Wastewater, are undergoing traditional cleaning and re-enter the rivers or lakes, from where the resources of drinking water are replenished.
There are varied ways of getting such pharmaceuticals into the water. In particular, due to the fact that
people take medications, some part of them are digested by the human organism, and those part that have not been digested (this is approximately 70% of the consumed medications) excreted naturally, without changing its chemical composition and accordingly falls into the sewage systems. Wastewater, are undergoing traditional cleaning and re-enter the rivers or lakes, from where the resources of drinking water are replenished.
The existing household-wastewater treatment system is not able to remove pharmaceuticals from the water. In addition, experts have found that adding chlorine and its compounds to the wastewater, as a standard procedure for water purification, on the contrary, increases the toxicity of certain medicinal products contained in water [1].
The effectiveness of methods for neutralizing pharmaceuticals (biodegradation, coagulation, sedimentation) is often low, and the accumulation of these compounds in the environment leads to the destruction of microflora and fauna, and the presence their background concentrations in water make the evolution of antibiotic-resistant bacteria in the environment [2].
Among the methods used to purify wastewater from organic pollutants, including antibiotics, should be prefered the methods of the group AOPs: ozonation in combination with other oxidants or irradiation, usage
of the Fenton/photo-fenton reagent, photolysis, semiconductor photocatalysis, electrochemical processes. It is believed that AOPs contribute to the degradation or mineralization of organic pollutants, in particular, antibiotics.
Sufficiently common pollutants of household and pharmaceutical wastewater are antibiotics of the p-lac-tam number. It was found that the degradation of the p-lactam ring by ozonation was highly effective in (COD removal> 50%), but with a low degree of mineralization (~ 20%) [3,4]. It was discovered, however, it is certainly not explained ambiguous influence of the pH medium on the process, the mechanism of ozone decomposition into free radicals and increasing the speed of mass transfer. In particular, it was noted that the accumulation of carboxylic acids in the destruction process leads to an undesirable decrease in the pH of the process.
It is expected that to make process of destroying sulfanilamides more effective is possible by combination ozonation with photocatalytic degradation using hydroxyl radicals (HO^), generated in the reaction medium. In source [5], was specified that at the initial stage of photocatalytic process proceed a reduction of toxicity and a significant increase of ability of sulfani-lides solutions to biological decomposition.
Many papers present the results of experiments on photocatalytic degradation of antibiotics in the presence of TiO2 as a catalyst. In the past few years, scientists have put some effort to increase the surface area of TiO2 by dispersing TiO2 nanoparticles on a large surface area of materials [6].
It is also known that the effectiveness of antibiotics degradation in the wastewater, especially sulfona-mides, can be significantly higher with the usage of Fe (III) salts, as a photocatalyst (eg, FeCl3 [5]) than with the presence of TiO2 only. Simultaneous using of a mixture of TiO2 and FeCl3 leads to an increase in the efficiency of the photocatalytic system through syner-gistic effects. In these solutions, the Fe3+ ions are partially hydrolyzed and, as a result, photosensitive Fe(OH)2+ are formed. After absorption of UV light by these ions, the hydroxyl radical is faster formed in solutions [5].
At the same time, taking into account the available scientific information, it can be stated that there are almost no data concerning the theoretical and experimental basis of oxidative degradation in the waste waters of substances with p-lactam structures.
The p -lactamine series of antibiotics include subclasses of penicillins, cephalosporins, carbapenems and monobactam. The similarity of the chemical structure determines the same mechanism of action of all p-lac-tams (a violation of the synthesis of the cell wall of bacteria), as well as cross-allergy to them in some patients.
Sulbactam is a semi-synthetic penicillinic bellon, which belongs to the p-lactam antibiotic of the penicillin series (Figure 1).
o
Figure 1 -The structure of sulbactam
Penicillins, cephalosporins and monoblots are sensitive to the hydrolysis of specific enzymes - p-lactamase, which is produced by a number of bacteria. Carbapenems have significantly higher resistance to p-lactamase. Considering, the high clinical efficacy and low toxicity, p-lactam antibiotics form the basis of antimicrobial chemotherapy at the present stage, occupying a leading position in the treatment of most infections. p-lactam antibiotics are the most widespread class of antimicrobial medicals for the treatment of infections.
Given the significant toxicity present in sulbactam wastewater, there is an urgent need to investigate the destructive processes of sulbactam in aqueous solutions.
Although AOPs processes are effective in the mineralization of various organic substances [7-8], however, there is no certainty that sulbactam can be completely mineralized through these processes.
The purpose of this research is to study the conditions and regularities of the sulbactam degradation process and changes of its antibacterial activity using the UV/O3 process.
2. Materials and methods
Investigation of the processes of extracting sulbactam from aqueous solutions was carried out on model waters with substrate concentrations: S-m 0,2 and 0,02 g/l. The antibiotic Sulbactamum (C8H11NO5S) (Figure 1) was obtained from a pharmaceutical plant in sterile packaging.
For the destruction process of sulbactam, was used a laboratory installation, the scheme of which is shown in Figure 2. It consists of a tank 1, pump 2 (TYP 2500 NH, Diaphragm booster pump., 50 Hz) with a flow rate of 10 to 100 cm3/min and a UV lamp 3, placed in a stainless steel chamber (model UVGERMISIDAL 254 POWER, 6 Watts), ozonator 4 (GL-3189, ozone concentration 0.5 g/year). The system is cyclical, water from the reservoir is fed through the UV camera and the ozone chamber, than returne to the reservoir with the constant speed.
Experiments were carried out in laboratory using a plant to determine the effect of UV and O3 in the process of antibiotics degradation at different pH values of water. In the research were used samples of model water with different values pH 6,47, 8,87 and 2,92.
Analysis of model water samples for residual organic content was carried out at regular intervals (10
min) using a sterile pipette 6. Determination of the re- UV-5800PC spectrophotometer at different wave-sidual sulbactam concentration was carried out on a lengths (223 and 254 nm) using a quartz cell.
purified water
Figure 2 - Scheme of laboratory installation
3. Result and discussion
The study of the model water purification process was carried out using various AOPs methods, in different combinations of oxidants, such as Оз and Н2О2 with UV radiation and without changing the pH of the medium in the range of 3 to 12.
Investigated the efficiency of degradation of S-m (200 mg/l) for the change of COD by different combinations of AOPs. Reducing the concentration of organic matter is observed using only irradiation and combination of UV+ Н2О2+Оз, UV+Оз with a duration of the process for more than 120 minutes. A combination of O3/UV reduces the concentration of organic matter by 39%, which occurs by recombination of functional groups in the S-m structure. Typically, the oxida-tive degradation of simple organic pollutants can lead to the decomposition of the structure and ultimately to mineralization. However, the complete mineralization of most antibiotics is often difficult to achieve due to their structural complexity and stability. The reduction
of the COD was 100% -through the method: UV/O3, and about 80% of the UV for 2 hours of oxidative action. The low degree of mineralization in other cases is probably due to the formation of stable intermediate products [9].
At the concentration of S-m 20 mg/l observed a different picture than the 200 mg/l partial reduction ABS showed a combination of UV+ Н2О2 and UV+Оз, but ABS initial substances was not completely removed during 120 minutes. The efficacy of other combinations, as with higher concentrations, was not observed. The combination of O3/UV and UV+Н2О2 achieves the best of all possible combinations of ABS reduction, but the degree of removal is only 25-29%.
The reduction of the COD with decreasing absorption peak intensity for the UV+Н2О2 oxidation system was not observed, 75% for UV+Оз, about 60% for UV+Н2О2+Оз and 50% for O3 for 2 hours of oxidative destruction (Figure 4).
Figure 3 - Efficiency of mineralization S-m (20 mg/l) with different combinations of AOPs
From the results obtained above, the best removal It was investigated the influence of pH on the ef-
of S-m is observed with the use of the combination of ficiency of removing S-m (200 mg/l). It is established UV + O3. that in an acidic environment the removal of organic
pollutant from waste water is reduced. In alkaline - the Probable mechanisms of destruction of sulbactam
process of oxidation is much faster. t was found that the are shown in Figures 5 and 6. maximum possible purification of Sulbactam water is observed at alkaline pH of the medium and is 39%.
+H-0
o3-■ ever- - ?OH-
o
Figure 4 - Degradation of sulbactam in alkaline medium
Figure 5 - Degradation of sulbactam in acidic medium
Investigated the influence of impurities on mineralization efficiency of sulbactam with usage of various model environments for preparation of model water, exactly distilled water and tap water. The efficiency of destruction of sulbactam is higher in a model solution
prepared on tap water (Fig. 7). The presence in the model solution of iron compounds contributes to destruction of sulbactam due to the formation of additional OH under the action of radiation, since the iron compound has a catalytic action.
700
600
500
400
300
200
100
lLLlI
0
20
90
120
60
Time, min Tap water Distillated water
Figure 6 - Influence of environment on mineralization efficiency of organic component
It was investigated the removal of a contaminant in alkaline medium at low initial concentrations of 20 mg/l. The best removal takes place 1 hour after the start of cleaning, then the cleaning efficiency is reduced.
300
250
_ 200
"SB
£ï 150 O O u 100
50
0
This can be explained by the fact that at low concentrations of sulbactam in an aqueous solution, the disclosure of lactam cycles and the formation of new polymeric compounds may take place (Fig. 8).
0
pH 3,6
20 pH 8,3
100
60 80 Time, min
Figure 7 - Dependence of COD with time in different environments
120
Conclusions
Based on the classical approaches to the regularities of the oxidation processes of organic substances, we proposed mechanisms for the destruction of sulbac-tam in alkaline and acidic media.
The combination of ozone and ultraviolet radiation can be effectively used to remove lactam antibiotics from the water. The destruction processes of antibiotics are better to run in alkaline environment and therefore to clean the actual wastewater is recommended to maintain the pH of purified water at 8 ... 8.5.
Since maximum excretion of sulbactam is only 39%, it is suggested to use doses of ozone greater than 0.5 g/year to improve the purification process.
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Verma Int. Journal of Engineering Research and Applications. 4 (2005) 58-65.
2. Balcioglu, I.A., Otker, M. Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes. Chemosphere 50, (2003) 85-95.
3. Arslan-Alaton, I., Caglayan, A.E. Ozonation of procaine penicillin G formulation effluent. Part I: Process optimization and kinetics. Chemosphere. 59 (2005) 31-39.
4. Justyna Ziemianska, Ewa Adamek, Andrzej Sobczak, Ilona Lipska, Andrzej Makowski, Wojciech Baran. The study of photocatalytic degradation of sul-fonamides applied to municipal wastewater. Physico-chem. Probl. Miner. Process.. 45 (1) (2005) 127-140.
5. N. A. Laoufi, S. Hout, D. Tassalit, A. Ounnar, A. Djouadi, N. Chekir, F. Bentahar. Removal of a Persistent Pharmaceutical Micropollutant by UV/TiO2 Process Using an Immobilized Titanium Dioxide Catalyst: Parametric Study .Chemical Engineering Transactions. Vol. 32 (2013).
6. D. Vogna, R. Marotta, A. Napolitano, R. An-dreozzi and M. d'Ischia, Advanced oxidation of the
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pharmaceutical drug diclofenac with UV/H2O2 and ozone, Water Research. 38 (2004) 414-422.
7. I. Arslan Alaton and S. Dogruel, Pre-treatment of penicillin formulation effluent by advanced oxidation processes, Journal of Hazardous Materials B. 112 (2004) 105-113.
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degradation and the toxicity change of degradation compounds in photo-irradiation process, Journal of Environmental Sciences. 20 (2008) 806-813.
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ON THE THERMODYNAMIC DIRECTION OF THE ORIGIN OF LIFE AND ITS EVOLUTION: A
NEW CONFIRMATION OF THE THEORY
Gladyshev G.
Doctor of chemical sciences, Professor Principal scientist N. N. Semenov Institute of Chemical Physics Russian Academy of Sciences; Russian Academy of Arts Moscow
О ТЕРМОДИНАМИЧЕСКОЙ НАПРАВЛЕННОСТИ ВОЗНИКНОВЕНИЯ ЖИЗНИ И ЕЕ ЭВОЛЮЦИИ: НОВЫЕ ПОДТВЕРЖДЕНИЯ ТЕОРИИ
Гладышев Г.П.
Доктор химических наук, профессор Главный научный сотрудник Институт химической физики им. Н. Н.Семенова Российская Академия наук, Отделение дизайна, Российская Академия Художеств
Москва
Abstract
Comparison of the standard free Gibbs energy of the formation of thermodynamically identical molecules and their fragments to the close chemical composition in physiological conditions allows determining with a good approximation the directional change in the stability of these molecules and fragments in the evolution and aging of living beings. This approach, based on the principle of substance stability, confirms the thermodynamic direction of the chemical and supramolecular composition changes in chemical and biological evolution. The paper presents quantitative estimates confirming the thermodynamic direction of nitrogen enrichment of organisms in their evolutionary development and the epigenetic processes of methylation of nucleic acids, and also discusses the possibility of the presence of geroprotective properties in some atmospheric gases, for example, in molecular hydrogen.
Аннотация
Сравнение стандартной свободной энергии Гиббса образования близких по химическому составу термодинамически однотипных молекул и их фрагментов в физиологических условиях позволяет с неким приближением определять направленное изменение стабильности этих молекул и их фрагментов в эволюции и старении живых существ. Указанный подход, опирающийся на принцип стабильности вещества, подтверждает термодинамическую направленность изменения химического и супрамолекулярного состава в химической и биологической эволюции. В работе представлены количественные оценки, подтверждающие термодинамическую направленность обогащения азотом организмов в эволюционном их развитии и эпигенетических процессов метилирования нуклеиновых кислот, а также обсуждается возможность наличия геропротекторных свойств у некоторых газов атмосферы, например у водорода, а также сероводорода.
Keywords: hierarchical thermodynamics, the origin of life, the principle of substance stability, biological evolution, epigenetics, aging
Ключевые слова: иерархическая термодинамика, возникновение жизни, принцип стабильности вещества, биологическая эволюция, эпигенетика, старение
Эпиграф
"One of the principal objects of theoretical research in any department of knowledge is to find the point of view from which the subject appears in its greatest simplicity."
Дж.У. Гиббс [1]
Ведение существование и превращение молекул. Химиче-
Химическая эволюция протекает в областях ская эволюция плавно переходит в биологическую вселенной, где с позиции термодинамики возможно
