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Mar 13, 2023 111 likes •498 views

METRONIDAZOLE IN A UV-TIO 2 PHOTOCATALYTIC SYSTEM: FATE, REMOVAL AND MINERALIZATION Authored by Neghi. N & Mathava Kumar * *Associate Professor Department of Civil Engineering, Indian Institute of Technology Madras, Chennai, Tamilnadu

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METRONIDAZOLE IN A UV-TIO2 PHOTOCATALYTIC SYSTEM: FATE, REMOVAL AND MINERALIZATION

*Associate Professor Department of Civil Engineering, Indian Institute of Technology Madras, Chennai, Tamilnadu – 600 036, India Tel: +91-44-2257 4267; E-mail: mathav@iitm.ac.in

Authored by

  • Neghi. N & Mathava Kumar*
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INTRODUCTION - ANTIBIOTICS

 Antibiotics - treat/prevent bacterial infections  Increasing trend in the consumption of antibiotics 2000-

2010:- Brazil - 68%, Russia -19%, India - 66%,China - 37%, South Africa - 219%(CDDEP,2015)

US 10% of the world’s antibiotic consumption

 Global antibiotic use by class  Broad spectrum penicillins  Cephalosporins  Macrolides  Trimethoprim and combinations  Quinolones  Aminoglycosides  Nitroimidazoles (Metronidazole falls under this class)

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ANTIBIOTICS IN THE ENVIRONMENT

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Consumers Excretion &

  • ther activities

PPCP along with Wastewater Wastewater treatment units Centralized De-Centralized DOC removal by biological process

Removal by biological process PPCP in effluent PPCP into Soil PPCP into SW

PPCP in sludge PPCP into Ecosystem

PPCP into GW

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ANTIBIOTICS IN THE ENVIRONMENT

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Reference: www.saveantibiotics.org

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ANTIBIOTICS IN THE ENVIRONMENT

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 Industrial wastewaters (Formulation)  Hospital Wastewaters  Aqua culture wastewaters  Meat processing units  Live-stock units  Feed manufacturing/growth supplement producing

units

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 Vanishing Vulture’s  Poisoned animal carcass

feeding with Diclofenac ANTIBIOTICS IN THE ENVIRONMENT

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ANTIBIOTICS IN THE ENVIRONMENT

 Develop antibiotic resistance in aquatic environments  Affect building blocks of the ecosystem processes  WHO report - different antibacterial resistant strains -

FS 194 -Updated April 2015 http://www.who.int/mediacentre/factsheets/fs194/en/

 Detection range observed to be more in pharmaceutical

production plant effluents

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ANTIBIOTICS IN WATER AND WASTEWATER

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Source/Point of Origin Collection System Wastewater treatment units Point of Disposal Away from disposal points Sampling Sampling Increase in antibiotics concentration

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WHY TO REMOVE ANTIBIOTICS..????

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Close the Loop in water use pattern

Water withdrawl Water Supply Wastewater Collection Wastewater Treatment Water Recharge into Ground

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  • 2-(2-methyl-5-nitroimidazol-1-yl)ethanol, (C6H9N3O3)
  • Water Solubility  10 mg/mL
  • Log Kow  0.1 (hydrophilic)
  • Vapor pressure  3.1 x 10-7 mm Hg at 25oC
  • 18% of drug excreted unchanged from human body

METRONIDAZOLE(MNZ)

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INTRODUCTION - PHOTOCATALYSIS

 Photocatalysis  One of the AOP’s

 h + + H2O → H+ + OH−  h + + OH− → HO•

 O2 + e− →.O2

−

 H2O2 + e − → HO• + OH-

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ATTRIBUTES OF PHOTOCATALYTIC SYSTEM

 Ideal photocatalyst -TiO2  HO· generated in the system - non-selective- high

  • xidation potential (E0 = 2.8V/SHE)

 UV-C band of light - ability to handle the antibiotic

resistant genes in real time wastewater

 Difficulties

 Post separation of the catalyst  Operation under continuous-mode  Support catalyst - overcome the difficulties  Support medium - Activated charcoal, Stainless steel

plate, Alumina.

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BACKGROUND

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OBJECTIVES

 Feasibility of MNZ removal by photocatalytic system

with TiO2 and GAC

 Quantify the roles of catalysts and UV power on MNZ

removal

 Correlate MNZ removal with economic analysis to

identify best suitable experimental condition

 Long term goal  Create a system for continuous-

mode photocatalysis for antibiotics removal

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BATCH PHOTOCATALYTIC REACTOR

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UV POWER SUPPLY PROBES CONNECTED TO pH/ORP/Temp METER ELECTRONIC STIRRER DOUBLE WALLED CYLINDRICAL GLASS REACTOR WITH WORKING VOLUME OF 1.9 L METRONIDAZOLE AND TiO2 IN SUSPENSION

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PHOTOGRAPHIC VIEW OF THE REACTOR

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EXPERIMENTAL CONDITION

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Initial MNZ concentration (mg/L) UV Power (W) Catalyst dosage (g/L) Type of catalyst Comments 15

  • Blank

16 Photolytic studies 32 15

  • 2.5

TiO2 Photocatalytic studies 16 32 15

  • 2.5

GAC Adsorption studies 32

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SLIDE 18

ANALYTICAL TECHNIQUES

I.

MNZ and its metabolites - HPLC/ LC-MS

II.

Organic carbon constituents of samples - TOC

III.

Surface morphology of the catalyst and the support chosen – SEM

IV.

Elemental composition of the catalyst/ adsorbent – EDS

V.

pH/Temperature/Oxidation-Reduction Potential of the system - Benchtop multi-parameter analyzer

VI.

COD analysis - Standard Methods (APHA, 2002)

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SLIDE 19

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MNZ REMOVAL BY CHOSEN PROCESSES

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0,0 0,2 0,4 0,6 0,8 1,0 1,2 20 40 60 80 100 120 C/C0 Time(min)

16W 32W TiO2 adsorption TiO2+16W TiO2+32W GAC adsorption GAC+32W

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SLIDE 21

ORP TREND

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100 200 300 400 20 40 60 80 100 120 ORP (mV)) Time (min) 16W 32W TiO2+16W TiO2+32W GAC+32W

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SLIDE 22

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23,6 33,8 61,1 62,4 52,9 21,7 15,6 23,9 42,4 94,1 96,4 77,5 32,5 18,7 20 40 60 80 100 16W 32W TiO2+ 16W TiO2 + 32W GAC + 32W GAC adsorption TiO2 adsorption

At 60 min At 120 min

COMPARISON OF MNZ REMOVAL

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SLIDE 23

ENERGY CONSUMPTION ANALYSIS

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Rate of Reaction: Energy Consumption:

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SLIDE 24

ENERGY CONSUMPTION OF THE SYSTEM

FOR DIFFERENT PROCESS

24 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1 16W 32 W TiO2+16W TiO2+32W GAC+32W GAC adsorption TiO2 adsorption

Energy Consumed* (KWh) EEO (KWh m-3 order-1)

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SLIDE 25

RESULTS OF BATCH ANALYSIS

25 Comments Removal (%) after 60 min Removal (%) after 120 min Rate constant ‘k1’ (min-1) Energy Consumed* (KWh) EEO (KWh m-3

  • rder-1)

MNZ COD MNZ COD Blank 1.4 4.0 1.4 4.0 0.000 0.000 0.000 16W 23.6 15.3 23.9 17.5 0.002 0.032 0.144 32W 33.8 16.9 42.4 31.1 0.004 0.064 0.141 TiO2+16W 61.1 56.3 94.1 72.2 0.022 0.172 0.077 TiO2+32W 62.4 60.0 96.4 80.7 0.026 0.204 0.080 GAC+ 32W 52.9

  • 77.5
  • 0.012

0.214 0.129 GAC adsorption 21.7

  • 32.5
  • 0.002

0.096 0.296 TiO2 adsorption 15.6 48.8 18.7 61.2 0.001 0.150 0.877

Energy consumed by (a) electronic overhead stirrer - 70/42 W (I/O), (b) UV Lamps - 16 W each, and (c) orbital shaker for adsorption studies - 48 W were included for energy consumption analysis.

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SLIDE 26

DEGRADATION OF 15 PPM OF MNZ IN PHOTOCATALYTIC SYSTEM

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MNZ removal COD reduction TOC removal Series1 96,4 80,7 66,5 96,4 80,7 66,5 Removal in percent

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SLIDE 27

SEM ANALYSIS OF ADSORPTION OF MNZ ONTO TIO2 & GAC

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(a) TiO2 before

treatment

(b) TiO2 after

treatment

(c)

GAC before treatment

(d) GAC after

treatment

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SLIDE 28

LC-MS ANALYSIS

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SLIDE 29

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LC-MS ANALYSIS

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CONCLUSIONS

 Highest MNZ removal

 with 32 W UV power and 2.5 g L-1 TiO2 in 120 min.

 Removal of MNZ using GAC as a photocatalyst

was remarkably higher than that of GAC used as an adsorbent.

 The concept of electrical energy consumed per

  • rder, i.e. EEO - ideal parameter for the economic

analysis.

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SLIDE 31

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Upgraded-Setup for PPCP Removal Research

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SLIDE 32

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REFERENCES

Asha, C.R., Kumar, M. 2015 Sulfamethoxazole in poultry wastewater: Identification, treatability and degradation pathway determination in a membrane-photocatalytic slurry reactor. Journal of Environmental Science and Health Part-A 50, 1011-9.

Andreozzi, R., Caprio, V., Insola, A., Marotta, R. 1999 Advanced oxidation processes for water purification and recovery. Catalysis Today 53(1), 51-9.

APHA, Standard Methods for the Examination of Water and Wastewater, 22nd ed., American Public Health Association, Washington, DC, 2005

Friedmann, D., Mendive, C., Bahnemann, D. 2010 TiO2 for water treatment; parameters affecting the kinetics and mechanism

  • f

photocatalysis. Applied Catalysis B- Environmental 99(3-4), 398-406.

Gao, Y.Q., Gao, N.Y., Deng Y., Yang, Y.Q., Ma, Y. 2012 Ultraviolet (UV) light- activated persulfate oxidation of sulfamethazine in water. Chemical Engineering Journal 195(1), 248-53.

Giri, R.R., Ozaki, H., Ota, S., Takanami, R., Taniguchi.S. 2010 Degradation of common pharmaceuticals and personal care products in mixed solution by advanced

  • xidation

techniques. International Journal

  • f

Environmental Science and Technology 7(2), 251-60.

Gros, M., Petrovic, M., Ginebreda, A., Barcelo, D. 2010 Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard

  • indices. Environment International 36, 15-26.

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Hapeshi, E., Achilleos, A., Vasquez, M.I., Michael, C., Xekoukoulotakis, N.P., Mantzavinos, D., Kassinos, D. 2010 Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions. Water Research 44, 1737-46.

Hu.L.H., Flanders, P.M., Miller, P.L., Strathman, T.J. 2007 Oxidation

  • f

sulfamethoxazole and related antimicrobial agents by TiO2 photocatalysis. Water Research 41(12), 2612-6.

Jallouli, N., Elghniji, K., Trabelsi, H., Ksibi, M. 2014 Photocatalytic degradation of paracetamol on TiO2 nanoparticles and TiO2/cellulosic fiber under UV and sunlight

  • irradiation. Arabian Journal of Chemistry (Article in press).

Kanakaraju, D., Glass, D.B., Oelgemoller, M. 2014 Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environmental Chemistry Letters 12, 27- 47.

Kim, I., Yamashita, N., Tanaka, H. 2009 Performance of UV and UV/H2O2 processes for the removal of pharmaceuticals detected in the secondary effluent of a sewage treatment plant in Japan. Journal of Hazardous Materials 166(2), 1134-40.

Kummerer, K. 2009 The presence of pharmaceuticals in the environment due to human use - present knowledge and future challenges. Journal for Environmental Management 90(8), 2354-66. 34

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Martinez, F., LopezMunoz, M.J., Aguado, M., Melero, J.A., Arsuaga, J., Sotto, A., Molina, R., Segura, Y., Parinete, M.I., Revilla, A, Cerro, L., Carenas, G. 2013 Coupling membrane separation and photocatalytic oxidation processes for the degradation of pharmaceutical pollutants. Water Research 47, 5647-58.

Lindberg, R., Jarnheimer,P., Olsen, B., Johansson, M., Tysklind, M. 2004 Determination of antibiotic substances in hospital sewage water using solid phase extraction and liquid chromatography/mass spectrometry and group analogue internal standards. Chemosphere 57, 1479-88.

Mompelat, S., Le Bot, B., Thomas, O. 2009 Occurrence and fate of pharmaceutical products and by-products from resource to drinking water. Environment International 35(5), 803-14.

Safari, G.H., Hoseini, M., Seyedsalehi, M., Kamani, H., Jaafari, J., Mahvi, A.H. 2015 Photocatalytic degradation of tetracycline using nanoized titanium dioxide in aqueous solution. International Journal of Environmental Science and Technology 12, 603-16.

Suarez, S., Carballa, M., Omil, F., Lema, J.M. 2008 How are pharmaceuticals and personal care products removed from urban wastewaters? Reviews in Environmental Science and Biotechnology 7, 125-38.

Velasco, F.L., Fonseco, M.I., Parra, B.J., Lima, C.J., Ania, O.C. 2012 Photochemical behaviour of activated carbons under UV irradiation. Carbon 50(1), 249-58.

Vishnuganth, M.A., Remya, N., Kumar, M., Selvaraju, N. 2016 Photocatalytic degradation of Carbofuran by TiO2-coated activated carbon: Model for kinetic, energy per order and economic analysis. Journal of Environmental Management 181, 201-207. 35

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INTRODUCTION - METRONIDAZOLE

 Antibacterial (Gram –ve anaerobic bacteria) and antiprotozoal

drug

 Clinical application- principal treatment for H.pylori infections,

giardiasis, trichomoniasis - Additive in poultry and fish feeds to eliminate parasites

 Activation of the compound - formation of cytotoxic intermediates

  • DNA, protein damage - carcinogenicity

 Highly soluble in water and poorly biodegradable - entry into

surface and groundwater resources

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MATERIALS

  • MNZ(99.9%)

Sigma Aldrich

  • Anatase form TiO2

Sigma Aldrich Average size range ~25 nm Surface area = 45-55 m2/g Density = 3.9 g mL-1 at 25°C

  • Granular activated carbon

SDFCL, India SBET = 1010 m2 g-1 VT ~ 0.532 cm3 g-1

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