Activated Carbon Tailored Surfaces for Pharmaceutical Pollution Control

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1 Activated Carbon Tailored Surfaces for Pharmaceutical Pollution Control El-Said I. El-Shafey Chemistry Department, College of science, Sultan Qaboos University World waterday 22 March 2017

2 Hospitals, Clinics & Pharmaceutical Companies Medical waste received attention as it is biohazardous

Hospital wastewater (HWW) Little attention is paid to Hospital wastewater Hospitals generate ~ 400-1200 L /bed/day (SQUH 960 L/day) Effluents are

3 Hospital wastewater (HWW) Little attention is paid to Hospital wastewater Hospitals generate ~ L /bed/day (SQUH 960 L/day) Effluents are loaded with Pharmaceuticals & metabolites Heavy metals Radioactive elements Dyes and pigments Pathogens Disinfectants Chloro-organics Endocrine chemicals

4 Pharmaceuticals in Aquatic Environment Sources: point source Hospitals Medical and health care facilities Medical institutions Pharmaceutical Companies Pharmacies Animal farms Diffuse source: Flushing unused or expired drugs down the sink or toilets Kummerer K., chemosphere 45 (2001)

EPA has detected 400 toxic and hazardous pollutants in hospital wastewater. U.S. EPA; Washington, DC.

5 Pharmaceuticals detected in Aquatic Environment Antibiotics Pain killers Hormones Anti-cancer drugs Lipid regulators Anti-epiliptics Cytotoxic compounds Endocrine chemicals U.S. EPA has detected 400 toxic and hazardous pollutants in hospital wastewater. U.S. EPA; Washington, DC. 1989b; EPA 440/1-89/060-n. Ayscough, N. T., Fawell, J., Franklin G., Young w, Review of human pharamceuticals in the environment. UK Environmental agency, Bristol.

6 Impact of Hospital Waste Water Directly affects human health: as many compounds are Genotoxic Suspected of increased cancer worldwide Antibiotic-resisting bacteria Biological imbalance Very dangerous to the biodiversity in the aquatic environment as they can contaminate the food chain.

7 In the last 40 years in Sultanate of Oman Hospital beds (2 hospitals) Hospital beds Hospital beds Hospital beds (49 hospitals) Population increase 1970: : 3,219,775 The Royal Hospital Muscat

8 The Challenge Many pharmaceuticals, radioactive elements, chloroorganics survive the conventional wastewater treatment (biological treatment). Many drugs are persistent High levels were detected in effluents from WWTP Levels detected in surface water, ground water, soil Accumulation in vegetables and crops Lillenberg M, Litvin S V, Nei L, Roasto M, Sepp K., Enrofloxacin and ciprofloxacin uptake by plants from soil. Agronomy Research, 8:

9 Date palm leaflets ~180,000 tons of palm leaflets are produced annually with no use El-Shafey E. I., Al-Lawati H., Al-Sumri A., Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets. J. Environ. Sci. 24 (2012) in press

10 Limitation of Activated Carbons Non selective for organics Depends on the surface area Slow adsorption Limited capacity

11 Chemical classification of pharmaceuticals Acidic: like Ibuprofen Basic Chloropheniramine Zwittter-ion: Levofloxacin

12 Objectives To provide tailored carbon surfaces for pharmaceutical control Acidic carbons for basic drugs and amphoteric Basic carbons for acidic drugs and amphoteric Hydrophobic carbon for less ionized Carbon characterization Test for drug removal Assemble a filter for pharmaceuticals

13 AC functionalization

14 SEM

15 FTIR - ACs

16 TGA- ACs

17 DTA- ACs

18 Surface chemistry ACs Surface functionality (meq/g) Surface Carbon ph zpc (meq/100g) CEC carboxyl lactone phenol carbonyl basicity (meq/g) AC OAC BAC-EDA BAC-PDA HAC-EA HAC-AN

19 Surface Area & porosity Carbon BET Surface area (m 2 /g) V t D (A o ) Mesopore Micropore V micro V meso (ml/g) surface area surface area (ml/g) (ml/g) (m 2 /g) (m 2 /g) Apparent density (g/cm 3 ) AC OAC BAC-EDA BAC-PDA HAC-EA HAC-AN

20 Pore size distribution AC OAC

21 Methylene Blue - Equilibrium

22 Kinetics constants Carbon Pseudo second order model rate const k 2, Initial adsorption q e (mg/g) R 2 (g/mg / hr) rate, h, (mg/g/hr) AC OAC BAC-EDA BAC-PDA HAC-EA HAC-AN HACs > OAC > AC is rate of reaction

23 Methylene Blue - Equilibrium

24 Capacity Adsorbent Langmuir Constants Correlation Freundlich Constants Correlation q (mg/g) b (L/mg) value, R 2 1/n K (L 1/n mg 1- Values, R 2 1/n g -1 ) AC OAC BAC-EDA BAC-PDA HAC-EA HAC-AN HAC-EA > OAC >> AC > BACs El-Shafey, E.I., Ali, S.N., Al-Busafi, S. and Al-Lawati, H.A., Preparation and characterization of surface functionalized activated carbons from date palm leaflets and application for methylene blue removal. Journal of Environmental Chemical Engineering, 4(3), pp citation (google scholar)

25 CPM sorption - kinetics

26 Kinetics parameters Sorbent Temp. Pore diffusion constant, k d (mg/g / hr 0.5 ) k 2 Pseudo second order model E a, Initial (g/mg/hr) adsorption (mg/g) rate, h, (mg/g/hr) q e R 2 (kj/mol) AC 25 o C o C OAC 25 o C o C BAC 25 o C o C HAC 25 o C o C Faster HAC> OAC > AC > BAC

27 CPM - equilibrium

28 Equilibrium Data CPM Carbon Temperature HWW AC OAC BAC HAC Faster HAC> OAC > AC > BAC

29 Hospital wastewater sample collection

30 Column work

31 Equilibrium Data IBU Carbon Temperature HWW AC OAC BAC HAC

32 Levofloxacin Equilibrium Data Carbon Temperatue HWW AC OAC BAC HAC

33 DC functionalization for pharmaceuticals

34 DC functionalization for heavy metals and radionuclides El-Shafey, E.I., Al-Lawati, H.A., Al-Busafi, S. and Al-Shiraiqi, B., Removal of Zn2+ and SO42 from aqueous solutions on acidic and chelating dehydrated carbon. Environmental Science and Pollution Research, pp.1-12.

35 Cationic & anionic exchangers DC O OH OH H O O HO O O 200 o C H 2 SO 4 Palm Leaflets Dehydrated Carbon (DC) NH 2 N H 2 N H 2 (65-70 o C) SOCl 2 O NH OH H N O H N O O O Cl OH Cl O Cl O O H 2 NCH 2 CH 2 CH 2 NH 2 90 o C BDC (primary amine) HCHO / HCOOH 30 o C 90 o C Pyridine O OH S O H 2 N H 3 C N CH 3 CH 3 H 3 C N H 3 C N CH 3 O H O S O H O O S O O H O S O H N O OH H N O H N O O NH O OH NH O NH O O BDC ( tertiary amine) SDC El-Shafey, E.I., Al-Busafi, S., Al-Lawati, H.A. and Al-Shibli, A.S., Removal of Cu 2+ and SO 4 2 from aqueous solutions on surface functionalized dehydrated carbon from date palm leaflets. Journal of Water Process Engineering, 15, pp

36 Conclusions Modified activated carbons: Larger Capacity Faster Removal Faster sorption Better breakthough curves regardless of the low surface area. Expected to have a role in the future

37 Acknowledgements TRC project for fund (RC/SCI/CHEM13/01) Dr haider Al-Lawati Dr Saleh Al-Busafi Syeda Nahed Furqan Ali, Amira Al-Shiraiqi, Amira Al-Moqrashi, Aisha Al-Shibli, Badriya Al-Shiraiqi

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