The Chemical Fate & Suggested Removal Technologies of Pharmaceutical Residues within the Israeli Aquatic Environment

Transcription

1 Wastewater Reuse Applications and Contaminants of Emerging Concern- September 13-14, Cyprus The Chemical Fate & Suggested Removal Technologies of Pharmaceutical Residues within the Israeli Aquatic Environment D. Avisar, and his research group Tel Aviv University 1

2 In addition to worldwide severe water scarcity (quantities), the issue of WATER QAULITY IS DRAMATICALLY AFFECT PUBLIC HEALH! 2

3 Drinking water and wastewater may contain toxic chemicals at very low concentrations such as herbicides, pesticides, dioxins, pharmaceuticals and more. These pharmaceuticals are not regulated and traditional treatments do little to break them down. These compounds may cause an adverse effects on various ecosystems and possibly on human. 3

4 Main Sources & pathways Animal Farming. 4

5 Fish ponds From the animal farming source: The aquaculture is one of the main contributors of antibiotic residues to the environment Lalumera et al (2004) found that 75% of the given drug is released from the fish body through secretions as a non-metabolite molecule and then directly discharge to the aquatic environment. 5

6 Mediterranean Sea In Israel. The intensive aquaculture industry mostly located above the sandy, phreatic coastal aquifer, a major drinking water source. Mt. Carmel 6

7 Study Area-Detailed B Locate up flow, but.. M/2 is intensively pumping production well, creating a local cone of depression Treatment Facility TC Discharge Pond B 7

8 Selected Antibiotic H CH3 H H3C H H CH3 N H Class: Tetracyclines Antibiotic: xytetracycline NH2 Symbol: TC MW: 460 g/mol Chemical Formula: C22H24N29 H H H TC is an antibiotic commonly used for veterinary therapy in aquaculture, mainly as a growth promoter and to prevent infections. Tetracycline's are strong chelators that sorb strongly to soil (Lindsey et al, 2001, Primor, 2008, Avisar et al, 2009). Studies indicated that these molecules are preferentially partitioning into solid phase rather than water 8

9 Main objective This study examines the potential recharge of TC towards groundwater wells located in a vicinity to a fish pond (B), which functioned as point source for antibiotic pollution. 9

10 14 days- pond resident time Results demonstrated: A rapid infiltration rate towards the local Groundwater Peak First arrival TC detected: 33 up to 110 ng/l For 55 days in local groundwater 10

11 Suggested mechanisms for TC Contamination 11

12 Summary and Conclusions: This study demonstrates the potential of groundwater contamination by antibiotic residues originated from aquaculture. Tetracycline group is highly considered as a potential human teratogenicity factor, which may cause deformations to fetus (Friedman et al, 1990; Schardein J.L., 2000). The TC which usually considered as an immobile compound (strongly absorbed), shows a relatively rapid mobility, by traveling trough the pond floor and the aquifer beds towards the local groundwater due to: The specific and unique hydrological conditions which developed under fish pond B (e.g. preferential saturated flow path), enable fraction of the TC to leak and rapidly reach to groundwater. 12

13 Antibiotics and their DP s: Detected antibiotics: Sulfamethoxazole- S.E.-700 ng/l; G.W. 40 ng/l Erythromycin DP s S.E.-700 ng/l; G.W. 40 ng/l Amoxicillin DP s S.E.-700 ng/l; G.W. 40 ng/l Avisar, D. Lester Y. and Ronen, D Sulfamethoxazole Detected in a Deep Phreatic Aquifer beneath Effluent Irrigated Land. The Science & the total Environment. Vol. 407,

14 Worldwide Traditional treatments do not sufficiently break down these chemicals World Health rganization: Nowadays, even the best tertiary treatment does little to disable antibiotics activity in water Thus, in some cases we need to develop technologies for treatment of contaminated waters and effluents 14

15 Suggested removal solutions: 1) ph induced direct photolysis: Multi-contaminant water treatment 'series' configuration- Example: 15

16 ph induced direct photolysismulti-contaminant water treatment- Avisar, D., Lester Y. and Mamane, H. (2010), Journal of Hazardous Materials. 175, Lester, Y., Mamane, H. and Avisar, D Removal of micropollutants from groundwater, using UV light and ph modification. Water, Air & Soil Pollution. 223, 4,

17 2) 3 based APs: Degradation of Cyclophosphamide (CPD) and Ciprofloxacin (CIP) 3+H H22 2 H + 32 H + Pollutant Lester, Y., Avisar, D. and Mamane, H. zone Degradation of Cyclophosphamide Effect of Alkalinity and Key Effluent rganic Matter Constituents. zone Science & Engineering (Accepted). Product Ln degradation CIP 0 CPD 0 CIP 0.2 CPD Time (min)

18 3) Combined Treatment: UV / H22 / 3 UV/H22 H H Degradation of Cyclophosphamide 3/H22 0 UV/H22 H H Pollutant H Ln degradation UV/H22 UV/3 3 UV/H22/ UV UV/3 UV/H22 UV/3/H Lester, Y., Avisar, D. and Mamane, H Removal of Pharmaceuticals Using Combination of UV/H22/3 Advanced xidation Process. Wat.Sci.Tech. DI: /wst Time (min) 18

19 Combination of technologies H22 Feed Tank Biological treatment (e.g. membrane bio-reactor) Acid 3 reactor Base UV reactor ph Induced 19

20 Thousands have lived without love. Not one without water. W.H. Auden ( ) Thank you for your attention 20

21 Erythromycin : possible degradation path in the aquatic environments Erythromycin (ERY) 10 H 3 C CH H H H 3 C H 3 C 12 8 CH 3 13 H 7 H N CH H 3 C CH CH CH H 3 C 5 H CH 3 CH 3 MW=733 -H 2 ERY Spiro ketal product ERY H 2 (other products) hν 2 MW=715 ERY-N-oxide 10 H 3 C CH H H H 3 C H 3 C 12 8 CH 3 13 H 7 H N CH H 6 3 C CH CH CH H 3 C 6 5 H 4 CH 3 CH 3 -H 2 ERY-N-oxide Spiro ketal product ERY-N-oxide H 2 (other products) MW=749 MW=731

22 LC/MS chromatograms of ERY degradation products in groundwater (Glil Yam) (instrument MSMS-Executive, Thermo, high resolution) Relative Abundance Relative Abundance Relative Abundance Relative Abundance RT: m/z= RT: 5.27 AA: RT: 6.34 AA: RT: 3.42 RT: 4.44 AA: AA: RT: 4.87 AA: m/z= ERY-N-oxide H2 ~10 ppt RT: 5.87 AA: RT: 3.09 AA: ERY H2 ~5 ppt NL: 3.50E5 m/z= MS ICIS w_o_spike_1 NL: 3.00E5 m/z= MS w_o_spike_1 ERY N/D NL: 2.50E5 m/z= MS ICIS w_o_spike_1 m/z= RT: 4.08 AA: ERY-N-oxide ~20 ppt m/z= Time (min) NL: 2.50E5 m/z= MS ICIS w_o_spike_1 22

23 Diketopiperazine = metabolite of Amoxicillin The most consuming antibiotic for human therapy! 1,160 ng/l Measured in Wastewater 60 ± 15 ng/l Measured in S. Effluent ADP H H H S N H NH2 N C H3 C H3 C H Lamm, A., Gozlan, I., Rotstein, A., and Avisar, D Detection of amoxicillin-diketopiperazine-2', 5' in wastewater samples, J. Environ. Sci. Health, Part A. Vol.44, No

24 HPLC chromatogram of Amoxicillin degradation products AMX ADP6 ADP3 ADP5 ADP4 ADP9* ADP8* H H H H N N H H2N NH2 H2N H S N + - CH3 H NH H H H N H S N CH3 H S CH3 H Toxic and detected in G.W! HN NH HN CH3 H HN H3C CH3 NH H S CH3 CH3 H Gozlan, I. and Rotstein, A., and Avisar, D Investigation of Amoxicillin xidative Degradation Product in Environmental Condition Using Natural Sun and zonation Process. Environmental Chemistry. 7,5,