Urban water management and Water demand management May 16-20th, 2014 / Antalya, Turkey Persistent Organic Pollutants and Pharmaceutical Residues in Selected Water Dams in Jordan Background • A vast array of pharmaceuticals including antibiotics, pain killers, mood stabilizers and sex hormones have been found in the water supplies • To be sure, the concentrations of these pharmaceuticals are tiny especially in drinking water, they are measured in quantities of parts per billion or trillion, far below the levels of a medical dose to be sure that the water is safe to be used. 2 5/18/2014 How do the drugs get into the water • People take pills. Their bodies absorb some of the medication, but the rest of it passes through and is flushed down the toilet. • while researchers do not yet understand the exact risks from decades of persistent exposure to random combinations of low levels of pharmaceuticals, recent studies which have gone virtually, unnoticed by the general public, have found alarming effects on human cells and wildlife. • People think that if they take a medication, their body absorbs it and it disappears, but of course that's not the case," said EPA scientist Christian Daughton, one of the first to draw attention to the issue of pharmaceuticals in water 3 5/18/2014 What was Investigate in Jordan pharmaceutical residue in selected dams in Jordan Other POP such as PAHs Phenols, PCB, CB, chlorinated pesticides residues and other parameters 4 5/18/2014 General Objectives i. Contribution to the sustainable management of water resources in Jordan. ii. Focusing on national capacity building in the fields of persistent organic pollutants and pharmaceutical residues through exchange of knowledge and experience with international research institution in Germany. iii. To fulfill the knowledge gaps concerning the presence of pharmaceutical and POPs residues in Jordanian environment. iv. To evaluate the current status of water and sediments quality in water reservoirs. v. To evaluate the dams water quality in terms of its microbial parameters. vi. Starting a new area of research in water quality in Jordan dealing with pharmaceutical and POPs residues 5 5/18/2014 Specific Goals Determination of persistent organic pollutants concentration in dam’s water and sediments Determination of environmental hazardous materials in term of pharmaceutical residues and microbial contamination. To establish a baseline for POPs and pharmaceutical residues in some Jordanian dams Investigate the impact of pharmaceutical residues on emerging of antibiotic resistant bacteria. 6 5/18/2014 Rainfall and Runoff Runoff annually amount = 733 MCM Amount can be stored = 534 MCM Current amount stored = 360 MCM in 14 Dams Study target dams Dam Capacity (MCM) King Tala Dam (KTD) 82 Al Mujeb Dam (MD) 35 Tannour Dam (TD) 17 7 5/18/2014 Dams in Jordan Jordan is among the ten most water stressed countries in word ,dam construction was on the top priority of the Jordan development plans . Six dams were constructed in the north and middle Jordan valley with a total storage capacity of 160 MCM . These dams include Arab , Ziglab , King Talal ,Karameh ,Shueib and Kafrein . Three other dams (Wala, Mujib and tannur ) were constructed in the southern Ghors with a total live storage of 30 MCM .Stored water from these dams is used8 for livestock and ground water recharge . 5/18/2014 KTD MD TD 9 Location s Map 5/18/2014 Mujib DAM Location On Wadi Mujib ,100 km south ofAmman Construction Construction Completed in 2003 Total cost 45 MJD Height 62 M Storage capacity 31.2 MCM Annual yield 17 MCM Purpose Municipal & industrial supply and irrigation 10 5/18/2014 Tannur DAM Location On Wadi Hassa ,175 km south of Amman Construction Construction Completed in 2001 Total cost 23 MJD Height 60 m Storage capacity 16.8 MCM Annual yield 8 MCM Purpose Irrigation 11 5/18/2014 King Talal DAM Location At Zarqa River Construction Completed in 1977, raised in 1987 Total cost 34 MJD Height 108 m Storage capacity 74 MCM Purpose Irrigation 12 5/18/2014 Sample Collection Bottom Water Sediments 13 5/18/2014 KTD Zarqa River 14 5/18/2014 Tannour Dam (TD): Sediment Sample Collection 15 5/18/2014 16 5/18/2014 Chemical and Biological Analyses 1. Polynuclear Aromatic Hydrocarbons PAHs. 2. Polychlorinated Biphenyls PCBs (PCB 28, PCB 52, PCB 101, PCB138, PCB 152 and PCB 180). 3. Chlorinated benzenes CBs (Pentachlorobenzene and Hexachlorobenzene) 4. Phenols and Chlorinated Phenols (o-Cresol, p-Cresol, 2,4- Dimethylphenol, 2,6-Dichlorophenol, 2,3,5-Trichlorophenol, 2,4,5- Trichlorophenol, 2,3,4-Trichlorophenol, 2,3,5,6-Tetrachlorophenol, 2,3,4,6-Tetrachlorophenol, and 4,6-Dinitro-o-cresol) 5. Chlorinated pesticides. 6. Liquid Chromatography Mass Spectrometry (LC/MS/MS) survey on Pharmaceutical Residues (sulfonamides, tetracyclines ,etc(. 7. General physical and chemical parameters of water samples such as electrical conductivity EC, pH, TDS, TSS, BOD5, COD, DO, Temp., salinity and electrical potential (mV). 8. Bulk sediment properties including organic carbon content, nitrogen, sulfur, phosphorus, and texture. 9. Identification of bacterial strains and look for their biological activity of 17 5/18/2014 dectected compounds. Results 18 5/18/2014 Detected PAHs concentrations in mg/L in water and mg/kg in sediments collected from King Talal Dam during summer season PAH Type Min Max Mean % of detected samples Fluorene 0.50 0.73 0.62 17% Phenanthrene 0.01 0.90 0.15 100% Anthracene 0.01 0.10 0.05 17% pyrene 0.01 0.01 0.01 9% Benzo(a) anthracene 0.02 0.04 0.03 17% Benzo(b) Fluoranthene 0.14 0.20 0.17 17% Water Benzo(g,h,i) perylene 0.01 0.02 0.01 25% ∑PAH 0.02 1.79 0.29 LMW/HMW 0.04 42.77 7.68 ANT/178 0.10 0.18 0.14 PHE/ANT 4.42 9.38 6.90 Fluorene 1.82 21.21 8.72 60% Phenanthrene 0.17 22.56 8.35 100% Anthracene 0.10 45.80 8.38 70% Pyrene 0.12 1.21 0.63 50% Benzo(a) anthracene 1.15 3.21 2.27 30% Chrysene 0.78 3.51 2.26 40% Benzo(b) Fluoranthene 5.56 8.10 6.83 20% Benzo(K) Fluoranthene 1.04 8.20 4.62 20% Sediments Benzo(g,h,i) perylene 0.21 8.21 2.93 90% ∑PAH 0.59 74.12 26.34 LMW/HMW 0.06 16.91 4.28 ANT/178 0.10 0.72 0.37 BaA/228 0.48 0.60 0.52 19 5/18/2014 PHE/ANT 0.38 8.78 3.27 Detected PAHs concentrations in mg/L in water and mg/kg in sediments collected from King Talal Dam during winter season % of detected PAH Type Min Max Mean samples Acenaphthene 2.58 6.73 4.63 60% Fluoroanthene 1.44 84.91 43.18 40% Fluorene 1.57 2.96 2.37 100% Phenanthrene 2.59 2.59 2.59 20% Benzo(a)pyrene 0.62 1.04 0.85 60% Chrysene 0.94 4.59 2.25 60% Dibenzo(a,h)anthracene 1.34 1.34 1.34 20% Benzo(k)fluoranthene 1.11 2.16 1.79 100% Benzo(a)anthracene 1.03 1.67 1.36 100% Water Benzo(b)fluoranthene 0.68 1.93 1.29 60% Indeno(1,2,3-c,d)pyrene 4.22 79.26 26.01 100% pyrene 1.26 1.26 1.26 20% ∑PAH 15.51 179.05 55.24 LMW/HMW 0.045 1.270 0.667 BaA/228 0.18 0.58 0.44 Fla/Fla+Pyr 0.985 1.000 0.993 Acenaphthene 33.76 133.21 83.49 66% Acenaphthylene 145.16 148.27 146.72 66% Anthracene 6.16 7.89 7.03 66% Benzo(a)anthracene 196.86 196.86 196.86 33% Chrysene 17.43 252.07 134.75 66% Fluoroanthene 14.69 17.69 16.46 100% Fluorene 19.41 25.62 22.52 66% Naphthalene 14.82 19.13 16.98 66% Phenanthrene 14.74 16.89 15.47 100% pyrene 22.33 28.86 25.60 66% Dibenzo(a,h)anthracene 16.20 27.00 21.60 66% Indeno(1,2,3-c,d)pyrene 62.89 62.89 62.89 33% Sediments Benzo(b)fluoranthene 9.61 26.35 17.98 66% Benzo(k)fluoranthene 46.89 1184.19 615.54 66% Benzo(g,h,i)perylene 14.63 17.36 16.00 66% Benzo(a)pyrene 11.06 11.06 11.06 33% ∑PAH 115.25 1525.50 860.99 LMW/HMW 0.17 4.80 1.72 ANT/178 0.19 0.29 0.24 20 BaA/228 0.39 0.64 0.52 5/18/2014 IcdP/(IcdP+FLA) 2.46 4.16 3.31 Summer Winter 1000 100 10 1 0,1 Concentration of PAHs in ppb of PAHs Concentration 0,01 Water Sediments Water Sediments Water Sediments King Talal Dam Mujeb Dam Tanour Dam Dams site and season PAHs concentration ppb during the summer and winter for three dams 21 5/18/2014 List of Target Pharmaceutical Compounds Compound Abbreviation Carbamazepien CBZ Sulfamethoxazole SMX Erythromycin (Total) ERY-H2O Ibuprofen IBU Naproxen NAP Diclofenac DIC Ketorolac KET Ketoprofen KTP 22 5/18/2014 Concentration range (Water ng/L, sediment ng/kg) of Human Pharmaceuticals in the surface water and sediment of Jordan dam's samples (first and second sampling periods 2011 and 2012) King Talat Dam (KTD), Mujib Dam (MD), and Tanour Dam (TD). Summer period 2012 Analyte Sample type ERY-H2O CBZ KTP KET SMX DIC IBU NAP 1050- nd nd nd nd 112-180 KTD water 3-50 1490 6-366 MD water blq blq nd nd blq blq nd nd TD water blq blq nd nd blq blq nd nd KTD sediment blq 740-5352 nd nd blq blq blq blq MD sediment blq blq nd nd blq blq blq blq TD sediment blq blq nd nd blq blq blq blq Winter period 2012 Analyte Sample type ERY-H2O CBZ KTP KET SMX DIC IBU NAP KTD water 82-3241 131-2026 nd nd 51-132 blq nd 53-493 MD water nd blq nd nd nd nd nd nd TD water nd nd nd nd nd nd nd nd KTD sediment 100-1100 300-7500 nd nd nd nd nd nd MD sediment nd nd nd nd nd nd nd nd TD sediment nd nd nd nd nd nd nd nd 23 5/18/2014 KTD Summer period water (ng/L) sediment (ng/kg) 4000 3046 3000 2000 1270 concentration 1000 0 0 16 0 0 0 0 0 171 0 0 0 0 0 146 sedimen… water… pharmaceutical compound 24 5/18/2014 KTD Winter Period water (ng/L) sediment (ng/kg) 5000 3900 4000 3000 600 2000 1661,5 concentration 1000 1078,5 0 0 0 0 0 0 0 91,5 0 0 0 ERY-H2O 0 273 CBZ KTP KET water… SMX DIC IBU pharmaceutical compound NAP 25 5/18/2014 Levels of the studied pharmaceuticals in surface water in different countries in ng/L Location Surface water Reference ) ng/L ( Carbamazepine Austria