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Determination of pharmaceutical residues and hormones in wastewater in

Chemicals released into the environment may have endocrine-disrupting effects in living organisms, including humans. The incidence of endocrine-related diseases and adverse physiological effects in wildlife is increasing, and there are indications that changes in the reproductive health of humans, including declining male fertility, birth defects, and breast and testicular cancer, could be linked to exposure to endocrine disrupting chemicals (EDCs). Most EDCs are synthetic organic chemicals (e.g. surfactants, pesticides, pharmaceuticals, brominated flame retardants, PAHs, PCBs, phthalates, etc.) introduced to the environment anthropogenically, although some (e.g. estrone, 17 ß –estradiol, testosterone and androstenedione) occur naturally (Natural hormones) [1-3]. Pharmaceuticals are an important group of potential EDCs which has recently attracted much attention of the international scientific community. They are emerging environmental contaminants, extensively and increasingly being used in human and veterinary medicine [4-5]. Wastewater is major contributors of pharmaceuticals in the environment. Due to their high consumption, pharmaceuticals along with their metabolites are continuously introduced to sewage waters, mainly through excreta, disposal of unused or expired drugs or directly from pharmaceutical discharges. The occurrence of pharmaceuticals and their metabolites and transformation products in the wastewater is becoming a matter of concern [4]. Based on all of the data reviewed on the toxicity of endocrine disrupting chemicals including pharmaceuticals residue and hormones and the effects that could occur to humans at very low levels which may result in adverse impact on human health, the pharmaceuticals residue and hormones in the effluent wastewaters from hospitals, influent and effluent wastewater treatment and effluent wastewater form pharmaceutical companies. Especially in the central part of Jordan (Amman district) should be studied. Aim of the present work.
The main objective of this project is to monitor the pharmaceuticals residue (acids, bases and neutral drugs) and hormones in aqueous environmental samples (wastewaters). This objective will be reached through: 1- Measuring the concentrations of pharmaceuticals of various therapeutic classes and hormones by using liquid chromatography electrospray tandem mass (LC-ES/MS/MS) or gas chromatography/mass spectrometry (GC/MS) in the wastewater collected from different place located in the central of Jordan (Amman). 2- Compared to areas of study with each other and see which areas is more
Literature Review (selected).

Prasse et al (2010) developed a new analytical method for the determination of nine antiviral drugs (acyclovir, abacavir, lamivudine, nevirapine oseltamivir, penciclovir, ribavirin, stavudine, zidovudine) and one active metabolite (oseltamivir carboxylate) in raw and treated wastewater as well as in surface water using LC/ESI tandem MS detection. They found all antiviral drugs, except ribavirin, were detected in raw wastewater. A significant reduction in concentrations was observed for acyclovir, lamivudine, and abacavir in treated wastewater indicating a substantial removal, while nevirapine, zidovudine and oseltamivir were found in similar concentrations in raw and treated wastewater. Concentrations in river waters were in the lower ng/ L range, with a maximum of 190 and 170 ng /L for acyclovir and zidovudine, respectively in the Hessian Ried. Gros et al (2006) described a method for the simultaneous determination of 29 multi-class pharmaceuticals using off line solid phase extraction (SPE) followed by liquid chromatography–triple quadrupole mass spectrometry (LC–MS–MS).the samples were collected from a WWTP located in Rubi (Barcelona, Spain), which receives urban, domestic and industrial wastewaters. they found Anti inflammatories and analgesics, lipid regulators, β-blockers and some antibiotics were the major groups detected in WWTP and among them acetaminophen, ketoprofen, sulfamethoxazole and trimetroprim were the most abundant, with concentrations in high ng/L or low g/L levels. Maximum concentrations were detected for acetaminophen (paracetamol), with average concentration of 10 g/L in WWTP influent and 2.1 g/L in effluent and for antimicrobial trimethoprim (1.1 and 0.29 g/L in WWTP influents and effluents, respectively). Other compounds frequently detected in WWTP samples were carbamazepine and ranitidine, with average concentrations of 400ng/L for carbamezapine in both influent and effluent samples (no elimination) and 188 and 135 ng/L for ranitidine in influent and effluent, respectively. Gomez et al (2006) studied a selection of 16 pharmaceuticals: the anti-epileptic carbamazepine, seven analgesic/anti-inflammatory drugs (mefenamic acid, indomethacine, ibuprofen, naproxen, diclofenac, ketorolac and acetaminophen), the analgesic opiate codeine, two antidepressants (fluoxetine and paroxetine), β - blockers (atenolol and propranolol), antibiotic (trimethoprim, metronidazole, and
erythromycin) and the anti-ulcer ranitidine in hospital effluent wastewaters the
samples were collected from the main sewer of a private health care centre, it is
located in Almeria, a province in the southeast of Spain on the Mediterranean
coast. They found antidepressants paroxetine and fluoxetine were not detected and
the two anti inflammatories, mefenamic acid and indomethacine, were non-
detectable too. Carbamazepine, trimethoprim and erythromycin were detected in
the lowest concentrations in the discharge being in the 10–70ng/L range.
Concentrations of the other pharmaceuticals were in the g/L range in most of the
cases. Ibuprofen and atenolol were detected eventually in the hospital effluents
with a very high concentration, more than 100 g/L, and the anti inflammatories
acetaminophen and ketorolac, the antibiotic metronidazole and the anti-
hypertensive propanolol were present in the samples at relative high concentration
of around 10 g/L.
Samples of influent and effluent from 18 sewage treatment plants (STPs) in 14
municipalities in Canada were analyzed from metcalfe et al (2003). Several neutral
and acidic drugs were detected in effluents, including analgesic/anti-inflammatory
agents, lipid regulators, and an antiepileptic drug, carbamazepine. Analgesic/anti-
inflammatory drugs such as ibuprofen and naproxen, as well as the metabolite of
acetylsalicyclic acid, salicylic acid, were often detected in final effluents at μg/L
concentrations. The acidic lipid regulator, clofibric acid, and the analgesic/anti-
inflammatory drug diclofenac were not detected in any final effluent samples. the
lipid regulators bezafibrate and gemfibrozil were detected in some samples of
influent and effluent. The chemotherapy drugs ifosfamide and cyclophosphamide
and the anti-inflam- matory phenazone were not detected in influent or effluent
samples, but the vasodilator drug pentoxyfylline was detected at ng/L
concentrations in some final effluents.
Ternes (2001) reported, Recently several methods have been developed for the
determination of drugs and their metabolites in the lower ng/l range using solid
phase extraction (SPE), derivatization, detection and confirmation by gas
chromatography/mass spectrometry (GC/ MS) and GC/MS/MS or LC-electrospray
tandem MS (LC-ES/MS/MS). He found In 40 German rivers and streams 31
pharmaceuticals and five metabolites were quantified in at least one sample. The
highest median values were found for bezafibrate with 0.35 μg/L and
carbamazepine with 0.25 μg/L.

Research Methodology & Tools
1- Ordering / Buying required chemicals, standards and material for this 2- Sampling from more than one place of the effluent wastewaters from hospitals, influent and effluent wastewater treatment and effluent wastewater form pharmaceutical companies in Jordan. 3- Samples will be homogenized well and will store at 4oC. 4- Separation and clean-up of pharmaceuticals residue and hormones in wastewater samples by using solid-phase extraction method. 5- Quantification using (LC/MS,MS) and ( GC/MS) 6- Interpretation of results. 7- Calculating the concentration of pharmaceuticals residue and hormones of 8- Assessment of the of pharmaceuticals residue and hormones levels in all Selected References
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2. MJ. Nieuwenh uijsen. Global Nest J. 2005, 7,128– 144.
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Quadrupole-Linear Ion Trap Mass Spectrometry and Time-of-Flight Mass
Spectrometry to the Determination of Pharmaceuticals and Related
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7. D.Löffler, J. Römbke, M.Meller and TH.A.Ternes. Environmental Fate of Pharmaceuticals in Water/Sediment Systems. German Federal Institute of
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