Analysis of Pharmaceuticals in Influents of Municipal Wastewater Treatment Plants in Jordan

Grab samples were collected in the summer to characterize selected pharmaceuticals and personal care products (PPCPs) in the influent of two wastewater treatment plants (WWTPs) in Jordan. Liquid chromatography tandem mass spectrometry (LC–MS/MS) was utilized to determine the concentrations of 18 compounds of PPCPs. Among all of the PPCPs analyzed, eight compounds were detected in the influent samples (1,7-dimethylxanthine, acetaminophen, caffeine, carbamazepine, cotinine, morphine, sulfamethoxazole and trimethoprim). However, five compounds (amphetamine, cimetidine, diphenhydramine, methylenedioxyamphetamine (MDA) and sulfachloropyridazine) were not detected in collected samples (below the detection limits

Carbamazepine Co-crystal Screening with Dicarboxylic Acids Co-Crystal Formers

Co-crystal is believed to improve the solubility and dissolution rates and thus, enhanced the bioavailability of poor water soluble drugs particularly during the oral route of administration. With the existing of poorly soluble drugs in pharmaceutical industry, the screening of co-crystal formation using carbamazepine (CBZ) as a model drug compound with dicarboxylic acids co-crystal formers (CCF) namely fumaric (FA) and succinic (SA) acids in ethanol has been studied. The co-crystal formations were studied by varying the mol ratio values of CCF to CBZ to access the effect of CCF concentration on the formation of the co-crystal. Solvent evaporation, slurry and cooling crystallization which representing the solution based method co-crystal screening were used. Based on the differential scanning calorimetry (DSC) analysis, the melting point of CBZ-SA in different ratio was in the range between 188oC-189oC. For CBZ-FA form A and CBZ-FA form B the melting point in different ratio were in the range of 174oC-175oC and 185oC-186oC respectively. The product crystal from the screening was also characterized using X-ray powder diffraction (XRPD). The XRPD pattern profile analysis has shown that the CBZ co-crystals with FA and SA were successfully formed for all ratios studied. The findings revealed that CBZ-FA co-crystal were formed in two different polymorphs. It was found that CBZ-FA form A and form B were formed from evaporation and slurry crystallization methods respectively. On the other hand, in cooling crystallization method, CBZ-FA form A was formed at lower mol ratio of CCF to CBZ and vice versa. This study disclosed that different methods and mol ratios during the co-crystal screening can affect the outcome of co-crystal produced such as polymorphic forms of co-crystal and thereof. Thus, it was suggested that careful attentions is needed during the screening since the co-crystal formation is currently one of the promising approach to be considered in research and development for pharmaceutical industry to improve the poorly soluble drugs.

Development of Molecular Imprinted Polymers (MIPs) for the Selective Removal of Carbamazepine from Aqueous Solution

The occurrence and removal of trace organic contaminants in the aquatic environment has become a focus of environmental concern. For the selective removal of carbamazepine from loaded waters molecularly imprinted polymers (MIPs) were synthesized with carbamazepine as template. Parameters varied were the type of monomer, crosslinker, and porogen, the ratio of starting materials, and the synthesis temperature. Best results were obtained with a template to crosslinker ratio of 1:20, toluene as porogen, and methacrylic acid (MAA) as monomer. MIPs were then capable to recover carbamazepine by 93% from a 10-5 M landfill leachate solution containing also caffeine and salicylic acid. By comparison, carbamazepine recoveries of 75% were achieved using a nonimprinted polymer (NIP) synthesized under the same conditions, but without template. In landfill leachate containing solutions carbamazepine was adsorbed by 93-96% compared with an uptake of 73% by activated carbon. The best solvent for desorption was acetonitrile, with which the amount of solvent necessary and dilution with water was tested. Selected MIPs were tested for their reusability and showed good results for at least five cycles. Adsorption isotherms were prepared with carbamazepine solutions in the concentration range of 0.01 M to 5*10-6 M. The heterogeneity index showed a more homogenous binding site distribution.

Removal of Ciprofloxazin and Carbamazepine by Adsorption on Functionalized Mesoporous Silicates

Ciprofloxacin (CIP) and Carbamazepine (CBZ), nonbiodegradable pharmaceutical residues, were become emerging pollutants in several aquatic environments. The objectives of this research were to study the possibility to recover these pharmaceuticals residues from pharmaceutical wastewater by increasing the selective adsorption on synthesized functionalized porous silicate, comparing with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS), functionalized HMSs (3- aminopropyltriethoxy, 3- mercaptopropyltrimethoxy and noctyldimethyl) were synthesized and characterized physico-chemical characteristics. Obtained adsorption kinetics and isotherms showed that 3-mercaptopropyltrimethoxy functional groups grafted on HMS provided highest CIP and CBZ adsorption capacities; however, it was still lower than that of PAC. The kinetic results were compatible with pseudo-second order. The hydrophobicity and hydrogen bonding might play a key role on the adsorption. Furthermore, the capacities were affected by varying pH values due to the strength of hydrogen bonding between targeted compounds and adsorbents. Electrostatic interaction might not affect the adsorption capacities.

Low-Cost Pre-Treatment of Pharmaceutical Wastewater

Pharmaceutical industries and effluents of sewage treatment plants are the main sources of residual pharmaceuticals in water resources. These emergent pollutants may adversely impact the biophysical environment. Pharmaceutical industries often generate wastewater that changes in characteristics and quantity depending on the used manufacturing processes. Carbamazepine (CBZ), {5Hdibenzo [b,f]azepine-5-carboxamide, (C15H12N2O)}, is a significant non-biodegradable pharmaceutical contaminant in the Jordanian pharmaceutical wastewater, which is not removed by the activated sludge processes in treatment plants. Activated carbon may potentially remove that pollutant from effluents, but the high cost involved suggests that more attention should be given to the potential use of low-cost materials in order to reduce cost and environmental contamination. Powders of Jordanian non-metallic raw materials namely, Azraq Bentonite (AB), Kaolinite (K), and Zeolite (Zeo) were activated (acid and thermal treatment) and evaluated by removing CBZ. The results of batch and column techniques experiments showed around 46% and 67% removal of CBZ respectively.