Study of the Influence of the Wastewater Matrix in the Adsorption of Three Pharmaceuticals by Powdered Activated Carbon

The use of powdered activated carbon (PAC) as an absorbent has become a promising option to upgrade wastewater treatment plants (WWTPs) that were not designed to remove pharmaceuticals. However, PAC adsorption mechanisms are not yet fully understood, especially with regard to the nature of the wastewater. In this study, we tested the adsorption of three pharmaceuticals, namely diclofenac, sulfamethoxazole and trimethoprim, onto PAC under four different water matrices: ultra-pure water, humic acid solution, effluent and mixed liquor from a real WWTP. The adsorption affinity was defined primarily by the pharmaceutical physicochemical properties (charge and hydrophobicity), with better results obtained for trimethoprim, followed by diclofenac and sulfamethoxazole. In ultra-pure water, the results show that all pharmaceuticals followed pseudo-second order kinetics, and they were limited by a boundary layer effect on the surface of the adsorbent. Depending on the water matrix and compound, the PAC capacity and the adsorption process varied accordingly. The higher adsorption capacity was observed for diclofenac and sulfamethoxazole in humic acid solution (Langmuir isotherm, R2 > 0.98), whereas better results were obtained for trimethoprim in the WWTP effluent. Adsorption in mixed liquor (Freundlich isotherm, R2 > 0.94) was limited, presumably due to its complex nature and the presence of suspended solids

Activated carbon coupled with advanced biological wastewater treatment: A review of the enhancement in micropollutant removal

This study consists of a review on the removal efficiencies of a wide spectrum of micropollutants (MPs) in biological treatment (mainly membrane bioreactor) coupled with activated carbon (AC) (AC added in the bioreactor or followed by an AC unit, acting as a post treatment). It focuses on how the presence of AC may promote the removal of MPs and the effects of dissolved organic matter (DOM) in wastewater. Removal data collected of MPs are analysed versus AC dose if powdered AC is added in the bioreactor, and as a function of the empty bed contact time in the case of a granular activated carbon (GAC) column acting as a post treatment. Moreover, the enhancement in macropollutant (organic matter, nitrogen and phosphorus compounds) removal is analysed as well as the AC mitigation effect towards membrane fouling and, finally, how sludge properties may change in the presence of AC. To sum up, it was found that AC improves the removal of most MPs, favouring their sorption on the AC surface, promoted by the presence of different functional groups and then enhancing their degradation processes. DOM is a strong competitor in sorption on the AC surface, but it may promote the transformation of GAC in a biologically activated carbon thus enhancing all the degradation processes. Finally, AC in the bioreactor increases sludge floc strength and improves its settling characteristics and sorption potential

Identification of Crizotinib Major Degradation Products Obtained Under Stress Conditions by RP-UHPLC-HRMS

The pharmaceutical industry routinely performs stability testing on new compounds before they are marketed to ensure their efficacy, quality, and safety. The focus of this study was to apply forced degradation as one of the stability testing methods to investigate the stability of crizotinib, an anticancer drug, and to gain insight into the degradation pathway and degradation products formed. The forced degradation study for crizotinib was performed under acidic and alkaline hydrolysis, oxidation, photolysis and thermal conditions. Drug degradation was observed under oxidative conditions. The structures of the three major degradation products formed by oxidative degradation were identified and characterized by UHPLC/QTOF/MS/MS studies and their possible fragmentation pathways were suggested. The toxicity evaluation of the tested compound and its proposed degradation products was also estimated using the computer program TEST (Toxicity Estimation Software Tool). This work is licensed under a Creative Commons Attribution 4.0 International License

A thorough analysis of the occurrence, removal and environmental risks of organic micropollutants in a full-scale hybrid membrane bioreactor fed by hospital wastewater

The recent draft of the Urban Wastewater Treatment Directive pays attention to contaminants of emerging concern including organic micropollutants (OMPs) and requires the removal of some of them at large urban wastewater treatment plants (WWTPs) calling for their upgrading. Many investigations to date have reported the occurrence of a vast group of OMPs in the raw influent and many technologies have been tested for their removal at a lab- or pilot-scale. Moreover, hospital wastewater (HWW) may contain specific OMPs at a high concentration and therefore its treatment deserves attention. In this study, a 1-year investigation was carried out at a full-scale membrane bioreactor (MBR) treating mainly HWW. To promote the removal of OMPs, powdered activated carbon (PAC) was added to the bioreactor at 0.1 g/L and 0.2 g/L which resulted in the MBR operating as a hybrid MBR. Its performance was tested for 232 target and 90 non-target OMPs, analysed by UHPLC-QTOF-MS using a direct injection method. The wastewater arriving at the WWTP was characterized and the performance of both the MBR and hybrid MBR was assessed for: key OMPs selected on the basis of their frequency, occurrence, persistence to removal, bioaccumulation and toxicity; OMP classes; and the whole list of OMPs. Finally, an environmental risk assessment of the OMP residues was conducted by means of the risk quotient approach. The results indicate that PAC addition increased the removal of most of the key OMPs (e.g., sulfamethoxazole, diclofenac, lidocaine) and OMP classes (e.g., antibiotics, psychiatric drugs and stimulants) with the highest loads in the WWTP influent. The hybrid MBR also reduced the risk in the receiving water as the PAC dosage increased mainly for spiramycin, lorazepam, oleandomycin. Finally, uncertainties and issues related to the investigation being carried out at full-scale under real conditions are discussed in depth

Chromatographic Analysis in the Quality System of Analytical Process in the Department of Analytical Chemistry of The Faculty of Chemical Engineering and Technology

Bez analitičke kemije nemoguće je zamisliti napredak mnogih područja ljudske djelatnosti. Spomenuti značaj ove grane kemije jedan je od glavnih razloga uspješnog opstanka i kontinuiranog razvoja Zavoda za analitičku kemiju unutar jednog tehničkog fakulteta, kao što je današnji Fakultet kemijskog inženjerstva i tehnologije (FKIT) Sveučilišta u Zagrebu. Dinamičnost razvoja analitičke kemije bila je neprestani poticaj nastavnicima Zavoda za prilagođavanjem svjetskim trendovima i sustavnim unaprjeđenjem nastavnog programa i istraživačkog rada. Početak nastavnog, znanstvenog, ali i stručnog djelovanja Zavoda temeljio se na klasičnim metodama analize, no potaknuta razvojem moderne analitičke opreme ubrzo se intenzivirala primjena brojnih kemijskih i fizikalno-kemijskih metoda analize, od kojih je danas najzastupljenija kromatografija. Naime, konac dvadesetog stoljeća ubrzanim je razvojem instrumentalnih tehnika, uvođenjem računala i činjenicom da su podatci analitičkih mjerenja postali temelj odlučivanja u medicini, zaštiti okoliša, razvoju materijala te osiguravanju kvalitete procesa i proizvoda, dao novi uzlet analitičkoj kemiji, a osobit procvat doživjela je kromatografija kao idealna tehnika za višekomponentnu analizu analita u tragovima. Ovo djelo je dano na korištenje pod licencom Creative Commons Imenovanje 4.0 međunarodna.Without analytical chemistry, it is impossible to imagine the progress of many areas of human activity. The aforementioned importance of this chemistry branch is one of the main reasons for the successful survival and continued development of the Department of analytical chemistry within a technical faculty, such as is the present-day Faculty of Chemical Engineering and Technology (FCET) University of Zagreb. The dynamics of the development of analytical chemistry was a constant encouragement to the teachers of the Department to adapt to world trends, and systematically improve the curriculum and research work. The beginning of the teaching, the scientific, as well as the professional activities of the Department of Analytical Chemistry was based on classical methods of analysis. However, stimulated by the development of modern analytical equipment, the application of numerous chemical and physicochemical methods of analysis was intensified, of which the most common being chromatography. Namely, the end of the twentieth century accelerated the development of instrumental techniques, the introduction of computers, and the fact that analytical measurement data became the basis of decision-making in medicine, environmental protection, material development, and assuring the quality of processes and products gave rise to analytical chemistry, especially chromatography, which is an ideal technique for multicomponent trace analyte analysis. This work is licensed under a Creative Commons Attribution 4.0 International License

Miniaturized analytical methods for determination of environmental contaminants of emerging concern - a review

The determination of contaminants of emerging concern (CECs) in environmental samples has become a challenging and critical issue. The present work focuses on miniaturized analytical strategies reported in the literature for the determination of CECs. The first part of the review provides brief overview of CECs whose monitoring in environmental samples is of particular significance, namely personal care products, pharmaceuticals, endocrine disruptors, UV-filters, newly registered pesticides, illicit drugs, disinfection by-products, surfactants, high technology rare earth elements, and engineered nanomaterials. Besides, an overview of downsized sample preparation approaches reported in the literature for the determination of CECs in environmental samples is provided. Particularly, analytical methodologies involving microextraction approaches used for the enrichment of CECs are discussed. Both solid phase- and liquid phase-based microextraction techniques are highlighted devoting special attention to recently reported approaches. Special emphasis is placed on newly developed materials used for extraction purposes in microextraction techniques. In addition, recent contributions involving miniaturized analytical flow techniques for the determination of CECs are discussed. Besides, the strengths, weaknesses, opportunities and threats of point of need and portable devices have been identified and critically compared with chromatographic methods coupled to mass chromatography. Finally, challenging aspects regarding miniaturized analytical methods for determination of CECs are critically discussed

Opinion paper about organic trace pollutants in wastewater: Toxicity assessment in a European perspective

This opinion paper focuses on the role of eco- toxicological tools in the assessment of possible impacts of emerging contaminants on the aquatic ecosystem, hence, on human health. Indeed, organic trace pollutants present in raw and treated wastewater are the pivot targets: a multidisciplinary approach allows defining the basic principles for managing this issue, from setting a proper monitoring campaign up to evaluating the optimal process treatment. Giving hints on trace pollutants fate and behavior, attention is focused on the choice of the bioassay( s), by analyzing the meaning of possible biological answers. Data interpretation and exploitation are detailed with the final goal of providing criteria in order to be able to select the best-targeted treatment options. The manuscript deals with conventional and innovative analytical approaches for assessing toxicity, by reviewing laboratory and field assays ; illustrative real scale and laboratory applications integrate and exemplify the proposed approach