Elucidation of transformation pathway of ketoprofen, ibuprofen, and furosemide in surface water and their occurrence in the aqueous environment using UHPLC-QTOF-MS

Abstract

The identification and determination of transformation products (TPs) of pharmaceuticals is essential nowadays, in order to track their fate in the aqueous environment and, thus, to estimate the actual pollution. However, this is a challenging task due to the necessity to apply high-resolution instruments enable to detect known and unknown compounds. This work presents the use of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) as a powerful tool for the identification of three selected pharmaceuticals, furosemide (FUR), ibuprofen (IBP), and ketoprofen (KET), and their TPs in various water samples. Laboratory degradation experiments were performed using xenon lamp as a source of the irradiation in order to simulate phototransformation processes which may occur in the environment. Furthermore, the photodegradation kinetics of three selected compounds were assessed in a reactor equipped with xenon lamp in river water samples. Five TPs of IBP, seven of KET, and five of FUR were identified; some of them are presented here for the first time. Accurate mass measurements and fragmentation pattern obtained during an LC-QTOF-MS analysis allowed for structure elucidation of TPs followed by the creation of transformation pathway of selected pharmaceuticals. Finally, different water samples (wastewater influent and effluent, river water, untreated and treated water) were analyzed in order to estimate the presence of parent and transformed compounds. Only KET was detected in untransformed form in considered samples. Most of the TPs of selected drugs were found at least once in all water samples. Although IBP and FUR were not present in water samples as parent compounds, their different TPs occur. A great potential of LC-QTOF-MS in the identification and structural elucidation of TPs in the environment, allowing the recognition of the fate of pharmaceuticals in the environment through the determination of transformation pathway, has been presented.Phototransformation of three selected pharmaceuticalsElectronic supplementary materialThe online version of this article (doi:10.1007/s00216-014-7614-1) contains supplementary material, which is available to authorized users.

Monitoring and Ecotoxicity Assessment of Emerging Contaminants in Wastewater Discharge in the City of Prague (Czech Republic)

“…Tramadol in particular is more soluble in water (1151 mg/L at 25 • C) [55] than furosemide (73.1 mg/L at 30 • C) [56] and hydrochlorothiazide (722 mg/L at 25 • C) [56]. Additionally, chemical degradation by light exposition is different for each compound, e.g., furosemide was quickly degraded (0.5 to 1.5 h) under artificial light or diffused daylight [57], whereas hydrochlorothiazide and tramadol persisted after 5 to 168 h under irradiation (150 W) at room temperature [58], Hg lamp, or direct sunlight [59]. Our results indicate that furosemide was more toxic than hydrochlorothiazide and tramadol, despite its quick degradation, suggesting its transformation products may be also responsible for the reduction in A. salina survival.…”

Analytical methodologies for the determination of pharmaceuticals and personal care products (PPCPs) in sewage sludge: A critical review

“…This study [37] described a non-targeted approach based on GCxGC-TOFMS. In contrast, numerous reports exist of a non-target approach for the determination of these contaminants in wastewater; some examples being [132,133]. may make up for matrix effects although it does not eliminate the underlying cause because the effect intensity may differ from one matrix or sample to another, and can be also affected by the matrix concentration.…”

Pharmaceutical pollution of aquatic environment: an emerging and enormous challenge

“…Furthermore, the concentrations of transformation products in water may be even higher than the parent compound as proven for carbamazepine, diclofenac and atorvastin (Langford and Thomas 2011). The scenario under which the concentrations of the parent compound are below detection limits but its transformation products are frequently present also needs to be taken into account (Jakimska et al 2014).…”