Fast determination of 40 drugs in water using large volume direct injection liquid chromatography–tandem mass spectrometry

Abstract

This work describes a rapid analytical method based on direct sample injection of water samples for the simultaneous identification/quantification of 40 emerging compounds, including pharmaceuticals and drugs of abuse. The water samples were analyzed by ultrahigh-performance liquid chromatography coupled to hybrid triple quadrupole mass spectrometer (UHPLC-MS/MS QqQ). Taking profit of the increasing sensitivity of nowadays's tandem mass spectrometers, direct sample injection of large volumes has been an attractive alternative to pre-concentration steps. In this work, the developed methodology has been validated at three concentration levels (10, 100 and 1000 ng/L) in 10 different water samples of different types (5 effluent wastewaters and 5 surface waters). The majority of compounds could be satisfactory validated at these concentrations, showing good recoveries and precision. With only few exceptions, the limits of quantification (LOQs), estimated from the sample chromatogram at lowest spiked level tested, were below 3 ng/L. The method was applied to the analysis of 10 effluent wastewaters and 10 surface water samples. Venlafaxine was the compound most frequently detected (80%) in surface water, followed by acetaminophen (70%). Regarding effluent wastewater, valsartan and 4-acetyl aminoantipyrine were detected in 9 out of 10 samples analyzed. These two compounds together with 4-formyl aminoantipyrine and naproxen showed the highest concentrations (>2000 ng/L). In these cases, a dilution step was required for a correct quantification. As an additional evaluation of the method performance, the same water samples were analyzed in other laboratory by a second analytical methodology, based on on-line solid-phase-extraction coupled to LC-MS/MS (QqQ). KeywordsDirect injection, illicit drugs of abuse, pharmaceuticals, effluent wastewater, surface water, liquid chromatography, triple quadrupole mass spectrometry.

Analysis, occurrence, fate and risks of proton pump inhibitors, their metabolites and transformation products in aquatic environment: A review

“…In the methods applied for the determination of PPIs (Table 2), the pre-treatment step includes usually various types of glass fiber filters (usually 0.45 μm or 0.7 μm glass fiber filters or nylon membrane filters), depending on the complexity of the sample (Bueno et al, 2010;Gómez et al, 2007;Pedrouzo et al, 2008;Sousa et al, 2011), while in some cases centrifugation is used by applying 4500 rpm for 5-10 min (Boix et al, 2013(Boix et al, , 2014(Boix et al, , 2015Gracia-Lor et al, 2010.…”

“…Therefore, the use of modern and sensitive instruments is commonly needed. An interesting example of the latter approach is that presented by Boix et al (2015) for the simultaneous quantification and confirmation of 40 human and veterinary pharmaceuticals and drugs of abuse in effluent wastewater and surface samples, including omeprazole and pantoprazole. The direct injection of water samples (100 μL) on UHPLC-MS/MS QqQ system, without any previous sample treatment, has been shown as an attractive approach as it avoids time consuming sample preparation steps and reduces the amounts of solvents used (Farré et al, 2012).…”

“…Furthermore, narrower and higher peaks can be obtained which facilitates the detection of the target analytes Vazquez-Roig et al, 2013). For the identification of the PPIs and specifically for the identification of their metabolites/TPs in most of the studies UHPLC columns are used (Boix et al, 2013(Boix et al, , 2014(Boix et al, , 2015Gracia-Lor et al, 2010Hernández et al, 2011;Ibáñez et al, 2009).…”

“…Additionally, the occurrence of its metabolites and TPs in various aqueous matrices was also studied. In most of the studies omeprazole was not detected at the samples analyzed may be due to the fact that it is found to be acid labile and sensitive to light and heat (Boix et al, 2013(Boix et al, , 2014(Boix et al, , 2015Castiglioni et al, 2005;DellaGreca et al, 2006;Gracia-Lor et al, 2012;Jiang et al, 2014Jiang et al, , 2015Sousa et al, 2011;Ternes et al, 2001;Zuccato et al, 2005). Nevertheless its occurrence is reported in some studies, with concentrations ranging in surface waters from below quantification limit (bLOQ) (Boleda et al, 2013) to 222 ng/L (Bueno et al, 2010), in influent wastewaters from bLOQ (Pedrouzo et al, 2011;Van Nuijs et al, 2010) to 2170 ng/L (Pedrouzo et al, 2008), in effluent wastewaters from b LOQ (Pedrouzo et al, 2011;Van Nuijs et al, 2010) to 922 ng/L (Rosal et al, 2010), while it was not detected in sea water (Jiang et al, 2014) or in drinking (or tap) water (Boleda et al, 2013;Pedrouzo et al, 2008;Valcárcel et al, 2011).…”

Flow Injection Chemiluminescence Determination of Acetylsalicylic Acid in Pharmaceutical Formulations

“…These include liquid chromatography (Boixa et al, 2015;Malisetty & Rambabu, 2013), high performance liquid chromatography (HPLC) (El-Din, Eid, & Zeid, 2013;Elmasry et al, 2011), spectrofluorimetry (Alves & Poppi, 2009;Zadeh, Kohansal, & Sadeghi, 2011), potentiometry (Pasekova, Sales, Montenegro, Araujo, & Polasek, 2001), voltammetry (Sanghavi & Srivastava, 2010;Torriero, Luco, Sereno, & Raba, 2004), capillary electrophoresis (Marra et al, 2014), UV-Vis spectrophotometry (Abdelrahman, 2014;Sena & Poppi, 2004;Yamamoto, Takakuwa, Kato, & Asakaw, 2007) and flow injection analysis (FIA) with spectrophotometric detection (Lopez-Fernandez, Castro, & Valcarcel, 1990;Pereira, Aniceto, & Fatibello-Filho, 1998) and chemiluminescence (Wabaidur, Alam, Alothman, & Eldesoky, 2014).…”