Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry.
ABSTRACT A simple and sensitive method for simultaneous analysis of 43 pharmaceutical compounds in sewage sludge and sediment samples was developed and validated. The target compounds were extracted using pressurized liquid extraction (PLE) and then purified and pre-concentrated by solid phase extraction (SPE) using a hydrophilic-lipophilic balanced polymer. PLE extraction was performed on temperature of 100 degrees C, with methanol/water mixture (1/2, v/v) as extraction solvent. The quantitative analysis was performed by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole-linear ion trap mass spectrometer (LC-QqLIT-MS). Data acquisition was carried out in selected reaction monitoring (SRM) mode, monitoring two SRM transitions to ensure an accurate identification of target compounds in the samples. Additional identification and confirmation of target compounds were performed using the Information Dependent Acquisition (IDA) function. The method was validated through the estimation of the linearity, sensitivity, repeatability, reproducibility and matrix effects. The internal standard approach was used for quantification because it efficiently corrected matrix effects. Despite the strong matrix interferences, the recoveries were generally higher of 50% in both matrixes and the detection and quantification limits were very low. Beside the very good sensitivity provided by LC-QqLIT-MS, an important characteristic of the method is that all the target compounds can be simultaneously extracted, treated and analysed. Hence, it can be used for routine analysis of pharmaceuticals providing large amount of data. The method was applied for the analysis of pharmaceuticals in river sediment and wastewater sludge from three treatment plants with different treatment properties (i.e. capacity, secondary treatment, quality of influent waters). The analysis showed a widespread occurrence of pharmaceuticals in the sludge matrices.
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ABSTRACT: An analytical method that facilitated the analysis of 11 pharmaceuticals residue (caffeine, prazosin, enalapril, carbamazepine, nifedipine, levonorgestrel, simvastatin, hydrochlorothiazide, gliclazide, diclofenac-Na, and mefenamic acid) with a single pre-treatment protocol was developed. The proposed method included an isolation and concentration procedure using solid phase extraction (Oasis HLB), a separation step using high-performance liquid chromatography, and a detection procedure that applies time-of-flight mass spectrometry. The method was validated for drinking water (DW), surface water (SW), sewage treatment plant (STP) influent and effluent, and hospital (HSP) influent and effluent. The limits of quantification were as low as 0.4, 1.6, 5, 3, 2.2 and 11ng/L in DW, SW, HSP influent and effluent, STP effluent, and STP influent, respectively. On average, good recoveries higher than 75% were obtained for most of the target analytes in all matrices. Matrix effect was evaluated for all samples matrices. The proposed method successfully determined and quantified the target compounds in raw and treated wastewater of four STPs and three hospitals in Malaysia, as well as in two SW sites. The results showed that a number of the studied compounds pose moderate to high persistency in sewage treatment effluents as well as in the recipient rivers, namely; caffeine, simvastatin, and hydrochlorothiazide. Ten out of 11 compounds were detected and quantified in 13 sampling points. Caffeine was detected with the highest level, with concentrations reaching up to 9099ng/L in STP influent.Journal of Chromatography A 04/2014; · 4.61 Impact Factor
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ABSTRACT: In this work, an analytical method was developed for the determination of pharmaceutical drugs in biosolids. Samples were extracted with an acidic mixture of water and acetone (1:2, v/v) and supported liquid extraction was used for the clean-up of extracts, eluting with ethyl acetate:methanol (90:10, v/v). The compounds were determined by gas chromatography-tandem mass spectrometry using matrix-match calibration after silylation to form their t-butyldimethylsilyl derivatives. This method presents various advantages, such as a fairly simple operation for the analysis of complex matrices, the use of inexpensive glassware and low solvent volumes. Satisfactory mean recoveries were obtained with the developed method ranging from 70 to 120% with relative standard deviations (RSDs)≤13%, and limits of detection between 0.5 and 3.6ngg(-1). The method was then successfully applied to biosolids samples collected in Madrid and Catalonia (Spain). Eleven of the sixteen target compounds were detected in the studied samples, at levels up to 1.1μgg(-1) (salicylic acid). Ibuprofen, caffeine, paracetamol and fenofibrate were detected in all of the samples analyzed.Journal of Chromatography A 02/2014; · 4.61 Impact Factor
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ABSTRACT: We developed a protocol to quantify 12 emerging contaminants (ECs) (pharmaceuticals and hormones) and pesticides extracted from suspended particulate matter (SPM) of river water and municipal wastewaters samples as well as river sediments. The separation of suspended solids was realized using filtration of water samples. We tested a series of six different filter types. The effect of filtration on the concentrations of dissolved contaminants was evaluated to minimize losses of target compounds. The river sediment samples were lyophilized, and both SPM and sediment samples were subjected to ultrasonic extraction combined with C18 cartridge clean-up. Quantifications were realized using mass spectrometry. The method recoveries of all compounds ranged from 38 to 112 % in all studied matrices; poorer recoveries were achieved for sulfamethoxazole and diclofenac (as low as 38 %), whereas the recoveries for all other compounds in the wastewater treatment plant (WWTP) samples were between 68 and 111 %. The detection limits in sediments and SPM from river samples for the 12 analytes varied from 0.7 to 9.4 ng g(-1) and from 21 to 92 ng g(-1) for WWTP SPM samples. All targeted ECs were detected with concentrations ranging from 3 to 5,440 ng g(-1) in the studied matrices with the highest concentrations observed in WWTP SPM samples. A significant portion of the contaminants in a water sample is clearly associated with the suspended particulates. Optimization of water-treatment processes and environmental fate must absolutely consider the fraction of contaminants that is particulate-bound if one hopes to have a reasonable mass balance.Archives of Environmental Contamination and Toxicology 02/2014; · 2.01 Impact Factor