Determination of fungicides in wine by mixed-mode solid phase extraction and liquid chromatography coupled to tandem mass spectrometry

A novel procedure for the determination of nine selected fungicides (metalaxyl-M, azoxystrobin, myclobutanil, flusilazole, penconazole, tebuconazole, propiconazole, diniconazole and difenoconazole) in wine samples is presented. Sample enrichment and purification is simultaneously performed using mixed-mode, anion exchange and reversed-phase, OASIS MAX solid-phase extraction (SPE) cartridges. Analytes were determined by liquid chromatography coupled to tandem mass spectrometry using atmospheric pressure electrospray ionization (LC-ESI-MS/MS). Parameters affecting the chromatographic determination and the extraction-purification processes were thoroughly investigated. Under optimized conditions, 10 mL of wine were firstly diluted 1:1 with ultrapure water and then passed through the mixed-mode SPE cartridge at a flow of ca. 5 mLmin(-1). After a washing step with 5 mL of an aqueous NH(4)OH solution (5%, w:v), analytes were recovered with just 1 mL of methanol and injected in the LC-MS/MS system without any additional purification. The selective extraction process avoided significant changes in the ionization efficiency for red and white wine extracts in comparison with pure standards in methanol. Performance of the method was good in terms of precision (RSDs<11%) and accuracy (absolute recoveries>72%, determined against pure standards in methanol) reporting method LOQs in the range of 0.01-0.79 ngmL(-1) for target compounds, which are far below the EU maxima residue levels (MRLs) for fungicides in vinification grapes and wine. Several commercial wines from different geographic areas in Spain were analyzed. In most samples, metalaxyl-M and azoxystrobin were found at concentrations up to several ngmL(-1).     

Liquid chromatography with time-of-flight mass spectrometry for simultaneous determination of chemotherapeutant residues in salmon

Liquid chromatography with time-of-flight mass spectrometry (LC-TOF-MS) method has been developed for simultaneous confirmation by accurate mass measurement and quantitative determination of antibiotics (enrofloxacin, oxolinic acid, flumequine, erythromycin), fungicides (malachite green MG, leucomalachite green LMG) and parasiticide (emamectin benzoate) residues in edible portion of salmon. Confirmation of chemotherapeutant residues has been based on the system of identification points (IPs) established in the Commission Decision 2002/657/EC concerning the use of mass spectrometry (MS) techniques. A validation study on matrix is presented evaluating accuracy in terms of precision (λ_ppm 0.83-1.15) and trueness (0.22-0.70 Da). Limits of detection (LODs) and limits of quantification (LOQs) were in ranges of 1-3 and 3-9 μg/kg, below the maximum residue limits (MRLs) established in current EU legislation (100-200 μg/kg) for these chemotherapeutants. Considering the EU guidelines, decision limits (CCα) and detection capabilities (CCβ) were determined (ranges of 103-218 and 107-234 μg/kg, respectively) for authorised substances. For no authorised compounds (MG and LMG), LODs were 2 and 1 μg/kg, respectively, but exceed the MRPL (minimum required performance limit) established in the legislation which corresponds to the sum of MG and LMG (2 μg/kg). Acceptable intra-day and inter-day variability, in terms of relative standard deviation (R.S.D.) of the analytical method, were obtained (2-15%). Linearity was demonstrated from the LOQs of the analytes to 600 μg/kg (r > 0.9991). The method has involved an extraction procedure based on solid-liquid extraction (SLE) with recoveries higher than 80% for most target chemotherapeutants, with exception of enrofloxacin (40%).     

Solid-phase extraction followed by liquid chromatography-tandem mass spectrometry for the determination of hydroxylated benzophenone UV absorbers in environmental water samples

A procedure for the determination of six derivatives of 2-hydroxybenzophenone, used as UV absorbers, in water samples is presented. Compounds were first concentrated using a solid-phase extraction (SPE) cartridge and then selectively determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) using electrospray ionization (ESI). The effect of different parameters on the performance of concentration and determination steps is discussed. The highly polar and acidic 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP-4) required the use of ammonium acetate as modifier during desorption of SPE cartridges and also to improve the performance of its separation in the LC column. Under optimized conditions, the proposed method provided limits of quantification from less than 1 to 32 ng L⁻¹, depending on the compound and the type of water sample. Recoveries from the SPE step (83-105%) remained unaffected by the nature of the matrix; however, the efficiency of electrospray ionization was compound and sample dependant. Real sample analysis reflected the presence of three of the six investigated species (BP-4, 2-hydroxy-4-methoxybenzophenone, BP-3, and 2,4-dihydroxybenzophenone, BP-1) in the aquatic environment, particularly in raw wastewater samples. In this latter matrix, BP-4 was the compound presenting the highest concentrations; moreover, it was poorly removed in sewage treatment plants and consequently it also appeared in river water.     

Determination of ochratoxin A in wine by liquid chromatography tandem mass spectrometry after combined anion-exchange/reversed-phase clean-up

Ochratoxin A (OTA) is a mycotoxin produced by Aspergillus ochraceus and Penicillium verrucosum. It has been found and analysed in several foods and feeds. Owing to its toxicity and occurrence in food and feed, the European Community has issued directives and some countries have their own regulations for OTA contents in food, feed and beverages. This work describes a method for the determination of OTA in mulled and red wine. It is based on combined anion exchange/reversed-phase clean-up and was analysed by liquid chromatography coupled with tandem mass spectrometry (multiple reaction monitoring). The method was validated with natural contaminated and spiked wine samples with OTA contents from 1.34 to 3.48 g kg^–1. Owing to its accuracy, good reproducibility and repeatability, this easy method is a good alternative to liquid chromatography–fluorescence detection methods.     

A general screening method for doping agents in human urine by solid phase extraction and liquid chromatography/time-of-flight mass spectrometry

A general screening method based on solid phase extraction (SPE) and liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) was developed and investigated with 124 different doping agents, including stimulants, -blockers, narcotics, -adrenergic agonists, agents with anti-estrogenic activity, diuretics and cannabinoids. Mixed mode cation exchange/C8 cartridges were applied to SPE, and chromatography was based on gradient elution on a C18 column. Ionization of the analytes was achieved with electrospray ionization in the positive mode. Identification by LC/TOFMS was based on retention time, accurate mass and isotopic pattern. Validation of the method consisted of analysis of specificity, analytical recovery, limit of detection and repeatability. The minimum required performance limit (MRPL), established by World Anti-Doping Agency (WADA), was attained to 97 doping agents. The extraction recoveries varied between 33 and 98% and the median was 58%. Mass accuracy was always better than 5 ppm, corresponding to a maximum mass error of 0.7 mDa. The repeatability of the method for spiked urine samples, expressed as median of relative standard deviations (RSD%) at concentrations of MRPL and 10 times MRPL, were 14% and 9%, respectively. The suitability of the LC/TOFMS method for doping control was demonstrated with authentic urine samples.     

Characterization of low-molecular weight peptides in champagne wine by liquid chromatography/tandem mass spectrometry

This paper reports the use of an on-line LC–ESI–MS/MS method for the identification and quantification of di- and tripeptides in champagne wine without laborious sample pretreatment. The identification of these compounds, in their underivatised form, is based on identical retention times and ESI–MS spectra to those of reference standards. The presence of nine dipeptides (Arg–Ile, Ile–Arg, Ile–Val, Lys–Phe, Lys–Tyr, Phe–Lys, Tyr–Gln, Tyr–Lys, Val–Ile) and the absence of two tripeptides (Phe–Arg–Arg and Lys–Met–Asn) have been evidenced in the matrix. Calibration curves for each analyte were established using Phe–Arg as internal standard. The calibration curves were linear in the concentration range 0.1–10 mg L⁻¹ with a determination coefficient, r², better than 0.992. The accuracy for the calibration standard was estimated at between 92 and 102%. This method allows high recovery and satisfies the necessary requirements with respect to accuracy, repeatability and sensitivity. The first application of this analytical method to the measurement of di- and tri-peptides in different vintages of champagne wine is reported. Compositional changes in the peptides occurred depending on the vintage.     

Mixed-mode solid-phase extraction followed by acetylation and gas chromatography mass spectrometry for the reliable determination of trans-resveratrol in wine samples

This work presents an advantageous analytical procedure for the accurate determination of free trans-resveratrol in red and white wines. The proposed method involves solid-phase extraction (SPE), acetylation of the analyte in aqueous media and further determination by gas chromatography (GC) with mass spectrometry detection (MS). The use of a mixed-mode SPE sorbent provides an improvement in the selectivity of the extraction step; moreover, the presence of several intense ions in the electron impact mass spectra of its acetyl derivative guarantees the unambiguous identification of trans-resveratrol. Considering a sample intake of 10 mL, the method provides a limit of quantification (LOQ) of 0.8 ng mL⁻¹ and linear responses for concentrations up to 2.5 μg mL⁻¹, referred to wine samples. The average recovery, estimated with samples fortified at different concentrations in the above range, was 99.6% and the inter-day precision stayed below 8%. Trans-resveratrol levels in the analyzed wines varied from 3.4 to 1810 ng mL⁻¹. Cis-resveratrol was also found in all samples. In most cases, equal or higher responses were measured for this latter form than for the trans-isomer. The reduced form of resveratrol, dihydro-resveratrol, was systematically identified in red wines.     

液相色谱串联四极杆质谱法同时测定婴幼儿配方食品中甲基香兰素和乙基香兰素

建立了混合阴离子交换固相萃取柱净化,液相色谱串联四极杆质谱法测定婴幼儿配方食品中甲基香兰素和乙基香兰素的方法.样品经水和乙腈提取,CuSO4溶液沉淀蛋白,NaOH调节pH,增加样品溶解性,阴离子交换固相萃取柱净化.目标化合物在梯度洗脱条件下经C18柱分离后采用ESI源负离子多反应监测模式进行检测.分别选取了婴幼儿配方乳...     

Assessment of benzophenone-4 reactivity with free chlorine by liquid chromatography quadrupole time-of-flight mass spectrometry

The stability of the UV filter benzophenone-4 (BP-4) in free chlorine-containing water was investigated, for the first time, by liquid chromatography quadrupole time-of-flight mass spectrometry (LC–QqTOF-MS). High mass accuracy and resolution capabilities of this hybrid mass spectrometer were used for the reliable assignation of empirical formulae and chemical structures of BP-4 derivatives. Time-course profiles of the parent compound and its by-products were simultaneously recorded by direct injection of sample aliquots, after quenching the excess of chlorine, in the LC–QqTOF-MS system. At neutral pHs, in excess of chlorine, BP-4 showed a limited stability fitting a pseudo-first-order degradation kinetics. A noticeable reduction in the half-lives of BP-4 was observed when increasing the sample pH between 6 and 8 units and also in presence of bromide traces. The reaction pathway of this UV filter involved a first electrophilic substitution of hydrogen per chlorine (or bromide) in the phenolic ring, followed by oxidation of the carbonyl moiety to an ester group, which induced a further electrophilic substitution in the same aromatic ring. Above reactions were also noticed when mixing a BP-4 containing personal care product with chlorinated tap water and in chlorinated swimming pool and sewage water, previously spiked with a BP-4 standard.     

Use of liquid chromatography quadrupole time-of-flight mass spectrometry in the elucidation of transformation products and metabolites of pesticides. Diazinon as a case study

Liquid chromatography (LC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) is a useful analytical tool in the elucidation and confirmation of transformation products (TPs)/metabolites of pesticides with a wide range of polarity, in both environmental and biological samples. Firstly, the versatility of LC allows the determination of very distinct TPs/metabolites as chromatographic conditions can be easily changed and optimized depending on the analytical problem. Secondly, the mass accuracy provided by the TOF analyser allows the assignment of a highly probable empirical formula for each compound and the differentiation between nominal isobaric compounds. Finally, the possibility of performing MS/MS spectra with accurate mass measurements can been used for the final characterization of the TPs/metabolites detected and for the differentiation of isomeric compounds. In this study, the insecticide diazinon was used as model compound, and its photodegradation and metabolism have been investigated by LC-QTOF-MS. On one hand, environmental spiked water was irradiated with a mercury lamp for 9 days, sampling 3-mL aliquots approximately every 12 h. On the other hand, both in vitro and in vivo metabolism experiments were carried out with different substrate concentrations and incubation times. After centrifugation, and protein precipitation in the in vitro and in vivo studies, 50-μL aliquots of both environmental and biological samples were directly injected into the LC electrospray ionization QTOF system. The most important transformation processes were found to be hydrolysis of the ester moiety, hydroxylation in the aromatic ring or in one of the alkylic groups, oxidation of the sulfur atom on the P=S cleavage or a combination of these processes, with the highest number of compounds being found in the photodegradation study. Very polar compounds, such as diethyl phosphate and diethyl thiophosphate, were detected after direct injection of the aqueous sample, which was feasible owing to the characteristics of the LC. In MS mode, mass errors were below 3 mDa, leading to an empirical formula for each compound. MS/MS spectra with accurate mass were used for the final elucidation of the compounds detected.     

Herbal medicine analysis by liquid chromatography/time-of-flight mass spectrometry

The fact that the effects of herbal medicines (HMs) are brought about by their chemical constituents has created a critical demand for powerful analytical tools performing the chemical analysis to assure their efficacy, safety and quality. Liquid chromatography coupled to mass spectrometry (LC–MS) is an excellent technique to analyze multi-components in complex herbal matrices. Due to its inherent characteristics of accurate mass measurements and high resolution, time-of-flight (TOF) MS is well-suited to this field, especially for qualitative applications. The purpose of this article is to provide an overview on the potential of TOF, including the hybrid quadrupole- and ion trap-TOF (QTOF and IT-TOF), hyphenated to LC for chemical analysis in HMs or HM-treated biological samples. The peculiarities of LC–(Q/IT)TOF-MS for the analysis of HMs are discussed first, including applied stationary phase, mobile-phase selection, accurate mass measurements, fragmentation and selectivity. The final section is devoted to describing the applicability of LC–(Q/IT)TOF-MS to routine analysis of multi-components, including target and non-target (unknown) compounds, in herbal samples, emphasizing both the advantages and limitations of this approach for qualitative and quantitative purposes. The potential and future trends of fast high-performance liquid chromatography (HPLC) (e.g. rapid resolution LC and ultra-performance LC) coupled to (Q)TOF-MS for chemical analysis of HMs are highlighted.     

Multiresidue determination of UV filters in water samples by solid‐phase extraction and liquid chromatography with tandem mass spectrometry analysis

UV filters, contained in sunscreens and other cosmetic products, as well as in some plastics and industrial products, are nowadays considered contaminants of emerging concern because their widespread and increasing use has lead to their presence in the environment. Furthermore, some UV filters are suspected to have endocrine disruption activity. In the present work, we developed an analytical method based on liquid chromatography with tandem mass spectrometry for the determination of UV filters in tap and lake waters. Sixteen UV filters were extracted from water samples by solid‐phase extraction employing graphitized carbon black as adsorbent material. Handling 200 mL of water sample, satisfactory recoveries were obtained for almost all the analytes. The limits of detection and quantification of the method were comparable to those reported in other works, and ranged between 0.7–3.5 and 1.9–11.8 ng/L, respectively; however in our case the number of investigated compounds was larger. The major encountered problem in method development was to identify the background contamination sources and reduce their contribution. UV filters were not detected in tap water samples, whereas the analyses conducted on samples collected from three different lakes showed that the swimming areas are most subject to UV filter contamination.     

Ultra-high capacity liquid chromatography chip/quadrupole time-of-flight mass spectrometry for pharmaceutical analysis

Nanoflow liquid chromatography/mass spectrometry (nano-LC/MS) has attracted increasing interest in virtue of high sensitivity, low sample consumption, and minimal matrix effect. In this work a HPLC-Chip/quadrupole time-of-flight (Q-TOF) MS device with a new ultra-high capacity small molecule chip (UHC-Chip) which features a 500 nL enrichment column and a 150 mm × 75 μm analytical column, was evaluated with a drug mixture covering a wide range of polarities. Excellent chromatographic precision with 0.1-0.5% RSD for retention time and 1.7-9.0% RSD for peak area, low limit of detection, good chip-to-chip reproducibility and linearity were obtained by using this UHC-Chip. Compared with the standard HPLC-Chip with 40 nL trapping column, the UHC-Chip showed higher enrichment capability and hence gave a higher response in signal detection. Additionally, 4-30 times increase in sensitivity was obtained compared with conventional LC/MS, which indicated that UHC-Chip/MS was a valuable tool for the quantitative analysis of low level impurities and degradation products in pharmaceuticals. Moreover, satisfactory results obtained from trace drug analysis of serum samples further proved its practicality and potential for use in drug testing and development.     

Simple and rapid method for the determination of ethylenebisdithiocarbamate fungicides in fruits and vegetables using liquid chromatography with tandem mass spectrometry

A simple and rapid method for determining ethylenebisdithiocarbamates (EBDCs; mancozeb, maneb, and zineb) in fruits and vegetables is described. EBDCs are transformed into dimethylethylenebisdithiocarbamate (EBDC-dimethyl) by methylation after their decomposition with ethylenediaminetetraacetic acid (EDTA). These processes were performed simultaneously in this method. Dimethyl sulfate was used as the methylation reagent, and acetonitrile extracts obtained from partitioning with anhydrous magnesium sulfate and sodium chloride were subjected to dispersive solid-phase extraction with the primary secondary amine sorbent. Liquid chromatography with tandem mass spectrometry in the positive heated-electrospray ionization mode was used for the determination of EBDC-dimethyl produced from EBDCs. The method was validated at levels of 10, 50, and 100 ng g⁻¹ maneb as a representative EBDC. The recoveries of the present method were between 71 and 101%. The limits of detection and quantification were 0.24 and 0.8 ng g⁻¹ maneb, respectively.     

Rapid confirmatory method for the determination of 11 nitroimidazoles in egg using liquid chromatography tandem mass spectrometry

A rapid confirmatory method has been developed and validated for the simultaneous identification, confirmation and quantitation of 11 nitroimidazoles in eggs by liquid chromatography tandem mass spectrometry (LC–MS/MS). The method is validated in accordance with Commission Decision 2002/657/EC and is capable of analysing metronidazole (MNZ), dimetridazole (DMZ), ronidazole (RNZ), ipronidazole (IPZ) and their hydroxy metabolites MNZ-OH, HMMNI (hydroxymethyl, methyl nitroimidazole), IPZ-OH. The method is also capable of analysing carnidazole (CRZ), ornidazole (ORZ), tinidazole (TNZ) and ternidazole (TRZ). MNZ, DMZ and RNZ have been assigned a recommended level (RL) of 3 μg kg⁻¹ by the Community Reference Laboratory (CRL) in Berlin. The developed method described in this study is easily able to detect all the nitroimidazole compounds investigated at this level and below. Egg samples are extracted with acetonitrile, and NaCl is added to help remove matrix contaminants. The acetonitrile extract undergoes a liquid–liquid wash step with hexane; it is then evaporated and reconstituted in mobile phase. The reconstituted samples are analysed by liquid chromatography tandem mass spectrometry (LC–MS/MS). The decision limits (CCα) range from 0.33 to 1.26 μg kg⁻¹ and the detection capabilities (CCβ), range from 0.56 to 2.15 μg kg⁻¹. The results of the inter-assay study, which was performed by fortifying hen egg samples (n = 18) on three separate days, show the accuracy calculated for the various analytes to range between 87.2 and 106.2%. The precision of the method, expressed as %CV values for the inter-assay variation of each analyte at the three levels of fortification (3, 4.5 and 6.0 μg kg⁻¹), ranged between 3.7 and 11.3%. A Day 4 analysis was carried out to examine species variances in eggs from different birds such as duck and quail and investigating differences in various battery and free range hen eggs.     

Environmentally friendly method for the determination of acrylamide and trimethylolpropane in paper packaging materials by liquid chromatography with tandem mass spectrometry

A simple, rapid, and environmentally friendly method was developed for the determination of acrylamide and trimethylolpropane in paper packaging materials. No organic solvent was used and the matrix effect was investigated. The extract was directly analyzed by liquid chromatography with tandem mass chromatography for quantification and confirmation. The chromatographic separations were performed on a ZORBAX HILIC Plus (2.1 mm × 150 mm, 3μm; Agilent, USA) column with only one mobile phase (100% water). Calibration curves for acrylamide and trimethylopropane were achieved with concentrations ranging from 0.4 to 20 mg/kg and the corresponding r² values were 0.998 and 0.999, respectively. The recoveries were >85% with relative standard deviations <10%. The validated method was applied to the analysis of 50 real samples, and positive results were obtained for 30 samples. The result indicated that trimethylolpropane is associated with inks and printing activity and acrylamide is widely used as a papermaking additive in many paper packages. The concentrations of acrylamide and trimethylolpropane ranged from 0.41 to 7.5 and 0.50 to 8.8 mg/kg, respectively. The results of this study revealed that this method could be used accurately and precisely.     

Construction of on-line supercritical fluid extraction with reverse phase liquid chromatography–tandem mass spectrometry for the determination of capsaicin

A column-switching system, composed of supercritical fluid extraction (SFE) and reverse phase liquid chromatography/mass spectrometry (RPLC/MS) was constructed for on-line extraction and reverse-phase separation of capsaicinoids in capsicum fruits.     

Residue determination of cyromazine and its metabolite melamine in chard samples by ion-pair liquid chromatography coupled to electrospray tandem mass spectrometry

A method has been developed for the sensitive and selective determination of cyromazine and its metabolite melamine in chard samples. Both compounds are small polar basic molecules, making their determination at residue levels complicated. The method involves an extraction procedure with phosphate buffer and methanol using high-speed blender, the addition of tridecafluoroheptanoic acid (TFHA) as ion-pair reagent and the injection of the five-fold diluted extract on liquid chromatography coupled to electrospray tandem mass spectrometry (LC–ESI–MS/MS). The method has been validated for chard samples, spiked at 0.05 and 0.5 mg kg⁻¹. Quantification was carried out by using matrix-matched standards calibration and recoveries were satisfactory, with mean values for cyromazine of 103% and 93%, and relative standard deviations lower than 7%. In the case of melamine, recoveries were 89% and 86%, with relative standard deviations lower than 13%. A limit of quantification of 0.05 mg kg⁻¹ was obtained for both compounds, with the limit of detection below 0.01 mg kg⁻¹. The method, with very little sample handling and good sensitivity, was applied to the rapid determination of low residue levels of these compounds in chards from field residue trials. All the quality controls included during the analysis were satisfactory with average recoveries of 92% and 78% for cyromazine and melamine, respectively.     

Untargeted metabolomic analysis using liquid chromatography quadrupole time-of-flight mass spectrometry for non-volatile profiling of wines

The current study presents a method for comprehensive untargeted metabolomic fingerprinting of the non-volatile profile of the Graciano Vitis vinifera wine variety, using liquid chromatography/electrospray ionization time of flight mass spectrometry (LC–ESI-QTOF). Pre-treatment of samples, chromatographic columns, mobile phases, elution gradients and ionization sources, were evaluated for the extraction of the maximum number of metabolites in red wine. Putative compounds were extracted from the raw data using the extraction algorithm, molecular feature extractor (MFE). For the metabolite identification the WinMet database was designed based on electronic databases and literature research and includes only the putative metabolites reported to be present in oenological matrices. The results from WinMet were compared with those in the METLIN database to evaluate how much the databases overlap for performing identifications. The reproducibility of the analysis was assessed using manual processing following replicate injections of Vitis vinifera cv. Graciano wine spiked with external standards. In the present work, 411 different metabolites in Graciano Vitis vinifera red wine were identified, including primary wine metabolites such as sugars (4%), amino acids (23%), biogenic amines (4%), fatty acids (2%), and organic acids (32%) and secondary metabolites such as phenols (27%) and esters (8%). Significant differences between varieties Tempranillo and Graciano were related to the presence of fifteen specific compounds.     

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

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 °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.