Solid-phase Extraction-liquid Chromatography-tandem Mass Spectrometry Research Articles

Synthesis of azo-linked covalent organic polymers for pipette tip solid-phase extraction of sedative residues from animal tissues samples.

Azo-linked covalent organic polymers (ACOPs) were synthesized by a simple azo reaction, with 2,2'-bis(trifluoromethyl)benzidine and 1,3,5-trihydroxybenzene as the monomers. The preparation process was mild, green, and environmental-friendly, avoiding the use of high temperature, metal catalysis, and harmful organic reagent. The obtained ACOPs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and Brunauer-Emmett-Teller. With the prepared ACOPs as adsorbent, a method of pipette tip solid-phase extraction-liquid chromatography-tandem mass spectrometry detection (PTSPE-LC-MS/MS) was proposed for the analysis of target sedatives in animal tissues. Furthermore, the parameters for the extraction of five sedatives, including the amount of adsorbent, pH value, ion strength, elution solvent and volume, were investigated. Under the optimized conditions, the linear dynamic range was found from 0.1 to 10.0μg kg-1, and the limits of detection were ranged from 0.02 to 0.1μg kg-1. The method was assessed by the analysis of target sedatives in animal tissues, and the recoveries for the spiked pork muscle and pork liver samples were 84-102% and 83-101%, respectively. The results show that the developed method of PTSPE-LC-MS/MS with ACOPs as adsorbent is efficient for the analysis of trace sedatives in animal tissues.

Estimation of the consumption level of four drugs in Beijing using wastewater-based epidemiology

Objective: To estimate the consumption level of four drugs in Beijing using wastewater-based epidemiology (WBE). Methods: The primary sludge from one large wastewater treatment plants (WWTPs) was collected in Beijing from July 2020 to February 2021. The concentrations of codeine, methadone, ketamine and morphine in the sludge were detected through solid-phase extraction-liquid chromatography-tandem mass spectrometry. The consumption, prevalence and number of users of four drugs were estimated by using the WBE approach. Results: Among 416 sludge samples, codeine had the highest detection rate (82.93%, n=345) with a concentration [M (Q1, Q3)] of 0.40 (0.22-0.8) ng·g-1, and morphine had the lowest detection rate (28.37%,n=118) with a concentration [M (Q1, Q3)] of 0.13 (0.09, 0.17) ng·g-1. There was no significant difference in the consumption of the four drugs on working days and weekends (all P values>0.05). Drug consumption was significantly higher in winter than that in summer and autumn (all P values <0.05). The consumption [M (Q1, Q3)] of codeine, methadone, ketamine and morphine in winter was 24.9 (15.58, 38.6), 9.39 (4.57, 26.72), 9.84 (5.18, 19.45) and 5.67 (3.57, 13.77) μg·inhabitant-1·day-1, respectively. For these drugs, there was an upward trend in the average drug consumption during summer, autumn and winter (the Z values of the trend test were 3.23, 3.16, 2.19, and 3.32, respectively and all P values<0.05). The prevalence [M (Q1, Q3)] of codeine, methadone, ketamine and morphine were 0.0056% (0.003 4%, 0.009 2%), 0.0148% (0.009 6%, 0.026 7%),0.0333% (0.0210%, 0.0710%) and 0.0072% (0.003 8%, 0.011 7%), respectively. The estimated number of drug users [M (Q1, Q3)] was 918 (549, 1 511), 2 429 (1 578, 4 383), 5 451 (3 444, 11 642) and 1 173 (626, 1 925),respectively. Conclusion: Codeine, methadone, ketamine and morphine have been detected in the sludge of WWTPs in Beijing, and the consumption level of these drugs varies in different seasons.

Simultaneous determination of fourteen pharmaceuticals in sewage sludge using online solid-phase extraction-liquid chromatography-tandem mass spectrometry combined with accelerated solvent extraction.

An online solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry method (HPLC-MS/MS) combined with accelerated solvent extraction (ASE) was developed for simultaneous determination of 14 pharmaceuticals in sludge. In the online SPE procedures, ultrapure water with no additives was used as the loading solvent. In addition, low molecular weight targets such as atenolol were difficult to retain on SPE column after acetone was added to the washing solvent. The response signal of analytes can be greatly improved by adding 0.2% formic acid to the mobile phase. Under the optimized conditions, the recoveries of all the analytes ranged between 75.1 and 112%. Moreover, the limit of detections ranged from 1.8 to 7.9 ug/kg. The precision of analytical data was determined with relative standard deviation (RSD) ≤ 4.87%. This method was successfully applied to determine the concentration of pharmaceuticals in sludge.

Simultaneous online SPE-HPLC-MS/MS quantification of gefitinib, osimertinib and icotinib in dried plasma spots: Application to therapeutic drug monitoring in patients with non-small cell lung cancer

Gefitinib, osimertinib and icotinib are the most commonly used tyrosine kinase inhibitors (TKIs) in non-small cell lung cancer (NSCLC) with EGFR mutation. Therapeutic drug monitoring (TDM) for these TKIs has become a standard and essential procedure. Dried plasma spots (DPS) was choosen for microsampling strategies for TDM, allowing easy and cost-effective logistics in many settings. This study developd and validated an assay for the simultaneous quantitative determination of gefitinib, osimertinib and icotinib in DPS by online solid-phase extraction-liquid chromatography–tandem mass spectrometry (online SPE-LC-MS) system. The TKIs were extracted from DPS with methanol and enriched on a Welch Polar-RP SPE column (30 × 4.6 mm, 5 µm), followed by separation on Waters X Bridge C18 analytical column(4.6 × 100 mm, 3.5 µm). The method achieved LLOQ of 2 ng mL−1 for gefitinib and osimertinib (4 ng mL−1 for icotinib), respectively (r2 > 0.99). Precision (within-run 1.54–7.41 % RSD; between-run 3.03–12.84 % RSD), accuracy (range from 81.47 % to 105.08 %; between-run bias 87.87–104.13 %). Osimertinib and icotinib were stable in DPS stored at − 40 °C for 30 days, 4 °C, 42 °C and 60 °C for 5 days and well-sealed 37 °C,75 % humidity (except gefitinib). Lastly, the assay was applied to TDM of TKIs in 46 patients and the results were compared to SALLE assisted LC-MS analysis, it could be confirmed that the developed method achieves similarly good results as the already established one and no bias could be detected. It implies that this method capable of supporting clinical follow-up TDM of TKIs in DPS from poor medical environment.

Application of wastewater-based epidemiology for estimating population-wide human exposure to phthalate esters, bisphenols, and terephthalic acid

Phthalates, bisphenols (BPs), and terephthalic acid (TPA) are widely used plasticizers and monomers in plastic manufacturing. Most of them are known to have an adverse effect on the human body, functioning as endocrine disruptors and suspected carcinogens. Access to near real-time data on population exposure to plasticizers is essential for identifying vulnerable communities and better protecting and managing public health locally. The objective of the present study was to evaluate population-level exposure to phthalates, BPs, and TPA by measuring urinary metabolites in community wastewater. Composited community wastewater (24-h samples) from five sewer sub-catchments of a southwestern city within the United States were analyzed for urinary biomarkers of phthalates, BPs, and TPA using solid-phase extraction-liquid chromatography-tandem mass spectrometry in conjunction with the isotope dilution method for absolute quantification. Ten of 16 analytes were detected at least once in community wastewater above the method detection limit (MDL), with MDLs ranging from 37 to 203 ng/L. The population normalized mass load of TPA was the highest, followed by the human metabolite of di-(2-ethylhexyl) phthalate (DEHP). Bisphenol S and monoethyl phthalate were detected with the highest frequency. Study findings suggest that analyzing municipal wastewater for chemical indicators of human exposure to plastic constituents is feasible, practicable, and informative, as long as appropriate steps are taken to determine, quantify and account for background levels of plastic analytes in the laboratory environment.

Unraveling the dynamics of organic micropollutants in wastewater: Online LC-MS/MS analysis at high temporal resolution

Online monitoring of organic micropollutants (OMPs) in the aquatic environment at high temporal resolution is an upcoming technique that provides insights into their dynamics and has the potential to bring water research and management to a new level. An online monitoring setup was developed to quantify OMPs in wastewater treatment plant (WWTP) influent and effluent using automated and continuous sampling, sample preparation, online solid-phase extraction-liquid chromatography-tandem mass spectrometry analysis and data evaluation. This online monitoring setup provided high selectivity and sensitivity (limit of quantification down to 1 ng/L) as well as a stable performance during one week of constant operation whilst using a high sampling frequency of 10 min (>1000 samples). Custom automated data evaluation enabled quantification within seconds after each measurement and results were comparable to those from a commercial software. Additionally, an alarm tool was included in the evaluation application, which automatically notified the user in case a substance exceeded a predefined threshold. The online monitoring setup was applied to WWTP influent and effluent, where 57 substances were monitored over a period of one week and two days, respectively. High temporal resolution enabled the observation of periodic patterns of pharmaceuticals as well as pollution by OMPs originating from point and diffuse sources, while dynamics of OMPs in WWTP effluent were less pronounced. These new insights into the dynamics of OMPs in WWTP influent, which would not be observable using 24 h composite samples, will be a starting point for new stormwater and wastewater research and management strategies.

Estimation of the psychoactive substances consumption within 12 wastewater treatment plants service areas in a certain city of Guangxi, China applying wastewater-based epidemiology.

The abuse of psychoactive substances has been increasing dramatically over the last few years, which is becoming a concern for human health and social stability. How to accurately estimate psychoactive substances' total consumption in certain areas is the key to manage such substances. In order to control psychoactive substances, 8 psychoactive substances' consumption within 12 wastewater treatment plants (WWTPs) service areas in a certain city of Guangxi, China was investigated in 2019. Firstly, a solid-phase extraction-liquid chromatography-tandem mass spectrometry method was used to determine the influent concentrations. Morphine (MOR), 3, 4-methylenedioxymethamphetamine (MDMA), methamphetamine (METH), ketamine (KET), and norketamine (NK) were detected, with the concentrations ranging from less than method detection limit (NK, MDMA) to 170.91 (METH) ng/L. Then, the back-estimation of consumption was conducted according to the objective and near real-time wastewater-based epidemiology (WBE). The results demonstrate that KET, MOR, and METH are the most abused psychoactive substances, with the mean consumption of 682.42, 167.81, and 44.56mg/day/1000inh, respectively. The psychoactive substance residues of WWTPs influent were analyzed to estimate such substances' consumption in specific areas, so as to provide support for risk prevention and control.

Automated sample preparation for the detection and confirmation of hypoxia-inducible factor stabilizers in urine.

As hypoxia-inducible factor stabilizers (HIFs) can artificially enhance an athlete's erythropoiesis, the World Anti-Doping Agency prohibits their use at all times. Every urine sample for doping control analysis has to be evaluated for the presence of HIFs and therefore sensitive methods that allow high sample throughput are needed. Samples suspicious for the presence of HIFs need to be confirmed following the identification criteria established by the World Anti-Doping Agency. Previous work has shown the advantages of using turbulent flow online solid-phase extraction (SPE) procedures to reduce matrix effects and retention time shifts. Furthermore, the use of online SPE allows for automation and high sample throughput. Both an initial testing procedure (ITP) and a confirmation method were developed and validated, using online SPE liquid chromatography-tandem mass spectrometry (LC-MS/MS), with limits of detection between 0.1 ng/ml (or possibly lower) and 4 ng/ml (or higher for GSK360a) and limits of identification between 0.1 ng/ml (or possibly lower) and 1.17 ng/ml. The ITP only takes 6.5 min per sample. To the best of our knowledge, these are the first ITP and confirmation methods that include more than three HIFs without the need for manual sample preparation.

Improved fully automated method for the determination of medium to highly polar pesticides in surface and groundwater and application in two distinct agriculture-impacted areas.

Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of water resources and represents an environmental risk. To control and reduce pesticide pollution, reliable multi-residue methods for the detection of these compounds in water are needed. In this context, the present work aimed at providing an analytical method for the simultaneous determination of trace levels of 51 target pesticides in water and applying it to the investigation of the target pesticides in two agriculture-impacted areas of interest. The method developed, based on an isotopic dilution approach and on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry, is fast, simple, and to a large extent automated, and allows the analysis of most of the target compounds in compliance with European regulations. Application of the method to the analysis of selected water samples collected at the lowest stretches of the two largest river basins of Catalonia (NE Spain), Llobregat and Ter, revealed the presence of a wide suite of pesticides in the Llobregat basin, some of them at concentrations above the water quality standards (irgarol and dichlorvos) or the acceptable method detection limits (methiocarb, imidacloprid, and thiacloprid), and much cleaner waters in the Ter River basin. Risk assessment of the pesticide concentrations measured in the Llobregat River indicated high risk due to the presence of irgarol, dichlorvos, methiocarb, azinphos ethyl, imidacloprid, and diflufenican (hazard quotient (HQ) values>10), and moderate potential risk in the Ter River, associated to the occurrence of bentazone and irgarol (HQ > 1).

Pollution Characteristics and Removal Effects of Antibiotics in Wastewater from Large-Scale Pig Farms in Guizhou

To understand the pollution characteristics and removal effect of antibiotics in the wastewater treatment process of large-scale pig farms in Guizhou, solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS) was used to investigate the removal of ten veterinary antibiotics from the influent and effluent of each treatment unit during the wastewater treatment process in two large-scale pig farms (named Farm A and Farm B). The results showed that the removal rates of conventional pollutants[including chemical oxygen demand (COD), NH4+-N, total nitrogen (TN), and total phosphorus (TP)] in Farm A and Farm B were above 88.10%. The antibiotics concentrations detected in the influent and effluent ranged from ND-120842.74 ng·L-1. The main antibiotics were sulfamonomethoxine (SMM), sulfamethoxazole (SMD), oxytetracycline (OTC), and ofloxacin (OFL), and the SMM concentration was highest at 120842.74 ng·L-1. The removal rate of the ten antibiotics was 99.23%-100.00% in Farm A and Farm B. In the wastewater treatment process of Farm A, the treatment section "USR+2A/O+disinfection pond+oxidation pond" removed antibiotics in wastewater effectively, with the total removal rate of SMM, SMD, and OTC reaching 100.00%. In the wastewater treatment process of Farm B, the treatment section "ultrafiltration (UF)+nanofiltration (NF)" removed antibiotics effectively by more than 99.23%. However, the concentrations of antibiotics investigated in the effluent were higher than the EU water environment antibiotic threshold (10 ng·L-1). Finally, through redundancy analysis, it was found that conventional indicators (COD, NH4+-N, TN, TP, and pH) in wastewater were related to the degradation of some antibiotics.

Fatalities associated with NPS stimulants in the Greater Cologne area.

This study centres on the prevalence of new psychoactive substances (NPS) stimulant use, and its relevance as a cause of death amongst individuals between the ages of 12 and 35 in the greater Cologne area. An automated solid-phase extraction-liquid chromatography-tandem mass spectrometry method was developed for the determination of 97 stimulants in urine (including conventional stimulants, e.g. amphetamine and MDMA), of which 68 analytes were fully validated for quantification. Samples of urine or kidney tissue (in cases where urine was unavailable) of 268 deceased were collected, during autopsy, between January 2011 and May 2017 and analyzed. Blood (if available) was also investigated in cases where urine/kidney samples were tested positive for NPS. An intake of stimulants (including NPS stimulants) was proven in 50 cases. In 33 cases, only conventional stimulants were detected. A total of 17 cases were tested positive for NPS. Of the 17 NPS-positive cases, 13 were also tested positive for other conventional drugs of abuse (mostly amphetamine and MDMA). In six NPS-positive cases, at least three different NPS were proven to be ingested. Due to the determined blood concentrations, NPS was assigned as the leading cause of death, or of toxicological relevance, in the cause of death in only 5 cases. In two of the cases, NPS was judged to be a component of a multidrug poisoning, but of minor relevance.

Determination of glyphosate, AMPA, and glufosinate in honey by online solid-phase extraction-liquid chromatography-tandem mass spectrometry

ABSTRACTA simple method was developed for the simultaneous determination of glyphosate, its main degradation product (aminomethylphosphonic acid), and glufosinate in honey. Aqueous honey solutions were derivatised offline prior to direct analysis of the target analytes using online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry. Using the developed procedure, accuracies ranging from 95.2% to 105.3% were observed for all analytes at fortification levels of 5, 50, and 150 μg kg−1 with intra-day precisions ranging from 1.6% to 7.2%. The limit of quantitation (LOQ) was 1 μg kg−1 for each analyte. Two hundred honey samples were analysed for the three analytes with AMPA and glyphosate being most frequently detected (99.0% and 98.5% of samples tested, respectively). The concentrations of glyphosate were found to range from <1 to 49.8 μg kg−1 while those of its degradation product ranged from <1 to 50.1 μg kg−1. The ratio of glyphosate to AMPA was found to vary significantly amongst the samples where both analytes were present above the LOQ. Glufosinate was detected in 125 of 200 samples up to a maximum concentration of 33.0 μg kg−1.

Maternal smoking and high BMI disrupt thyroid gland development

BackgroundMaternal lifestyle factors, including smoking and increased body weight, increase risks of adult diseases such as metabolic syndrome and infertility. The fetal thyroid gland is essential for the control of fetal metabolic rate, cardiac output, and brain development. Altered fetal thyroid function may contribute to increased disease onset later in life. Here, we investigated the impact of maternal smoking and high maternal weight on human fetal thyroid function during the second trimester.MethodsThyroid glands and plasma were collected from fetuses electively terminated in the second trimester (normally progressing pregnancies). Plasma total triiodothyronine (T3) and total thyroxine (T4) were measured by solid-phase extraction-liquid chromatography-tandem mass spectrometry. Fetal plasma thyroid-stimulating hormone (TSH) levels were measured using a multiplex assay for human pituitary hormones. Histology and immunolocalization of thyroid developmental markers were examined in thyroid sections. Transcript levels of developmental, functional, apoptotic, and detoxification markers were measured by real-time PCR. Statistical analyses were performed using multivariate linear regression models with fetal age, sex, and maternal smoking or maternal body mass index (BMI) as covariates.ResultsMaternal smoking was associated with significant changes in fetal plasma T4 and TSH levels during the second trimester. Smoke-exposed thyroids had reduced thyroid GATA6 and NKX2-1 transcript levels and altered developmental trajectories for ESR2 and AHR transcript levels. Maternal BMI > 25 was associated with increased fetal thyroid weight, increased plasma TSH levels, and abnormal thyroid histology in female fetuses. Normal developmental changes in AHR and ESR1 transcript expression were also abolished in fetal thyroids from mothers with BMI > 25.ConclusionsFor the first time, we show that maternal smoking and high maternal BMI are associated with disturbed fetal thyroid gland development and endocrine function in a sex-specific manner during the second trimester. These findings suggest that predisposition to post-natal disease is mediated, in part, by altered fetal thyroid gland development.

Determination of 74 new psychoactive substances in serum using automated in-line solid-phase extraction-liquid chromatography-tandem mass spectrometry.

A detailed description is given of the development and validation of a fully automated in-line solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method capable of detecting 90 central-stimulating new psychoactive substances (NPS) and 5 conventional amphetamine-type stimulants (amphetamine, 3,4-methylenedioxy-methamphetamine (MDMA), 3,4-methylenedioxy-amphetamine (MDA), 3,4-methylenedioxy-N-ethyl-amphetamine (MDEA), methamphetamine) in serum. The aim was to apply the validated method to forensic samples. The preparation of 150μL of serum was performed by an Instrument Top Sample Preparation (ITSP)-SPE with mixed mode cation exchanger cartridges. The extracts were directly injected into an LC-MS/MS system, using a biphenyl column and gradient elution with 2mM ammonium formate/0.1% formic acid and acetonitrile/0.1% formic acid as mobile phases. The chromatographic run time amounts to 9.3min (including re-equilibration). The total cycle time is 11min, due to the interlacing between sample preparation and analysis. The method was fully validated using 69 NPS and five conventional amphetamine-type stimulants, according to the guidelines of the Society of Toxicological and Forensic Chemistry (GTFCh). The guidelines were fully achieved for 62 analytes (with a limit of detection (LOD) between 0.2 and 4μg/L), whilst full validation was not feasible for the remaining 12 analytes. For the fully validated analytes, the method achieved linearity in the 5μg/L (lower limit of quantification, LLOQ) to 250μg/L range (coefficients of determination>0.99). Recoveries for 69 of these compounds were greater than 50%, with relative standard deviations≤15%. The validated method was then tested for its capability in detecting a further 21 NPS, thus totalling 95 tested substances. An LOD between 0.4 and 1.6μg/L was obtained for these 21 additional qualitatively-measured substances. The method was subsequently successfully applied to 28 specimens from routine forensic case work, of which 7 samples were determined to be positive for NPS consumption.

Development and validation of an analytical method based on liquid chromatography-tandem mass spectrometry detection for the simultaneous determination of 13 relevant wastewater-derived contaminants in lettuce.

We present an analytical method developed and validated to study the potential uptake of 13 selected drugs (ten pharmaceuticals, one illicit drug, and two transformation products) into lettuce plants from contaminated water and soil. Some of the selected drugs (i.e., cocaine, methadone, cis-diltiazem, valsartan, and valsartan acid), which are commonly present in treated wastewater, were investigated for the first time in plant tissues. The method is based on ultrasonic solvent extraction with acetonitrile-methanol (1:1, v/v) and subsequent automated extract cleanup and analysis by means of online solid-phase extraction-liquid chromatography-tandem mass spectrometry. Optimum extraction conditions were selected after evaluation of analyte recoveries with four different extraction techniques (ultrasonic solvent extraction, solid-liquid extraction, pressurized liquid extraction, and a "quick, easy, cheap, effective, rugged, and safe" based method) and six different solvent mixtures. Furthermore, two different solid-phase extraction cleanup sorbents were evaluated. The method developed has high sensitivity (with limits of detection between 0.1 and 12.6 ng per gram dry weight and limits of quantification between 0.5 and 42.0 ng per gram dry weight), satisfactory accuracy (with analyte relative recoveries above 80% for all analytes but acridone and oxcarbazepine), and good repeatability (with relative standard deviations below 9% for all analytes). As part of the validation procedure, the analytical method was applied to the analysis of lettuce plants irrigated with water fortified with the selected compounds for the entire growing period. The results obtained evidenced the transfer of all the investigated drugs into lettuce leaves. Graphical Abstract ᅟ.

Wastewater-Based Epidemiology as a New Tool for Estimating Population Exposure to Phthalate Plasticizers.

This study proposes the monitoring of phthalate metabolites in wastewater as a nonintrusive and economic alternative to urine analysis for estimating human exposure to phthalates. To this end, a solid-phase extraction-liquid chromatography-tandem mass spectrometry method was developed, allowing for the determination of eight phthalate metabolites in wastewater (limits of quantification between 0.5 and 32 ng L-1). The analysis of samples from the NW region of Spain showed that these substances occur in raw wastewater up to ca. 1.6 μg L-1 and in treated wastewater up to ca. 1 μg L-1. Concentrations in raw wastewater were converted into levels of exposure to six phthalate diesters. For two of them, these levels were always below the daily exposure thresholds recommended by the U.S. Environmental Protection Agency and the European Food Safety Authority. For the other four, however, estimates of exposure surpassed such a threshold (especially the toddler threshold) in some cases, highlighting the significance of the exposure to phthalates in children. Finally, concentrations in wastewater were also used to estimate metabolite concentrations in urine, providing a reasonable concordance between our results and the data obtained in two previous biomonitoring studies.

Multiresidue trace analysis of pharmaceuticals, their human metabolites and transformation products by fully automated on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry

A novel, fully automated analytical methodology based on dual column liquid chromatography coupled to tandem mass spectrometry (LC-LC-MS2) has been developed and validated for the analysis of 12 pharmaceuticals and 20 metabolites and transformation products in different types of water (influent and effluent wastewaters and surface water). Two LC columns were used – one for pre-concentration of the sample and the second for separation and analysis – so that water samples were injected directly in the chromatographic system. Besides the many advantages of the methodology, such as minimization of the sample volume required and its manipulation, both compounds ionized in positive and negative mode could be analyzed simultaneously without compromising the sensitivity. A comparative study of different mobile phases, gradients and LC pre-concentration columns was carried out to obtain the best analytical performance. Limits of detection (MLODs) achieved were in the low ngL−1 range for all the compounds. The method was successfully applied to study the presence of the target analytes in different wastewater and surface water samples collected near the city of Girona (Catalonia, Spain). Data on the environmental presence and fate of pharmaceutical metabolites and TPs is still scarce, highlighting the relevance of the developed methodology.

Ecological risk assessment associated to the removal of endocrine-disrupting parabens and benzophenone-4 in wastewater treatment

The occurrence of four widely used and endocrine disrupting parabens (PBs) (methylparaben, propylparaben, butylparaben and benzylparaben) and a polar UV filter (benzophenone-4) were determined in influent and effluent wastewater from the 19 major wastewater treatment plants (WWTPs) of Catalonia, Spain. For their analysis an on-line solid-phase extraction-liquid chromatography–tandem mass spectrometry (SPE-HPLC–MS/MS) method was developed and validated. Laboratory analysis revealed high levels for both PBs and BP4, with maximum concentrations of 5700ngL−1 and 1806ngL−1, respectively, in influent samples, and 137ngL−1 and 1080ngL−1, respectively in effluent wastewaters. Removal rates (RE%) for the target compounds in each WWTPs were calculated. RE% for parabens were almost 100%, whereas for BP4 values where in the range 5–91%. The half-life time (t1/2), hydraulic retention time (HRT), and annual mass load (ML) for each facility was estimated. Results indicated that there was no clear influence of HRT on the RE% of BP4. MLs for BP4 were in the range 0.9–110.1kgy−1, with the highest values in the most populated areas. Finally, a risk assessment, estimated in terms of hazard quotients (HQs), was carried out for aquatic biota. HQs for the target compounds in effluent wastewaters indicated a negligible effect, whereas for some influent wastewaters’ HQs pointed out that some species are at risk.

Fully automated analysis of four tobacco-specific N-nitrosamines in mainstream cigarette smoke using two-dimensional online solid phase extraction combined with liquid chromatography–tandem mass spectrometry

A fully automated method for the detection of four tobacco-specific nitrosamines (TSNAs) in mainstream cigarette smoke (MSS) has been developed. The new developed method is based on two-dimensional online solid-phase extraction–liquid chromatography–tandem mass spectrometry (SPE/LC–MS/MS). The two dimensional SPE was performed in the method utilizing two cartridges with different extraction mechanisms to cleanup disturbances of different polarity to minimize sample matrix effects on each analyte. Chromatographic separation was achieved using a UPLC C18 reversed phase analytical column. Under the optimum online SPE/LC–MS/MS conditions, N′-nitrosonornicotine (NNN), N′-nitrosoanatabine (NAT), N′-nitrosoanabasine (NAB), and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) were baseline separated with good peak shapes. This method appears to be the most sensitive method yet reported for determination of TSNAs in mainstream cigarette smoke. The limits of quantification for NNN, NNK, NAT and NAB reached the levels of 6.0, 1.0, 3.0 and 0.6pg/cig, respectively, which were well below the lowest levels of TSNAs in MSS of current commercial cigarettes. The accuracy of the measurement of four TSNAs was from 92.8 to 107.3%. The relative standard deviations of intra-and inter-day analysis were less than 5.4% and 7.5%, respectively. The main advantages of the method developed are fairly high sensitivity, selectivity and accuracy of results, minimum sample pre-treatment, full automation, and high throughput. As a part of the validation procedure, the developed method was applied to evaluate TSNAs yields for 27 top-selling commercial cigarettes in China.

Determination of hydroxylated polychlorinated biphenyls by offline solid-phase extraction-liquid chromatography–tandem mass spectrometry using a molecularly imprinted polymer as a sorbent for sample preconcentration

Hydroxylated polychlorinated biphenyls (OH-PCBs) can be detected by liquid chromatography–mass spectrometry coupled to solid-phase extraction (SPE) using a dummy molecularly imprinted polymer (DMIP) as a sorbent. The DMIP is prepared by using an analogue of OH-PCBs (i.e., 4, 4-dihydroxybiphenyl) as a dummy template, to avoid the leakage of the target molecules. The DMIP-SPE sorbent shows good recoveries for OH-PCBs at pH 11 due to the charge-assisted hydrogen bondings between OH-PCBs and the DMIP. It has been found that the DMIP is much more effective and selective than the traditional C18-SPE method. The sample pH, polymer dosage, elution solvent and volume have been optimized for higher recoveries. Under the optimum experimental conditions, OH-PCBs can be detected in the linear concentration range of 0.05–1.0pM, with the detection limits ranging from 11fM to 82fM for 4′-OH-CB 9, 4′-OH-CB 30, 4′-OH-CB 61, 4′-OH-CB 106 and 4′-OH-CB 112. The proposed system has been successfully applied to the determination of trace OH-PCBs in spiked water samples with recoveries in the range of 89–110%.