Automated Solid-phase Extraction Research Articles

Development and validation of an LC-MS/MS method for the detection of sodium pentachlorophenolate residues on cutting boards.

The objective of this study was to develop and validate an automated solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the detection of sodium pentachlorophenolate (PCP-Na) residues on cutting boards. Given the potential hazards and environmental persistence of PCP-Na, a sensitive and reliable method is crucial for monitoring its residues in food contact materials to ensure consumer safety. Wood shavings from cutting boards were extracted using 10% methanol in water, followed by purification using an automated SPE system. The eluent was concentrated, reconstituted, and analyzed by UPLC-MS/MS. An isotope-labeled internal standard was used to mitigate matrix effects, enhancing detection sensitivity. The method was validated by assessing linearity, limit of detection (LOD), limit of quantification (LOQ), recovery rates, and relative standard deviations (RSDs) across various concentration levels. The method demonstrated excellent linearity over a concentration range of 0 to 100 μg/L with a regression equation of Y = 1.035X-0.7771 and an R² of 0.9996. The LOD and LOQ were determined to be 0.4 and 1.0 μg/kg, respectively. Recovery rates ranged from 71.75% to 96.50% with RSDs between 5.19% and 16.66%. When applied to 30 market cutting board samples, PCP-Na residues were detected in 50% of the samples, with concentrations ranging from 0 to 83,990 µg/kg. This study presents a robust UPLC-MS/MS method for the detection of PCP-Na on cutting boards, offering improved sensitivity and simplified sample preparation. The high detection rate in commercial samples underscores the need for stringent monitoring and regulatory measures to mitigate the exposure risk to consumers.

Evaluation of the presence of emerging contaminants in wastewater and seawater using automated solid-phase extraction and ultra-high-performance liquid chromatography coupled to tandem mass spectrometry

The presence of emerging contaminants in water constitutes one of the main ways of human exposure to them, which can cause severe effects on health. In this sense, their adequate elimination through appropriate treatments plays a fundamental role, being necessary to monitor the effluents from wastewater treatment plants, as well as the areas close to their discharge. The aim of the present work has been the development and validation of an analytical methodology to determine 15 organic contaminants of emerging concern in wastewater as well as in seawater samples using an automated solid-phase extraction system and an ultra-high-performance liquid chromatography coupled to tandem mass spectrometry instrument. Matrix-matched calibration showed good linearity with determination coefficients ≥ 0.990. Likewise, matrix effect assessment showed a significant signal suppression in almost all the analytes demonstrating the need to consider such effect for a proper quantification of the analytes. Recovery values ranged from 74.7 to 109% with relative standard deviation values ≤ 20.5% for most analytes. Regarding seawater and wastewater samples, 11 of the target analytes were detected in, at least, one sample at concentrations from below limit of quantification of the method to 217 ± 92 ng l-1 in seawater and up to 2340 ± 107 ng l-1 in wastewater samples.

Rapid Determination of Tetracyclines in Drinking and Environmental Waters Using Fully Automatic Solid-Phase Extraction with Ultra-Performance Liquid Chromatography–Tandem Mass Spectrometry

The abuse and irrational use of tetracyclines (TCs) in human medicine and animal husbandry has become a serious concern, affecting the ecological environment and human health. The aim of this study was to develop a sensitive and selective method using fully automatic solid-phase extraction coupled with ultra-performance liquid chromatography–tandem mass spectrometry for the determination of twelve TCs in water. Four isotope-labeled internal standards for TCs were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the optimum experimental conditions found were 1.0 L water sample with 0.5 g/L Na2EDTA (pH 3.0) extracted and enriched by CNW HLB cartridge and eluted by 4 mL of acetone:methanol (v/v, 1:1). The enrichment factors were up to 798−1059 but only requiring about 60 min per six samples. Under the optimized conditions, the linearity of the method ranged from 0.2 to 100 μg/L for 12 TCs, the detection limits were as low as 0.01−0.15 ng/L, and the recoveries were in the range of 70%–118%, with relative standard deviations less than 15%. The developed method can be successfully utilized for the determination of 12 TCs in pure water, tap water, river water, and mariculture seawater. In summary, three and six TCs were detected in river water and mariculture seawater, respectively, with total concentrations of 0.074–0.520 ng/L (mean 0.248 ng/L) and 0.792–58.369 ng/L (12.629 ng/L), respectively. Tetracycline (TC) and oxytetracycline (OTC) were the dominant TCs in river water, while doxytetracycline (DXC) and OTC were dominant in mariculture seawater.

Development of a rapid and reliable method to simultaneously detect seven food allergens in processed foods using LC-MS/MS

Rapid analysis of multiple food allergens is required to confirm the appropriateness of food allergen labelling in processed foods. This study aimed to develop a rapid and reliable method to simultaneously detect trace amounts of seven food allergenic proteins (wheat, buckwheat, milk, egg, crustacean, peanut, and walnut) in processed foods using LC-MS/MS. Suspension-trapping (S-Trap) columns and on-line automated solid-phase extraction were used to improve the complex and time-consuming pretreatment process previously required for allergen analysis using LC-MS/MS. The developed method enabled the simultaneous detection of selected marker peptides for specific proteins derived from seven food ingredients in five types of incurred samples amended with trace amounts of allergenic proteins. The limit of detection values of the method for each protein were estimated to be <1 mg/kg. The developed analytical approach is considered an effective screening method for confirming food allergen labelling on a wide range of processed foods.

Using differential mobility spectrometry to improve the specificity of targeted measurements of 2,3-dinor 11β-Prostaglandin F2α

Introduction2,3-dinor 11β-Prostaglandin F2α (BPG) is an arachidonic acid derivative and the most abundant metabolic byproduct of prostaglandin D2, which is released during mast cell activation. Therefore, measurements of BPG in urine using liquid chromatography-tandem mass spectrometry (LC-MS/MS) provide a noninvasive method for evaluation and management of mast cell disorders. Measurements obtained by LC-MS/MS exhibit a high prevalence of chromatographic interferences resulting in challenges with optimal determination of BGP. In this investigation, differential mobility spectrometry (DMS) is utilized to overcome the limitations of current testing. MethodsUrine samples were extracted using an automated solid-phase extraction method. Samples were then analyzed with and without DMS devices installed on two commercially available mass spectrometry platforms to assess the benefits of DMS. Following promising results from a preliminary analytical evaluation, LC-DMS-MS/MS measurements of BPG in urine were fully validated to assess the analytical implications of using this technology. Results and discussionThe addition of DMS devices to the LC-MS/MS systems evaluated in this investigation significantly reduced interferences observed in the chromatograms. Concomitantly, DMS reduced the number of discordant quantifier/qualifier fragment ion results that significantly exceeded the ± 20 % limits, suggesting greater analytical specificity. The validation studies yielded low interday imprecision, with %CVs less than 6.5 % across 20 replicate measurements. Validation studies assessing other aspects of analytical performance also met acceptance criteria. ConclusionsIncorporating DMS devices greatly improved the specificity of BPG measurements by LC-MS/MS, as evidenced by the comparison of chromatograms and fragment ion results. Validation studies showed exceptional performance for established analytical metrics, indicating that this technology can be used to minimize the impact of interferences without adversely impacting other aspects of analytical or clinical performance.

Determination of 21 organophosphate esters and their metabolites in drinking water by automatic solid phase extraction-liquid chromatography-tandem mass spectrometry

To establish a method for simultaneous determination of 21 organophosphate esters(OPEs) and their metabolites in drinking water by automatic solid phase extraction-liquid chromatography-tandem mass spectrometry. The drinking water was purified by automatic solid phase extraction with HLB column, eluted by methanol, determined by liquid chromatography tandem mass spectrometry with ACQUITY UPLC BEH(100 mm×2.1mm, 1.7 μm) column, and quantified by internal standard method. The optimized method could simultaneously detect 21 organophosphate esters and their metabolites in drinking water. The detection limit was 0.01-0.24 ng/L, the quantitation limit was 0.03-0.77 ng/L. The recovery range was 57.6%-121.2% and the relative standard deviation is 1.2%-11.1% when the concentration was 0.8-20 ng/L. Senventeen tap water and 30 packaged drinking water collected by the supermarket were measured. The ΣOPEs range was 16.8-177 ng/L, and the Σdi-OPEs range was 0.328-16.3ng/L, indicating the exposure risk of organophosphates and their metabolites in water. The pretreatment of the method is simple, automatic and sensitive, and is suitable for simultaneous high-throughput determination of organophosphate esters and their metabolites in large quantities of drinking water.

Characteristics and Ecological Risk Assessment of Pharmaceutical Active Compounds in Guangdong Province

Pharmaceutically active compounds(PhACs) have become a class of new pollutants in the environment after extensive production and use of PhACs in China. To investigate the pollution characteristics of PhACs in Guangdong Province, raw sewage was collected from 186 sewage treatment plants in 21 cities, including 178 townships and administrative districts in Guangdong Province. The pollution levels of ten typical PhACs in influent water of sewage treatment plants were analyzed using automatic solid phase extraction and high performance liquid chromatography-triple quadrupole mass spectrometry. The spatial distribution characteristics of PhACs in Guangdong Province were fully revealed, and the potential ecological risks of PhACs were evaluated. The results showed that PhACs were detected in all wastewater plants, and the mass concentration of PhACs ranged from 21.00 to 9558.25 ng·L-1. Metoprolo, acetaminophen, bezafibrate, and caffeine were the main pollutants. In terms of spatial distribution, the average mass concentration of ΣPhACs in various regions of Guangdong Province was in the following order:Pearl River Delta>North Guangdong>East Guangdong≈West Guangdong. When the mass concentration of ΣPhACs was over 2500 ng·L-1 in the influent water of sewage treatment plants, the concentration of PhACs in effluent was estimated according to the sewage disposal technology. The ecological risk of PhACs was carried out based on the effluent. The results revealed that the ecological risk of PhACs was low in Guangdong Province, and the risk of bezafibrate was moderate in the cities of Shaoguan, Jiangmen, and Shenzhen. The highest ecological risk of ΣPhACs was located in Shaoguan.

Analytical quality by design using a D-optimal design and parallel factor analysis in an automatic solid phase extraction system coupled to liquid chromatography. Determination of nine PAHs in coffee samples

Optimizing a multi-residue analysis when using an automatic SPE (solid phase extraction) system and complex matrices becomes a difficult problem because of the large number of experimental factors that can influence the recovery of the analytes. Furthermore, in most cases, the conditions of the factors that enhance the response of one analyte are in conflict with those suitable for some others.In this work, AQbD (Analytical Quality by Design) is applied to the development of an analytical procedure based on automatic SPE coupled to HPLC-FLD in the determination of nine polycyclic aromatic hydrocarbons (PAHs) in coffee samples.Focussing on the SPE, the elution volume, the dry time, and volume in the wash stage, and the organic solvent (at two, three, three, and four levels, respectively) were considered.The first problem is to handle these four factors (control method parameters, CMPs) at different levels to optimize responses (critical quality attributes, CQAs). This task has been carried out using a D-optimal design that, starting from a full factorial design of four factors with 72 experiments, reduced this number to 19, maintaining the precision of the estimates, saving time and costs in the laboratory.The second problem is related to the choice of CQAs to apply the AQbD methodology. A complex matrix such as coffee contains impurities that interferes with the target analytes and may even coelute in the chromatographic determination. A PARAFAC decomposition allows avoiding this problem and uses the “second order advantage” to unequivocally identify each analyte. Then, the obtained sample loadings were used as responses. Specifically, each CQA is the difference between spiked and blank coffee samples. All these CQAs must be maximized.Once the experimental data were obtained, two alternatives were posed: on the one hand, the classical optimization based on the estimation of the effects of CMPs on the CQAs, and on the other hand, applying the AQbD methodology to construct the design space that allows to increase the knowledge of the automatic SPE system.Because the experimental domain of CMPs is discrete and the SPE system performs differently for each analyte, it is not possible to obtain the maximum of all CQAs at the same factor levels. Therefore, the design space of the CMPs is obtaining through the Pareto front of the non-dominated values of CQAs.The nine PAHs selected were phenanthrene (PHE), anthracene (ANT), fluoranthene (FLN), pyrene (PYR), chrysene (CHR), benzo[a]anthracene (BaA), perylene (PER), benzo[b]fluoranthene (BbF) and benzo[a]pyrene (BaP). European regulations amending foodstuff set maximum levels for BaP and the sum of the content of four compounds (PAH4): BaP, BaA, BbF and CHR.

An Automated Solid-Phase Extraction-UPLC-MS/MS Method for Simultaneous Determination of Sulfonamide Antimicrobials in Environmental Water.

The large-scale use of sulfonamide antimicrobials in human and veterinary medicine has seriously endangered the ecological environment and human health. The objective of this study was to develop and validate a simple and robust method for the simultaneous determination of seventeen sulfonamides in water using ultra-high performance liquid chromatography-tandem mass spectrometry coupled with fully automated solid-phase extraction. Seventeen isotope-labeled internal standards for sulfonamides were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the enrichment factors were up to 982-1033 and only requiring about 60 min per six samples. Under the optimized conditions, this method manifested good linearity (0.05-100 μg/L), high sensitivity (detection limits: 0.01-0.05 ng/L), and satisfactory recoveries (79-118%) with acceptable relative standard deviations (0.3-14.5%, n = 5). The developed method can be successfully utilized for the determination of 17 sulfonamides in pure water, tap water, river water, and seawater. In total, six and seven sulfonamides were detected in river water and seawater, respectively, with a total concentration of 8.157-29.676 ng/L and 1.683-36.955 ng/L, respectively, and sulfamethoxazole was the predominant congener.

Determination of antibiotics during treatment of hospital wastewater using automated solid-phase extraction followed by UHPLC-MS: occurrence, removal and environmental risks

ABSTRACT The extent of removal of pharmaceuticals by African-based wastewater treatment plants (WWTPs) is relatively unknown with various studies observing high concentrations in effluents. This is mainly due to WWTPs still utilising the traditional treatment methods which are known to be less effective. In this study, 15 selected antibiotics (amoxicillin, ampicillin, azithromycin, ciprofloxacin, doxycycline, erythromycin, gentamicin, metronidazole, norfloxacin, ofloxacin, penicillin, sulfamethoxazole, sulfapyridine, tetracycline and trimethoprim) were monitored in wastewater as it goes through sedimentation (primary and secondary), aeration and chlorination stages of a WWTP. Analytical method involved solid-phase extraction followed by liquid chromatographic determination. Removal efficiencies during sedimentation were generally positive with doxycycline achieving 80–95.8%, while negative removal efficiencies were observed for penicillin V (−46.4 to −17.1%) and trimethoprim (−26.2 to −18.9%). The aeration and agitation stage resulted in concentration enhancement for several antibiotics with seven of them ranging between −273 and −15.5%. This stage was responsible for the relatively low overall removal efficiencies in which only 4 antibiotics (doxycycline, tetracycline, ciprofloxacin, and erythromycin) experienced overall removal efficiencies above 50%. The recorded effluent concentrations ranging between 0.0130 and 0.383 ng/mL were translated to low potential for development of antibiotic resistance genes in the receiving environments while ecotoxicity risk was high for only amoxicillin, ampicillin and sulfapyridine. The study has provided an overview of the performance of common wastewater treatment processes in South Africa and hopes that more monitoring and environmental risk data can be made available towards drafting of antibiotic priority lists that cater for Africa.

Simultaneous determination of multiple perfluoroalkyl and polyfluoroalkyl substances in aquatic products by ultra-performance liquid chromatography-tandem mass spectrometry with automated solid-phase extraction

Diet is an important route of human exposure to perfluoroalkyl and polyfluoroalkyl substances (PFASs), and aquatic products are the main dietary source of PFASs. This study aimed to establish a method for the analysis of 52 PFASs in typical aquatic products, such as crucian carp, large yellow croaker, shrimp, and clam, by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) after automated solid phase extraction (SPE). After optimization of the conditions of SPE, the recovery and precision of the method is within an acceptable range. The intra-day and inter-day average recoveries of spiked samples ranged from 66.5% to 122.3% and 64.5%-128.0% for crucian carp, large yellow croaker, shrimp, and clam, with intra-day and inter-day relative standard deviation (RSD) of 0.78%-11.4%, and 2.54%-24.2%. The ranges of method detection limits (MDLs) and quantification limits (MQLs) of PFASs were 0.003–0.60 ng/g and 0.005–2.0 ng/g, respectively. The accuracy of the method was also verified by standard reference material (SRM), and the measured values of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were in the allowable range.The method was applied to analyze aquatic products from the local supermarket. The concentrations of ∑PFASs ranged from 13.9 ng/g ww to 75.5 ng/g ww. PFOS was the dominant pollutant, accounting for 79.6% of ∑PFASs. The branch-chain isomers, perfluoro-3-methylheptane sulfonate (P3MHpS) and perfluoro-6-methylheptane sulfonate (P6MHpS) accounted for one-quarter of PFOS. Long-chain perfluoro carboxylic acids (PFCAs) were also detected in most samples. The estimated daily intake of PFOS was over the recommended tolerable intake by several organizations such as the Minnesota Department of Health (MDH), the New Jersey Drinking Water Quality Institute (NJDWQI), and the European Food Safety Authority (EFSA). PFOS would have posed health risks to consumers through dietary exposure.

Determination of sixteen antibiotics and four β-agonists in human urine samples using ultra-performance liquid chromatography-tandem mass spectrometry based on high-throughput automatic solid-phase extraction

An analytical method combining high-throughput automatic solid-phase extraction with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed to determine 16 antibiotics (macrolides, tetracyclines, quinolones, and sulfonamides) and 4 β-agonists (terbutaline, salbutamol, ractopamine, and clenbuterol) in human urine samples. After thawing at room temperature, 1 mL of urine was sampled and the internal standard was added, followed by the addition of 200 μL ammonium acetate buffer and 20 μL β-glucuronidase, and the mixture was incubated at 37 ℃ overnight. Automatic solid-phase extraction was used to extract the target compounds from the urine samples, and the recoveries were compared using different solid-phase extraction 96-well plates (PRiME MCX, Sep-Pak C18, PRiME HLB), types and volumes of rinse solutions and eluents. Satisfactory recoveries of the 20 target compounds were obtained using the Oasis PRiME HLB 96-well plate, with 1.5 mL 10% (v/v) methanol aqueous solution and 2.0 mL methanol as the rinse solution and eluent, respectively. The eluent was concentrated under nitrogen gas at 45 ℃, and the recoveries of the target compounds were compared under different conditions (completely or almost dry, drying to 1 mL, and adding water as a protective agent), and the recovery rate was optimal when water was added as a protective agent. In this study, two types of analytical columns (ACQUITY BEH C18 and ACQUITY HSS T3) and different gradient elution procedures and mobile phases were compared. The optimal chromatographic effect was realized using an HSS T3 column (100 mm×3.0 mm, 1.8 μm) and 0.1% (v/v) formic acid aqueous solution-0.1% (v/v) formic acid in acetonitrile as the mobile phase in gradient elution at a flow rate of 0.3 mL/min. Comparing the peaks observed using different proportions of methanol aqueous solution and the initial mobile phase as the injection solvent revealed that 30% (v/v) methanol aqueous solution was the optimal solution in terms of peak shape and signal-to-noise ratio. MS was conducted using positive electrospray ionization (ESI+) in multiple reaction monitoring (MRM) mode, and the MS parameters were optimized, including the curtain (CUR) and collision gases (CAD). The standard curve obtained using this method exhibited a good linearity (correlation coefficient>0.997), and the respective limits of detection and quantification were 0.02-0.12 ng/mL and 0.06-0.41 ng/mL. At spiked levels of 0.25, 2.5, and 12.5 ng/mL, the recoveries were in the range of 81.7%-120.0% (except that of tetracycline), the intra- and inter-day RSDs (n=6) were 1.1%-11.0% and 1.2%-13.0%, respectively. Azithromycin, trimethoprim, terbutaline, salbutamol, ractopamine, and clenbuterol displayed moderate matrix effects, but all targets exhibited weak matrix effects after correction using the isotope internal standard. To evaluate the accuracy of this method, BCR-503 (containing salbutamol and clenbuterol) and internal quality control samples were used and the concentrations of salbutamol and clenbuterol were within the reference ranges. Additionally, the mean concentrations of the 20 target compounds of two different internal quality control samples after 7 measurements were in the ranges of 0.44-0.59 ng/mL (0.5 ng/mL) and 1.72-2.16 ng/mL (2.0 ng/mL), respectively, which were satisfactory. In this study, the analytical method employed automatic sample pretreatment with a 96-well solid-phase extraction plate, and the detection efficiency was considerably improved. This method displays the advantages of simple operation, ideal recovery, a high sensitivity and weak matrix effect, which satisfies the requirements for the simultaneous determination of 16 antibiotics and 4 β-agonists in human urine samples. This study provides a crucial method for use in monitoring antibiotics and β-agonists in human urine and studying their exposure characteristics and health risks.

Quick and high-throughput quantification of 22 β-agonists residues in animal-derived foods using enzymatic probe sonication

A high demand exists in veterinary drug residual analysis for rapid, automatic and high-throughput analytical techniques that produce data simultaneous and faster. Here, we describe a combined automated solid-phase extraction (SPE) and enzymatic probe sonication (EPS), subsequently ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the quick extraction, automated clean-up as well as simultaneous quantification of 22 β-agonists residues in animal-derived foods. Enhanced by the ultrasonic probe, only 2 min was needed for exhaustively extraction of β-agonists from foods of animal-origin; whereas traditional enzymatic digestion methods require hours or even days, which making it more appropriate for high-throughput biomonitoring. Moreover, the clean-up and pre-concentration procedures were conducted on the automatic SPE, which allowed 36 samples being performed simultaneously within 30 min. The method was successfully applied for analyzing 56 animal-derived food samples, 53.6 % of which contained detectable levels of at least one kind of β-agonists. Interestingly, both the detection rate and residual level of β-agonists in the ruminants (bovine and sheep) were higher as compared with the swine. Concerning the real food samples analyzed, the findings of this study suggest that stricter measures should be adopted to control the illegal usage of β-agonists on the farm animals, particularly for the ruminants.

Evaluation of a septumless mini-cartridge for automated solid-phase extraction cleanup in gas chromatographic analysis of >250 pesticides and environmental contaminants in fatty and nonfatty foods

The QuEChERSER mega-method has recently been introduced to quantify and identify a wide range of chemical residues (pesticides, veterinary drugs, environmental contaminants, among others) in nearly all types of foods. The approach calls for taking a small amount of the initial extract to cover analytes amenable to liquid chromatography, and the remainder is salted out for analysis by gas chromatography (GC), both with mass spectrometry (MS) based detection. In the case of GC-MS(/MS), the extract undergoes automated robotic mini-cartridge solid-phase extraction (SPE) cleanup in a technique known as µSPE or instrument-top sample preparation (ITSP). In 2022, a septumless mini-cartridge for µSPE was introduced to improve upon the ITSP design. The new design houses a bed of 20 mg anhydrous MgSO4, 12 mg each of C18 and primary secondary amine sorbents, and 1 mg of graphitized carbon black, the latter substituting for CarbonX used in the ITSP product. The septumless µSPE mini-cartridge employs a different gripping mechanism with the syringe needle that allows leak-free operation at higher flow rates (e.g. 10 µL/s), whereas the ITSP design is limited to 2 µL/s. Based on cleanup and analyte elution profiles, the extract load volume and flow rate was increased in µSPE for QuEChERSER from 300 µL at 2 µL/s to 500 µL at 5 µL/s, which improved accuracy of results, sped the cleanup step, and obviated the need for micro-vial inserts in the receiving vials. The new design also reduced both the amount and consistency of dead (void) volumes in the mini-cartridges from 83 ± 14 µL to 52 ± 7 µL for 200-600 µL load volumes. Normalization of peak areas to internal standards led to recoveries between 80 and 120% with typical RSDs <5% in low-pressure GC-MS/MS of 227-242 out of 252 pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons in hemp powder, spinach, whole milk, egg, avocado, and lamb meat.

Antidepressants as emerging contaminants: Occurrence in wastewater treatment plants and surface waters in Hangzhou, China.

AimsAntidepressants have aroused wide public concern due to their widespread presence in water and their harm to human health and environment. This study was designed to evaluate the contribution of wastewater treatment plants (WWTPs) to the presence of antidepressants in the surface water.MethodsData was evaluated by analyzing water samples collected from the influent, effluent, upstream and downstream of the WWTPs on the rivers of interest in Hangzhou, Zhejiang Province, China. Besides, the study also assessed the impact of the release of antidepressants from WWTPs to the surface water on the drinking water. An automatic solid-phase extraction combined with ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometry (UPLC-MS/MS) was used to detect antidepressants.ResultsThe most abundant compound was venlafaxine, followed by citalopram, sertraline, and fluvoxamine with concentrations between 0.6 and 87 ng/L. Antidepressants showed maximum concentrations at the effluent outlets of the WWTPs, and greater concentrations were found downstream than upstream of the WWTPs in Qiantang River. The results of source water and finished water showed that the detection concentration was lower than the detection limit of the method.ConclusionsThe less impact of the release of antidepressants from WWTPs to the surface water on the drinking water was identified. Nevertheless, these compounds were hardly removed by wastewater treatment processes. Thus, their risks deserve close attention.

Determination of quinolone antibiotics in environmental water using automatic solid-phase extraction and isotope dilution ultra-performance liquid chromatography tandem mass spectrometry

The widespread use of quinolones in humans and animals has become a major threat to public health. In this study, a simple, rapid, sensitive, and high throughput method based on automatic solid-phase extraction and isotope dilution ultra-performance liquid chromatography tandem mass spectrometry was described for the determination of trace quinolones in environmental water. The proposed automated solid-phase extraction method was initially optimized, and the optimum experimental conditions found were 1 L water sample with 0.5 g/L Na2EDTA (pH 3) extracted and enriched by CNW Poly-Sery HLB cartridge at a flow rate of 50 mL/min and eluted by 8 mL of methanol. The linearity of the method ranged from 0.05 to 100 μg/L for 15 quinolones, with correlation coefficients ranging from 0.9993 to 0.9999. The limits of detection were in the low ng/L level, ranging from 0.005 to 0.051 ng/L. Finally, the optimized method was applied for determining trace levels of 15 quinolones in Wahaha pure water, tap water, river water, and seawater samples with good recoveries of 93 %–119 % and satisfactory relative standard deviations of 0.1 %–13.9 %. Fourteen quinolones were detected, and ofloxacin was the predominant congener in river water and seawater.

Determination of Fe, Ni, Cu, Zn, Cd and Pb in seawater by isotope dilution automatic solid-phase extraction—ICP-MS

Determination of Fe, Ni, Cu, Zn, Cd and Pb in seawater by isotope dilution automatic solid-phase extraction—ICP-MS

Rapid pretreatment for multi-sample analysis of advanced glycation end products and their role in nephropathy.

Advanced glycation end products (AGEs), produced by the Maillard reaction between carbohydrates and proteins, may be involved in diabetes and its complications. Accurate quantification of AGEs in vivo can demonstrate the relation between AGEs and pathological conditions, but it is not widely used in clinical practice because of the multiple pretreatment steps before analyses. We developed a fully automated solid-phase extraction system (FSPES) to simplify rate-limiting pretreatment using a cation exchange column. We applied this device to evaluate AGEs in nephropathy. Among the standard samples, we used arginine, lysine, N‍ε-(carboxymethyl)lysine (CML), N‍ω-(carboxymethyl)arginine (CMA), N‍ε-(carboxyethyl)lysine (CEL), and N‍δ-(5-hydro-5-methyl-4-imidazolone-2-yl)-ornithine (MG-H1) for FSPES. We analyzed the coefficient of variation (CV) by mass spectrometry. FSPES performed column operations rapidly at a pressure three times higher compared with the conventional method. FSPES stably performed pretreatment. CV results for CML, CMA, CEL, and MG-H1 measurements in bovine and human serum were the same as those in the conventional pretreatment. Among the AGE structures we measured, CML and CEL increased with the decline in kidney function. The CML and CEL levels of patients with nephropathy were significantly higher than those in normal subjects. Thus, FSPES is useful for clarifying the relation between AGEs and various pathological conditions.

Evaluation of a Septumless Mini-Cartridge for Automated Solid-Phase Extraction Cleanup in GS-MS(/MS) Analysis of &amp;gt;250 Pesticides and Environmental Contaminants in Fatty and Nonfatty Foods

Evaluation of a Septumless Mini-Cartridge for Automated Solid-Phase Extraction Cleanup in GS-MS(/MS) Analysis of &amp;gt;250 Pesticides and Environmental Contaminants in Fatty and Nonfatty Foods

Simultaneous determination of seven bisphenol analogues in surface water by solid-phase extraction and ultra-performance liquid chromatography-tandem mass spectrometry

For the simultaneous determination of seven types of bisphenol analogues (BPs) in surface water, a method combining solid-phase extraction (SPE) with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed. The extraction efficiency was improved by optimizing the parameters that affect it, including the sorbent types of SPE cartridge, pH, enrichment factor, flow rate, rinsing and elution volume. On the basis of the single factor experiments, an attempt to obtain the result of optimizing by response surface methodology was made, and the optimal parameters were as follows: at a flow rate of 8 mL/min, 1000 mL of water sample was run through the hydrophilic-lipophilic balance cartridge, rinsed with 10% methanol, eluted with 9 mL methanol, and concentrated with nitrogen using an automatic SPE system. The analytes were separated on an Acquity UPLC BEH C18 column using gradient elution with a mobile phase of acetonitrile and 0.05% (v/v) ammonia, and then analyzed using UPLC-MS/MS with multiple reaction monitoring in the negative-ion mode, with an 8-minute chromatographic run time. In the range of 1.0–500 μg/L, seven BPs showed good linearity with the correlation coefficient greater than 0.998. The recovery ranged from 82.3 to 96.7%, and the range of matrix effect was 89.2 to 107%. These results indicated excellent recovery and minimal matrix effect. The limits of detection were 0.05–1.5 ng/L, the relative standard deviation ranged from 2.9 to 8.5%. Applying the developed method, seven BPs in Luoma Lake and its inflow rivers were analyzed. Only five BPs were detected in Luoma Lake and four BPs were detected in inflow rivers, and the concentrations of the detected BPs were determined. BPA and BPF were the predominant BPs, and the concentration of BPA was the highest.