•Innovative sample preparation of multiple-class surfactants.•Quantification by LC–MS/MS using synthetic matrices.•Application to both dissolved and solid matrices of wastewater treatment plants.
...Discharges of surfactants from wastewater treatment plants are often considered as the principal vector of pollution into the environment. The analysis of complex matrices, such as urban wastewater, suspended solids and biological sludge requires careful preparation of the sample to obtain a sensitive, selective and reproducible analysis. A simple, fast, effective and multi-residue method based on the SPE (water) and QuEChERS (solid matrices) approaches using synthetic matrices for validation and quantification, has been developed for the determination of 16 surfactants in wastewater, suspended solids and biological sludge.
This work resulted in an innovative method that was validated to detect and assess several classes of surfactants such as quaternary ammonium compounds, betaïns, alkylphenols and their ethoxylated or sulfated derivatives in urban wastewater and solid matrices. The optimised extraction method exhibited recoveries comprised between 83% and 120% for all the tested compounds in the dissolved matrix and between 50% and 109% for particulate matrix. The limits of quantification of all compounds were comprised between 0.1 and 1.0μg/L for dissolved matrix and between 2 and 1000ng/g (dry weight) in particulate matrix. Linearity was assessed for all compounds within the LOQ–250LOQ range. Confidence intervals were also computed in real matrices with less than 15% margin of error for all studied surfactants. This work has confirmed, first and foremost, that surfactants are indeed highly concentrated in urban wastewater. As expected, linear alkylbenzene sulfonates were present at significant concentrations (up to 1–2mg/L). In addition, although biological processing results in significant removal of the total pollution, the residual concentrations at output of WWTP remain significant (up to 100μg/L).
Increasing production and use of chemicals and awareness of their impact on ecosystems and humans has led to large interest for broadening the knowledge on the chemical status of the environment and ...human health by suspect and non-target screening (NTS). To facilitate effective implementation of NTS in scientific, commercial and governmental laboratories, as well as acceptance by managers, regulators and risk assessors, more harmonisation in NTS is required. To address this, NORMAN Association members involved in NTS activities have prepared this guidance document, based on the current state of knowledge. The document is intended to provide guidance on performing high quality NTS studies and data interpretation while increasing awareness of the promise but also pitfalls and challenges associated with these techniques. Guidance is provided for all steps; from sampling and sample preparation to analysis by chromatography (liquid and gas—LC and GC) coupled via various ionisation techniques to high-resolution tandem mass spectrometry (HRMS/MS), through to data evaluation and reporting in the context of NTS. Although most experience within the NORMAN network still involves water analysis of polar compounds using LC–HRMS/MS, other matrices (sediment, soil, biota, dust, air) and instrumentation (GC, ion mobility) are covered, reflecting the rapid development and extension of the field. Due to the ongoing developments, the different questions addressed with NTS and manifold techniques in use, NORMAN members feel that no standard operation process can be provided at this stage. However, appropriate analytical methods, data processing techniques and databases commonly compiled in NTS workflows are introduced, their limitations are discussed and recommendations for different cases are provided. Proper quality assurance, quantification without reference standards and reporting results with clear confidence of identification assignment complete the guidance together with a glossary of definitions. The NORMAN community greatly supports the sharing of experiences and data via open science and hopes that this guideline supports this effort.
The aims of this work are to develop suitable analytical methods to determine the widely used anticonvulsant carbamazepine and 12 of its degradation/transformation products in water, sediment, fish (
...Gasterosteus aculeatus
) and mollusc (
Dreissena polymorpha
). Protocols based on solid phase extraction for water, pressurized-liquid extraction for sediments and QuEChERS (quick easy cheap efficient rugged and safe) extraction for both organisms followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) are developed, validated and finally applied to samples collected during a 6-month experiment in outdoor mesocosms. Very low detection limits are reached, allowing environmentally realistic doses (namely, 0.05, 0.5 and 5 μg/L nominal concentrations) to be employed. The results indicate several metabolites and/or transformation products in each compartment investigated, with concentrations sometimes being greater than that of the parent carbamazepine. Biotic degradation of carbamazepine is demonstrated in water, leading to 10,11-dihydrocarbamazepine and 10,11-epoxycarbamazepine. In sediment, the degradation results in the formation of acridine, and 2- and 3-hydroxycarbamazepine. Finally, in both organisms, a moderate bioaccumulation is observed together with a metabolization leading to 10,11-epoxycarbamazepine in fish and 2-hydroxycarbamazepine in mollusc. Acridone is also present in fish. This study provides new and interesting data, helping to elucidate how chronic exposure to carbamazepine at relevant concentrations may affect impact freshwater ecosystems.
Abstract
Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental ...samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using one pre-defined method and one locally (i.e. in-house) developed method. The data generated represents a valuable resource (i.e. benchmark) for future developments of algorithms and workflows for NTA experiments.
Antibiotics used in agriculture may reach the environment and stimulate the development and dissemination of antibiotic resistance in the soil microbiome. However, the scope of this phenomenon and ...the link to soil properties needs to be elucidated. This study compared the short-term effects of a range of gentamicin concentrations on the microbiome and resistome of bacterial enrichments and microcosms of an agricultural soil using a metagenomic approach. Gentamicin impact on bacterial biomass was roughly estimated by the number of 16SrRNA gene copies. In addition, the soil microbiome and resistome response to gentamicin pollution was evaluated by 16SrRNA gene and metagenomic sequencing, respectively. Finally, gentamicin bioavailability in soil was determined. While gentamicin pollution at the scale of µg/g strongly influenced the bacterial communities in soil enrichments, concentrations up to 1 mg/g were strongly adsorbed onto soil particles and did not cause significant changes in the microbiome and resistome of soil microcosms. This study demonstrates the differences between the response of bacterial communities to antibiotic pollution in enriched media and in their environmental matrix, and exposes the limitations of culture-based studies in antibiotic-resistance surveillance. Furthermore, establishing links between the effects of antibiotic pollution and soil properties is needed.
An analytical method for the determination of 12 selected estrogens, progestagens and corticosteroids is presented. The optimization of the method, including liquid chromatography separation, ...extraction on a solid phase, purification on a silica gel cartridge and detection by mass spectrometry, is described. Both the repeatability, with relative standard deviation ranging from 1.4 to 2.7%, and the accuracy, with recoveries ranging from 92.7 to 102.4%, were very satisfactory for ten of the target analytes. The limits of detection were lower than 1 ng/L for progestagens, androgens and corticosteroids, and ranged between 0.9 and 4.3 ng/L for estrogens. The results of the analysis of two sewage treatment plants in the area of Lyon (France) by this method reveal that all the compounds investigated are present in the effluents. The estrogen most frequently detected was estrone, with a median of 26.1 ng/L. The target progestagens were detected with concentrations ranging between 5 and 41 ng/L. Androgens were also present in most of the samples in the range 1-30 ng/L, while the corticosteroids were present only in one plant, with a median of 31.9 ng/L.
This study focuses on the preparation of innovative nanocomposite materials based on surface modification of commercial nano-ZrO2 optimized from Brønsted acid–base surface reactions. This surface ...modification was carried out by direct grafting of suitable phosphonic acids bearing a vinylic or phenylic substituent in aqueous solution. Different loading quantities of the anchoring organophosphorus compounds were applied for each materials synthesis. The resulting nanohybrids were thoroughly characterized by infrared spectroscopy (DRIFT), solid-state nuclear magnetic resonance (NMR), nitrogen adsorption-desorption (BET), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS), demonstrating the reliability and efficient tunability of the surface functionalization based on the starting Zr/P ratio. Our nanocomposite materials exhibited a high specific surface area as well as complex porosity networks with well-defined meso-pore. The as-prepared materials were investigated for the adsorption of a mixture of 16 polycyclic aromatic hydrocarbons (PAHs) at 200 ng·mL−1 in an aqueous solution. Adsorption kinetics experiments of each individual material were carried out on the prepared PAHs standard solution for a contact time of up to 6 h. Pretreatments of the adsorption test samples were performed by solid-phase extraction (SPE), and the resulting samples were analyzed using an ultrasensitive GC-orbitrap-MS system. The pseudo-first-order and the pseudo-second-order models were used to determine the kinetic data. The adsorption kinetics were best described and fitted by the pseudo-second-order kinetic model. The correlation between the nature of the substituent (vinylic or phenylic) and the parameters characterizing the adsorption process were found. In addition, an increase of PAHs adsorption rates with phosphonic acid loading was observed.
In the last decade, beta-lactams use in veterinary and human medicine increased to represent today about 15% of the overall consumption. Beta-lactams tend to degrade and metabolize in the ...environment. Therefore, analytical methods must be sensitive enough to quantify low concentrations of the parent molecules and also allow detection of metabolites. This study presents the development of a modified QuEChERS method for the extraction of seven beta-lactams and one degradation product (Amoxicillin, Ampicillin, Cefapirin, Cefoperazone, Cefquinome, Ceftiofur, Cloxacillin, and Amoxicillin-Diketopiperazine) from sewage treatment plant sludge and their analysis by liquid chromatography coupled with tandem mass spectrometry. Before the QuEChERS extraction, a dispersion step of the sample with EDTA-treated sand was optimized and added, allowing to facilitate the exchanges between the matrix and the extraction solvent. Then, to decrease the interferences present in the extract, a fast and efficient pass-through SPE was implemented.
The optimized method was validated and showed satisfactory performances, in adequacy with the analysis of beta-lactams in solid environmental matrices. Limits of quantification lower than 20 ng.g−1 for all analytes, high accuracy (96%–114% quantification on spiked samples nominal concentration) and interday precision (2%–12% RSD) were obtained. This method was then applied to eight sludge samples. Cefapirin and amoxicillin-diketopiperazine were detected in four samples each, at concentrations of 10.2–53.3 ng.g−1 and 3.0–9.5 ng.g−1 respectively. Thus, the developed method is very effective for the extraction of beta-lactams from environmental solid matrices.
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•Effective extraction and sensitive detection of 7 beta-lactams in sludge.•First dispersive QuEChERS extraction based on the addition of EDTA-treated sand.•Significant reduction of matrix effect thanks to a fast pass-through SPE clean-up.•Quantification of cefapirin and amoxicillin metabolite in WWTP sludges.
When dealing with complex matrices such as wastewater treatment plant (WWTP) sludge or animal manure, usual MRM quantification may lack enough sensitivity or accuracy due to the presence of numerous ...interfering compounds co-extracted from the matrix. To circumvent the sensitivity and specificity loss, the method development can be focused on sample extraction, purification or/and optimisation of the detection. In this study, we propose an enhancement of a method for the analysis of five beta-lactams (Amoxicillin, Ampicillin, Cefapirin, Ceftiofur, and Cloxacillin) in WWTP, with the use of a hybrid triple quadrupole-Linear Ion Trap (LIT) spectrometer, enabling triple stage MS acquisition, namely MRM3, in place of the usual MS/MS detection. The adaptation of various parameters such as the secondary fragmentation energy, excitation, and accumulation times of the secondly generated ion are described. The method was then validated and enabled quantification limits between 0.8 and 14.7 ng g−1 associated with accurate quantification (between 98% and 113%). This method is the first to report the use of MRM3 acquisition in an environmental matrix as complex as sludge.
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•First use of MRM3 acquisition for the quantification of beta-lactams in sludge.•Step-by-step optimisation of each compound fragmentation.•Comparison with MRM acquisition.
During recent decades, ultrasmall inorganic nanoparticles have attracted considerable interest due to their favorable biodistribution, pharmacokinetics and theranostic properties. In particular, ...AGuIX nanoparticles made of polysiloxane and gadolinium chelates were successfully translated to the clinics. In an aqueous medium, these nanoparticles are in dynamic equilibrium with polysiloxane fragments due to the hydrolysis of Si-O-Si bonds. Thanks to high-performance liquid chromatography coupled with electrospray ionization mass spectrometry, all these fragments were separated and identified.
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