Performance of free-flow field-step electrophoresis as cleanup step for the non-target analysis of environmental water samples.

For the analysis of low concentrations of micropollutants in environmental water samples, efficient sample enrichment and cleanup are necessary to reduce matrix effects and to reach low detection limits. For analytes of low and medium polarity, solid-phase extraction is used, but robust methods for the preconcentration of highly polar or ionizable analytes are scarce. In this work, field-step electrophoresis (FSE) was developed as an environmental sample cleanup technique for ionizable micropollutants and ionic transformation products. The FSE electrolyte system preconcentrated 15 acidic model analytes (pKa from -2.2 to 9.1) present in aqueous samples in two fractions by factors of 5-10. Simultaneously, highly mobile matrix compounds were removed including inorganic ions such as sulfate and chloride. The fractions were either directly injected for downstream analysis by reversed-phase liquid chromatography (RPLC) or further processed by evaporative preconcentration with subsequent reconstitution in an organic solvent suitable for separation methods like hydrophilic interaction chromatography. The FSE/RPLC-MS method exhibited high quantitative precision with RSDs of 3-6%. The method was successfully applied to a spiked river water sample and its performance compared with common solid-phase extraction and evaporative concentration, demonstrating a high analyte coverage. FSE combined with non-target screening by RPLC-MS revealed a strong reduction in matrix load especially at low retention times. Seventeen compounds were identified in the FSE fractions sampled at the field step boundary by retention time, accurate mass, and mass fragments. Suspect screening by FSE/RPLC-MS was facilitated by FSE's selectivity for anionic compounds.

Chlorothalonil transformation products in drinking water resources: Widespread and challenging to abate.

Chlorothalonil, a fungicide applied for decades worldwide, has recently been banned in the European Union (EU) and Switzerland due to its carcinogenicity and the presence of potentially toxic transformation products (TPs) in groundwater. The spread and concentration range of chlorothalonil TPs in different drinking water resources was examined (73 groundwater and four surface water samples mainly from Switzerland). The chlorothalonil sulfonic acid TPs (R471811, R419492, R417888) occurred more frequently and at higher concentrations (detected in 65-100% of the samples, ≤2200 ngL-1) than the phenolic TPs (SYN507900, SYN548580, R611968; detected in 10-30% of the samples, ≤130 ngL-1). The TP R471811 was found in all samples and even in 52% of the samples above 100 ngL-1, the drinking water standard in Switzerland and other European countries. Therefore, the abatement of chlorothalonil TPs was investigated in laboratory and pilot-scale experiments and along the treatment train of various water works, comprising aquifer recharge, UV disinfection, ozonation, advanced oxidation processes (AOPs), activated carbon treatment, and reverse osmosis. The phenolic TPs can be abated during ozonation (second order rate constant kO3 ∼104 M-1s-1) and by reaction with hydroxyl radicals (OH) in AOPs (kOH ∼109 M-1s-1). In contrast, the sulfonic acid TPs, which occurred in higher concentrations in drinking water resources, react only very slowly with ozone (kO3 <0.04 M-1s-1) and OH (kOH <5.0 × 107 M-1s-1) and therefore persist in ozonation and OH-based AOPs. Activated carbon retained the very polar TP R471811 only up to a specific throughput of 25 m3kg-1 (20% breakthrough), similarly to the X-ray contrast agent diatrizoic acid. Reverse osmosis was capable of removing all chlorothalonil TPs by ≥98%.

Enrichment-free analysis of anionic micropollutants in the sub-ppb range in drinking water by capillary electrophoresis-high resolution mass spectrometry.

Reversed-phase liquid chromatography (RPLC) used for water analysis is not ideal for the analysis of highly polar and ionic contaminants because of low retention. Capillary electrophoresis (CE), on the other hand, is perfectly suited for the separation of ionic compounds but rarely applied in environmental analysis due to the weak concentration sensitivity when coupled to mass spectrometry (MS). However, novel interface designs and MS technology strongly improve the sensitivity. Here, a method is presented enabling the screening of anionic micropollutants in drinking water without sample pretreatment by coupling of CE to an Orbitrap mass spectrometer by a nanoflow sheath liquid interface. Targeted analysis of halogenated acetic acids, trifluoromethanesulfonic acid, and perfluorooctanoic and perfluorooctanesulfonic acid was conducted in drinking water samples which were chlorinated for disinfection. A bare fused silica capillary with an optimized background electrolyte (BGE) for separation consisting of 10% acetic acid with 10% isopropanol with large volume sample injection and optimized interface parameters offer limits of quantification in the range of < 0.1 to 0.5 µg/L with good linearity (R2 > 0.993) and repeatability (14% standard deviation in area). Concentrations of the target analytes ranged from 0.1 to 6.2 µg/L in the water samples. Masses corresponding to halogenated methanesulfonic acids have been found as suspects and were subsequently verified by standards. Mono-, dichloro-, and bromochloro methanesulfonic acid were quantified in a range of 0.2 to 3.6 µg/L. Furthermore, five sulfonic acids, four organosulfates, and the artificial sweeteners acesulfame and cyclamate as well as inorganics such as halides, halogenates, phosphate, and sulfate could be determined as suspects among more than 300 features in a non-targeted screening. Overall, this approach demonstrates the great potential of CE-nanoESI-MS for the screening of ionic contaminants in environmental samples, complementary to chromatographic approaches.

Column bleed in the analysis of highly polar substances: an overlooked aspect in HRMS.

To close the "analytical gap" in the liquid chromatographic (LC) analysis of highly polar substances, two techniques which have been suggested earlier were tested in terms of retention factors and detection limits: hydrophilic interaction liquid chromatography (HILIC) and mixed-mode chromatography (MMC). A substance mix of 55 analytes ranging from logD - 8.2 to 3.4 and 17 different LC columns, also comprising additional reversed-phase columns were used. Contrary to most reversed-phase columns, column bleed has been identified as an important factor, which may cause serious restrictions during high-resolution mass spectrometric detection (HRMS). We found that highly abundant background masses continuously eluting from the columns heavily influence ion transmission to the detector. As a result, the linear dynamic range as well as the sensitivity decreases and thus limits the HRMS applicability of some columns. We therefore recommend a thorough investigation of ion transmission during HRMS method development. This will help to maintain the high potential of HRMS in terms of qualitative and quantitative screening analysis.

[Coercive interventions: historical summary and review of subjective experience]. / Zwangsmaßnahmen in der Psychiatrie: Aus der Steinzeit in eine bessere Zukunft.

Psychiatric treatment has always been associated with violence and coercion. Involuntary admission and coercive measures are still frequently occurring components in everyday clinical practice.Up to 15% of psychiatric inpatients experience coercive treatment at least once during hospital stay. Particularly patients suffering from schizophrenia, organic mental disorders and mania have a high risk for such incidents.There is an ongoing intense debate on the need and justification of coercive measures, although most clinicians and scientists currently agree that there is no alternative. Several investigations have shown that seclusion and mechanical restraint go along with physical and psychological problems affecting both, patients and staff. However, it was possible to identify aspects that could be improved: Maintaining an objective and professional communication during coercive treatment seems just as important as making comprehensible decisions. Alternative treatment options should be focus of further investigations.

LC-HRMS Data Processing Strategy for Reliable Sample Comparison Exemplified by the Assessment of Water Treatment Processes.

The behavior of micropollutants in water treatment is an important aspect in terms of water quality. Nontarget screening by liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) offers the opportunity to comprehensively assess water treatment processes by comparing the signal heights of all detectable compounds before and after treatment. Without preselection of known target compounds, all accessible information is used to describe changes across processes and thus serves as a measure for the treatment efficiency. In this study, we introduce a novel LC-HRMS data processing strategy for the reliable classification of signals based on the observed fold changes. An approach for filtering detected features was developed and, after parameter adjustment, validated for its recall and precision. As proof of concept, the fate of 411 target compounds in a 0.1 µg/L standard mix was tracked throughout the data processing stages, where 406 targets were successfully recognized and retained during filtering. Potential pitfalls in signal classification were addressed. We found the recursive peak integration to be a key point for the reliable classification of signal changes across a process. For evaluating the repeatability, a combinatorial approach was conducted to verify the consistency of the final outcome using technical replicates of influent and effluent samples taken from an ozonation process during drinking water treatment. The results showed sufficient repeatability and thus emphasized the applicability of nontarget screening for the assessment of water treatment processes. The developed data processing strategies may be transferred to other research fields where sample comparisons are conducted.

General strategies to increase the repeatability in non-target screening by liquid chromatography-high resolution mass spectrometry.

This article focuses on the data evaluation of non-target high-resolution LC-MS profiles of water samples. Taking into account multiple technical replicates, the difficulties in peak recognition and the related problems of false positive and false negative findings are systematically demonstrated. On the basis of a combinatorial approach, different models involving sophisticated workflows are evaluated, particularly with regard to the repeatability. In addition, the improvement resulting from data processing was systematically taken into consideration where the recovery of spiked standards emphasized that real peaks of interest were barely or not removed by the derived filter criteria. The comprehensive evaluation included different matrix types spiked with up to 263 analytical standards which were analyzed repeatedly leading to a total number of more than 250 injections that were incorporated in the assessment of different models of data processing. It was found that the analysis of multiple replicates is the key factor as, on the one hand, it provides the option of integrating valuable filters in order to minimize the false positive rate and, on the other hand, allows correcting partially false negative findings occurring during the peak recognition. The developed processing strategies including replicates clearly point to an enhanced data quality since both the repeatability as well as the peak recognition could be considerably improved. As proof of concept, four different matrix types, including a wastewater treatment plant (WWTP) effluent, were spiked with 130 isotopically labeled standards at different concentration levels. Despite the stringent filter criteria, at 100 ng L(-1) recovery rates of up to 93% were reached in the positive ionization mode. The proposed model, comprising three technical replicates, filters less than 5% and 2% of the standards recognized at 100 and 500 ng L(-1), respectively and thus indicates the general applicability of the presented strategies.