Advanced wastewater treatment such as powdered activated carbon (PAC) reduces the load of organic micropollutants entering the aquatic environment. Since mobile and persistent compounds accumulate in ...water cycles, treatment strategies need to be evaluated for the removal of (very) polar compounds. Thereby, non-targeted analysis gives a global picture of the molecular fingerprint (including these very polar molecules) of water samples. Target and non-target screening were conducted using polarity-extended chromatography hyphenated with mass spectrometry. Samples treated with different types and concentrations of PAC were compared to untreated samples. Molecular features were extracted from the analytical data to determine fold changes, perform a principal component analysis and for significance testing. The results suggest that a part of the polar target analytes was adsorbed but also some byproducts might be formed or desorbed from the PAC.
► Retention behavior of structural related benzoic acids on a sulfobetaine phase in ZIC-HILIC. ► The retention is due to number, position and H-bond properties of the functional groups. ► Benzoic ...acids retention is well described by partition-like models. ► Adsorption-like processes contribute to the retention of analytes with H-donor groups. ► ACN and salt content in the mobile phase affect the thickness of the water layer in which partition takes place.
The retention behavior of fifteen isomeric hydroxy- and aminobenzoic acids in zwitterionic hydrophilic interaction chromatography was studied using a sulfobetaine phase (ZIC-HILIC). By an inspection of their molecular structures, the retention was related to the number, the position and hydrogen bond properties of the functional groups. The effect of the chromatographic conditions was analyzed in order to investigate the retention mechanism of the stationary phase. The increased retention observed for negative charged compounds when the mobile phase pH decreased was ascribed to a diminishing of the electrostatic repulsion with the underivatized silanol groups. Also the salt buffer concentration in the mobile was proved to have a great influence in the modulation of the electrostatic interactions. However, the retention behavior of the benzoic acids was not described by conventional ion-exchange models. Subsequently, a systematical analysis of partition, adsorption, and hydrophilic chromatographic models was presented. The results from the fittings indicated that partition processes govern mainly the ZIC-HILIC separation, but also adsorption processes via hydrogen bonds occurred for hydrogen donor analytes. Finally, the influence of the chromatographic conditions on the water enriched layer in which partition takes place has been evaluated by the elution behavior of toluene.
Micro-, submicro- and nanoplastic particles are increasingly regarded as vectors for trace organic chemicals. In order to determine adsorbed trace organic chemicals on polymers, it has usually been ...necessary to carry out complex extraction steps. With the help of a newly designed thermal desorption pyrolysis gas chromatography mass spectrometry (TD-Pyr-GC/MS) method, it is possible to identify adsorbed trace organic chemicals on micro-, submicro- and nanoparticles as well as the particle short chain polymers in one analytical setup without any transfers. This ensures a high sample throughput for the qualitative analysis of trace substances and polymer type. Since the measuring time per sample is only 2 h, a high sample throughput is possible. It is one of the few analytical methods which can be used also for the investigation of nanoplastic particles. Initially adsorbed substances are desorbed from the particle by thermal desorption (TD); subsequently, the polymer is fragmented by pyrolysis (PYR). Both particle treatment techniques are directly coupled with the same GC-MS system analyzing desorbed molecules and pyrolysis products, respectively. In this study, we developed a systematic and optimized method for this application. For method development, the trace organic chemicals phenanthrene, α-cypermethrin and triclosan were tested on reference polymers polystyrene (PS), polymethyl methacrylate (PMMA) and polyethylene (PE). Well-defined particle fractions were used, including polystyrene (sub)micro- (41 and 40 µm) and nanoparticles (78 nm) as well as 48-µm sized PE and PMMA particles, respectively. The sorption of phenanthrene (PMMA << PS 40 µm < 41 µm < PE < PS 78 nm) and α-cypermethrin (PS 41 µm < PS 40 µm < PE < PMMA < PS 78 nm) to the particles was strongly polymer-dependent. Triclosan adsorbed only on PE and on the nanoparticles of PS (PE < PS78).
The information obtained from the chemical analysis of specific human excretion products (biomarkers) in urban wastewater can be used to estimate the exposure or consumption of the population under ...investigation to a defined substance. A proper biomarker can provide relevant information about lifestyle habits, health and wellbeing, but its selection is not an easy task as it should fulfil several specific requirements in order to be successfully employed. This paper aims to summarize the current knowledge related to the most relevant biomarkers used so far. In addition, some potential wastewater biomarkers that could be used for future applications were evaluated. For this purpose, representative chemical classes have been chosen and grouped in four main categories: (i) those that provide estimates of lifestyle factors and substance use, (ii) those used to estimate the exposure to toxicants present in the environment and food, (iii) those that have the potential to provide information about public health and illness and (iv) those used to estimate the population size. To facilitate the evaluation of the eligibility of a compound as a biomarker, information, when available, on stability in urine and wastewater and pharmacokinetic data (i.e. metabolism and urinary excretion profile) has been reviewed. Finally, several needs and recommendations for future research are proposed.
•Wastewater biomarkers provide information on lifestyle habits, health and wellbeing.•Specific criteria should be followed to select a suitable biomarker.•Report of the current knowledge of the most relevant biomarkers used so far•Proposal of potential wastewater biomarkers for future applications•Review of pharmacokinetic data and stability in urine and wastewater for each biomarker
Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an ...extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography–mass spectrometry (LC-MS) and gas chromatography–mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.
Micro- and nanoplastic particles are increasingly seen not only as contaminants themselves, but also as potential vectors for trace organic chemicals (TOrCs) that might sorb onto these particles. An ...analysis of the sorbed TOrCs can either be performed directly from the particle or TOrCs can be extracted from the particle with a solvent. Another possibility is to analyze the remaining concentration in the aqueous phase by a differential approach. In this review, the focus is on analytical methods that are suitable for identifying and quantifying sorbed TOrCs on micro- and nano-plastics. Specific gas chromatography (GC), liquid chromatography (LC) and ultraviolet-visible spectroscopy (UV-VIS) methods are considered. The respective advantages of each method are explained in detail. In addition, influencing factors for sorption in the first place are being discussed including particle size and shape (especially micro and nanoparticles) and the type of polymer, as well as methods for determining sorption kinetics. Since the particles are not present in the environment in a virgin state, the influence of aging on sorption is also considered.
Certain persistent and polar substances may pose a hazard to drinking water resources. To foster the knowledge exchange in this field the Working Group
Environmental Monitoring
of the German Chemical ...Society (GDCh) Division
Environmental Chemistry and Ecotoxicology
discussed at their meeting in December 2018 the significance and relevance of persistent, mobile and toxic chemicals (PMT substances) in the environment. Five oral contributions highlighted not only various aspects such as the identification of potential PMT substances based on certain properties and their possible regulation under the European REACH regulation, but also current developments in the analysis of PMT substances and results from environmental monitoring. The data presented prove that many persistent and mobile substances can be detected in surface waters. Once detected, it can be complex and costly to identify sources and reduce inputs, as a case study on 1,4-dioxane in Bavarian surface waters shows. The same applies to the removal of polar substances from raw water for drinking water production. Today, scientific advances in analytical methods make it easier to identify and quantify even very polar substances in water samples. In addition to the targeted analysis of critical chemicals, non-target screening is playing an increasingly important role. This opens up the possibility of detecting substances in water samples that have not previously been investigated in routine monitoring and testing their relevance for humans and the environment. However, the list of potentially occurring PM substances that have not yet been investigated is still very long. Further methodological improvements seem necessary here. In view of the evidence for the presence of PMT substances in the environment (e.g., trifluoroacetic acid and 1,4-dioxane) and the potential risks for drinking water abstraction, it seems important under consideration of the precautionary principle to identify and prioritise relevant REACH-registered substances. The assessment should be based on the intrinsic properties and the emission potential of the compounds. The implementation of a detailed proposal made at European level to regulate PMT and very persistent and very mobile (vPvM) substances in the context of REACH would ensure that chemicals identified as being substances of very high concern according to the PMT and vPvM criteria are subject to authorisation in future.
(Mass spectrometric) non-target screening is a preferably comprehensive and untargeted (predominantly organic molecules detecting) approach combining (robust) analytical measurements with adapted ...data evaluation concepts, systematic compound identification workflows, and statistical data interpretation. It is well suitable for the identification of new, unexpected and/or unknown organic compounds as well as monitoring ‘molecular fingerprints’ and profiling ‘process-relevant’ molecules via statistical methods. In recent years, 14 articles in various disciplines were published and presented in this Special Issue, whereby it contains 4 peer-reviewed review articles and 10 peer-reviewed research articles dealing with non-target screening strategies and solutions.
(Mass spectrometric) non-target screening is a preferably comprehensive and untargeted (predominantly organic molecules detecting) approach combining (robust) analytical measurements with adapted ...data evaluation concepts, systematic compound identification workflows, and statistical data interpretation. It is well suitable for the identification of new, unexpected and/or unknown organic compounds as well as monitoring ‘molecular fingerprints’ and profiling ‘process-relevant’ molecules via statistical methods. In recent years, 14 articles in various disciplines were published and presented in this Special Issue, whereby it contains 4 peer-reviewed review articles and 10 peer-reviewed research articles dealing with non-target screening strategies and solutions.
Detoxification of xenobiotic compounds and heavy metals is a pivotal capacity of organisms, in which glutathione (GSH) plays an important role. In plants, electrophilic herbicides are conjugated to ...the thiol group of GSH, and heavy metal ions form complexes as thiolates with GSH-derived phytochelatins (PCs). In both detoxification processes of plants, phytochelatin synthase (PCS) emerges as a key player. The enzyme is activated by heavy metal ions and catalyzes PC formation from GSH by transferring glutamylcysteinyl residues (γ-EC) onto GSH. In this study with Arabidopsis, we show that PCS plays a role in the plant-specific catabolism of glutathione conjugates (GS-conjugates). In contrast to animals, breakdown of GS-conjugates in plants can be initiated by cleavage of the carboxyterminal glycine residue that leads to the generation of the corresponding γ-EC-conjugate. We used the xenobiotic bimane in order to follow GS-conjugate turnover. Functional knockout of the two PCS of Arabidopsis, AtPCS1 and AtPCS2, revealed that AtPCS1 provides a major activity responsible for conversion of the fluorescent bimane-GS-conjugate (GS-bimane) into γ-EC-bimane. AtPCS1 deficiency resulted in a γ-EC-bimane deficiency. Transfection of PCS-deficient cells with AtPCS1 recovered γ-EC-bimane levels. The level of the γ-EC-bimane conjugate was enhanced several-fold in the presence of Cd²⁺ ions in the wild type, but not in the PCS-deficient double mutant, consistent with a PCS-catalyzed GS-conjugate turnover. Thus AtPCS1 has two cellular functions: mediating both heavy metal tolerance and GS-conjugate degradation.
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