Non-target screening reveals time trends of polar micropollutants in a riverbank filtration system

The historic emissions of polar micropollutants in a natural drinking water source were investigated by nontarget screening with high-resolution mass spectrometry and open cheminformatics tools. The study area consisted of a riverbank filtration transect fed by the river Lek, a branch of the lower Rhine, and exhibiting up to 60-year travel time. More than 18,000 profiles were detected. Hierarchical clustering revealed that 43% of the 15 most populated clusters were characterized by intensity trends with maxima in the 1990s, reflecting intensified human activities, wastewater treatment plant upgrades and regulation in the Rhine riparian countries. Tentative structure annotation was performed using automated in silico fragmentation. Candidate structures retrieved from ChemSpider were scored based on the fit of the in silico fragments to the experimental tandem mass spectra, similarity to openly accessible accurate mass spectra, associated metadata, and presence in a suspect list. Sixty-seven unique structures (72 over both ionization modes) were tentatively identified, 25 of which were confirmed and included contaminants so far unknown to occur in bank filtrate or in natural waters at all, such as tetramethylsulfamide. This study demonstrates that many classes of hydrophilic organics enter riverbank filtration systems, persisting and migrating for decades if biogeochemical conditions are stable

Per- and Polyfluoroalkyl Substances (PFAS) in PubChem: 7 Million and Growing.

peer reviewedPer- and polyfluoroalkyl substances (PFAS) are of high concern, with calls to regulate them as a class. In 2021, the Organisation for Economic Co-operation and Development (OECD) revised the definition of PFAS to include any chemical containing at least one saturated CF2 or CF3 moiety. The consequence is that one of the largest open chemical collections, PubChem, with 116 million compounds, now contains over 7 million PFAS under this revised definition. These numbers are several orders of magnitude higher than previously established PFAS lists (typically thousands of entries) and pose an incredible challenge to researchers and computational workflows alike. This article describes a dynamic, openly accessible effort to navigate and explore the >7 million PFAS and >21 million fluorinated compounds (September 2023) in PubChem by establishing the "PFAS and Fluorinated Compounds in PubChem" Classification Browser (or "PubChem PFAS Tree"). A total of 36500 nodes support browsing of the content according to several categories, including classification, structural properties, regulatory status, or presence in existing PFAS suspect lists. Additional annotation and associated data can be used to create subsets (and thus manageable suspect lists or databases) of interest for a wide range of environmental, regulatory, exposomics, and other applications

Open and FAIR transformation product data for improved suspect/non-target screening: REFTPs in the NORMAN-SLE, PubChem and patRoon

peer reviewedPresentation given at ICCE, Venice, 11 - 15 June 2023

Avoiding the Next Silent Spring: Our Chemical Past, Present, and Future

Rachel Carson's Silent Spring,1 published just over 60 years ago, outlined how the indiscriminate use of dichlorodiphenyltrichloroethane (DDT), a potent, environmentally persistent insecticide, was damaging the world's ecosystems, animals and food supply. There were many other chemicals more persistent than DDT accumulating in the environment when Carson was writing, including per- and polyfluoroalkyl substances (PFAS). Whilst man-made, PFAS were not intended to cause harm, contrary to pesticides such as DDT. Today, ambient PFAS levels are contaminating rain, soil and drinking water resources worldwide to such an extent that they have caused substantial, irreversible health and environmental damage.2 Like DDT, PFAS were long in use by the time Rachel Carson was writing Silent Spring (see Figure 1). However, their environmental presence went unnoticed by Carson and other contemporary environmental researchers. PFAS were entering the environment under the radar, except to those who were manufacturing and emitting them.

HESI UVCB Meeting - Integrating UVCBs and Related Data into Open Chemical Knowledgebases - PubChem and NORMAN-SLE

Presentation and poster (given remotely) for the HESI UVCB Meeting in Iceland, 18-19 September, 2023

ShinyTPs: Curating Transformation Products from Text Mining Results.

peer reviewedTransformation product (TP) information is essential to accurately evaluate the hazards compounds pose to human health and the environment. However, information about TPs is often limited, and existing data is often not fully Findable, Accessible, Interoperable, and Reusable (FAIR). FAIRifying existing TP knowledge is a relatively easy path toward improving access to data for identification workflows and for machine-learning-based algorithms. ShinyTPs was developed to curate existing transformation information derived from text-mined data within the PubChem database. The application (available as an R package) visualizes the text-mined chemical names to facilitate the user validation of the automatically extracted reactions. ShinyTPs was applied to a case study using 436 tentatively identified compounds to prioritize TP retrieval. This resulted in the extraction of 645 reactions (associated with 496 compounds), of which 319 were not previously available in PubChem. The curated reactions were added to the PubChem Transformations library, which was used as a TP suspect list for identification of TPs using the open-source workflow patRoon. In total, 72 compounds from the library were tentatively identified, 18% of which were curated using ShinyTPs, showing that the app can help support TP identification in non-target analysis workflows.U-AGR-8049 - H2020 - ZeroPM (01/10/2021 - 30/09/2026) - SCHYMANSKI Emm

HESS Opinions: Functional units: a novel framework to explore the link between spatial organization and hydrological functioning of intermediate scale catchments

This opinion paper proposes a novel framework for exploring how spatial organization alongside with spatial heterogeneity controls functioning of intermediate scale catchments of organized complexity. Key idea is that spatial organization in landscapes implies that functioning of intermediate scale catchments is controlled by a hierarchy of functional units: hillslope scale lead topologies and embedded elementary functional units (EFUs). We argue that similar soils and vegetation communities and thus also soil structures "co-developed" within EFUs in an adaptive, self-organizing manner as they have been exposed to similar flows of energy, water and nutrients from the past to the present. Class members of the same EFU (class) are thus deemed to belong to the same ensemble with respect to controls of the energy balance and related vertical flows of capillary bounded soil water and heat. Class members of superordinate lead topologies are characterized by the same spatially organized arrangement of EFUs along the gradient driving lateral flows of free water as well as a similar surface and bedrock topography. We hence postulate that they belong to the same ensemble with respect to controls on rainfall runoff transformation and related vertical and lateral fluxes of free water. We expect class members of these functional units to have a distinct way how their architecture controls the interplay of state dynamics and integral flows, which is typical for all members of one class but dissimilar among the classes. This implies that we might infer on the typical dynamic behavior of the most important classes of EFU and lead topologies in a catchment, by thoroughly characterizing a few members of each class. A major asset of the proposed framework, which steps beyond the concept of hydrological response units, is that it can be tested experimentally. In this respect, we reflect on suitable strategies based on stratified observations drawing from process hydrology, soil physics, geophysics, ecology and remote sensing which are currently conducted in replicates of candidate functional units in the Attert basin (Luxembourg), to search for typical and similar functional and structural characteristics. A second asset of this framework is that it blueprints a way towards a structurally more adequate model concept for water and energy cycles in intermediate scale catchments, which balances necessary complexity with falsifiability. This is because EFU and lead topologies are deemed to mark a hierarchy of "scale breaks" where simplicity with respect to the energy balance and stream flow generation emerges from spatially organized process-structure interactions. This offers the opportunity for simplified descriptions of these processes that are nevertheless physically and thermodynamically consistent. In this respect we reflect on a candidate model structure that (a) may accommodate distributed observations of states and especially terrestrial controls on driving gradients to constrain the space of feasible model structures and (b) allows testing the possible added value of organizing principles to understand the role of spatial organization from an optimality perspective

Identification strategy for unknown pollutants using high-resolution mass spectrometry: Androgen-disrupting compounds identified through effect-directed analysis

Effect-directed analysis has been applied to a river sediment sample of concern to identify the compounds responsible for the observed effects in an in vitro (anti-)androgenicity assay. For identification after non-target analysis performed on a high-resolution LTQ-Orbitrap, we developed a de novo identification strategy including physico-chemical parameters derived from the effect-directed analysis approach. With this identification strategy, we were able to handle the immense amount of data produced by non-target accurate mass analysis. The effect-directed analysis approach, together with the identification strategy, led to the successful identification of eight androgen-disrupting compounds belonging to very diverse compound classes: an oxygenated polyaromatic hydrocarbon, organophosphates, musks, and steroids. This is one of the first studies in the field of environmental analysis dealing with the difficult task of handling the large amount of data produced from non-target analysis. The combination of bioassay activity assessment, accurate mass measurement, and the identification and confirmation strategy is a promising approach for future identification of environmental key toxicants that are not included as priority pollutants in monitoring programs

Should Transformation Products Change the Way We Manage Chemicals?

peer reviewedWhen chemical pollutants enter the environment, they can undergo diverse transformation processes, forming a wide range of transformation products (TPs), some of them benign and others more harmful than their precursors. To date, the majority of TPs remain largely unrecognized and unregulated, particularly as TPs are generally not part of routine chemical risk or hazard assessment. Since many TPs formed from oxidative processes are more polar than their precursors, they may be especially relevant in the context of persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances, which are two new hazard classes that have recently been established on a European level. We highlight herein that as a result, TPs deserve more attention in research, chemicals regulation, and chemicals management. This perspective summarizes the main challenges preventing a better integration of TPs in these areas: (1) the lack of reliable high-throughput TP identification methods, (2) uncertainties in TP prediction, (3) inadequately considered TP formation during (advanced) water treatment, and (4) insufficient integration and harmonization of TPs in most regulatory frameworks. A way forward to tackle these challenges and integrate TPs into chemical management is proposed

Advancing catchment hydrology to deal with predictions under change

Throughout its historical development, hydrology as an earth science, but especially as a problem-centred engineering discipline has largely relied (quite successfully) on the assumption of stationarity. This includes assuming time invariance of boundary conditions such as climate, system configurations such as land use, topography and morphology, and dynamics such as flow regimes and flood recurrence at different spatio-temporal aggregation scales. The justification for this assumption was often that when compared with the temporal, spatial, or topical extent of the questions posed to hydrology, such conditions could indeed be considered stationary, and therefore the neglect of certain long-term non-stationarities or feedback effects (even if they were known) would not introduce a large error. However, over time two closely related phenomena emerged that have increasingly reduced the general applicability of the stationarity concept: the first is the rapid and extensive global changes in many parts of the hydrological cycle, changing formerly stationary systems to transient ones. The second is that the questions posed to hydrology have become increasingly more complex, requiring the joint consideration of increasingly more (sub-) systems and their interactions across more and longer timescales, which limits the applicability of stationarity assumptions. Therefore, the applicability of hydrological concepts based on stationarity has diminished at the same rate as the complexity of the hydrological problems we are confronted with and the transient nature of the hydrological systems we are dealing with has increased. The aim of this paper is to present and discuss potentially helpful paradigms and theories that should be considered as we seek to better understand complex hydrological systems under change. For the sake of brevity we focus on catchment hydrology. We begin with a discussion of the general nature of explanation in hydrology and briefly review the history of catchment hydrology. We then propose and discuss several perspectives on catchments: as complex dynamical systems, self-organizing systems, co-evolving systems and open dissipative thermodynamic systems. We discuss the benefits of comparative hydrology and of taking an information-theoretic view of catchments, including the flow of information from data to models to predictions. In summary, we suggest that these perspectives deserve closer attention and that their synergistic combination can advance catchment hydrology to address questions of change