Trace organic compounds are important in environmental analysis because they impact water quality and introduce potential (eco)toxicological effects. Current analytical methods mostly rely on gas chromatography (GC) or reversed-phase liquid chromatography (RPLC) coupled with (tandem) mass spectrometry. However, neither method can easily separate very polar molecules. This study presents two chromatographic separation strategies, a serial RPLC-hydrophilic interaction liquid chromatography (RPLC-HILIC) coupling and an analytical scale supercritical fluid chromatography (SFC) system, and validates their separation effectiveness as polarity-extended chromatographic methods for 274 environmentally relevant compounds. Compounds tested were grouped into three polarity classes, "very polar" {log D (pH 7) below -2.5}, "polar" {log D (pH 7) -2.5 to +2}, and "non-polar" {log D (pH 7) higher than +2}). Nearly all compounds could be retained in both systems with relative standard deviations of retention times (RT; n = 6) typically between 2 and 5%. Both techniques have considerable benefits when combined with accurate mass spectrometric detection. Molecules RT and accurate mass were recorded in a database for each set up. This information was used for compound screening measurements like "hidden-target screening" in complex environmental matrices (such as wastewater treatment plant effluents). Results of both techniques are complementary and useful for all types of molecules polarity. In this study, more than 80% of the compounds found in wastewater treatment plant effluent samples possessed a negative log D (pH 7) value. This result highlights the basic necessity to include "very polar" compounds in water monitoring techniques and protocols.

Non‐target screening of trace organic compounds complements routine monitoring of water bodies. So‐called features need to be extracted from the raw data that preferably represent a chemical compound. Relevant features need to be prioritized and further be interpreted, for instance by identifying them. Finally, quantitative data is required to assess the risks of a detected compound. This review presents recent and noteworthy contributions to the processing of non‐target screening (NTS) data, prioritization of features as well as (semi‐) quantitative methods that do not require analytical standards. The focus lies on environmental water samples measured by liquid chromatography, electrospray ionization and high‐resolution mass spectrometry. Examples for fully‐integrated data processing workflows are given with options for parameter optimization and choosing between different feature extraction algorithms to increase feature coverage. The regions of interest‐multivariate curve resolution method is reviewed which combines a data compression alternative with chemometric feature extraction. Furthermore, prioritization strategies based on a confined chemical space for annotation, guidance by targeted analysis and signal intensity are presented. Exploiting the retention time (RT) as diagnostic evidence for NTS investigations is highlighted by discussing RT indexing and prediction using quantitative structure‐retention relationship models. Finally, a seminal technology for quantitative NTS is discussed without the need for analytical standards based on predicting ionization efficiencies.

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Highly polar trace organic compounds, which are persistent, mobile, and toxic (PMT) or are very persistent and very mobile (vPvM) in the aquatic environment, may pose a risk to surface water, ground water, and drinking water supplies. Despite the advances in liquid chromatography-mass spectrometry, there often exists an analytical blind spot when it comes to very polar chemicals. This study seeks to make a broad polarity range analytically accessible by means of serially coupling reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) to high-resolution mass spectrometry (HRMS). Moreover, a workflow is presented using optimized data processing of nontarget screening (NTS) data and subsequently generating candidate lists for the identification of very polar molecules via an open-access NTS platform and implemented compound database. First, key input parameters and filters of the so-called feature extraction algorithms were identified, and numerical performance indicators were defined to systematically optimize the data processing method. Second, all features from the very polar HILIC elution window were uploaded to the STOFF-IDENT database as part of the FOR-IDENT open-access NTS platform, which contains additional physicochemical information, and the features matched with potential compounds by their accurate mass. The hit list was filtered for compounds with a negative log D value, indicating that they were (very) polar. For instance, 46 features were assigned to 64 candidate compounds originating from a set of 33 samples from the Isar river in Germany. Three PMT candidates (e.g., guanylurea, melamine, and 1,3-dimethylimidazolidin-2-one) were illustratively validated using the respective reference standards. In conclusion, these findings demonstrate that polarity-extended chromatography reproducibly retards and separates (very) polar compounds from surface waters. These findings further indicate that a transparent and robust data processing workflow for nontarget screening data is available for addressing new (very) polar substances in the aqueous environment.

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