Computational Tools to Facilitate Early Warning of New Emerging Risk Chemicals.

Innovative tools suitable for chemical risk assessment are being developed in numerous domains, such as non-target chemical analysis, omics, and computational approaches. These methods will also be critical components in an efficient early warning system (EWS) for the identification of potentially hazardous chemicals. Much knowledge is missing for current use chemicals and thus computational methodologies complemented with fast screening techniques will be critical.

Wide-Scope Target and Suspect Screening of Antibiotics in Effluent Wastewater from Wastewater Treatment Plants in Europe.

The occurrence of antibiotics in the environment could result in the development of antibiotic-resistant bacteria, which could result in a public health crisis. The occurrence of 676 antibiotics and the main transformation products (TPs) was investigated in the 48 wastewater treatment plants (WWTPs) from 11 countries (Germany, Romania, Serbia, Croatia, Slovenia, Hungary, Slovakia, Czechia, Austria, Cyprus, and Greece) by target and suspect screening. Target screening involved the investigation of antibiotics with reference standards (40 antibiotics).

European scale assessment of the potential of ozonation and activated carbon treatment to reduce micropollutant emissions with wastewater.

Micropollutants (MPs) in wastewater pose a growing concern for their potential adverse effects on the receiving aquatic environment, and some countries have started requiring that wastewater treatment plants remove them to a certain extent. Broad spectrum advanced treatment processes, such as ozonation, activated carbon or their combination, are expected to yield a significant reduction in the toxicity of effluents. Here we quantify the reduction of effluent toxicity potentially achieved by implementing these advanced treatment solutions in a selection of European wastewater treatment plants.

First Novel Workflow for Semiquantification of Emerging Contaminants in Environmental Samples Analyzed by Gas Chromatography-Atmospheric Pressure Chemical Ionization-Quadrupole Time of Flight-Mass Spectrometry.

The ionization efficiency of emerging contaminants was modeled for the first time in gas chromatography-high-resolution mass spectrometry (GC-HRMS) which is coupled to an atmospheric pressure chemical ionization source (APCI). The recent chemical space has been expanded in environmental samples such as soil, indoor dust, and sediments thanks to recent use of high-resolution mass spectrometric techniques; however, many of these chemicals have remained unquantified. Chemical exposure in dust can pose potential risk to human health, and semiquantitative analysis is potentially of need to semiquantify these newly identified substances and assist with their risk assessment and environmental fate.

Application of a novel prioritisation strategy using non-target screening for evaluation of temporal trends (1969-2017) of contaminants of emerging concern (CECs) in archived lynx muscle tissue samples.

Most environmental monitoring studies of contaminants of emerging concern (CECs) focus on aquatic species and target specific classes of CECs. Even with wide-scope target screening methods, relevant CECs may be missed. In this study, non-target screening (NTS) was used for tentative identification of potential CECs in muscle tissue of the terrestrial top predator Eurasian lynx (Lynx lynx).

Novel prioritisation strategies for evaluation of temporal trends in archived white-tailed sea eagle muscle tissue in non-target screening.

Environmental monitoring studies based on target analysis capture only a small fraction of contaminants of emerging concern (CECs) and miss pollutants potentially harmful to wildlife. Environmental specimen banks, with their archived samples, provide opportunities to identify new CECs by temporal trend analysis and non-target screening. In this study, archived white-tailed sea eagle (Haliaeetus albicilla) muscle tissue was analysed by non-targeted high-resolution mass spectrometry.

Screening of legacy and emerging substances in surface water, sediment, biota and groundwater samples collected in the Siverskyi Donets River Basin employing wide-scope target and suspect screening.

Siverskyi Donets is the fourth longest river in Ukraine and its ecosystem is heavily affected by numerous agricultural and industrial activities. An impact of the on-going armed military conflicts in the Eastern Ukraine to the overall pollution by the chemicals has been studied. Considering the uncontrolled activities in the catchment due to the conflict, there is a high demand to assess the contamination status of the Siverskyi Donets basin.

Development and Application of Liquid Chromatographic Retention Time Indices in HRMS-Based Suspect and Nontarget Screening.

There is an increasing need for comparable and harmonized retention times () in liquid chromatography (LC) among different laboratories, to provide supplementary evidence for the identity of compounds in high-resolution mass spectrometry (HRMS)-based suspect and nontarget screening investigations. In this study, a rigorously tested, flexible, and less system-dependent unified retention time index (RTI) approach for LC is presented, based on the calibration of the elution pattern. Two sets of 18 calibrants were selected for each of ESI+ and ESI-based on the maximum overlap with the retention times and chemical similarity indices from a total set of 2123 compounds.

Assessment of the chemical pollution status of the Dniester River Basin by wide-scope target and suspect screening using mass spectrometric techniques.

The quality of the Dniester River Basin has been seriously impacted by the chemicals released by agriculture, industry, and wastewater discharges. To assess its current chemical pollution status, a transboundary monitoring campaign was conducted in May 2019. Thirteen surface water, 13 sediment, and three biota samples were collected and analyzed using generic sample preparation methods for the determination of organic substances by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and metals by inductively coupled plasma mass spectrometry (ICP-MS).

Evaluation of chemical and biological contaminants of emerging concern in treated wastewater intended for agricultural reuse.

The occurrence of chemical and biological contaminants of emerging concern (CECs) was investigated in treated wastewater intended for reuse in agriculture. An agarose hydrogel diffusion-based passive sampler was exposed to the outlet of a wastewater treatment plant (WWTP) located in Cyprus, which is equipped with membrane bioreactor (MBR). Passive samplers in triplicate were exposed according to a time-series exposure plan with maximum exposure duration of 28 days.

Wide-scope target screening of >2000 emerging contaminants in wastewater samples with UPLC-Q-ToF-HRMS/MS and smart evaluation of its performance through the validation of 195 selected representative analytes.

This study presents the development and validation of a comprehensive quantitative target methodology for the analysis of 2316 emerging pollutants in water based on Ultra-Performance Liquid Chromatography Quadrupole-Time-Of-Flight Mass Spectrometry (UPLC-Q-ToF-HRMS/MS). Target compounds include pesticides, pharmaceuticals, drugs of abuse, industrial chemicals, doping compounds, surfactants and transformation products, among others. The method was validated for 195 analytes, chosen to be representative of the chemical space of the target list, enabling the assessment of the performance of the method.

Spatio-temporal assessment of illicit drug use at large scale: evidence from 7 years of international wastewater monitoring.

Background And Aims: Wastewater-based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population-normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011-17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data.

Design: Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017.

Occurrence and potential environmental risk of surfactants and their transformation products discharged by wastewater treatment plants.

Seven-day composite effluent samples from a German monitoring campaign including 33 conventional wastewater treatment plants (WWTP) were analyzed for linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES) and were screened by wide-scope suspect screening for 1564 surfactants and their transformation products (TPs) by UHPLC-ESI-QTOF-MS. Corresponding seven-day composite influent samples of selected WWTPs showed high influent concentrations as well as very high removal rates for LAS and AES. However, average total LAS and AES effluent concentrations were still 14.

Characterization of wastewater effluents in the Danube River Basin with chemical screening, in vitro bioassays and antibiotic resistant genes analysis.

Averaged 7-day composite effluent wastewater samples from twelve wastewater treatment plants (WWTPs) in nine countries (Romania, Serbia, Hungary, Slovenia, Croatia, Slovakia, Czechia, Austria, Germany) in the Danube River Basin were collected. WWTPs' selection was based on countries' dominant technology and a number of served population with the aim to get a representative holistic view of the pollution status. Samples were analyzed for 2248 chemicals of emerging concern (CECs) by wide-scope target screening employing LC-ESI-QTOF-MS.

Untargeted time-pattern analysis of LC-HRMS data to detect spills and compounds with high fluctuation in influent wastewater.

Peak prioritization plays a key role in non-target analysis of complex samples in order to focus the elucidation efforts on potentially relevant substances. The present work shows the development of a computational workflow capable of detecting compounds that exhibit large variation in intensity over time. The developed approach is based on three open-source R packages (xcms, CAMERA and TIMECOURSE) and includes the use of the statistical test Multivariate Empirical Bayes Approach to rank the compounds based on the Hotelling T2 coefficient, which is an indicator of large concentration variations of unknown components.

Exploring the Potential of a Global Emerging Contaminant Early Warning Network through the Use of Retrospective Suspect Screening with High-Resolution Mass Spectrometry.

A key challenge in the environmental and exposure sciences is to establish experimental evidence of the role of chemical exposure in human and environmental systems. High resolution and accurate tandem mass spectrometry (HRMS) is increasingly being used for the analysis of environmental samples. One lauded benefit of HRMS is the possibility to retrospectively process data for (previously omitted) compounds that has led to the archiving of HRMS data.

Two stage algorithm vs commonly used approaches for the suspect screening of complex environmental samples analyzed via liquid chromatography high resolution time of flight mass spectroscopy: A test study.

LC-HR-QTOF-MS recently has become a commonly used approach for the analysis of complex samples. However, identification of small organic molecules in complex samples with the highest level of confidence is a challenging task. Here we report on the implementation of a two stage algorithm for LC-HR-QTOF-MS datasets.

Olive oil authenticity studies by target and nontarget LC-QTOF-MS combined with advanced chemometric techniques.

Food analysis is continuously requiring the development of more robust, efficient, and cost-effective food authentication analytical methods to guarantee the safety, quality, and traceability of food commodities with respect to legislation and consumer demands. Hence, a novel reversed-phase ultra high performance liquid chromatography-electrospray ionization quadrupole time of flight tandem mass spectrometry analytical method was developed that uses target, suspect, and nontarget screening strategies coupled with advanced chemometric tools for the investigation of the authenticity of extra virgin olive oil. The proposed method was successfully applied in real olive oil samples for the identification of markers responsible for the sensory profile.

Reflection of Socioeconomic Changes in Wastewater: Licit and Illicit Drug Use Patterns.

The economic crisis plaguing Greece was expected to impact consumption of pharmaceuticals and illicit drugs - a priori to an unknown extent. We quantified the change of use for various classes of licit and illicit drugs by monitoring Athens' wastewater from 2010 to 2014. A high increase in the use of psychoactive drugs was detected between 2010 and 2014, especially for antipsychotics (35-fold), benzodiazepines (19-fold), and antidepressants (11-fold).

Occurrence and spatial distribution of 158 pharmaceuticals, drugs of abuse and related metabolites in offshore seawater.

The occurrence and spatial distribution of 158 pharmaceuticals and drugs of abuse were studied in seawater of the Eastern Mediterranean Sea (Saronikos Gulf and Elefsis Bay in central Aegean Sea). This area is affected by various anthropogenic pressures as it receives the treated wastewater of the greatest Athens area and off-shore input fluxes. This study constitutes the largest one in terms of number of analytes in this environmental compartment.