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The rapid increase in the production and global use of chemicals and their mixtures has raised concerns about their potential impact on human and environmental health. With advances in analytical techniques, in particular, high-resolution mass spectrometry (HRMS), thousands of compounds and transformation products with potential adverse effects can now be detected in environmental samples. However, identifying and prioritizing the toxicity drivers among these compounds remain a significant challenge. Effect-directed analysis (EDA) emerged as an important tool to address this challenge, combining biotesting, sample fractionation, and chemical analysis to unravel toxicity drivers in complex mixtures. Traditional EDA workflows are labor-intensive and time-consuming, hindering large-scale applications. The concept of high-throughput (HT) EDA has recently gained traction as a means of accelerating these workflows. Key features of HT-EDA include the combination of microfractionation and downscaled bioassays, automation of sample preparation and biotesting, and efficient data processing workflows supported by novel computational tools. In addition to microplate-based fractionation, high-performance thin-layer chromatography (HPTLC) offers an interesting alternative to HPLC in HT-EDA. This review provides an updated perspective on the state-of-the-art in HT-EDA, and novel methods/tools that can be incorporated into HT-EDA workflows. It also discusses recent studies on HT-EDA, HT bioassays, and computational prioritization tools, along with considerations regarding HPTLC. By identifying current gaps in HT-EDA and proposing new approaches to overcome them, this review aims to bring HT-EDA a step closer to monitoring applications.

Climate change has been projected to cause increased temperature and amplified inflows of terrestrial organic matter to coastal areas in northern Europe. Consequently, changes at the base of the food web favoring heterotrophic bacteria over phytoplankton are expected, affecting the food web structure. We tested this hypothesis using an outdoor shallow mesocosm system in the northern Baltic Sea in early summer, where the effects of increased temperature (+ 3°C) and terrestrial matter inputs were studied following the system dynamics and conducting grazing experiments. Juvenile perch constituted the highest trophic level in the system, which exerted strong predation on the zooplankton community. Perch subsequently released the microbial food web from heavy grazing by mesozooplankton. Addition of terrestrial matter had a stronger effect on the microbial food web than the temperature increase, because terrestrial organic matter and accompanying nutrients promoted both heterotrophic bacterial production and phytoplankton primary production. Moreover, due to the shallow water column in the experiment, terrestrial matter addition did not reduce the light below the photosynthesis saturation level, and in these conditions, the net-autotrophy was strengthened by terrestrial matter enrichment. In combination with elevated temperature, the terrestrial matter addition effects were intensified, further shifting the size distribution of the microbial food web base from picoplankton to microphytoplankton. These changes up the food web led to increase in the biomass and proportion of large-sized ciliates (>60 µm) and rotifers. Despite the shifts in the microbial food web size structure, grazing experiments suggested that the pathway from picoplankton to nano- and microzooplankton constituted the major energy flow in all treatments. The study implies that the microbial food web compartments in shallow coastal waters will adjust to climate induced increased inputs of terrestrial matter and elevated temperature, and that the major energy path will flow from picoplankton to large-sized ciliates during the summer period.

The analysis of emerging contaminants (ECs) remains a dynamic and challenging field because this involves analyzing chemicals with widely varying properties in a large variety of environmental matrices. Usually, concentration levels of ECs are particularly low, such that sensitive and selective analytical methods are required for their analysis. This chapter focuses on five classes of ECs (pharmaceuticals and personal care products, disinfection by-products, perfluorinated compounds, polybrominated diphenyl ethers, and benzotriazoles and dioxane [B and D]) in terms of their occurrence and level of detection. It also highlights the rule of regulatory agencies on the EC detection limit. Sampling techniques used to detect ECs in different environmental matrices are discussed, such as (1) water grab samples from inland and offshore; (2) large-volume solid-phase extraction for water samples; (3) passive samplers (Polar Organic Chemical Integrative Sampler, Chemcatcher, Altesil SR sheet, and semipermeable membrane devices); (4) sediment grab samples (Van Veen and gravity-free fall corer); (5) biota grab samples with different trophic levels (sediment microorganisms, mussels, fish, and mammals; and (6) air passive samplers (inland and/or offshore). In addition, the latest progress is reviewed in sample preparation, extraction, and cleanup.

Climate change is expected to alter global temperature and precipitation patterns resulting in complex environmental impacts. The proposed higher precipitation in northern Scandinavia would increase runoff from land, hence increase the inflow of terrestrial dissolved organic matter (tDOM) in coastal regions. This could promote heterotrophic bacterial production and shift the food web structure, by favoring the microbial food web. The altered climate is also expected to affect transport and availability of organic micropollutants (MPs), with downstream effects on exposure and accumulation in biota. This study aimed to assess climate-induced changes in a Bothnian Sea food web structure as well as bioaccumulation patterns of MPs. We performed a mesocosms-study, focusing on aquatic food webs with fish as top predator. Alongside increased temperature, mesocosm treatments included tDOM and MP addition. The tDOM addition affected nutrient availability and boosted both phytoplankton and heterotrophic bacteria in our fairly shallow mesocosms. The increased tDOM further benefitted flagellates, ciliates and mesozooplankton, while the temperature increase and MP addition had minor effect on those organism groups. Temperature, on the other hand, had a negative impact on fish growth and survival, whereas tDOM and MP addition only had minor impact on fish. Moreover, there were indications that bioaccumulation of MPs in fish either increased with tDOM addition or decreased at higher temperatures. If there was an impact on bioaccumulation, moderately lipophilic MPs (log Kow 3.6 - 4.6) were generally affected by tDOM addition and more lipophilic MPs (log Kow 3.8 to 6.4) were generally affected by increased temperature. This study suggest that both increased temperatures and addition of tDOM likely will affect bioaccumulation patterns of MPs in shallow coastal regions, albeit with counteracting effects.

The removal of organic contaminants from wastewater using cost-efficient and easily accessible methods have been increasingly studied in recent years. Most studies have focused on municipal sewage treatment plants; however, our study investigated treatment with char-fortified filter beds for on-site sewage treatment facilities (OSSFs). OSSFs are commonly used in rural and semi-urban areas all over the world to treat wastewater to reduce eutrophication and water-related diseases. To screen for a wide range of organic contaminants in order to improve the understanding of wastewater treatment efficiency and molecular properties, samples were taken from an OSSF field study site that used three filter types: sand, char-fortified sand, and char-fortified gas concrete. First, we screened for organic contaminants with state-of-the-art gas chromatography and liquid chromatography mass spectrometry-based targeted and untargeted analysis and then we developed quantitative structure-property relationship models to find the key molecular features responsible for the removal of organic contaminants. We identified 74 compounds, of which 24 were confirmed with reference standards. Amongst these 74 compounds were plasticizers, UV stabilizers, fragrances, pesticides, surfactant and polymer impurities, pharmaceuticals and their metabolites, and many biogenic compounds. Sand filters that are sometimes used as a last treatment step in OSSFs can remove hydrophobic contaminants. The addition of biochar significantly increases the removal of these and a few hydrophilic compounds (Wilcoxon signed-rank test, α = 0.05). Gas concrete did not appear to be suitable for the removal of organic contaminants. This study showed that, besides hydrophobic effects, biodegradation is the most important removal pathway in long-term field applications. However, further improvements are necessary to remove very hydrophilic contaminants as they were not removed with sand and biochar-fortified sand.

Many environmental mutagens, including polyaromatic compounds are present in surface waters, often in complex mixtures and at low concentrations. The present study provides and applies a novel, integrated approach to isolate polyaromatic mutagens in river water using a sample from the River Elbe. The sample was taken downstream of industrial discharges using blue rayon (BR) as a passive sampler that selectively adsorbs polyaromatic compounds and was subjected to effect-directed fractionation in order to characterise the compounds causing the detected effect(s). The procedure relies on three complementary fractionation steps, the Ames fluctuation assay with strains TA98, YG1024 and YG1041 with and without S9 activation and analytical screening. Several mutagenic fractions were isolated by combining mutagenicity testing with fractionation. The enhanced mutagenicity in the nitroreductase and/or O-acetyltransferase overexpressing strains YG1024 and YG1041 strains suggested amino- and/or nitro-compounds causing mutagenicity in several fractions. Analytical screening of mutagenic fractions with LC-HRMS/MS provided a list of molecular formulas typically containing one to ten nitrogen and at least two oxygen atoms supporting the presence of amino and nitro-compounds in the mutagenic fractions.

Materials in car cabins contain performance-enhancing semi-volatile organic compounds (SVOCs). As these SVOCs are not chemically bound to the materials, they can emit from the materials at slow rates to the surrounding, causing human exposure. This study aimed at increasing the understanding on abundance of SVOCs in car cabins by studying 18 potential endocrine disrupting chemicals in car cabin air (gas phase and airborne particles) and dust. We also studied how levels of these chemicals varied by temperature inside the car cabin along with ventilation settings, relevant to human exposure. A positive correlation was observed between temperature and SVOC concentration in both the gas and the particle phase, where average gas phase levels at 80 °C were a factor of 18–16,000 higher than average levels at 25 °C, while average particle phase levels were a factor of 4.6–40,000 higher for the studied substances. This study also showed that levels were below the limit of detection for several SVOCs during realistic driving conditions, i.e., with the ventilation activated. To limit human exposure to SVOCs in car cabins, it is recommended to ventilate a warm car before entering and have the ventilation on during driving, as both temperature and ventilation have a significant impact on SVOC levels.

We present a sensitive, selective and robust method for the determination of 14 thiol compounds in aqueous samples. Thiols were derivatized with omega-bromoacetonylquinolinium bromide (BQB) and its deuterium labeled equivalent D7-ω-bromoacetonylquinolinium bromide (D7). Derivatized thiols were preconcentrated by online solid-phase extraction (SPE) followed by liquid chromatography separation and electrospray ionization tandem mass spectrometry determination (SPE/LC-ESI-MS/MS). The robustness of the method was validated for wide ranges in pH, salinity, and concentrations of sulfide and dissolved organic carbon (DOC) to cover contrasting natural water types. The limits of detection (LODs) for the thiols were 3.1-66 pM. Between 6 and 14 of the thiols were detected in different natural sample types at variable concentrations: boreal wetland porewater (0.7-51 nM), estuarine sediment porewater (50 pM-11 nM), coastal sea water (60 pM-16 nM), and sulfate reducing bacterium cultures (80 pM-4 nM). MS/MS fragmentation of the compounds produces two pairs of common product ions, m/z 130.2/137.1 and 218.1/225.1, which enables scanning for unknown thiols in precursor ion scan mode. Using this approach, we identified cysteine, mercaptoacetic acid, N-acetyl-L-cysteine and sulfurothioic S-acid in boreal wetland porewater. The performance of the developed method sets a new state of the art for the determination of thiol compounds in environmental and biological samples.

The toxicological characterization of sediments is an essential task to monitor the quality of aquatic environments. Many hazardous pollutants may accumulate in sediments and pose a risk to the aquatic community. The present study provides an attempt to integrate a diagnostic whole mixture assessment workflow based on a slightly modified Danio rerio embryo acute toxicity test with chemical characterization. Danio rerio embryos were directly exposed to sieved sediment (≤ 63 μm) for 96 h. Sediment samples were collected from three polluted sites (Kramfors, Sundsvall and Örnsköldsvik) in the Gulf of Bothnia (Sweden) which are characterized by a long history of pulp and paper industry impact. Effect data were supported by chemical analyses of 237 organic pollutants and 30 trace elements.

Emerging contaminants are found in all parts of our environment. Adsorption of these contaminants by activated carbon in water treatment plants is well-known; however, a problem resides in the handling of the spent adsorbents. As current regenerative technologies are expensive, the adsorbents are often destructed or landfilled. Here, we examine a novel regeneration method for the used adsorbents with subcritical water – i.e., hydrothermal treatment. The degradation of three well-known emerging contaminants – caffeine, trimethoprim and sulfamethoxazole – was studied with regard to processing temperature (160–280 °C), concentration (2 and 20 mg/L), and the impact of adsorbents. In addition to trimethoprim in the mix at 20 mg/L, the other contaminants were entirely degraded at 280 °C. To obtain insight into transformation products formed during hydrothermal regeneration, we performed non-target and targeted analyses with LC-MS-QTOF using two types of columns, C18 and ZIC-HILIC. This approach ensured a wide range of hydrophilicities. Results showed more transformation products for trimethoprim (20) compared to sulfamethoxazole and caffeine (4). To assess the regeneration efficiencies of the activated carbons, we conducted three cycles of regeneration at 280 °C and between 61 and 120 % degradation was achieved. Moreover, only two transformation products were detected and readsorbed on the adsorbent after regeneration. Hydrothermal regeneration efficiently degraded the target emerging contaminants, suggesting a potential approach for enabling alternative, sequential uses for regenerated activated carbon.

The rate of decline in regulated persistent organic pollutant (POP) concentrations in Baltic Sea biota has leveled off in recent years, with new contaminants frequently being discovered. There is, therefore, a need for comprehensive approaches to study occurrence and temporal trends of a wide range of environmental contaminants, including legacy POPs, contaminants of emerging concern (CECs), and new contaminants. In the current work, non-target screening (NTS) workflows were developed and used for, to the best of our knowledge, the first time-trend directed NTS of biota using gas chromatography–high-resolution mass spectrometry (GC-HRMS). To maximize contaminant coverage, both electron ionization (EI) and electron capture negative ion chemical ionization (ECNI) were used. The EI data were treated using highly automated workflows to find, prioritize, and tentatively identify contaminants with statistically significant temporal trends. The ECNI data were manually processed and reviewed prior to time-trend analysis. Altogether, more than 300 tentatively identified contaminants were found to have significant temporal trends in samples of Baltic guillemot, harbor porpoise, or white-tailed sea eagle. Significant decreases were found for many regulated chemicals, as could be expected, such as PCBs, polychlorinated terphenyls, chlorobenzenes, toxaphenes, DDT, other organochlorine pesticides, and tri- and tetra- bromodiphenyl ethers (BDEs). The rate of decline of legacy POPs agreed well with data reported from targeted analyses. Significant increases were observed for small polycyclic aromatic hydrocarbons, heptaBDEs, CECs, and terpenes and related compounds. The CECs included, among others, one plasticizer tributyl acetylcitrate (ATBC), two antioxidants 2,6-bis(1,1-dimethylethyl)phenol and 2,6-bis(tert-butyl)-4-(4-morpholinyl-methyl)phenol, and two compounds used in polymer production, trimethyl isocyanurate and 2-mercaptobenzothiazole, which had not previously been reported in biota. Their increased concentrations in biota indicate increased use and release. The increase in ATBC may be linked to increased use of it as a substitute for di-2-ethylhexyl phthalate (DEHP), which has been phased out over the last decade.

Predicted consequences of future climate change in the northern Baltic Sea include increases in sea surface temperatures and terrestrial dissolved organic carbon (DOC) runoff. These changes are expected to alter environmental distribution of anthropogenic organic contaminants (OCs). To assess likely shifts in their distributions, outdoor mesocosms were employed to mimic pelagic ecosystems at two temperatures and two DOC concentrations, current: 15 °C and 4 mg DOC L− 1 and, within ranges of predicted increases, 18 °C and 6 mg DOC L− 1, respectively. Selected organic contaminants were added to the mesocosms to monitor changes in their distribution induced by the treatments. OC partitioning to particulate matter and sedimentation were enhanced at the higher DOC concentration, at both temperatures, while higher losses and lower partitioning of OCs to DOC were observed at the higher temperature. No combined effects of higher temperature and DOC on partitioning were observed, possibly because of the balancing nature of these processes. Therefore, changes in OCs' fates may largely depend on whether they are most sensitive to temperature or DOC concentration rises. Bromoanilines, phenanthrene, biphenyl and naphthalene were sensitive to the rise in DOC concentration, whereas organophosphates, chlorobenzenes (PCBz) and polychlorinated biphenyls (PCBs) were more sensitive to temperature. Mitotane and diflufenican were sensitive to both temperature and DOC concentration rises individually, but not in combination.

Decades of intensive discharge from industrial activities into coastal systems has resulted in the accumulation of a variety of persistent organic pollutants (POPs) in marine waters and sediments, having detrimental impacts on aquatic ecosystems and the resident biota. POPs are among the most hazardous chemicals originating from industrial activities due to their biotoxicity and resistance to environmental degradation. Bacterial communities are known to break down many of these aromatic compounds, and different members of naturally occurring bacterial consortia have been described to work in syntrophic association to thrive in heavily contaminated waters and sediments, making them potential candidates as bioindicators of environmental pollution. In this study environmental, sampling was combined with chemical analysis of pollutants and high-resolution sequencing of bacterial communities using Next Generation Sequencing molecular biology tools. The aim of the present study was to describe the bacterial communities from marine sediments containing high loads of POPs and to identify relevant members of the resident microbial communities that may act as bioindicators of contamination. Marine sediments were collected from a coastal bay area of the Baltic Sea historically influenced by intense industrial activity, including metal smelting, oil processing, and pulp and paper production. Different types of POPs were detected at high concentrations. Fiberbank sediments, resulting from historic paper industry activity, were found to harbour a clearly distinct bacterial community including a number of bacterial taxa capable of cellulolytic and dechlorination activities. Our findings indicate that specific members of the bacterial communities thrive under increasing levels of POPs in marine sediments, and that the abundances of certain taxa correlate with specific POPs (or groups), which could potentially be employed in monitoring, status assessment and environmental management purposes.

Coastal ecosystems are highly dynamic and can be strongly influenced by climate change, anthropogenic activities (e.g. pollution) and a combination of the two pressures. As a result of climate change, the northern hemisphere is predicted to undergo an increased precipitation regime, leading in turn to higher terrestrial runoff and increased river inflow. This increased runoff will transfer terrestrial dissolved organic matter (tDOM) and anthropogenic contaminants to coastal waters. Such changes can directly influence the resident biology, particularly at the base of the food web, and can influence the partitioning of contaminants and thus their potential impact on the food web. Bacteria have been shown to respond to high tDOM concentration and organic pollutants loads, and could represent the entry of some pollutants into coastal food webs. We carried out a mesocosm experiment to determine the effects of: 1) increased tDOM concentration, 2) organic pollutant exposure, and 3) the combined effect of these two factors, on pelagic bacterial communities. This study showed significant responses in bacterial community composition under the three environmental perturbations tested. The addition of tDOM increased bacterial activity and diversity, while the addition of organic pollutants led to an overall reduction of these parameters, particularly under concurrent elevated tDOM concentration. Furthermore, we identified 33 bacterial taxa contributing to the significant differences observed in community composition, as well as 35 bacterial taxa which responded differently to extended exposure to organic pollutants. These findings point to the potential impact of organic pollutants under future climate change conditions on the basal coastal ecosystem, as well as to the potential utility of natural bacterial communities as efficient indicators of environmental disturbance.

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 (GCxGC) 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.