Natural Silicates Encapsulated Enzymes as Green Biocatalysts for Degradation of Pharmaceuticals.

Biocatalytic degradation with the use of enzymes has gained great attention in the past few years due to its advantages of high efficiency and environmental friendliness. Novel, cost-effective, and green nanoadsorbents were produced in this study, using natural silicates as an enzyme host matrix for core-shell immobilization technique. With the natural silicate as a core and silica layer as a shell, it was possible to encapsulate two different enzymes: horseradish peroxidase (HRP) and laccase, for removal and degradation of three pharmaceuticals: diclofenac (DFC), carbamazepine (CBZ), and paracetamol (PC). The biocatalysts demonstrated high oxidation rates for the selected pollutants. In particular HRP immobilized fly ash and perlite degraded DFC and PC completely during 3 days of interaction and also showed high degradation rates for CBZ. Immobilized laccase was successful in PC degradation, where up to 70-80% degradation of the compounds with aromatic rings was reported by NMR measurements for a high drug concentration of 10 µg/mL. The immobilization method played a significant role in this process by providing stability and protection for the enzymes over 3 weeks. Furthermore, the enzymes acted differently in the three chosen supports due to their complex chemical composition, which could have an effect on the overall enzyme activity.

Summary recommendations on "Analytical methods for substances in the Watch List under the Water Framework Directive".

The Watch List (WL) is a monitoring program under the European Water Framework Directive (WFD) to obtain high-quality Union-wide monitoring data on potential water pollutants for which scarce monitoring data or data of insufficient quality are available. The main purpose of the WL data collection is to determine if the substances pose a risk to the aquatic environment at EU level and subsequently to decide whether a threshold, the Environmental Quality Standards (EQS) should be set for them and, potentially to be listed as priority substance in the WFD. The first WL was established in 2015 and contained 10 individual or groups of substances while the 4th WL was launched in 2022. The results of monitoring the substances of the first WL showed that some countries had difficulties to reach an analytical Limit of Quantification (LOQ) below or equal to the Predicted No-Effect Concentrations (PNEC) or EQS. The Joint Research Centre (JRC) of the European Commission (EC) organised a series of workshops to support the EU Member States (MS) and their activities under the WFD. Sharing the knowledge among the Member States on the analytical methods is important to deliver good data quality. The outcome and the discussion engaged with the experts are described in this paper, and in addition a literature review of the most important publications on the analysis of 17-alpha-ethinylestradiol (EE2), amoxicillin, ciprofloxacin, metaflumizone, fipronil, metformin, and guanylurea from the last years is presented.

Comprehensive profiling and semi-quantification of exogenous chemicals in human urine using HRMS-based strategies.

Chemicals infiltrate our daily experiences through multiple exposure pathways. Human biomonitoring (HBM) is routinely used to comprehensively understand these chemical interactions. Historically, HBM depended on targeted screening methods limited to a relatively small set of chemicals with triple quadrupole instruments typically. However, recent advances in high-resolution mass spectrometry (HRMS) have facilitated the use of broad-scope target, suspect, and non-target strategies, enhancing chemical exposome characterization within acceptable detection limits. Despite these advancements, establishing robust and efficient sample treatment protocols is still essential for trustworthy broad-range chemical analysis. This study sought to validate a methodology leveraging HRMS-based strategies for accurate profiling of exogenous chemicals and related metabolites in urine samples. We evaluated five extraction protocols, each encompassing various chemical classes, such as pharmaceuticals, plastic additives, personal care products, and pesticides, in terms of their extraction recoveries, linearity, matrix effect, sensitivity, and reproducibility. The most effective protocol was extensively validated and subsequently applied to 10 real human urine samples using wide-scope target analysis encompassing over 2000 chemicals. We successfully identified and semi-quantified a total of 36 chemicals using an ionization efficiency-based model, affirming the methodology's robust performance. Notably, our results dismissed the need for a deconjugation step, a typically labor-intensive and time-consuming process.

What is in the fish? Collaborative trial in suspect and non-target screening of organic micropollutants using LC- and GC-HRMS.

A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9-69 % of spiked compounds using LC-HRMS and 20-60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants' own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from -9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.

Insights into environmental caffeine contamination in ecotoxicological biomarkers and potential health effects of Danio rerio.

Caffeine (CAF) exposures have been shown to cause several pharmacological and biological effects in target and non-target organisms. Although there are already several ecotoxicological studies with CAF in non-target organisms, they are focused on marine organisms, with relevant concentrations in these ecosystems, therefore, less ecologically relevant to freshwater ecosystems (the main ecoreceptor of this type of anthropogenic contaminant). The present study aimed to assess the chronic effects (28 days) of sub-lethal and environmentally relevant concentrations of CAF (0.16, 0.42, 1.09, 2.84, 7.40, 19.23, and 50 µg/L) in Danio rerio. Biochemical endpoints as biomarkers of antioxidant defense, biotransformation, lipid peroxidation, energy sources, and neurotransmission were assessed. CAF exposure induced alterations in antioxidant defenses (superoxide dismutase and glutathione reductase activities, and glutathione content) preventing lipid peroxidation. Lactate dehydrogenase activity decreased in all the concentrations tested, while acetylcholinesterase activity was only affected by the highest concentrations tested (19.23 and 50 µg/L). We also utilized a multi-biomarker approach (Integrated Biomarker Response version 2, IBRv2) to investigate the effects of CAF in the dispersion scope of individual biochemical responses of D. rerio. IBRv2 showed that the concentration of 50 µg/L promotes the highest stress. However, the results showed that CAF induced disturbances in the metabolic pathways studied in D. rerio. These results demonstrated the toxic effects of CAF on freshwater fish, compromising their physiological functions and evidencing the need for monitoring the residues of CAF released into the inland aquatic environments. Furthermore, this research evidence that phylogenetically and physiologically different species may present different biological responses with concern for ecologically relevant environmental conditions. In this sense, the present study generated ecotoxicologically relevant data, that can be considered by environment regulators, since the here-endpoints evaluated showed sensitivity and consistency in the evaluation of caffeine risks in freshwater environments.

Hazard screening of contaminants of emerging concern (CECs) in Sweden's three largest lakes and their associated rivers.

Persistent, mobile, and toxic (PMT) substances have recently garnered increased attention by environmental researchers, the water sector and environmental protection agencies. In this study, acute and chronic species sensitivity distributions (SSDs) were retrieved from literature data for previously quantified contaminants of emerging concern (CECs) in Swedish surface waters (n = 92) and risk quotients (RQ) were calculated. To better understand the characteristics of the detected CECs in non-urban lake sites (n = 71), these compounds were checked against established criteria for potentially toxic PMs (PM(T)s) and occurrence in the aquatic environment, respectively. For the CECs with missing SSDs (n = 15 [acute], n = 41 [chronic]), ecotoxicity data were extracted for eight taxonomic groups, and if data were sufficient (n ≥ 3), SSDs were derived. The retrieved and newly developed SSDs were then used in an environmental hazard assessment (EHA) in the investigated Swedish rivers and lakes. In the rivers, 8 CECs had RQ> 1 in at least one location, and 20 CECs posed a moderate risk (0.01 < RQ < 1). In total, 21 of the 71 detected substances had already been identified as PM(T)/vPvM substances. Our study shows the importance of studying field data at large spatial scale to reveal potential environmental hazards far from source areas.

Occurrence and fate of contaminants of emerging concern and their transformation products after uptake by pak choi (Brassica rapa subsp. chinensis).

Recovery and reuse of nutrients is a major challenge in agriculture. A new process contributing to a circular economy is the anaerobic digestion of food waste, which is a sustainable way of recycling nutrients as the digestate can be used as fertiliser in agriculture and horticulture. However, the digestate may be polluted with contaminants of emerging concern (CECs) that can be circulated back into the food chain, posing a risk to the environment and human health. In this work, the nutrient solution was spiked with 18 selected CECs frequently detected in food waste biogas facilities, and subsequent uptake and fate of these CECs were evaluated in pak choi grown in two different nutrient solutions (mineral and organic). All spiked compounds except two (propylparaben, fenbendazole) were taken up by pak choi plants, with perfluorobutanoic acid (PFBA) and sertraline displaying the highest concentrations (270 and 190 µg/kg fresh weight, respectively). There were no statistically significant differences in uptake between mineral and organic nutrient solutions. Uptake of per- and polyfluoroalkyl substances (PFAS) was negatively correlated with perfluorocarbon chain length and dependent on the functional group (r = -0.73). Sixteen transformation products (TPs) were tentatively identified using suspect screening, most of which were Phase II or even Phase III metabolites. Six of these TPs were identified for the first time in plant metabolism and their metabolic pathways were considered.

Are preserved coastal water bodies in Spanish Mediterranean basin impacted by human activity? Water quality evaluation using chemical and biological analyses.

The Spanish Mediterranean basin is particularly susceptible to climate change and human activities, making it vulnerable to the influence of anthropogenic contaminants. Therefore, conducting comprehensive and exhaustive water quality assessment in relevant water bodies of this basin is pivotal. In this work, surface water samples from coastal lagoons or estuaries were collected across the Spanish Mediterranean coastline and subjected to target and suspect screening of 1,585 organic micropollutants by liquid chromatography coupled to ion mobility separation and high resolution mass spectrometry. In total, 91 organic micropollutants could be confirmed and 5 were tentatively identified, with pharmaceuticals and pesticides being the most prevalent groups of chemicals. Chemical analysis data was compared with data on bioanalysis of those samples (recurrent aryl hydrocarbon receptor (AhR) activation, and estrogenic receptor (ER) inhibition in wetland samples affected by wastewater streams). The number of identified organic contaminants containing aromatic rings could explain the AhR activation observed. For the ER antagonistic effects, predictions on estrogenic inhibition potency for the detected compounds were used to explain the activities observed. The integration of chemical analysis with bioanalytical observations allowed a comprehensive overview of the quality of the water bodies under study.

Organic micropollutants, heavy metals and pathogens in anaerobic digestate based on food waste.

Anaerobic digestate based on food waste is increasingly used as fertilizer in food production. This study examined the characteristics of anaerobic digestate based on food waste from three biogas plants in Sweden. The characterization included measurements of heavy metals (n = 7), chemicals of emerging concern (CECs), such as currently used drugs and pesticides (n = 133), and an extended range of food-borne pathogens, including two notable sporeformers and some widespread antibiotic-resistant bacteria. The amounts of Escherichia coli, enterococci, and Salmonella and the concentrations of the target heavy metals were all below the maximum accepted levels at all three locations studied. However, the spore-forming Bacillus cereus was found to be present at high levels in samples from all three biogas plants. Among the 133 CECs investigated, 48 were detected at least once, and the highest concentrations were found for pyroxidine, nicotine, caffeine, theobromine, and nicotine. The biofertilizers from the different biogas plants had similar CEC profiles, which indicate similarities in household waste composition and thorough mixing in the biogas plants. If this profile is found to be spatially and temporally consistent, it can help regulators to establish priority lists of CECs of top concern. Assuming increasing use of biofertilizers for food production in the future, it would be beneficial to have concentration limits for CECs Risk estimation based on risk quotients (RQs) indicated generally low environmental risks associated with application of biofertilizer to soils for food crop production. However, the toxicity of CEC mixtures needs to be considered when estimating the risks from application of biofertilizers on agricultural land or in other production systems.

Occurrence and mass flows of contaminants of emerging concern (CECs) in Sweden's three largest lakes and associated rivers.

Contaminants of emerging concern (CECs) are a concern in aquatic environments due to possible adverse effects on the environment and humans. This study assessed the occurrence and mass flows of CECs in Sweden's three largest lakes and 24 associated rivers. The occurrence and distribution of 105 CECs was investigated, comprising 71 pharmaceuticals, 13 perfluoroalkyl substances (PFASs), eight industrial chemicals, four personal care products (PCPs), three parabens, two pesticides, and four other CECs (mostly anthropogenic markers). This is the first systematic study of CECs in Sweden's main lakes and one of the first to report environmental concentrations of the industrial chemicals tributyl citrate acetate and 2,2'-dimorpholinyldiethyl-ether. The ∑CEC concentration was generally higher in river water (31-5200 ng/L; median 440 ng/L) than in lake water (36-900 ng/L; median 190 ng/L). At urban lake sites, seasonal variations were observed for PCPs and parabens, and also for antihistamines, antidiabetics, antineoplastic agents, antibiotics, and fungicides. The median mass CEC load in river water was 180 g/day (range 4.0-4300 g/day), with a total mass load of 5000 g/day to Lake Vänern, 510 g/day to Lake Vättern, and 5600 g/day to Lake Mälaren. All three lakes are used as drinking water reservoirs, so further investigations of the impact of CECs on the ecosystem and human health are needed.

Risk-based screening for prioritisation of organic micropollutants in Swedish freshwater.

Concerns about environmental contamination by organic micropollutants (OMPs) are increasing, due to their potential bioaccumulative and toxic properties. This study evaluated the risk posed by OMPs to aquatic ecosystems in Swedish freshwaters. The assessment was based on measured environmental concentrations (MEC) of OMPs in surface waters upstream and downstream of Swedish wastewater treatment plants (WWTPs). A novel optimised risk quotient (RQf) was used to identify potential high-risk substances in the aquatic environment. A secondary objective was to assess the impact of WWTP effluent on aquatic ecosystems using a novel impact factor (I) based on the risk quotient (RQ). Among the 126 substances investigated, four compounds (metformin, N,N-dimethyltetradecylamine, oxazepam, and venlafaxine) were identified as likely to pose a risk to aquatic ecosystems in Swedish surface waters (RQf>1), and five compounds (clindamycin, gemfibrozil, sertraline, o-desmethylvenlafaxine, and diclofenac) were identified as posing a moderate risk to aquatic ecosystems ( 0.1 

Uptake of perfluoroalkyl substances, pharmaceuticals, and parabens by oyster mushrooms (Pleurotus ostreatus) and exposure risk in human consumption.

Organic micropollutants (MPs) pose potential threats to environmental ecosystems and human health. This study investigated uptake of perfluoroalkyl substances (PFASs), pharmaceuticals, and paraben by edible oyster mushrooms (Pleurotus ostreatus), cultivated on spiked growth substrate. Concentrations of pharmaceuticals and paraben in substrate showed a decreasing trend over a 20-day harvesting period, whereas PFAS concentrations were variable over the harvesting period. However, only propylparaben, clarithromycin, and PFASs were detected in fruiting bodies of oyster mushroom. Uptake of PFASs by oyster mushroom fruit bodies was negatively correlated with perfluorocarbon chain length. An impact of MPs on fungal colonization was observed, with decreased respiration in treatments with the highest concentration of MPs, but production of fruiting bodies was not affected by exposure level. The potential human risk from ingestion of MPs was evaluated for oyster mushrooms exposed to the highest concentration of MPs in substrate, based on acceptable daily intake (ADI).

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. Univariate statistical tests (Mann-Kendall and Spearman rank) for temporal trend analysis were applied as prioritisation methods. A workflow for non-target data was developed and validated using an artificial time series spiked at five levels with gradient concentrations of selected CECs (n = 243). Pooled eagle muscle tissues collected 1965-2017 were then investigated with an eight-point time series using the validated screening workflow. Following peak detection, peak alignment, and blank subtraction, 14 409 features were considered for statistical analysis. Prioritisation by time-trend analysis detected 207 features with increasing trends. Following unequivocal molecular formula assignment to prioritised features and further elucidation with MetFrag and EU Massbank, 13 compounds were tentatively identified, of which four were of anthropogenic origin. These results show that it is possible to prioritise new CECs in archived biological samples using univariate statistical approaches.

Thyroid function and immune status in perch (Perca fluviatilis) from lakes contaminated with PFASs or PCBs.

The environment contains a multitude of man-made chemicals, some of which can act as endocrine disruptors (EDCs), while others can be immunotoxic. We evaluated thyroid disruption and immunotoxic effects in wild female perch (Perca fluviatilis) collected from two contaminated areas in Sweden; one site contaminated with per- and polyfluoroalkyl substances (PFASs) and two sites contaminated with polychlorinated biphenyls (PCBs), with one reference site included for each area. The hepatic mRNA expression of thyroid receptors α and ß, and the thyroid hormone metabolising iodothyronine deiodinases (dio1, dio2 and dio3) were measured using real-time PCR, while the levels of thyroid hormone T3 in plasma was analysed using a radioimmunoassay. In addition, lymphocytes, granulocytes, and thrombocytes were counted microscopically. Our results showed lower levels of T3 as well as lower amounts of lymphocytes and granulocytes in perch collected from the PFAS-contaminated site compared to reference sites. In addition, expressions of mRNA coding for thyroid hormone metabolising enzymes (dio2 and dio3) and thyroid receptor α (thra) were significantly different in these fish compared to their reference site. For perch collected at the two PCB-contaminated sites, there were no significant differences in T3 levels or in expression levels of the thyroid-related genes, compared to the reference fish. Fish from one of the PCB-contaminated sites had higher levels of thrombocytes compared with both the second PCB lake and their reference lake; hence PCBs are unlikely to be the cause of this effect. The current study suggests that lifelong exposure to PFASs could affect both the thyroid hormone status and immune defence of perch in the wild.

Gene co-expression network analysis reveals mechanisms underlying ozone-induced carbamazepine toxicity in zebrafish (Danio rerio) embryos.

Sewage effluent ozonation can reduce concentrations of chemical pollutants including pharmaceutical residues. However, the formation of potentially toxic ozonation byproducts (OBPs) is a matter of concern. This study sought to elucidate toxicity mechanisms of ozonated carbamazepine (CBZ), an anti-epileptic drug frequently detected in sewage effluents and surface water, in zebrafish embryos (Danio rerio). Embryos were exposed to ozonated and non-ozonated CBZ from 3 h post-fertilization (hpf) until 144 hpf. Embryotoxicity endpoints (proportion of dead and malformed embryos) were assessed at 24, 48, and 144 hpf. Heart rate was recorded at 48 hpf. Exposure to ozonated CBZ gave rise to cardiovascular-related malformations and reduced heart rate. Moreover, embryo-larvae exposed to ozonated CBZ displayed a lack of swim bladder inflation. Hence, the expression patterns of CBZ target genes involved in cardiovascular and embryonal development were investigated through a stepwise gene co-expression analysis approach. Two co-expression networks and their upstream transcription regulators were identified, offering mechanistic explanations for the observed toxicity phenotypes. The study presents a novel application of gene co-expression analysis elucidating potential toxicity mechanisms of an ozonated pharmaceutical with environmental relevance. The resulting data was used to establish a putative adverse outcome pathway (AOP).

What's in the water? - Target and suspect screening of contaminants of emerging concern in raw water and drinking water from Europe and Asia.

There is growing worry that drinking water can be affected by contaminants of emerging concern (CECs), potentially threatening human health. In this study, a wide range of CECs (n = 177), including pharmaceuticals, pesticides, perfluoroalkyl substances (PFASs) and other compounds, were analysed in raw water and in drinking water collected from drinking water treatment plants (DWTPs) in Europe and Asia (n = 13). The impact of human activities was reflected in large numbers of compounds detected (n = 115) and high variation in concentrations in the raw water (range 15-7995 ng L-1 for ∑177CECs). The variation was less pronounced in drinking water, with total concentration ranging from 35 to 919 ng L-1. Treatment efficiency was on average 65 ± 28%, with wide variation between different DWTPs. The DWTP with the highest ∑CEC concentrations in raw water had the most efficient treatment procedure (average treatment efficiency 89%), whereas the DWTP with the lowest ∑177CEC concentration in the raw water had the lowest average treatment efficiency (2.3%). Suspect screening was performed for 500 compounds ranked high as chemicals of concern for drinking water, using a prioritisation tool (SusTool). Overall, 208 features of interest were discovered and three were confirmed with reference standards. There was co-variation between removal efficiency in DWTPs for the target compounds and the suspected features detected using suspect screening, implying that removal of known contaminants can be used to predict overall removal of potential CECs for drinking water production. Our results can be of high value for DWTPs around the globe in their planning for future treatment strategies to meet the increasing concern about human exposure to unknown CECs present in their drinking water.

Occurrence and removal of chemicals of emerging concern in wastewater treatment plants and their impact on receiving water systems.

Wastewater treatment plants (WWTPs) are considered the main sources of chemicals of emerging concern (CECs) in aquatic environments, and can negatively impact aquatic ecosystems. In this study, WWTP influent, effluent, and sludge, and upstream and downstream waters from the WWTP recipient were investigated at 15 locations for a total of 164 CECs, including pharmaceuticals, personal care products, industrial chemicals, per- and polyfluoroalkyl substances (PFASs), and pesticides. In addition, zebrafish (Danio rerio) embryo toxicity tests (ZFET) were applied to WWTP influent and effluent, and upstream and downstream waters from WWTP recipients. A total of 119 CECs were detected in at least one sample, mean concentrations ranging from 0.11 ng/L (propylparaben) to 64,000 ng/L (caffeine), in wastewater samples and from 0.44 ng/L (ciprofloxacin) to 19,000 ng/L (metformin) in surface water samples. Large variations of CEC concentrations were found between the selected WWTPs, which can be explained by differences in CEC composition in influent water and WWTP treatment process. The sludge-water partitioning coefficient (Kd) of CECs showed a significant linear correlation to octanol/water partition coefficient (KOW) (p < 0.001), and thus could be used for predicting their fate in the aqueous and solid phase. The ΣCEC concentrations in WWTPs declined by on average 60%, based on comparisons of WWTP influent and effluent concentrations. The high concentrations of CECs in WWTP effluent resulted in, on average, 50% higher concentrations of CECs in water downstream of WWTPs compared with upstream. Some WWTP samples showed toxicity in ZFET compared with the respective control group, but no individual CECs or groups of CECs could explain this toxicity. These results could provide a theoretical basis for optimization of existing treatment systems of different designs, and could significantly contribute to protecting recipient waters.

In situ calibration of polar organic chemical integrative sampler (POCIS) for monitoring of pharmaceuticals in surface waters.

POCIS is the most widely applied passive sampler of polar organic substances, because it was one of the first commercially available samplers for that purpose on the market, but also for its applicability for a wide range of substances and conditions. Its main weakness is the variability of sampling performance with exposure conditions. In our study we took a pragmatic approach and performed in situ calibration for a set of 76 pharmaceuticals and their metabolites in five sampling campaigns in surface water, covering various temperature and flow conditions. In individual campaigns, RS were calculated for up to 47 compounds ranging from 0.01 to 0.63 L d-1, with the overall median value of 0.10 L d-1. No clear changes of RS with water temperature or discharge could be found for any of the investigated substances. The absence of correlation of experimental RS with physical-chemical properties in combination with the lack of mechanistic understanding of compound uptake to POCIS implies that practical estimation of aqueous concentrations from uptake in POCIS depends on compound-specific experimental calibration data. Performance of POCIS was compared with grab sampling of water in seven field campaigns comprising multiple sampling sites, where sampling by both methods was done in parallel. The comparison showed that for 25 of 36 tested compounds more than 50% of POCIS-derived aqueous concentrations did not differ from median of grab sampling values more than by a factor of 2. Further, for 30 of 36 compounds, more than 80% of POCIS data did not differ from grab sampling data more than by a factor of 5. When accepting this level of accuracy, in situ derived sampling rates are sufficiently robust for application of POCIS for identification of spatial and temporal contamination trends in surface waters.

New extraction method prior to screening of organic micropollutants in various biota matrices using liquid chromatography coupled to high-resolution time-of-flight mass spectrometry.

A new extraction method with limited clean-up requirements prior to screening various matrices for organic micropollutants using liquid chromatography-high resolution mass spectrometry (LC-HRMS) for analysis was developed. First, the performance of three extraction methods (QuEChERS with SPE clean-up, ultrasonication with SPE clean-up, extraction without SPE clean-up) was tested, optimized, and compared using >200 contaminants of emerging concern (CECs) together covering a wide range of physicochemical properties applicable for suspect and non-target screening in biota. White-tailed sea eagle (Haliaeetus albicilla) muscle tissue was used in method development and optimization. The method without SPE clean-up was then applied to European perch (Perca fluviatilis) muscle, heart, and liver tissues. The optimization and application of the method demonstrated a wide applicable domain of the novel extraction method regarding species, tissues, and chemicals. For future applications, the suitability of the method for suspect and non-target screening was tested. Overall, our extraction method appears to be sufficiently simple and broad (relatively non-discriminant) for use prior to analysis of CECs in various biota.

Organic micropollutants in water and sediment from Lake Mälaren, Sweden.

The occurrence and distribution of 111 organic micropollutants (OMPs) were evaluated in water and sediment samples from Lake Mälaren, Sweden, using a liquid chromatography-tandem mass spectrometry method. The partitioning of contaminants between lake compartments was estimated using solid water distribution coefficients (Kd) and organic carbon-water partitioning coefficients (KOC). In total, 30 and 24 OMPs were detected in lake water and sediment, respectively. Concentrations ranged from low ng/L to 89 ng/L (lamotrigine) in lake water and from low ng/g dry weight (dw) to 28 ng/g dw (citalopram) in sediment. Carbamazepine, lamotrigine, caffeine, and tolyltriazole were the dominant compounds in Lake Mälaren samples (both water and sediment). Seventeen OMPs were detected in both water and sediment samples, including carbamazepine, DEET, tolyltriazole, bicalutamide, caffeine, lamotrigine, and cetirizine. Log Kd values varied between 0.84 for lamotrigine and 4.4 for citalopram, while log KOC values varied between 2.1 for lamotrigine and 5.9 for citalopram. These results indicate that sorption to sediment plays a minor role in removal of all OMPs analyzed in the aqueous phase except for citalopram and cetirizine, which showed high sorption potential. The environmental risks of OMPs were assessed based on the RQ values. The worst-case scenario for environmental risk assessment was conducted using the maximum measured environment concentration. For most of the target OMPs, including tolyltriazole, bicalutamide, fexofenadine, oxazepam, cetirizine, and diclofenac, the RQ values were below 0.01, indicating low or no risk to lake ecosystems.