Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Identification of hot spots and co-occurrence patterns of activities on thyroid hormone receptor and transthyretin binding in passive samplers from Czech surface waters.

One of the less studied in vitro biological activities in the aquatic environment are thyroid hormone receptor beta (TRß)-mediated agonistic and antagonistic activities and transthyretin (TTR) binding activity. They were measured mostly using active sampling methods, but rarely found. It is unclear if these activities co-occur, and the drivers of the (anti-)TRß activity are mostly unknown. Therefore, the main aim of the study was to determine (anti-)TRß activities as well as transthyretin (TTR) binding activity in passive samplers from Czech surface waters in combination with the search for the effect drivers based on liquid chromatography-high resolution mass spectrometry (LC-HRMS) analysis by applying suspect screening. Passive samplers (polar organic chemical integrative samplers, POCIS) were deployed at twenty-one sites (all ends of watersheds and other important sites in Elbe River) in the Czech rivers. The (anti-)TRß and TTR binding activity were measured using (anti-)TRß-CALUX and TTR-TRß-CALUX bioassays. Anti-TRß activity was found at eight sites, and TTR binding activity co-occurred there at six of these sites. The co-occurrence of TRß-mediated antagonistic activity and TTR binding indicate that they may have common effect drivers. No sample exhibited TRß agonistic activity. The extract from the site Bílina River, the most burdened with anti-TRß activity, was further successfully fractionated, and this activity was revealed in the fraction, where mid-polar compounds prevailed. However, the suspect LC-HRMS analysis did not reveal the chemical effect drivers. Our results showed that anti-TRß activity can be found in surface waters by employing passive sampling and frequently co-occurs with TTR binding activity. Overall, the fractionation procedure and non-target data acquisition used in this study can serve as a basis for searching the effect drivers in future research.

Novel nontarget LC-HRMS-based approaches for evaluation of drinking water treatment.

A conventional evaluation methodology for drinking water pollution focuses on analysing hundreds of compounds, usually by liquid chromatography-tandem mass spectrometry. High-resolution mass spectrometry allows comprehensive evaluation of all detected signals (compounds) based on their elemental composition, intensity, and numbers. We combined target analysis of 192 emerging micropollutants with nontarget (NT) full-scan/MS/MS methods to describe the impact of treatment steps in detail and assess drinking water treatment efficiency without compound identification. The removal efficiency based on target analytes ranged from - 143 to 97%, depending on the treatment section, technologies, and season. The same effect calculated for all signals detected in raw water by the NT method ranged between 19 and 65%. Ozonation increased the removal of micropollutants from the raw water but simultaneously caused the formation of new compounds. Moreover, ozonation byproducts showed higher persistence than products formed during other types of treatment. We evaluated chlorinated and brominated organics detected by specific isotopic patterns within the developed workflow. These compounds indicated anthropogenic raw water pollution but also potential treatment byproducts. We could match some of these compounds with libraries available in the software. We can conclude that passive sampling combined with nontargeted analysis shows to be a promising approach for water treatment control, especially for long-term monitoring of changes in technology lines because passive sampling dramatically reduces the number of samples and provides time-weighted average information for 2 to 4 weeks.

Methamphetamine pollution elicits addiction in wild fish.

Illicit drug abuse presents pervasive adverse consequences for human societies around the world. Illicit drug consumption also plays an unexpected role in contamination of aquatic ecosystems that receive wastewater discharges. Here, we show that methamphetamine, considered as one of the most important global health threats, causes addiction and behavior alteration of brown trout Salmo trutta at environmentally relevant concentrations (1 µg l-1). Altered movement behavior and preference for methamphetamine during withdrawal were linked to drug residues in fish brain tissues and accompanied by brain metabolome changes. Our results suggest that emission of illicit drugs into freshwater ecosystems causes addiction in fish and modifies habitat preferences with unexpected adverse consequences of relevance at the individual and population levels. As such, our study identifies transmission of human societal problems to aquatic ecosystems.

On the Use of Mechanistic Soil-Plant Uptake Models: A Comprehensive Experimental and Numerical Analysis on the Translocation of Carbamazepine in Green Pea Plants.

Food contamination is a major worldwide risk for human health. Dynamic plant uptake of pollutants from contaminated environments is the preferred pathway into the human and animal food chain. Mechanistic models represent a fundamental tool for risk assessment and the development of mitigation strategies. However, difficulty in obtaining comprehensive observations in the soil-plant continuum hinders their calibration, undermining their generalizability and raising doubts about their widespread applicability. To address these issues, a Bayesian probabilistic framework is used, for the first time, to calibrate and assess the predictive uncertainty of a mechanistic soil-plant model against comprehensive observations from an experiment on the translocation of carbamazepine in green pea plants. Results demonstrate that the model can reproduce the dynamics of water flow and solute reactive transport in the soil-plant domain accurately and with limited uncertainty. The role of different physicochemical processes in bioaccumulation of carbamazepine in fruits is investigated through Global Sensitivity Analysis, which shows how soil hydraulic properties and soil solute sorption regulate transpiration streams and bioavailability of carbamazepine. Overall, the analysis demonstrates the usefulness of mechanistic models and proposes a comprehensive numerical framework for their assessment and use.

Prescribed aggression of fishes: Pharmaceuticals modify aggression in environmentally relevant concentrations.

Traces of psychoactive substances have been found in freshwaters globally. Fish are chronically exposed to pollution at low concentrations. The changes of aggressive behaviour of chub (Squalius cephalus) were determined under the exposure to four psychoactive compounds (sertraline, citalopram, tramadol, methamphetamine) at environmentally relevant concentrations of 1 µg/L for 42 days. We tested whether (A) the behavioural effect of compounds varies within a single species; (B) there is a correlation between the individual brain concentration of the tested pollutants and fish aggression using the novel analysis of pollutants in brain; and (C) there is detectable threshold to effective pollutant concentration in brain. Behaviour and pollutant concentrations in brain were determined repeatedly (1st, 7th, 21st, 42nd and 56th days), including a two-week-long depuration period. The effect of particular compounds varied. Citalopram and methamphetamine generally increased the fish aggression, while no such effect was found after exposure to tramadol or sertraline. The longitudinal analysis showed an aggression increase after depuration, indicating the presence of withdrawal effects in methamphetamine- and tramadol-exposed fish. The analysis of pollutant concentration in brain revealed a positive linear relationship of citalopram concentration and aggression, while no such effect was detected for other compounds and/or their metabolites. Structural break analyses detected concentration thresholds of citalopram (1 and 3 ng/g) and sertraline (1000 ng/g) in brain tissue, from which a significant effect on behaviour was manifested. While the effect of sertraline was not detected using traditional approaches, there was a reduction in aggression after considering its threshold concentration in the brain. Our results suggest that pursuing the concentration threshold of psychoactive compounds can help to reduce false negative results and provide more realistic predictions on behavioural outcomes in freshwater environments, especially in the case of compounds with bioaccumulation potential such as sertraline.

Traces of tramadol in water impact behaviour in a native European fish.

Tramadol is a widely used analgesic with additional antidepressant and anxiolytic effects. This compound has been reported in continental waters reaching concentrations of µg/L as a consequence of its inefficient removal in sewage treatment plants and increasing use over time. In this study, European chubs (Squalius cephalus) were exposed to 1 µg/L of tramadol in water for 42 days with a subsequent 14 days of depuration. Our results revealed that chubs exposed to this analgesic underwent changes in their behaviour as compared to the control group. The behavioural outcome was also influenced by the individual concentration of tramadol in brain tissue. In particular, experimental fish presented anxiolytic-like effects, characterized by less bold and less social individuals. Exposed animals were less frequently out of the shelter and moved a shorter distance, indicating that they explored the new environment less during the boldness test. In the novel object recognition experiment, although they distinguished the new item, they examined it less and displayed a reduced activity. Shoal cohesion was disrupted as observed in an increased distance between individuals. After the depuration phase, this alteration remained whereas the boldness effect disappeared. Moreover, the degree of behavioural changes was correlated with the concentration of the substance in brain. According to our findings, chronic presence of tramadol in the environment can impact the fitness of exposed aquatic fauna by altering evolutionary crucial behaviours.

Determination of citalopram in fish brain tissue: benefits of coupling laser diode thermal desorption with low- and high-resolution mass spectrometry.

Recent state-of-the-art methods developed for the analysis of polar xenobiotics from different types of biological matrices usually employ liquid chromatography with mass spectrometry. However, there are limitations when a small amount of sample mass is available. For example, individual benthic invertebrates or fish tissue samples often weigh less than 100 mg (e.g., brain, liver) but are necessary to understand environmental fate and bioaccumulation dynamics. We developed ultra-fast methods based on a direct sample introduction technique. This included coupling laser diode thermal desorption with atmospheric pressure chemical ionization mass spectrometry (LDTD-APCI-MS). We then quantitated a common selective serotonin reuptake inhibitor (citalopram) in brain tissues of individual juvenile fish after in vivo exposure to environmentally relevant concentration. Two mass spectrometric methods based on low (LDTD-APCI-triple quadrupole (QqQ)-MS/MS) and high (LDTD-APCI-high-resolution product scan (HRPS)) resolutions were developed and evaluated. Individual instrument conditions were optimized to achieve an accurate and robust analytical method with minimum sample preparation requirements. We achieved very good recovery (97-108%) across the range of 1-100 ng g-1 for LDTD-APCI-HRPS. LDTD-APCI-QqQ-MS/MS showed poorer performance due to interferences from the matrix at the lowest concentration level. LDTD-APCI ionization was successfully validated for analysis of non-filtered sample extracts. Evaluation of final methods was performed for a set of real fish brain samples, including comparison of LDTD-APCI-HRPS with a previously validated LC-heated electrospray ionization-HRPS method. This new LDTD-APCI-HRPS method avoids the chromatographic step and provides important benefits such as analysis of limited sample masses, lower total sample volume (typically µL), and reduction in analysis time per sample run to a few seconds. Graphical abstract.

Chronic simultaneous exposure of common carp (Cyprinus carpio) from embryonic to juvenile stage to drospirenone and gestodene at low ng/L level caused intersex.

Synthetic progestins are emerging contaminants of the aquatic environment with endocrine disrupting potential. The main aim of the present study was to investigate the effects of the synthetic progestins gestodene, and drospirenone on sex differentiation in common carp (Cyprinus carpio) by histological analysis. To gain insights into the mechanisms behind the observations from the in vivo experiment on sex differentiation, we analyzed expression of genes involved in hypothalamus-pituitary-gonad (HPG) and hypothalamus-pituitary-thyroid (HPT) axes, histology of hepatopancreas, and in vitro bioassays. Carp were continuously exposed to concentrations of 2 ng/L of single progestins (gestodene or drospirenone) or to their mixture at concentration 2 ng/L of each. The exposure started 24 h after fertilization of eggs and concluded 160 days post-hatching. Our results showed that exposure of common carp to a binary mixture of drospirenone and gestodene caused increased incidence of intersex (32%) when compared to clean water and solvent control groups (both 3%). Intersex most probably was induced by a combination of multiple modes of action of the studied substances, namely anti-gonadotropic activity, interference with androgen receptor, and potentially also with HPT axis or estrogen receptor.

Soil influences on uptake and transfer of pharmaceuticals from sewage sludge amended soils to spinach.

Sewage sludge from wastewater treatment plants, which may contain various contaminants including pharmaceuticals, is often used as a soil amendment. These contaminants may subsequently be taken up by plants. In the present study we examined uptake of select pharmaceuticals from sewage sludge applied to soils by spinach plants. Seven soils were amended with sewage sludge from two wastewater treatment plants (A and B). Concentrations of compounds in plant tissues (roots and leaves) of spinach planted 45 days in these soils under greenhouse conditions were evaluated after harvest. The largest bioaccumulation in the roots and leaves was observed for sertraline (bioaccumulation factors (BAF) of 3.3-37.9 and 1-13.4, respectively), tramadol (1.3-10.0 and 4.8-30.0), and carbamazepine (2.2-17.2 and 6.1-48.8) and its metabolite carbamazepine 10,11-epoxide (not-quantified to 7.3 and 9.3-96.7). Elevated bioaccumulation in spinach roots was also identified for telmisartan (3.0-20.3) and miconazole (4.3-15.1), and leaves for metoprolol acid (not-quantified to 24.3). BAF values resulting from application of sludge B were similar to or moderately higher than BAFs from sludge A. The BAF values of carbamazepine and carbamazepine 10,11-epoxide in all tissues were negatively correlated with soil cation exchange capacity (CEC). This negative correlation between BAF and CEC was also observed for tramadol (A-roots and B-leaves), citalopram (B-roots), and telmisartan (B-roots) or between BAF and clay content for metoprolol acid (A-leaves and B-roots), tramadol (B-roots and A-leaves) and venlafaxine (B-roots). However, in the case of some other compounds (i.e. sertraline, amitriptyline, mirtazapine, metoprolol), uptake and the subsequent translocation and transformation from 3 soils of a higher pH and base cation saturation (Stagnic Chernozem Siltic, Haplic Chernozem and Greyic Phaeozem) significantly differed from 4 soils with a lower pH and base cation saturation (Haplic Luvisol, Haplic Cambisol, Dystric Cambisol and Arenosol Epieutric). Such observations proved strong compound dependent influences of soil conditions on various compounds bioaccumulations in plants and necessity of studying these processes always in diverse soils.

Correction to: Effects of multi-component mixtures from sewage treatment plant effluent on common carp (Cyprinus carpio) under fully realistic condition.

The original version of this Article unfortunately contained an error. The authors' given and family names were transposed erroneously. It has been corrected now in this Erratum.

Effects of Multi-Component Mixtures from Sewage Treatment Plant Effluent on Common Carp (Cyprinus carpio) under Fully Realistic Condition.

This study characterized changes in biomarker responses in common carp (Cyprinus carpio) upon exposure to effluent water discharged from a sewage treatment plant (STP) under real conditions. Fish were exposed to contamination in Cezarka pond, which receives all of its water input from the STP in the town of Vodnany, Czech Republic. Five sampling events were performed at day 0, 30, 90, 180, and 360 starting in April 2015. In total, 62 pharmaceutical and personal care products (PPCPs) were detected in the polar organic chemical integrative sampler. Compared to a control pond, the total concentration of PPCPs was 45, 16, 7, and 7 times higher in Cezarka pond at day 30, 90, 180, and 360, respectively. The result of oxidative stress and antioxidant enzyme biomarkers indicated alterations in the liver and intestine tissues of fish from Cezarka pond at day 30 and 360, respectively. High plasma vitellogenin levels were observed in both exposed females (180 and 360 days) and males (360 days) compared with their respective controls. However, only exposed female fish had higher vitellogenin mRNA expression than the control fish in these periods. Exposed female fish showed irregular structure of the ovary with scattered oocytes, which further developed to a vitellogenic stage at day 360. Low white blood cell levels were indicated in all exposed fish. Despite numerous alterations in exposed fish, favorable ecological conditions including high availability of food resulted in a better overall condition of the exposed fish after 1 year of exposure compared to the controls.

Complex effects of pollution on fish in major rivers in the Czech Republic.

Monitoring the contamination level in aquatic environments and assessing the impact on aquatic life occurs throughout the world. In the present study, an approach based on a combination of biomarkers and the distribution of various industrial and municipal pollutants was used to investigate the effect of aquatic environmental contamination on fish. Monitoring was performed in ten rivers in the Czech Republic (Berounka, Dyje, Elbe, Luznice, Odra, Ohre, Otava, Sázava, Svratka, and Vltava rivers, with one or two locations in each river) at the same sites that were regularly monitored within the Czech National Monitoring Program in 2007-2011. Health status, hepatic ethoxyresorufin-O-deethylase (EROD) activity, total cytochrome P450 content, and the plasma vitellogenin concentration were assessed in wild chub (Squalius cephalus) males caught at the monitored sites. The contamination level was the highest in the Svratka River downstream of Brno. Among all measured persistent organic pollutants (POPs), polychlorinated biphenyls and dichlorodiphenyltrichloroethane and its metabolites were the major contributors of POPs in fish muscle. Elbe, Odra, and Svratka rivers were identified as the most polluted. Fish from these locations showed reduced gonad size, increased vitellogenin concentration in male plasma, EROD, and total cytochrome P450 content. These biomarkers can be used for future environmental monitoring assessments. Overall, this study improves our understanding of the relationship between human activities and pollutant loads and further contributes to the decision to support local watershed managers to protect water quality in this region.

Estimation of amount of selected pharmaceuticals sorbed onto digested sludge from wastewater treatment plant Bratislava-Petrzalka.

Antibiotics and antidepressants are among the most successful drugs used for human therapy. Their concentration in influent on WWTP is relative high and there can be removed by biodegradation or sorption. The aim of this study was to define the amounts of sorbed pharmaceuticals on digested sludge from WWTP Bratislava - Petrzalka. The amounts of sorbed pharmaceuticals were calculated from knowing partition coefficients for selected pharmaceuticals and from analytically measured pharmaceutical´s concentrations in sludge liquor. From this calculation were estimated the one-year sorbed amount of pharmaceutical onto sludge from wastewater treatment plant Petrzalka (26,066g/y for ciprofloxacin, 756g/y for azithromycin, 647g/y for clarithromycin, 445g/y for venlafaxine and 148g/y for citalopram).

Investigation of diltiazem metabolism in fish using a hybrid quadrupole/orbital trap mass spectrometer.

RATIONALE: Diltiazem, a calcium channel blocker drug, is widespread in the environment because of its incomplete elimination during water treatment. It can cause negative effects on aquatic organisms; thus, a rapid and sensitive liquid chromatography/mass spectrometry (LC/MS) method to detect its presence was developed. Our approach is based on accurate mass measurements using a hybrid quadrupole-orbital trap mass spectrometer that was used to measure diltiazem and its metabolites in fish tissue. METHODS: Blood plasma, muscle, liver, and kidney tissues of rainbow trout (Oncorhynchus mykiss), exposed for 42 days to 30 µg L(-1) diltiazem, were used for the method development. No metabolite standards were required to identify the diltiazem biotransformation products in the fish tissue. RESULTS: Overall, 17 phase I diltiazem metabolites (including isomeric forms) were detected and tentatively identified using the MassFrontier spectral interpretation software. A semi-quantitative approach was used for organ-dependent comparison of the metabolite concentrations. CONCLUSIONS: These data increase our understanding about diltiazem and its metabolites in aquatic organisms, such as fish. These encompass desmethylation, desacetylation and hydroxylation as well as their combinations. This study represents the first report of the complex diltiazem phase I metabolic pathways in fish.

Perfluoroalkyl substances in aquatic environment-comparison of fish and passive sampling approaches.

The concentrations of seven perfluoroalkyl substances (PFASs) were investigated in 36 European chub (Squalius cephalus) individuals from six localities in the Czech Republic. Chub muscle and liver tissue were analysed at all sampling sites. In addition, analyses of 16 target PFASs were performed in Polar Organic Chemical Integrative Samplers (POCISs) deployed in the water at the same sampling sites. We evaluated the possibility of using passive samplers as a standardized method for monitoring PFAS contamination in aquatic environments and the mutual relationships between determined concentrations. Only perfluorooctane sulphonate was above the LOQ in fish muscle samples and 52% of the analysed fish individuals exceeded the Environmental Quality Standard for water biota. Fish muscle concentration is also particularly important for risk assessment of fish consumers. The comparison of fish tissue results with published data showed the similarity of the Czech results with those found in Germany and France. However, fish liver analysis and the passive sampling approach resulted in different fish exposure scenarios. The total concentration of PFASs in fish liver tissue was strongly correlated with POCIS data, but pollutant patterns differed between these two matrices. The differences could be attributed to the metabolic activity of the living organism. In addition to providing a different view regarding the real PFAS cocktail to which the fish are exposed, POCISs fulfil the Three Rs strategy (replacement, reduction, and refinement) in animal testing.

Wastewater analysis: the mean of the monitoring of frequently prescribed pharmaceuticals in Slovakia.

The estimation of medication use is based on the statistical data from pharmacies and hospitals. Excessive use or misuse of some compounds, especially psychoactive medications, has not yet been monitored in Slovakia. Wastewater analysis provides useful data about the medication use and misuse in individual regions. This study is focused on the analysis of 23 substances in the wastewaters of Slovakia. The monitoring programme has included stimulants, opioid and morphine derivatives, benzodiazepines, antidepressants, drug precursors and their metabolites. Urinary markers of these compounds were analysed at WWTP influent in seven regions (Bratislava, Kosice, Zvolen, Banská Bystrica, Trencín, Presov a Piestany) using LC-MS/MS technique. The analysis was performed from March to October 2013. The pattern in use of these compounds was also monitored. Tramadol and venlafaxine were found to be the most concentrated compounds among of all studied psychoactive pharmaceuticals. The highest specific loads of tramadol were detected in Piestany (409 mg/day/1000 inhabitants) and Zvolen (366 mg/day/1000 inhabitants). There is a considerable number of spa facilities (hotels) situated in these cities and this fact contributes to a higher occurrence of these psychoactive compounds in respective wastewaters.

The challenge presented by progestins in ecotoxicological research: a critical review.

Around 20 progestins (also called gestagens, progestogens, or progestagens) are used today in assisting a range of medical conditions from endometrial cancer to uterine bleeding and as an important component of oral contraception. These progestins can bind to a wide range of receptors including progestin, estrogen, androgen, glucocorticoid, and mineralocorticoid receptor, as well as sex hormone and corticosteroid binding globulins. It appears that only five of these (four synthetic and one natural) progestins have so far been studied in sewage effluent and surface waters. Analysis has reported values as either nondetects or low nanograms per liter in rivers. Seven of the progestins have been examined for their effects on aquatic vertebrates (fish and frogs). The greatest concern is associated with levonorgestrel, norethisterone, and gestodene and their ability to reduce egg production in fish at levels of 0.8-1.0 ng/L. The lack of environmental measurements, and some of the contradictions in existing values, however, hampers our ability to make a risk assessment. Only a few nanograms per liter of ethynodiol diacetate and desogestrel in water would be needed for fish to receive a human therapeutic dose for these progestins according to modeled bioconcentration factors. But for the other synthetic progestins levels would need to reach tens or hundreds of nanograms per liter to achieve a therapeutic dose. Nevertheless, the wide range of compounds, diverse receptor targets, and the effect on fish reproduction at sub-nanogram-per-liter levels should prompt further research. The ability to impair female reproduction at very low concentrations makes the progestins arguably the most important pharmaceutical group of concern after ethinylestradiol.

Contamination of fish in important fishing grounds of the Czech Republic.

The aim of this study was to compare the contamination levels of certain important fishing grounds in the Czech Republic and to assess the health risk of consuming the fish from these localities. The assessment was performed from 2006 to 2010 in 27 fishing grounds. Within this project, 707 fish from 14 different species were sampled. The concentration of selected toxic metals (Hg, Pb, Cd) and persistent organic pollutants (POPs), such as non-dioxin-like polychlorinated biphenyls (NDL-PCBs), hexachlorocyclohexane (HCH) isomers, dichlorodiphenyltrichloroethane (DDT) and its metabolites (o,p´-DDE; p,p´-DDE; o,p´-DDD; p,p´-DDD; o,p´-DDT; p,p´-DDT) and hexachlorobenzene (HCB), were analysed in the muscle tissue of the sampled fish. Atomic absorption spectrometry (AAS) was used for the analysis of toxic metals. All of the POPs were analysed using gas chromatography with an electron capture detector (GC/ECD). Common bream (Abramis brama) was chosen as a reference fish species for the comparison of fishing grounds. Mercury was found as a major pollutant in fish flesh at all of the sampling sites. Concentrations in excess of the maximum level (ML) of mercury in the muscle tissue of fish (0.5 mg kg(-1)) were registered in 32 samples. Concentrations of other monitored toxic metals in fish muscle were low, typically below the limit of quantification (LOQ). From the tested POPs, DDTs and NDL-PCBs were found as major pollutants. ML for NDL-PCBs (ICES-6) in muscle tissue of fish (0.125 mg kg(-1)) was exceeded in 7 samples. In case of tested pesticides, concentrations in excess of the MRL were not registered.

Identifying organic micropollutants' transformation products from the soil dissipation experiment by non-targeted high-resolution mass spectrometry approach: Can we gain more than transformation product identity?

Risk assessment of environmental hazards originating from xenobiotics extensively used worldwide (e.g., pharmaceuticals, bisphenols, or preservatives) requires a combined study of their effects, mobility, dissipation mechanisms, and subsequent transformation product identification and evaluation. We have developed an efficient accelerated solvent extraction method for a broad range of micropollutants of variable physical-chemical properties in soils to enable more accurate hazard characterisation. Micropollutant recoveries from freeze-dried soils were 60-120%, with the exception of atorvastatin, fexofenadine, and telmisartan, which had reduced recoveries (40-66%). The observed matrix effect ranged from -26% to 17% and was corrected by the matrix matching standard for quantitative analysis. The method allows sensitive and reliable determination of a wide range of analytes in soil samples and, consequently, qualitative analysis of transformation products (TP) with variable physicochemical properties. We identified TPs of five compounds (venlafaxine, telmisartan, valsartan, atorvastatin, and sertraline) by applying suspect and non-targeted data analyses. To our knowledge, the transformation product of atorvastatin was reported for the first time. All others were found in soil or other matrices. Valsartan (formed valsartan acid) and atorvastatin (transformed probably by oxidative decarboxylation of beta, delta dihydroxy heptanoic acid chain to propionic acid) were modified to a relatively large extent. All other compounds identified were only hydroxylated (sertraline and telmisartan) or demethylated (venlafaxine). We estimated the stability and presence of the identified TPs based on the constructed time trends and the ratio between TP formation and degradation rates. We demonstrated how valuable a non-targeted approach can be for complex evaluation of the fate and effect of soil pollutants.