Even though the occurrence of pharmaceuticals in the water environment is thought to be a potential problem for human health and aquatic organisms, the level of knowledge of their sources and ...presence in the marine ecosystem is still insufficient. Therefore, this study was designed to determine the emergence of sixteen pharmaceuticals and caffeine in groundwater, submarine groundwater discharge (SGD), rivers and coastal seawater in the southern Baltic Sea. It has been recognized that chemical substances load associated with SGD can affect coastal ecosystems equally or even greater than surface runoff. Hence, the Bay of Puck, which is an active groundwater discharge area, has been chosen as a model study site to assess the preliminary risk of pharmaceutical and caffeine residues supply in coastal ecosystem. A special focus was placed on tracing the possible sources of pollution for groundwater and SGD based on the composition of collected samples. Five pharmaceuticals (carbamazepine, sulfapyridine, sulfamethoxazole, ketoprofen and diclofenac) and caffeine were detected in varying concentrations from below the detection limit to 1528.2 ng L−1. Caffeine and diclofenac were the most widespread compounds. Groundwater was mostly enriched in the analysed compounds and consequently SGD has been recognized as an important source of identified pharmaceutical and caffeine residues to the Bay of Puck. A predicted no-effect concentration (PNEC) was determined in order to perform an environmental risk assessment of five pharmaceuticals and caffeine detected in water samples. Finally, future challenges and potential amendments in monitoring strategies are discussed.
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•Groundwater, SGD, seawater and river water samples were collected.•16 pharmaceutical and caffeine residues were analysed in all (61) collected samples.•3 of 17 measured residues were quantified in at least 7 samples.•Among all residues, caffeine and diclofenac, were the most widespread.•SGD is an important source of pharmaceutical and caffeine residues to the Bay of Puck.
Antibiotic residues have been commonly detected worldwide in freshwater, estuarine, and marine ecosystems. The review summarizes the up-to-date information about the toxic effects of over 60 ...antibiotics on nontarget autotrophic microorganisms with a particular focus on marine microalgae. A comprehensive overview of the available reports led to the identification of significant knowledge gaps. The data on just one species of freshwater green algae (
) constitute 60% of the total information on the toxicity of antibiotics, while data on marine species account for less than 14% of the reports. Moreover, there is a clear knowledge gap regarding the chronic effects of antibiotic exposure (only 9% of studies represent exposition time values longer than 7 days). The review summarizes the information on different physiological endpoints, including processes involved in photosynthesis, photoprotective and antioxidant mechanisms. Currently, the hazard assessment is mostly based on the results of the evaluation of individual chemicals and acute toxicity tests of freshwater organisms. Future research trends should involve chronic effect studies incorporating sensitive endpoints with the application of environmentally relevant concentrations, as well as studies on the mixture effects and combined environmental factors influencing toxicity.
The end-Devonian global Hangenberg event (359 Ma) is among the most devastating mass extinction events in Earth's history, albeit not one of the "Big Five". This extinction is linked to worldwide ...anoxia caused by global climatic changes. These changes could have been driven by astronomical forcing and volcanic cataclysm, but ultimate causes of the extinction still remain unclear. Here we report anomalously high mercury (Hg) concentration in marine deposits encompassing the Hangenberg event from Italy and Austria (Carnic Alps). The Hangenberg event recorded in the sections investigated can be here interpreted as caused by extensive volcanic activity of large igneous provinces (LIPs), arc volcanism and/or hydrothermal activity. Our results (very large Hg anomalies) imply volcanism as a most possible cause of the Hangenberg event, similar to other first order mass extinctions during the Phanerozoic. For the first time we show that apart from anoxia, proximate kill mechanism of aquatic life during the event could have been methylmercury formed by biomethylation of a volcanically derived, huge concentration of inorganic Hg supplied to the ocean. Methylmercury as a much more toxic Hg form, potentially could have had a devastating impact on end-Devonian biodiversity, causing the extinction of many pelagic species.
•Oxytetracycline affects non-target organisms•Oxytetracycline can impact cyanobacteria and microalgae•Presentation of a possible mode of action of oxytetracycline on non-target ...organisms•Implementation of prolonged standard toxicity tests required
The study aimed at measuring the influence of a wide range of oxytetracycline concentrations, with particular attention to the low levels of the antibiotic on cyanobacteria Microcystis aeruginosa and Nodularia spumigena, diatom Phaeodactylum tricornutum and the model green algae Chlorella vulgaris by conducting prolonged toxicity tests (lasting 10 days). Standard measurements (cell number, optical density, chlorophyll a concentration) were combined with photosynthetic parameters measurements. The obtained results show that concentrations of oxytetracycline present in the environment can affect tested microorganisms. It was found to decrease photosystem II efficiency and disrupt the photosynthesis process. A careful interpretation of photosynthetic parameters allowed a better understanding of the mode of action of oxytetracycline in relation to non-target photoautotrophic organisms like cyanobacteria and microalgae. In conclusion, it would appear that the use of standard chronic toxicity tests (72 h) does not allow to accurately and reliably assess the chronic impact of bioactive compounds including drugs and their metabolites on water organisms. On this basis, we recommend the application of extended duration tests.
The main objective of this study was to adapt analytical procedures for determining antibiotic residues in solid and aquatic samples to marine sediments and to investigate the occurrence of 9 ...sulfonamides, trimethoprim and 2 quinolones in southern Baltic Sea sediments. The analytical procedure was applied to sediment samples characterized as sand and silty sand. The validation results showed that a sensitive and efficient method applying tandem solid-phase extraction (SPE) and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) was obtained. Analytes were determined in the lower ngg−1 range with good accuracy and precision. The proposed analytical procedure was applied to the analysis of 13 sediment samples collected from the Baltic Sea along the Polish coast. Concentrations of antibiotic residues in environmental samples were calculated based on external matrix-matched calibration. Residues of nine out of twelve of the above antibiotics were detected in sediment samples in a concentrations of up to 419.2ngg−1 d.w. (dry weight). Sulfamethoxazole and sulfachloropyridazine were the most frequently detected compounds (58% of the analyzed samples). The occurrence frequency of trimethoprim was 42% and it was always detected simultaneously with sulfamethoxazole. Preliminary studies on the spatial distribution of the analyzed antibiotics indicate a high level of antibiotics occurring in the Pomeranian Bay and close to the mouths of Polish rivers. The study is the first one to demonstrate the occurrence of antibiotic residues in sediments of the Polish coastal area. The obtained results suggest that sediment can be an important secondary source of antibiotic residues in the marine environment.
The number of applications and commercialized processes utilizing ionic liquids has been increasing, and it is anticipated that this trend will persist and even intensify in the future. Ionic liquids ...possess desirable characteristics, such as low vapor pressure, good water solubility, amphiphilicity, and stability. Nevertheless, these properties can influence their environmental behavior, resulting in resistance to biotic and abiotic degradation and subsequent water contamination with more harmful derivatives. However, there is a notable scarcity of data regarding the impact of mixtures comprising ionic liquids and other micropollutants. Identifying potential potentiation of ionic liquids (Ils) toxicity in the presence of other xenobiotics is a proactive risk assessment measure. Therefore, the study aims to fill an important knowledge gap and identify possible interactions between imidazolium-based ionic liquid (IM1–12Br) and the common antibiotic oxytetracycline (OXTC). During 11-day experiments, selected marine, brackish and freshwater microorganisms (diatom Phaeodactylum tricornutum, cyanobacterium Microcystis aeruginosa and green algae Chlorella vulgaris) were exposed to binary mixtures of target substances. The assessed responses encompassed chlorophyll a kinetic parameters related to photosynthesis efficiency, as well as pigment concentrations, specifically phycobilin content. Additionally, the impact on the luminescent marine bacterium Aliivibrio fischeri has been evaluated. Significant effects on the growth, photosynthetic processes, and pigment content were observed in all the targeted microorganisms. The concentration addition (CA) and independent action (IA) mathematical models followed by the Model Deviation Ratio (MDR) evaluation enabled the identification of mainly synergistic interactions in the studied mixtures. The findings of present study offer valuable insights into the impacts of ionic liquids and other organic micropollutants.
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•Synergistic effect of mixtures of representative antibiotic and ionic liquid•Alternations and inhibition of the photosystem II photochemical efficiency•Impact on the production of phycobiliproteins in cyanobacteria M. aeruginosa•The IA and CA models accurately predict the interactions in the given mixtures
Concentrations of selected antibiotic compounds from different groups were measured in sediment samples (14 analytes) and in near-bottom water samples (12 analytes) collected in 2011–2013 from the ...southern Baltic Sea (Polish coastal zone). Antibiotics were determined at concentration levels of a few to hundreds of ng g− 1 d.w. in sediments and ng L− 1 in near-bottom waters. The most frequently detected compounds were sulfamethoxazole, trimethoprim, oxytetracycline in sediments and sulfamethoxazole and trimethoprim in near-bottom waters. The occurrence of the identified antibiotics was characterized by spatial and temporal variability. A statistically important correlation was observed between sediment organic matter content and the concentrations of sulfachloropyridazine and oxytetracycline. Risk assessment analyses revealed a potential high risk of sulfamethoxazole contamination in near-bottom waters and of contamination by sulfamethoxazole, trimethoprim and tetracyclines in sediments. Both chemical and risk assessment analyses show that the coastal area of the southern Baltic Sea is highly exposed to antibiotic residues.
Coastal marine areas of densely populated countries are exposed to a wide array of human activities having an impact on their ecological status. The Baltic Sea is particularly susceptible to ...pollution by hazardous substances (limited water exchange, shallowness, and large catchment area). Polish media regularly reports ecological catastrophes in the Gulf of Gdańsk area caused by eg. shipwrecks leaking. Thus, there is a need of a broad scientific based report on recent contaminant loads and distribution. In this review paper, we report loads of contaminants from different obvious and non-obvious sources. We also gather data on legacy and new emerging contaminant concentrations measured in the Gulf of Gdańsk within the last decade (2008–2018). The paper also includes available biological effect measurements performed recently as well as a summary of needs and gaps to be filled for the development of reliable risk assessment.
•Despite sensational media reports the Gulf of Gdańsk is not exceptionally contaminated.•Although restrictions on use of legacy pollutants their concentrations are not decreasing.•The national monitoring of pollutant concentrations performed currently is inconsistent.•The amount of information needed to perform a reliable environmental assessment is too small.
Methylmercury (MeHg) is the most toxic and dangerous form of mercury occurring in the environment. MeHg is highly bioaccumulative in organisms and undergoes biomagnification via the food chain. In ...the Baltic Sea munition dumpsites, methylmercury can be formed from mercury fulminate contained in primary explosives, as environmental conditions there favour methylation. MeHg in analysed sediments ranged from 19 to 2362 pg g−1d.w., the concentration of mercury (HgTOT) ranged from 4 to 294 ng g−1 d.w., and the values of MeHg/Hg ratio ranged from 0.1 to 2.0%. The obtained results confirmed that munition dumpsites are a source of mercury. The concentration of MeHg is elevated in a wider area than immediately next to dumped munitions. Presented results suggest that physical processes responsible for sediment and near-bottom water movement are diffusing MeHg signal, making munition dumpsites rather a diffuse source of MeHg than a number of point sources associated with particular munitions.
•Dumped ammunition is a source of mercury to marine bottom sediments.•Presence of ammunition can limit methylmercury production.•Methylmercury concentration in sediments was range from 19 pg g−1 up to over 2.4 ng g−1•The methylmercury/mercury ratio in sediments was from 0.1 to 2.0%.•Measured concentrations were comparable to studies in years 2008–2019, but lower than reported in 1990s.
•A new approach for analysis of pharmaceuticals in environmental samples is presented.•Estimation of the expanded uncertainty of an analytical procedure is highlighted.•An alternative clean-up ...procedure based on the use of SPE speed disks is proposed.•A new method for the determination of antibiotics in seawater was developed.•Determination of target compounds in seawater sampled in the southern Baltic Sea.
Although the uncertainty estimate should be a necessary component of an analytical result, the presentation of measurements together with their uncertainties is still a serious problem, especially in the monitoring of the presence of pharmaceuticals in the environment. Here we discuss the estimation of expanded uncertainty in analytical procedures for determining residues of twelve pharmaceuticals in seawaters using solid-phase extraction (SPE) with H2O-Philic BAKERBOND speed disks and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS). Matrix effects, extraction efficiency and absolute recovery of the developed analytical method were determined. A validation was performed to obtain the method's linearity, precision, accuracy, limits of detection (LODs) and quantification (LOQs). The expanded uncertainty of the data obtained was estimated according to the Guide to the Expression of Uncertainty in Measurement and ISO 17025:2005 standard. We applied our method to the analysis of drugs in seawaters samples from the coastal area of the southern Baltic Sea. As a result, a new approach (concerning the uncertainty estimation as well as the development of analytical method) to the analysis of pharmaceutical residues in environmental samples is presented. The information given here should facilitate the introduction of uncertainty estimation in chromatographic measurements on a much greater scale than is currently the case.
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