•Review of analytical methods for the determination of pharmaceuticals in biota.•Bioaccumulative pharmaceuticals are present in the environment.•Occurrence of pharmaceuticals is evident in aquatic ...and terrestrial organisms.
The presence of pharmaceutical residues in various environmental compartments is an issue of increasing concern. The widespread occurrence of these compounds in water and soil samples has been demonstrated in a number of analytical studies. However, the data about their concentrations in biota samples is scarce. Moreover, the trophic transfer of pharmaceuticals remains largely unexplored, despite increasing evidence of the potential bioaccumulation of those compounds. Therefore, the main aim of this review is to present an overview of the current state of data about the bioaccumulation and analytical methodologies used for the determination of pharmaceutical residues in biota samples. This work focuses on the most commonly found pharmaceuticals in the environment: antibiotics, analgesic and anti-inflammatory drugs, steroid hormones, antihypertensives and antidepressants. We do hope that the collected data will allow a better understanding of pharmaceutical pollution and the exposure of non-target organisms. However, although impressive progress has undoubtedly been made, in order to fully understand the behavior of these chemicals in the environment, there are still numerous gaps to be filled in our overall knowledge in this field.
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.
Display omitted
•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.
The synthesis of photoswitchable
-dibenzo
,
oxepine derivatives and microtubule inhibitors were described. Subsequently, we examined the reaction of methoxy derivative 3-nitrodibenzo
,
oxepine with ...different aldehydes and in the presence of BF
·OEt
as a catalyst. Our study provided a very concise method for the construction of the
-dibenzo
,
oxepine skeleton. The analysis of products was run using experimental and theoretical methods. Next, we evaluated the
/
isomerization of
-dibenzo
,
oxepine derivatives, which could be photochemically controlled using visible-wavelength light.
•Sulfamethoxazole and sulfapyridine are the most toxic to C. vulgaris.•Trimethoprim is the least toxic pharmaceutical to selected organism.•Toxicities were negatively correlated with increasing ...salinities.•The effects of tested drugs towards algae are caused by specific mode of action.
This paper presents the investigation of the influence of salinity variations on the toxicity of sulfapyridine, sulfamethoxazole, sulfadimethoxine and trimethoprim towards the green algae Chlorella vulgaris after exposure times of 48 and 72h. In freshwater the EC50 values ranged from 0.98 to 123.22mgL−1 depending on the compound. The obtained results revealed that sulfamethoxazole and sulfapyridine were the most toxic, while trimethoprim was the least toxic pharmaceutical to the selected organism. Deviations between the nominal and real test concentrations were determined via instrumental analysis to support the interpretation of ecotoxicological data. The toxicity effects were also tested in saline water (3, 6 and 9PSU). The tendency that the toxicity of selected pharmaceuticals decreases with increasing salinity was observed. Higher salinity implies an elevated concentration of inorganic monovalent cations that are capable of binding with countercharges available on algal surfaces (hydroxyl functional groups). Hence it can reduce the permeability of pharmaceuticals through the algal cell walls, which could be the probable reason for the observed effect. Moreover, for the classification of the mode of toxic action, the toxic ratio concept was applied, which indicated that the effects of the investigated drugs towards algae are caused by the specific mode of toxic action.
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.
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.
•Review of selected aspects of the analysis of pharmaceuticals in the environment.•Presentation of recent improvements in the determination of pharmaceuticals.•Discussion of methodological challenges ...in the analysis of pharmaceuticals.•Presentation of application of carbon nanotubes in the analysis of pharmaceuticals.
Recent developments and improvements in advanced instruments and analytical methodologies have made the detection of pharmaceuticals at low concentration levels in different environmental matrices possible. As a result of these advances, over the last 15 years residues of these compounds and their metabolites have been detected in different environmental compartments and pharmaceuticals have now become recognized as so-called ‘emerging’ contaminants. To date, a lot of papers have been published presenting the development of analytical methodologies for the determination of pharmaceuticals in aqueous and solid environmental samples. Many papers have also been published on the application of the new methodologies, mainly to the assessment of the environmental fate of pharmaceuticals. Although impressive improvements have undoubtedly been made, in order to fully understand the behavior of these chemicals in the environment, there are still numerous methodological challenges to be overcome. The aim of this paper therefore, is to present a review of selected recent improvements and challenges in the determination of pharmaceuticals in environmental samples. Special attention has been paid to the strategies used and the current challenges (also in terms of Green Analytical Chemistry) that exist in the analysis of these chemicals in soils, marine environments and drinking waters. There is a particular focus on the applicability of modern sorbents such as carbon nanotubes (CNTs) in sample preparation techniques, to overcome some of the problems that exist in the analysis of pharmaceuticals in different environmental samples.
•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.
•Presentation of a method for the determination of pharmaceuticals in seawater.•Evaluation of contamination of the southern Baltic Sea by pharmaceuticals.•Pollution hotspots found in semi-enclosed ...bodies of water: bays and river mouths.•Concentrations of drugs in marine waters too low to cause acute toxic effects.•The first such extensive study of this topic.
In this study the occurrence of thirteen pharmaceuticals in seawaters collected from southern Baltic Sea was evaluated for the first time. It was performed by applying newly developed analytical procedure. The method was characterized in terms of its basic validation parameters as well as matrix effects, extraction efficiency and absolute recovery. The results were expressed as result±expanded uncertainty, which was estimated according to the Guide to the Expression of Uncertainty in Measurement. Additionally, in order to verify the influence of variable parameters of the analyzed samples on method performance parameters, chemometric analysis was carried out. The obtained results revealed that residues of pharmaceuticals were present in seawaters at a concentration level of ngL−1. Trimethoprim, sulfamethoxazole and enrofloxacin were most frequently detected compounds. The highest concentration was determined for ketoprofen (135.0±10.9ngL−1). Marine pollution potential hotspots were found in enclosed or semi-enclosed bodies of water.
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.
Display omitted
•Data on antibiotics residues in southern the Baltic Sea is limited.•14 antibiotics detected in the southern Baltic Sea near-bottom waters and sediments•The SMX and OTC exhibited the highest concentration in the samples.•Linear regression between OTC and total organic carbon in sediments•Potentially high environmental risk (RQ>1) for some antibiotics in the Baltic Sea
PDF
