Ksenia Pazdro

A new approach for the estimation of expanded uncertainty of results of an analytical method developed for determining antibiotics in seawater using solid-phase extraction disks and liquid chromatography coupled with tandem mass spectrometry technique

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 methods 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.

Contamination of the southern Baltic Sea waters by the residues of selected pharmaceuticals: Method development and field studies

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 ng L(-1). Trimethoprim, sulfamethoxazole and enrofloxacin were most frequently detected compounds. The highest concentration was determined for ketoprofen (135.0 ± 10.9 ng L(-1)). Marine pollution potential hotspots were found in enclosed or semi-enclosed bodies of water.

Survey of perfluorinated compounds (PFCs) in surface waters of Poland

Perfluorochemicals (PFCs) are wide-spread contaminants on a global scale. There is an increasingly growing number of data on environmental occurrence, sources and risk of PFCs to humans and aquatic biota in highly industrialised countries but inadequate information exists for less industrialised regions. In the present study, concentrations and profiles of PFCs were examined in surface waters (rivers, lakes, streams, coastal region of the Baltic Sea) of Poland. PFOS was the dominant compound found in water at most of the sites surveyed and its concentration varied between < 0.5 and 150 ng/L and next was PFHxS with < 0.25 to 110 ng/L, while at much smaller concentration of < 0.5 to 18 ng/L occurred PFOA. The long-chain carboxylates (C11–C16) could be found only in water of a drainage ditch near to the Sarzyna site, i.e., PFUnDA occurred at 0.17 ng/L, PFTeDA of 0.06 ng/L, PFDoDA at 0.1 ng/L and PFHxDA at 0.12 ng/L. PFDA was found at several locations in the Gulf of Gdańsk and its concentration varied between < 0.01 and 0.07 ng/L. The profile of PFCs in surface water at several sites of Poland with PFOS as a major compound, followed by PFOA is similar to that reported for other countries in Europe as well as for India, while this is different from that of Korea, Japan and the USA, where PFOA was the predominant contaminant.

The influence of salinity on the toxicity of selected sulfonamides and trimethoprim towards the green algae Chlorella vulgaris.

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 72 h. In freshwater the EC50 values ranged from 0.98 to 123.22 mg L(-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 9 PSU). 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.

Spatial and Temporal Gradients of Triazines in the Baltic Sea off Poland

The herbicides atrazine, simazine and terbuthylazine (and the degradation product deethylatrazine) were analysed in two river-to-open-sea transects and two vertical (open-sea) profiles in the southern Baltic off Poland. Samples taken in September 1995 and April 1997 contained total triazine concentrations ranging from 7 to 31 and 4.5 to 13 ng/dm3, respectively. Concentrations of the individual compounds ranged from 0 to 8 ng/dm3. These are generally higher than levels reported, for example, in the North Sea. The largest surface concentrations were found close to the Vistula and Odra river mouths, endorsing river run-off as a primary source of the triazines. Temporal variability can be related to the late-spring and early-summer agricultural applications of the compounds. Variations in ratios between the individual triazines can be explained by usage patterns and differing residence times. Offshore vertical profiles indicate enrichment of the surface layer through atmospheric triazines inputs, highest concentrations above the halocline associated with colloidal organics and lowest concentrations in the bottom waters, probably as a result of particulate scavenging. The influence of the North Sea inflow to the Baltic is also discussed.

A very fast and simple method for the determination of sulfonamide residues in seawaters

The development of simple and reproducible analytical methods for the determination of new organic pollutants like pharmaceuticals and personal care products in seawaters is of the highest priority. In the present study, a new analytical method based on offline solid phase extraction and liquid chromatography with standard UV detection (SPE-HPLC-UV) was developed to determine the presence of sulfonamides in seawaters. Special attention was paid to the sample preparation step. Different variables affecting the extraction process, such as seawater salinity and the humic acid content were studied. As a result, the presented SPE procedure for the extraction of sulfonamides from seawaters is also applicable to other techniques like LC-MS and LC-MS/MS. This method was optimized and fully validated for its performance parameters. It has very good selectivity, linearity (R2 > 0.995), precision (RSD 75%), even in highly saline waters and in the presence of humic acids.

Determination of indole-3-acetic acid in the Gulf of Gdańsk by high-performance liquid chromatography of its 4-methyl-7-methoxycoumarin derivative

Abstract A modified procedure for the high-performance liquid chromatographic determination of auxin indole-3-acetic acid (IAA) in the marine environment is described. 4-(Bromomethyl)-7-methoxycoumarin (BrMmc) was used as a fluorescence labelling reagent for chromatographic analysis of IAA. The conversion of IAA into a coumaryl ester (IAA-Mmc) was carried out in the presence of potassium carbonate and with crown ether as a catalyst. The detection limit for the ester was about 20 fmol per injection. The new procedure was applied to the analysis of seawater and marine sediment samples collected from the Gulf of Gdansk. For the first time, gas chromatography–mass spectrometry was used to confirm the presence of IAA in marine sediment.

The use of theVibrio harveyi luminescence mutagenicity assay as a rapid test for preliminary assessment of mutagenic pollution of marine sediments

Mutagenic pollution of the natural environment is currently one of the most serious environmental problems. It includes the pollution of marine sediments. Therefore, rapid detection of the presence of mutagens is an important issue. Recently, we have developed a novel microbiological assay for rapid assessment of mutagenicity of samples from the natural environment. This assay is based on bioluminescence of a mutantVibrio harveyi strain, and was shown to be useful in testing samples of marine water and plant tissues. Here we demonstrate the usefulness of this assay in preliminary assessment of mutagenic pollution of marine sediments. Mutagenicity of environmental samples taken from the Baltic Sea, is documented and compared here with a commercially available standard sediment sample (IAEA 383), which contains known amounts of mutagenic compounds. The whole procedure, from obtaining a sample in the laboratory to getting final results, is very short (less than 4 h).

Determination of Tetracyclines Residues in the Gulf of Gdańsk (Southern Baltic Sea) Sediments Using a Tandem Solid-Phase Extraction with Liquid Chromatography Coupled with Tandem Mass Spectrometry

Pharmaceuticals are biologically active and relatively persistent substances which have been recently recognized as a continuing threat to the aquatic environment. Numerous adverse effects may arise for aquatic non-target organisms from the presence of pharmaceutical residues. One of the main pharmaceutical contaminants are antibiotics which are in the environment in considerable concentrations and can have negative biological effects to marine microorganisms. Despite of this, the knowledge on antibiotics occurrence, behaviour and fate in the Baltic Sea is very limited. This study presents the preliminary results on tetracycline and oxytetracycline residues occurrence in the sediments collected from the Gulf of Gdansk (southern Baltic Sea). Among the antibiotics, tetracyclines are one of the most popular class used for human and animal therapy and for animal breeding. The method for tetracyclines residues determination was optimized, using two types of Baltic sediments (sandy and muddy) spiked at nine concentration levels (from 1 to 1,000 ng g−1 d.w.) to achieve the best validation parameters. Acetonitrile and EDTA-McIlvaine extraction buffer solution (pH 4) (1:1) for extraction and tandem SPE technique with Discovery SAX and Oasis HLB cartridges for extracts clean-up were applied. Quantitative and qualitative determination of analysed antibiotics was performed with the use of liquid chromatography tandem mass spectrometry (LC-MS/MS) with electrospray ionization source in the positive mode. The recoveries for target antibiotics ranged from 78.8 to 131.1 % for tetracycline and 75.5–114.8 % for oxytetracycline. The LOD values ranged from 1.5 to 3.5 ng g−1 d.w. for tetracycline and from 1.2 to 2.2 ng g−1 d.w. for oxytetracycline. The developed method was applied in the determination of tetracyclines in six sediments collected in 2012 during r/v “Oceania” cruises. Oxytetracycline was identified in four of analyzed samples at concentrations from 21 to 625 ng g−1 d.w. Tetracycline was determined only in one sediment sample collected close to WWTP “Gdansk Wschod” outlet (13.8 ng g−1 d.w.). None of the target compounds was identified in the accumulation area—the Gdansk Deep.

Toxicants accumulation rates and effects in Mytilus trossulus and Nereis diversicolor exposed separately or together to cadmium and PAHs.

Two invertebrates, Mytilus trossulus and Nereis diversicolor, were exposed in aquaria to cadmium (50 μ g L− 1) and a mixture of three- to six-ring PAHs (2 μ g L− 1 each) for 2 weeks. Organisms of two species were reared in separate tanks or together in the same one. Concentrations of Cd, PAHs and activities of selected biomarkers: catalase (CAT), glutathione S-transferase (GST) and acetylcholinesterase (AChE) were measured within 2 weeks of exposure. When reared separately, higher accumulation rates for cadmium were measured in mussels (16.4 μ g day− 1 g− 1 d.w. lipid-free tissue) than in polychaeta (0.7 μ g Cd g− 1 d.w day− 1). When co-exposed, a difference in bioaccumulation was maintained but the accumulation rate in N. diversicolor increased to 1.0 μ g Cd g− 1 d.w. day− 1 and decreased to 9.6 μ g Cd g− 1 d.w. day− 1 in M. trossulus. On the contrary, faster bioaccumulation rates of PAHs were seen in polychaeta than in mussels when exposed separately (19.3 vs 4.5 μ g PAHs day− 1 g− 1 lipid weight) than together (12.0 vs 3.1 μ g PAHs g− 1 l.w. day− 1). Substantial changes in the bioaccumulation patterns of the different M. trossulus organs were observed when both species were reared together. Biochemical responses indicated no effect of the accumulated contaminants on AChE, enhancement of CAT in both species and depletion of GST in Mytilus. The observed differences are discussed in terms of different bioavailability of contaminants, route of uptake and detoxification mechanism, under the two modes of exposure.