Procjena metalotioneina u dagnjama (Mytilus galloprovincialis) kao biomarkera žive i kadmija u slovenskim vodama tršćanskog zaljeva: studija dugoročnog istraživanja

In order to assess the spatial distribution and temporal trends of pollution with metals in the coastal sea of Slovenia, the level of metallothioneins (MT) was determined in blue mussels from three sampling locations, twice per year for a period of 10 years. MT concentrations ranged from 45 to 163 μg g-1 w.w. in March, and from 46 to 144 μg g-1 w.w. in the September sampling. The metals content was determined in whole mussel tissue once per year at two stations. The cadmium (Cd) concentration was in the range from 0.50 to 1.11 mg kg-1, while the concentration of mercury (Hg) was in the range from 0.70 to 0.237 mg kg-1. Results revealed no significant seasonal differences or differences between sampling sites in MT content, as well as variations in the content of Cd and Hg in mussels’ tissue during the examined period. The MT and metal content in mussels are not well correlated and other factors may have caused the fluctuations observed in MT content between years. This supports the notion that biomonitoring data have to be interpreted cautiously, taking into account various other factors that may influence MT induction.Kako bi se mogao ocijeniti prostorni raspored i vremenski trendovi onečišćenja metalima u priobalnom moru Slovenije, razina metalotioneina (MT) utvrđena je u dagnjama na tri mjesta uzorkovanja, dva puta godišnje za razdoblje od 10 godina. Koncentracije MT kretale su se od 45 do 163 μg g-1 mokre težine u ožujku, te od 47 do 144 μg g-1 mokre težine u rujanskom uzorkovanju. Sadržaj metala utvrđen je u cijelom tkivu dagnji na dvjema postajama, jednom godišnje. Koncentracija kadmija (Cd) kretala se u rasponu od 0,50 do 1,11 mg kg-1, dok je koncentracija žive (Hg) kolebala u rasponu od 0,70 do 0,237 mg kg-1. Rezultati nisu pokazali značajne sezonske razlike ili razliku između postaja glede sadržaja metalotioneina tijekom uzorkovanja, dok se sadržaj kadmija i žive u tkivu školjki mijenjao tijekom promatranog razdoblja. Prisutnost metalotioneina i metala u dagnjama nije usko povezana što ukazuje na druge moguće čimbenike kao uzroke fluktuacija promatranih tijekom godina. To podržava ideju da se podaci iz biomonitoringa moraju tumačiti oprezno, uzimajući u obzir razne druge čimbenike koji mogu utjecati na indukciju metalotioneina (MT)

Adjuvant TNF-a therapy to electrochemotherapy with intravenous cisplatin in murine sarcoma exerts synergistic antitumor effectiveness

Background. Electrochemotherapy is a tumour ablation modality, based on electroporation of the cell membrane, allowing non-permeant anticancer drugs to enter the cell, thus augmenting their cytotoxicity by orders of magnitude. In preclinical studies, bleomycin and cisplatin proved to be the most suitable for clinical use. Intravenous administration of cisplatin for electrochemotherapy is still not widely accepted in the clinics, presumably due to its lower antitumor effectiveness, but adjuvant therapy by immunomodulatory or vascular-targeting agents could provide a way for its potentiation. Hence, the aim of the present study was to explore the possibility of adjuvant tumour necrosis factor % (TNF-%) therapy to potentiate antitumor effectiveness of electrochemotherapy with intravenous cisplatin administration in murine sarcoma. Materials and methods. In vivo study was designed to evaluate the effect of TNF-% applied before or after the electrochemotherapy and to evaluate the effect of adjuvant TNF-% on electrochemotherapy with different cisplatin doses. Results. A synergistic interaction between TNF-% and electrochemotherapy was observed. Administration of TNF-% before the electrochemotherapy resulted in longer tumour growth delay and increased tumour curability, and was significantly more effective than TNF-% administration after the electrochemotherapy. Tumour analysis revealed increased platinum content in tumours, TNF-% induced blood vessel damage and increased tumour necrosis after combination of TNF-% and electrochemotherapy, indicating an anti-vascular action of TNF-%. In addition, immunomodulatory effect might have contributed to curability rate of the tumours. Conclusion. Adjuvant intratumoural TNF-% therapy synergistically contributes to electrochemotherapy with intravenous cisplatin administration. Due to its potentiation at all doses of cisplatin, the combined treatment is predicted to be effective also in tumours, where the drug concentration is suboptimal or in bigger tumours, where electrochemotherapy with intravenous cisplatin is not expected to be sufficiently effective

Chemical and toxicological characterisation of anticancer drugs in hospital and municipal wastewaters from Slovenia and Spain

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Potentially toxic elements in the riparian soils of the Sava River

Purpose Riparian zone contamination is a growing problem for several European catchments due to high anthropogenic pressures. This study investigates As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in the Sava River riparian zone, characterized by wide agricultural areas, various geological substrates, and different types of industrial pollution. The accumulation and mobility of these elements were studied because they are listed as priority substances in the Water Framework Directive and environmental objectives for surface waters. Materials and methods Sampling was performed during the sampling campaign of the EU 7th FW-funded GLOBAQUA project in September 2015 during a low-water event. Soil samples were collected along the Sava River at 12 selected sampling sites, from a depth of 0–30 cm, at a distance of 10–15 m from the river bank. The extent of pollution was estimated by determining total and readily soluble element concentrations in the soils. Potential ecological risk and the source of the selected elements in the soils was determined using the enrichment factor (EF), potential ecological risk index (RI), and statistical methods such as the principal component analysis (PCA) and multiple linear regression analysis (MLRA). Results and discussion This study showed that concentrations of the selected elements increase along the Sava. In terms of origin, PCA and MLRA indicated that Cr and Ni in soils are predominantly lithogenic, while As, Cd, Pb, and Zn are both lithogenic and anthropogenic (ore deposits, industry, and agriculture). PCA singled out Cu since its origin in soil is most probably from specific point-source pollution. EF was generally minor to moderate for most of the examined elements, apart from Cu, for which the EF was significant at one sampling site. Overall ecological risk (RI) fell within the low-risk category for most sites, apart from Belgrade sampling site (BEO), where high total Cd content affected individual and overall ecological risk indicators, indicating Cd could represent a considerable ecological risk for the downstream riparian zone. Conclusions Purpose: Riparian zone contamination is a growing problem for several European catchments due to high anthropogenic pressures. This study investigates As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in the Sava River riparian zone, characterized by wide agricultural areas, various geological substrates, and different types of industrial pollution. The accumulation and mobility of these elements were studied because they are listed as priority substances in the Water Framework Directive and environmental objectives for surface waters. Materials and methods: Sampling was performed during the sampling campaign of the EU 7th FW-funded GLOBAQUA project in September 2015 during a low-water event. Soil samples were collected along the Sava River at 12 selected sampling sites, from a depth of 0–30 cm, at a distance of 10–15 m from the river bank. The extent of pollution was estimated by determining total and readily soluble element concentrations in the soils. Potential ecological risk and the source of the selected elements in the soils was determined using the enrichment factor (EF), potential ecological risk index (RI), and statistical methods such as the principal component analysis (PCA) and multiple linear regression analysis (MLRA). Results and discussion: This study showed that concentrations of the selected elements increase along the Sava. In terms of origin, PCA and MLRA indicated that Cr and Ni in soils are predominantly lithogenic, while As, Cd, Pb, and Zn are both lithogenic and anthropogenic (ore deposits, industry, and agriculture). PCA singled out Cu since its origin in soil is most probably from specific point-source pollution. EF was generally minor to moderate for most of the examined elements, apart from Cu, for which the EF was significant at one sampling site. Overall ecological risk (RI) fell within the low-risk category for most sites, apart from Belgrade sampling site (BEO), where high total Cd content affected individual and overall ecological risk indicators, indicating Cd could represent a considerable ecological risk for the downstream riparian zone. Conclusions: At downstream sites, there was a noticeable increase in PTE content, with Cd, Cr, Ni, and Zn exceeding the proposed threshold values for European soils, indicating rising contamination in riparian soils. In terms of the ecological risk, only Cd could pose a potential ecological threat for the downstream riparian zone

Electroporation with nanosecond pulses and bleomycin or cisplatin results in efficient cell kill and low metal release from electrodes

Nanosecond electric pulses have several potential advantages in electroporation-based procedures over the conventional micro- and millisecond pulses including low level of heating, reduced electrochemical reactions and reduced muscle contractions making them alluring for use in biomedicine and food industry. The aim of this study was to evaluate if nanosecond pulses can enhance the cytotoxicity of chemotherapeutics bleomycin and cisplatin in vitro and to quantify metal release from electrodes in comparison to 100 μs pulses commonly used in electrochemotherapy. The effects of nanosecond pulse parameters (voltage, pulse duration, number of pulses) on cell membrane permeabilization, resealing and on cell survival after electroporation only and after electrochemotherapy with bleomycin and cisplatin were evaluated on Chinese hamster ovary cells. Application of permeabilizing nanosecond pulses in combination with chemotherapeutics resulted in successful cell kill. Higher extracellular concentrations of bleomycin – but not cisplatin – were needed to achieve the same decrease in cell survival with nanosecond pulses as with eight 100 μs pulses, however, the tested bleomycin concentrations were still considerably lower compared to doses used in clinical practice. Decreasing the pulse duration from microseconds to nanoseconds and concomitantly increasing the amplitude to achieve the same biological effect resulted in reduced release of aluminum ions from electroporation cuvettes

Following the Occurrence and Origin of Titanium Dioxide Nanoparticles in the Sava River by Single Particle ICP-MS

Titanium dioxide nanoparticles (TiO2NPs) are widely produced and used NPs in different applications. To evaluate the risk from anthropogenic TiO2NPs, more information is needed on their occurrence in the environment. For the first time, this study reports the levels of TiO2NPs in waters and sediments at selected sampling sites along the Sava River using inductively coupled plasma mass spectrometry in single particle mode (spICP-MS). The highest concentrations of TiO2NPs were determined in river water at Vrhovo (VRH), Jasenovac (JAS), and Slavonski Brod (SLB) sampling locations impacted by urban, agricultural, and/or industrial activities, suggesting that these NPs are likely of anthropogenic origin. The results further showed that hydrological conditions and sediment composition significantly influence the levels of TiO2NPs in river water at most locations. Moreover, the Ti/Al elemental concentration ratios of NPs in water and sediments at JAS were higher than the natural background ratios, further confirming their anthropogenic origin. The outcome of this study provides first information on the presence of (anthropogenic) TiO2NPs in different environmental compartments of the Sava River, contributing to more reliable risk assessments and better regulation of TiO2NPs emissions in the future

Determination of Cd, Pb and As in sediments of the Sava River by electrothermal atomic absorption spectrometry

Abstract: The applicability of nitric acid, palladium nitrate and a mixture of palladium and magnesium nitrate as matrix modifiers was estimated for the accurate and reproducible determination of cadmium (Cd), lead (Pb) and arsenic (As) in sediments of the Sava River by electrothermal atomic absorption spectrometry, ETAAS. Decomposition of the samples was done in a closed vessel microwave-assisted digestion system using nitric, hydrochloric and hydrofluoric acids, followed by the addition of boric acid to convert the fluorides into soluble complexes. The parameters for the determination of Cd, Pb and As in sediments were optimised for each individual element and for each matrix modifier. In addition, two sediment reference materials were also analysed. In determination of Cd and Pb, nitric acid was found to be the most appropriate matrix modifier. The accurate and reliable determination of Cd and Pb in sediments was possible also in the presence of boric acid. The use of a mixture of palladium and magnesium nitrate efficiently compensated for matrix effects and enabled the accurate and reliable determination of As in the sediments

Determination of Cd, Pb and As in sediments of the Sava River by electrothermal atomic absorption spectrometry

The applicability of nitric acid, palladium nitrate and a mixture of palladium and magnesium nitrate as matrix modifiers were estimated for the accurate and reproducible determination of cadmium (Cd), lead (Pb) and arsenic (As) in sediments of the Sava River by electrothermal atomic absorption spectrometry, ETAAS. Decomposition of the samples was done in a closed vessel microwave-assisted digestion system using nitric, hydrochloric and hydrofluoric acids, followed by the addition of boric acid to convert the fluorides into soluble complexes. The parameters for the determination of Cd, Pb and As in sediments were optimised for each individual element and for each matrix modifier. In addition, two sediment reference materials were also analysed. In determination of Cd and Pb, nitric acid was found to be the most appropriate matrix modifier. The accurate and reliable determination of Cd and Pb in sediments was possible also in the presence of boric acid. The use of a mixture of palladium and magnesium nitrate efficiently compensated for matrix effects and enabled the accurate and reliable determination of As in the sediments. Quantification of Cd and As was performed by calibration using acid matched standard solutions, while the standard addition method was applied for the quantification of Pb. The repeatability of the analytical procedure for the determination of Cd, Pb and As in sediments was ±5 % for Cd, ±4 % for Pb and ±2 % for As. The LOD values of the analytical procedure were found to be 0.05 mg/kg for Cd and 0.25 mg/kg for Pb and As, while the LOQ values were 0.16 mg/kg for Cd and 0.83 mg/kg for Pb and As. Finally, Cd, Pb and As were successfully determined in sediments of the Sava River in Slovenia