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Biliary tract cancers (BTCs) are usually diagnosed at an advanced stage, when the disease is incurable. Currently used tumor biomarkers have limited diagnostic value for BTCs, so there is an urgent need for sensitive and specific biomarkers for their earlier diagnosis. Deregulation of the homeostasis of trace elements is involved in the carcinogenesis of different cancers, including BTCs. The objective of the study is to determine/compare the total concentrations of copper (Cu), zinc (Zn) and iron (Fe) and the proportions of free Cu and Cu bound to ceruloplasmin (Cp) and the isotopic ratio of 65Cu/63Cu in serum samples from healthy volunteers and cancer patients using inductively coupled plasma-mass spectrometry-based methods (ICP-MS).

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as decabromodiphenyl ethane (DBDPE) and halogenated norbornenes, as well as organophosphate flame retardants (OPFRs) were analysed in 52 sediments and 27 fish samples from three European river basins, namely the Evrotas (Greece), the Adige (Italy) and the Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia). This is the first time that FR levels have been reported in these three European river basins. The highest contamination was found in the Adige and Sava rivers, whereas lower values were obtained for the Evrotas. The levels in sediment samples ranged between 0.25 and 34.0ng/g dw, and between 0.31 and 549ng/g dw, for HFRs and OPFRs respectively. As regards levels in fish, concentrations ranged between 9.32 and 461ng/g lw and between 14.4 and 650ng/g lw, for HFRs and OPFRs, respectively. Thus, whereas OPFR values were higher in sediments, similar concentrations (in the Evrotas) and even lower concentrations than HFRs (Sava) were found for OPFRs in the fish samples, indicating the lower bioaccumulation potential of OPFRs. Biota to sediment accumulation factors (BSAFs) were calculated and higher values were obtained for HFRs compared to those assessed for OPFRs., (Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.)

Water scarcity is a serious environmental problem in many European regions, and will likely increase in the near future as a consequence of increased abstraction and climate change. Water scarcity exacerbates the effects of multiple stressors, and thus results in decreased water quality. It impacts river ecosystems, threatens the services they provide, and it will force managers and policy-makers to change their current practices. The EU-FP7 project GLOBAQUA aims at identifying the prevalence, interaction and linkages between stressors, and to assess their effects on the chemical and ecological status of freshwater ecosystems in order to improve water management practice and policies. GLOBAQUA assembles a multidisciplinary team of 21 European plus 2 non-European scientific institutions, as well as water authorities and river basin managers. The project includes experts in hydrology, chemistry, biology, geomorphology, modelling, socio-economics, governance science, knowledge brokerage, and policy advocacy. GLOBAQUA studies six river basins (Ebro, Adige, Sava, Evrotas, Anglian and Souss Massa) affected by water scarcity, and aims to answer the following questions: how does water scarcity interact with other existing stressors in the study river basins? How will these interactions change according to the different scenarios of future global change? Which will be the foreseeable consequences for river ecosystems? How will these in turn affect the services the ecosystems provide? How should management and policies be adapted to minimise the ecological, economic and societal consequences? These questions will be approached by combining data-mining, field- and laboratory-based research, and modelling. Here, we outline the general structure of the project and the activities to be conducted within the fourteen work-packages of GLOBAQUA., (Copyright © 2014. Published by Elsevier B.V.)

The objective of this work was to develop a synthesis procedure for the deposition of β-TCP coatings with tailored physico-chemical properties on zirconia bioceramics. The synthesis procedure involved two steps: (i) a rapid wet-chemical deposition of a biomimetic CaP coating and (ii) a subsequent post-deposition processing of the biomimetic CaP coating, which included a heat treatment between 800 and 1200 °C, followed by a short sonication in a water bath. By regulating the heating temperature the topography of the β-TCP coatings could be controlled. The average surface roughness (Ra) ranged from 42 nm for the coating that was heated at 900 °C (TCP-900) to 630 nm for the TCP-1200 coating. Moreover, the heating temperature also affected the dissolution rate of the coatings in a physiological solution, their protein-adsorption capacity and their bioactivity in a simulated body fluid.

Copper dyshomeostasis has been suggested as an aetiological risk factor for some neurodegenerative diseases, such as Alzheimer's disease. However, the precise mechanism at the base of this involvement is still obscure. In this work, we show the effects of a copper-deficient diet in aged CD1 mice and the influence of such a diet on: a) the concentration of various metal ions (aluminium, copper, iron, calcium, zinc) in the main organs and in different brain areas; b) the alteration of metallothioneins I-II and tyrosine hydroxylase immunopositivity in the brain; c) behavioural tests (open field, pole, predatory aggression, and habituation/dishabituation smell tests). Our data suggested that the copper-deficiency was able to produce a sort of "domino effect" which altered the concentration of the other tested metal ions in the main organs as well as in the brain, without, however, significantly affecting the animal behaviour.

The Sava River is the biggest tributary to the Danube River. As a part of the 6th FW EU project, Sava River Basin: Sustainable Use, Management and Protection of Resources (SARIB), ecological status of sediments was investigated. In order to assess the geographical distribution in sediment contamination of the Sava River, inorganic and persistent organic pollutants were analyzed in sediments at 20 selected sampling sites along the Sava River from its spring to its outfall into the Danube River. For comparability of data to other river basins the sediment fraction below 63 microm was studied. Due to complexity of the work performed, the results are published separately ("Part I: Selected elements" and "Part II: Persistent organic pollutants"). In the present study, the extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions and anthropogenic inputs of elements to sediments. To assess the mobile metal fraction extraction in 0.11 mol L(-1), acetic acid was performed (first step of the Community Bureau of Reference extraction procedure), while anthropogenic inputs of elements were estimated on the basis of normalization to aluminum (Al) concentration. According to the Water Framework Directive, the following elements were investigated in sediments: cadmium (Cd), lead (Pb), nickel (Ni), and mercury (Hg). Furthermore, copper (Cu), zinc (Zn), chromium (Cr), arsenic (As), and phosphorous (P) were determined. The analyses of sediments demonstrated slightly elevated values for Hg, Cr, and Ni in industrially exposed sites (concentrations up to 0.6, 380, and 210 mg kg(-1), respectively). However, the latter two elements exist in sparingly soluble forms and therefore do not represent an environmental burden. P concentrations were found in elevated concentrations at agricultural areas and big cities (up to 1,000 mg kg(-1)).

Sediment pollution of the biggest Danube tributary, the Sava River, was investigated within the sixth framework European Union project "Sava River Basin: Sustainable Use, Management and Protection of Resources" (SARIB). The extent of pollution was estimated by determining the amount of inorganic and persistent organic pollutants in sediment samples at 20 selected sampling sites along the Sava River. For the purpose of clarity, the findings are presented and published separately (part I: selected elements and part II: persistent organic pollutants). This study presents an investigation into the presence of organic pollutants in the Sava River sediment. According to the Water Framework Directive, the following persistent organic pollutants were investigated: polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), selected chlorinated pesticides and organotin compounds. The results reveal that PAHs were present in moderate concentrations (sum of 16 PAHs: up to 4,000 ng g(-1)) and their concentrations increased downstream. Concentrations of PCB were low (sum of seven indicator PCBs: below 4 ng g(-1)) and among the pesticides analyzed only p,p-dichlorodiphenyltrichloroethane was found in moderate concentrations at two sampling sites in Croatia (up to 3 ng g(-1)) and hexachlorobenzene was found in a high concentration in the city of Belgrade (91 ng g(-1)), although the use of these persistent pesticides has been banned for decades. Repeated sampling at the same location revealed point pollution near Belgrade. Among the organic pollutants surveyed, organotin compounds were not detected. Overall results reveal the presence of persistent organic pollutants in 20 of the Sava River sediments tested that is, in general, comparable or lower than the levels in the Danube River and other moderately polluted European rivers.

The toxicity and bioaccumulation of organotin compounds (OTCs) led to the development of sensitive and selective analytical methods for their determination. In the past much attention was assigned to the study of OTCs in biological samples, water and sediments, coming mostly from marine environment. Little information about OTCs pollution of terrestrial ecosystems is available. In order to optimise the extraction method for simultaneous determination of butyl-, phenyl- and octyltin compounds in sewage sludge five different extractants (tetramethylammonium hydroxide, HCl in methanol, glacial acetic acid, mixture of acetic acid and methanol (3:1), and mixture of acetic acid, methanol and water (1:1:1)), the presence or not of a complexing agent (tropolone), and the use of different modes of extraction (mechanical stirring, microwave and ultrasonic assisted extraction) were tested. Extracted OTCs were derivatised with sodium tetraethylborate and determined by gas chromatography coupled with mass spectrometer. Quantitative extraction of butyl-, phenyl- and octyltin compounds was obtained by the use of glacial acetic acid as extractant and mechanical stirring for 16h or sonication for 30 min. The limits of detection and quantification for OTCs investigated in sewage sludge were in the ng S ng(-1) range., (Copyright (c) 2009 Elsevier B.V. All rights reserved.)

Aluminium (Al) is associated with many clinical disorders in renal patients. Al accumulation in brain has also been related to the neurodegenerative processes in Alzheimer's disease. In order to better understand Al transport in the human body, it is necessary to identify and quantify chemical species in which Al is present in body fluids and tissues. Among a variety of biological samples, Al speciation was the most frequently investigated in human serum. Improvements were made in the development of analytical techniques for the determination of the amount and composition of high molecular mass Al (HMM-Al) and low molecular mass Al (LMM-Al) species in human serum. However, due to the complex chemistry of Al in serum, its low total concentration and the high risk of contamination, speciation of Al in biological samples is still a difficult task for analytical chemists. In this work, problems related to speciation of Al in human serum are critically discussed. An overview of the progress that was made by the use of different analytical procedures, in order to propose analytical protocols for reliable speciation of Al in serum at low ng mL(-1) concentration range, is presented.

Liquid chromatography combined with element specific detection is commonly applied in speciation analysis. In these analyses, to obtain reliable data chemical species should not be transformed. To preserve chemical species during the separation step, fast chromatographic procedures and mild separation conditions are required. Monolithic supports that enable rapid chromatographic separations have rarely been used in speciation analysis. Methacrylate-based anion- and cation-exchange monolithic supports offer separation of charged chemical species of elements and can be used as a complementary tool to particle-packed liquid chromatographic columns. The present paper presents an overview of successful applications of methacrylate-based monolithic supports in speciation of zinc (Zn), chromium (Cr), and aluminium (Al) in environmental, occupational health, and biological samples. Measures of analytical performance of convective interaction media (CIM) monolithic chromatographic supports, namely selectivity, sensitivity, and time of analysis, are compared to those of particle-packed columns. The potential of CIM monolithic chromatography in speciation analysis is critically discussed. Direct comparison of the experimental data in speciation of elements by ion-exchange monolithic and fast protein liquid chromatography is reported for the first time. Finally, some recommendations are given for further investigations of the potential of monolithic chromatography and its implementations in different fields of element speciation analysis.

Electric arc filter dust (EAF dust) is a waste by-product which occurs in the production of steel. Instead of being disposed of, it can be used in cement composites for civil engineering, and for balances in washing machines. To estimate the environmental impact of the use of EAF dust in cement composites leachability tests based on diffusion were performed using water and salt water as leaching agents. Compact and ground cement composites, and cement composites with addition of 1.5% of EAF dust by mass were studied. The concentrations of total Cr and Cr(VI) were determined in leachates over a time period of 175 days. At the end of the experiment the concentrations of some other metals were also determined in leachates. The results indicated that Cr in leachates was present almost solely in its hexavalent form. No leaching of Cr(VI) was observed in aqueous leachates from compact cement composites and compact cement composites to which different quantities of EAF dust have been added. In ground cement composites and in ground cement composites with addition of EAF dust, Cr(VI) was leached with water in very low concentrations up to 5 microg L(-1). Cr(VI) concentrations were higher in salt water leachates. In compact and ground cement composites with addition of EAF dust Cr(VI) concentrations were 40 and 100 microg L(-1), respectively. It was experimentally found that addition of EAF dust had almost no influence on leaching of Cr(VI) from cement composites. Leaching of Cr(VI) originated primarily from cement. Leaching of other metals from composites investigated did not represent an environmental burden. From the physico-mechanical and environmental aspects EAF dust can be used as a component in cement mixtures.

A new analytical procedure using separation support based on Convective Interaction Media (CIM) was developed for speciation of Al in human serum at normal concentration levels. The separation of proteins was performed on a weak anion exchange CIM diethylamine monolithic column. Isocratic elution with buffer A (0.05 M tris(hydroxymethyl)aminomethane-hydrochloric acid + 0.03 M sodium hydrogen carbonate) was applied for 5 min, followed by linear gradient elution from 100% buffer A to 100% buffer B (buffer A + 1 M ammonium chloride) for the next 40 min. Separation of proteins was followed by UV detection at 278 nm. Separated Al species were detected online by inductively coupled plasma mass spectrometry. It was experimentally proven that 91 +/- 7% of Al in human serum was eluted under the transferrin peak. Transferrin was identified on the basis of the retention volume and by ACQUITY ultraperformance liquid chromatography-electrospray ionization mass spectrometry. The problem of extraneous contamination with Al was successfully overcome by using efficient cleaning procedures of eluents and chromatographic supports. The efficient cleaning was of paramount importance to perform Al speciation at extremely low concentration levels. The repeatability of measurement tested for six consecutive separations of unspiked serum was +/-8.6%. The limits of detection and quantification (based on 3 and 10 s of the blank) were 0.15 and 0.49 ng mL(-1) Al bound to transferrin, respectively. This is the first report on quantitative and reliable speciation of Al in human serum at normal concentration levels.

The potential use of filter dust in asphalt composites for road construction was investigated. Filter dust contains high concentrations of metals, of which Cr(VI) and Pb are leached with water. Compact and ground asphalt composites with addition of 2% of filter dust by mass were studied. In order to evaluate their environmental impact, leachability tests were performed using water and salt water as leaching agents. The concentrations of Cr(VI) and Pb were determined in leachates over a time period of 182 days. The results indicated that Pb was not leached with leaching agents from asphalt composites. Cr(VI) was also not leached with leaching agents from compact asphalt composites. However, in ground asphalt composites, Cr(VI) was leached with water in concentrations up to 220 microg L(-1) and in salt water up to 150 microg L(-1). From the physico-mechanical and environmental aspects, filter dust can be used as a component in asphalt mixtures.

An investigation of the operating conditions of a pulsed flame photometric detection (PFPD) system for the determination of organotin compounds (OTCs) in sewage sludge is reported. During the analyses, some spectral interferences were observed. For their elimination detector parameters such as gate delay and gate width were investigated. In addition, the applicability of three different internal standards was evaluated. Under optimised analytical conditions (gate delay 3 ms, gate width 2 ms, tripropyltin as internal standard) limits of detection (LOD) were determined. The LOD for butyltins ranged between 8 and 16 ng Sn g(-1), for phenyltins around 8 ng Sn g(-1) and for octyltins between 5 and 10 ng Sn g(-1). Since there is no certified reference material (CRM) available for sewage sludge, the accuracy of the analytical procedure was checked by the analysis of CRM PACS-2 (marine sediment) and a spiked sludge sample. Good agreement between determined and certified values was obtained. Sewage sludge from a local wastewater treatment plant was analysed and the results compared with data from the literature.

The Sava River, the largest and most commercially valuable water body in the riparian countries, receives inputs of organic and inorganic compounds from a variety of domestic and industrial activities that may affect the health of human beings and wildlife. In this work, the chronic toxicity of sediment, sediment porewater and surface water from the Sava River and connecting tributaries to the freshwater algae Pseudokirchneriella subcapitata was assessed to characterise the potential impact on aquatic organisms. Samples of different environmental matrices were either tested directly (porewater) or subjected to pre-concentration (sediments and surface water) prior to testing in a 72 h growth inhibition assay using P. subcapitata. The results show that a combination of pre-concentration and bioassay testing was able to characterise the toxic potential and to identify several compartment-specific "hot spots" along the Sava River. Based on the resulting data, a crude risk assessment identified that some of the locations may represent a risk to algae. Additional testing using multiple species and exposure phases is required to conduct a thorough risk assessment, however.

The etiopathogenesis of Alzheimer's disease is far from being clearly understood. However, the involvement of metal ions as a potential key factor towards conformational modifications and aggregation of amyloid is widely recognized. The aim of the present study is to shed some light on the relationship between metal ions, amyloid conformation/aggregation, and their potential relationship with the conformational aspects of AD. We compare the effects of beta-amyloid(1-42) and its various metal complexes (beta-amyloid-Al, beta-amyloid-Zn, beta-amyloid-Cu, beta-amyloid-Fe) in human neuroblastoma cells in terms of cell viability, membrane structure properties, and cell morphology. No significant toxic effects were observed in neuroblastoma cells after 24h treatment both with beta-amyloid and beta-amyloid-metals (beta-amyloid-Zn, beta-amyloid-Cu, beta-amyloid-Fe); on the other hand, there was a marked reduction of cellular viability after treatment with beta-amyloid-Al complex. In addition, treatment with beta-amyloid-Al increased membrane fluidity much more than other beta-amyloid-metal complexes, whose contribution was negligible. Furthermore, the cellular morphology, as observed by electron microscopy, was deeply altered by beta-amyloid-Al. Importantly, beta-amyloid-Al toxicity is closely and significantly associated with a great difference in the structure/aggregation of this complex with respect to that of beta-amyloid alone and other beta-amyloid-metal complexes. In addition, beta-amyloid, as a consequence of Al binding, becomes strongly hydrophobic in character. These findings show a significant involvement of Al, compared to the other metal ions used in our experiments, in promoting a specific amyloid(1-42) aggregation, which is able to produce marked toxic effects on neuroblastoma cells, as clearly demonstrated for the first time in this study.

A new analytical procedure using anion-exchange separation support based on convective-interaction media (CIM) was developed for the speciation of Al in human serum. The separation of proteins was performed on a weak anion-exchange CIM diethylamine (DEAE) fast-monolithic disk. To prevent co-elution of low molecular mass (LMM) Al species with high molecular mass (HMM) Al compounds on CIM disk serum proteins were first separated from LMM-Al species by the use of size exclusion chromatography (SEC). For this purpose 1 mL of serum was injected onto SEC (Superdex 75 HR 10/30) column. Isocratic elution using 0.05 M TRIS-HCl+0.03 M NaHCO(3) was applied and separation of proteins was followed by UV detection at 278 nm. It was experimentally proven that proteins were eluted in 5.5 mL peak that was collected into a polyethylene cup. A 0.1 mL of the sample aliquot was then injected onto the CIM DEAE disk. The separation of serum proteins was obtained in 10 min by applying linear gradient elution from 100% buffer A (0.05 M TRIS-HCl+0.03 M NaHCO(3)) to 100% buffer B (A+1M NH(4)Cl) and followed by UV detection at 278 nm. Separated Al species were detected on-line by inductively coupled plasma mass spectrometry (ICP-MS). Well-resolved protein peaks were obtained. It was experimentally proven that 90+/-3% of Al in spiked serum of renal patient was eluted under the transferrin peak. The proposed speciation procedure removes LMM-Al species and enables reliable determination of the concentration and composition of Al bound to proteins by CIM DEAE-ICP-MS when the concentration of Al in serum is higher than 5 ng mL(-1). In comparison to chromatographic columns CIM disks enable faster separation and simpler manipulation during cleaning procedure and coupling to ICP-MS.

The extent of pollution with organotin compounds and Cd, Pb, Ni, Cu, Zn, Cr, Mn, V, Co and Al was investigated in sediments and mussels (Mytilus galloprovincialis) from the Slovenian costal area of the Northern Adriatic Sea. Sampling was performed in Marina Portoroz, Dockyard Izola, non exposed area of the Bay of Mesecev zaliv and in Mariculture Secovlje. Mussels were taken in the summer and winter time, while sediments were collected during the winter sampling. Organotin compounds were determined by gas chromatography-mass spectrometry and metals by flame or electrothermal atomic absorption spectrometry. The accuracies of the analytical procedures were checked by the analysis of standard reference materials CRM 477 mussel tissue and PACS 2 marine sediment (organotin compounds) and SRM 2976 mussel tissue and CRM 320 river sediment (metals). Good agreements between certified and determined values were obtained. Normalization procedure to Al was applied to estimate the anthropogenic inputs of metals in sediments. The analyses of sediments demonstrated moderate pollution with organotin compounds in Marina Portoroz and in Dockyard Izola. Concentrations of tributyltin species were higher than those of dibutyltin and monobutyltin. In mussels substantial contamination with tributyltin was observed in Marina Porotroz and Dockyard Izola. The extent of pollution was higher in the winter time. The analysis of metals in sediments exhibited elevated concentrations in Marina Portoroz and Dockyard Izola. Data from the normalization procedure indicated the anthropogenic inputs of Cu, Zn and Cr in Marina Portoroz and Mn in Bay of Mesecev zaliv and Dockyard Izola. Mussels, as accumulators of pollutants, in general contained higher metal concentrations during winter time in Dockyard Izola.

Organotin compounds (OTCs) have been identified in a variety of environmental media (air, surface water, groundwater, soil and sediments). In the past, much attention was assigned to the study of the OTCs content in biological samples, water and sediments. Little information about OTCs in soil is available. In this work, a procedure for butyl and phenyltin determination in soils by headspace-solid-phase microextraction (HS-SPME) gas chromatography-pulsed flame photometric detection (GC-PFPD) was investigated. For SPME analysis, a polydimethylsiloxane (PDMS) coating was applied. Peat soil rich in organic matter and with a high cation-exchange capacity (CEC), and clay soil low in organic matter and with a low CEC were analysed. The influence of these different soil matrices on HS-SPME analysis was evaluated by spiking of samples. In general, the recoveries for the two spiked soils exceeded 80%. The repeatability of the method was better than 10%. The limits of detection (LODs) and limits of quantification (LOQs) were in the ng S ng(-1) range. The technique may be reliably applied for the determination of butyltins and monophenyltin in soils, while it shows some limitations for the analysis of di- and triphenyltin (TPhT).