Determination of copper and other trace elements in serum samples from patients with biliary tract cancers: prospective noninterventional nonrandomized clinical study protocol.

BACKGROUND: 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). PATIENTS AND METHODS: In this prospective, noninterventional, nonrandomized study 20 patients and 20 healthy volunteers will be enrolled to identify serum Cu, Zn and Fe levels, Cu isotopic fractionation as a predictive biomarker of response to systemic therapy of BTCs, which will be evaluated by computed tomography. Newly developed analytical methods based on ICP-MS will be applied to metal-based biomarker research in oncology. CONCLUSIONS: In the study the comparison of the total concentration of selected trace elements, the proportion of free Cu and Cu bound to Cp and the isotopic ratio of 65Cu/63Cu in serum samples from healthy volunteers and cancer patients will be conducted to provide the foundation for the development of a BTC cancer screening methodology and the data on their usability as a potential predictive biomarker for BTCs of response to systemic therapy.

Development of an analytical method for the determination of polybrominated diphenyl ethers in mussels and fish by gas chromatography-Inductively coupled plasma mass spectrometry.

Six congeners of polybrominated diphenyl ethers (PBDEs): BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154, were determined by a reliable and sensitive analytical method based on gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) in mussel and fish tissue samples. For their extraction, 30min of ultrasound-assisted extraction with a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) and an additional 2h of mechanical shaking with tris(hydroxymethyl)aminomethane (Tris)-citrate buffer and iso-octane were applied. An effective cleaning, with minor solvent consumption, was achieved by passing the extract through a column filled with Florisil. PBDEs in the organic phase were quantified by GC-ICP-MS. Accuracy checks were performed by analyzing reference materials NIST SRM 2974a (freeze-dried mussel tissue) and SRM 1946 (fresh fish tissue homogenate) samples with a standard addition calibration method and by comparative analysis with species-specific isotope-dilution GC-ICP-MS. Good agreement of results between the determined and certified values were obtained (recoveries lied between 94 and 105%). Limits of detection (LODs) expressed on wet weight (ww) basis were 0.003ngg-1 for BDE 28, 0.006ngg-1 for BDE 47, 0.008ngg-1 for BDE 99, 0.004ngg-1 for BDE100, 0.005ngg-1 for BDE 153 and 0.009ngg-1 for BDE 154. The analytical method was applied for the determination of PBDEs in marine mussels and fish samples from the northern Adriatic Sea and fish samples from the Sava River. Among the six PBDEs congeners determined, BDE 47, BDE 100 and BDE 99 were commonly detected in the samples analysed.

Nickel speciation in cocoa infusions using monolithic chromatography - Post-column ID-ICP-MS and Q-TOF-MS.

Nickel (Ni) is considered to be a potentially harmful element for humans. Its levels in foodstuffs are normally low (below 0.2mgkg-1), but sensitive individuals may develop allergy to Ni as a result of dietary consumption. Cocoa contains relatively high Ni concentrations (around 3mgkg-1). Ni bioavailability, its role in the flavour of food and its potential impact on human health depends primarily on its chemical species. However, there is a lack of information about Ni speciation in cocoa. In this work Ni species were separated on a weak convective interaction media diethylamine (CIM DEAE) monolithic chromatographic column and quantified by the post-column isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). The Ni binding ligands in the separated fractions were identified "off line" by quadrupole time-of-flight mass spectrometry (Q-TOF MS). Ni was found to be present in the cocoa infusions as Ni2+ and Ni-gluconate and Ni-citrate complexes.

The fate of iron nanoparticles in environmental waters treated with nanoscale zero-valent iron, FeONPs and Fe3O4NPs.

Among the different nanoparticles (NPs) that are used in the remediation of contaminated environmental waters, iron nanoparticles (FeNPs) are the most frequently applied. However, if these FeNPs remain in the waters after the treatment, they can cause a hazard to the environment. In this work the time dependent size distribution of iron particles was investigated in Milli-Q water, forest spring water and landfill leachate after a variety of FeNP treatments. The efficiency of the metal removal by the FeNPs was also examined. The concentrations of the metals in the aqueous samples were determined before and after the nano-remediation by inductively coupled plasma mass spectrometry (ICP-MS). The data revealed that the settling and removal of the FeNPs after the treatment of the waters was related to the sample characteristics and the ways of dispersing the NPs. When mixing was used for the dispersion, the nano zero-valent iron (nZVI), FeONPs and Fe3O4NPs settled quickly in the Milli-Q water, the forest spring water and the landfill leachate. Dispersion with tertramethylammonium hydroxide (TMAH) resulted in a slower settling of the iron aggregates. In the Milli-Q and forest spring waters treated with FeONPs and dispersed by TMAH, the nanosized iron remained in solution as long as 24 h after the treatment and could represent a potential threat in environmental waters with a low ionic strength. The removal of the metals strongly depended on the type of FeNPs, the chemical speciation of the elements and the sample matrix. If the FeNPs are contaminated by a particular metal, this contaminant could be, during the NPs treatment, released into the water that is being remediated.

Development of an analytical method for the determination of polybrominated diphenyl ethers in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry.

Polybrominated diphenyl ethers (PBDEs) are flame retardants. As a consequence of their widespread use, they have been released into the environment. PBDEs are lipophilic organic contaminants that enter wastewater treatment plants (WWTPs) from urban, agricultural and industrial discharges. Because of their low aqueous solubility and resistance to biodegradation, up to 90% of the PBDEs are accumulated in the sewage sludge during the wastewater treatment. To assess the possibilities for sludge re-use, a reliable determination of the concentrations of these PBDEs is of crucial importance. Six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances under the EU Water Framework Directive. In the present work a simple analytical method with minimal sample-preparation steps was developed for a sensitive and reliable determination of the six PBDEs in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). For this purpose an extraction procedure was optimised. Different extracting agents (methanol (MeOH), acetic acid (AcOH)/MeOH mixture (3:1) and 0.1 mol L(-1) hydrochloric acid (HCl) in MeOH) followed by the addition of a Tris-citrate buffer (co-extracting agent) and iso-octane were applied under different modes of extraction (mechanical shaking, microwave- and ultrasound-assisted extraction). Mechanical shaking or the microwave-assisted extraction of sewage sludge with 0.1 mol L(-1) HCl in MeOH and the subsequent addition of the Tris-citrate buffer and the iso-octane extracted the PBDEs from the complex sludge matrix most effectively. However, due to easier sample manipulation during the extraction step, mechanical shaking was used. The PBDEs in the organic phase were quantified with GC-ICP-MS by applying a standard addition calibration method. The spike recovery test (recoveries between 95 and 104%) and comparative analyses with the species-specific isotope-dilution (ID) GC-ICP-MS confirmed the accuracy of the developed analytical procedure. The procedure is sensitive (limits of detection (LODs) for PBDEs congeners between 0.2 and 0.3 ng g(-1)), repeatable and reproducible (RSDs 2.2-5.7%) and was applied for the determination of PBDEs in sewage sludge samples collected three times at the municipal WWTP over a period of 16 years.

Environmental impacts of asphalt mixes with electric arc furnace steel slag.

Electric arc furnace (EAF) steel slag can be used as an alternative high-quality material in road construction. Although asphalts with slag aggregates have been recognized as environmentally acceptable, there is a lack of data concerning the potential leaching of toxic Cr(VI) due to the highly alkaline media of EAF slag. Leaching of selected water extractable metals from slag indicated elevated concentrations of total chromium and Cr(VI). To estimate the environmental impacts of asphalt mixes with slag, leachability tests based on diffusion were performed using pure water and salt water as leaching agents. Compact and ground asphalt composites with natural aggregates, and asphalt composites in which the natural aggregates were completely replaced by slag were prepared. The concentrations of total chromium and Cr(VI) were determined in leachates over a time period of 6 mo. After 1 and 6 mo, the concentrations of some other metals were also determined in the leachates. The results indicated that chromium in leachates from asphalt composites with the addition of slag was present almost solely in its hexavalent form. However, the concentrations were very low (below 25 µg L) and did not represent an environmental burden. The leaching of other metals from asphalt composites with the addition of slag was negligible. Therefore, the investigated EAF slag can be considered as environmentally safe substitute for natural aggregates in asphalt mixes.

Influence of the soil matrices on the analytical performance of headspace solid-phase microextraction for organotin analysis by gas chromatography-pulsed flame photometric detection.

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).