Search

The performance of a mixture of CH3F/He (1/9) as a reaction gas for the determination of As in biological fluids using a quadrupole ICP-MS instrument has been explored. A simple (dilute-and-shoot) interference-free method has been developed to quantify As concentrations at trace and ultra-trace levels in matrices with a high Cl content. As+ reacts with CH3F (through CH3F addition, followed by HF elimination) with high efficiency forming AsCH2 + as the primary reaction product, which can be monitored at a mass-to-charge ratio of 89, free from the Cl-based interferents (e.g., 40Ar35Cl+ and 40Ca35Cl+) that hamper the monitoring of 75As+. Matrix effects are overcome by the use of Te as an internal standard and the addition of 3% v/v ethanol to all samples and calibration standard solutions. The method presented was validated by analysing a set of reference materials (blood, serum and urine) and by assessing As recovery from a set of real blood samples. With this method, the limit of detection was calculated to be 0.8 ng L-1 As, favourably comparable to the vast majority of values reported in the literature, even with those obtained using more sophisticated sector-field instrumentation.

The increase in the use of SiO2 nanoparticles (NPs) is raising concern about their environmental and health effects, thus necessitating the development of novel methods for their straightforward detection and characterization. Single particle ICP-mass spectrometry (SP-ICP-MS) is able to provide information on the size of NPs, their particle number density and mass concentration. However, the determination of Si via ICP-MS is strongly hampered by the occurrence of spectral overlap from polyatomic species (e.g., CO+ and N2+). The use of tandem ICP-MS (ICP-MS/MS) enables interference-free conditions to be obtained, even in the most demanding applications. Upon testing several gases, the use of CH3F (monitoring of SiF+, mass-shift approach) and of H2 (monitoring of Si+, on-mass approach) were demonstrated to be the most suitable to overcome the spectral interference affecting ultra-trace Si determination (LoD < 15 ng L-1). By using these approaches, SiO2 NPs (ranging between 80 and 400 nm) can be detected and characterized. For SiO2 NPs > 100 nm, it was possible to provide accurate results in a straightforward way, as the signals they give rise to are well resolved from those of the background. In the case of 80 and 100 nm NPs, the use of a simple deconvolution approach following a Gaussian model was needed to characterize SiO2 NPs apparently showing incomplete distributions as a result of the presence of the background signal. Overall, the methods developed using SP-ICP-MS/MS are sensitive and selective enough for the interference-free determination of Si at ultra-trace levels, also in the form of SiO2 NPs.

Item does not contain fulltext Alkaline phosphatase (ALP), an enzyme involved in mineralization of bone, is incorporated into three hydrogel biomaterials to induce their mineralization with calcium phosphate (CaP). These are collagen type I, a mussel-protein-inspired adhesive consisting of PEG substituted with catechol groups, cPEG, and the PEG/fumaric acid copolymer OPF. After incubation in Ca-GP solution, FTIR, EDS, SEM, XRD, SAED, ICP-OES, and von Kossa staining confirm CaP formation. The amount of mineral formed decreases in the order cPEG > collagen > OPF. The mineral:polymer ratio decreases in the order collagen > cPEG > OPF. Mineralization increases Young's modulus, most profoundly for cPEG. Such enzymatically mineralized hydrogel/CaP composites may find application as bone regeneration materials. 01 augustus 2012

The Denizli Basin in the West Anatolian Extensional Province in western Turkey is well-known for its numerous travertine occurrences. A combined sedimentological, diagenetic and geochemical investigation is executed on the Ece and Faber travertines of the Ballk area, the largest travertine site in the Denizli Basin. The first aim of this study is the reconstruction of a three-dimensional geo-model in combination with a detailed sedimentological description from fabric to lithotype, lithofacies and geobody scale, with a focus on integrating pore-typing. The second aim involves the delineation of the CO2-origin of ancient travertine precipitating waters. Peloidal, phyto and dendritic lithotypes dominate the studied travertines and honeycomb and bacteriform shapes and encrusted bacterial or fungal filaments related to their fabrics suggest a microbial influence. The environment of travertine precipitation evolved from dominantly sub-aqueous, as represented by the sub-horizontal and biostromal reed travertine facies, to dominantly sub-aerial in a thin water film, resulting in the cascade, waterfall and biohermal reed travertine facies. A general progradation of the travertine mound is indicated by the occurrence of stacked waterfall travertines. This results in sigmoidal clinoforms inside a general mound boundary configuration. Strontium and oxygen-carbon isotope signatures of the travertines point to a mixing mechanism of palaeofluids with deeply originated, heavy carbon CO2 with lighter carbon CO2 of shallow origin. These deposits can thus be considered as endogenic travertines. Carbonates of the Lycian Nappes acted as main parent carbon source rocks. The relative contribution of the lighter carbon isotopes is most likely to have originated from organic matter or soil CO2. This study provides a unique three-dimensional insight into the Ballk travertine architecture that potentially can be used as an analogue for subsurface travertine reservoirs worldwide and illustrates the importance of the combined use of C-13 and Sr-87/Sr-86 signatures in the delineation of the CO2-origin of travertine precipitating waters.

The Denizli Basin in the West Anatolian Extensional Province in western Turkey is well-known for its numerous travertine occurrences. A combined sedimentological, diagenetic and geochemical investigation is executed on the Ece and Faber travertines of the Ballık area, the largest travertine site in the Denizli Basin. The first aim of this study is the reconstruction of a three-dimensional geo-model in combination with a detailed sedimentological description from fabric to lithotype, lithofacies and geobody scale, with a focus on integrating pore-typing. The second aim involves the delineation of the CO2-origin of ancient travertine precipitating waters. Peloidal, phyto and dendritic lithotypes dominate the studied travertines and honeycomb and bacteriform shapes and encrusted bacterial or fungal filaments related to their fabrics suggest a microbial influence. The environment of travertine precipitation evolved from dominantly sub-aqueous, as represented by the sub-horizontal and biostromal reed travertine facies, to dominantly sub-aerial in a thin water film, resulting in the cascade, waterfall and biohermal reed travertine facies. A general progradation of the travertine mound is indicated by the occurrence of stacked waterfall travertines. This results in sigmoidal clinoforms inside a general mound boundary configuration. Strontium and oxygen-carbon isotope signatures of the travertines point to a mixing mechanism of palaeofluids with deeply originated, heavy carbon CO2 with lighter carbon CO2 of shallow origin. These deposits can thus be considered as endogenic travertines. Carbonates of the Lycian Nappes acted as main parent carbon source rocks. The relative contribution of the lighter carbon isotopes is most likely to have originated from organic matter or soil CO2. This study provides a unique three-dimensional insight into the Ballık travertine architecture that potentially can be used as an analogue for subsurface travertine reservoirs worldwide and illustrates the importance of the combined use of δ13C and 87Sr/86Sr signatures in the delineation of the CO2-origin of travertine precipitating waters. © 2015 The Authors. Sedimentology and 2015 International Association of Sedimentologists.

The Denizli Basin is a fault-bounded Neogene-Quaternary depression located in the Western Anatolian Extensional Province, Western Turkey. The basin is a unique geological site with abundant active and fossil (Quaternary) travertine and tufa deposits. Fluid inclusion microthermometry and isotopic analysis were applied to study the genesis of the Ballk fossil travertine deposits, located in the south-eastern part of the basin. Microthermometry on fluid inclusions indicates that the main travertine precipitating and cementing fluids are characterized by low salinity (

Item does not contain fulltext Interest is growing in the use of hydrogels as bone tissue-engineering (TE) scaffolds due to advantages such as injectability and ease of incorporation of active substances such as enzymes. Hydrogels consisting of gellan gum (GG), an inexpensive calcium-crosslinkable polysaccharide, have been applied in cartilage TE. To improve GG suitability as a material for bone TE, alkaline phosphatase (ALP), an enzyme involved in mineralization of bone by cleaving phosphate from organic phosphate, was incorporated into GG hydrogels to induce mineralization with calcium phosphate (CaP). Incorporated ALP induced formation of apatite-like material on the submicron scale within GG gels, as shown by FTIR, SEM, EDS, XRD, ICP-OES, TGA and von Kossa staining. Increasing ALP concentration increased amounts of CaP as well as stiffness. Mineralized GG was able to withstand sterilization by autoclaving, although stiffness decreased. In addition, mineralizability and stiffness of GG was enhanced by the incorporation of polydopamine (PDA). Furthermore, mineralization of GG led to enhanced attachment and vitality of cells in vitro while cytocompatibility of the mineralized gels was comparable to one of the most commonly used bone substitute materials. The results proved that ALP-mediated enzymatic mineralization of GG could be enhanced by functionalization with PDA.

In this study, we have evaluated the applicability of Nd isotopic analysis for the provenancing of Roman glass and we present a database of Nd isotopic compositions of possible sand raw materials from the western Mediterranean, as a means of comparison for the growing number of isotopic studies on ancient glass. The 143Nd/144Nd isotope ratio of sands is a good indicator for their geological (and sometimes geographical) provenance. The use of the isotopic signature of Nd as a proxy for the source of silica in glass is, however, not always straightforward because of the possible overlap of signatures from different suppliers. ispartof: Archaeometry vol:55 issue:3 pages:449-464 status: published

The accumulation of trace elements (Mg, Mn, Sr, Ba) in Unio pictorum L. mussel shells from Lake Balaton has been assessed using a Laser Ablation (LA) system coupled to either a quadrupole-based or a sector-field inductively coupled plasma–mass spectrometer (ICP – MS), as well as by a combination of micro-drill sampling and solution ICP–MS. The LA–ICP–MS measurements were carried out in the holes made by the micro-drilling system. The longitudinal concentration profiles obtained with the different methods show similar patterns. However, the absolute concentrations determined at individual spots (holes) can be quite different. Especially Ba shows erratic peaks at a very small spatial scale. A paired, two-sample t-test between LA–ICP–MS longitudinal profiles and between LA–ICP–MS and micro-drill/solution ICP–MS profiles indicates that, in most cases, there is no significant difference between the concentration profiles of Ba, Mg, Mn and Sr.Average shell concentrations of Mg, Mn, Sr and Ba, as obtained by LA–ICP–MS and micro-drill/solution ICP–MS, compare well with bulk shell concentrations as obtained by acid digestion/ICP–MS of larger shell pieces. Next to the four elements mentioned above, also the concentrations of Cd, Co, Cr, Cu, Ni, Pb and Zn could be determined by bulk shell analysis. The element concentrations in 11 shells, all sampled at the same site, show a relative standard deviation (RSD) between 2% (Ni) and 46% (Zn).LA–ICP–MS and micro-drill solution ICP–MS are not sensitive enough for the determination of ultra-trace elements in Lake Balaton's mussel shells. We estimated the amount of shell material necessary to determine Ni, Pb, Cr and Cu by micro-drilling ICP–MS (for a concentration that equals 3 times their limit of detection) at, respectively, 0.04, 0.82, 2.7 and 0.4 mg, while the amount sampled by micro-drilling is about 0.06 mg.

The provenancing of Roman natron glass is one of the most challenging problems in the field of archaeometry. Although the use of Sr and Nd isotope ratios and trace element signatures as an indication of provenance has proven promising, there are still many unknowns. In this study, the influence of the different raw materials on the final Sr isotopic composition of Roman natron glass is examined. It is shown that the 87Sr/86Sr ratio in natron glass is significantly influenced by the silicate fraction of the sand used and does not always provide a clear indication of the lime source used.

In this study, we have evaluated the applicability of Nd isotopic analysis for the provenancing of Roman glass and we present a database of Nd isotopic compositions of possible sand raw materials from the western Mediterranean, as a means of comparison for the growing number of isotopic studies on ancient glass. The 143Nd/144Nd isotope ratio of sands is a good indicator for their geological (and sometimes geographical) provenance. The use of the isotopic signature of Nd as a proxy for the source of silica in glass is, however, not always straightforward because of the possible overlap of signatures from different suppliers.

Forty-seven window and vessel glasses from the ‘Great Temple’ at Petra (Jordan), dating to the first/second and fourth centuries CE, were analysed by EPMA for major and minor elements. A subset of 29 samples from Petra and 15 samples from Khirbet et-Tannur were additionally analysed for trace elements, using LA–ICP–MS. Six compositional groups were identified on the basis of the presence of decolouring agents. The majority of the glasses derive ultimately from the Levantine coast, but most of the groups show evidence for highly selective recycling. The observed differences between the two sites could be related to different chronological ranges, functions, relative wealth and trade connections. ispartof: Archaeometry vol:54 pages:997-1022 status: published

International audience

ispartof: The Ancient Near East, A Life! Festschrift Karel Van Lerberghe pages:131-142 ispartof: Orientalia Lovaniensia Analecta vol:220 pages:131-142 status: published

In order to study the effect of anthropogenic substances on freshwater and marine ecosystems and to develop methods to derive water-quality criteria, ecotoxicological testing is required. While toxicity assessments are traditionally based on dissolved metal concentrations, assuming that toxicity is caused by waterborne metal only, it was recently pointed out that also the dietary exposure route should be carefully considered and interpreted in regulatory assessments of zinc. In this context, the aim of this experimental study was to develop a method which allows the uptake of waterborne and dietary zinc by Daphnia magna and the interaction between both exposure routes to be studied. Therefore, the setup of a dual isotopic tracer study was required. During several days, daphnids were exposed to 67Zn and 68Zn via the dietary and the waterborne routes, respectively, and after several time intervals the daphnids were sampled and subjected to isotopic analysis by means of inductively coupled plasma mass spectrometry (ICP-MS). In order to obtain reliable and accurate results for zinc, special care was taken to prevent contamination and to deal with the spectral interferences traditionally hindering the determination of zinc. The figures of merit of both a quadrupole-based ICP-MS instrument equipped with a dynamic reaction cell, and a sector field ICP-MS unit were studied, and it was concluded that by using a sector field mass spectrometer operated at medium mass resolution all interferences could be overcome adequately. Although the set-up of the exposure experiments seems to be rather simple at first sight, it was shown in this work that several (dynamic) variables can have an influence on the results obtained and on the subsequent data interpretation. The importance of these confounding factors was examined, and on the basis of preliminary calculations it became clear that not only the isotopic composition of the daphnids has to be studied-adequate monitoring of the isotopic composition of the dissolved phase and the algae during the exposure of the daphnids is also required to accurately discriminate between uptake from water and from food.

International audience