Search

Background Anatomic factors associated with static posterior translation of the humeral head with or without glenohumeral osteoarthritis are unknown. We tested the hypothesis that there is an association between glenoid wear, glenoid version, and/or anteroposterior acromial tilt. Methods Ninety-nine patients with glenohumeral joint degeneration involving advanced glenoid cartilage wear and/or rotator cuff disease scheduled for anatomic or reverse total shoulder replacement underwent standardized conventional radiographic and computed tomographic shoulder imaging. Measurements included glenoid version, humeral torsion, posterior acromial slope, and critical shoulder angle. The glenoid shape was classified according to Walch et al, and the integrity of the rotator cuff was assessed. Results Patients with glenoid type B2 or C had a median of 4° more glenoid retroversion (P =.022), a 5° less steep acromion (posterior acromial slope, 61° vs 56°; P =.004), and a higher combined score (glenoid version minus slope; odds ratio, 0.93 [95% confidence interval, 0.89-0.97]; P <.001; cutoff, –27°) than those with type A or B1. When the rotator cuff was torn, osteoarthritic changes were milder than when the cuff was intact (eg, P <.001 for supraspinatus). Conclusion The study's hypothesis that the bony anatomy of the scapula and in particular the acromion is correlated with the type of glenoid wear was confirmed. Both a more horizontal acromial orientation in the sagittal plane and increased posterior glenoid version are found in osteoarthritis of the shoulder associated with eccentric, posterior glenoid wear. Tears of the rotator cuff are significantly associated with concentric osteoarthritis of the glenoid. [ABSTRACT FROM AUTHOR]

The application of synthetic pesticides to agricultural fields for the protection of crops leads to the formation of residues in soils. While the short-term behavior of pesticide residues in soils after an application is generally known from laboratory and field studies required for authorization (prospective risk assessments), there is still a lack of in-situ observations that address their long-term fate. Long-term soil monitoring programs, with comprehensive site-specific records of pesticide application data, constitute an invaluable, complementary, retrospective exposure assessment tool to address this gap. Considering the pesticide applications over the past 10–15 years, this study assessed the occurrence of pesticides in agricultural soils of Switzerland and put their presence or absence, as well as their concentrations, in the context of their previous application. The results showed that pesticides could also be detected at sites without a connection to previous applications and that small residual mass fractions of pesticides, even of some non-persistent compounds, were found in soils, years or decades after their last application. This finding points to an environmental issue that may not be adequately captured in prospective risk assessment and calls attention to the need for comprehensive long-term recording and monitoring as a complementary retrospective exposure assessment. [Display omitted] • Soils from 31 agricultural sites were analyzed for 34 pesticides and 7 metabolites. • The presence or absence of pesticides was related to their previous application. • Pesticides were also detected at sites not associated with previous applications. • Some pesticides persisted much longer than predicted from their half-lives. • Residual mass fractions of a few % were found years after the last application. [ABSTRACT FROM AUTHOR]

Abstract: An experimental procedure for precise and accurate measurements of isotope abundances by a miniature laser ablation mass spectrometer for space research is described. The measurements were conducted on different untreated NIST standards and galena samples by applying pulsed UV laser radiation (266nm, 3ns and 20Hz) for ablation, atomisation, and ionisation of the sample material. Mass spectra of released ions are measured by a reflectron-type time-of-flight mass analyser. A computer controlled performance optimiser was used to operate the system at maximum ion transmission and mass resolution. At optimal experimental conditions, the best relative accuracy and precision achieved for Pb isotope compositions are at the per mill level and were obtained in a range of applied laser irradiances and a defined number of accumulated spectra. A similar relative accuracy and precision was achieved in the study of Pb isotope compositions in terrestrial galena samples. The results for the galena samples are similar to those obtained with a thermal ionisation mass spectrometer (TIMS). The studies of the isotope composition of other elements yielded relative accuracy and precision at the per mill level too, with characteristic instrument parameters for each element. The relative accuracy and precision of the measurements is degrading with lower element/isotope concentration in a sample. For the elements with abundances below 100ppm these values drop to the percent level. Depending on the isotopic abundances of Pb in minerals, 207Pb/206Pb ages with accuracy in the range of tens of millions of years can be achieved. [Copyright &y& Elsevier]

• The combination of spot and imaging techniques revealed the painting's conservation history. • Discrimination of varnishes and overpaint was crucial to the conservation treatment. • UV fluorescence guided the selective sampling of overlayed varnishes and overpainting. • The exact number and composition of overlayered varnishes were determined. A multi-analytical investigation and ad hoc sampling method designed to support the conservation treatment of a 16th-century panel painting are described in this work. The painting, titled Madonna of the Tent and owned by the Musei Reali Torino (Turin, Italy), had been historically attributed to Raffaello Sanzio and subsequently identified as a copy after the Master – the original version of which is displayed at the Alte Pinakothek in Munich (Germany). The conservation treatment was recently carried out at Centro per la Conservazione ed il Restauro dei Beni Culturali "La Venaria Reale" (CCR), located in Venaria Reale (Turin, Italy). The work was particularly opaque and yellowed, suggesting the presence of different overlaying varnishes and, likely, overpainting. The scientific study of this work had two main aims: knowing the exact number and composition of the overlaying varnishes to select the best cleaning solution, and detecting the possible presence of overpainting, over the original stratigraphy. Coupling macro X-ray fluorescence scanning (MA-XRF), hypercolorimetric multispectral imaging (HMI), and UV–vis–NIR fiber optic reflectance spectroscopy (FORS) allowed for general mapping and characterization of color paints and pigments. Observing and analyzing some cross sections with an optical microscope under Vis and UV light and SEM/EDS was essential for understanding the stratigraphy. An ad hoc sampling method and further micro-invasive analyses were required for an accurate study of the chemical composition of the varnishes and their position in the stratigraphy. Especially the image of a cross section under UV light was a guide to selectively remove the scrapings for Fourier transform infrared spectroscopy (FTIR) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analyses; based on perceptible differences in UV-induced luminescence (UVL) of the layers, sampling of the varnishes was carried out, layer by layer, under a UV lamp. This work describes the complex process necessary to answer crucial questions in the conservation field. The adopted protocol exploited the full ability and complementarity of each imaging and spot technique used. The outcomes and methodological approach enabled us to trace the history of the past treatments and support the recent conservation treatment of the painting. [ABSTRACT FROM AUTHOR]

The incorporation of plating additives into Cu films was studied by means of complementary Laser Ablation/Ionization Mass Spectrometry (LIMS) and Secondary Ion Mass Spectrometry (SIMS) depth profiling techniques combined with Focused Ion Beam (FIB) analysis. Cu test samples were electrodeposited in the presence of a new prototypical two-component additive package for advanced Damascene applications consisting of a hybrid-type suppressor additive (Imep: polymerizate of epichlorohydrin and imidazole) and its essential co-additive (SPS: bis-(sodium-sulfopropyl)-disulfide). The tunable non-linear interplay between the Imep and the SPS during oscillatory Cu electrodeposition is used to fabricate samples bearing spatially confined layers with sequential high and marginal additive embedment. These test samples constitute an excellent platform to conduct true quantitative chemical depth profiling analysis of electrodeposited Cu films. In particular LIMS depth profiling measurements with an unmatched nano-meter depth-resolution demonstrate a preferential inclusion and accumulation of contaminants at grain boundaries inside the Cu deposit whereas the Cu grains remain largely contamination-free. A novel LIMS desorption approach is presented which allows for a molecular structure analysis of the polymeric additive ensembles preferentially embedded at grain boundaries of the Cu deposit. Our LIMS analysis confirms a recently discussed mechanism on the action of these hybrid additives which relies on their interaction with thiolate-stabilized Cu(I) intermediates. [ABSTRACT FROM AUTHOR]

Pesticides are widely applied in agriculture to combat disease, pests, and weeds, leading to long-lasting contamination of agricultural soils with pesticide residues. While classical risk assessment experiments have repeatedly addressed immediate pesticide effects, we employ an ecological approach to investigate how pesticide residues persisting in soils influence the soil microbiome under realistic agricultural conditions. We assessed a wide range of soil characteristics, including the occurrence of 48 widely-used pesticides in 60 fields under conventional, no-tillage and organic management. We then tested which factors best explain soil microbiome traits. Environmental factors, including climate, geography, and soil characteristics, were the soil microbiome's leading drivers. Remarkably, of all management factors, pesticide residues showed the strongest associations with soil microbiome traits, which were even more pronounced than the effects of cropping systems. Pesticide residues were almost exclusively positively associated with the relative abundance of 113 bacterial and 130 fungal taxa, many of them being assigned to taxa of known pesticide degraders. While fungal diversity and abundance were primarily positively associated with pesticide residues, bacterial diversity and abundance of the gene nifH - essential for biological nitrogen fixation - were negatively linked to the concentration of individual pesticide residues. Our results suggest that pesticide residues alter the soil microbiome, with potential long-term implications for the functioning of agricultural soils. • Contamination of agricultural soils with pesticide residues influences the microbiome. • Pesticide effects on the soil microbiome exceeded other management factors. • A wide range of microbial taxa were primarily positively associated with pesticides. • Pesticides were negatively linked to bacterial diversity and the nitrogen fixation gene nifH. [ABSTRACT FROM AUTHOR]

The abundances of C, O, S, Na, K, Li, Mn, P, Cr, Si, Fe, Mg, Ni, Co, V, Ca, Ti, Al and Sc were determined in-situ in a sample of the Allende meteorite using a laser ablation/ionization mass spectrometer to quantify the bulk chemical composition of the matrix and its spatial chemical variability. The high lateral resolution of the instrument makes it possible to measure the elemental composition of Allende matrix, without any sample treatment prior to analysis. The measurements of solely Allende matrix allow investigating the variability of the element abundances in the matrix material on different scales from 50 ​μm to 0.5 ​mm. The comprehensive data set provides constraints on models for the formation of matrix material of carbonaceous chondrites in the solar nebula. A key observation of this study is a high degree of chemical homogeneity of the matrix, indicating that it formed independently from or in parallel with the chondrules and that the process that led to the formation of the parent body was a fast collapse of the dust-gas cloud following chondrule formation. Fs-LIMS instrument, used in this study (left), and a detail of the Allende sample after a test measurement series (right).These pictures are not part of the manuscript, but can serve as graphical abstract. [Display omitted] • The composition of the Allende meteorite matrix derived from >1000 individual measurements. • The Allende bulk chemical composition derived from >1500 individual measurements. • The Allende matrix shows a high degree of homogeneity. [ABSTRACT FROM AUTHOR]

Laser ablation ionization mass spectrometry studies on polished surface structures of hard, high melting point multicomponent interconnect structures using our femtosecond-laser time-of-flight mass spectrometer have previously been proven capable of providing spatially resolved chemical depth profile data at the micro- and nanometer level. Transfer of experimental protocols tailored to suit such type of samples to low melting point materials with high surface roughness, however, is highly challenging, as thermal effects caused by interactions of the laser light with the targeted surface play a severe role in the latter case and may significantly deteriorate the analysis outcome. In this contribution we present a dedicated and detailed comparison of the distinct effects of near infrared and ultraviolet irradiation on the ablation process in femtosecond laser ablation ionization mass spectrometry studies on low melting point materials. As model substrate we use high surface roughness, as-deposited SnAg solder alloy, a material of major industrial relevance in microchip fabrication. We will demonstrate herein that polydimethylsiloxane replica casting is possible also from granularly structured, high surface roughness samples. Characterization of the laser ablation craters as well as of their polydimethylsiloxane replicas is carried out by mass spectrometric analysis, Scanning Electron Microscopy imaging, and furthermore, as a novel approach for this purpose, by white light interferometry. Integration of all obtained results significantly adds to the detailed understanding of laser ablation processes on low melting point, high surface roughness materials and allows identifying optimal depth profiling conditions for these demanding samples. [Display omitted] • Laser ablation studies on technologically highly relevant SnAg bump. • Measurement procedure for low melting point, high surface roughness, solder alloys. • Demonstration of improved fs-LIMS capabilities by moving from NIR to UV irradiation. • UV reduces thermal effects, increases ablation rate and decreases the crater size. • UV laser ablation provides better shot-to-shot stability of the ablation process. [ABSTRACT FROM AUTHOR]

We measured the elemental composition on a sample of Allende meteorite with a miniature laser ablation mass spectrometer. This laser mass spectrometer (LMS) has been designed and built at the University of Bern in the Department of Space Research and Planetary Sciences with the objective of using such an instrument on a space mission. Utilising the meteorite Allende as the test sample in this study, it is demonstrated that the instrument allows the in situ determination of the elemental composition and thus mineralogy and petrology of untreated rocky samples, particularly on planetary surfaces. In total, 138 measurements of elemental compositions have been carried out on an Allende sample. The mass spectrometric data are evaluated and correlated with an optical image. It is demonstrated that by illustrating the measured elements in the form of mineralogical maps, LMS can serve as an element imaging instrument with a very high spatial resolution of µm scale. The detailed analysis also includes a mineralogical evaluation and an investigation of the volatile element content of Allende. All findings are in good agreement with published data and underline the high sensitivity, accuracy and capability of LMS as a mass analyser for space exploration. [ABSTRACT FROM AUTHOR]

Abstract: We report on the photovoltaic properties of organic solar cells based on pentacene and C60 thin films with a focus on their spectral responses and the effect of thermal annealing. Spectra of external quantum efficiency (EQE) are measured and analyzed with a one-dimensional exciton diffusion model dependent upon the complex optical functions of pentacene films, which are measured by spectroscopic ellipsometry. An improvement in EQE is observed when the thickness of the bathocuproine (BCP) layer is decreased from 12nm to 6nm. Detailed analysis of the EQE spectra indicates that large exciton diffusion lengths in the pentacene films are responsible for the overall high EQE values near wavelengths of 668nm. Analysis also shows that improvement in the EQE of devices with the thinner BCP layer can be attributed to a net gain in optical field distribution and improvement in carrier collection efficiency. An improvement in open-circuit voltage (V OC) is also achieved through a thermal annealing process, leading to a net increase in power conversion efficiency. Integration of the EQE spectrum with an AM1.5 G spectrum yields a predicted power conversion efficiency of 1.8±0.2%. The increase in V OC is attributed to a significant reduction in the diode reverse saturation current upon annealing. [Copyright &y& Elsevier]

• Demonstration of in situ composition measurements of rocks on planetary surfaces. • Measurement of chemical maps of rocks from major to trace elements. • Derived the mineralogical composition for individual grains of the rock. • Measured the crystallization temperature and Pb/U age of zircon. [ABSTRACT FROM AUTHOR]

Tobacco dependence is a complex phenomenon in which physical and psychological components go hand in hand, and it is often considered as one of the major barriers to quit smoking. However, we still need to increase our understanding of the processes through which tobacco dependence relates to smoking cessation. This research aimed to investigating whether changes in smoker versus ex-smoker (abstainer) self-concept account for the association between tobacco dependence and successful smoking cessation. We used longitudinal data drawn from the evaluation of a smoking cessation intervention. A sample of smokers enrolled in the program filled in a questionnaire at the beginning of the intervention (baseline: N = 779), 6 months later (i.e., at the end of the intervention: T1, N = 532), and 9 months later (T2; N = 387). We assessed tobacco dependence (baseline), smoker versus ex-smoker self-concept (baseline, T1, and T2) and smoking status (baseline, T1 and T2). Tobacco dependence was negatively associated with smoking cessation maintenance, and this effect was mediated by changes in self-concept: The greater tobacco dependence, the lower the likelihood that former smokers develop an ex-smoker self-concept during the program, which results in relapse at T1 or T2. Successful smoking cessation interventions should provide strategies preventing the negative effects of tobacco dependence on identity transition. [ABSTRACT FROM AUTHOR]

• Raw agars have a different amount of anhydro units, responsible for gel strength. • The greater the amount of anhydro units, the greater the mechanical performances. • The strength of agar gels increases with increasing the polymer concentration. • The annealing process promotes the formation of additional crosslinking points. • Addition of the chelating agent leads to an enhancement of the gel stiffness. Agar is a natural polymer commonly used in various fields of application ranging from cosmetics to the food industry. In particular, for over forty years agar gels have been used in the field of conservation of Cultural Heritage where they are considered as one of the main well-performing tools in cleaning procedures. In the present work, the relation between the chemical composition and the mechanical strength of four different agar hydrogels was evaluated by comparing the results obtained via pyrolysis-gas chromatography/mass spectrometry and rheological characterization. Agar composition was studied by means of a pyrolysis-gas chromatography/mass spectrometry approach in order to differentiate the anhydrous, galactose and glucose units. Pristine agar gels, gels after double annealing, and gels with and without chelating agent were studied by means of amplitude, frequency and time sweep rheological tests to evaluate all the preparation approaches commonly used by conservators, also taking into account changes in the transparency via UV–vis spectroscopy. A high percentage of anhydrous units in the polymer backbone was found to provide superior mechanical stiffness to the pristine hydrogels, even if it did not seem to affect their long-term stability. The annealing process significantly improved the rheological response of galactose-rich agar hydrogels being able to promote the establishment of additional crosslinking points, whereas the additive presence showed to improve the hydrogel stiffness owing to a more structured polymer network. Moreover, the progressive reduction of the impurities and/or network defects within the hydrogels occurring due to the annealing process slightly increased the transparency of the hydrogels, which is an important aspect for applications in the conservation of Cultural Heritage. [ABSTRACT FROM AUTHOR]