Chemical and lead isotope characterisation of First World War shrapnel balls and bullets used on the Alpine Austrian–Italian Front

Chemical and lead isotope characterisation was carried out on shrapnel balls and bullets dating back to the First World War (WWI). These ammunitions were widely utilised in the Alpine Austrian–Italian front located in the Italian Alps. The investigation has been performed using inductively coupled plasma quadrupole mass spectrometry equipped with an octopole reaction system (ORS-ICP-QMS). The main goal of this work was to identify the elemental and lead isotope composition of raw materials and to discriminate between the military objects analysed. The results of multi-elemental analysis indicate that the shrapnel ball samples consisted of soft Pb or hard Pb with Sb depending on the use, the weapon type and the specific nation. The Italian shrapnel balls were made from hard Pb, as opposed to those of the Austrian– Hungarian samples. Through the investigation of lead isotope ratios, it has been possible to differentiate most of the Italian shrapnel balls from those of Austrian– Hungarian origin. Furthermore, some Italian shrapnel balls had a different lead isotope composition depending on their calibre. The elemental composition and lead isotopic signature of bullets show a clear discrimination between the external jacket and the core in relation to projectile type and nationality. The bullet cores consist of  Pb–Sb alloy regardless of the region of origin. This work allowed us to investigate the potential applications of trace elements and lead isotope analyses to discriminate military artefacts of different origins.Keywords: ICP-MS, trace element, source identification, principal component analysis, forensic scienc

Fast Liquid Chromatography Coupled with Tandem Mass Spectrometry for the Analysis of Vanillic and Syringic Acids in Ice Cores

The development of new analytical systems and the improvement of the existing ones to obtain high-resolution measurements of chemical markers in samples from ice cores, is one of the main challenges the paleoclimatic scientific community is facing. Different chemical species can be used as markers for tracking emission sources or specific environmental processes. Although some markers, such as methane sulfonic acid (a proxy of marine productivity), are commonly used, there is a lack of data on other organic tracers in ice cores, making their continuous analysis analytically challenging. Here, we present an innovative combination of fast liquid chromatography coupled with tandem mass spectrometry (FLC-MS/MS) to continuously determine organic markers in ice cores. After specific optimization, this approach was applied to the quantification of vanillic and syringic acids, two specific markers for biomass burning. Using the validated method, detection limits of 3.6 and 4.6 pg mL–1 for vanillic and syringic acids, respectively, were achieved. Thanks to the coupling of FLC-MS/MS with the continuous flow analytical system, we obtained one measurement every 30 s, which corresponds to a sampling resolution of a sample every 1.5 cm with a melting rate of 3.0 cm min–1. To check the robustness of the method, we analyzed two parallel sticks of an alpine ice core over more than 5 h. Vanillic acid was found with concentrations in the range of picograms per milliliter, suggesting the combustion of coniferous trees, which are found throughout the Italian Alps.publishedVersio

Atomic spectrometry update: a review of advances in environmental analysis

This is the 33th annual review of the application of atomic spectrometry to the chemical analysis of environmental samples. This update refers to papers published approximately between August 2016 and June 2017 and continues the series of Atomic Spectrometry Updates (ASUs) in environmental analysis that should be read in conjunction with other related ASUs in the series, namely: clinical and biological materials, foods and beverages; advances in atomic spectrometry and related techniques; elemental speciation; X-ray spectrometry; and metals, chemicals and functional materials. In the field of air analysis, highlights within this review period included the fabrication of new air samplers using 3D printer technology, development of a portable aerosol concentrator unit based upon electrostatic precipitation and instrumental developments such as a prototype portable spark emission spectrometer to quantify metal particles in workplace air. The advent of ICP-MS/MS systems has enabled analysts to develop improved methods for the determination of PGEs and radioactive elements present in airborne particles. With such instruments, the capacity to eliminate or minimise many isobaric interferences now enables analysts to forego the use of many onerous sample clean-up procedures. Improvements in the capabilities of aerosol mass spectrometers were noted as were developments in other complimentary measurement techniques such as Raman. In the arena of water analysis there are growing concerns regarding engineered NPs e.g. Ag NPs, entering water courses resulting in the development and optimisation of new methods based upon FFF and sp-ICP-MS techniques to measure such inputs. Similar concerns exist for MRI contrasting agents e.g. Gd-based compounds and here improved methodologies that involve the use of sample preconcentration using chelating columns and ICP-MS analysis have been proposed. In the field of plant and soil analysis, similar to developments in the water sector, there has been increased interest in the measurement of NPs. Many comparisons of sample digestion or extraction methods have been reported but a key issue rarely addressed is transferability, i.e. whether methods preferred by one group of researchers using particular apparatus are also optimal in a different laboratory using different apparatus. New sample preconcentration methods continued to appear although – as in previous years – the CRMs selected for method validation often failed to reflect the nature of the intended sample(s). A noteworthy advance is the use of HR-CS-ETMAS for elemental analysis. Developments in LIBS included greater use of TEA CO2 lasers in place of Nd:YAG lasers and increased use of stand-off measurement. The past year has also seen a rise in proximal sensing using LIBS and pXRFS. In the field of geological analysis, the quest continues for well-characterised matrix-matched materials suitable for the calibration of elemental and, particularly, isotopic measurements by microanalytical techniques. Increasing interest in stable isotope analysis by SIMS is reflected by the number of matrix-matched RMs developed specifically for this technique. Much work continues on ways of improving isotope ratio measurements by ICP-MS and TIMS for a wide range of different isotope systems relevant to geochemical studies. High spatial resolution analysis by LIBS, LA-ICP-MS and SIMS to obtain data on chemical and isotopic variations in minerals and biogenic materials in two and three dimensions are the foundation for many new insights in geoscientific research. In XRFS and LIBS, the advantages and limitations of portable instrumentation continue to be major focus of activity

Atomic spectrometry update – a review of advances in environmental analysis

This is the 34th annual review of the application of atomic spectrometry to the chemical analysis of environmental samples. This Update refers to papers published approximately between August 2017 and June 2018 and continues the series of Atomic Spectrometry Updates (ASUs) in Environmental Analysis that should be read in conjunction with other related ASUs in the series, namely: clinical and biological materials, foods and beverages; advances in atomic spectrometry and related techniques; elemental speciation; X-ray spectrometry; and metals, chemicals and functional materials. The review is not intended to be a comprehensive overview but selective with the aim of providing a critical insight into developments in instrumentation, methodologies and data handling that represent a significant advance in the use of atomic spectrometry in the environmental science

Aerosol and snow transfer processes: An investigation on the behavior of water-soluble organic compounds and ionic species

The concentrations of water-soluble compounds (ions, carboxylic acids, amino acids, sugars, phenolic compounds) in aerosol and snow have been determined at the coastal Italian base "Mario Zucchelli" (Antarctica) during the 2014-2015 austral summer. The main aim of this research was to investigate the air-snow transfer processes of a number of classes of chemical compounds and investigate their potential as tracers for specific sources.The composition and particle size distribution of Antarctic aerosol was measured, and water-soluble compounds accounted for 66% of the PM10 total mass concentration. The major ions Na+, Mg2+, Cl- and SO42- made up 99% of the total water soluble compound concentration indicating that sea spray input was the main source of aerosol. These ionic species were found mainly in the coarse fraction of the aerosol resulting in enhanced deposition, as reflected by the snow composition.Biogenic sources were identified using chemical markers such as carboxylic acids, amino acids, sugars and phenolic compounds. This study describes the first characterization of amino acids and sugar concentrations in surface snow. High concentrations of amino acids were found after a snowfall event, their presence is probably due to the degradation of biological material scavenged during the snow event. Alcohol sugars increased in concentration after the snow event, suggesting a deposition of primary biological particles, such as airborne fungal spores. (C) 2017 Elsevier Ltd. All rights reserved

Overview: Integrative and Comprehensive Understanding on Polar Environments (iCUPE) – concept and initial results

The role of polar regions is increasing in terms of megatrends such as globalization, new transport routes, demography, and the use of natural resources with consequent effects on regional and transported pollutant concentrations. We set up the ERA-PLANET Strand 4 project “iCUPE – integrative and Comprehensive Understanding on Polar Environments” to provide novel insights and observational data on global grand challenges with an Arctic focus. We utilize an integrated approach combining in situ observations, satellite remote sensing Earth observations (EOs), and multi-scale modeling to synthesize data from comprehensive long-term measurements, intensive campaigns, and satellites to deliver data products, metrics, and indicators to stakeholders concerning the environmental status, availability, and extraction of natural resources in the polar areas. The iCUPE work consists of thematic state-of-the-art research and the provision of novel data in atmospheric pollution, local sources and transboundary transport, the characterization of arctic surfaces and their changes, an assessment of the concentrations and impacts of heavy metals and persistent organic pollutants and their cycling, the quantification of emissions from natural resource extraction, and the validation and optimization of satellite Earth observation (EO) data streams. In this paper we introduce the iCUPE project and summarize initial results arising out of the integration of comprehensive in situ observations, satellite remote sensing, and multi-scale modeling in the Arctic context

New insights into the genetic etiology of Alzheimer's disease and related dementias

Characterization of the genetic landscape of Alzheimer's disease (AD) and related dementias (ADD) provides a unique opportunity for a better understanding of the associated pathophysiological processes. We performed a two-stage genome-wide association study totaling 111,326 clinically diagnosed/'proxy' AD cases and 677,663 controls. We found 75 risk loci, of which 42 were new at the time of analysis. Pathway enrichment analyses confirmed the involvement of amyloid/tau pathways and highlighted microglia implication. Gene prioritization in the new loci identified 31 genes that were suggestive of new genetically associated processes, including the tumor necrosis factor alpha pathway through the linear ubiquitin chain assembly complex. We also built a new genetic risk score associated with the risk of future AD/dementia or progression from mild cognitive impairment to AD/dementia. The improvement in prediction led to a 1.6- to 1.9-fold increase in AD risk from the lowest to the highest decile, in addition to effects of age and the APOE ε4 allele

Leisure in later life : a case study in Korea

Socio-economic, -demographic, and cultural factors have a major impact on the elderly's leisure patterns. Korea has developed rapidly in a short period of time which makes it hard for the contemporary elderly to keep up with the changes. This can affect their leisure lives after retirement and thus their satisfaction with life. This-research examines how the elderly's leisure patterns change following retirement, and its role alongside socio-economic and demographic factors influencing life satisfaction. The socio-economic anddemographic factors included in the analysis are gender, age, occupation education, cohabitation, irregular work, health status, and income. The data is intended to be a foundation and stepping stone for developing an elderly leisure policy and an elderly leisure education system for Korea , The research comprised a survey of 120 persons in the Gang- N am region of Seoul in South Korea. Male and Female participants aged 50 and over were selected as a sample. For measuring leisure participation, 20 leisure activities 'were utilised from the White Paper on Leisure 2008 conducted by the Ministry of Culture and Tourism, and they were further grouped into 7 categories by Classification of Leisure Activities based on Edginton, Compton, and Hanson's (1990) research. The main findings are as follows. Continuity is the most common trend in leisure activity after retirement rather than developments predicted by activity and disengagement Theories. Socio-economic factors such as income, occupation, education, cohabitation, and health condition influence the elderly's leisure activity patterns as well as their life satisfaction. Men seemed to be more leisure active than women, the younger compared to the older, and the better educated than the less educated. All the various groups in the research reported increased levels of activity since they had retired. Life satisfaction scores were the lowest among those who were / living alone, and those with chronic health conditions. However, as with leisure participation, all the groups reported an upward trend in life satisfaction after retirement. The increased satisfaction was mainly due to increased social participation. It was mainly the individuals who continued or increased their participation in leisure activities which they practised prior to retirement who showed a boost in their life satisfaction.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Development and application of methods for the determination of silver in polymeric dressings used for the care of burns

Open vessel and microwave digestion methods have been developed for the determination of total silver in six commercial dressing used for the treatment of skin burns. An extraction method using TMAH has also been developed to determine the amount of silver present in the exudates found on the surface after dressing removal so an estimation of the patient dose can be made. All microwave methods had a quantitative recovery, whereas the open vessel had recoveries that ranged from 80 to 100%. The silver concentrations were determined by inductively coupled plasma mass spectrometry using an external calibration. In the absence of suitable reference materials, isotope dilution analysis was applied to validate the accuracy of results obtained by external calibration. All the products had a total Ag content that agreed with the values declared by the producer, which ranged from 10 to 0.2% Ag by weight. One of the methods was applied to the indirect determination of Ag released in vivo by ActicoatTM Flex 3, a dressing composed of silver nanoparticles on a polymer net. Silver levels were determined in used dressings after application to patients with partial thickness skin burns. A maximum of 62% of the silver was found to have been released onto the patient where hemopurulent exudate occured, indicating that the dressing was virtually exhausted after 3 days of use. We conclude that the Ag released into the patient's tissues is closely correlated with the local severity of the wound

Development and application of methods for the determination of silver in polymeric dressings used for the care of burns

Open vessel and microwave digestion methods have been developed for the determination of total silver in six commercial dressing used for the treatment of skin burns. An extraction method using TMAH has also been developed to determine the amount of silver present in the exudates found on the surface after dressing removal so an estimation of the patient dose can be made. All microwave methods had a quantitative recovery, whereas the open vessel had recoveries that ranged from 80 to 100%. The silver concentrations were determined by inductively coupled plasma mass spectrometry using an external calibration. In the absence of suitable reference materials, isotope dilution analysis was applied to validate the accuracy of results obtained by external calibration. All the products had a total Ag content that agreed with the values declared by the producer, which ranged from 10 to 0.2% Ag by weight. One of the methods was applied to the indirect determination of Ag released in vivo by ActicoatTM Flex 3, a dressing composed of silver nanoparticles on a polymer net. Silver levels were determined in used dressings after application to patients with partial thickness skin burns. A maximum of 62% of the silver was found to have been released onto the patient where hemopurulent exudate occured, indicating that the dressing was virtually exhausted after 3 days of use. We conclude that the Ag released into the patient's tissues is closely correlated with the local severity of the wound