Interfacing High Performance Liquid Chromatography with Inductively Coupled Plasma Mass Spectrometry for Speciation Studies

A novel interface for the coupling of high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) for the speciation of organometallic compounds has been developed and utilised for a number of diverse applications. Desolvation of the sample prior to reaching the plasma is shown to facilitate a more versatile coupling of the two instrumental techniques. This has been achieved by first volatilising the aerosol after nebulisation of the sample in a heated cyclone spray chamber. The resulting vapour is removed using a membrane drier and a thermoelectrically cooled condenser. The apparatus developed has been fully optimised to facilitate the introduction of a range of organic solvents, particularly those used as mobile phases for HPLC separations such as acetonitrile and methanol. This interface also facilitates gradient elutions to be used with ICP-MS for the first time. The interface developed has enabled the use of HPLC-ICP-MS to speciate the metabolites of a novel platinum based chemotherapy drug, JM-216, in human plasma ultrafiltrate. This approach offers a number of advantages over existing techniques especially in terms of speed of analysis and sensitivity. The platinum containing metabolites derived from this drug have been separated, identified, and compared to those arising from the breakdown of cisplatin and carboplatin in both plasma ultrafiltrate and an aqueous solution. A detection limit of 119 pg of Pt has been achieved for real samples. The interface has also been used for the speciation of organotin and organolead compounds in environmental samples, and to investigate the speciation of metals in tea liquors. It was found that although the apparatus proved beneficial for both the determination of organotins and the identification of metal containing species in tea, its use adversely affected the analysis of organolead compounds. The results of these latter studies are critically assessed and discussed with respect to HPLC-ICP-MS interface design.Fisons Instruments Elemental, Ion Path Road 3, Winsford, Cheshire, CW7 3BX and Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading, RG4 9N

Atomic spectrometry update : a review of advances in environmental analysis

This is the 31st annual review of the application of atomic spectrometry to the chemical analysis of environmental samples. This update refers to papers published approximately between August 2014 and July 2015 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 development of a new laser fluorescence instrument for the ultratrace determination of mercury vapour; single particle ICP-MS studies and the coupling of elemental analysers to mass spectrometers for the improved characterisation of carbonaceous aerosols. In the arena of water analysis, methods continue to be developed: for the extraction and preconcentration of elements, As, Cr, Hg and Sb species and determination of elemental constituents in colloidal and NP fractions. Emerging elements of interest include Gd derived from MRI agents discharged at low level from medical facilities in water courses. Instrumental developments reported included the use of MC-ICP-MS for isotopic tracer studies and a review of TXRF techniques and associated preconcentration procedures for trace element analysis. In the period covered by this update several articles have explored the analysis of soil extracts for geochemical prospecting. There has been widening interest in the use of CS-AAS and in the application of techniques capable of direct sample analysis such as slurry sampling ETAAS and ETV-ICP-AES. Portable XRF instrumentation is now being used in many disciplines to quantify trace elements in soils – bringing a need for better transfer of analytical knowledge to non-specialist users – and the growing use of portable XRF in proximal sensing is also noteworthy. Recent research indicates that geological applications still drive many of the instrumental and methodological advances in LA-ICP-MS. Fundamental studies continued to shed light on the processes involved and hence ways of improving the analysis of laser-produced aerosols and to minimise matrix and fractionation effects. A new technique LA-DOF-MS (distance of flight) was described. The utility of LIBS and portable XRF for in situ survey work continues to show promise but issues such as appropriate calibration regimes and data processing protocols will still need to be addressed

Prognostic factors for recent‐onset interstitial cystitis/painful bladder syndrome

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/96701/1/bju11422.pd

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

Chemical and Lead Isotope characterisation of First World War shrapnel balls and bullets used on the Alpine Austrian\u2013Italian 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\u2013Italian 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\u2013 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\u2013 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 164 Scientia Militaria, South African Journal of Military Studies, Vol 46, Nr 1, 2018. doi: 10.5787/46-1-1230 Pb\u2013Sb 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 origin

Delusions in frontotemporal lobar degeneration

We assessed the significance and nature of delusions in frontotemporal lobar degeneration (FTLD), an important cause of young-onset dementia with prominent neuropsychiatric features that remain incompletely characterised. The case notes of all patients meeting diagnostic criteria for FTLD attending a tertiary level cognitive disorders clinic over a three year period were retrospectively reviewed and eight patients with a history of delusions were identified. All patients underwent detailed clinical and neuropsychological evaluation and brain MRI. The diagnosis was confirmed pathologically in two cases. The estimated prevalence of delusions was 14 %. Delusions were an early, prominent and persistent feature. They were phenomenologically diverse; however paranoid and somatic delusions were prominent. Behavioural variant FTLD was the most frequently associated clinical subtype and cerebral atrophy was bilateral or predominantly right-sided in most cases. We conclude that delusions may be a clinical issue in FTLD, and this should be explored further in future work

Correction: Spatiotemporal distribution and speciation of silver nanoparticles in the healing wound.

Correction for 'Spatiotemporal distribution and speciation of silver nanoparticles in the healing wound' by Marco Roman et al., Analyst, 2020, 145, 6456–6469, DOI: 10.1039/D0AN00607F

Antarctic bottom and lower circumpolar deep water circulation in the eastern Indian Ocean

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 111 (2006): C02006, doi:10.1029/2005JC003011.Net northward transport below γn > 28.1 kgm−3 (≈3200 m) into the Perth Basin of between 4.4 and 5.8 Sv is estimated from a year-long current meter mooring array between the Broken and Naturaliste Plateaus. Northward transport of between 2.0 and 2.5 Sv of Antarctic Bottom Water (γn >28.2 kgm−3), that must upwell within the southern region of the Perth Basin, results in an area-averaged diapycnal velocity and diffusivity of w*=2.5− 3.1× 10−6 ms−1 and κ = 13−15×10−4 m2s−1, respectively. Diffusivity estimates for the Perth Basin are several times larger than area averaged mixing estimates for the abyssal subtropical South Atlantic and Pacific Oceans. However, the dissipation of turbulent kinetic energy required to maintain the abyssal mixing in the Perth basin, ε=O(10−9 Wkg−1), is similar to that required in the South Atlantic Ocean. The area-averaged diffusivity in the Perth Basin does not require unreasonable energy dissipation rates as this ocean basin is only weakly stratified. The abyssal diffuvisity of the Perth Basin results from intense mixing at the basin boundary and in the basin interior over rough topography. The complex bathymetry and low abyssal stratification suggests that the Indian Ocean, for a given energy dissipation, may support a larger meridional overturning circulation than other subtropical basins.BMS was supported by funds from the Ocean and Climate Change Institute at the Woods Hole Oceanographic Institution, and The James S. Cole and Cecily C. Selby Endowed Fund and The Penzance Endowed Fund in support of Assistant Scientists. The mooring array was funded by Australia’s CSIRO Marine Research

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