Decadal Scale Variability of Larsen Ice Shelf Melt Captured by Antarctic Peninsula Ice Core

In this study, we used the stable water isotope record (δ18O) from an ice core drilled in Palmer Land, southern Antarctic Peninsula (AP). Utilizing δ18O we identified two climate regimes during the satellite era. During the 1979–1998 positive interdecadal Pacific oscillation (IPO) phase, a low-pressure system north of the Weddell Sea drove southeasterly winds that are associated with an increase in warm air mass intrusion onto the Larsen shelves, which melted and a decreased sea ice concentration in the Weddell Sea/increase in the Bellingshausen Sea. This climate setting is associated with anomaly low δ18O values (compared with the latter IPO period). There is significantly more melt along the northern AP ice shelf margins and on the Larsen D and southern Larsen C during the 1979–1998 IPO positive phase. The IPO positive climatic setting was coincidental with the Larsen A ice shelf collapse. In contrast, during the IPO negative phase (1999–2011), northerly winds caused a reduction in sea ice in the Bellingshausen Sea/Drake Passage region. Moreover, a Southern Ocean north of the Weddell Sea high-pressure system caused low-latitude warm humid air over the tip and east of the AP, a setting that is associated with increased northern AP snowfall, a high δ18O anomaly, and less prone to Larsen ice shelf melt

Ice Core Chronologies from the Antarctic Peninsula: The Palmer, Jurassic, and Rendezvous Age-Scales

In this study, we present the age scales for three Antarctic Peninsula (AP) ice cores: Palmer, Rendezvous, and Jurassic. The three cores are all intermediate-depth cores, in the 133–141 m depth range. Non-sea-salt sulfate ([nssSO42−]) and hydrogen peroxide (H2O2) display marked seasonal variability suitable for annual-layer counting. The Palmer ice core covers 390 years, 1621–2011 C.E., and is one of the oldest AP cores. Rendezvous and Jurassic are lower elevation high-snow accumulation sites and therefore cover shorter intervals, 1843–2011 C.E. and 1874–2011 C.E., respectively. The age scales show good agreement with known volcanic age horizons. The three chronologies’ start and end dates of volcanic events are compared to the volcanic events in the published WAIS Divide core. The age difference for the Palmer age scale is ±6 months, Rendezvous ±9 months, and Jurassic ±7 months. Our results demonstrate the advantage of dating several cores from the same region at the same time. Additional confidence can be gained in the age scales by evaluating and finding synchronicity of [nssSO42−] peaks amongst the sites.</jats:p

Continuous flow analysis methods for sodium, magnesium and calcium detection in the Skytrain ice core

Dissolved and particulate sodium, magnesium and calcium are analyzed in ice cores to determine past changes in sea ice extent, terrestrial dust variability and atmospheric aerosol transport efficiency. They are also used to date ice cores if annual layers are visible. Multiple methods have been developed to analyze these important compounds in ice cores. Continuous flow analysis (CFA) is implemented with instruments that sample the meltstream continuously. In this study, CFA with ICP-MS (inductively coupled-plasma mass spectrometry) and fast ion chromatography (FIC) methods are compared for analysis of sodium and magnesium. ICP-MS, FIC and fluorescence methods are compared for analysis of calcium. Respective analysis of a 10 m section of the Antarctic WACSWAIN Skytrain Ice Rise ice core shows that all of the methods result in similar levels of the compounds. The ICP-MS method is the most suitable for analysis of the Skytrain ice core due to its superior precision (relative standard deviation: 1.6% for Na, 1.3% for Mg and 1.2% for Ca) and sampling frequency compared to the FIC method. The fluorescence detection method may be preferred for calcium analysis due to its higher depth resolution (1.4 cm) relative to the ICP-MS and FIC methods (~4 cm)

The ST22 chronology for the Skytrain Ice Rise ice core – Part 2: An age model to the last interglacial and disturbed deep stratigraphy

We present an age model for the 651 m deep ice core from Skytrain Ice Rise, situated inland of the Ronne Ice Shelf, Antarctica. The top 2000 years have previously been dated using age markers interpolated through annual layer counting. Below this, we align the Skytrain core to the AICC2012 age model using tie points in the ice and air phase, and we apply the Paleochrono program to obtain the best fit to the tie points and glaciological constraints. In the gas phase, ties are made using methane and, in critical sections, δ18Oair; in the ice phase ties are through 10Be across the Laschamps event and through ice chemistry related to long-range dust transport and deposition. This strategy provides a good outcome to about 108 ka (∼ 605 m). Beyond that there are signs of flow disturbance, with a section of ice probably repeated. Nonetheless values of CH4 and δ18Oair confirm that part of the last interglacial (LIG), from about 117–126 ka (617–627 m), is present and in chronological order. Below this there are clear signs of stratigraphic disturbance, with rapid oscillation of values in both the ice and gas phase at the base of the LIG section, below 628 m. Based on methane values, the warmest part of the LIG and the coldest part of the penultimate glacial are missing from our record. Ice below 631 m appears to be of age > 150 ka

Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions

In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorption. These materials do not incorporate open metal sites and thus provide an excellent platform to investigate the effect of the incorporation of ligand functionality via amide and alkyne groups on substrate binding. By reducing the linker length of our previously reported MFM-136, we report much improved CO2/CH4 (50:50) and CO2/N2 (15:85) selectivity values of 20.2 and 65.4, respectively (1 bar and 273 K), in the new amide-decorated MOF, MFM-126. The CO2 separation performance of MFM-126 has been confirmed by dynamic breakthrough experiments. In situ inelastic neutron scattering and synchrotron FT-IR microspectroscopy were employed to elucidate dynamic interactions of adsorbed CO2 molecules within MFM-126. Upon changing the functionality to an alkyne group in MFM-127, the CO2 uptake decreases but the C2H2 uptake increases by 68%, leading to excellent C2H2/CO2 and C2H2/CH4 selectivities of 3.7 and 21.2, respectively. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-126 and MFM-127, and, to the best of our knowledge, we report the first example of acetylene binding to an alkyne moiety in a porous material, with over 50% of the acetylene observed within MFM-127 displaying interactions (less than 4 Å) with the alkyne functionality of the framework

BHPR research: qualitative1. Complex reasoning determines patients' perception of outcome following foot surgery in rheumatoid arhtritis

Background: Foot surgery is common in patients with RA but research into surgical outcomes is limited and conceptually flawed as current outcome measures lack face validity: to date no one has asked patients what is important to them. This study aimed to determine which factors are important to patients when evaluating the success of foot surgery in RA Methods: Semi structured interviews of RA patients who had undergone foot surgery were conducted and transcribed verbatim. Thematic analysis of interviews was conducted to explore issues that were important to patients. Results: 11 RA patients (9 ♂, mean age 59, dis dur = 22yrs, mean of 3 yrs post op) with mixed experiences of foot surgery were interviewed. Patients interpreted outcome in respect to a multitude of factors, frequently positive change in one aspect contrasted with negative opinions about another. Overall, four major themes emerged. Function: Functional ability & participation in valued activities were very important to patients. Walking ability was a key concern but patients interpreted levels of activity in light of other aspects of their disease, reflecting on change in functional ability more than overall level. Positive feelings of improved mobility were often moderated by negative self perception ("I mean, I still walk like a waddling duck”). Appearance: Appearance was important to almost all patients but perhaps the most complex theme of all. Physical appearance, foot shape, and footwear were closely interlinked, yet patients saw these as distinct separate concepts. Patients need to legitimize these feelings was clear and they frequently entered into a defensive repertoire ("it's not cosmetic surgery; it's something that's more important than that, you know?”). Clinician opinion: Surgeons' post operative evaluation of the procedure was very influential. The impact of this appraisal continued to affect patients' lasting impression irrespective of how the outcome compared to their initial goals ("when he'd done it ... he said that hasn't worked as good as he'd wanted to ... but the pain has gone”). Pain: Whilst pain was important to almost all patients, it appeared to be less important than the other themes. Pain was predominately raised when it influenced other themes, such as function; many still felt the need to legitimize their foot pain in order for health professionals to take it seriously ("in the end I went to my GP because it had happened a few times and I went to an orthopaedic surgeon who was quite dismissive of it, it was like what are you complaining about”). Conclusions: Patients interpret the outcome of foot surgery using a multitude of interrelated factors, particularly functional ability, appearance and surgeons' appraisal of the procedure. While pain was often noted, this appeared less important than other factors in the overall outcome of the surgery. Future research into foot surgery should incorporate the complexity of how patients determine their outcome Disclosure statement: All authors have declared no conflicts of interes

Levels and distribution profiles of Per- and Polyfluoroalkyl Substances (PFAS) in a high Arctic Svalbard ice core

Per- and polyfluoroalkyl substances (PFAS) are a group of persistent organic contaminants of which some are toxic and bioaccumulative. Several PFAS can be formed from the atmospheric degradation of precursors such as fluorotelomer alcohols (FTOHs) as well as hydrochlorofluorocarbons (HFCs) and other ozone-depleting chlorofluorocarbon (CFC) replacement compounds. Svalbard ice cores have been shown to provide a valuable record of long-range atmospheric transport of contaminants to the Arctic. This study uses a 12.3 m ice core from the remote Lomonosovfonna ice cap on Svalbard to understand the atmospheric deposition of PFAS in the Arctic. A total of 45 PFAS were targeted, of which 26 were detected, using supercritical fluid chromatography (SFC) tandem mass spectrometry (MS/MS) and ultra-performance liquid chromatography (UPLC) MS/MS. C2 to C11 perfluoroalkyl carboxylic acids (PFCAs) were detected continuously in the ice core and their fluxes ranged from 2.5 to 8200 ng m−2 yr−1 (9.51–16,500 pg L−1). Trifluoroacetic acid (TFA) represented 71 % of the total mass of C2 – C11 PFCAs in the ice core and had increasing temporal trends in deposition. The distribution profile of PFCAs suggested that FTOHs were likely the atmospheric precursor to C8 – C11 PFCAs, whereas C2 – C6 PFCAs had alternative sources, such as HFCs and other CFC replacement compounds. Perfluorooctanesulfonic acid (PFOS) was also widely detected in 82 % of ice core subsections, and its isomer profile (81 % linear) indicated an electrochemical fluorination manufacturing source. Comparisons of PFAS concentrations with a marine aerosol proxy showed that marine aerosols were insignificant for the deposition of PFAS on Lomonosovfonna. Comparisons with a melt proxy showed that TFA and PFOS were mobile during meltwater percolation. This indicates that seasonal snowmelt and runoff from post-industrial accumulation on glaciers could be a significant seasonal source of PFAS to ecosystems in Arctic fjords