Controls on lithium concentration and diffusion in zircon

This study was supported by ETH Research Grants ETH-34 15-2 (JS), ETH-14 16-1 (FM) and by Swiss National Science Foundation research grant 200020-153112/1 (NK).Thermal annealing of zircons prior to uranium-lead dating by laser ablation inductively coupled plasma mass spectrometry is a commonly-implemented procedure which improves data accuracy and precision by partially repairing radiation damage from the decay of uranium and thorium. However, it also leads to significantly higher concentrations of lithium in the zircon lattice, which become positively correlated with trivalent yttrium and rare earth elements. Prior to such treatments, zircons typically contain lithium below detection limits (typically <0.55 μg g−1), unless correlated with lanthanum and aluminum (i.e., melt/mineral inclusion tracer elements). This suggests that lithium in zircon is primarily sequestered within inclusions, and is able to permeate the crystal lattice to couple with yttrium and rare earth elements during the thermal annealing procedure. This process occurs 2–3 orders of magnitude faster than diffusion experiments have previously determined, indicating that another diffusion mechanism may apply. A model is proposed, whereby: (i) charge compensation of stoichiometrically over-abundant trivalent cations under water-rich magmatic conditions is likely accomplished by hydrogen, given the incompatibility of lithium in zircon and the abundance of hydrogen. However, (ii) conditions that are high temperature and low pressure (characteristic of both thermal annealing and the syn-eruptive environment), drive silicate melt inclusions to exsolve water, generating a motive force for both hydrogen and lithium from inclusions to permeate the lattice in order to reestablish electrochemical equilibrium between the interior and exterior of the zircon. To test the pressure dependency of lithium migration in the zircon lattice, thermal annealing experiments were performed at 850 °C and 1 bar, 2 kbar and 6 kbar using zircons from the Fish Canyon Tuff. The experiments demonstrate that thermal annealing at 2 and 6 kbar inhibits lithium mobility, with zircons registering lithium concentrations below detection limits similar to controls. The experimental results suggest that lithium concentrations in zircon are vulnerable to rapid perturbation by decompression (concurrent with high temperatures), which further indicate that lithium-in-zircon diffusion data should be interpreted with caution.Publisher PDFPeer reviewe

Eruption of Shallow Crystal Cumulates during Explosive Phonolitic Eruptions on Tenerife, Canary Islands

The recent eruptive history on the island of Tenerife is characterized in part by the presence of zoned phonolitic ignimbrites, some of which prominently display two types of juvenile clasts (i.e. light-colored, aphyric pumices alongside darker, more crystal-rich pumices, here dubbed ‘crystal-poor' and ‘crystal-rich', respectively). Petrographic observation of the crystal-rich pumices reveals intensely resorbed and intergrown mineral textures, consistent with the system reaching a high crystallinity, followed by perturbation and remobilization prior to eruption. Some trace elements show anomalous concentrations in such crystal-rich pumices (e.g. bulk Ba > 2000 ppm alongside low Zr and a positive Eu anomaly) indicative of crystal accumulation (of feldspar ± biotite). Many biotite and feldspar crystals are reversely zoned, with rim concentrations that are high in Ba but low in Sr, implying crystallization from an ‘enriched' melt, potentially derived from remobilization by partial melting of the aforementioned cumulate zones. Given (1) the presence of cumulates in the eruptive record on Tenerife and a bimodality of pumice textures, (2) the presence of three dominant compositions (basanite, phonotephrite, phonolite, separated by compositional gaps) in the volcanic record, and (3) abundant support for crystal fractionation as the dominant drive for magmatic evolution in Tenerife, it is hypothesized that crystal-poor magmas are extracted from mushy reservoirs in both the lower and upper crust. The thermodynamic software MELTS is used to test a polybaric differentiation model whereby phonolites (sensu lato) are generated by extraction of residual liquids from an intermediate-crystallinity phonotephritic mush in the upper crust, which is in turn generated from the residual liquids of an intermediate-crystallinity basanitic mush at deeper levels. Latent heat spikes following crystallization of successive phases in the upper crustal reservoir provide a thermal buffering mechanism to slow down cooling and crystallization, permitting enhanced melt extraction at a particular crystallinity interval (mostly ∼40-60 vol. % crystals). MELTS modeling typically fits the observed chemical data adequately, although some major elements (mostly Al2O3) also indicate partial ‘cannibalization' of feldspar along with some magma mixing (and potentially minor crustal contamination

Continuous Processing and Efficient in Situ\textit{in Situ} Reaction Monitoring of a Hypervalent Iodine(III) Mediated Cyclopropanation Using Benchtop NMR Spectroscopy

Real-time NMR spectroscopy has proven to be a rapid and an effective monitoring tool to study the hypervalent iodine(III) mediated cyclopropanation. With the ever increasing number of new synthetic methods for carbon−carbon bond formation, the NMR $\textit{in situ}$ monitoring of reactions is becoming a highly desirable enabling method. In this study, we have demonstrated the versatility of benchtop NMR using inline and online real-time monitoring methods to access mutually complementary information for process understanding, and we developed new approaches for real-time monitoring addressing challenges associated with better integration into continuous processes.University of Cambridge (Daphne Jackson Fellowship), iCON through CMAC (Grant ID: RG74817), Engineering and Physical Sciences Research Council (Critical Mass grant (Grant ID: EP/K009494K/1), Core Capability grant (Grant ID: EP/K039520/1

Age differences in everyday stressor-related negative affect: A coordinated analysis.

Advancing age is often characterized by preserved or even enhanced emotion regulation, which is thought to manifest in terms of age-related reductions in the within-person association between stressors and negative affect. Existing research from ecological momentary assessment and end-of-day daily diary studies examining such age-related benefits have yielded mixed results, potentially due to differences in samples, design, and measurement of everyday stressors and negative affect. We conducted a coordinated analysis of 5 ecological momentary assessments and 2 end-of-day daily diary studies to examine adult age differences in the within-person association between everyday stressors and negative affect. Reported stressor occurrences are robustly associated with higher negative affect, regardless of study design and sample characteristics. Across studies, interactions between age and everyday stressors predicting negative affect revealed a pattern of age-related decreases in the stressor-negative affect association, but this interaction was only significant for 2 studies. Further, examination of statistical power of the included studies suggests that, despite differences in the number of repeated assessments, power to detect within-person stressor-negative affect associations is quite good. In contrast, despite possessing wider age ranges, observed age differences were relatively small in magnitude, and studies are potentially underpowered to detect age differences in these within-person associations. We discuss the importance of study design, interval of repeated assessments and number of participants for examining age differences in everyday stressors and negative affect, as well as the virtue of coordinated analyses for detecting consistent direction of associations, but inconsistent patterns of statistical significance. (PsycINFO Database Record (c) 2019 APA, all rights reserved)

Polymorphisms of the dna base excision repair gene mutyh in head and neck cancer

Background: Head and neck squamous cell carcinomas (HNSCC) comprise about 6% of all malignant neoplasms. The major risk factors of HNSCC are smoking and alcohol consumption. Genetic polymorphisms of DNA repair enzymes may lead to genetic instability and carcinogenesis. MUTYH gene encodes a DNA glycosylase that can initiate the base excision repair (BER) pathway and prevent G:C > T:A transversion by excising adenine mispaired with 8-hydroxyguanine produced by reactive oxygen species (ROS). Aim: to perform a case-control study to test the association between polymorphism in the MUTYH gene: Tyr165Cys and head and neck cancer risk progression. Methods: Genotypes were determined in DNA from peripheral blood lymphocytes of 193 patients (among them 97 subjects with precancerous hyperplastic laryngeal lesions and 96 subjects with head and neck cancer) and 140 age, sex and ethnic-matched cancer-free controls by tetra-primer amplification refractory mutation system PCR (T-ARMS-PCR). Results: We found an association between head and neck cancer risk and the Tyr165Tyr variant of the MUTYH gene (OR 2.18; 95% CI 1.19–3.97). For Tyr165Tyr genotype we also observed positive correlation with cancer progression assessed by tumor size (OR 4.56; 95% CI 1.60–12.95). We did not observe any correlation between Tyr165Cys polymorphism of MUTYHgene and precancerous hyperplastic laryngeal lesions risk. Conclusion: The Tyr165Tyr polymorphic variant of the MUTYHgene may be associated with head and neck cancer in Polish population

Sleep and cardiometabolic comorbidities in the obstructive sleep apnoea–COPD overlap syndrome: data from the European Sleep Apnoea Database

Aim The impact of obstructive sleep apnoea (OSA)-COPD overlap syndrome (OVS) on sleep quality and cardiovascular outcomes has not been fully explored. We aimed to compare clinical and polysomnographic characteristics of patients with OVS versus patients with OSA, and to explore pathophysiological links between OVS and comorbidities.Study design and methods This cross-sectional analysis initially included data from 5600 patients with OSA and lung function in the European Sleep Apnoea Database. Two subgroups of patients with OSA (n=1018) or OVS (n=509) were matched (2:1) based on sex, age, body mass index and apnoea-hypopnea index at baseline. Results After matching, patients with OVS had more severe hypoxia, lower sleep efficiency and presented with higher prevalences of arterial hypertension, ischaemic heart disease and heart failure compared with patients with OSA. OVS was associated with a significant decrease in sleep efficiency (mean difference (beta) -3.0%, 95% CI -4.7 to -1.3) and in nocturnal mean peripheral oxyhaemoglobin saturation (S-pO2) (beta -1.1%, 95% CI -1.5 to -0.7). Further analysis revealed that a decrease in forced expiratory volume in 1 s and arterial oxygen tension was related to a decrease in sleep efficiency and in mean nocturnal S-pO2. A COPD diagnosis increased the odds of having heart failure by 1.75 (95% CI 1.15-2.67) and systemic hypertension by 1.36 (95% CI 1.07-1.73). Nocturnal hypoxia was strongly associated with comorbidities; the mean nocturnal S-pO2 and T90 (increase in time below S-pO2 of 90%) were associated with increased odds of systemic hypertension, diabetes and heart failure but the oxygen desaturation index was only related to hypertension and diabetes.Conclusion Patients with OVS presented with more sleep-related hypoxia, a reduced sleep quality and a higher risk for heart failure and hypertension

Exploring the Role of Relational Practices in Water Governance Using a Game-Based Approach

The growing complexity and interdependence of water management processes requires the involvement of multiple stakeholders in water governance. Multi-party collaboration is increasingly vital at both the strategy development and implementation levels. Multi-party collaboration involves a process of joint decision-making among key stakeholders in a problem domain directed towards the future of that domain. However, the common goal is not present from the beginning; rather, the common goal emerges during the process of collaboration. Unfortunately, when the conflicting interests of different actors are at stake, the large majority of environmental multi-party efforts often do not reliably deliver sustainable improvements to policy and/or practice. One of the reasons for this, which has been long established by many case studies, is that social learning with a focus on relational practices is missing. The purpose of this paper is to present the design and initial results of a pilot study that utilized a game-based approach to explore the effects of relational practices on the effectiveness of water governance. This paper verifies the methods used by addressing the following question: are game mechanisms, protocols for facilitation and observation, the recording of decisions and results, and participant surveys adequate to reliably test hypotheses about behavioral decisions related to water governance? We used the “Lords of the Valley” (LOV) game, which focuses on the local-level management of a hypothetical river valley involving many stakeholders. We used an observation protocol to collect data on the quality of relational practices and compared this data with the quantitative outcomes achieved by participants in the game. In this pilot study, we ran the game three times with different groups of participants, and here we provide the outcomes within the context of verifying and improving the methods

Polymorphisms in RAD51, XRCC2 and XRCC3 genes of the homologous recombination repair in colorectal cancer—a case control study

XRCC2 and XRCC3 proteins are structurally and functionally related to RAD51 which play an important role in the homologous recombination, the process frequently involved in cancer transformation. In our previous work we show that the 135G>C polymorphism (rs1801320) of the RAD51 gene can modify the effect of the Thr241Met polymorphism (rs861539) of the XRCC3 gene. We tested the association between the 135G>C polymorphism of the RAD51 gene, the Thr241Met polymorphism of the XRCC3 gene and the Arg188His polymorphism (rs3218536) of the XRCC2 gene and colorectal cancer risk and clinicopathological parameters. Polymorphisms were evaluated by restriction fragment length polymorphism polymerase chain reaction (RFLP-PCR) in 100 patients with invasive adenocarcinoma of the colon and in 100 sex, age and ethnicity matched cancer–free controls. We stratified the patients by genotypes, tumour Duke’s and TNM stage and calculated the linkage of each genotype with each stratum. Carriers of Arg188Arg/Me241tMet, His188His/Thr241Thr and His188His/G135G genotypes had an increased risk of colorectal cancer occurrence (OR 5.70, 95% CI 1.10–29.5; OR 12.4, 95% CI 1.63–94.9; OR 5.88, 95% CI 1.21–28.5, respectively). The C135C genotype decreased the risk of colorectal cancer singly (OR 0.06, 95% CI 0.02–0.22) as well as in combination with other two polymorphisms. TNM and Duke’s staging were not related to any of these polymorphisms. Our results suggest that the 135G>C polymorphism of the RAD51 gene can be an independent marker of colorectal cancer risk. The Thr241Met polymorphism of the XRCC3 gene and the Arg188His polymorphism of the XRCC2 gene can modify the risk of colorectal cancer