Windstorms are the most damaging natural hazard across western Europe. Risk modellers are limited by the observational data record to only ∼ 60 years of comprehensive reanalysis data that are ...dominated by considerable inter-annual variability. This makes estimating return periods of rare events difficult and sensitive to the choice of the historical period used. This study proposes a novel statistical method for estimating wind gusts across Europe based on observed windstorm footprints. A good description of extreme wind speeds is obtained by assuming that gust speed peaks over threshold are distributed exponentially, i.e. a generalised Pareto distribution having a zero shape parameter. The threshold and tail scale parameter are estimated at each location and used to calculate estimates of the 10- and 200-year return levels. The North Atlantic Oscillation (NAO) is particularly important for modulating lower return levels and modulating the threshold, with a less detectable influence on rarer extremes and the tail scale parameter. The length of historical data required to have the lowest error in estimating return levels is quantified using both observed and simulated time series of the historical NAO. For reducing errors in estimating 200-year return levels of an independent 10-year period, a data catalogue of at least 20 years is required. For lower return levels the NAO has a stronger influence on estimated return levels, and so there is more variability in estimates. Using theoretical estimates of future NAO states, return levels are largely outside the historical uncertainty, indicating significant increases in risk potential from windstorms in the next 100 years. Our method presents a framework for assessing high-return-period events across a range of hazards without the additional complexities of a full catastrophe model.
Summary
We use teleseismic waveform inversion, along with depth phase analysis, to constrain the centroid depths and source parameters of large African earthquakes. The majority of seismic activity ...is concentrated along the East African Rift System, with additional active regions along stretches of the continental margins in north and east Africa, and in the Congo Basin. We examine variations in the seismogenic thickness across Africa, based on a total of 227 well-determined earthquake depths, 112 of which are new to this study. Seismogenic thickness varies in correspondence with lithospheric thickness, as determined from surface wave tomography, with regions of thick lithosphere being associated with seismogenic thicknesses of up to 40 km. In regions of thin lithosphere, the seismogenic thickness is typically limited to ≤20 km. Larger seismogenic thicknesses also correlate with regions that have dominant tectonothermal ages of ≥1500 Ma, where the East African Rift passes around the Archean cratons of Africa, through the older Proterozoic mobile belts. These correlations are likely to be related to the production, affected by method and age of basement formation, and preservation, affected by lithospheric thickness, of a strong, anhydrous lower crust. The Congo Basin contains the only compressional earthquakes in the continental interior. Simple modelling of the forces induced by convective support of the African plate, based on long-wavelength free-air gravity anomalies, indicates that epeirogenic effects are sufficient to account for the localization and occurrence of both extensional and compressional deformation in Africa. Seismicity along the margins of Africa reflects a mixture between oceanic and continental seismogenic characteristics, with earthquakes in places extending to 40 km depth.
ABSTRACT
Recent advances in identifying giant molecular filaments in Galactic surveys allow us to study the interstellar material and its dense, potentially star forming phase on scales comparable to ...resolved extragalactic clouds. Two large filaments detected in the 13CO/C18O(J = 3–2) Heterodyne Inner Milky Way Plane Survey (CHIMPS) survey, one in the Sagittarius-arm and one in an interarm region, were mapped with dense gas tracers inside a 0.06 square degrees area and with a spatial resolution of around 0.4 and 0.65 pc at the distance of the targets using the 30 m telescope of the Institut de Radioastronomie Millimétrique (IRAM) to investigate the environmental dependence of the dense gas fraction. The N2H+(1 − 0) transition, an excellent tracer of the dense gas, was detected in parsec-scale, elliptical clumps and with a filling factor of around 8.5 per cent in our maps. The N2H+-emitting areas appear to have higher dense gas fraction (e.g. the ratio of N2H+ and 13CO emission) in the interarm than in the arm which is opposite to the behaviour found by previous studies, using dust emission rather than N2H+ as a tracer of dense gas. However, the arm filament is brighter in 13CO and the infrared emission of dust, and the dense gas fraction determined as above is governed by the 13CO brightness. We caution that measurements regarding the distribution and fraction of dense gas on these scales may be influenced by many scale- and environment-dependent factors, as well as the chemistry and excitation of the particular tracers, then consider several scenarios that can reproduce the observed effect.
Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, ...we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl–VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 × 105 molecules cm-3 from ClNO2 alone, peaking at 09:30 LT and up to 8.4 × 105 molecules cm-3 when including the supporting inorganic halogen measurements.Cl–VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.
Recent studies have recognised highly oxygenated organic molecules (HOMs) in the atmosphere as important in the formation of secondary organic aerosol (SOA). A large number of studies have focused on ...HOM formation from oxidation of biogenically emitted monoterpenes. However, HOM formation from anthropogenic vapours has so far received much less attention. Previous studies have identified the importance of aromatic volatile organic compounds (VOCs) for SOA formation. In this study, we investigated several aromatic compounds, benzene (C6H6), toluene (C7H8), and naphthalene (C10H8), for their potential to form HOMs upon reaction with hydroxyl radicals (OH). We performed flow tube experiments with all three VOCs and focused in detail on benzene HOM formation in the Jülich Plant Atmosphere Chamber (JPAC). In JPAC, we also investigated the response of HOMs to NOx and seed aerosol. Using a nitrate-based chemical ionisation mass spectrometer (CI-APi-TOF), we observed the formation of HOMs in the flow reactor oxidation of benzene from the first OH attack. However, in the oxidation of toluene and naphthalene, which were injected at lower concentrations, multi-generation OH oxidation seemed to impact the HOM composition. We tested this in more detail for the benzene system in the JPAC, which allowed for studying longer residence times. The results showed that the apparent molar benzene HOM yield under our experimental conditions varied from 4.1 % to 14.0 %, with a strong dependence on the OH concentration, indicating that the majority of observed HOMs formed through multiple OH-oxidation steps. The composition of the identified HOMs in the mass spectrum also supported this hypothesis. By injecting only phenol into the chamber, we found that phenol oxidation cannot be solely responsible for the observed HOMs in benzene experiments. When NOx was added to the chamber, HOM composition changed and many oxygenated nitrogen-containing products were observed in CI-APi-TOF. Upon seed aerosol injection, the HOM loss rate was higher than predicted by irreversible condensation, suggesting that some undetected oxygenated intermediates also condensed onto seed aerosol, which is in line with the hypothesis that some of the HOMs were formed in multi-generation OH oxidation. Based on our results, we conclude that HOM yield and composition in aromatic systems strongly depend on OH and VOC concentration and more studies are needed to fully understand this effect on the formation of HOMs and, consequently, SOA. We also suggest that the dependence of HOM yield on chamber conditions may explain part of the variability in SOA yields reported in the literature and strongly advise monitoring HOMs in future SOA studies.
Background and purpose:
5‐HT is a vasoconstrictor exhibiting enhanced effects in systemic arteries from subjects with cardiovascular disease. The effect of endogenous 5‐HT on arteries is ...controversial, because the concentration of free circulating 5‐HT is low and a 5‐hydroxytryptaminergic system has not been identified in peripheral arteries. We hypothesized that a local 5‐hydroxytryptaminergic system (including 5‐HT synthesis, metabolism, uptake and release) with physiological function exists in peripheral arteries.
Experimental approach:
The presence of key components of a 5‐hydroxytryptaminergic system in rat aorta and superior mesenteric artery was examined using western blot analyses, immunohistochemistry and immunocytochemistry. The function of the rate‐limiting enzyme in 5‐HT biosynthesis, tryptophan hydroxylase (TPH), and 5‐HT transporter was tested by measuring enzyme activity and 5‐HT uptake, respectively. Isometric contraction of arterial strips was used to demonstrate the function of released endogenous 5‐HT in arterial tissues.
Key results:
mRNA for TPH‐1 was present in arteries, with low levels of TPH protein and TPH activity. Expression and function of MAO A (5‐HT metabolizing enzyme) was supported by immunohistochemistry, western analyses and the elevation of concentrations of 5‐hydroxyindoleacetic acid (5‐HT metabolite) after exposure to exogenous 5‐HT. The 5‐HT transporter was localized to the plasma membrane of freshly isolated aortic smooth muscle cells. Peripheral arteries actively took up 5‐HT in a time‐dependent and 5‐HT transporter‐dependent manner. The 5‐HT transporter substrate, (+)‐fenfluramine, released endogenous 5‐HT from peripheral arteries, which potentiated noradrenaline‐induced arterial contraction.
Conclusions and implications:
This study revealed the existence of a local 5‐hydroxytryptaminergic system in peripheral arteries.
British Journal of Pharmacology (2008) 154, 663–674; doi:10.1038/bjp.2008.111; published online 14 April 2008
Aromatic volatile organic compounds (VOCs) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. ...Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas- and particle-phase ions measured by online mass spectrometry during the hydroxyl radical oxidation of substituted C9-aromatic isomers (1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, propylbenzene and isopropylbenzene) and a substituted polyaromatic hydrocarbon (1-methylnaphthalene) under low- and medium-NOx conditions. A time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) with iodide–anion ionisation was used with a filter inlet for gases and aerosols (FIGAERO) for the detection of products in the particle phase, while a Vocus proton-transfer-reaction mass spectrometer (Vocus-PTR-MS) was used for the detection of products in the gas phase. The signal of product ions observed in the mass spectra were compared for the different precursors and experimental conditions. The majority of mass spectral product signal in both the gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas- and particle-phase composition are distinct from one another. Ions corresponding to products contained in the near-explicit gas phase Master Chemical Mechanism (MCM version 3.3.1) are utilised as a benchmark of current scientific understanding, and a comparison of these with observations shows that the MCM is missing a range of highly oxidised products from its mechanism. In the particle phase, the bulk of the product signal from all precursors comes from ring scission ions, a large proportion of which are more oxidised than previously reported and have undergone further oxidation to form highly oxygenated organic molecules (HOMs). Under the perturbation of OH oxidation with increased NOx, the contribution of HOM-ion signals to the particle-phase signal remains elevated for more substituted aromatic precursors. Up to 43 % of product signal comes from ring-retaining ions including HOMs; this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.
Protease-activated receptor 4 (PAR4) is a G-protein coupled receptor that is expressed on human platelets and activated by the coagulation enzyme thrombin. PAR4 plays a key role in blood coagulation, ...and its importance in pathological thrombosis has been increasingly recognized in recent years. Herein, we describe the optimization of a series of imidazothiadiazole PAR4 antagonists to a first-in-class clinical candidate, BMS-986120 (43), and a backup clinical candidate, BMS-986141 (49). Both compounds demonstrated excellent antithrombotic efficacy and minimal bleeding time prolongation in monkey models relative to the clinically important antiplatelet agent clopidogrel and provide a potential opportunity to improve the standard of care in the treatment of arterial thrombosis.
Every year, from December to April, anthropogenic haze spreads over most of the North Indian Ocean, and South and Southeast Asia. The Indian Ocean Experiment (INDOEX) documented this Indo‐Asian haze ...at scales ranging from individual particles to its contribution to the regional climate forcing. This study integrates the multiplatform observations (satellites, aircraft, ships, surface stations, and balloons) with one‐ and four‐dimensional models to derive the regional aerosol forcing resulting from the direct, the semidirect and the two indirect effects. The haze particles consisted of several inorganic and carbonaceous species, including absorbing black carbon clusters, fly ash, and mineral dust. The most striking result was the large loading of aerosols over most of the South Asian region and the North Indian Ocean. The January to March 1999 visible optical depths were about 0.5 over most of the continent and reached values as large as 0.2 over the equatorial Indian ocean due to long‐range transport. The aerosol layer extended as high as 3 km. Black carbon contributed about 14% to the fine particle mass and 11% to the visible optical depth. The single‐scattering albedo estimated by several independent methods was consistently around 0.9 both inland and over the open ocean. Anthropogenic sources contributed as much as 80% (±10%) to the aerosol loading and the optical depth. The in situ data, which clearly support the existence of the first indirect effect (increased aerosol concentration producing more cloud drops with smaller effective radii), are used to develop a composite indirect effect scheme. The Indo‐Asian aerosols impact the radiative forcing through a complex set of heating (positive forcing) and cooling (negative forcing) processes. Clouds and black carbon emerge as the major players. The dominant factor, however, is the large negative forcing (‐20±4 W m−2) at the surface and the comparably large atmospheric heating. Regionally, the absorbing haze decreased the surface solar radiation by an amount comparable to 50% of the total ocean heat flux and nearly doubled the lower tropospheric solar heating. We demonstrate with a general circulation model how this additional heating significantly perturbs the tropical rainfall patterns and the hydrological cycle with implications to global climate.
Aromatic hydrocarbons are a class of volatile organic compounds associated with anthropogenic activity and make up a significant fraction of urban volatile organic compound (VOC) emissions that ...contribute to the formation of secondary organic aerosol (SOA). Benzene is one of the most abundant species emitted from vehicles, biomass burning and industry. An iodide time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) and nitrate ToF-CIMS were deployed at the Jülich Plant Atmosphere Chamber as part of a series of experiments examining benzene oxidation by OH under high- and low-NOx conditions, where a range of organic oxidation products were detected. The nitrate scheme detects many oxidation products with high masses, ranging from intermediate volatile organic compounds (IVOCs) to extremely low volatile organic compounds (ELVOCs), including C12 dimers. In comparison, very few species with C≥6 and O≥8 were detected with the iodide scheme, which detected many more IVOCs and semi-volatile organic compounds (SVOCs) but very few ELVOCs and low volatile organic compounds (LVOCs). A total of 132 and 195 CHO and CHON oxidation products are detected by the iodide ToF-CIMS in the low- and high-NOx experiments respectively. Ring-breaking products make up the dominant fraction of detected signal and 21 and 26 of the products listed in the Master Chemical Mechanism (MCM) were detected. The time series of highly oxidised (O≥6) and ring-retaining oxidation products (C6 and double-bond equivalent = 4) equilibrate quickly, characterised by a square form profile, compared to MCM and ring-breaking products which increase throughout oxidation, exhibiting sawtooth profiles. Under low-NOx conditions, all CHO formulae attributed to radical termination reactions of first-generation benzene products, and first-generation auto-oxidation products are observed. Several N-containing species that are either first-generation benzene products or first-generation auto-oxidation products are also observed under high-NOx conditions. Hierarchical cluster analysis finds four clusters, of which two describe photo-oxidation. Cluster 2 shows a negative dependency on the NO2/NOx ratio, indicating it is sensitive to NO concentration and thus likely to contain NO addition products and alkoxy-derived termination products. This cluster has the highest average carbon oxidation state (OSC‾) and the lowest average carbon number. Where nitrogen is present in a cluster member of cluster 2, the oxygen number is even, as expected for alkoxy-derived products. In contrast, cluster 1 shows no dependency on the NO2/NOx ratio and so is likely to contain more NO2 addition and peroxy-derived termination products. This cluster contains fewer fragmented species, as the average carbon number is higher and OSC‾ lower than cluster 2, and more species with an odd number of oxygen atoms. This suggests that clustering of time series which have features pertaining to distinct chemical regimes, for example, NO2/NOx perturbations, coupled with a priori knowledge, can provide insight into identification of potential functionality.
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