Coccolithophore export fluxes were investigated via the analysis of sinking matter, obtained from Eastern Mediterranean time-series sediment traps moored in three open sites of the north-eastern ...Mediterranean Sea located in the Athos Basin of North Aegean (M2 site), Cretan Sea of South Aegean (M3 site) and at Ionian Sea (Nestor site). The aim of our study was to determine the spatial, temporal and seasonal variability in coccolithophore fluxes, as well as to estimate coccolith biogenic carbonate contribution to the sedimentation process. Data from an additional time-series sediment trap located in the southwestern Black Sea were also considered for the comparison of the oligotrophic Eastern Mediterranean setting with the eutrophic Black Sea. Coccolithophore fluxes revealed a highly seasonal pattern during February–March in the North Aegean (peak in late February 2015: 85.6 x 105 coccospheres m−2 day−1; 27.9 x 108 coccoliths m−2 day−1), during March–May in the Cretan Sea (peak in late March 2015: 33.7 x 105 coccospheres m−2 day−1; 19.5 x 108 coccoliths m−2 day−1) and during February–March and May–June in the Ionian Sea (peak in late May 2012: 14.3 x 105 coccospheres m−2 day−1; 1.53 x 108 coccoliths m−2 day−1). The recorded maxima coincide with low sea surface temperatures, increased precipitation and high PIC fluxes. Coccosphere fluxes were dominated by Emiliania huxleyi comprising ~70% of the total abundance, in the North Aegean and ~50% in the Cretan and Ionian Seas. Syracosphaera pulchra was also prominent in the study sites, where its abundance reached 14% in the North Aegean and ~10% in the Cretan and Ionian Seas respectively. Florisphaera profunda represented one of the major taxa in the coccolith fluxes of all three Eastern Mediterranean sites (~25% in North Aegean, ~20% in Cretan and Ionian Seas), while Algirosphaera robusta and Umbilicosphaera sibogae were the most abundant among the minor taxa. The North Aegean Sea exhibited a considerably higher coccolith flux when compared to other sediment traps due to the prominent seasonal peak of E. huxleyi during winter (February–March) (>95% of the total abundance). In contrast to the Eastern Mediterranean sediment traps, the time-series data from the Black Sea showed presence of monospecific E. huxleyi assemblage increasing its abundance during late September–November (max 320 x 105 coccospheres m−2 day−1; at least 7.79 x 108 coccoliths m−2 day−1, coccolith flux derived only from coccospheres converted to coccoliths). In the Eastern Mediterranean, biogenic carbonate fluxes followed the general pattern of the total mass flux in all investigated areas, with the Black Sea coccolithophore CaCO3 flux being the lowest due to low the E. huxleyi coccolith mass. Overall, in the North Aegean Sea, coccolithophore fluxes are strongly dependent on surface waters nutrients enrichment due to winter vertical water column mixing, riverine inputs and Black Sea water inflows, while the fertilization and/or formation of fast-sinking aggregates due to episodic dust input event are affecting the coccolithophore fluxes in the Cretan and Ionian Seas. The intercomparison of the coccolith export fluxes in the studied NE-SW mooring transects implies a north-south and east-west decreasing pattern, depending on the variable oceanographic regimes and the associated environmental factors controlling the investigated areas.
Perovskite solar cells have shown a rapid increase of performance and overcome the threshold of 20% power conversion efficiency (PCE). The main issues hampering commercialization are the lack of ...deposition methods for large areas, missing long-term device stability and the toxicity of the commonly used Pb-based compounds. In this work, we present a novel chemical vapor deposition (CVD) process for Pb-free air-stable methylammonium bismuth iodide (MBI) layers, which enables large-area production employing close-coupled showerhead technology. We demonstrate the influence of precursor rates on the layer morphology as well as on the optical and crystallographic properties. The impact of substrate temperature and layer thickness on the morphology of MBI crystallites is discussed. We obtain smooth layers with lateral crystallite sizes up to 500 nm. Moreover, the application of CVD-processed MBI layers in non-inverted perovskite solar cells is presented.
Long-term (1999 to 2013) data from the Southeastern Aerosol Research and Characterization (SEARCH) network are used to show that anthropogenic emission reductions led to important decreases in ...fine-particle organic aerosol (OA) concentrations in the southeastern US On average, 45 % (range 25 to 63 %) of the 1999 to 2013 mean organic carbon (OC) concentrations are attributed to combustion processes, including fossil fuel use and biomass burning, through associations of measured OC with combustion products such as elemental carbon (EC), carbon monoxide (CO), and nitrogen oxides (NOx). The 2013 mean combustion-derived OC concentrations were 0.5 to 1.4 µg m−3 at the five sites operating in that year. Mean annual combustion-derived OC concentrations declined from 3.8 ± 0.2 µg m−3 (68 % of total OC) to 1.4 ± 0.1 µg m−3 (60 % of total OC) between 1999 and 2013 at the urban Atlanta, Georgia, site (JST) and from 2.9 ± 0.4 µg m−3 (39 % of total OC) to 0.7 ± 0.1 µg m−3 (30 % of total OC) between 2001 and 2013 at the urban Birmingham, Alabama (BHM), site. The urban OC declines coincide with reductions of motor vehicle emissions between 2006 and 2010, which may have decreased mean OC concentrations at the urban SEARCH sites by > 2 µg m−3. BHM additionally exhibits a decline in OC associated with SO2 from 0.4 ± 0.04 µg m−3 in 2001 to 0.2 ± 0.03 µg m−3 in 2013, interpreted as the result of reduced emissions from industrial sources within the city. Analyses using non-soil potassium as a biomass burning tracer indicate that biomass burning OC occurs throughout the year at all sites. All eight SEARCH sites show an association of OC with sulfate (SO4) ranging from 0.3 to 1.0 µg m−3 on average, representing ∼ 25 % of the 1999 to 2013 mean OC concentrations. Because the mass of OC identified with SO4 averages 20 to 30 % of the SO4 concentrations, the mean SO4-associated OC declined by ∼ 0.5 to 1 µg m−3 as SO4 concentrations decreased throughout the SEARCH region. The 2013 mean SO4 concentrations of 1.7 to 2.0 µg m−3 imply that future decreases in mean SO4-associated OC concentrations would not exceed ∼ 0.3 to 0.5 µg m−3. Seasonal OC concentrations, largely identified with ozone (O3), vary from 0.3 to 1.4 µg m−3 ( ∼ 20 % of the total OC concentrations).
We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the ...summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1-C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission sources of amines.
Although ocean acidification is expected to impact (bio) calcification by decreasing the seawater carbonate ion concentration, CO32−, there is evidence of nonuniform response of marine calcifying ...plankton to low seawater CO32−. This raises questions about the role of environmental factors other than acidification and about the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including seawater temperature, nutrient (nitrate and phosphate) availability, and carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi, the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying above the modern lysocline (with the exception of eight samples that are located at or below the lysocline). The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of seawater nutrient availability (phosphate and nitrate) and carbonate chemistry (pH and pCO2) in determining coccolith mass by affecting primary calcification and/or the geographic distribution of E. huxleyi morphotypes. Our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high-CO2 world and improve interpretation of paleorecords.
Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric ...O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/-3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.
Abstract
A large repulsion between particles in a quantum system can lead to their localization, an effect responsible for the Mott insulator phases in strongly correlated materials. In a system with ...multiple orbitals, an orbital-selective Mott insulator can form, where electrons in some orbitals are predicted to localize while others remain itinerant. Here we demonstrate a more general version of this phenomenon by observing flavour-selective localization in an atom-based quantum simulator. Our experiment realizes Fermi–Hubbard models with an SU(3) symmetry that can be broken using a tunable coupling between flavours. We observe an enhancement of the localization associated with a selective Mott transition and the emergence of flavour-dependent correlations. Our realization of flavour-selective Mott physics demonstrates the potential of cold atoms to simulate interacting multicomponent materials such as superconductors and topological insulators.
Measurements of OH reactivity, the inverse lifetime of the OH radical, can provide a top–down estimate of the total amount of reactive carbon in an air mass. Using a comprehensive measurement suite, ...we examine the measured and modeled OH reactivity above an isoprene-dominated forest in the southeast United States during the 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign. Measured and modeled species account for the vast majority of average daytime reactivity (80–95 %) and a smaller portion of nighttime and early morning reactivity (68–80 %). The largest contribution to total reactivity consistently comes from primary biogenic emissions, with isoprene contributing ∼ 60 % in the afternoon, and ∼ 30–40 % at night and monoterpenes contributing ∼ 15–25 % at night. By comparing total reactivity to the reactivity stemming from isoprene alone, we find that ∼ 20 % of the discrepancy is temporally related to isoprene reactivity, and an additional constant ∼ 1 s−1 offset accounts for the remaining portion. The model typically overestimates measured OVOC concentrations, indicating that unmeasured oxidation products are unlikely to influence measured OH reactivity. Instead, we suggest that unmeasured primary emissions may influence the OH reactivity at this site.
Mutations in the mtDNA have been found to fulfill all of the criteria expected for pathogenic mutations causing prostate cancer. Focusing on the cytochrome oxidase subunit I (COI) gene, we found that ...11-12% of all prostate cancer patients harbored COI mutations that altered conserved amino acids (mean conservation index = 83%), whereas <2% of no-cancer controls and 7.8% of the general population had COI mutations, the latter altering less conserved amino acids (conservation index = 71%). Four conserved prostate cancer COI mutations were found in multiple independent patients on different mtDNA backgrounds. Three other tumors contained heteroplasmic COI mutations, one of which created a stop codon. This latter tumor also contained a germ-line ATP6 mutation. Thus, both germ-line and somatic mtDNA mutations contribute to prostate cancer. Many tumors have been found to produce increased reactive oxygen species (ROS), and mtDNA mutations that inhibit oxidative phosphorylation can increase ROS production and thus contribute to tumorigenicity. To determine whether mutant tumors had increased ROS and tumor growth rates, we introduced the pathogenic mtDNA ATP6 T8993G mutation into the PC3 prostate cancer cell line through cybrid transfer and tested for tumor growth in nude mice. The resulting mutant (T8993G) cybrids were found to generate tumors that were 7 times larger than the wild-type (T8993T) cybrids, whereas the wild-type cybrids barely grew in the mice. The mutant tumors also generated significantly more ROS. Therefore, mtDNA mutations do play an important role in the etiology of prostate cancer.
Introduction
Haemophilia is characterized by frequent haemarthrosis, leading to acute/chronic joint pain.
Aim
To assess self‐reported prevalence, description and management of pain in adult males ...with mild‐to‐severe haemophilia and history of joint pain/bleeding.
Methods
Participants completed a pain survey and five patient‐reported outcome instruments assessing pain, functional impairment and health‐related quality of life (HRQoL).
Results
Of 381 participants enrolled, median age was 34 years; 77% had haemophilia A, 71% had severe disease and 65% were overweight/obese. Many (56%) were not receiving routine infusions; 30% never received routine infusions. During the prior 6 months, 20% experienced acute pain, 34% chronic pain and 32% both acute/chronic pain. Subjects with both acute/chronic pain (vs. none, acute or chronic) were more likely to be depressed (30% vs. 0–15%), obese (35% vs. 20–29%) and have lower HRQoL (mean EQ‐5D visual analog scale, 69 vs. 83–86) and function (median overall Hemophilia Activities List, 60 vs. 88–99). Most common analgesics used for acute/chronic pain during the prior 6 months were acetaminophen (62%/55%) and non‐steroidal anti‐inflammatory drugs (34%/49%); most common non‐pharmacologic strategies were ice (65%/33%) and rest (51%/33%). Hydrocodone‐acetaminophen was the most common opioid for both acute/chronic pain (30%); other long‐acting opioids were infrequently used specifically for chronic but not acute pain (morphine, 7%; methadone, 6%; fentanyl patch, 2%).
Conclusion
Patients with chronic pain, particularly those with both acute/chronic pain, frequently experience psychological issues, functional disability and reduced HRQoL. Treatment strategies for acute pain (e.g. routine infusions to prevent bleeding) and for chronic pain (e.g. long‐acting opioids) may be underused.