Replacement of Toxic Hydrazines in Satellite Propulsion with Greener Dinitramide-Based Energetic Ionic Liquid Candidates.

Satellite propulsion uses liquid mono or bi-propellants composed of a hydrazine in combination with a strong oxidant. However, hydrazines are highly toxic. As a result, many research efforts for more environmentally compatible propellants have been made over the past decade. In this study we evidence green formulations that retain high propulsive performances. They are based on the dinitramide anion. From an initial library of 37 ammonium dinitramides 3 best candidates were selected after evaluation of their potential syntheses, calculated theoretical performances, experimental synthesis optimizations and decomposition temperatures. These three salts were then formulated to obtain acceptable sensitivities and melting points, which eventually led to only one formulation being retained: a 40 : 60 mixture of dimethylammonium dinitramide and ammonium dinitramide phlegmatized by 10 % of glycerol.

Permafrost thaw causes large carbon loss in boreal peatlands while changes to peat quality are limited.

Rapid, ongoing permafrost thaw of peatlands in the discontinuous permafrost zone is exposing a globally significant store of soil carbon (C) to microbial processes. Mineralization and release of this peat C to the atmosphere as greenhouse gases is a potentially important feedback to climate change. Here we investigated the effects of permafrost thaw on peat C at a peatland complex in western Canada. We collected 15 complete peat cores (between 2.7 and 4.5 m deep) along four chronosequences, from elevated permafrost peat plateaus to saturated thermokarst bogs that thawed up to 600 years ago. The peat cores were analysed for peat C storage and peat quality, as indicated by decomposition proxies (FTIR and C/N ratios) and potential decomposability using a 200-day aerobic laboratory incubation. Our results suggest net C loss following thaw, with average total peat C stocks decreasing by ~19.3 ± 7.2 kg C m-2 over <600 years (~13% loss). Average post-thaw accumulation of new peat at the surface over the same period was ~13.1 ± 2.5 kg C m-2 . We estimate ~19% (±5.8%) of deep peat (>40 cm below surface) C is lost following thaw (average 26 ± 7.9 kg C m-2 over <600 years). Our FTIR analysis shows peat below the thaw transition in thermokarst bogs is slightly more decomposed than peat of a similar type and age in permafrost plateaus, but we found no significant changes to the quality or lability of deeper peat across the chronosequences. Our incubation results also showed no increase in C mineralization of deep peat across the chronosequences. While these limited changes in peat quality in deeper peat following permafrost thaw highlight uncertainty in the exact mechanisms and processes for C loss, our analysis of peat C stocks shows large C losses following permafrost thaw in peatlands in western Canada.

Diet and landscape characteristics drive spatial patterns of mercury accumulation in a high-latitude terrestrial carnivore.

Limited information exists on mercury concentrations and environmental drivers of mercury bioaccumulation in high latitude terrestrial carnivores. Spatial patterns of mercury concentrations in wolverine (Gulo gulo, n = 419) were assessed across a 1,600,000 km2 study area in relation to landscape, climate, diet and biological factors in Arctic and boreal biomes of western Canada. Hydrogen stable isotope ratios were measured in wolverine hair from a subset of 80 animals to assess the spatial scale for characterizing environmental conditions of their habitat. Habitat characteristics were determined using GIS methods and raster datasets at two scales, the collection location point and a 150 km radius buffer, which was selected based on results of a correlation analysis between hydrogen stable isotopes in precipitation and wolverine hair. Total mercury concentrations in wolverine muscle ranged >2 orders of magnitude from 0.01 to 5.72 µg/g dry weight and varied geographically, with the highest concentrations in the Northwest Territories followed by Nunavut and Yukon. Regression models at both spatial scales indicated diet (based on nitrogen stable isotope ratios) was the strongest explanatory variable of mercury concentrations in wolverine, with smaller though statistically significant contributions from landscape variables (soil organic carbon, percent cover of wet area, percent cover of perennial snow-ice) and distance to the Arctic Ocean coast. The carbon and nitrogen stable isotope ratios of wolverine muscle suggested greater mercury bioaccumulation could be associated with feeding on marine biota in coastal habitats. Landscape variables identified in the modelling may reflect habitat conditions which support enhanced methylmercury transfer to terrestrial biota. Spatially-explicit estimates of wet atmospheric deposition were positively correlated with wolverine mercury concentrations but this variable was not selected in the final regression models. These landscape patterns provide a basis for further research on underlying processes enhancing methylmercury uptake in high latitude terrestrial food webs.

Remobilization of legacy arsenic from sediment in a large subarctic waterbody impacted by gold mining.

Arsenic contamination from mining poses an environmental challenge due to the mobility of this redox-sensitive element. This study evaluated arsenic mobility in sediments of Yellowknife Bay (Canada), a large subarctic water body impacted by gold mining during the 20th century. Short-term measurements of arsenic flux from sediment, arsenic profiling of the water column and sediment porewater, and mass balance modelling were conducted to assess the importance of sediment as an arsenic source. Sediment arsenic fluxes were highly variable throughout Yellowknife Bay and ranged from - 65-1520 µg m-2 day-1. Elevated fluxes measured near the mine site were among the highest published for well-oxygenated lakes. Redox boundaries were typically 2-3 cm below the sediment surface as indicated by porewater profiles of iron, manganese, and arsenic, with arsenic maxima of 65-3220 µg L-1 predominately as arsenite. Sediment arsenic flux was positively related to its solid-phase concentration. Modelling indicated sediment was a principal source of arsenic to the water column. Adsorption and precipitation processes in the oxidizing environment of near-surface sediments did not effectively attenuate arsenic remobilized from contaminated sediments. Internal recycling of legacy arsenic between sediment and surface water will impede a return to background conditions in Yellowknife Bay for decades.

An Inflamed and Infected Reconstructed Human Epidermis to Study Atopic Dermatitis and Skin Care Ingredients.

Atopic dermatitis (AD), the most common inflammatory skin disorder, is a multifactorial disease characterized by a genetic predisposition, epidermal barrier disruption, a strong T helper (Th) type 2 immune reaction to environmental antigens and an altered cutaneous microbiome. Microbial dysbiosis characterized by the prevalence of Staphylococcus aureus (S. aureus) has been shown to exacerbate AD. In recent years, in vitro models of AD have been developed, but none of them reproduce all of the pathophysiological features. To better mimic AD, we developed reconstructed human epidermis (RHE) exposed to a Th2 pro-inflammatory cytokine cocktail and S. aureus. This model well reproduced some of the vicious loops involved in AD, with alterations at the physical, microbial and immune levels. Our results strongly suggest that S. aureus acquired a higher virulence potential when the epidermis was challenged with inflammatory cytokines, thus later contributing to the chronic inflammatory status. Furthermore, a topical application of a Castanea sativa extract was shown to prevent the apparition of the AD-like phenotype. It increased filaggrin, claudin-1 and loricrin expressions and controlled S. aureus by impairing its biofilm formation, enzymatic activities and inflammatory potential.

Recent climate change has driven divergent hydrological shifts in high-latitude peatlands.

High-latitude peatlands are changing rapidly in response to climate change, including permafrost thaw. Here, we reconstruct hydrological conditions since the seventeenth century using testate amoeba data from 103 high-latitude peat archives. We show that 54% of the peatlands have been drying and 32% have been wetting over this period, illustrating the complex ecohydrological dynamics of high latitude peatlands and their highly uncertain responses to a warming climate.

Wildfires trigger multi-decadal increases in sedimentation rate and metal loading to subarctic montane lakes.

We evaluated how two large wildfires affected the sedimentation rate and accumulation of lead (Pb), mercury (Hg), and cadmium (Cd) in sediment of four subarctic montane lakes in the Yukon, Canada. The wildfires occurred 60 and 20 years (1958, 1998) before sediment collection in 2018. Site-specific fire exposure was inferred from the charcoal accumulation histories in the lake sediments and the burned catchment area was determined from historical fire maps. The two major wildfires caused a two to five-fold increase in sedimentation rates and a two to eight-fold increase in sediment metal accumulation rates in Little Fox Lake. The mass accumulation rates of metals in Little Fox Lake sediment increased by a maximum of 2.7-4.7 mg Pb m-2 yr-1, 19-29 µg Hg m-2 yr-1 and 37-114 µg Cd m-2 yr-1 following wildfires. Modelling using elemental ratios of lithogenic sources suggested a large proportion of the Pb and Hg accumulating in post-fire sediment was from remobilized legacy anthropogenic pollution. In contrast, Cd fluxes were consistent with variation in catchment weathering. Impacts of wildfires were visible but more muted in the sediment of Little Braeburn Lake, whereas Fox Lake and Grayling Lake sediments showed little to no wildfire impact and served as a reference for external (long-range) metal deposition. Major changes to lake sediment geochemistry in Little Fox Lake were caused by the lack of vegetation and soil recovery in the catchment following the severe 1998 fire. Wildfire impacts were persistent in the lake more than 20 years after the last fire, with no sign of a return to pre-fire Pb, Hg, and Cd accumulation rates. This study shows that wildfires in northern montane catchments can significantly increase the rate of metal accumulation in affected lakes, thereby impeding recovery from reductions in anthropogenic air emissions of these metals.

Climate change and mercury in the Arctic: Abiotic interactions.

Dramatic environmental shifts are occuring throughout the Arctic from climate change, with consequences for the cycling of mercury (Hg). This review summarizes the latest science on how climate change is influencing Hg transport and biogeochemical cycling in Arctic terrestrial, freshwater and marine ecosystems. As environmental changes in the Arctic continue to accelerate, a clearer picture is emerging of the profound shifts in the climate and cryosphere, and their connections to Hg cycling. Modeling results suggest climate influences seasonal and interannual variability of atmospheric Hg deposition. The clearest evidence of current climate change effects is for Hg transport from terrestrial catchments, where widespread permafrost thaw, glacier melt and coastal erosion are increasing the export of Hg to downstream environments. Recent estimates suggest Arctic permafrost is a large global reservoir of Hg, which is vulnerable to degradation with climate warming, although the fate of permafrost soil Hg is unclear. The increasing development of thermokarst features, the formation and expansion of thaw lakes, and increased soil erosion in terrestrial landscapes are increasing river transport of particulate-bound Hg and altering conditions for aquatic Hg transformations. Greater organic matter transport may also be influencing the downstream transport and fate of Hg. More severe and frequent wildfires within the Arctic and across boreal regions may be contributing to the atmospheric pool of Hg. Climate change influences on Hg biogeochemical cycling remain poorly understood. Seasonal evasion and retention of inorganic Hg may be altered by reduced sea-ice cover and higher chloride content in snow. Experimental evidence indicates warmer temperatures enhance methylmercury production in ocean and lake sediments as well as in tundra soils. Improved geographic coverage of measurements and modeling approaches are needed to better evaluate net effects of climate change and long-term implications for Hg contamination in the Arctic.

Lead contamination from gold mining in Yellowknife Bay (Northwest Territories), reconstructed using stable lead isotopes.

The contributions of contaminant sources are difficult to resolve in the sediment record using concentration gradients and flux reconstruction alone. In this study, we demonstrate that source partitioning using lead isotopes provide complementary and unique information to concentration gradients to evaluate point-source releases, transport, and recovery of metal mining pollution in the environment. We analyzed eight sediment cores, collected within 24 km of two gold mines, for Pb stable isotopes, Pb concentration, and sediment chronology. Stable Pb isotope ratios (206Pb/207Pb, 208Pb/204Pb) of mining ore were different from those of background (pre-disturbance) sediment, allowing the use of a quantitative mixing model. As previously reported for some Arctic lakes, Pb isotope ratios indicated negligible aerosol inputs to sediment from regional or long-range pollution sources, possibly related to low annual precipitation. Maximum recorded Pb flux at each site reached up to 63 mg m-2 yr-1 in the period corresponding to early years of mining when pollution mitigation measures were at a minimum (1950s-1960s). The maximum contribution of mining-derived Pb to these fluxes declined with distance from the mines from 92 ± 8% to 8 ± 4% at the farthest site. Mining-derived Pb was still present at the sediment surface within 9 km of Giant Mine more than ten years after mine closure (5-26 km, 95% confidence interval) and model estimates suggest it could be present for another ∼50-100 years. These results highlight the persistence of Pb pollution in freshwater sediment and the usefulness of Pb stable isotopes to quantify spatial and temporal trends of contamination from mining pollution, particularly as concentrations approach background.

No plastics detected in seal (Phocidae) stomachs harvested in the eastern Canadian Arctic.

Through collaboration with Inuit hunters, we examined the stomach contents of 142 seals (ringed seals [Phoca hispida; n = 135], bearded seals [Erignathus barbatus; n = 6], and one harbour seal [Phoca vitualina; n = 1]) hunted between 2007 and 2019 from communities around Nunavut to assess whether seals in the eastern Canadian Arctic ingest and retain plastics in their stomachs. The seals in this study ranged from juveniles to adults of up to 30 years of age, and 55% of the seals were males. We found no evidence of plastic ingestion in any of the seals suggesting that seals in Nunavut are not accumulating plastics (>425 µm) in their stomachs. These data provide important baseline information for future plastic pollution monitoring programs in the Arctic.

Genomic, proteomic, and transcriptomic analysis of virulent and avirulent Rickettsia prowazekii reveals its adaptive mutation capabilities.

Rickettsia prowazekii, the agent of epidemic typhus, is an obligate intracellular bacterium that is transmitted to human beings by the body louse. Several strains that differ considerably in virulence are recognized, but the genetic basis for these variations has remained unknown since the initial description of the avirulent vaccine strain nearly 70 yr ago. We use a recently developed murine model of epidemic typhus and transcriptomic, proteomic, and genetic techniques to identify the factors associated with virulence. We identified four phenotypes of R. prowazekii that differed in virulence, associated with the up-regulation of antiapoptotic genes or the interferon I pathway in the host cells. Transcriptional and proteomic analyses of R. prowazekii surface protein expression and protein methylation varied with virulence. By sequencing a virulent strain and using comparative genomics, we found hotspots of mutations in homopolymeric tracts of poly(A) and poly(T) in eight genes in an avirulent strain that split and inactivated these genes. These included recO, putative methyltransferase, and exported protein. Passage of the avirulent Madrid E strain in cells or in experimental animals was associated with a cascade of gene reactivations, beginning with recO, that restored the virulent phenotype. An area of genomic plasticity appears to determine virulence in R. prowazekii and represents an example of adaptive mutation for this pathogen.

Specific recognition of the major capsid protein of Acanthamoeba polyphaga mimivirus by sera of patients infected by Francisella tularensis.

Francisella tularensis, a Gram-negative cocobacillus responsible for tularemia, especially severe pneumonia, is a facultative intracellular bacterium classified as a biological agent of category A. Acanthamoeba polyphaga mimivirus (APM) is a recently discovered giant virus suspected to be an agent of both community- and hospital-acquired pneumonia. During specificity testing of antibody to APM detection, it was observed that nearly all patients infected by F. tularensis had elevated antibody titers to APM. In the present study, we investigated this cross-reactivity by immunoproteomics. Apart from the detection of antibodies reactive to new immunoreactive proteins in patients infected by F. tularensis, we showed that the sera of those patients recognize specifically two proteins of APM: the capsid protein and another protein of unknown function. No common protein motif can be detected in silico based on genome analysis of the involved protein. Furthermore, this cross-reactivity was confirmed with the recombinant capsid protein expressed in Escherichia coli. This emphasizes the pitfalls of a serological diagnosis of pneumonia.

Quantitative analysis of enhanced light irradiance in waveguide-based fluorescent microarrays.

Probing microarray assays in the presence of a hybridization mix retrieves precious information on hybridization kinetics. However, in common detection schemes, useful surface signals compete with the high supernatant background from labelled targets in the mix. A known solution consists in exciting specifically the microarray surface with evanescent fields. Configurations using planar optical waveguides to produce such fields are shown here to present also a dramatic excitation irradiance enhancement at the guide/surrounding matter interface. We compare theoretically and experimentally a guided excitation with a classical external excitation. A full electromagnetic analysis predicts an irradiance increase higher than 10(4) for adequately tailored waveguides. We deposited high-index TiO(2) sol-gel waveguides on glass substrates according to best simulations. Quantitative enhancement analysis exploiting actual biological fluorescent spots perfectly confirms the irradiance amplification effect of a thin waveguide. The impact of amplification on the design of biochip readers is discussed since it leaves ample margin for simple and low-cost light couplers, advantageous in affordable readers and sensor systems.

First characterisation of the active oligomer form of sulfur oxygenase reductase from the bacterium Aquifex aeolicus.

Sulfur oxygenase reductase (SOR) enzyme is responsible for the initial oxidation step of elemental sulfur in archaea. Curiously, Aquifex aeolicus, a hyperthermophilic, chemolithoautotrophic and microaerophilic bacterium, has the SOR-encoding gene in its genome. We showed, for the first time the presence of the SOR enzyme in A. aeolicus, its gene was cloned and recombinantly expressed in Escherichia coli and the protein was purified and characterised. It is a 16 homo-oligomer of approximately 600 kDa that contains iron atoms indispensable for the enzyme activity. The optimal temperature of SOR activity is 80 degrees C and it is inactive at 20 degrees C. Studies of the factors involved in getting the fully active molecule at high temperature show clearly that (1) incubation at high temperature induces more homogeneous form of the enzyme, (2) conformational changes observed at high temperature are required to get the fully active molecule and (3) acquisition of an active conformation induced by the temperature seems to be more important than the subunit number. Differences between A. aeolicus SOR and the archaea SORs are described.

Exaggerated hypotensive effect of vascular endothelial growth factor in spontaneously hypertensive rats.

Vascular endothelial growth factor (VEGF) induces hypotension in normotensive subjects, which is considered to be a major side effect for treatment of ischemic diseases. However, the hypotensive effect of VEGF has not been investigated in the setting of hypertension. This study determined effects of VEGF on hemodynamics, pharmacokinetics, and release of NO and prostaglandin I2 (PGI2) in vivo and on vasorelaxation of mesentery artery rings in vitro in spontaneously hypertensive rats (SHR) compared with Wistar-Kyoto rats (WKY). Intravenous infusion of VEGF for 2 hours produced a dose-related decrease in arterial pressure, which was enhanced in conscious SHR compared with WKY (P<0.01), and an increase in heart rate in WKY but not in SHR. In response to similar doses of VEGF, compared with WKY, SHR had a higher plasma VEGF level and lower VEGF clearance (P<0.01). Circulating NO and PGI2 levels after VEGF administration were not increased in SHR versus WKY, and VEGF-induced vasorelaxation was blunted in SHR versus WKY in vitro, suggesting endothelial dysfunction in SHR. One-week VEGF infusion also caused greater hypotension (P<0.05) in the absence of tachycardia in SHR compared with WKY controls. Thus, despite blunted vasorelaxation in vitro because of endothelial dysfunction, SHR exhibited exaggerated hypotension without tachycardia in response to VEGF, which was independent of NO and PGI2. The exaggerated hypotensive response to VEGF in SHR may be owing to impaired baroreflex function and reduced VEGF clearance. The data may also suggest that more caution should be taken when VEGF is administered in patients with hypertension.