Correlative geochemical imaging of Desmophyllum dianthus reveals biomineralisation strategy as a key coral vital effect.

The chemical and isotopic composition of stony coral skeletons form an important archive of past climate. However, these reconstructions are largely based on empirical relationships often complicated by "vital effects" arising from uncertain physiological processes of the coral holobiont. The skeletons of deep-sea corals, such as Desmophyllum dianthus, are characterised by micron-scale or larger geochemical heterogeneity associated with: (1) centres of calcification (COCs) where nucleation of new skeleton begins, and (2) fibres that thicken the skeleton. These features are difficult to sample cleanly using traditional techniques, resulting in uncertainty surrounding both the causes of geochemical differences and their influence on environmental signals. Here we combine optical, and in-situ chemical and isotopic, imaging tools across a range of spatial resolutions (~ 100 nm to 10 s of µm) in a correlative multimodal imaging (CMI) approach to isolate the microstructural geochemistry of each component. This reveals COCs are characterised by higher organic content, Mg, Li and Sr and lower U, B and δ11B compared to fibres, reflecting the contrasting biomineralisation mechanisms employed to construct each feature. CMI is rarely applied in Environmental/Earth Sciences, but here we illustrate the power of this approach to unpick the "vital effects" in D. dianthus, and by extension, other scleractinian corals.

Arctic and Antarctic forcing of ocean interior warming during the last deglaciation.

Subsurface water masses formed at high latitudes impact the latitudinal distribution of heat in the ocean. Yet uncertainty surrounding the timing of low-latitude warming during the last deglaciation (18-10 ka) means that controls on sub-surface temperature rise remain unclear. Here we present seawater temperature records on a precise common age-scale from East Equatorial Pacific (EEP), Equatorial Atlantic, and Southern Ocean intermediate waters using new Li/Mg records from cold water corals. We find coeval warming in the tropical EEP and Atlantic during Heinrich Stadial 1 (+ 6 °C) that closely resemble warming recorded in Antarctic ice cores, with more modest warming of the Southern Ocean (+ 3 °C). The magnitude and depth of low-latitude ocean warming implies that downward accumulation of heat following Atlantic Meridional Overturning Circulation (AMOC) slowdown played a key role in heating the ocean interior, with heat advection from southern-sourced intermediate waters playing an additional role.

Enhanced subglacial discharge from Antarctica during meltwater pulse 1A.

Subglacial discharge from the Antarctic Ice Sheet (AIS) likely played a crucial role in the loss of the ice sheet and the subsequent rise in sea level during the last deglaciation. However, no direct proxy is currently available to document subglacial discharge from the AIS, which leaves significant gaps in our understanding of the complex interactions between subglacial discharge and ice-sheet stability. Here we present deep-sea coral 234U/238U records from the Drake Passage in the Southern Ocean to track subglacial discharge from the AIS. Our findings reveal distinctively higher seawater 234U/238U values from 15,400 to 14,000 years ago, corresponding to the period of the highest iceberg-rafted debris flux and the occurrence of the meltwater pulse 1A event. This correlation suggests a causal link between enhanced subglacial discharge, synchronous retreat of the AIS, and the rapid rise in sea levels. The enhanced subglacial discharge and subsequent AIS retreat appear to have been preconditioned by a stronger and warmer Circumpolar Deep Water, thus underscoring the critical role of oceanic heat in driving major ice-sheet retreat.

Life on the edge-a changing genetic landscape within an iconic American pika metapopulation over the last half century.

Declines and extirpations of American pika (Ochotona princeps) populations at historically occupied sites started being documented in the literature during the early 2000s. Commensurate with global climate change, many of these losses at peripheral and lower elevation sites have been associated with changes in ambient air temperature and precipitation regimes. Here, we report on a decline in available genetic resources for an iconic American pika metapopulation, located at the southwestern edge of the species distribution in the Bodie Hills of eastern California, USA. Composed of highly fragmented habitat created by hard rock mining, the ore dumps at this site were likely colonized by pikas around the end of the 19th century from nearby natural talus outcrops. Genetic data extracted from both contemporary samples and archived natural history collections allowed us to track population and patch-level genetic diversity for Bodie pikas across three distinct sampling points during the last half- century (1948-1949, 1988-1991, 2013-2015). Reductions in within-population allelic diversity and expected heterozygosity were observed across the full time period. More extensive sampling of extant patches during the 1988-1991 and 2013-2015 periods revealed an increase in population structure and a reduction in effective population size. Furthermore, census records from the last 51 years as well as archived museum samples collected in 1947 from a nearby pika population in the Wassuk range (Nevada, USA) provide further support of the increasing isolation and genetic coalescence occurring in this region. This study highlights the importance of museum samples and long-term monitoring in contextualizing our understanding of population viability.

Reaction-Induced Metal-Metal Oxide Interactions in Pd-In2 O3 /ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol.

Ternary Pd-In2 O3 /ZrO2 catalysts exhibit technological potential for CO2 -based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd-In2 O3 /ZrO2 systems prepared by wet impregnation evolves under CO2 hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal-metal oxide interaction energetics. The proximity of InPdx alloy particles decorated by InOx layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction-induced restructuring in complex CO2 hydrogenation catalysts and offer insights into the optimal integration of acid-base and redox functions for practical implementation.

Direct Observation of Ni Nanoparticle Growth in Carbon-Supported Nickel under Carbon Dioxide Hydrogenation Atmosphere.

Understanding nanoparticle growth is crucial to increase the lifetime of supported metal catalysts. In this study, we employ in situ gas-phase transmission electron microscopy to visualize the movement and growth of ensembles of tens of nickel nanoparticles supported on carbon for CO2 hydrogenation at atmospheric pressure (H2:CO2 = 4:1) and relevant temperature (450 °C) in real time. We observe two modes of particle movement with an order of magnitude difference in velocity: fast, intermittent movement (vmax = 0.7 nm s-1) and slow, gradual movement (vaverage = 0.05 nm s-1). We visualize the two distinct particle growth mechanisms: diffusion and coalescence, and Ostwald ripening. The diffusion and coalescence mechanism dominates at small interparticle distances, whereas Ostwald ripening is driven by differences in particle size. Strikingly, we demonstrate an interplay between the two mechanisms, where first coalescence takes place, followed by fast Ostwald ripening due to the increased difference in particle size. Our direct visualization of the complex nanoparticle growth mechanisms highlights the relevance of studying nanoparticle growth in supported nanoparticle ensembles under reaction conditions and contributes to the fundamental understanding of the stability in supported metal catalysts.

Wildfire facilitates upslope advance in a shade-intolerant but not a shade-tolerant conifer.

Wildfires may facilitate climate tracking of forest species moving upslope or north in latitude. For subalpine tree species, for which higher elevation habitat is limited, accelerated replacement by lower elevation montane tree species following fire may hasten extinction risk. We used a dataset of postfire tree regeneration spanning a broad geographic range to ask whether the fire facilitated upslope movement of montane tree species at the montane-to-subalpine ecotone. We sampled tree seedling occurrence in 248 plots across a fire severity gradient (unburned to >90% basal area mortality) and spanning ~500 km of latitude in Mediterranean-type subalpine forest in California, USA. We used logistic regression to quantify differences in postfire regeneration between resident subalpine species and the seedling-only range (interpreted as climate-induced range extension) of montane species. We tested our assumption of increasing climatic suitability for montane species in subalpine forest using the predicted difference in habitat suitability at study plots between 1990 and 2030. We found that postfire regeneration of resident subalpine species was uncorrelated or weakly positively correlated with fire severity. Regeneration of montane species, however, was roughly four times greater in unburned relative to burned subalpine forest. Although our overall results contrast with theoretical predictions of disturbance-facilitated range shifts, we found opposing postfire regeneration responses for montane species with distinct regeneration niches. Recruitment of shade-tolerant red fir declined with fire severity and recruitment of shade-intolerant Jeffrey pine increased with fire severity. Predicted climatic suitability increased by 5% for red fir and 34% for Jeffrey pine. Differing postfire responses in newly climatically available habitats indicate that wildfire disturbance may only facilitate range extensions for species whose preferred regeneration conditions align with increased light and/or other postfire landscape characteristics.

Competition between reverse water gas shift reaction and methanol synthesis from CO2: influence of copper particle size.

Converting CO2 into value-added chemicals and fuels, such as methanol, is a promising approach to limit the environmental impact of human activities. Conventional methanol synthesis catalysts have shown limited efficiency and poor stability in a CO2/H2 mixture. To design improved catalysts, crucial for the effective utilization of CO2, an in-depth understanding of the active sites and reaction mechanism is desired. The catalytic performance of a series of carbon-supported Cu catalysts, with Cu particle sizes in the range of 5 to 20 nm, was evaluated under industrially relevant temperature and pressure, i.e. 260 °C and 40 bar(g). The CO2 hydrogenation reaction exhibited clear particle size effects up to 13 nm particles, with small nanoparticles having the lower activity, but higher methanol selectivity. MeOH and CO formation showed a different size-dependence. The TOFCO increased from 1.9 × 10-3 s-1 to 9.4 × 10-3 s-1 with Cu size increasing from 5 nm to 20 nm, while the TOFMeOH was size-independent (8.4 × 10-4 s-1 on average). The apparent activation energies for MeOH and CO formation were size-independent with values of 63 ± 7 kJ mol-1 and 118 ± 6 kJ mol-1, respectively. Hence the size dependence was ascribed to a decrease in the fraction of active sites suitable for CO formation with decreasing particle size. Theoretical models and DFT calculations showed that the origin of the particle size effect is most likely related to the differences in formate coverage for different Cu facets whose abundancy depends on particle size. Hence, the CO2 hydrogenation reaction is intrinsically sensitive to the Cu particle size.

Stylasterid corals build aragonite skeletons in undersaturated water despite low pH at the site of calcification.

Anthropogenic carbon emissions are causing seawater pH to decline, yet the impact on marine calcifiers is uncertain. Scleractinian corals and coralline algae strongly elevate the pH of their calcifying fluid (CF) to promote calcification. Other organisms adopt less energetically demanding calcification approaches but restrict their habitat. Stylasterid corals occur widely (extending well below the carbonate saturation horizon) and precipitate both aragonite and high-Mg calcite, however, their mode of biocalcification and resilience to ocean acidification are unknown. Here we measure skeletal boron isotopes (δ11B), B/Ca, and U/Ca to provide the first assessment of pH and rate of seawater flushing of stylasterid CF. Remarkably, both aragonitic and high-Mg calcitic stylasterids have low δ11B values implying little modification of internal pH. Collectively, our results suggest stylasterids have low seawater exchange rates into the calcifying space or rely on organic molecule templating to facilitate calcification. Thus, despite occupying similar niches to Scleractinia, Stylasteridae exhibit highly contrasting biocalcification, calling into question their resilience to ocean acidification.

Manganese Oxide as a Promoter for Copper Catalysts in CO2 and CO Hydrogenation.

In this work, we discuss the role of manganese oxide as a promoter in Cu catalysts supported on graphitic carbon during hydrogenation of CO2 and CO. MnOx is a selectivity modifier in an H2/CO2 feed and is a highly effective activity promoter in an H2/CO feed. Interestingly, the presence of MnOx suppresses the methanol formation from CO2 (TOF of 0.7 ⋅ 10-3 s-1 at 533 K and 40 bar) and enhances the low-temperature reverse water-gas shift reaction (TOF of 5.7 ⋅ 10-3 s-1) with a selectivity to CO of 87 %C. Using time-resolved XAS at high temperatures and pressures, we find significant absorption of CO2 to the MnO, which is reversed if CO2 is removed from the feed. This work reveals fundamental differences in the promoting effect of MnOx and ZnOx and contributes to a better understanding of the role of reducible oxide promoters in Cu-based hydrogenation catalysts.

Microfabrication Enables Quantification of Interfacial Activity in Thermal Catalysis.

A myriad of heterogeneous catalysts comprises multiple phases that need to be precisely structured to exert their maximal contribution to performance through electronic and structural interactions at their peripheries. In view of the nanometric, tridimensional, and anisotropic nature of these materials, a quantification of the interface and the impact of catalytic sites located there on the global performance is a highly challenging task. Consequently, the true origin of catalysis often remains subject of debate even for widely studied materials. Herein, an integrated strategy based on microfabricated catalysts and a custom-designed reactor is introduced for determining interfacial contributions upon catalytic activity assessment under process-relevant conditions, which can be easily implemented in the common catalysis research infrastructure and will accelerate the rational design of multicomponent heterogeneous catalysts for diverse applications. The method is validated by studying the high-pressure continuous-flow hydrogenation of CO and CO2 over Cu-ZnO catalysts, revealing linear correlations between the methanol formation rate and the interface between the metal and the oxide. Characterization of fresh and used materials points to the model catalyst preparation as the current challenge of the methodology that can be addressed through further development of nanotechnological tools.

Noncanonical outcomes of break-induced replication produce complex, extremely long-tract gene conversion events in yeast.

Long-tract gene conversions (LTGC) can result from the repair of collapsed replication forks, and several mechanisms have been proposed to explain how the repair process produces this outcome. We studied LTGC events produced from repair collapsed forks at yeast fragile site FS2. Our analysis included chromosome sizing by contour-clamped homogeneous electric field electrophoresis, next-generation whole-genome sequencing, and Sanger sequencing across repair event junctions. We compared the sequence and structure of LTGC events in our cells to the expected qualities of LTGC events generated by proposed mechanisms. Our evidence indicates that some LTGC events arise from half-crossover during BIR, some LTGC events arise from gap repair, and some LTGC events can be explained by either gap repair or "late" template switch during BIR. Also based on our data, we propose that models of collapsed replication forks be revised to show not a one-end double-strand break (DSB), but rather a two-end DSB in which the ends are separated in time and subject to gap repair.

Methanol Synthesis by Hydrogenation of Hybrid CO2 -CO Feeds.

The impact of carbon monoxide on CO2 -to-methanol catalysts has been scarcely investigated, although CO will comprise up to half of the carbon feedstock, depending on the origin of CO2 and process configuration. In this study, copper-based systems and ZnO-ZrO2 are assessed in cycling experiments with hybrid CO2 -CO feeds and their CO sensitivity is compared to In2 O3 -based materials. All catalysts are found to be promoted upon CO addition. Copper-based systems are intrinsically more active in CO hydrogenation and profit from exploiting this carbon source for methanol production, whereas CO induces surplus formation of oxygen vacancies (i. e., the catalytic sites) on ZnO-ZrO2 , as in In2 O3 -based systems. Mild-to-moderate deactivation occurs upon re-exposure to CO2 -rich streams, owing to water-induced sintering for all catalysts except ZnO-ZrO2 , which responds reversibly to feed variations, likely owing to its more hydrophobic nature and the atomic mixing of its metal components. Catalytic systems are categorized for operation in hybrid CO2 -CO feeds, emphasizing the significance of catalyst and process design to foster advances in CO2 utilization technologies.

Nanostructure of nickel-promoted indium oxide catalysts drives selectivity in CO2 hydrogenation.

Metal promotion in heterogeneous catalysis requires nanoscale-precision architectures to attain maximized and durable benefits. Herein, we unravel the complex interplay between nanostructure and product selectivity of nickel-promoted In2O3 in CO2 hydrogenation to methanol through in-depth characterization, theoretical simulations, and kinetic analyses. Up to 10 wt.% nickel, InNi3 patches are formed on the oxide surface, which cannot activate CO2 but boost methanol production supplying neutral hydrogen species. Since protons and hydrides generated on In2O3 drive methanol synthesis rather than the reverse water-gas shift but radicals foster both reactions, nickel-lean catalysts featuring nanometric alloy layers provide a favorable balance between charged and neutral hydrogen species. For nickel contents >10 wt.%, extended InNi3 structures favor CO production and metallic nickel additionally present produces some methane. This study marks a step ahead towards green methanol synthesis and uncovers chemistry aspects of nickel that shall spark inspiration for other catalytic applications.

Effects of postfire climate and seed availability on postfire conifer regeneration.

Large, severe fires are becoming more frequent in many forest types across the western United States and have resulted in tree mortality across tens of thousands of hectares. Conifer regeneration in these areas is limited because seeds must travel long distances to reach the interior of large burned patches and establishment is jeopardized by increasingly hot and dry conditions. To better inform postfire management in low elevation forests of California, USA, we collected 5-yr postfire recovery data from 1,234 study plots in 19 wildfires that burned from 2004-2012 and 18 yrs of seed production data from 216 seed fall traps (1999-2017). We used these data in conjunction with spatially extensive climate, topography, forest composition, and burn severity surfaces to construct taxon-specific, spatially explicit models of conifer regeneration that incorporate climate conditions and seed availability during postfire recovery windows. We found that after accounting for other predictors both postfire and historical precipitation were strong predictors of regeneration, suggesting that both direct effects of postfire moisture conditions and biological inertia from historical climate may play a role in regeneration. Alternatively, postfire regeneration may simply be driven by postfire climate and apparent relationships with historical climate could be spurious. The estimated sensitivity of regeneration to postfire seed availability was strongest in firs and all conifers combined and weaker in pines. Seed production exhibited high temporal variability with seed production varying by over two orders of magnitude among years. Our models indicate that during droughts postfire conifer regeneration declines most substantially in low-to-moderate elevation forests. These findings enhance our mechanistic understanding of forecasted and historically documented shifts in the distribution of trees.

Rapid shifts in circulation and biogeochemistry of the Southern Ocean during deglacial carbon cycle events.

The Southern Ocean plays a crucial role in regulating atmospheric CO2 on centennial to millennial time scales. However, observations of sufficient resolution to explore this have been lacking. Here, we report high-resolution, multiproxy records based on precisely dated deep-sea corals from the Southern Ocean. Paired deep (∆14C and δ11B) and surface (δ15N) proxy data point to enhanced upwelling coupled with reduced efficiency of the biological pump at 14.6 and 11.7 thousand years (ka) ago, which would have facilitated rapid carbon release to the atmosphere. Transient periods of unusually well-ventilated waters in the deep Southern Ocean occurred at 16.3 and 12.8 ka ago. Contemporaneous atmospheric carbon records indicate that these Southern Ocean ventilation events are also important in releasing respired carbon from the deep ocean to the atmosphere. Our results thus highlight two distinct modes of Southern Ocean circulation and biogeochemistry associated with centennial-scale atmospheric CO2 jumps during the last deglaciation.

Morphological, elemental, and boron isotopic insights into pathophysiology of diseased coral growth anomalies.

Coral growth anomalies (GAs) are tumor-like lesions that are detrimental to colony fitness and are commonly associated with high human population density, yet little is known about the disease pathology or calcification behavior. SEM imagery, skeletal trace elements and boron isotopes (δ11B) have been combined as a novel approach to study coral disease. Low Mg/Ca, and high U/Ca, Mo/Ca, and V/Ca potentially suggest a decreased abundance of "centers of calcification" and nitrogen-fixation in GAs. Estimates of carbonate system parameters from δ11B and B/Ca measurements indicate reduced pH (-0.05 units) and [CO32-] within GA calcifying fluid. We theorize GAs re-allocate resources away from internal pH upregulation to sustain elevated tissue growth, resulting in a porous and fragile skeleton. Our findings show that dystrophic calcification processes could explain structural differences seen in GA skeletons and highlight the use of skeletal geochemistry to shed light on disease pathophysiology in corals.

Atomic-scale engineering of indium oxide promotion by palladium for methanol production via CO2 hydrogenation.

Metal promotion is broadly applied to enhance the performance of heterogeneous catalysts to fulfill industrial requirements. Still, generating and quantifying the effect of the promoter speciation that exclusively introduces desired properties and ensures proximity to or accommodation within the active site and durability upon reaction is very challenging. Recently, In2O3 was discovered as a highly selective and stable catalyst for green methanol production from CO2. Activity boosting by promotion with palladium, an efficient H2-splitter, was partially successful since palladium nanoparticles mediate the parasitic reverse water-gas shift reaction, reducing selectivity, and sinter or alloy with indium, limiting metal utilization and robustness. Here, we show that the precise palladium atoms architecture reached by controlled co-precipitation eliminates these limitations. Palladium atoms replacing indium atoms in the active In3O5 ensemble attract additional palladium atoms deposited onto the surface forming low-nuclearity clusters, which foster H2 activation and remain unaltered, enabling record productivities for 500 h.

Habitat restoration opportunities, climatic niche contraction, and conservation biogeography in California's San Joaquin Desert.

A recent global trend toward retirement of farmland presents opportunities to reclaim habitat for threatened and endangered species. We examine habitat restoration opportunities in one of the world's most converted landscapes, California's San Joaquin Desert (SJD). Despite the presence of 35 threatened and endangered species, agricultural expansion continues to drive habitat loss in the SJD, even as marginal farmland is retired. Over the next decades a combination of factors, including salinization, climate change, and historical groundwater overdraft, are projected to lead to the retirement of more than 2,000 km2 of farmland in the SJD. To promote strategic habitat protection and restoration, we conducted a quantitative assessment of habitat loss and fragmentation, habitat suitability, climatic niche stability, climate change impacts, habitat protection, and reintroduction opportunities for an umbrella species of the SJD, the endangered blunt-nosed leopard lizard (Gambelia sila). We use our suitability models, in conjunction with modern and historical land use maps, to estimate the historical and modern rate of habitat loss to development. The estimated amount of habitat lost since the species became protected under endangered species law in 1967 is greater than the total amount of habitat currently protected through public ownership and conservation easement. We document climatic niche contraction and associated range contraction away from the more mesic margins of the species' historical distribution, driven by the anthropogenic introduction of exotic grasses and forbs. The impact of exotic species on G. sila range dynamics appears to be still unfolding. Finally, we use NASA fallowed area maps to identify 610 km2 of fallowed or retired agricultural land with high potential to again serve as habitat. We discuss conservation strategies in light of the potential for habitat restoration and multiple drivers of ongoing and historical habitat loss.

Apparent climate-mediated loss and fragmentation of core habitat of the American pika in the Northern Sierra Nevada, California, USA.

Contemporary climate change has been widely documented as the apparent cause of range contraction at the edge of many species distributions but documentation of climate change as a cause of extirpation and fragmentation of the interior of a species' core habitat has been lacking. Here, we report the extirpation of the American pika (Ochotona princeps), a temperature-sensitive small mammal, from a 165-km2 area located within its core habitat in California's Sierra Nevada mountains. While sites surrounding the area still maintain pikas, radiocarbon analyses of pika fecal pellets recovered within this area indicate that former patch occupancy ranges from before 1955, the beginning of the atmospheric spike in radiocarbon associated with above ground atomic bomb testing, to c. 1991. Despite an abundance of suitable rocky habitat climate warming appears to have precipitated their demise. Weather station data reveal a 1.9°C rise in local temperature and a significant decline in snowpack over the period of record, 1910-2015, pushing pika habitat into increasingly tenuous climate conditions during the period of extirpation. This is among the first accounts of an apparently climate-mediated, modern extirpation of a species from an interior portion of its geographic distribution, resulting in habitat fragmentation, and is the largest area yet reported for a modern-era pika extirpation. Our finding provides empirical support to model projections, indicating that even core areas of species habitat are vulnerable to climate change within a timeframe of decades.