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In this work, the effects of finite size on the determination of the three-phase coexistence temperature (T3) of the carbon dioxide (CO2) hydrate have been studied by molecular dynamic simulations and using the direct coexistence technique. According to this technique, the three phases involved (hydrate–aqueous solution–liquid CO2) are placed together in the same simulation box. By varying the number of molecules of each phase, it is possible to analyze the effect of simulation size and stoichiometry on the T3 determination. In this work, we have determined the T3 value at 8 different pressures (from 100 to 6000 bar) and using 6 different simulation boxes with different numbers of molecules and sizes. In two of these configurations, the ratio of the number of water and CO2 molecules in the aqueous solution and the liquid CO2 phase is the same as in the hydrate (stoichiometric configuration). In both stoichiometric configurations, the formation of a liquid drop of CO2 in the aqueous phase is observed. This drop, which has a cylindrical geometry, increases the amount of CO2 available in the aqueous solution and can in some cases lead to the crystallization of the hydrate at temperatures above T3, overestimating the T3 value obtained from direct coexistence simulations. The simulation results obtained for the CO2 hydrate confirm the sensitivity of T3 depending on the size and composition of the system, explaining the discrepancies observed in the original work by Míguez et al. [J. Chem Phys. 142, 124505 (2015)]. Non-stoichiometric configurations with larger unit cells show a convergence of T3 values, suggesting that finite-size effects for these system sizes, regardless of drop formation, can be safely neglected. The results obtained in this work highlight that the choice of a correct initial configuration is essential to accurately estimate the three-phase coexistence temperature of hydrates by direct coexistence simulations. [ABSTRACT FROM AUTHOR]

In this work, the effect of the range of dispersive interactions in determining the three-phase coexistence line of the CO2 and CH4 hydrates has been studied. In particular, the temperature (T3) at which solid hydrate, water, and liquid CO2/gas CH4 coexist has been determined through molecular dynamics simulations using different cutoff values (from 0.9 to 1.6 nm) for dispersive interactions. The T3 of both hydrates has been determined using the direct coexistence simulation technique. Following this method, the three phases in equilibrium are put together in the same simulation box, the pressure is fixed, and simulations are performed at different temperatures T. If the hydrate melts, then T > T3. Conversely, if the hydrate grows, then T < T3. The effect of the cutoff distance on the dissociation temperature has been analyzed at three different pressures for CO2 hydrate: 100, 400, and 1000 bar. Then, we have changed the guest and studied the effect of the cutoff distance on the dissociation temperature of the CH4 hydrate at 400 bar. Moreover, the effect of long-range corrections for dispersive interactions has been analyzed by running simulations with homo- and inhomogeneous corrections and a cutoff value of 0.9 nm. The results obtained in this work highlight that the cutoff distance for the dispersive interactions affects the stability conditions of these hydrates. This effect is enhanced when the pressure is decreased, displacing the T3 about 2–4 K depending on the system and the pressure. [ABSTRACT FROM AUTHOR]

Cities represent a significant and growing portion of global carbon dioxide (CO2) emissions. Quantifying urban emissions and trends over time is needed to evaluate the efficacy of policy targeting emission reductions as well as to understand more fundamental questions about the urban biosphere. A number of approaches have been proposed to measure, report, and verify (MRV) changes in urban CO2 emissions. Here we show that a modest capital cost, spatially dense network of sensors, the Berkeley Environmental Air Quality and CO2 Network (BEACO2N), in combination with Bayesian inversions, result in a synthesis of measured CO2 concentrations and meteorology to yield an improved estimate of CO2 emissions and provide a cost-effective and accurate assessment of CO2 emissions trends over time. We describe nearly 5 years of continuous CO2 observations (2018-2022) in a midsized urban region (the San Francisco Bay Area). These observed concentrations constrain a Bayesian inversion that indicates the interannual trend in urban CO2 emissions in the region has been a modest decrease at a rate of 1.8 ± 0.3%/year. We interpret this decrease as primarily due to passenger vehicle electrification, reducing on-road emissions at a rate of 2.6 ± 0.7%/year.

Heat stress results in significant economic losses to the poultry industry. Genetics plays an important role in chickens adapting to the warm environment. Physiological parameters such as hematochemical parameters change in response to heat stress in chickens. To explore the genetics of heat stress resilience in chickens, a genome-wide association study (GWAS) was conducted using Hy-Line Brown layer chicks subjected to either high ambient temperature or combined high temperature and Newcastle disease virus infection. Hematochemical parameters were measured during three treatment phases: acute heat stress, chronic heat stress, and chronic heat stress combined with NDV infection. Significant changes in blood parameters were recorded for 11 parameters (sodium (Na+, potassium (K+), ionized calcium (iCa2+), glucose (Glu), pH, carbon dioxide partial pressure (PCO2), oxygen partial pressure (PO2), total carbon dioxide (TCO2), bicarbonate (HCO3), base excess (BE), and oxygen saturation (sO2)) across the three treatments. The GWAS revealed 39 significant SNPs (p < 0.05) for seven parameters, located on Gallus gallus chromosomes (GGA) 1, 3, 4, 6, 11, and 12. The significant genomic regions were further investigated to examine if the genes within the regions were associated with the corresponding traits under heat stress. A candidate gene list including genes in the identified genomic regions that were also differentially expressed in chicken tissues under heat stress was generated. Understanding the correlation between genetic variants and resilience to heat stress is an important step towards improving heat tolerance in poultry.

Plants with the C4 photosynthesis pathway typically respond to climate change differently from more common C3-type plants, due to their distinct anatomical and biochemical characteristics. These different responses are expected to drive changes in global C4 and C3 vegetation distributions. However, current C4 vegetation distribution models may not predict this response as they do not capture multiple interacting factors and often lack observational constraints. Here, we used global observations of plant photosynthetic pathways, satellite remote sensing, and photosynthetic optimality theory to produce an observation-constrained global map of C4 vegetation. We find that global C4 vegetation coverage decreased from 17.7% to 17.1% of the land surface during 2001 to 2019. This was the net result of a reduction in C4 natural grass cover due to elevated CO2 favoring C3-type photosynthesis, and an increase in C4 crop cover, mainly from corn (maize) expansion. Using an emergent constraint approach, we estimated that C4 vegetation contributed 19.5% of global photosynthetic carbon assimilation, a value within the range of previous estimates (18-23%) but higher than the ensemble mean of dynamic global vegetation models (14 ± 13%; mean ± one standard deviation). Our study sheds insight on the critical and underappreciated role of C4 plants in the contemporary global carbon cycle.

An animals preference for many chemosensory cues remains constant despite dramatic changes in the animals internal state. The mechanisms that maintain chemosensory preference across different physiological contexts remain poorly understood. We previously showed that distinct patterns of neural activity and motor output are evoked by carbon dioxide (CO2) in starved adults vs dauers of Caenorhabditis elegans, despite the two life stages displaying the same preference (attraction) for CO2. However, how the distinct CO2-evoked neural dynamics and motor patterns contribute to CO2 attraction at the two life stages remained unclear. Here, using a CO2 chemotaxis assay, we show that different interneurons are employed to drive CO2 attraction at the two life stages. We also investigate the molecular mechanisms that mediate CO2 attraction in dauers vs adults. We show that insulin signaling promotes CO2 attraction in dauers but not starved adults and that different combinations of neurotransmitters and neuropeptides are used for CO2 attraction at the two life stages. Our findings provide new insight into the distinct molecular and cellular mechanisms used by C. elegans at two different life stages to generate attractive behavioral responses to CO2.

The resident human skin microbiome is responsible for the production of most of the human scents that are attractive to mosquitoes. Hence, engineering the human skin microbiome to synthesize less of mosquito attractants or produce repellents could potentially reduce bites and prevent the transmission of deadly mosquito-borne pathogens. In order to further characterize the human skin volatilome, we quantified the major volatiles of 39 strains of skin commensals (Staphylococci and Corynebacterium). Importantly, to validate the behavioral activity of these volatiles, we first assessed landing behavior triggered by human skin volatiles. We demonstrated that landing behavior is gated by the presence of carbon dioxide and L-(+)-lactic acid. This is similar to the combinatorial coding triggering mosquito short range attraction. Repellency behavior to selected skin volatiles and terpenes was tested in the presence of carbon dioxide and L-(+)-lactic acid. In a 2-choice landing behavior context, the skin volatiles 2- and 3-methyl butyric acids reduced mosquito landing by 62.0-81.6% and 87.1-99.6%, respectively. Similarly, the terpene geraniol was capable of reducing mosquito landing behavior by 74.9%. We also tested the potential repellency effects of terpenes in mosquitoes at short-range using a 4-port olfactometer. In these assays, geraniol reduced mosquito attraction (69-78%) to a mixture of key human kairomones carbon dioxide, L-(+)-lactic acid, and ammonia. These findings demonstrate that carbon dioxide and L-(+)-lactic acid change the valence of other skin volatiles towards mosquito landing behavior. Moreover, this study offers candidate odorants to be targeted in a novel strategy to reduce attractants or produce repellents by the human skin microbiota that may curtail mosquito bites, and subsequent mosquito-borne disease.

Microbial electrosynthesis (MES) constitutes a bioelectrochemical process where bacteria uptake electrons extracellularly from a polarized electrode to incorporate them into their anabolic metabolism. However, the efficiency of current MES reactor designs can be lower than expected due to limitations regarding electron transfer and mass transport. One of the most promising bioreactor configurations to overcome these bottlenecks is the Microbial Electrochemical Fluidized Bed Reactor (ME-FBR). In this study, microbial CO2 fixation is investigated for the first time in a ME-FBR operated as a 3-phase reactor (solid-liquid-gas). An electroconductive carbon bed, acting as a working electrode, was fluidized with gas and polarized at different potentials (-0.6, -0.8 and -1 V vs. Ag/AgCl) so it could act as an electron donor (biocathode). Under these potentials, CO2 fixation and electron transfer were evaluated. Autotrophic electroactive microorganisms from anaerobic wastewater were enriched in a ME-FBR in the presence of 2-bromoethanosulfonic acid (BES) to inhibit the growth of methanogens. Cyclic voltammetry analysis revealed interaction between the microorganisms and the cathode. Furthermore, volatile fatty acids like propionate, formate and acetate were detected in the culture supernatant. Acetate production had a maximum rate of ca. 1 g L-1  day-1 . Planktonic cell biomass was produced under continuous culture at values as high as ca. 0.7 g L-1 dry weight. Overall, this study demonstrates the feasibility of employing a fluidized electrode with gaseous substrates and electricity as the energy source for generating biomass and carboxylic acids.

The transfer of photosynthetically produced organic carbon from surface to mesopelagic waters draws carbon dioxide from the atmosphere1. However, current observation-based estimates disagree on the strength of this biological carbon pump (BCP)2. Earth system models (ESMs) also exhibit a large spread of BCP estimates, indicating limited representations of the known carbon export pathways3. Here we use several decades of hydrographic observations to produce a top-down estimate of the strength of the BCP with an inverse biogeochemical model that implicitly accounts for all known export pathways. Our estimate of total organic carbon (TOC) export at 73.4 m (model euphotic zone depth) is 15.00 ± 1.12 Pg C year-1, with only two-thirds reaching 100 m depth owing to rapid remineralization of organic matter in the upper water column. Partitioned by sequestration time below the euphotic zone, τ, the globally integrated organic carbon production rate with τ > 3 months is 11.09 ± 1.02 Pg C year-1, dropping to 8.25 ± 0.30 Pg C year-1 for τ > 1 year, with 81% contributed by the non-advective-diffusive vertical flux owing to sinking particles and vertically migrating zooplankton. Nevertheless, export of organic carbon by mixing and other fluid transport of dissolved matter and suspended particles remains regionally important for meeting the respiratory carbon demand. Furthermore, the temperature dependence of the sequestration efficiency inferred from our inversion suggests that future global warming may intensify the recycling of organic matter in the upper ocean, potentially weakening the BCP.

The rare earth alloy Y 2 Co 17 − x Ni x was prepared by a low-cost co-precipitation reduction-diffusion process, and its crystal structure, static magnetic properties, and microscopic morphology were systematically characterized. The effects of Ni doping with different contents on the electromagnetic parameters and wave absorption properties of Y 2 Co 17 − x Ni x /polyurethane(PU) compounds were researched in the frequency range of 0.1–18 GHz. The results show that the static magnetic properties and wave absorption properties change significantly with Ni doping, and the maximum reflection loss of Y 2 Co 14 Ni 3 /PU reaches − 89.7 dB at 2.9 mm thickness, and the maximum reflection loss peaks of Y 2 Co 17 /PU and Y 2 Co 16 Ni 1 /PU are at 1.316 and 1.515 GHz, which is at the center frequency of the L-band. With Ni doping, the effective absorption bandwidth of the compounds at a frequency above 3 GHz is greatly increased. The physical factor in the bandwidth calculation was modified, and the effective absorption bandwidth of the material was calculated theoretically, and the error was less than 5 % compared with the experimental value. [ABSTRACT FROM AUTHOR]

In this study, activated carbon fibers (ACFs) were produced from mechanically recycled acrylic (PAN) and cotton (CO) fibers and their blend (PAN/CO) in felt form as an adsorbent for carbon dioxide capture. For this purpose, stabilization, carbonization, and chemical activation processes were applied consecutively. The effects of recycled fiber type, carbonization temperature, and activation agent impregnation ratio were investigated. The resultant ACFs were characterized by elemental analysis, SEM, FTIR, XPS, and BET analyses, and carbon dioxide adsorption capacity was tested. It was observed that the fibrous structure of all samples was preserved at all stages, although the fiber diameters were reduced. The maximum quantity of adsorbed C[O.sub.2] was found to be 3.79, 3.47, and 3.28 mmol C[O.sub.2]/g for recycled PAN, CO, and PAN/CO based samples, respectively, at 298 K at a relative pressure of 0.989. It was conducted that the carbon dioxide adsorption performance was affected by both the ACF surface area and the nitrogen content in the structure. It was concluded that recycled fiber-based ACFs as C[O.sub.2] adsorbents could be successfully produced with reasonable adsorption performance as a sustainable alternative. Highlights * Activated carbon fibers were produced from recycled acrylic and cotton fibers * Fibrous structure was preserved, but fiber diameters decreased * Reasonable carbon dioxide adsorption capacity was attained * Recycled fiber-based ACFs could be a sustainable alternative to C[O.sub.2] adsorbents KEYWORDS acrylic, activated carbon fiber, carbon dioxide adsorption, cotton, recycled fiber, 1 | INTRODUCTION Climate change is one of the main problems today, and the concentration of greenhouse gases in the atmosphere is directly linked to the average global temperature on [...]

Background and aimsCAM photosynthesis is hypothesized to have evolved in atmospheres of low CO2 concentration in recent geological time because of its ability to concentrate CO2 around Rubisco and boost water use efficiency relative to C3 photosynthesis. We assess this hypothesis by compiling estimates of when CAM clades arose using phylogenetic chronograms for 73 CAM clades. We further consider evidence of how atmospheric CO2 affects CAM relative to C3 photosynthesis.ResultsWhere CAM origins can be inferred, strong CAM is estimated to have appeared in the past 30 million years in 46 of 48 examined clades, after atmospheric CO2 had declined from high (near 800 ppm) to lower (

Identification of the breathing cycle forms the basis of any breath-by-breath gas exchange analysis. Classically, the breathing cycle is defined as the time interval between the beginning of two consecutive inspiration phases. Based on this definition, several research groups have developed algorithms designed to estimate the volume and rate of gas transferred across the alveolar membrane ("alveolar gas exchange"); however, most algorithms require measurement of lung volume at the beginning of the ith breath (VLi-1; i.e., the end-expiratory lung volume of the preceding ith breath). The main limitation of these algorithms is that direct measurement of VLi-1 is challenging and often unavailable. Two solutions avoid the requirement to measure VLi-1 by redefining the breathing cycle. One method defines the breathing cycle as the time between two equal fractional concentrations of lung expired oxygen (Fo2) (or carbon dioxide; Fco2), typically in the alveolar phase, whereas the other uses the time between equal values of the Fo2/Fn2 (or Fco2/Fn2) ratios [i.e., the ratio of fractional concentrations of lung expired O2 (or CO2) and nitrogen (N2)]. Thus, these methods identify the breathing cycle by analyzing the gas fraction traces rather than the gas flow signal. In this review, we define the traditional approach and two alternative definitions of the human breathing cycle and present the rationale for redefining this term. We also explore the strengths and limitations of the available approaches and provide implications for future studies.

Permafrost thaw causes the seasonally thawed active layer to deepen, causing the Arctic to shift toward carbon release as soil organic matter becomes susceptible to decomposition. Ground subsidence initiated by ice loss can cause these soils to collapse abruptly, rapidly shifting soil moisture as microtopography changes and also accelerating carbon and nutrient mobilization. The uncertainty of soil moisture trajectories during thaw makes it difficult to predict the role of abrupt thaw in suppressing or exacerbating carbon losses. In this study, we investigated the role of shifting soil moisture conditions on carbon dioxide fluxes during a 13-year permafrost warming experiment that exhibited abrupt thaw. Warming deepened the active layer differentially across treatments, leading to variable rates of subsidence and formation of thermokarst depressions. In turn, differential subsidence caused a gradient of moisture conditions, with some plots becoming consistently inundated with water within thermokarst depressions and others exhibiting generally dry, but more variable soil moisture conditions outside of thermokarst depressions. Experimentally induced permafrost thaw initially drove increasing rates of growing season gross primary productivity (GPP), ecosystem respiration (Reco ), and net ecosystem exchange (NEE) (higher carbon uptake), but the formation of thermokarst depressions began to reverse this trend with a high level of spatial heterogeneity. Plots that subsided at the slowest rate stayed relatively dry and supported higher CO2 fluxes throughout the 13-year experiment, while plots that subsided very rapidly into the center of a thermokarst feature became consistently wet and experienced a rapid decline in growing season GPP, Reco , and NEE (lower carbon uptake or carbon release). These findings indicate that Earth system models, which do not simulate subsidence and often predict drier active layer conditions, likely overestimate net growing season carbon uptake in abruptly thawing landscapes.

Carboxysomes are proteinaceous organelles that encapsulate key enzymes of CO2 fixation-Rubisco and carbonic anhydrase-and are the centerpiece of the bacterial CO2 concentrating mechanism (CCM). In the CCM, actively accumulated cytosolic bicarbonate diffuses into the carboxysome and is converted to CO2 by carbonic anhydrase, producing a high CO2 concentration near Rubisco and ensuring efficient carboxylation. Self-assembly of the α-carboxysome is orchestrated by the intrinsically disordered scaffolding protein, CsoS2, which interacts with both Rubisco and carboxysomal shell proteins, but it is unknown how the carbonic anhydrase, CsoSCA, is incorporated into the α-carboxysome. Here, we present the structural basis of carbonic anhydrase encapsulation into α-carboxysomes from Halothiobacillus neapolitanus. We find that CsoSCA interacts directly with Rubisco via an intrinsically disordered N-terminal domain. A 1.98 Å single-particle cryoelectron microscopy structure of Rubisco in complex with this peptide reveals that CsoSCA binding is predominantly mediated by a network of hydrogen bonds. CsoSCAs binding site overlaps with that of CsoS2, but the two proteins utilize substantially different motifs and modes of binding, revealing a plasticity of the Rubisco binding site. Our results advance the understanding of carboxysome biogenesis and highlight the importance of Rubisco, not only as an enzyme but also as a central hub for mediating assembly through protein interactions.

A hybrid approach combining water-splitting electrochemistry and H2-oxidizing, CO2-fixing microorganisms offers a viable solution for producing value-added chemicals from sunlight, water, and air. The classic wisdom without thorough examination to date assumes that the electrochemistry in such a H2-mediated process is innocent of altering microbial behavior. Here, we report unexpected metabolic rewiring induced by water-splitting electrochemistry in H2-oxidizing acetogenic bacterium Sporomusa ovata that challenges such a classic view. We found that the planktonic S. ovata is more efficient in utilizing reducing equivalent for ATP generation in the materials-biology hybrids than cells grown with H2 supply, supported by our metabolomic and proteomic studies. The efficiency of utilizing reducing equivalents and fixing CO2 into acetate has increased from less than 80% of chemoautotrophy to more than 95% under electroautotrophic conditions. These observations unravel previously underappreciated materials impact on microbial metabolism in seemingly simply H2-mediated charge transfer between biotic and abiotic components. Such a deeper understanding of the materials-biology interface will foster advanced design of hybrid systems for sustainable chemical transformation.

Low carbon fuel and waste management policies at the federal and state levels have catalyzed the construction of Californias wet anaerobic digestion (AD) facilities. Wet ADs can digest food waste and dairy manure to produce compressed natural gas (CNG) for natural gas vehicles or electricity for electric vehicles (EVs). Carbon capture and sequestration (CCS) of CO2 generated from AD reduces the fuel carbon intensity by carbon removal in addition to avoided methane emissions. Using a combined lifecycle and techno-economic analysis, we determine the most cost-effective design under current and forthcoming federal and state low carbon fuel policies. Under many scenarios, designs that convert biogas to electricity for EVs (Biogas to EV) are favored; however, CCS is only cost-effective in these systems with policy incentives that exceed $200/tonne of CO2 captured. Adding CCS to CNG-producing systems (Biogas to CNG) only requires a single unit operation to prepare the CO2 for sequestration, with a sequestration cost of $34/tonne. When maximizing negative emissions is the goal, incentives are needed to either (1) fund CCS with Biogas to EV designs or (2) favor CNG over electricity production from wet AD facilities.

The temperature sensitivity of ecosystem respiration regulates how the terrestrial carbon sink responds to a warming climate but has been difficult to constrain observationally beyond the plot scale. Here we use observations of atmospheric CO2 concentrations from a network of towers together with carbon flux estimates from state-of-the-art terrestrial biosphere models to characterize the temperature sensitivity of ecosystem respiration, as represented by the Arrhenius activation energy, over various North American biomes. We infer activation energies of 0.43 eV for North America and 0.38 eV to 0.53 eV for major biomes therein, which are substantially below those reported for plot-scale studies (approximately 0.65 eV). This discrepancy suggests that sparse plot-scale observations do not capture the spatial-scale dependence and biome specificity of the temperature sensitivity. We further show that adjusting the apparent temperature sensitivity in model estimates markedly improves their ability to represent observed atmospheric CO2 variability. This study provides observationally constrained estimates of the temperature sensitivity of ecosystem respiration directly at the biome scale and reveals that temperature sensitivities at this scale are lower than those based on earlier plot-scale studies. These findings call for additional work to assess the resilience of large-scale carbon sinks to warming.

Terrestrial ecosystems have taken up about 32% of the total anthropogenic CO2 emissions in the past six decades1. Large uncertainties in terrestrial carbon-climate feedbacks, however, make it difficult to predict how the land carbon sink will respond to future climate change2. Interannual variations in the atmospheric CO2 growth rate (CGR) are dominated by land-atmosphere carbon fluxes in the tropics, providing an opportunity to explore land carbon-climate interactions3-6. It is thought that variations in CGR are largely controlled by temperature7-10 but there is also evidence for a tight coupling between water availability and CGR11. Here, we use a record of global atmospheric CO2, terrestrial water storage and precipitation data to investigate changes in the interannual relationship between tropical land climate conditions and CGR under a changing climate. We find that the interannual relationship between tropical water availability and CGR became increasingly negative during 1989-2018 compared to 1960-1989. This could be related to spatiotemporal changes in tropical water availability anomalies driven by shifts in El Niño/Southern Oscillation teleconnections, including declining spatial compensatory water effects9. We also demonstrate that most state-of-the-art coupled Earth System and Land Surface models do not reproduce the intensifying water-carbon coupling. Our results indicate that tropical water availability is increasingly controlling the interannual variability of the terrestrial carbon cycle and modulating tropical terrestrial carbon-climate feedbacks.

Carbon fixation is the process by which CO2 is converted from a gas into biomass. The Calvin-Benson-Bassham cycle (CBB) is the dominant carbon-consuming pathway on Earth, driving >99.5% of the ∼120 billion tons of carbon that are converted to sugar by plants, algae, and cyanobacteria. The carboxylase enzyme in the CBB, ribulose-1,5-bisphosphate carboxylase/oxygenase (rubisco), fixes one CO2 molecule per turn of the cycle into bioavailable sugars. Despite being critical to the assimilation of carbon, rubisco's kinetic rate is not very fast, limiting flux through the pathway. This bottleneck presents a paradox: Why has rubisco not evolved to be a better catalyst? Many hypothesize that the catalytic mechanism of rubisco is subject to one or more trade-offs and that rubisco variants have been optimized for their native physiological environment. Here, we review the evolution and biochemistry of rubisco through the lens of structure and mechanism in order to understand what trade-offs limit its improvement. We also review the many attempts to improve rubisco itself and thereby promote plant growth.

Large greenhouse gas emissions occur via the release of carbon dioxide (CO2) and methane (CH4) from the surface layer of lakes. Such emissions are modeled from the air-water gas concentration gradient and the gas transfer velocity (k). The links between k and the physical properties of the gas and water have led to the development of methods to convert k between gases through Schmidt number normalization. However, recent observations have found that such normalization of apparent k estimates from field measurements can yield different results for CH4 and CO2. We estimated k for CO2 and CH4 from measurements of concentration gradients and fluxes in four contrasting lakes and found consistently higher (on an average 1.7 times) normalized apparent k values for CO2 than CH4. From these results, we infer that several gas-specific factors, including chemical and biological processes within the water surface microlayer, can influence apparent k estimates. We highlight the importance of accurately measuring relevant air-water gas concentration gradients and considering gas-specific processes when estimating k.

Diatoms, dinoflagellates, and coccolithophores are dominant groups of marine eukaryotic phytoplankton that are collectively responsible for the majority of primary production in the ocean.1 These phytoplankton contain additional intracellular membranes around their chloroplasts, which are derived from ancestral engulfment of red microalgae by unicellular heterotrophic eukaryotes that led to secondary and tertiary endosymbiosis.2 However, the selectable evolutionary advantage of these membranes and the physiological significance for extant phytoplankton remain poorly understood. Since intracellular digestive vacuoles are ubiquitously acidified by V-type H+-ATPase (VHA),3 proton pumps were proposed to acidify the microenvironment around secondary chloroplasts to promote the dehydration of dissolved inorganic carbon (DIC) into CO2, thus enhancing photosynthesis.4,5 We report that VHA is localized around the chloroplasts of centric diatoms and that VHA significantly contributes to their photosynthesis across a wide range of oceanic irradiances. Similar results in a pennate diatom, dinoflagellate, and coccolithophore, but not green or red microalgae, imply the co-option of phagocytic VHA activity into a carbon-concentrating mechanism (CCM) is common to secondary endosymbiotic phytoplankton. Furthermore, analogous mechanisms in extant photosymbiotic marine invertebrates6,7,8 provide functional evidence for an adaptive advantage throughout the transition from endosymbiosis to symbiogenesis. Based on the contribution of diatoms to ocean biogeochemical cycles, VHA-mediated enhancement of photosynthesis contributes at least 3.5 Gtons of fixed carbon per year (or 7% of primary production in the ocean), providing an example of a symbiosis-derived evolutionary innovation with global environmental implications.

The Southern Ocean is among the largest contemporary sinks of atmospheric carbon dioxide on our planet; however, remoteness, harsh weather and other circumstances have led to an undersampling of the ocean basin, compared with its northern hemispheric counterparts. While novel data interpolation methods can in part compensate for such data sparsity, recent studies raised awareness that we have hit a wall of unavoidable uncertainties in air-sea [Formula: see text] flux reconstructions. Here, we present results from autonomous observing campaigns using a novel platform to observe remote ocean regions: sailboats. Sailboats are at present a free of charge environmentally friendly platform that recurrently pass remote ocean regions during round-the-globe racing events. During the past 5 years, we collected [Formula: see text] measurements of the sea surface partial pressure of [Formula: see text] (p[Formula: see text]) around the globe including the Southern Ocean throughout an Antarctic circumnavigation during the Vendée Globe racing event. Our analysis demonstrates that the sailboat tracks pass regions where large uncertainty in the air-sea [Formula: see text] flux reconstruction prevails, with regional oversaturation or undersaturation of the sea surface p[Formula: see text]. Sailboat races provide an independent cross-calibration platform for autonomous measurement devices, such as Argo floats, ultimately strengthening the entire Southern Ocean observing system. This article is part of a discussion meeting issue 'Heat and carbon uptake in the Southern Ocean: the state of the art and future priorities'.

We investigated whether CO2-induced ocean acidification (OA) affects dopamine receptor-dependent behavior in bicolor damselfish (Stegastes partitus). Damselfish were kept in aquaria receiving flow through control (pH ~ 8.03; pCO2 ~ 384 μatm) or OA (pH ~ 7.64; CO2 ~ 1100 μatm) seawater at a rate of 1 L min-1. Despite this relatively fast flow rate, fish respiration further acidified the seawater in both control (pH ~7.88; pCO2 ~ 595 μatm) and OA (pH ~7.55; pCO2 ~ 1450 μatm) fish-holding aquaria. After five days of exposure, damselfish locomotion, boldness, anxiety, and aggression were assessed using a battery of behavioral tests using automated video analysis. Two days later, these tests were repeated following application of the dopamine D1 receptor agonist SKF 38393. OA-exposure induced ceiling anxiety levels that were significantly higher than in control damselfish, and SKF 38393 increased anxiety in control damselfish to a level not significantly different than that of OA-exposed damselfish. Additionally, SKF 38393 decreased locomotion and increased boldness in control damselfish but had no effect in OA-exposed damselfish, suggesting an alteration in activity of dopaminergic pathways that regulate behavior under OA conditions. These results indicate that changes in dopamine D1 receptor function affects fish behavior during exposure to OA. However, subsequent measurements of seawater sampled using syringes during the daytime (~3-4 pm local time) from crevasses in coral reef colonies, which are used as shelter by damselfish, revealed an average pH of 7.73 ± 0.03 and pCO2 of 925.8 ± 62.2 μatm; levels which are comparable to Representative Concentration Pathway (RCP) 8.5 predicted end-of-century mean OA levels in the open ocean. Further studies considering the immediate environmental conditions experienced by fish as well as individual variability and effect size are required to understand potential implications of the observed OA-induced behavioral effects on damselfish fitness in the wild.

The effects of a dissolved gas on the behavior of liquid in cylindrical nanopores are investigated in the framework of Gibbsian composite system thermodynamics and classical nucleation theory. An equation is derived relating the phase equilibrium of a mixture of a subcritical solvent and a supercritical gas to the curvature of the liquid–vapor interface. Both the liquid and the vapor phases are treated nonideally, which is shown to be important for the accuracy of the predictions in the case of water with dissolved nitrogen or carbon dioxide. The behavior of water in nanoconfinement is found to be only affected when the gas amount is significantly more than the saturation concentration of these gases at atmospheric conditions. However, such concentrations can be easily reached at high pressures during intrusion if there is sufficient gas present in the system, especially considering gas oversolubility in confinement. By including an adjustable line tension term in the free energy equation (−44 pJ/m for all points), the theory can make predictions in line with the few data points available from recent experimental work. However, we note that such a fitted value empirically accounts for multiple effects and should not be interpreted as the energy of the three-phase contact line. Compared to molecular dynamics simulations, our method is easy to implement, requires minimal computational resources, and is not limited to small pore sizes and/or short simulation times. It provides an efficient path for first-order estimation of the metastability limit of water–gas solutions in nanopores. [ABSTRACT FROM AUTHOR]

We investigate the effect of pressure on the carbon dioxide (CO2) hydrate–water interfacial free energy along its dissociation line using advanced computer simulation techniques. In previous works, we have determined the interfacial energy of the hydrate at 400 bars using the TIP4P/Ice and TraPPE molecular models for water and CO2, respectively, in combination with two different extensions of the Mold Integration technique [J. Colloid Interface Sci. 623, 354 (2022) and J. Chem. Phys. 157, 134709 (2022)]. Results obtained from computer simulation, 29(2) and 30(2) mJ/m2, are found to be in excellent agreement with the only two measurements that exist in the literature, 28(6) mJ/m2 determined by Uchida et al. [J. Phys. Chem. B 106, 8202 (2002)] and 30(3) mJ/m2 determined by Anderson et al. [J. Phys. Chem. B 107, 3507 (2002)]. Since the experiments do not allow to obtain the variation of the interfacial energy along the dissociation line of the hydrate, we extend our previous studies to quantify the effect of pressure on the interfacial energy at different pressures. Our results suggest that there exists a correlation between the interfacial free energy values and the pressure, i.e., it decreases with the pressure between 100 and 1000 bars. We expect that the combination of reliable molecular models and advanced simulation techniques could help to improve our knowledge of the thermodynamic parameters that control the interfacial free energy of hydrates from a molecular perspective. [ABSTRACT FROM AUTHOR]

This paper aims at the theoretical study of the CO2 magnetic-dipole ν2 + ν3 rovibrational absorption band that was recently detected in the Martian atmosphere. Specific characteristics of the magnetic dipole operator are carefully examined. Our evaluation of the magnetic-dipole line intensities is based on the variational calculations and the use of molecular properties is determined through specially performed ab initio quantum chemical calculations. The comparison of our simulated magnetic-dipole spectrum with available laboratory taken data also requires the knowledge of line intensities in the quadrupole band, which partially overlaps with that magnetic-dipole. Quadrupole intensities, once reconsidered, are permitted to correct previously reported values of the integrated intensity as well as the intensity of selected branches. The sum of our calculated magnetic-dipole and quadrupole rovibrational lines is shown to be in good agreement with both sets of presently available data from FTIR and OFCEAS laboratory observations. [ABSTRACT FROM AUTHOR]

We used an interface-sensitive resistance measurement technique to observe the time evolution of the early stages of redox reactions at the interface between the metallic oxide SrRuO 3 and a silver epoxy electrode at around room temperature (∼ 280 –320 K). On exposure to a reducing gas (CO or H 2), the interface resistance gradually increased. The time variation functions of the resistance increases for CO and H 2 were similar, although the magnitude was greater for H 2 than for CO. After substitution of O 2 for the reducing gas, the interface resistance decreased to almost the initial value, i.e., that before exposure to a reducing gas. The resistance variations can be well explained by the time variations of the oxygen deficiency at the SrRuO 3 interface and subsurfaces as a result of reduction or oxidation. We regarded the reactions as pseudo-first-order reactions and evaluated the rate constants of the SrRuO 3 redox reactions at a SrRuO 3 –Ag interface. For the reduction (resistance increase) process, a single exponential component was enough to fit the data, which suggests that the reduction proceeds successively from outside to inside the bulk. Adsorption of oxygen atoms in the oxidation (resistance decrease) process involved several rate constants, at least up to three exponential components, depending on the prior degradation by a reducing gas. The effective activation energy of each redox reaction was evaluated from an Arrhenius plot. [ABSTRACT FROM AUTHOR]

Spectra of rare gas atom clusters containing a single carbon dioxide molecule are observed using a tunable mid-infrared (4.3 µm) source to probe a pulsed slit jet supersonic expansion. There are relatively few previous detailed experimental results on such clusters. The assigned clusters include CO2–Arn with n = 3, 4, 6, 9, 10, 11, 12, 15, and 17, and CO2–Krn and CO2–Xen with n = 3, 4, and 5. Each spectrum has (at least) a partially resolved rotational structure, and each yields precise values for the shift of the CO2 vibrational frequency (ν3) induced by the nearby rare gas atoms, together with one or more rotational constants. These results are compared with theoretical predictions. The more readily assigned CO2–Arn species tend to be those with symmetric structures, and CO2–Ar17 represents completion of a highly symmetric (D5h) solvation shell. Those not assigned (e.g., n = 7 and 13) are probably also present in the observed spectra but with band structures that are not well-resolved and, thus, are not recognizable. The spectra of CO2–Ar9, CO2–Ar15, and CO2–Ar17 suggest the presence of sequences involving very low frequency (≈2 cm−1) cluster vibrational modes, an interpretation which should be amenable to theoretical confirmation (or rejection). [ABSTRACT FROM AUTHOR]

To study the contribution of three-body dispersion to crystal lattice energies, we compute the three-body contributions to the lattice energies for crystalline benzene, carbon dioxide, and triazine using various computational methods. We show that these contributions converge quickly as the intermolecular distances between the monomers grow. In particular, the smallest value among the three pairwise intermonomer closest-contact distances, Rmin, shows a strong correlation with the three-body contribution to the lattice energy, and, here, the largest of the closest-contact distances, Rmax, serves as a cutoff criterion to limit the number of trimers to be considered. We considered all trimers up to R max = 15 A ̊ . The trimers with R min < 4 A ̊ contribute 90.4%, 90.6%, and 93.9% of the total three-body contributions for crystalline benzene, carbon dioxide, and triazine, respectively, for the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] method. For trimers with R min > 4 A ̊ , the second-order Møller–Plesset perturbation theory (MP2) supplemented with the Axilrod–Teller–Muto (ATM) three-body dispersion correction reproduces the CCSD(T) values for the cumulative three-body contributions with errors of less than 0.1 kJ mol−1. Moreover, three-body contributions are converged within 0.15 kJ mol−1 by R max = 10 A ̊ . From these results, it appears that in molecular crystals where dispersion dominates the three-body contribution to the lattice energy, the trimers with R min > 4 A ̊ can be computed with the MP2+ATM method to reduce the computational cost, and those with R max > 10 A ̊ appear to be basically negligible. [ABSTRACT FROM AUTHOR]