Speciation Model Research Articles

Patterns of Genomic Heterogeneity in a Classic Field Cricket Mosaic Hybrid Zone

ABSTRACTBarriers to gene exchange can be semi‐permeable; some genes are expected to freely flow across species boundaries whereas others, under divergent selection or responsible for reproductive isolation, might not. Genome scans in recently diverged species have identified divergent genomic regions, a pattern that has often been interpreted as islands of restricted introgression in a background of relatively free gene exchange (“genomic islands of speciation”). Areas of high differentiation, most located in the X chromosome (females XX, males X0), have been identified in the hybridizing field crickets Gryllus firmus and Gryllus pennsylvanicus. These species were assumed to follow an islands of speciation model, with highly differentiated areas interpreted as areas of reduced introgression. We sequenced the G. firmus genome to localize previously studied SNPs and sample a larger area around them in 8 allopatric populations (4 of each species). We use these data to test expectations for the islands model, in which non‐introgressing areas should have both high absolute and relative differentiation. We find that in the allopatric populations, the areas with high relative differentiation (mostly X‐linked), previously interpreted as non‐introgressing, do not have high absolute differentiation as would be expected under the “islands model.” We also show that the estimated divergence time based on nuclear DNA is about 4× older than that estimated based on mtDNA (800 K vs. 200 K years ago). We discuss the implications of our results for introgression into allopatric populations.

Influence of Organic Matter and Speciation on the Dynamics of Trace Metal Adsorption on Microplastics in Marine Conditions.

Dissolved organic matter (DOM), primarily in the form of humic acid (HA), plays a crucial role in trace metal (TM) speciation and their subsequent adsorption dynamics on microplastics (MP) in aquatic environments. This study evaluates the impact of environmentally relevant concentrations of HA on the adsorption behaviors of essential (Co, Cu, Ni, and Zn) and toxic (Cd and Pb) TMs onto polyethylene (PE) and polypropylene (PP) pellets, as well as PP fibers under marine conditions, during a six-week experiment. The HA concentrations were 0.1, 1, and 5 mg/L, while all metals were in the same amounts (10 µg/L). Results reveal that HA significantly influences the adsorption of Cu, Pb, and Zn on MP, particularly on PP fibers, which exhibited the greatest TM adsorption dynamics. The adsorption patterns correspond to the concentrations of these metals in seawater, with the sequence for pellets being Zn > Cu > Pb > Ni > Co~Cd, and for fibers Cu > Zn > Pb > Co~Ni > Cd. Speciation modeling supported these findings, indicating that Cu, Pb, and Zn predominantly associate with HA in seawater, facilitating their adsorption on MP, whereas Cd, Co, and Ni mainly form free ions and inorganic complexes, resulting in slower adsorption dynamics. Statistical analysis confirmed the influence of HA on the adsorption of Cd, Pb, Cu, and Ni. By investigating the dynamics of TM adsorption on plastics, the influence of DOM on these two contaminants under marine conditions was evaluated. The presented results can help in forming a better understanding of synergistic plastic and trace metal pollution in marine systems that are relevant at the global level, since both contaminants pose a serious threat to aquatic ecosystems.

Microbial species and intraspecies units exist and are maintained by ecological cohesiveness coupled to high homologous recombination

Recent genomic analyses have revealed that microbial communities are predominantly composed of persistent, sequence-discrete species and intraspecies units (genomovars), but the mechanisms that create and maintain these units remain unclear. By analyzing closely-related isolate genomes from the same or related samples and identifying recent recombination events using a novel bioinformatics methodology, we show that high ecological cohesiveness coupled to frequent-enough and unbiased (i.e., not selection-driven) horizontal gene flow, mediated by homologous recombination, often underlie these diversity patterns. Ecological cohesiveness was inferred based on greater similarity in temporal abundance patterns of genomes of the same vs. different units, and recombination was shown to affect all sizable segments of the genome (i.e., be genome-wide) and have two times or greater impact on sequence evolution than point mutations. These results were observed in both Salinibacter ruber, an environmental halophilic organism, and Escherichia coli, the model gut-associated organism and an opportunistic pathogen, indicating that they may be more broadly applicable to the microbial world. Therefore, our results represent a departure compared to previous models of microbial speciation that invoke either ecology or recombination, but not necessarily their synergistic effect, and answer an important question for microbiology: what a species and a subspecies are.

Stoichiometric Lanthanide Compounds with Diglycolamides: A Synthetic Approach toward Understanding Rare-Earth Speciation in Solution.

A fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining the chemical behavior of rare-earth metals in complex liquid-liquid extraction processes. Probing the exact bonding between the extractant and the metal is sometimes done through the synthesis of solid-state compounds that can serve as models for metal speciation in solution. In the case of diglycolamide (DGA), a commonly used neutral diamide extractant, extensive studies identify the stepwise formation of 1:1 [Ln(DGA)(H2O)6]3+, 1:2 [Ln(DGA)2(H2O)3]3+, and 1:3 [Ln(DGA)3]3+ complexes in solution. The crystallographic reports, however, exclusively show a 1:3 [Ln(DGA)3]3+ moiety in the solid state, while the structures of 1:1 and 1:2 complexes are yet to be isolated and comprehensively studied. In this work, we report the synthesis and characterization of three new families of stoichiometric N,N,N',N'-tetramethyldiglycolamide (TMDGA) compounds: [Ln(TMDGA)(H2O)5Cl]Cl2·2H2O, [Ln(TMDGA)2(H2O)3]Cl3·3H2O, and [Ln(TMDGA)3]Cl3·7H2O, where Ln = Nd, Eu, Gd, with Ln:TMDGA ratios of 1:1, 1:2, and 1:3, respectively. The compounds have been analyzed using vibrational spectroscopy (both Raman and FT-IR), as well as variable temperature fluorescence spectroscopy. A spectrophotometric titration of Eu(III) was performed to confirm the presence of the [Eu(TMDGA)n]3+ (n = 1, 2, and 3) species in solution and to compare the individual solid-state emission spectra to their respective analogues in solution.

Opening the species box: what parsimonious microscopic models of speciation have to say about macroevolution.

In the last two decades, lineage-based models of diversification, where species are viewed as particles that can divide (speciate) or die (become extinct) at rates depending on some evolving trait, have been very popular tools to study macroevolutionary processes. Here, we argue that this approach cannot be used to break down the inner workings of species diversification and that "opening the species box" is necessary to understand the causes of macroevolution, but that too detailed speciation models also fail to make robust macroevolutionary predictions. We set up a general framework for parsimonious models of speciation that rely on a minimal number of mechanistic principles: (a) reproductive isolation is caused by excessive dissimilarity between genotypes; (b) dissimilarity results from a balance between differentiation processes and homogenizing processes; and (c) dissimilarity can feed back on these processes by decelerating homogenization. We classify such models according to the main homogenizing process: (a) clonal evolution models (ecological drift), (b) models of genetic isolation (gene flow), and (c) models of isolation by distance (spatial drift). We review these models and their specific predictions on macroscopic variables such as species abundances, speciation rates, interfertility relationships, or phylogenetic tree structure. We propose new avenues of research by displaying conceptual questions remaining to be solved and new models to address them: the failure of speciation at secondary contact, the feedback of dissimilarity on homogenization, and the emergence in space of breeding barriers.

New thermodynamic insights into pregabalin interactions with H+, Na+, Mg2+, Ca2+, Cu2+, Zn2+: Equilibrium constants, enthalpy changes and sequestering ability

The thermodynamics of the interaction between (S)-(+)-3-aminomethyl-5-methylhexanoic acid (pregabalin) and protons was studied potentiometrically at different temperatures (288.15 ≤ T/K ≤ 310.15), ionic strengths (0.16 ≤ I/mol kg−1(H2O) ≤ 0.97, NaCl), (0.11 ≤ I/mol kg−1(H2O) ≤ 1.11, (C2H5)4NI), (0.10 ≤ I/mol kg−1(H2O) ≤ 1.03, NaClO4, only at T = 298.15 K). The protonation constants at infinite dilution and the corresponding enthalpy change values were determined, as well as their parameters for the dependence on the temperature and ionic strength. The results showed that the protonation reactions are exothermic, and that the entropic contribution is the driving force of the processes.Formation constants of pregabalin (L) with Zn2+, Cu2+, Ca2+, and Mg2+ were determined in NaCl(aq) at different ionic strength values, at 298.15 K. Different speciation models were proposed for the various metal/Pregabalin systems: ZnHL2+, ZnLOH0(aq), CuL+, CuL20(aq), CaL+, CaHL2+, and MgL+, depending on the different acid–base properties of the metals and the possible formation of sparingly soluble species. The modelling of the thermodynamic formation parameters respect to the temperature and ionic strength variation was carried out by using both the Specific Ion Interaction Theory (SIT) and an extended Debye-Hückel type equation.Being Pregabalin an emerging contaminant, it was interesting to investigate its distribution in presence of the investigated metal cations in aqueous solution simulating both biological fluid (urine) and natural water (seawater).

Color polymorphic carnivores have faster speciation rates

Variation in coat color is a prominent feature in carnivores, thought to be shaped by environmental factors. As new traits could allow populations to occupy novel niches and habitats, color polymorphism may be maintained by balancing selection. Consequently, color polymorphic species may speciate more rapidly and can give rise to monomorphic daughter species. We thus predicted that, within the Carnivora, (i) speciation rate is higher in polymorphic lineages, (ii) divergence between color polymorphic lineages is more recent, and (iii) within closely related groups, polymorphic lineages are ancestral and monomorphic lineages derived. We also tested whether accelerated speciation rates relate to niche breadth, measured by the number of occupied habitats and range size. We collected data of 48 polymorphic and 192 monomorphic carnivore species, and assessed speciation rates using phylogenetic comparative methods. We found that polymorphic carnivores had higher speciation rates (λ1 = 0.29, SD = 0.13) than monomorphic species (λ0 = 0.053, SD = 0.044). Hidden and quantitative state speciation and extinction models inferred that color polymorphism was the main contributing factor, and that niche breadth was not of influence. Therefore, other selective forces than spatial niche segregation, such as predator-prey coevolution, may contribute to color polymorphism in wild carnivores.

Tantalum in hydrothermal fluids

Understanding the behaviour of tantalum (Ta) in hydrothermal systems is pivotal for understanding its geochemical enrichment processes and economic extraction via hydrometallurgy. Yet, its behaviour in hydrothermal systems remains poorly characterised. This study investigates the coordination chemistry, speciation, and solubility of pentavalent Ta(V) in fluoride (F) − and chloride (Cl) −rich hydrothermal solutions up to 413 °C and 800 bar, utilising in-situ High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy (HERFD-XAS). The results reveal the stability of high order fluoridotantalate complexes in fluoride-rich fluids solutions up to the highest investigated temperature, highlighting fluoride’s paramount role in enhancing Ta solubility through the formation of stable fluoridotantalate complexes in aqueous solutions. A transition from nonafluoridotantalate tetraanion (TaF94−) to heptafluoridotantalate dianion (TaF72−) complexes was observed as a function of temperature in solutions containing ≥1 m fluoride. Conversely, our findings indicate a negligible role for chloride in Ta complexation even in high Cl (∼6 m) aqueous solutions, suggesting that Ta chloride complexes do not contribute significantly to Ta transport in hydrothermal systems. Existing solubility data were reinterpreted based on an updated speciation model that integrates the in-situ XAS results. This confirms that Ta(OH)5(aq) predominates in solutions containing <0.02 m fluoride; oxyfluoridotantalate anions such as [TaF3(OH)3−] dominate in solutions containing intermediate fluoride concentrations (0.02–1 m), and the fluoridotantalate anions [TaF94− to TaF72−] occur in more concentrated fluoride solutions (>1 m) at hydrothermal conditions (∼100–400 °C). Derived thermodynamic data for these species enable better understanding and geochemical modelling of Ta transport in hydrothermal fluids, highlighting the potential of F-rich fluids to transport significant amounts of Ta.

Quantifying mass-dependent isotope fractionation and nuclear field shift effects for the light rare Earth elements in hydrous systems

The improving sensitivity of mass-spectrometers has opened the potential of using stable isotope signatures of the rare Earth elements (REE) as geochemical tracers. However, thus far only limited studies have utilised REE stable isotopes, despite resolvable variations having been observed in a range of systems. An interesting but poorly explored area remains variations in aqueous environments across a range of temperatures including seawater, marine sediments, ion adsorption deposits or hydrothermal systems. Furthermore, the magnitudes and competing effects of mass-dependent isotope fractionation and mass-independent nuclear field shift effects, which can be significant factor for heavy elements especially at high temperatures, remain poorly understood.To contribute to a holistic understanding of REE isotope signatures, we calculated reduced partition function ratios (as 103lnβ) for mass-dependent and nuclear field shift effects for aqueous La, Ce, and Nd complexes from first principles. Theoretical calculations were compared with experimental data, and this demonstrates that calculations involving a combination of two explicit hydration shells and additional implicit solvation effects are required to accurately describe the coordination and molecular vibrations of aqueous complexes. This data was then combined with speciation modelling of seawater and hydrothermal fluids to assess isotope fractionation in hydrous systems. The predicted magnitude of isotope fractionation is significant in low (T = 25 °C) temperature systems (Δ139/138LaMax-Min = 0.20 ‰, Δ142/140CeMax-Min = 0.33 ‰, Δ146/144NdMax-Min = 0.34 ‰) and remains above currently achievable analytical uncertainties even at high (T = 500 °C) temperatures (±0.015 ‰ for δ146/144Nd; ±0.040 ‰ for δ142/140Ce). Unless oxidation occurs, which is only relevant for Ce in terrestrial environments, nuclear field shift effects are negligible even at temperatures up to 500 °C. The large difference in nuclear charge radius between 140Ce and 142Ce strongly enriches the lighter Ce isotope in the higher oxidation state (103lnβCe(IV)-Ce(III) = −0.45 at 25 °C) which almost completely cancels out the opposing mass-dependent effect (103lnβCe(IV)-Ce(III) = +0.46 at 25 °C). This means that variations in δ142/140Ce isotope signatures cannot easily be related to oxidation in ancient or recent environments.

Thermodynamic simulation of stepwise precipitation of NH4VO3 and NaHCO3 from carbonating Na3VO4 solution

Thermodynamic simulation was conducted to design a new process of stepwise precipitating NH4VO3 and NaHCO3 from regulating the CO2 carbonation of Na3VO4 solution. Firstly, a new V(V) speciation model for the aqueous solution containing vanadate and carbonate is established by using the Bromley−Zemaitis activity coefficient model. Subsequently, thermodynamic equilibrium calculations are conducted to clarify the behavior of vanadium, carbon, sodium, and impurity species in atmospheric or high-pressure carbonation. To ensure the purity and recovery of vanadium products, Na3VO4 solution is initially carbonated to the pH of 9.3−9.4, followed by precipitating NH4VO3 by adding (NH4)2CO3. After vanadium precipitation, the solution is deeply carbonated to the final pH of 7.3−7.5 to precipitate NaHCO3, and the remaining solution is recycled to dissolve Na3VO4 crystals. Finally, verification experiments demonstrate that 99.1% of vanadium and 91.4% of sodium in the solution are recovered in the form of NH4VO3 and NaHCO3, respectively.

Leaching and geochemical modeling of asbestos-cement waste and mine asbestos

Asbestos-Containing Materials (ACMs) were widely used in the construction sector but, due to their harmful health effects, many countries have banned their use. ACMs are classified as hazardous and, in contact with water, produce potentially harmful leachates. The objective of this work was to determine the leaching behavior of 20 elements from two asbestos-cement materials and mine asbestos samples across the entire pH range and varying liquid-to-solid ratios (column tests). The pH-dependence tests showed consistent leaching patterns across the three materials. Geochemical speciation model (LeachXS) predictions were successful in most cases of the batch experiments and were improved by adjusting iron oxides concentration for some elements. Model predictions were successful for fewer elements in the column experiments. Depending on the pH, element release was controlled by respective solid phase dissolution, sorption onto iron oxides and substitution in ettringite. Some leaching concentrations exceeded the EU limits for granular non-hazardous waste landfills. Considering the strongly alkaline nature of monolithic asbestos-cement waste undergoing carbonation, we propose all three materials to be disposed of in non-hazardous waste landfills, according to EU legislation. A case study concluded that geochemical modeling of ACMs leaching is a useful tool in estimating element release under various environmental conditions.

Binding mechanisms of trivalent chromium on colloidal phases from ultramafic systems: Insights from batch experiments and XAS analysis

Understanding the availability and mobility of chromium is a key factor in gaining insight into the fate of chromium and thus essential for assessing the risk of contamination and developing effective remediation strategies. In the natural environment, such as ultramafic systems, which are natural pools of chromium, chromium occurs mostly in the trivalent state (Cr(III)), which is known to have a high affinity for the solid phases such as particles and colloids. However, since Cr(VI) is more toxic, the vast majority of experimental studies focus on its reduction to Cr(III), which is often considered to form (hydr)oxide precipitates due to its poor solubility. Furthermore, while the oxidation state of Cr dictates its geochemical behavior, its interaction with particles and colloids is rarely controlled or monitored. Therefore, the interaction mechanisms between Cr(III) and particles or colloids require further attention. In this study, ten mineral phases (goethite, hematite, pyrolusite, kaolinite, montmorillonite, chlorite, serpentine, fuchsite, amphibole, and chromite) and one organic phase (humic acid), relevant to chromium bearing and carrier phases in ultramafic soils, were investigated to explore their interaction with Cr(III) species. These phases were first characterized by various techniques (including XRD, XRF, SEM, and BET). Adsorption and desorption experiments of Cr(III) on these phases were then carried out, and the distribution of Cr oxidation states in both the aqueous and solid phases was carefully monitored using UV–vis spectroscopy, geochemical speciation modeling, and Cr K-edge XAS spectroscopy. With the exception of pyrolusite, where partial oxidation of Cr(III) to Cr(VI) occurred, Cr(III) was shown to persist as a single oxidation state in all experiments. Desorption analyses showed significantly low desorbed rates, which further confirmed the prevalence of Cr(III). Experimental sorption isotherm data were interpreted using the Langmuir model and its linearized form, which provides important thermodynamic characteristics of adsorbents related to their structural and surface features. This study will provide better constraints for the understanding and prediction of Cr behavior and fate in the environment, especially in ultramafic systems.

Geochemical Modeling and Quality Assessment of the Surface Waters from the Mouhoun River System, Burkina Faso: Implications of Water–Rock Interactions and Anthropogenic Activities

Major ion and heavy metal geochemistry was used to investigate the factors that control the Mouhoun River water quality in western Burkina Faso. Major cation concentrations was in the following decreasing order: Ca2+&gt; Na+&gt; K+&gt; Mg2+, reflecting silicate weathering. However, relatively high HCO3- and SO42- concentrations could be related to dissolution of calcite and sulfide minerals, respectively. The average heavy metal concentrations in the riverine system were in the following order: FeT&gt;Ag&gt;Mn&gt;Zn&gt;Pb&gt;Cu&gt;Ni&gt;AsT&gt;Cr&gt;Hg&gt;Co&gt;Cd with FeT and Ag exceeding the World Health Organization permissible limits. Concentrations of all heavy metals, except Cr, were higher in the Mouhoun system compared to the average world river concentrations. Adsorption and speciation models showed that Zn, Ag, Cd, Co, Cr and Ni are likely to remain in their free ionic forms, and thus posing serious threats to aquatic life and human health. Ag-Hg-Ni-Cd association around Poura and Tenado on the principal component plot suggested that the widespread artisanal gold mining in these areas may have contributed to these metals’ loading. In contrast, NH4+, Pb, Cu, Cr, AsT and Zn were clustered around a densely populated and industrialized Kou watershed, pointing to agricultural and industrial sources of these pollutants. Furthermore, the Kou River had the highest metal index followed by Tenado, Samendeni, Poura and Boromo. Hence, the chemistry of the Mouhoun River and its tributary appears to be mainly controlled by population density and various anthropogenic activities taking place in their drainage basins. The findings could provide avenues for sound and sustainable water resource management in a water scarce semi-arid environment.

Reactive transport of Cd2+ in porous media in the presence of xanthate: Experimental and modeling study

In mining regions, flotation reagents can interact with heavy metals, thereby increasing the complexity of their migration. However, most current studies solely focus on the migration of heavy metals, neglecting the influence of flotation reagents in their models concerning mining area pollution. This study developed the reactive transport model, Multisurface Speciation Model (MSM), which integrated the reaction processes of the three main soil components (iron oxides, organic matter, clay minerals) and ethyl xanthate (EX), a typical flotation reagent, with cadmium (Cd²⁺) to investigate the effects of EX on the transport and retention of Cd²⁺ in natural porous media under varying pH conditions. The study revealed that EX formed new adsorption sites for Cd²⁺, enhancing its retention and inhibiting transport with increased EX loading (0 to 2.5 mmol·L−1), while higher pH levels (ranging from 4 to 8) further strengthened the retention capability of Cd²⁺. The MSM further predicted the solid-phase concentration distribution of Cd²⁺ among various components. With increasing EX-loaded concentrations, xanthate became the dominant adsorbing component, accounting for 48.93 % to 95.31 % of adsorption, and competitively interacted with other components. Xanthate retention was lower under acidic conditions compared to neutral and alkaline environments. Sensitivity analysis highlighted the concentrations of iron oxide adsorption sites (SurfaOH, SurfbOH) as critical parameters in the models, underscoring the need for precise determination of soil physicochemical indicators. This study stressed the crucial role of flotation reagents and pH conditions in controlling heavy metal mobility, offering important insights for environmental management in mining regions.

Bis(amino acidato)copper(II) compounds in blood plasma: a review of computed structural properties and amino acid affinities for Cu2+ informing further pharmacological research.

Neutral bis(amino acidato)copper(II) [Cu(aa)2] coordination compounds are the physiological species of copper(II) amino acid compounds in blood plasma taking the form of bis(l-histidinato)copper(II) and mixed ternary copper(II)-l-histidine complexes, preferably with l-glutamine, l-threonine, l-asparagine, and l-cysteine. These amino acids have three functional groups that can bind metal ions: the common α-amino and carboxylate groups and a side-chain polar group. In Cu(aa)2, two coordinating groups per amino acid bind to copper(II) in-plane, while the third group can bind apically, which yields many possibilities for axial and planar bonds, that is, for bidentate and tridentate binding. So far, the experimental studies of physiological Cu(aa)2 compounds in solutions have not specified their complete geometries. This paper provides a brief review of my group's research on structural properties of physiological Cu(aa)2 calculated using the density functional theory (DFT) to locate low-energy conformers that can coexist in aqueous solutions. These DFT investigations have revealed high conformational flexibility of ternary Cu(aa)2 compounds for tridentate or bidentate chelation, which may explain copper(II) exchange reactions in the plasma and inform the development of small multifunctional copper(II)-binding drugs with several possible copper(II)-binding groups. Furthermore, our prediction of metal ion affinities for Cu2+ binding with amino-acid ligands in low-energy conformers with different coordination modes of five physiological Cu(aa)2 in aqueous solution supports the findings of their abundance in human plasma obtained with chemical speciation modelling.

Modeling the vulnerability of water resources to pollution in a typical mining area, SE Nigeria using speciation, geospatial, and multi-path human health risk modeling approaches

Modeling the vulnerability of water resources to pollution in a typical mining area, SE Nigeria using speciation, geospatial, and multi-path human health risk modeling approaches

Persistent Gene Flow Suggests an Absence of Reproductive Isolation in an African Antelope Speciation Model.

African antelope diversity is a globally unique vestige of a much richer world-wide Pleistocene megafauna. Despite this, the evolutionary processes leading to the prolific radiation of African antelopes are not well understood. Here, we sequenced 145 whole genomes from both subspecies of the waterbuck (Kobus ellipsiprymnus), an African antelope believed to be in the process of speciation. We investigated genetic structure and population divergence and found evidence of a mid-Pleistocene separation on either side of the eastern Great Rift Valley, consistent with vicariance caused by a rain shadow along the so-called 'Kingdon's Line'. However, we also found pervasive evidence of both recent and widespread historical gene flow across the Rift Valley barrier. By inferring the genome-wide landscape of variation among subspecies, we found 14 genomic regions of elevated differentiation, including a locus that may be related to each subspecies' distinctive coat pigmentation pattern. We investigated these regions as candidate speciation islands. However, we observed no significant reduction in gene flow in these regions, nor any indications of selection against hybrids. Altogether, these results suggest a pattern whereby climatically driven vicariance is the most important process driving the African antelope radiation, and suggest that reproductive isolation may not set in until very late in the divergence process. This has a significant impact on taxonomic inference, as many taxa will be in a gray area of ambiguous systematic status, possibly explaining why it has been hard to achieve consensus regarding the species status of many African antelopes. Our analyses demonstrate how population genetics based on low-depth whole genome sequencing can provide new insights that can help resolve how far lineages have gone along the path to speciation.

Exploring the Macroevolutionary Signature of Asymmetric Inheritance at Speciation.

Popular comparative phylogenetic models such as Brownian Motion, Ornstein-Ulhenbeck, and their extensions, assume that, at speciation, a trait value is inherited identically by two descendant species. This assumption contrasts with models of speciation at a micro-evolutionary scale where descendants' phenotypic distributions are sub-samples of the ancestral distribution. Different speciation mechanisms can lead to a displacement of the ancestral phenotypic mean among descendants and an asymmetric inheritance of the ancestral phenotypic variance. In contrast, even macro-evolutionary models that account for intraspecific variance assume symmetrically conserved inheritance of ancestral phenotypic distribution at speciation. Here we develop an Asymmetric Brownian Motion model (ABM) that relaxes the assumption of symmetric and conserved inheritance of the ancestral distribution at the time of speciation. The ABM jointly models the evolution of both intra- and inter-specific phenotypic variation. It also infers the mode of phenotypic inheritance at speciation, which can range from a symmetric and conserved inheritance, where descendants inherit the ancestral distribution, to an asymmetric and displaced inheritance, where descendants inherit divergent phenotypic means and variances. To demonstrate this model, we analyze the evolution of beak morphology in Darwin finches, finding evidence of displacement at speciation. The ABM model helps to bridge micro- and macro-evolutionary models of trait evolution by providing a more robust framework for testing the effects of ecological speciation, character displacement, and niche partitioning on trait evolution at the macro-evolutionary scale.

Engine-out hydrocarbon speciation and DOC reaction modeling for dual-fuel combustion concept

The concerns for global warming have pushed very harsh regulations on conventional propulsion systems based on the use of fossil fuels. New technologies are being promoted, but their current technological status needs further research and development to become a competitive substitute for the ever-present internal combustion engine. Transition technologies like hybrid-electric platforms are the preferred solution, but their dependence on the internal combustion engine demands continued developing and improving this technology. Advanced combustion modes like dual-mode dual-fuel combustion are attractive solutions with room for improvement. This work evaluates the specifics of the hydrocarbon composition emitted during the operation of a medium-duty dual-mode dual-fuel engine, analyzing the specific requirements of a diesel oxidation catalyst for this application. Also, the modeling approach of this after-treatment component is revised for this type of application, proposing a new approach and evaluating numerically the performance of a conventional diesel oxidation catalyst. The results show that the new modeling approach brings better accuracy when modeling the transient operation of the engine.

Oxidized Sulfur Species in Slab Fluids as a Source of Enriched Sulfur Isotope Signatures in Arcs

AbstractRecycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO2) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ34S &gt; 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H2O‐NaCl solutions to calibrate a high‐pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at log fO2 from FMQ‐2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite at fO2 conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur‐rich and high δ34S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke 34S‐rich subducted lithologies.