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Environmental science & technology 57(7), 2768 - 2778 (2023). doi:10.1021/acs.est.2c06985, Rare earth elements (REEs) are strategic metals strongly involved in low-carbon energy conversion. However, these emerging contaminants are increasingly disseminated into ecosystems, raising concern regarding their toxicity. REE-accumulating plants are crucial subjects to better understand REE transfer to the trophic chain but are also promising phytoremediation tools. In this analysis, we deciphered REE accumulation sites in the REE-accumulating fern Dryopteris erythrosora by synchrotron X-ray μfluorescence (μXRF). This technique allows a high-resolution and in situ analysis of fresh samples or frozen-hydrated cross sections of different organs of the plant. In the sporophyte, REEs were translocated from the roots to the fronds by the xylem sap and were stored within the xylem conductive system. The comparison of REE distribution and accumulation levels in the healthy and necrotic parts of the frond shed light on the differential mobility between light and heavy REEs. Furthermore, the comparison emphasized that necrotized areas were not the main REE-accumulating sites. Finally, the absence of cell-to-cell mobility of REEs in the gametophyte suggested the absence of REE-compatible transporters in photosynthetic tissues. These results provide valuable knowledge on the physiology of REE-accumulating ferns to understand the REE cycle in biological systems and the expansion of phytotechnologies for REE-enriched or REE-contaminated soils., Published by American Chemical Society, Columbus, Ohio

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO2 catalyst for the oxidative coupling of methane. The catalyst performance and characterisation measurements suggest that the W species are directly involved in the catalyst active site responsible for CH4 conversion. Under operating conditions, the active components, present in the form of a Na-W-O-Mn molten state, are highly mobile and volatile. By varying the parameters of the calcination protocol, it was shown that these molten components can be partially stabilised, resulting in a catalyst with lower activity (due to loss of surface area) but higher stability even for long duration OCM reaction experiments. This journal is

Genome-based data is helping to reveal the diverse strategies plants and algae use to maintain metal homeostasis. In addition to acquisition, distribution and storage of metals, acclimating to feast or famine can involve a wealth of genes that we are just now starting to understand. The fast-paced acquisition of genome-based data, however, is far outpacing our ability to experimentally characterize protein function. Computational genomic approaches are needed to fill the gap between what is known and unknown. To avoid misconstruing bioinformatically derived data, which is the root cause of the inaccurate functional annotations that plague databases, functional inferences from diverse sources and contextualization of that evidence with a robust understanding of protein family evolution is needed. Phylogenomic- and comparative-genomic-based studies can aid in the interpretation of experimental data or provide a spark for the discovery of a new function. These analyses not only lead to novel insight into a target protein's function but can generate thought-provoking insights across protein families.

International audience; The rapid development of green energy sources and new medical technologies contributes to the increased exploitation of rare earth elements (REEs). They can be subdivided into light (LREEs) and heavy (HREEs) REEs. Mining, industrial processing, and end-use practices of REEs has led to elevated environmental concentrations and raises concerns about their toxicity to organisms and their impact on ecosystems. REE toxicity has been reported, but its precise underlying molecular effects have not been well described. Here, transcriptomic and proteomic approaches were combined to decipher the molecular responses of the model organism Saccharomyces cerevisiae to La (LREE) and Yb (HREE). Differences were observed between the early and late responses to La and Yb. Several crucial pathways were modulated in response to both REEs, such as oxidative-reduction processes, DNA replication, and carbohydrate metabolism. REE-specific responses involving the cell wall and pheromone signalling pathways were identified, and these responses have not been reported for other metals. REE exposure also modified the expression and abundance of several ion transport systems, with strong discrepancies between La and Yb. These findings are valuable for prioritizing key genes and proteins involved in La and Yb detoxification mechanisms that deserve further characterization to better understand REE environmental and human health toxicity.

The evolution of zinc (Zn) as a protein cofactor altered the functional landscape of biology, but dependency on Zn also created an Achilles' heel, necessitating adaptive mechanisms to ensure Zn availability to proteins. A debated strategy is whether metallochaperones exist to prioritize essential Zn-dependent proteins. Here, we present evidence for a conserved family of putative metal transferases in human and fungi, which interact with Zn-dependent methionine aminopeptidase type I (MetAP1/Map1p/Fma1). Deletion of the putative metal transferase in Saccharomyces cerevisiae (ZNG1; formerly YNR029c) leads to defective Map1p function and a Zn-deficiency growth defect. In vitro, Zng1p can transfer Zn

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO

This work presents multi-scale approaches to investigate 3D printed structured Mn–Na–W/SiO2 catalysts used for the oxidative coupling of methane (OCM) reaction. The performance of the 3D printed catalysts has been compared to their conventional analogues, packed beds of pellets and powder. The physicochemical properties of the 3D printed catalysts were investigated using scanning electron microscopy, nitrogen adsorption and X-ray diffraction (XRD). Performance and durability tests of the 3D printed catalysts were conducted in the laboratory and in a miniplant under real reaction conditions. In addition, synchrotron-based X-ray diffraction computed tomography technique (XRD-CT) was employed to obtain cross sectional maps at three different positions selected within the 3D printed catalyst body during the OCM reaction. The maps revealed the evolution of catalyst active phases and silica support on spatial and temporal scales within the interiors of the 3D printed catalyst under operating conditions. These results were accompanied with SEM-EDS analysis that indicated a homogeneous distribution of the active catalyst particles across the silica support.

Rare earth elements (REEs) are now considered emerging pollutants in the environment. Phytolacca americana, an REE hyperaccumulating plant, has been proposed for the remediation of REE-contaminated soils. However, there is no REE-related information for other Phytolacca species. Here, we examined five species (P. americana, P. acinosa, P. clavigera, P. bogotensis, and P. icosandra) for their response to REEs. REE accumulation and fractionation traits both occurred on the same order of magnitude among the five species. Heavy REEs were preferentially transferred to leaves relative to light REEs. Regardless of the species, lateral root length and chlorophyll content decreased under REE exposure, and lateral roots and foliar anthocyanins increased. However, plants did not experience or only slightly experienced oxidative stress. Finally, REE exposure strongly modulated the ionome of roots and, to a lesser extent, that of leaves, with a negative correlation between REE and Mn contents. In conclusion, our study provides new data on the response of several Phytolacca species to REEs. Moreover, we highlighted that the REE accumulation trait was conserved among Phytolacca species. Thus, we provide valuable information for the phytoremediation of REE-contaminated sites since the most appropriate Phytolacca species could be selected depending on the climatic/pedological area to be remediated.

International audience; Progressive rare earth element (REE) enrichment in aquatic environments worldwide and their resulting anthropogenic anomalies have highlighted the need for a better understanding of their biological effects, with a special emphasis on microbial cells since they play a crucial role in good ecosystem functioning. Therefore, the primary aim of this work was to achieve simultaneous characterization of the 16 REE toxicity effects on the growth kinetics of the commonly found Gram-negative bacterium E. coli (BW25113 strain). Bacterial growth curve modelling showed hormetic effects in the presence of REEs, while EC50 determination (in the mid-log phase) indicated that the four HREEs from Er to Lu in addition to Y were the most toxic metals (EC50 in the range of 8.3 to 3 µM), just after Sc (EC50 of 1.1 µM). Additional subcellular parameter assessment revealed cell membrane lipid peroxidation as well as enhanced membrane depolarization and permeability in the presence of La, Gd, or Yb as representatives of LREEs and HREEs. These subcellular effects appeared to be more intense with Gd and Yb compared with La-exposed cells, in relation to the overall higher toxicity potential reported for HREEs on bacterial growth. Also, the cellular ATP production decreased after REE exposure at their EC50. Finally, these results emphasize the importance of growth kinetic consideration as well as the complexity of REE biological effect mechanisms towards bacteria.

International audience; Motivated by issues arising in population dynamics, we consider the problem of iterating a given analytic function a number of times. We use the celebrated technique known as Carleman linearization that turns (for a certain class of functions) this problem into simply taking the power of a real number. We expand this method, showing in particular that it can be used for population models with immigration, and we also apply it to the famous logistic map. We also are able to give a number of results for the invariant density of this map, some being related to the Carleman linearization.

A MnNa2WO4/SiO2 catalyst was exposed to various gas compositions at high temperature in order to assess the effect of each poison on the catalyst. After these poisoning procedures, the catalysts were tested for their performances in the oxidative coupling of methane reaction. X-ray diffraction and inductively coupled plasma mass spectrometry were used to study and compare the catalyst before and after aging and these observations were used to understand the effect each poison had. It was found that exposure to hydrogen at 950 °C led to a significant reduction in activity and selectivity towards ethylene and ethane as well as significant changes in crystal phase structure and almost total loss of sodium loading. H2O and CO2 also appeared to have minor deactivating effects.

Environmental contextRare earth elements (REEs) are strategic metals and emerging contaminants for which plant-based remediation measures are needed. We screened a collection of hardy ferns and identified new accumulator species that preferentially transferred light REEs to their fronds. This study is an important step towards understanding the mechanisms of REE accumulation in plants. AbstractRare earth elements (REEs) include the lanthanides plus yttrium and scandium, and can be split according to their atomic mass into light (LREEs) and heavy REEs (HREEs). The increasing demand for REEs is mainly driven by new technologies, and their current low recyclability has led them to become emerging contaminants. The identification of new REE accumulators may help in determining the REE transfer mechanisms and may result in interesting candidates for phytoremediation techniques. To that end, a collection of 49 hardy fern species, grown in REE-spiked substrate, were screened for their potential in REE accumulation. REE concentrations were very low in the fronds of all Polypodium species, whereas all Athyrium species highly accumulated REEs. The REE accumulation level was more variable among the different species of Dryopteris, Blechnum, Woodwardia, Cystopteris and Polystichum. However, whatever the species, LREEs were preferentially transferred to the fronds over HREEs. This conserved trait was independent of the availability of different REEs in the substrate and instead may arise from specific transfer systems in ferns for the two groups of REEs. Furthermore, REE accumulation was correlated to Ca and Al, which suggested the existence of common uptake pathways. Altogether, these results are of great interest for phytoremediation purposes since appropriate species can be chosen according to the area to be remediated, and they also provide new insights into a more in-depth characterisation of the underlying REE accumulation mechanisms in ferns.

International audience

We first recall some basic facts from the theory of discrete-time Markov chains arising from two types neutral and non-neutral evolution models of population genetics with constant size. We then define and analyse a version of such models whose fluctuating total population size is conserved on average only. In our model, the population of interest is seen as being embedded in a frame process which is a critical Galton-Watson process. In this context, we address problems such as extinction, fixation, size of the population at fixation and survival probability to a bottleneck effect of the environment. Running title: constant population size on average, Comment: \`a paraitre: International Journal of Biomathematics. arXiv admin note: text overlap with arXiv:0811.1015

Coalescence processes have received a lot of attention in the context of conditional branching processes with fixed population size and non-overlapping generations. Here we focus on similar problems in the context of the standard unconditional Bienaym\'e-Galton-Watson branching processes, either (sub)-critical or supercritical. Using an analytical tool, we derive the structure of some counting aspects of the ancestral genealogy of such processes, including: the transition matrix of the ancestral count process and an integral representation of various coalescence times distributions, such as the time to most recent common ancestor of a random sample of arbitrary size, including full size. We illustrate our results on two important examples of branching mechanisms displaying either finite or infinite reproduction mean, their main interest being to offer a closed form expression for their probability generating functions at all times. Large time behaviors are investigated., Comment: 23 pages. This is an Accepted Manuscript of an article to be published by Taylor & Francis in Stochastic Models

The xenobiotic hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a toxic explosive and environmental pollutant. This study examines three bacterial species that degrade RDX, using it as a sole source of nitrogen for growth. Although isolated from diverse geographical locations, the species contain near identical copies of genes encoding the RDX-metabolising cytochrome P450, XplA and accompanying reductase, XplB. Sequence analysis indicates a single evolutionary origin for xplA and xplB as part of a genomic island, which has been distributed around the world via horizontal gene transfer. Despite the fact that xplA and xplB are highly conserved between species, Gordonia sp. KTR9 and Microbacterium sp. MA1 degrade RDX more slowly than Rhodococcus rhodochrous 11Y. Both Gordonia sp. KTR9 and Microbacterium sp. MA1 were found to contain single base-pair mutations in xplB which, following expression and purification, were found to encode inactive XplB protein. Additionally, the Gordonia sp. KTR9 XplB was fused to glutamine synthetase, which would be likely to sterically inhibit XplB activity. Although the glutamine synthetase is fused to XplB and truncated by 71 residues, it was found to be active. Glutamine synthetase has been implicated in the regulation of nitrogen levels; controlling nitrogen availability will be important for effective bioremediation of RDX.

We define and analyze a coalescent process as a recursive box-filling process whose genealogy is given by an ancestral time-reversed, time-inhomogeneous Bienyam\'{e}-Galton-Watson process. Special interest is on the expected size of a typical box and its probability of being empty. Special cases leading to exact asymptotic computations are investigated when the coalescing mechanisms are either linear-fractional or quadratic., Comment: 10 pages, one figure

We derive some additional results on the Bienyam\'e-Galton-Watson branching process with $\theta -$linear fractional branching mechanism, as studied in \cite{Sag}. This includes: the explicit expression of the limit laws in both the sub-critical cases and the super-critical cases with finite mean, the long-run behavior of the population size in the critical case, limit laws in the super-critical cases with infinite mean when the $\theta $-process is either regular or explosive, results regarding the time to absorption, an expression of the probability law of the $\theta $-branching mechanism involving Bell polynomials, the explicit computation of the stochastic transition matrix of the $\theta -$process, together with its powers., Comment: To appear in Annals of the Institute of Statistical Mathematics

After an introduction to the general topic of models for a given locus of a diploid population whose quadratic dynamics is determined by a fitness landscape, we consider more specifically the models that can be treated using genetic (or train) algebras. In this setup, any quadratic offspring interaction can produce any type of offspring and after the use of specific changes of basis, we study the evolution and possible stability of some examples. We also consider some examples that cannot be treated using the framework of genetic algebras. Among these are bistochastic matrices., Comment: To appear in Theory in Biosciences

Deterministic population growth models with power-law rates can exhibit a large variety of growth behaviors, ranging from algebraic, exponential to hyperexponential (finite time explosion). In this setup, selfsimilarity considerations play a key role, together with two time substitutions. Two stochastic versions of such models are investigated, showing a much richer variety of behaviors. One is the Lamperti construction of selfsimilar positive stochastic processes based on the exponentiation of spectrally positive processes , followed by an appropriate time change. The other one is based on stable continuous-state branching processes, given by another Lamperti time substitution applied to stable spectrally positive processes., Comment: \`aparaitre dans: Physica A: Statistical Mechanics and its Applications

We consider general cyclic representations of the 6-vertex Yang-Baxter algebra and analyze the associated quantum integrable systems, the Bazhanov-Stroganov model and the corresponding chiral Potts model on finite size lattices. We first determine the propagator operator in terms of the chiral Potts transfer matrices and we compute the scalar product of separate states (including the transfer matrix eigenstates) as a single determinant formulae in the framework of Sklyanin's quantum separation of variables. Then, we solve the quantum inverse problem and reconstruct the local operators in terms of the separate variables. We also determine a basis of operators whose form factors are characterized by a single determinant formulae. This implies that the form factors of any local operator are expressed as finite sums of determinants. Among these form factors written in determinant form are in particular those which will reproduce the chiral Potts order parameters in the thermodynamic limit., Comment: 45 pages

We study the impact of having a non-spatial branching mechanism with infinite variance on some parameters (height, width and first hitting time) of an underlying Bienayme–Galton–Watson branching process. Aiming at providing a comparative study of the spread of an epidemics whose dynamics is given by the modulus of a branching Brownian motion (BBM) we then consider spatial branching processes in dimension d , not necessarily integer. The underlying branching mechanism is either a binary branching model or one presenting infinite variance. In particular we evaluate the chance p ( x ) of being hit if the epidemics started away at distance x . We compute the large x tail probabilities of this event, both when the branching mechanism is regular and when it exhibits very large fluctuations.

Grosjean, Nicolas Descorme, Claude Besson, Michele; N,N-dimethylformamide (DMF) is largely used as versatile solvent in various processes It is thus present in large quantities in many industrial effluents Oxidation of aqueous solutions of DMF with air was conducted at 180-230 degrees C under 50-70 bar total pressure in a batch reactor, in the absence or in the presence of heterogeneous noble metal catalysts (platinum, palladium, and ruthenium) supported on TiO2 or ZrO2 Under the examined reaction conditions. DMF decomposition and oxidation produced dimethylamine (DMA). methylamine (MA), and ammonium as the major N-containing products Formic acid was also intermediately formed from the scission of the C-N bond Nitrites and nitrates were only present in very low amounts. The addition of a catalyst accelerated the initial rates of DMF and TOC (total organic carbon) conversions. but the selectivity to N-2 was low. The production of DMA and MA was demonstrated to be very much detrimental to the chemical stability of these catalysts A dramatic leaching of the noble metals occurred because of the complexation with the free lone pair electrons on the nitrogen atom of these amines. (C) 2010 Elsevier B V All rights reserved

Are globalisation and territorialisation two contradictory processes? Can they operate simultaneously and in the same place? Research conducted on the subject frequently reaches diametrically opposed conclusions. On the one hand, globalisation is considered to be the triumph of ‘global capital’ over autonomy and local identity. Now that transnational forms have rolled back national frontiers, national states have lost their importance. On the other hand, territorialisation is considered to be one of the forms of organisation which makes it possible to enter the globalisation process. Thus, territorialisation represents the process which ensures the emergence of an endogenous development capacity.