The Duration of Dry Events Promotes PVC Film Fragmentation in Intermittent Rivers.

The majority of microplastics (MPs) found in the environment originate from plastic fragmentation occurring in the environment and are influenced by environmental factors such as UV irradiation and biotic interactions. However, the effects of river drying on plastic fragmentation remain unknown, despite the global prevalence of watercourses experiencing flow intermittence. This study investigates, through laboratory experiments, the coupled effects of drying duration and UV irradiation on PVC film fragmentation induced by artificial mechanical abrasion. This study shows that PVC film fragmentation increases with drying duration through an increase in the abundance and size of formed MPs as well as mass loss from the initial plastic item, with significant differences for drying durations >50% of the experiment duration. The average abundance of formed MPs in treatments exposed to severe drying duration was almost two times higher than in treatments nonexposed to drying. Based on these results, we developed as a proof of concept an Intermittence-Based Plastic Fragmentation Index that may provide insights into plastic fragmentation occurring in river catchments experiencing large hydrological variability. The present study suggests that flow intermittence occurring in rivers and streams can lead to increasing plastic fragmentation, unraveling new insights into plastic pollution in freshwater systems.

Euryhaline ecology of early tetrapods revealed by stable isotopes.

The fish-to-tetrapod transition-followed later by terrestrialization-represented a major step in vertebrate evolution that gave rise to a successful clade that today contains more than 30,000 tetrapod species. The early tetrapod Ichthyostega was discovered in 1929 in the Devonian Old Red Sandstone sediments of East Greenland (dated to approximately 365 million years ago). Since then, our understanding of the fish-to-tetrapod transition has increased considerably, owing to the discovery of additional Devonian taxa that represent early tetrapods or groups evolutionarily close to them. However, the aquatic environment of early tetrapods and the vertebrate fauna associated with them has remained elusive and highly debated. Here we use a multi-stable isotope approach (δ13C, δ18O and δ34S) to show that some Devonian vertebrates, including early tetrapods, were euryhaline and inhabited transitional aquatic environments subject to high-magnitude, rapid changes in salinity, such as estuaries or deltas. Euryhalinity may have predisposed the early tetrapod clade to be able to survive Late Devonian biotic crises and then successfully colonize terrestrial environments.

Online adaptive identification of multichannel systems for audio applications.

Impulse responses (IRs) estimation of multi-input acoustic systems is a prerequisite for many audio applications. In this paper, an adaptive identification problem based on the Autostep algorithm is extended to the simultaneous estimation of room IRs for multiple input single output linear time invariant systems without any a priori information. To do so, the proposed algorithm is initially evaluated in a simulated room with several sound sources active at the same time. Finally, an experimental validation is proposed for the cases of a semi-anechoic chamber and an arbitrary room. Special attention is dedicated to the algorithm convergence behavior, considering different meta parameters settings. Results are eventually compared with the other normalized version of the least mean square algorithm.

Estimation of volatile organic compound exposure concentrations and time to reach a specific dermal absorption using physiologically based pharmacokinetic modeling.

A procedure was proposed to estimate dermal exposures based on a physiologically based pharmacokinetic (PBPK) model developed in rats. The study examined vapor concentrations ranging from 500 to 10,000 ppm for dibromomethane and 2,500 to 40,000 ppm for bromochloromethane. These concentrations were reconstructed based on chemical blood levels measured in 4 hr, with errors varying from 0.0% to 52.0%. The PBPK approach adequately predicted the blood concentrations and helped simulate contaminant transport through the stratum corneum and distribution in the body compartments. The proposed technique made it possible to estimate the skin absorption time (SAT) obtained from acute inhalation toxicity data. An inverse relationship exists between the SAT and exposure concentration. The method can be helpful in toxicology and risk assessment of hazardous volatile organic compounds.

A physiologically based pharmacokinetic model for the transdermal uptake of semivolatile organic compounds from the atmosphere and through clothing.

This study focuses on the semivolatile organic compound (SVOC) absorption through clothing and the skin. SVOCs are ubiquitous in daily life, in products like personal care items, plastics, and building materials. Understanding their permeation through the skin barrier is crucial for evaluating potential health risks of complete exposure. A PBPK model was developed to comprehend the dynamic interplay between SVOCs and human skin and to estimate tissue distribution throughout the body. The framework incorporated parameters such as skin permeability, physicochemical properties of the chemicals, and the impact of protective clothing and adsorbents. This model predicted the rate and extent of SVOC absorption under diverse scenarios. The PBPK predictions matched the experimental amount of mono-ethyl phthalate (MEP), a phthalate metabolite, when urine samples were collected for bare-skinned and clothed participants. Urine concentrations of MEP during a 6-hr exposure and for the next 48 hr show that clean clothing effectively decreased dermal uptake and the buildup of chemicals in the body. Additional removal of MEP was achieved through adsorption on activated carbon fabric. An increase in the maximum monolayer adsorption capacity or the Langmuir equilibrium constant further reduced the amount of MEP in the urine.

Inferring odontocete life history traits in dentine using a multiproxy approach (δ15 N, δ44/42 Ca and trace elements).

RATIONALE: Understanding the interactions between marine mammals and their environment is critical for ecological and conservation purposes. Odontocetes offer a continuous record of their life history from birth as recorded in annual increments of their tooth dentine. Because dentine is not remodeled and contains collagen, nitrogen stable isotope compositions (δ15 N) reflect nursing and weaning events, life history traits that would otherwise be impossible to retrieve in such elusive marine animals. Yet, capturing the magnitude and temporal changes in these events is constrained by tooth size and sampling resolution. Moreover, historical and fossil specimens undergo collagen decay, hence the need to develop the measurements of other proxies. METHODS: Here, we present a multiproxy approach to investigate the use of Ca isotope compositions (δ44/42 Ca) in relation to δ15 N and laser ablation profiles for different trace metal (Ba, Mg, Sr, Zn) concentrations across the dentine of a single individual of the common bottlenose dolphin Tursiops truncatus. RESULTS: To help interpret the dentine data, we provide milk elemental compositions and δ44/42 Ca values for two odontocete individuals. We discuss the observed changes in δ44/42 Ca across the dentine as potential markers of birth, weaning interval, incidental ingestion of seawater, trophic level and physiology. Incidental ingestion of seawater during nursing induces a positive offset in δ44/42 Ca values recorded in the early formed dentine. CONCLUSIONS: Life history parameters of individual marine mammals are extremely difficult to retrieve due to limitations in observing specimens in the wild and the methodology presented here offers new ecological and paleoecological perspectives.

Microplastics in Freshwater Sediments Impact the Role of a Main Bioturbator in Ecosystem Functioning.

While microplastic transport, fate, and effects have been a focus of studies globally, the consequences of their presence on ecosystem functioning have not received the same attention. With increasing evidence of the accumulation of microplastics at sediment-water interfaces there is a need to assess their impacts on ecosystem engineers, also known as bioturbators, which have direct and indirect effects on ecosystem health. This study investigated the impact of microplastics on the bioturbator Tubifex tubifex alongside any effects on the biogeochemical processes at the sediment-water interface. Bioturbators were exposed to four sediment microplastic concentrations: 0, 700, 7000, and 70000 particles kg-1 sediment dry weight. Though no mortality was present, a significant response to oxidative stress was detected in tubificid worms after exposure to medium microplastic concentration (7000 particles kg-1 sediment dry weight). This was accompanied by a reduction in worm bioturbation activities assessed by their ability to rework sediment and to stimulate exchange water fluxes at the sediment-water interface. Consequently, the contributions of tubificid worms on organic matter mineralization and nutrient fluxes were significantly reduced in the presence of microplastics. This study demonstrated that environmentally realistic microplastic concentrations had an impact on biogeochemical processes at the sediment-water interface by reducing the bioturbation activities of tubificid worms.

A method to assess dermal absorption dynamics of chemical warfare agents: Finite doses of volatile compounds.

Chemical warfare agents are absorbed into the body from various entry routes and may have detrimental effects on human health. As many chemical compounds in this group are lipophilic, the outer layer of the skin is at an elevated risk. This contribution explores the dynamics of skin penetration for risk assessment. A previously validated model was applied to describe how an agent is transported across the stratum corneum following dermal exposure to a finite dose of a chemical. A mathematical construct was implemented for estimating the time constants and the cumulative amount of permeant entering the bloodstream or being released into the environment. Empirical equations were selected to determine the ratio of the steady-state evaporation rate to the steady-state dermal absorption rate and the physicochemical properties of the chemical warfare agents. Wolfram Mathematica was employed to run the simulations. The results from the newly derived expressions for the time constants matched those directly obtained from the validated model. For example, sarin gas had steady-state evaporation to an absorption rate of 991.25, and a total fractional absorption and evaporation of 5.1% and 94.9%, respectively. Combined with occupational exposure limits, the findings can help researchers assess an individual's risk level and develop protection programs.

Who is eating fructose within the Aedes albopictus gut microbiota?

The Asian tiger mosquito Aedes albopictus is a major public health concern because of its invasive success and its ability to transmit pathogens. Given the low availability of treatments against mosquito-borne diseases, vector control remains the most suitable strategy. The methods used thus far are becoming less effective, but recent strategies have emerged from the study of mosquito-associated microorganisms. Although the role of the microbiota in insect biology does not require further proof, much remains to be deciphered in mosquitoes, especially the contribution of the microbiota to host nutrient metabolism. Mosquitoes feed on plant nectar, composed of mostly fructose. We used stable isotope probing to identify bacteria and fungi assimilating fructose within the gut of Ae. albopictus. Mosquitoes were fed a 13 C-labelled fructose solution for 24 h. Differences in the active microbial community according to the sex of mosquitoes were highlighted. The bacterium Lelliottia and the fungi Cladosporium and Aspergillus dominated the active microbiota in males, whereas the bacterium Ampullimonas and the yeast Cyberlindnera were the most active in females. This study is the first to investigate trophic interactions between Ae. albopictus and its microbiota, thus underscoring the importance of the microbial component in nectar feeding in mosquitoes.

Combined oxygen and sulphur isotope analysis-a new tool to unravel vertebrate (paleo)-ecology.

Reconstructing the living environment of extinct vertebrates is often challenging due to the lack of proxies. We propose a new proxy to the living environment based on the combined oxygen and sulphur stable isotope analysis of vertebrate hydroxyapatite. We tested this isotopic proxy to 64 biogenic apatite (bones) samples that represent a wide spectrum of the extant vertebrate phylogenetic diversity including crocodiles, snakes, turtles, mammals, birds, lizards, fish and amphibians. We show that the combination of these two isotopic systems allows the living environment of all these vertebrates to be unambiguously distinguished between freshwater (aquatic vs semi-aquatic), seawater (aquatic vs semi-aquatic) and terrestrial. The main goal of this study is to provide a present-day isotopic reference frame and to discuss methodological issues that will serve to interpret future oxygen and sulphur isotope results obtained either from fossil or modern skeletal material. This new isotopic approach of combined oxygen and sulphur isotope analysis will be particularly useful to document major aquatic-terrestrial transitions in the fossil record but also to better constrain the living environment of some present-day species.

Energy transport and light propagation mechanisms in organic single crystals.

Unambiguous information about spatiotemporal exciton dynamics in three-dimensional nanometer- to micrometer-sized organic structures is difficult to obtain experimentally. Exciton dynamics can be modified by annihilation processes, and different light propagation mechanisms can take place, such as active waveguiding and photon recycling. Since these various processes and mechanisms can lead to similar spectroscopic and microscopic signatures on comparable time scales, their discrimination is highly demanding. Here, we study individual organic single crystals grown from thiophene-based oligomers. We use time-resolved detection-beam scanning microscopy to excite a local singlet exciton population and monitor the subsequent broadening of the photoluminescence (PL) signal in space and on pico- to nanosecond time scales. Combined with Monte Carlo simulations, we were able to exclude photon recycling for our system, whereas leakage radiation upon active waveguiding leads to an apparent PL broadening of about 20% compared to the initial excitation profile. Exciton-exciton annihilation becomes important at high excitation fluence and apparently accelerates the exciton dynamics leading to apparently increased diffusion lengths. At low excitation fluences, the spatiotemporal PL broadening results from singlet exciton diffusion with diffusion lengths of up to 210 nm. Surprisingly, even in structurally highly ordered single crystals, the transport dynamics is subdiffusive and shows variations between different crystals, which we relate to varying degrees of static and dynamic electronic disorders.

Grazing high and low: Can we detect horse altitudinal mobility using high-resolution isotope (δ13 C and δ15 N values) time series in tail hair? A case study in the Mongolian Altai.

RATIONALE: Carbon and nitrogen stable isotope time series performed in continuously growing tissues (hair, tooth enamel) are commonly used to reconstruct the dietary history of modern and ancient animals. Predicting the effects of altitudinal mobility on animal δ13 C and δ15 N values remains difficult as several variables such as temperature, water availability or soil type can contribute to the isotope composition. Modern references adapted to the region of interest are therefore essential. METHODS: Between June 2015 and July 2018, six free-ranging domestic horses living in the Mongolian Altaï were fitted with GPS collars. Tail hairs were sampled each year, prepared for sequential C and N isotope analysis using EA-IRMS. Isotopic variations were compared with altitudinal mobility, and Generalized Additive Mixed (GAMMs) models were used to model the effect of geographic and environmental factors on δ13 C and δ15 N values. RESULTS: Less than half of the pasture changes were linked with a significant isotopic shift while numerous isotopic shifts did not correspond to any altitudinal mobility. Similar patterns of δ13 C and δ15 N variations were observed between the different horses, despite differences in mobility patterns. We propose that water availability as well as seasonal availability of N2 fixing type plants primarily controlled horse hair δ13 C and δ15 N values, overprinting the influence of altitude. CONCLUSIONS: Our study shows that altitudinal mobility is not the main factor that drives the variations in horse tail hair δ13 C and δ15 N values and that seasonal change in the animal dietary preference also plays an important role. It is therefore risky to interpret variations in δ13 C and δ15 N values of animal tissues in terms of altitudinal mobility alone, at least in C3 -dominated environments.

Localization of sound-producing fish in a water-filled tank.

In this paper, the authors introduce an algorithm for locating sound-producing fish in a small rectangular tank that can be used, e.g., in behavioral bioacoustical studies to determine which fish in a group is sound-producing. The technique consists of locating a single sound source in the tank using signals gathered by four hydrophones placed in the tank together with a group of fish under study. The localization algorithm used in this paper is based on a ratio of two spectra ratios: the spectra ratio between the sound pressure measured by hydrophones at two locations and the spectra ratio between the theoretical Green's functions at the same locations. The results are compared to a localization based on image processing technique and with video recordings acquired synchronously with the acoustic recordings.

No Evidence That Nitrogen Limitation Influences the Elemental Composition of Isopod Transcriptomes and Proteomes.

The field of stoichiogenomics aims at understanding the influence of nutrient limitations on the elemental composition of the genome, transcriptome, and proteome. The 20 amino acids and the 4 nt differ in the number of nutrients they contain, such as nitrogen (N). Thus, N limitation shall theoretically select for changes in the composition of proteins or RNAs through preferential use of N-poor amino acids or nucleotides, which will decrease the N-budget of an organism. While these N-saving mechanisms have been evidenced in microorganisms, they remain controversial in multicellular eukaryotes. In this study, we used 13 surface and subterranean isopod species pairs that face strongly contrasted N limitations, either in terms of quantity or quality. We combined in situ nutrient quantification and transcriptome sequencing to test if N limitation selected for N-savings through changes in the expression and composition of the transcriptome and proteome. No evidence of N-savings was found in the total N-budget of transcriptomes or proteomes or in the average protein N-cost. Nevertheless, subterranean species evolving in N-depleted habitats displayed lower N-usage at their third codon positions. To test if this convergent compositional change was driven by natural selection, we developed a method to detect the strand-asymmetric signature that stoichiogenomic selection should leave in the substitution pattern. No such signature was evidenced, indicating that the observed stoichiogenomic-like patterns were attributable to nonadaptive processes. The absence of stoichiogenomic signal despite strong N limitation within a powerful phylogenetic framework casts doubt on the existence of stoichiogenomic mechanisms in metazoans.

Low loss optical waveguiding in large single crystals of a thiophene-based oligomer.

Active optical waveguides based on functional small organic molecules in micro/nano regime have attracted great interest for their potential applications in high speed miniaturized photonic integrations. Here, we report on the active waveguiding properties of millimeter sized single crystals of a newly synthesized thiophene-based oligomer. These large crystals exhibit low optical loss compared to other organic nanostructures, and optical losses depend on the emission energy. Moreover, we find that the coupling of photoluminescence to waveguide modes is very efficient, typically greater than 40%. These features indicate that such perfect single crystals with a low density of defects and extremely smooth surfaces exhibit low propagation loss, which makes them good candidates for the design and the fabrication of novel organic optical fibers and lasers.

High-precision (34) S/(32) S measurements in vertebrate bioapatites using purge-and-trap elemental analyser/isotope ratio mass spectrometry technology.

RATIONALE: In ecological studies, the sulfur isotope compositions (δ(34) S values) of soft tissues (e.g. hair, skin, nail, muscle, collagen) allow the determination of both past and present-day living environments of organisms. However, technical limitations have so far prevented reliable sulfur isotope analyses of minerals having low sulfur content, such as bioapatite, which is the crystalline component of skeletal tissues. The development of 'purge-and-trap' technology in elemental analysers recently demonstrated new possibilities to solve some of those technical difficulties. METHODS: We have used a VarioPYROcube elemental analyser (EA) equipped with 'purge-and-trap' technology, interfaced in continuous flow mode to an Isoprime 100 isotope ratio mass spectrometer, to measure the sulfur isotope compositions of bioapatite samples. We first characterised a working calibrated material of chemical composition close to those of our samples, the low-S bearing phosphorite BCR32, against the two δ(34) SV-CDT reference-calibrated materials, NBS-127 and IAEA-SO-5. We have confirmed a δ(34) SV-CDT value of +18.4‰ (1σ = 0.5; n = 18) in agreement with the previously published value. Using BCR32 as a compositional and isotopic reference material, we have then measured the δ(34) SV-CDT values of various bioapatite tissues (bone, dentine and enamel) from both modern and fossil vertebrates living in different environments (marine, freshwater and terrestrial). RESULTS: Our results demonstrate the capacity of this analytical setup to measure the δ(34) SV-CDT values of low-S bioapatite samples (0.14 to 1.19 wt%) with a good analytical precision (1σ = 0.5; n = 14). Our results also show that the δ(34) SV-CDT values of modern and fossil vertebrate bioapatites allow discrimination between marine environments and freshwater or terrestrial ones. CONCLUSIONS: Sulfur isotope analysis of bioapatite has great potential to track the living environment of extinct vertebrates for which only fossilised bones or teeth have been preserved. Copyright © 2016 John Wiley & Sons, Ltd.

Perceptual attributes for the comparison of head-related transfer functions.

The benefit of using individual head-related transfer functions (HRTFs) in binaural audio is well documented with regards to improving localization precision. However, with the increased use of binaural audio in more complex scene renderings, cognitive studies, and virtual and augmented reality simulations, the perceptual impact of HRTF selection may go beyond simple localization. In this study, the authors develop a list of attributes which qualify the perceived differences between HRTFs, providing a qualitative understanding of the perceptual variance of non-individual binaural renderings. The list of attributes was designed using a Consensus Vocabulary Protocol elicitation method. Participants followed an Individual Vocabulary Protocol elicitation procedure, describing the perceived differences between binaural stimuli based on binauralized extracts of multichannel productions. This was followed by an automated lexical reduction and a series of consensus group meetings during which participants agreed on a list of relevant attributes. Finally, the proposed list of attributes was then evaluated through a listening test, leading to eight valid perceptual attributes for describing the perceptual dimensions affected by HRTF set variations.

Ecological Engineering Approaches to Improve Hydraulic Properties of Infiltration Basins Designed for Groundwater Recharge.

Infiltration systems are increasingly used in urban areas for groundwater recharge. The reduction of sediment permeability by physical and/or biological processes is a major problem in management of infiltration systems often requiring expensive engineering operations for hydraulic performance maintenance. To reduce these costs and for the sake of sustainable development, we proposed to evaluate the ability of ecological engineering approaches to reduce the biological clogging of infiltration basins. A 36-day field-scale experiment using enclosures was performed to test the influences of abiotic (light reduction by shading) and biotic (introduction of the macrophyte Vallisneria spiralis (L.) or the gastropod Viviparus viviparus (Linnaeus, 1758)) treatments to limit benthic biofilm biomass and to maintain or even increase hydraulic performances. We coupled biological characterization of sediment (algal biomass, bacterial abundance, total organic carbon, total nitrogen, microbial enzymatic activity, photosynthetic activity, and photosystem II efficiency) with hydraulic conductivity measurements to assess the effects of treatments on sediment permeability. The grazer Viviparus viviparus significantly reduced benthic biofilm biomass and enhanced hydraulic conductivity. The other treatments did not produce significant changes in hydraulic conductivity although Vallisneria spiralis affected photosynthetic activity of biofilm. Finally, our results obtained with Viviparus viviparus are promising for the development of ecological engineering solutions to prevent biological fouling in infiltration systems.

Bioconcentration of (15)N-tamoxifen at environmental concentration in liver, gonad and muscle of Danio rerio.

Pharmaceutical compounds (PCs) are ubiquitous in aquatic ecosystems. In addition to the direct ecotoxicological risk presented by certain PCs, others can accumulate inside organisms and along trophic webs, subsequently contaminating whole ecosystems. We studied the bioconcentration of a bioaccumulative PC already found several times in the environment: tamoxifen. To this end, we exposed Danio rerio for 21d to (15)N-tamoxifen concentrations ranging from 0.1 to 10µg/L and used an analytic method based on stable isotopes to evaluate the tamoxifen content in these organisms. The evolution of the (15)N/(14)N ratio was thus measured in liver, muscle and gonads of exposed fish compared to control fish. We succeeded in quantifying (15)N-tamoxifen bioconcentrations at all the exposure concentrations tested. The highest bioconcentration factors of tamoxifen measured were 14,920 in muscle, 73,800 in liver and 85,600 in gonads of fish after 21d exposure at a nominal concentration of 10µg/L. However, these bioconcentration factors have to be considered as maximal values (BCFMAX). Indeed, despite its proven stability, tamoxifen can be potentially partially degraded during experiments. We now need to refine these results by using a direct analytic method (i.e. LC-MS/MS).

One- and two-photon absorption and emission properties of an oligo(phenylenethienylene)s series.

The photophysical and nonlinear absorption properties of an oligo(phenylenethienylene)s series (nTBT) are investigated in this article. The length of the chromophore is gradually increased from one to four phenylenethienylene repeating units in order to evaluate the effects of the electronic delocalization on the two-photon absorption cross sections (δ). According to the excitation anisotropy measurements and quantum chemical calculations, two electronic transitions with distinctive symmetries, 1Ag → 1Bu and 1Ag → 2Ag, are present in the low energy region of the linear absorption spectrum. The lowest-energy transition 1Ag → 1Bu is one-photon allowed but two-photon forbidden and implies an electronic charge delocalization all along the oligomer segment whereas the weakly-allowed 1Ag → 2Ag transition exhibits a transition moment perpendicular to the average plane of the chromophore. The latter transition mainly contributes to the two-photon absorption ability of the oligomers. All derivatives are poorly solvatochromic and the breakdown of the mirror symmetry rule observed between absorption and fluorescence spectra at room temperature has been attributed to a photoinduced geometrical relaxation leading to a very efficient planarization process of the oligomer irrespective of its size. Increasing the oligomer length results in a slight shift of the two-photon absorption band (∼1300 cm(-1)) and in a drastic increase of δ from 2 ± 1 GM up to 802 ± 160 GM for 1TBT and 4TBT respectively. Based on a three-level model, it was found that main contributions to the strong increase of δ stem from the transition moments Mge and Mee' which are multiplied by a factor of 2.8 and 5 when going from 1TBT to 4TBT.