From land to ocean: One month for southern elephant seal pups to acquire aquatic skills prior to their first departure to sea.

Weaned southern elephant seals (SES) quickly transition from terrestrial to aquatic life after a 5- to 6-week post-weaning period. At sea, juveniles and adult elephant seals present extreme, continuous diving behaviour. Previous studies have highlighted the importance of the post-weaning period for weanlings to prepare for the physiological challenges of their future sea life. However, very little is known about how their body condition during this period may influence the development of their behaviour and brain activities. To characterise changes in the behavioural and brain activity of weanlings prior to ocean departure, we implemented a multi-logger approach combining measurements of movements (related to behaviour), pressure (related to diving), and brain electrical activity. As pups age, the amount of time allocated to resting decreases in favour of physical activity. Most resting (9.6 ± 1.2 h/day) takes place during daytime, with periods of slow-wave sleep representing 4.9 ± 0.9 h/day during the first 2 weeks. Furthermore, an increasing proportion of physical activity transitions from land to shore. Additionally, pups in poorer condition (lean group) are more active earlier than those in better condition (corpulent group). Finally, at weaning, clear circadian activity with two peaks at dawn and dusk is observed, and this pattern remains unchanged during the 4 weeks on land. This circadian pattern matches the one observed in adults at sea, with more prey catches at dawn and dusk, raising the question of whether it is endogenous or triggered by the mother during lactation.

Contrasting offspring dependence periods and diving development rates in two closely related marine mammal species.

Understanding the ontogeny of diving behaviour in marine megafauna is crucial owing to its influence on foraging success, energy budgets, and mortality. We compared the ontogeny of diving behaviour in two closely related species-northern elephant seals (Mirounga angustirostris, n = 4) and southern elephant seals (Mirounga leonina, n = 9)-to shed light on the ecological processes underlying migration. Although both species have similar sizes and behaviours as adults, we discovered that juvenile northern elephant seals have superior diving development, reaching 260 m diving depth in just 30 days, while southern elephant seals require 160 days. Similarly, northern elephant seals achieve dive durations of approximately 11 min on their first day of migration, while southern elephant seals take 125 days. The faster physiological maturation of northern elephant seals could be related to longer offspring dependency and post-weaning fast durations, allowing them to develop their endogenous oxygen stores. Comparison across both species suggests that weaned seal pups face a trade-off between leaving early with higher energy stores but poorer physiological abilities or leaving later with improved physiology but reduced fat stores. This trade-off might be influenced by their evolutionary history, which shapes their migration behaviours in changing environments over time.

Beneath the Antarctic sea-ice: Fine-scale analysis of Weddell seal (Leptonychotes weddellii) behavior and predator-prey interactions, using micro-sonar data in Terre Adélie.

Lactation is the most energy-demanding event in mammals' reproduction. In pinnipeds, females are the only food providers to the young and have developed numerous behavioral and physiological lactation strategies, from capital-breeding to income-breeding. Lactating females' fine-scale foraging strategy, and precise understanding of how females supplement their pup's needs as well as their own are important to understand the species' ecology and energetic balance. Polar pinnipeds, inhabiting extreme environments, are sensitive to climate change and variability, understanding their constraints and foraging strategy during lactation is therefore important. In 2019, three sonar tags were deployed on lactating Weddell seals in Terre Adélie (East Antarctica) for 7 days, to study fine-scale predator-prey interactions. Feeding activity was mostly benthic, reduced, central-placed, and spatially limited. Females spent most of their time hauled-out. A total of 331 prey capture attempts (PrCAs) were recorded using triaxial acceleration data, with 125 prey identified on echograms (5 cm, acoustic size). All PrCAs occurred on the seafloor, shallower than usual records (mean depth of 88 m, vs 280 m after their molt). We also found that they only fed in three of the five identified dive shapes, during the ascent or throughout the dive. Half of the prey were reactive to the seal's approach, either leaving the seafloor, or escaping just above the seafloor, suggesting that the seals hunt by chasing them from the seabed. Seals continuously scanned the area during the approach phase, evoking opportunistic foraging. Our results provide additional evidence that Weddell seal forage during lactation, displaying a mix of capital-breeding and income-breeding strategies during this period of physiological stress. This work sheds light on previously unexplored aspects of their foraging behavior, such as shallow water environments, targeting benthic prey, generally focusing on single prey rather than schools, and evidence of visual scanning through observed head movements.

Diving behaviour of southern elephant seals: new models of behavioural and ecophysiological adjustments of oxygen store management.

Among pinnipeds, southern elephant seals (SESs, Mirounga leonina) are extreme divers that dive deeply and continuously along foraging trips to restore their body stores after fasting on land during breeding or moulting. Their replenishment of body stores influences their energy expenditure during dives and their oxygen (O2) reserves (via muscular mass), yet how they manage their O2 stores during their dives is not fully understood. In this study, 63 female SESs from Kerguelen Island were equipped with accelerometers and time-depth recorders to investigate changes in diving parameters through their foraging trips. Two categories of dive behaviour were identified and related to the body size of individuals, with smaller SESs performing shallower and shorter dives requiring greater mean stroke amplitude compared with larger individuals. In relation to body size, the larger seals had lower estimated oxygen consumption levels for a given buoyancy (i.e. body density) compared with smaller individuals. However, both groups were estimated to have the same oxygen consumption of 0.079±0.001 ml O2 stroke-1 kg-1 for a given dive duration and at neutral buoyancy when the cost of transport was minimal. Based on these relationships, we built two models that estimate changes in oxygen consumption according to dive duration and body density. The study highlights that replenishing body stores improves SES foraging efficiency, as indicated by increased time spent at the bottom of the ocean. Thus, prey-capture attempts increase as SES buoyancy approaches the neutral buoyancy point.

Track and dive-based movement metrics do not predict the number of prey encountered by a marine predator.

BACKGROUND: Studying animal movement in the context of the optimal foraging theory has led to the development of simple movement metrics for inferring feeding activity. Yet, the predictive capacity of these metrics in natural environments has been given little attention, raising serious questions of the validity of these metrics. The aim of this study is to test whether simple continuous movement metrics predict feeding intensity in a marine predator, the southern elephant seal (SES; Mirounga leonine), and investigate potential factors influencing the predictive capacity of these metrics. METHODS: We equipped 21 female SES from the Kerguelen Archipelago with loggers and recorded their movements during post-breeding foraging trips at sea. From accelerometry, we estimated the number of prey encounter events (nPEE) and used it as a reference for feeding intensity. We also extracted several track- and dive-based movement metrics and evaluated how well they explain and predict the variance in nPEE. We conducted our analysis at two temporal scales (dive and day), with two dive profile resolutions (high at 1 Hz and low with five dive segments), and two types of models (linear models and regression trees). RESULTS: We found that none of the movement metrics predict nPEE with satisfactory power. The vertical transit rates (primarily the ascent rate) during dives had the best predictive performance among all metrics. Dive metrics performed better than track metrics and all metrics performed on average better at the scale of days than the scale of dives. However, the performance of the models at the scale of days showed higher variability among individuals suggesting distinct foraging tactics. Dive-based metrics performed better when computed from high-resolution dive profiles than low-resolution dive profiles. Finally, regression trees produced more accurate predictions than linear models. CONCLUSIONS: Our study reveals that simple movement metrics do not predict feeding activity in free-ranging marine predators. This could emerge from differences between individuals, temporal scales, and the data resolution used, among many other factors. We conclude that these simple metrics should be avoided or carefully tested a priori with the studied species and the ecological context to account for significant influencing factors.

Phosphine-Free Aminocarbonylation Using Pd/DBU Catalyst: Carbonylative Coupling of Aryl Iodides and Amines.

An improved carbonylation method allowing amide bond formation between aryl iodides and aromatic amines is presented. In contrast to usual methods based on Pd catalysis, this method does not require a phosphine ligand. The catalyst system simply employs bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). The method was applied to the synthesis of various aromatic amides from aryl iodides and amines, and was scaled to gram order synthesis under as low as 1 atm of carbon monoxide.

New directions in radical carbonylation chemistry: combination with electron catalysis, photocatalysis and ring-opening.

Radical carbonylation offers potent methods for introducing carbon monoxide into organic molecules. This feature article focuses on our current efforts to develop new strategies for radical carbonylation, which include electron-transfer carbonylation, site-selective C(sp3)-H carbonylation by a photocatalyst and ring-opening carbonylation.

Electron-Catalyzed Aminocarbonylation: Synthesis of α,ß-Unsaturated Amides from Alkenyl Iodides, CO, and Amines.

Aminocarbonylation of alkenyl iodides with CO and amines proceeded under heating to produce α,ß-unsaturated amides in good yields (23 examples, 71% average yield). This catalyst-free method exhibited good functional-group tolerance, and open a straightforward access to functionalized acrylamides, as illustrated by the synthesis of Ilepcimide. A hybrid radical/ionic mechanism involving chain electron transfer is proposed for this transformation.

Convergent Synthesis of 2-Oxazolone-4-carboxylates Esters by Reaction of Aldehydes with Ambivalent N-Cbz-α-Tosylglycinate Ester.

N-Cbz-α-tosylglycinate ester was combined with aldehydes in a redox-neutral sequence leading to 2-oxazolone-4-carboxylates with high functional group tolerance. While the scope of the method was delineated to primary and secondary aliphatic aldehydes as well as aromatics, no racemization occurred with chiral aldehydes such as Garner's. Hitherto unknown, this process relies on the ambivalent role of N-Cbz-α-tosylglycinate ester acting as a pronucleophile.

Contaminants, prolactin and parental care in an Arctic seabird: Contrasted associations of perfluoroalkyl substances and organochlorine compounds with egg-turning behavior.

Incubating eggs represents a trade-off for parent birds between spending enough time fasting to take care of the clutch and to get enough nutrients for self-maintenance. It is believed that the pituitary hormone prolactin plays an important role in such allocation processes. Incubation does not solely imply the active warming of the eggs but also the active egg-turning to facilitate absorption of albumen by the embryo, reduce malposition and prevent the embryo from adhering to the inner shell membrane. However, how prolactin secretion is related to egg-turning behaviors is presently poorly addressed. In addition, several environmental contaminants can affect parental care behaviors through their endocrine disrupting properties but the effects of such contaminants on egg-turning behaviors remain so far unexplored. Using artificial eggs equipped with miniaturized data loggers, we investigated the relationships between egg-turning behaviors, prolactin secretion and contaminants burden in Arctic black-legged kittiwakes (Rissa tridactyla). Specifically, we examined the relationships between blood concentrations of poly- and perfluoroalkyl substances (PFASs), organochlorines (OCs), mercury (Hg), plasma prolactin levels and both egg-turning frequency and angular change. We also incorporated baseline corticosterone levels since this glucocorticoid is known to affect parental care. Plasma prolactin levels were positively related to angular change in female kittiwakes while corticosterone was not related to egg-turning behaviors in either sex. Hg was not related to egg-turning behaviors in either sex. We found contrasting associations between OCs and PFASs, since polychlorinated biphenyls (PCBs) were negatively associated with angular change in females, contrary to linear perfluorooctanesulfonate (PFOSlin) and perfluoroalkyl carboxylic acids (PFCAs) which were positively related to egg-turning frequency and angular change in both sexes. Additionally, PFASs concentrations were positively related to prolactin levels in female kittiwake. The possible stimulation of prolactin secretion by PFASs could therefore make adult kittiwakes to allocate more time taking care of their eggs, and thus possibly modify the trade-off between spending enough time caring for the clutch and obtaining enough nutrients at sea.

Introduction to chemical warfare agents, relevant simulants and modern neutralisation methods.

Despite international prohibition, some ill-intentioned states and organisations have shown their will and capacity to run chemical weapon programs, and the number of incidents involving chemical warfare agents (CWA) has significantly increased in recent years. Herein, we aimed to offer a clear overview of chemical warfare agents to organic chemists not specialized in this field by (1) introducing the main CWAs and their relevant simulants legally usable in academic laboratories and (2) presenting a selection of recent and soft neutralisation methods, such as organocatalysis and continuous flow, and materials such as metal-organic frameworks and polyoxometalates. These modern approaches offer potential future alternatives to "heavy" decontamination methods.

Organochlorines, perfluoroalkyl substances, mercury, and egg incubation temperature in an Arctic seabird: Insights from data loggers.

In birds, incubation-related behaviors and brood patch formation are influenced by hormonal regulation such as prolactin secretion. Brood patch provides efficient heat transfer between the incubating parent and the developing embryo in the egg. Importantly, several environmental contaminants are already known to have adverse effects on avian reproduction. However, relatively little is known about the effect of contaminants on incubation temperature (Tinc ) in wild birds. By using temperature thermistors placed into artificial eggs, we investigated whether the most contaminated parent birds are less able to provide appropriate egg warming and thus less committed to incubating their clutch. Specifically, we investigated the relationships among 3 groups of contaminants (organochlorines, perfluoroalkyl substances [PFASs], and mercury [Hg]) with Tinc and also with prolactin concentrations and brood patch size in incubating Arctic black-legged kittiwakes (Rissa tridactyla). Our results reveal that among the organochlorines considered, only blood levels of oxychlordane, the main metabolite of chlordane, a banned pesticide, were negatively related to the minimum incubation temperature in male kittiwakes. Levels of PFASs and Hg were unrelated to Tinc in kittiwakes. Moreover, our study suggests a possible underlying mechanism: since we reported a significant and negative association between blood oxychlordane concentrations and the size of the brood patch in males. Finally, this reduced Tinc in the most oxychlordane-contaminated kittiwakes was associated with a lower egg hatching probability. Environ Toxicol Chem 2018;37:2881-2894. © 2018 SETAC.

Coastal polynyas: Winter oases for subadult southern elephant seals in East Antarctica.

Antarctic coastal polynyas are regions of persistent open water and are thought to be key bio-physical features within the sea-ice zone. However, their use by the upper trophic levels of ecosystems remains unclear. A unique bio-physical dataset recorded by southern elephant seals reveals that East Antarctic polynyas are a key winter foraging habitat for male seals. During their post-moult trips from Isles Kerguelen to the Antarctic continental shelf, a total of 18 out of 23 seals visited 9 different polynyas, spending on average 25 ± 20% (up to 75%) of their total trip time inside polynyas. Changes in seal foraging and diving behaviours are observed inside polynyas as compared to outside polynyas. Two polynya usages by seals are observed for the inactive and active polynya phases, pointing to different seasonal peaks in prey abundance. During the active polynya phase, we link seal foraging behaviour to changes in the physical stability of the water-column, which likely impact the seasonal biological dynamics within polynyas.

High peripheral temperatures in king penguins while resting at sea: thermoregulation versus fat deposition.

Marine endotherms living in cold water face an energetically challenging situation. Unless properly insulated, these animals will lose heat rapidly. The field metabolic rate of king penguins at sea is about twice that on land. However, when at sea, their metabolic rate is higher during extended resting periods at the surface than during foraging, when birds descend to great depth in pursuit of their prey. This is most likely explained by differences in thermal status. During foraging, peripheral vasoconstriction leads to a hypothermic shell, which is rewarmed during extended resting bouts at the surface. Maintaining peripheral perfusion during rest in cold water, however, will greatly increase heat loss and, therefore, thermoregulatory costs. Two hypotheses have been proposed to explain the maintenance of a normothermic shell during surface rest: (1) to help the unloading of N2 accumulated during diving; and (2) to allow the storage of fat in subcutaneous tissue, following the digestion of food. We tested the latter hypothesis by maintaining king penguins within a shallow seawater tank, while we recorded tissue temperature at four distinct sites. When king penguins were released into the tank during the day, their body temperature immediately declined. However, during the night, periodic rewarming of abdominal and peripheral tissues occurred, mimicking temperature patterns observed in the wild. Body temperatures, particularly in the flank, also depended on body condition and were higher in 'lean' birds (after 10 days of fasting) than in 'fat' birds. While not explicitly tested, our observation that nocturnal rewarming persists in the absence of diving activity during the day does not support the N2 unloading hypothesis. Rather, differences in temperature changes throughout the day and night, and the effect of body condition/mass supports the hypothesis that tissue perfusion during rest is required for nutritional needs.

Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring.

The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea-H2 O2 adduct/MeSO3 H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR =3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.

Marine Bioluminescence: Measurement by a Classical Light Sensor and Related Foraging Behavior of a Deep Diving Predator.

Bioluminescence is produced by a broad range of organisms for defense, predation or communication purposes. Southern elephant seal (SES) vision is adapted to low-intensity light with a peak sensitivity, matching the wavelength emitted by myctophid species, one of the main preys of female SES. A total of 11 satellite-tracked female SESs were equipped with a time-depth-light 3D accelerometer (TDR10-X) to assess whether bioluminescence could be used by SESs to locate their prey. Firstly, we demonstrated experimentally that the TDR10-X light sensor was sensitive enough to detect natural bioluminescence; however, we highlighted a low-distance detection of the sensor. Then, we linked the number of prey capture attempts (PCAs), assessed from accelerometer data, with the number of detected bioluminescence events. PCA was positively related to bioluminescence, which provides strong support that bioluminescence is involved in predator-prey interactions for these species. However, the limitations of the sensor did not allow us to discern whether bioluminescence (i) provided remote indication of the biological richness of the area to SES, (ii) was emitted as a mechanic reaction or (iii) was emitted as a defense mechanism in response to SES behavior.

How Elephant Seals (Mirounga leonina) Adjust Their Fine Scale Horizontal Movement and Diving Behaviour in Relation to Prey Encounter Rate.

Understanding the diving behaviour of diving predators in relation to concomitant prey distribution could have major practical applications in conservation biology by allowing the assessment of how changes in fine scale prey distribution impact foraging efficiency and ultimately population dynamics. The southern elephant seal (Mirounga leonina, hereafter SES), the largest phocid, is a major predator of the southern ocean feeding on myctophids and cephalopods. Because of its large size it can carry bio-loggers with minimal disturbance. Moreover, it has great diving abilities and a wide foraging habitat. Thus, the SES is a well suited model species to study predator diving behaviour and the distribution of ecologically important prey species in the Southern Ocean. In this study, we examined how SESs adjust their diving behaviour and horizontal movements in response to fine scale prey encounter densities using high resolution accelerometers, magnetometers, pressure sensors and GPS loggers. When high prey encounter rates were encountered, animals responded by (1) diving and returning to the surface with steeper angles, reducing the duration of transit dive phases (thus improving dive efficiency), and (2) exhibiting more horizontally and vertically sinuous bottom phases. In these cases, the distance travelled horizontally at the surface was reduced. This behaviour is likely to counteract horizontal displacement from water currents, as they try to remain within favourable prey patches. The prey encounter rate at the bottom of dives decreased with increasing diving depth, suggesting a combined effect of decreased accessibility and prey density with increasing depth. Prey encounter rate also decreased when the bottom phases of dives were spread across larger vertical extents of the water column. This result suggests that the vertical aggregation of prey can regulate prey density, and as a consequence impact the foraging success of SESs. To our knowledge, this is one of only a handful of studies showing how the vertical distributions and structure of prey fields influence the prey encounter rates of a diving predator.

Southern Elephant Seals Replenish Their Lipid Reserves at Different Rates According to Foraging Habitat.

Assessing energy gain and expenditure in free ranging marine predators is difficult. However, such measurements are critical if we are to understand how variation in foraging efficiency, and in turn individual body condition, is impacted by environmentally driven changes in prey abundance and/or accessibility. To investigate the influence of oceanographic habitat type on foraging efficiency, ten post-breeding female southern elephant seals Mirounga leonina (SES) were equipped and tracked with bio-loggers to give continuous information of prey catch attempts, body density and body activity. Variations in these indices of foraging efficiency were then compared between three different oceanographic habitats, delineated by the main frontal structures of the Southern Ocean. Results show that changes in body density are related not only to the number of previous prey catch attempts and to the body activity (at a 6 day lag), but also foraging habitat type. For example, despite a lower daily prey catch attempt rate, SESs foraging north of the sub-Antarctic front improve their body density at a higher rate than individuals foraging south of the sub-Antarctic and polar fronts, suggesting that they may forage on easier to catch and/or more energetically rich prey in this area. Our study highlights a need to understand the influence of habitat type on top predator foraging behaviour and efficiency when attempting a better comprehension of marine ecosystems.

"On water" reaction of deactivated anilines with 4-methoxy-3-buten-2-one, an effective butynone surrogate.

Poorly nucleophilic aromatic amines (nitroanilines, chloroanilines, etc.) react readily and selectively with trans-4-methoxy-3-buten-2-one, a convenient, effective and inexpensive surrogate for 3-butyn-2-one, to afford (Z)-enaminones. The efficiency of the reaction mostly lies in the use of water as a solvent, which enhances the reaction rate by a 45 to 200-fold factor with regard to other media.

Sequential Friedel-Crafts-Type α-Amidoalkylation/Intramolecular Hydroarylation: Distinct Advantage of Combined Tf2NH/Cationic LAu(I) as a Consecutive or Binary Bicatalytic System.

The combined use of Tf2NH and L(Au)(+)X(-) as a dual or binary catalytic system clearly improves the efficiency and enlarges the scope of the tandem intermolecular Friedel-Crafts α-amidoalkylation/intramolecular hydroarylation sequence, compared to an "all gold" multicatalysis approach.