Christine Paillès

Transfer, Transformation, and Impacts of Ceria Nanomaterials in Aquatic Mesocosms Simulating a Pond Ecosystem

Mesocosms are an invaluable tool for addressing the complex issue of exposure during nanoecotoxicological testing. This experimental strategy was used to take into account parameters as the interactions between the NPs and naturally occurring (in)organic colloids (heteroaggregation), or the flux between compartments of the ecosystems (aqueous phase, sediments, biota) when assessing the impacts of CeO2 NPs in aquatic ecosystems. In this study, we determine the transfer, redox transformation, and impacts of 1 mg L(-1) of bare and citrate coated CeO2-NPs toward an ecologically relevant organism (snail, Planorbarius corneus) exposed 4 weeks in a complex experimental system mimicking a pond ecosystem. Over time, CeO2-NPs tend to homo- and heteroaggregate and to accumulate on the surficial sediment. The kinetic of settling down was coating-dependent and related to the coating degradation. After 4 weeks, Ce was observed in the digestive gland of benthic organisms and associated with 65-80% of Ce(IV) reduction into Ce(III) for both bare and coated CeO2 NPs. A transitory oxidative stress was observed for bare CeO2-NPs. Coated-NPs exposed snails did not undergo any lipid peroxidation nor change in the antioxidant contents, while Ce content and reduction in the digestive gland were identical to bare CeO2-NPs. We hypothesized that the presence of citrate coating enhanced the defense capacity of the cells toward the oxidative stress induced by the CeO2 core.

IR Laser Extraction Technique Applied to Oxygen Isotope Analysis of Small Biogenic Silica Samples

An IR-laser fluorination technique is reported here for analyzing the oxygen isotope composition (delta18O) of microscopic biogenic silica grains (phytoliths and diatoms). Performed after a controlled isotopic exchanged (CIE) procedure, the laser fluorination technique that allows one to visually check the success of the fluorination reaction is faster than the conventional fluorination technique and allows analyzing delta18O of small to minute samples (1.6-0.3 mg) as required for high-resolution paleoenvironmental reconstructions. The long-term reproducibility achieved with the IR laser-heating fluorination/O2 delta18O analysis is lower than or equal to +/-0.26 per thousand (1 SD; n = 99) for phytoliths and +/-0.17 per thousand (1 SD; n = 47) for diatoms. When several CIE are taken into account in the SD calculation, the resulting reproducibility is lower than or equal to +/-0.51 per thousand for phytoliths (1 SD; n = 99; CIE > 5) and +/-0.54 per thousand (1 SD; n = 47; CIE = 13) for diatoms. A minimum reproducibility of +/-0.5 per thousand leads to an estimated uncertainty on delta18Osilica close to +/-0.5 per thousand. Resulting uncertainties on reconstructed temperature and delta18Oforming water are, respectively, +/-2 degrees C and +/-0.5 per thousand and fit in the precisions required for intertropical paleoenvironmental reconstructions. Several methodological points such as optimal extraction protocols and the necessity or not of performing two CIE prior to oxygen extraction are assessed.

High-resolution paleolimnology opens new management perspectives for lakes adaptation to climate warming

Varved lake sediments provide opportunities for high-resolution paleolimnological investigations that may extend monitoring surveys in order to target priority management actions under climate warming. This paper provides the synthesis of an international research program relying on >150 years-long, varved records for three managed perialpine lakes in Europe (Lakes Geneva, Annecy and Bourget). The dynamics of the dominant, local human pressures, as well as the ecological responses in the pelagic, benthic and littoral habitats were reconstructed using classical and newly developed paleo-proxies. Statistical modelling achieved the hierarchization of the drivers of their ecological trajectories. All three lakes underwent different levels of eutrophication in the first half of the XXth century, followed by re-oligotrophication. Climate warming came along with a 2°C increase in air temperature over the last century, to which lakes were unequally thermally vulnerable. Unsurprisingly, phosphorous concentration has been the dominant ecological driver over the last century. Yet, other human-influenced, local environmental drivers (fisheries management practices, river regulations) have also significantly inflected ecological trajectories. Climate change has been impacting all habitats at rates that, in some cases, exceeded those of local factors. The amplitude and ecological responses to similar climate change varied between lakes, but, at least for pelagic habitats, rather depended on the intensity of local human pressures than on the thermal effect of climate change. Deep habitats yet showed higher sensitivity to climate change but substantial influence of river flows. As a consequence, adapted local management strategies, fully integrating nutrient inputs, fisheries management and hydrological regulations, may enable mitigating the deleterious consequences of ongoing climate change on these ecosystems.

Role of molting on the biodistribution of CeO2 nanoparticles within Daphnia pulex

As all arthropods, microcrustaceans shed their chitinous exoskeleton (cuticule, peritrophic membrane) to develop and grow. While the molting is the most crucial stage in their life cycle, it remains poorly investigated in term of pollutant biodistribution within the organisms. In this paper, we used optical, electronic, and X ray-based microscopies to study the uptake and release of CeO2 nanoparticles by/from Daphnia pulex over a molting stage. We measured that D. pulex molts every 59 ± 21 h (confidence interval) with growth rates about 1.1 or 1.8 μm per stage as a function of the pieces measured. Ingestion via food chain was the main route of CeO2 nanoparticles uptake by D. pulex. The presence of algae during the exposure to nanoparticles (sub-lethal doses) enhanced by a factor of 3 the dry weight concentration of Ce on the whole D. pulex. Nanoparticles were localized in the gut content, in direct contact with the peritrophic membrane, and on the cuticle. Interestingly, the depuration (24 h with Chlorella pseudomonas) was not efficient to remove the nanoparticles from the organisms. From 40% to 100% (depending on the feeding regime during exposure) of the CeO2 taken up by D. pulex is not release after the depuration process. However, we demonstrated for the first time that the shedding of the chitinous exoskeleton was the crucial mechanism governing the released of CeO2 nanoparticles regardless of the feeding regime during exposure.

An adaptable mesocosm platform for performing integrated assessments of nanomaterial risk in complex environmental systems

Physical-chemists, (micro)biologists, and ecologists need to conduct meaningful experiments to study the environmental risk of engineered nanomaterials with access to relevant mechanistic data across several spatial and temporal scales. Indoor aquatic mesocosms (60L) that can be tailored to virtually mimic any ecosystem appear as a particularly well-suited device. Here, this concept is illustrated by a pilot study aimed at assessing the distribution of a CeO2-based nanomaterial within our system at low concentration (1.5 mg/L). Physico-chemical as well as microbiological parameters took two weeks to equilibrate. These parameters were found to be reproducible across the 9-mesocosm setup over a 45-day period of time. Recovery mass balances of 115 ± 18% and 60 ± 30% of the Ce were obtained for the pulse dosing and the chronic dosing, respectively. This demonstrated the relevance of our experimental approach that allows for adequately monitoring the fate and impact of a given nanomaterial.

Evidence of moist niches in the Bolivian Andes during the mid-Holocene arid period

To examine the climate of the mid-Holocene and early human settings in the Andes when the Altiplano was recording the most arid phase of the Holocene, we analyzed plant-related proxies (pollen, phytoliths, diatoms, stable isotopes) from a sediment core sampled at high elevation in the Eastern Cordillera of Bolivia. Our study was carried out in the wetland of Tiquimani (16°12′06.8″S; 68°3′51.5″W; 3760 m), on a well-known pathway between Amazonia and Altiplano. The 7000-year old record shows a two-step mid-Holocene with a dry climate between 6800 and 5800, followed by a wetter period that lasted until 3200 cal. yr BP. In the Central Andes of Bolivia, a widespread aridity was observed on the Altiplano during the mid-Holocene. However, here, we show that moisture was maintained locally by convective activity from the Amazon lowlands. During the arid interval between 5000 and 4000 yr BP, these niches of moisture produced specific grasslands that may have enabled the survival of an archaic culture of hunter–gatherers on the Puna. This development occurred 2000 years before expansion of quinoa cultivation on the Puna.

5000 years of lacustrine ecosystem changes from Lake Petit (Southern Alps, 2200 m a.s.l.): Regime shift and resilience of algal communities

Sediments from Lake Petit (2200 m a.s.l., Southern Alps) are particularly relevant for analysis of coupled landscape palaeoecology and palaeolimnology. Diatom assemblages, organic matter composition of sediments (total nitrogen and organic carbon) and Pediastrum boryanum concentrations were obtained from a 144-cm-long core, enabling the reconstruction of the aquatic ecosystem over nearly the last 5000 cal. BP. From 4800 to 4300 cal. BP, Lake Petit was a stable diatom-productive water body dominated by alkaliphilous diatoms (Staurosirella pinnata). During this period, nutrients and cations were supplied by the chemical weathering of podzols that developed under conifer woodlands. This overall stability was suddenly interrupted at 4200 cal. BP by a major detrital pulse that was probably climate linked (4200 cal. BP event) and that triggered a drop in diatom productivity and diversity. From 4100 to 2400 cal. BP, diatom productivity progressively decreased, whereas Pediastrum developed. Diatom assemblages were more diversified (predominance of Pseudostaurosira robusta, P. brevistriata and P. pseudoconstruens) and reflected a regime of continuous erosion, whereas slopes were colonised by grazed grasslands. Finally, from 2400 cal. BP to the present day, diatom assemblages reveal a slight acidification and nutrient enrichment of waters concomitant with increasing human pressure in the catchment. These results demonstrate the close links between ecosystems and the ready propagation of disturbances throughout watersheds that might lead to abrupt regime shifts in such alpine environments.

Entomoneis calixasini sp. nov., a new fossil diatom from the Turkish Marmara Sea sediments

A new fossil diatom with a well-developed raphe-bearing keel and continuous junction line in the strongly bilobate wings is described as Entomoneis calixasini Paillès, Blanc-Valleron & Poulin sp. nov. This species was found at numerous levels within a 4.6-m-long core recovered from the north-western slope of the Central High of the Marmara Sea, Turkey. Detailed light and scanning electron microscopy were used to characterize this species. Entomoneis calixasini is unique by a wing resembling interconnecting dunces’ caps. This species, sometimes the most abundant, is present between 44 and 395 cm of MET09-GR02 core sediments, corresponding to the Pleistocene last glacial period (brackish lacustrine sediments). It was not observed in the marine sediments above, or in other core sediments from the Marmara Sea or elsewhere in Pleistocene or Holocene sequences. It is absent in modern collections and from the literature, and is considered extinct.

The Holocene deposits of Lake Petit (2200 m asl, Southern French Alps): climatic and anthropogenic controls on mountain sediment dynamics?

Numerous archaeological studies carried out in high-elevation areas of the Southern French Alps have documented ancient human occupation of mountains, mainly characterized by pastoral and mining activities. Besides, the area was affected by both continental and Mediterranean climate instability throughout the Holocene. Lake Petit, located in the Mercantour massif, was investigated in order to reconstruct past interactions between humans, the environment and climate, using a multidisciplinary approach. This study was carried out on a 144 cm-long gravity core providing a continuous record spanning the last 5000 years. Our multi-proxy investigation (sedimentological, geochemical and palynological analyses), allowed us to reconstruct three main phases, evidencing a progressive destabilization of the local environment. The first phase (ca. 4800 to 4300 cal. BP) was characterized by relatively stable environmental conditions, as attested by a high lake productivity (deposition of pure diatomite) and by the local presence of trees (presence of conifer stomata). The second phase (ca. 4300 to 1500 cal. BP) could correspond to a drastic cleaning of landscapes since the lake record highlights an abrupt switch in sediment source marked by an input of terrestrial organic matter. Regular occurrences of anthropogenic pollen assemblages might indicate early pastoral activity in the lake vicinity, while wetter conditions characteristic of the Neoglacial period may have trigger hillslopes destabilization. The most recent phase (since ca. 1500 cal. BP) is marked by a final degradation of the environment: the lake productivity dramatically decreased contemporaneously with a fall of the AP/NAP pollen curve. This phase also exhibits the highest values of anthropogenic pollen taxa and concentrations of lead. It undoubtedly corresponded to one of an intensive agro-pastoral pressure as well to local mining activities.