Benthic geochemistry of manganese in the Bay of Biscay,and sediment mass accumulation rate

Manganese is a major redox reactive element of benthic metabolism. We have built a database of existing knowledge on the benthic geochemistry of Mn in the Bay of Biscay, in order to comprehensively assess the behaviour of Mn in a variety of environments during early diagenesis. The database contains vertical profiles of particulate and dissolved Mn species of 59 cores collected during 17 cruises between 1997 and 2006 at nine stations positioned between 140 and 4,800 m water depths. At all studied stations, Mn species follow the conventional distribution, where Mn(III,IV) species are enriched in the oxic layer, and dissolved Mn is present in the anoxic sediments. A minor part of Mn-oxides originates from sedimenting particles. The major part is of diagenetic origin, and derives from the oxidation of upward-diffusing dissolved Mn(II). Mn-oxide inventories are higher at the deeper stations than at the shallower ones. This difference cannot be attributed to different sources of sedimenting particles, but it must depend on sedimentation rate and diagenetic processes. At depth, dissolved Mn(II) concentrations are constant. This probably reflects equilibrium with an authigenic Mn(II) phase, which is the ultimate phase into which Mn is fossilized. The Mn content of deeper anoxic sediments is similarly low in all the cores studied, associated with corresponding trends of Mn content in sedimenting particles of the Bay of Biscay. Bioturbation, rather than redox oscillations, can convey Mn(III,IV) species downwards into the anoxic sediments where they are reduced, associated with a peak of dissolved Mn. Because dissolved Mn(II) is re-oxidized when it diffuses towards the oxic layer, the inventory of the diagenetic Mn(III,IV) phase remains at steady state, especially at stations where the oxic layer is thick. It then becomes possible to calculate the residence time of diagenetic Mn(III,IV) particles within the oxic layer, using the upward-directed flux of pore water Mn(II). By applying this residence time to the accumulation of sediments within the oxic layer, we obtain the sediment mass accumulation rate. The values calculated for the sediments of the Bay of Biscay fit well with accumulation rates obtained from radionuclides or sediment traps. The method has also been validated with data collected in other marine sedimentary environments. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Interactions between groundwater and seasonally ice‐covered lakes: Using water stable isotopes and radon‐222 multilayer mass balance models

Interactions between lakes and groundwater are of increasing concern for freshwater environmental management but are often poorly characterized. Groundwater inflow to lakes, even at low rates, has proven to be a key in both lake nutrient balances and in determining lake vulnerability to pollution. Although difficult to measure using standard hydrometric methods, significant insight into groundwater–lake interactions has been acquired by studies applying geochemical tracers. However, the use of simple steady‐state, well‐mixed models, and the lack of characterization of lake spatiotemporal variability remain important sources of uncertainty, preventing the characterization of the entire lake hydrological cycle, particularly during ice‐covered periods. In this study, a small groundwater‐connected lake was monitored to determine the annual dynamics of the natural tracers, water stable isotopes and radon‐222, through the implementation of a comprehensive sampling strategy. A multilayer mass balance model was found outperform a well‐mixed, one‐layer model in terms of quantifying groundwater fluxes and their temporal evolution, as well as characterizing vertical differences. Water stable isotopes and radon‐222 were found to provide complementary information on the lake water budget. Radon‐222 has a short response time, and highlights rapid and transient increases in groundwater inflow, but requires a thorough characterization of groundwater radon‐222 activity. Water stable isotopes follow the hydrological cycle of the lake closely and highlight periods when the lake budget is dominated by evaporation versus groundwater inflow, but continuous monitoring of local meteorological parameters is required. Careful compilation of tracer evolution throughout the water column and over the entire year is also very informative. The developed models, which are suitable for detailed, site‐specific studies, allow the quantification of groundwater inflow and internal dynamics during both ice‐free and ice‐covered periods, providing an improved tool for understanding the annual water cycle of lakes.     

Reconstruction of Late-Quaternary sea- and lake-level changes in a tectonically active marginal basin using seismic stratigraphy: The Gulf of Cariaco,NE Venezuela

The Gulf of Cariaco is a marginal basin located between the Cariaco Basin and the Paria Gulf, offshore NE Venezuela, along a system of active right-lateral strike-slip faults. It is connected to the Caribbean Sea via a shallow 58-m-deep sill implying that the gulf was disconnected from the global ocean during eustatic lowstands. A dense grid of high-resolution reflection seismic profiles has been used to determine the overall tectonic structure of the gulf and to establish the seismic stratigraphy of its sedimentary infill. Six unconformity-bounded seismic–stratigraphic units were identified in the upper ~ 200 m of the sedimentary infill. Detailed seismic–stratigraphic and seismic-facies analysis allowed defining a series of sedimentary features that can be used as indicators of past sea or lake level in the Gulf of Cariaco: i) delta offlap breaks, ii) evaporites, and iii) erosional unconformities. Using accurate measurements of these various indicators at several locations in the gulf and a simple total subsidence model, a relative sea/lake-level history encompassing the last 130 kyr could be reconstructed. In periods of connection with the open ocean, reconstructed relative sea level correlates well with eustatic sea level. In times of disconnection, distinct lake-level fluctuations occurred, which sometimes resulted in total dessication of the gulf. Lake-level fluctuations appear to correlate with major Heinrich Events, stadials and interstadials. MIS 4, the LGM and the Younger Dryas were thus identified in the Gulf of Cariaco sedimentary record. The last reconnection to the Caribbean Sea occurred during MWP1b (around 11.5 kyr). The very good fit of the Cariaco sea/lake-level curve with the eustatic sea-level curves (both in terms of amplitude and of timing) underscores potential for future paleoclimate research of the sedimentary record contained in this marginal basin, despite its active tectonic setting.     

Structure,composition, and location of organic matter in the enstatite chondrite Sahara 97096 (EH3)

Abstract– The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine‐grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar δ¹⁵N and δ¹³C; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium‐heterogeneity and having mean H‐ and N‐isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer‐sized areas highly enriched in ¹⁵N (δ¹⁵N up to 1600‰). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.     

A Case Study of Spectral and Non‐Spectral Interferences on Copper Isotope Measurements by Multi‐Collector ICP‐MS (Wet Plasma)

Mathematical modelling was combined with experimental Cu isotope measurements to demonstrate the effect of the sample matrix in changing the absolute and relative abundances of spectral interferences from Ti and Cr species. This unforeseen non‐spectral effect, evidenced by variable inaccuracies of the different Zn‐normalised Cu isotope ratios, was investigated by comparing real sedimentary samples and artificial solutions intended to match the Cu:Ti:Cr ratios of the real samples after (one or two step) chromatographic processing. Artificial solutions showed positive bias in δ⁶⁵Cu_X/Y with the magnitude depending on (a) the ^6XZn/^6YZn ratio used for normalisation, (b) the Ti/Cu ratio and (c) the transmission coefficient of the TiO species. In contrast, real samples showed different δ⁶⁵Cu_X/Y patterns and displayed a more complex population of Ti and Cr oxides and hydroxides, giving rise to positive and negative inaccuracies that were two to six times higher compared with the artificial samples. The results evidence contrasting behaviour of Ti and Cr when forming polyatomic species in the plasma and stress that artificial solutions may fail to predict how residual elements interact with the analyte/dopant pair during MC‐ICP‐MS analyses. More importantly, the study shows that all Zn isotope ratios do not have the same merit in correcting for mass bias in the presence of matrix elements and should all be monitored to verify the absence of spectral interferences for Cu isotope measurements. In this respect, accurate Cu data could be generally obtained by a two‐step chromatographic purification providing a minimum reduction of ~ 21000 and ~ 3000 times the initial amounts of Ti and Cr, respectively.     

A method for regional climate change detection using smooth temporal patterns

This paper introduces an original method for climate change detection, called temporal optimal detection method. The method consists in searching for a smooth temporal pattern in the observations. This pattern can be either the response of the climate system to a specific forcing or to a combination of forcings. Many characteristics of this new method are different from those of the classical “optimal fingerprint” method. It allows to infer the spatial distribution of the detected signal, without providing any spatial guess pattern. The spatial properties of the internal climate variability doesn’t need to be estimated either. The estimation of such quantities being very challenging at regional scale, the proposed method is particularly well-suited for such scale. The efficiency of the method is illustrated by applying it on real homogenized datasets of temperatures and precipitation over France. A multimodel detection is performed in both cases, using an ensemble of atmosphere-ocean general circulation models for estimating the temporal patterns. Regarding temperatures, new results are highlighted, especially by showing that a change is detected even after removing the uniform part of the warming. The sensitivity of the method is discussed in this case, relatively to the computation of the temporal patterns and to the choice of the model. The method also allows to detect a climate change signal in precipitation. This change impacts the spatial distribution of the precipitation more than the mean over the domain. The ability of the method to provide an estimate of the spatial distribution of the change following the prescribed temporal patterns is also illustrated.     

Modelling the behaviour of a large landslide with respect to hydrogeological and geomechanical parameter heterogeneity

Thanks to a sophisticated transient hydrogeological modelling allowing the determination of the pore pressure fields in La Frasse landslide mass during a crisis, it has been possible to model the mechanical behaviour of the slide and obtain results that prove to be similar to the monitored data, in terms of peak velocity, distribution of velocity with time and space and total displacements. Such results are reached only when appropriate constitutive modelling laws are used, and when geotechnical tests supply all the required parameters. The main results concern the potential effect of a drainage system during a crisis, like the one experienced in 1994. It can include vertical boreholes equipped with pumps or drains drilled from a gallery. The draining system reduces horizontal displacements down to 5% of the values modelled during the crisis. This effect, which appears to extend over a large width, will be even more significant if the boreholes discharge the drained water into the gallery, due to its extension in the presently stabilised landslide mass below the active zone. The modelling tools developed for La Frasse landslide thus provide all the necessary information to optimise the drainage scheme.     

Towards a better understanding of changes in wintertime cold extremes over Europe: a pilot study with CNRM and IPSL atmospheric models

Recent winter seasons have evidenced that global warming does not exclude the occurrence of exceptionally cold and/or snowy episodes in the Northern mid-latitudes. The expected rarefaction of such events is likely to exacerbate both their societal and environmental impacts. This paper therefore aims to evaluate model uncertainties underlying the fate of wintertime cold extremes over Europe. Understanding why climate models (1) still show deficiencies in simulating present-day features and (2) differ in their responses under future scenarios for the twentyfirst century indeed constitutes a crucial challenge. Here we propose a weather-regime approach in order to separate the contributions of large-scale circulation and non-dynamical processes to biases or changes in the simulated mean and extreme temperatures. We illustrate our methodology from the wintertime occurrence of extremely cold days in idealized atmosphere-only experiments performed with two of the CMIP5 climate models (CNRM-CM5 and IPSL-CM5A-LR). First we find that most of the present-day temperature biases are due to systematic errors in non-dynamical processes, while the main features of the large-scale dynamics are well captured in such experiments driven by observed sea-surface temperatures, with the exception of a generalized underestimation of blocking episodes. Then we show that uncertainties associated with changes in large-scale circulation modulate the depletion in cold extremes under an idealized scenario for the late twentyfirst century. These preliminary results suggest that the original methodology proposed in this paper can be helpful for understanding spreads of larger model-ensembles when simulating the response of temperature extremes to climate change.