First insights on spatial and temporal distribution patterns of humpback whales in the breeding ground at Sainte Marie Channel,Madagascar

The Sainte Marie Channel on the northeast coast of Madagascar is an important breeding ground for humpback whales; the first observation of birth was documented there, yet it has never been investigated for phenology and habitat use of humpback whales. The present study was aimed at examining temporal and spatial distribution patterns and the encounter rate of different social groups of humpback whales during the breeding season. We used a large set of opportunistic sightings data collected from whale-watching boats. A total of 3 247 sightings were collected during 897 whale-watching trips conducted between June and September from 2009 to 2013. Our study complements previous information on the seasonal presence of humpback whale social groups by demonstrating a persistent and well-structured temporal pattern in the succession of the different groups. Over the different years of the study period, groups without calves consistently dominated the first 30 days of the breeding season, followed by an increase in groups with calves. Interannual differences were observed in the encounter rates, with significantly higher global encounter rates in 2009, 2011 and 2013 (2.2, 2.3 and 2.3 sightings h^–1, respectively), and likewise for the mean encounter rates for groups with calves. In contrast, the encounter rate of groups without calves was similar over the study period. Although our study area exhibits a narrow configuration and poorly contrasting physiographic features due to its restricted spatial extent, we report a spatially segregated pattern of humpback whale social groups in the Sainte Marie Channel. A general linear model showed that groups with calves were influenced by water depth and distance from shore, being observed mostly in shallow waters (to 20 m depth) and close to the coastline (6 km). Our findings will be useful for the development of strategic sustained management plans by providing baseline information on humpback whale distribution at an important but poorly documented breeding site.     

Geostatistical seismic inversion for non‐stationary patterns using direct sequential simulation and co‐simulation

Geostatistical seismic inversion methods are routinely used in reservoir characterisation studies because of their potential to infer the spatial distribution of the petro‐elastic properties of interest (e.g., density, elastic, and acoustic impedance) along with the associated spatial uncertainty. Within the geostatistical seismic inversion framework, the retrieved inverse elastic models are conditioned by a global probability distribution function and a global spatial continuity model as estimated from the available well‐log data for the entire inversion grid. However, the spatial distribution of the real subsurface elastic properties is complex, heterogeneous, and, in many cases, non‐stationary since they directly depend on the subsurface geology, i.e., the spatial distribution of the facies of interest. In these complex geological settings, the application of a single distribution function and a spatial continuity model is not enough to properly model the natural variability of the elastic properties of interest. In this study, we propose a three‐dimensional geostatistical inversion technique that is able to incorporate the reservoir's heterogeneities. This method uses a traditional geostatistical seismic inversion conditioned by local multi‐distribution functions and spatial continuity models under non‐stationary conditions. The procedure of the proposed methodology is based on a zonation criterion along the vertical direction of the reservoir grid. Each zone can be defined by conventional seismic interpretation, with the identification of the main seismic units and significant variations of seismic amplitudes. The proposed method was applied to a highly non‐stationary synthetic seismic dataset with different levels of noise. The results of this work clearly show the advantages of the proposed method against conventional geostatistical seismic inversion procedures. It is important to highlight the impact of this technique in terms of higher convergence between real and inverted reflection seismic data and the more realistic approximation towards the real subsurface geology comparing with traditional techniques.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

Origin of high Zn contents in Jurassic limestone of the Jura mountain range and the Burgundy: evidence from Zn speciation and distribution

In order to better understand the origin and enrichment mechanisms leading to elevated Zn concentrations in Jurassic limestone of the Jura mountain range (JMR) and the Burgundy (B), we investigated four locations of Bajocian age (JMR: Lausen–Schleifenberg, Gurnigel; B: Vergisson–Davayé, Lucy-le-Bois) and two locations of Oxfordian age (JMR: Dornach, Pichoux) for their Zn distribution and speciation. Measurements of the acid-extractable and bulk Zn contents showed that Zn is stratigraphically and spatially heterogeneously distributed, in association with permeable carbonate levels. Up to 3,580 and 207 mg/kg Zn was detected in Bajocian and Oxfordian limestone, respectively, with numerous limestone samples having Zn contents above 50 mg/kg. Using X-ray absorption near edge structure spectroscopy and micro-X-ray fluorescence spectrometry, the speciation and micro-scale distribution of Zn was investigated for selected limestone samples. In Bajocian limestone sphalerite and/or Zn-substituted goethite and a minor fraction of Zn-bearing carbonates were identified. In contrast, Zn-bearing carbonates (Zn-substituted calcite and hydrozincite) were accounting for most of the total Zn in Oxfordian limestone. The micro-scale distribution of Zn for Bajocian and Oxfordian limestone was however similar with localized Zn-rich zones in the limestone cement and at the rim of oolites. The stratigraphic sporadicity and microscale heterogeneity of the Zn distribution together with the Zn speciation results point to a hydrothermal origin of Zn. Occurence of Zn-goethite is probably linked to the oxidative transformation of framboidal pyrite and hydrothermal sphalerite in contact with meteoritic waters. Difference in speciation between Bajocian limestone and Oxfordian limestone may be related to differences in rock permeability and/or to various hydrothermal events. Isotopic dating of the different mineralizations will be needed to decipher differences in Zn speciation and the precise chronology of hydrothermal episodes.     

Formation of Zn-rich phyllosilicate, Zn-layered double hydroxide and hydrozincite in contaminated calcareous soils

Recent studies demonstrated that Zn-phyllosilicate- and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2-7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322-30,090 mg/kg Zn). Based on 12 bulk and 23 micro-focused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from ∼20% to ∼80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn (∼30-80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH₄NO₃ followed by 1 M NH₄-acetate at pH 6.0. Even though the formation of Zn-precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited.     

The effect of hedgerow wild-margins on topsoil hydraulic properties,and overland-flow incidence,magnitude and water-quality

Overland and shallow-subsurface flows from agricultural catchments are believed to contribute towards flood-risk and water-quality degradation across the globe. Hedgerows are commonplace agricultural features that may disrupt these rapid hydrological pathways. Research into the hydrological functioning of hedgerows is very limited however, with no field-based quantitative comparison of overland-flows within hedgerows versus other land-uses. This research is the first globally to observe changes in overland-flow incidence, volume and water-quality, alongside topsoil hydraulic and physico-chemical properties, induced by a hedgerow and adjoining wild-margin within a grassland landscape. Observations were conducted within two replicated paired-plots between a hedgerow wild-margin and a bordering pasture, within Cumbria, UK. Compared to adjacent pasture, hedge-margins significantly reduced topsoil dry bulk-density and increased porosity, and significantly increased the topsoil median permeability by a factor of 22–27. Overland-flow models, based on direct observations, highlight that hedge-margins are slower to produce overland-flows than pastures, requiring an equal or greater amount of saturation before the onset of overland-flow generation. Hedge-margins resultantly produced less overland-flow volume, likely due to increased infiltration, percolation and/or evapotranspiration. Soil saturation models, also based on direct observations, confirm pastures saturate faster than hedge-margins, with hedge-margins having extremely variable dynamics in relation to precipitation, whereas pastures have more moderate and consistent dynamics. Overland-flow water-quality from ‘wash-off’ experiments highlight that hedge-margins may store substantially more nitrate (70–260%), nitrate-nitrite (640–650%), and loose sediment (540–3970%) on the ground surface compared to pastures; although further experimentation is needed to determine contaminant mobilization potential.     

Nanociliates of the order Prostomatida: Their relevance in the microbial food web of a mesotrophic lake

Two nanociliates of the order Prostomatida,Pseudobalanion planctonicum (12–18 µm) andUrotricha furcata (12–21 µm), were found to be the most abundant ciliates in the epilimnion of Piburger See, a small mesotrophic lake. Temperature and food availability were the main factors controlling the sudden increase in abundance, which reached a maximum of 101 cell ml^–1 at the beginning of summer. During their exponential development in numbers and biomass, a strong decrease in chlorophylla and in the abundance of phytoplankton, especiallyRhodomonas, was observed. We assume, therefore, thatPseudobalanion planctonicum andUrotricha furcata together with rotifers, mainlyPolyarthra dolichoptera, are able to reduce the phytoplankton biomass in the upper epilimnion to the same level as found during the clearwater phase. Preliminary results of grazing on bacteria suggest that these nanociliates are omnivorous, although their impact on bacterial assemblages was low (3.1% of the standing stock grazed per day). Feeding on the base of the food web combined with their high abudance at certain times makes them an important link for higher trophic levels. This study constitutes the second report onPseudobalanion as an important component of the microbial food web in lakes.     

Paleomagnetism of early cretaceous arapey formation (Northern Uruguay)

We report detailed rock-magnetic and paleomagnetic directional data from 35 lava flows (302 standard paleomagnetic cores) sampled in the Central-Northern region of Uruguay in order to contribute to the study of the paleosecular variation of the Earth’s magnetic field during early Cretaceous and to obtain precise Cretaceous paleomagnetic pole positions for stable South America. The average unit direction is rather precisely determined from 29 out of 35 sites. All A₉₅ confidence angles are less than 8°, which points to small within-site dispersion and high directional stability. Normal polarity magnetizations are revealed for 19 sites and 10 are reversely magnetized. Two other sites yield well defined intermediate polarities. The mean direction, supported by a positive reversal test is in reasonably good agreement with the expected paleodirection for Early Cretaceous stable South America and in disagreement with a 10° clockwise rotation found in the previous studies. On the other hand, paleomagnetic poles are significantly different from the pole position suggested by hotspot reconstructions, which may be due to true polar wander or the hotspot motion. Our data suggest a different style of secular variation during (and just before) the Cretaceous Normal Superchron and the last 5 Ma, supporting a link between paleosecular variation and reversal frequency.     

Characterization of dissolved organic matter in anoxic rock extracts and in situ pore water of the Opalinus Clay

Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O₂ exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.