Mobility of potentially harmful metals in latosols impacted by the municipal solid waste deposit of Londrina,Brazil

The contamination of soils by metals issuing from municipal solid waste (MSW) disposal in tropical environments has hardly been studied with regard to the particular problems associated with them, i.e., generally a high permeability of soils despite the abundance of clay, and the role of reactive Fe compounds. From a previous geotechnical and chemical survey, three latosol profiles differently affected by MSW leachates in the region of Londrina (Paraná, Brazil) were selected. The aims were to evaluate the extent of their contamination, to better understand the fate of potentially harmful metals in tropical soils and rank the determining factors. Samples between 0.5 and 7 m depth were analyzed for their physical, mineralogical and chemical properties, and their micro-morphology was described by optical and transmission electron microscopy. Two steps of a sequential extraction procedure helped to assess the mobility of elements and to better discriminate between metals originating from pedogenesis and issued from MSW. These combined approaches showed that exposed soil profiles have been impacted at various depths, down to 7 m, through increased metal content, especially enhanced mobility of Zn, Co, Mn, Cu and Fe, and through increased salinity and organic matter. The mobility of potentially harmful metals should decrease with pH, which significantly increased in some impacted horizons, but other factors can reverse this trend.     

Characterization and migration of atmospheric REE in soils and surface waters

Rainwater and snow collected from three different sites in France (Vosges Mountains, French Alps and Strasbourg) show more or less similar shapes of their REE distribution patterns. Rainwater from Strasbourg is the most REE enriched sample, whereas precipitations from the two mountainous, less polluted catchments are less REE enriched and have concentrations close to seawater. They are all strongly LREE depleted.Different water samples from an Alpine watershed comprising snow, interstitial, puddle and streamwater show similar REE distributions with LREE enrichment (rainwater normalized) but MREE and HREE depletion. In this environment, where water transfer from the soil to the river is very quick due to the low thickness of the soils, it appears that REE in streamwater mainly originate from atmospheric inputs. Different is the behaviour of the REE in the spring- and streamwaters from the Vosges Mountains. These waters of long residence time in the deep soil horizons react with soil and bedrock REE carrying minerals and show especially significant negative Eu anomalies compared to atmospheric inputs. Their Sr and Nd isotopic data suggest that most of the Sr and Nd originate from apatite leaching or dissolution. Soil solutions and soil leachates from the upper soil horizons due to alteration processes strongly depleted in REE carrying minerals, have REE distribution patterns close to those of lichens and throughfall. Throughfall is slightly more enriched especially in light REE than filtered rainwater probably due to leaching of atmospheric particles deposited on the foliage and also to leaf excretion.Data suggest that Sr and Nd isotopes of the soil solutions in the upper soil horizons originate from two different sources: 1) An atmospheric source with fertilizer, dust and seawater components and 2) A source mainly determined by mineral dissolution in the soil. These two different sources are also recognizable in the Sr and Nd isotopic composition of the tree’s throughfall solution. The atmospheric contributions of Sr and Nd to throughfall and soil solution are of 20 to 70 and 20%, respectively. In springwater, however, the atmospheric Sr and REE contribution is not detectable.     

Evolution of a Holocene banner bank controlled by morphodynamics and structural setting of a macrotidal coast: Saint-Brieuc Bay(NW-Europe)

The morphology and internal structure of the Horaine Bank(Bay of Saint-Brieuc, NW France) are described based on multibeam echosounder and high-resolution seismic datasets coupled with vibro-core data. The Horaine Bank shows large-scale bedforms in the lee of a submerged rocky shoal, which allowed defining it as a Banner Bank.The internal structure of the sandbank reveals four seismic units(U1–U4) on a Cambrian basement(U0). The basal unit U1 is interpreted as reworked lowstand fluvial sediments those infilled micro incised valleys during a rise in sea level. This unit is overlain by paleo-coastal barrier sand-spit(U2) whose development was controlled by swell in the context of a rapid rise in sea level. The successive prograding unit(U3) is interpreted as flooding deposits in continuity with unit U2. The unit U4 is characterized by oblique reflectors oriented in two opposite directions. This last unit, dated post 3500 yr BP, corresponds to migrating dunes superimposed on the bank and observable in the high-resolution bathymetric data. The strong correlation between tidal currents and the apparent clockwise migration of dune crests suggests the presence of a tidal gyre controlling the present-day dynamics of most of the Horaine bank dunes. This study proposes a new model for the construction of banner banks characterized by the gradual transition of a sand spit to a banner bank during marine transgression and ensuing hydrodynamic variability.     

Provenance of Pleistocene Rhine River Middle Terrace sands between the Swiss–German border and Cologne based on U–Pb detrital zircon ages

Detrital zircon U–Pb age distributions derived from samples representing ancient or relatively young large-scale continental drainage networks are commonly taken to reflect the geochronological evolution of the tapped continental area. Here, we present detrital zircon U–Pb ages and associated heavy mineral data from Pleistocene Rhine River Middle Terrace sands and equivalents between the Swiss–German border and Cologne in order to test the commonly assumed Alpine provenance of the material. Samples from eight localities were analyzed for their heavy mineral assemblages. Detrital zircon U–Pb ages were determined by laser ablation inductively coupled mass spectrometry on selected samples from five locations along the Rhine River. The zircon age populations of all samples show a similar distribution, their main peaks being between 300 and 500 Ma. Minor age populations are recognized at 570 and 1,070 Ma. The 300–400 Ma maximum reflects the Variscan basement drained by or recycled into the Rhine River and its tributaries. The 400–500 Ma peak with predominantly Early Silurian ages points to Baltica or to the mid-German crystalline rise as original sources. One distinct peak at c. 570 Ma probably represents input from Cadomian terranes. The Precambrian U–Pb ages are compatible with derivation from sources in Baltica and in northern Gondwana. The heavy mineral populations of Middle Terrace sands and equivalents are characterized to a variable extend by garnet, epidote, and green hornblende. This association is often referred to as the Alpine spectrum and is considered to be indicative of an Alpine provenance. However, hornblende, epidote, and garnet are dominant heavy minerals of collisional orogens in general and may also be derived from Variscan and Caledonian units or from intermittent storage units. A remarkable feature of the detrital zircon age distribution in the Rhine River sediments from the Swiss–German border to Cologne is the absence of ages younger than 200 Ma and in particular of any ages reflecting the Alpine orogeny between c. 100 and 35 Ma. Sediments from rivers draining the equally collisional Himalaya orogen contain detrital zircons as young as 20 Ma. Our results question the assumption that Pleistocene Rhine River sediments were directly derived from the Alps. The lag time between the formation and deposition age of the youngest zircon in the studied Pleistocene Rhine River deposits is 200 Ma. Together with the absence of Alpine zircon ages, this stresses that detrital zircon age data from ancient sedimentary units found in poorly understood tectonic or paleogeographic settings need to be interpreted with great care, one could miss an entire orogenic cycle.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Aquatic hydrocarbon distributions in the Seine estuary: Biogenic polyaromatics and n-alkanes

Dissolved and particulate hydrocarbons of biogenic origin were investigated for the first time in surface waters along the Seine River and its estuary. They comprise n-alkanes (n-ALKs) and diagenetic polycyclic aromatic hydrocarbons (PAHs). Samples were collected in three different sections of the estuary: the riverine zone, the mixing zone, and the marine zone. At the river mouth, two mooring stations were used for the collection of samples over tidal cycles. Total particulate n-ALK concentrations ranged from 31 ng 1^?1 to 2,918 ng 1^?1, or 5 μg g^?1 dry ng 1^?1, or 2 μg g^?1 of SM. Concentrations varied with the SM load and could be related to sedimentation and estuarine mixing. The sources of the n-ALKs were different in each zone of the estuary. The dissolved n-ALKs displayed lower concentrations than the particulate phase, varying from 136 ng 1^?1 to 344 ng 1^?1, while biogenic dissolved PAHs were almost absent.