8000 years of vegetation history in the northern Iberian Peninsula inferred from the palaeoenvironmental study of the Zalama ombrotrophic bog (Basque‐Cantabrian Mountains,Spain)

This paper focuses on pollen, spores, non‐pollen palynomorphs (NPPs) and certain geochemical elements from the ombrotrophic blanket bog of Zalama (Basque‐Cantabrian Mountains, northern Iberian Peninsula), with the support of a robust chronology based on 17 AMS ¹⁴C dates. The main results related to the last 8000 years show that, during the early middle Holocene, pines and deciduous forests were the most extensive tree formations. At the beginning of the succession, pines reach 44%, showing regional presence, whereas after 7600 cal. a BP, deciduous forests were particularly abundant. From c. 6500 cal. a BP the pollen diagram constructed from our samples shows the first anthropogenic evidence, linked with the new economic practices related to the Neolithic of the Basque‐Cantabrian Mountains. From 3300 cal. a BP the expansion of Fagus sylvatica is particularly clear, and has since then become one of the dominant forest species in this region. We also discuss the Holocene evolution of other noteworthy plant communities in southwestern Europe, such as Taxus baccata, Juglans and shrublands.     

K–Ar and Ar/Ar ages of dikes emplaced in the onshore basement of the Santos Basin, Resende area, SE Brazil: implications for the south Atlantic opening and Tertiary reactivation

New K–Ar and ⁴⁰Ar/³⁹Ar data of tholeiitic and alkaline dike swarms from the onshore basement of the Santos Basin (SE Brazil) reveal Mesozoic and Tertiary magmatic pulses. The tholeiitic rocks (basalt, dolerite, and microgabbro) display high TiO₂ contents (average 3.65 wt%) and comprise two magmatic groups. The NW-oriented samples of Group A have (La/Yb)_N ratios between 15 and 32.3 and range in age from 192.9±2.2 to 160.9±1.9 Ma. The NNW-NNE Group B samples, with (La/Yb)_N ratios between 7 and 16, range from 148.3±3 to 133.9±0.5 Ma. The alkaline rocks (syenite, trachyte, phonolite, alkaline basalts, and lamprophyre) display intermediate–K contents and comprise dikes, plugs, and stocks. Ages of approximately 82 Ma were obtained for the lamprophyre dikes, 70 Ma for the syenite plutons, and 64–59 Ma for felsic dikes. Because Jurassic–Early Cretaceous basic dikes have not been reported in SE Brazil, we might speculate that, during the emplacement of Group A dikes, extensional stresses were active in the region before the opening of the south Atlantic Ocean and coeval with the Karoo magmatism described in South Africa. Group B dikes yield ages compatible with those obtained for Serra Geral and Ponta Grossa magmatism in the Paraná Basin and are directly related to the breakup of western Gondwana. Alkaline magmatism is associated with several tectonic episodes that postdate the opening of the Atlantic Ocean and related to the upwelling of the Trindade plume and the generation of Tertiary basins southeast of Brazil. In the studied region, alkaline magmatism can be subdivided in two episodes: the first one represented by lamprophyre dykes of approximately 82 Ma and the second comprised of felsic alkaline stocks of approximately 70 Ma and associated dikes ranging from 64 to 59 Ma.

Resumo

Novos dados K–Ar e ⁴⁰Ar/³⁹Ar de enxames de diques toleíticos e alcalinos localizados no embasamento onshore da Bacia de Santos (SE Brasil) apontam para diferentes pulsos magmáticos ocorridos entre o Jurássico e o Terciário. Os diques de rochas toleíticas (basalto, diabásio e microgabro), são mais velhos, exibem altos teores de TiO₂ (3,65% peso na média) e podem ser subdivididos em dois grupos magmáticos. O Grupo A aflora a norte da Bacia de Resende, compreende diques orientados na direção NW, com razões (La/Yb)_N entre 15 e 32,3, e idades entre 192.9±2.2 e 160.9±1.9 Ma. O Grupo B aflora a sul e a leste da Bacia de Resende, engloba diques orientados na direção NNW e NNE, com razões (La/Yb)_N entre 7 e 16, e idades obtidas entre 148.3±3 e 133.9±0.5 Ma. As rochas alcalinas (sienito, traquito, fonolito, basalto alcalino e lamprófiro) possuem teores médios de K, e afloram como diques, plugs e stocks.. As idades obtidas são de ca. 82 Ma para os diques lamprofíricos, de ca. 70 Ma para os plugs sieníticos, e entre 64 e 59 Ma para os diques félsicos. Como estas idades Jurássicas para diques toleíticos ainda não foram descritas para a região sudeste do Brasil, pode-se especular que durante o emplacement dos diques do GrupoA o cenário tectônico indicaria esforços extensionais anteriores à abertura do Oceano atlântico Sul, e contemporânea ao derrame basáltico do Karoo na África do Sul. Já os diques do Grupo B são contemporâneos ao magmatismo Serra Geral e ao enxame de diques de Ponta Grossa, e portanto este episódio está diretamente relacionado à separação entre o Brasil e África no Cretáceo. O magmatismo alcalino está associado a diversos episódios tectônicos que sucedem à abertura do Oceano Atlântico Sul e que resultaram no desenvolvimento das Bacias terciárias do sudeste brasileiro. Está provavelmente relacionado à chegada da Pluma de Trindade e as idades obtidas para a região em estudo indicam que o magmatismo lamprofírico é mais antigo (ca. 82 Ma), seguido pelos plútons sieníticos (ca. 70 Ma) e diques associados (64 a 59 Ma.)     

Prediction of ground displacements and velocities from groundwater level changes at the Vallcebre landslide (Eastern Pyrenees, Spain)

In active landslides, the prediction of acceleration of movement is a crucial issue for the design and performance of warning systems. The landslide of Vallcebre in the Eastern Pyreenes, Spain, has been monitored since 1996 and data on rainfall, groundwater levels and ground displacements are measured on a regular basis. Displacements observed in borehole wire extensometers have shown an immediate response of the landslide to rainfall episodes. This rapid response is likely due to the presence of preferential drainage ways. The occurrence of nearly constant rates of displacement in coincidence with steady groundwater levels suggests the presence of viscous forces developed during the movement. An attempt to predict both landslide displacements and velocities was performed at Vallcebre by solving the momentum equation in which a viscous term (Bingham and power law) was added. Results show that, using similar rheological parameters for the entire landslide, computed displacements reproduce quite accurately the displacements observed at three selected wire extensometers. These results indicate that prediction of displacements from groundwater level changes is feasible.     

Multi-Modal Monitoring of Slip Along Frictional Discontinuities

Seismic wave transmission and digital image correlation (DIC) are employed to study slip processes along frictional discontinuities. A series of biaxial compression experiments are performed on gypsum specimens with non-homogeneous contact surfaces. The specimens are composed of two blocks with perfectly mated contact surfaces with a smooth surface with low frictional strength on the upper half and a rough surface with high frictional strength on the lower half. Compressional, P, and shear, S, wave pulses were transmitted through the discontinuity while digital images of the specimen surface were acquired during the test. A distinct peak in the amplitude of transmitted wave occurs prior to the peak shear strength and is considered a “precursor” to the failure. Precursors indicate that slip initiates from the smooth surface and extends to the rough surface as the shear load is increased. From the DIC data, slip is identified as a jump in the displacement field along the fracture that initiates from the smooth surface and propagates to the rough surface. Precursors are associated with an increase in the rate of slip across the discontinuity and are a measure of the reduction in the fracture shear stiffness.     

Use of targets to track 3D displacements in highly vegetated areas affected by landslides

Monitoring landslides with terrestrial laser scanning (TLS) is currently a well-known technique. One problem often encountered is the vegetation that produces shadow areas on the scans. Indeed, the points behind a given obstacle are hidden and thus occluded on the point cloud. Thereby, locations monitored with terrestrial laser scanner are mostly rock instabilities and few vegetated landslides, being difficult or even impossible to survey vegetated slopes using this method with its classical non-full wave form. The Peney landslide (Geneva, Switzerland) is partially vegetated by bushes and trees, and in order to monitor its displacements during the drawdown of the Verbois reservoir located at its base, an alternative solution has been found. We combined LiDAR technique with 14 targets made of polystyrene placed at different locations inside and outside the landslide area. The obtained displacements were compared with classical measurement methods (total station and extensometer), showing good resemblance of results, indicating that the use of targets in highly vegetated areas could be an efficient alternative for mass movements monitoring.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

Carbonate platform depositional sequences, Upper Cretaceous, south-central Pyrenees (Spain)

The Upper Cretaceous (Cenomanian-Maastrichtian) of the south-central Pyrenees shows five carbonate platform sequences where the major parameters are tectonism, relative sea-level fluctuations and inherited depositional profile. Depositional geometries and basin analysis permit an understanding of the depositional history.Five depositional sequences have been recognized: (1) The Santa Fe sequence (Middle-Upper Cenomanian), a ramp to a skeletal rimmed shelf with an escarpment bypass margin. The lower boundary is an angular unconformity and the upper one records a sea-level drop. The platform location of the margin was determined by a listric normal fault. (2) An abrupt sea-level rise drowned the former platform. The Congost sequence (Turonian-Lower Coniacian), a distally steepened ramp with erosional distal deep slope. The depositional model was largely controlled by pre-existing basin morphology. Cessation of platform development was due to a relative sea-level drop. (3) The Sant Corneli sequence (Upper Coniacian-Lower Santonian), a mixed terrigenous-skeletal homoclinal ramp with upright margin, deep slope and dysaerobic basin. The slope results from the backstepping by 24 km of the previous margin and gentle basin tilting. The platform margin remained more or less at the same position, and relief between platform and slope increased indicating continuous relative sea-level rise. The upper boundary is an angular unconformity at the platform margin produced by an abrupt sea-level rise and platform drowning, and by listric normal faulting. (4) The Vallcarga sequence (Upper Santonian-Campanian), a distal-steepened skeletal homoclinal ramp, erosional escarpment and turbidite basin, which corresponds to the Mesozoic maximum marine expansion. A listric normal fault created two depositional areas: a more or less flat footwall block with a north-northwest prograding carbonate ramp.     

Granulite-amphibolite facies metasediments from the Serre (Calabria,Southern Italy): their protoliths and the processes controlling their chemistry

In the northwestern Serre, a near continuous section through the Palaeozoic lower continental crust crops out. This paper deals with granulite facies metasedimentary rocks of this section. Fifty-five chemical analyses (major elements, Sc, V, Cr, Co, Ni, Rb, Sr, Y, Nb and Ba) are given. Chemical data indicate that the original sedimentary sequence was made up of arenites in the lower part and mainly Fe and Mg rich pelites in the upper part. The metapelites experienced anatexis and removal of some melt, whereas the meta-arenites suffered only incipient anatexis and became dehydration granulites. The various rock types display an overall relatively low K/Rb ratio due mainly to the stability of K- and Rb-retaining phases. A weighted mean composition of the fragment of the lower continental crust outcropping in the Serre has been established by integrating the chemical data for metasediments (55 analyses), metabasites (92 analyses) and dioritic and tonalitic gneisses (10 analyses) with the field data. This composition compared to the compositions of the bulk continental crust and of other sections considered as belonging to the lower crust, confirms the hypothesis that (1) the lower crust is heterogeneous, and (2) it is more basic than the continental crust.