Isotermes d'adsorpció d'alquilfenols en sediments i altres materials

Projecte de recerca elaborat a partir d’una estada al Center of Applied Geosciences de la Eberhard Karls Universität entre abril i octubre del 2007. Durant l'estada es va adquirir la tècnica per a la realització d'isotermes d'adsorció aplicant-la posteriorment a l'estudi de dos compostos del grup dels alquilfenols (nonilfenol i octilfenol). Aquestes isotermes es van realitzar en diversos sediments provinents de la conca hidrogràfica del riu Ebre i en altres dos materials (lignit i torba), tots ells amb diferent contingut de carboni orgànic total (que varia entre 0,4% per a un dels sediments i 47,8% per a la torba), per a estudiar la influència d'aquest paràmetre en els comportament del nonilfenol pel que fa a l'adsorció. Per altra banda es va afegir l’octilfenol a l’estudi, tant per separat com en combinació amb el nonilfenol, i es va extendre la isoterma per al nonilfenol a concentracions més baixes, properes a les concentracions que es poden trobar d’aquest compost al medi. Aquestes últimes isotermes es van realitzar utilitzant en tots els casos un dels sediments del riu Ebre, amb un contingut de carboni orgànic del 5,8 %, per a poder comparar els resultats sense la influència d’aquest paràmetre. Totes les mostres es van analitzar utilitzant un cromatogràf de gasos acoblat a un espectròmetre de masses.

Analisi de compostos orgànics persistents i estudi de la procedència d'hidrocarburs en sediments del mar Mediterrani català

Els sediments del fons marí són molt importants en els ecosistemes aquàtics. Aquests sediments són considerats absorbents naturals, ja que s’hi acumulen moltes substàncies nocives, com ara metalls pesants i contaminants orgànics persistents (COPs). En aquest estudi s’han analitzat mostres de sediments del mar Mediterrani amb la finalitat d’examinar els COPs i la possible procedència d’hidrocarburs derivats del petroli. Les mostres han estat extretes davant de la desembocadura del riu Besòs (se n’ha fet una extracció a 8 km i una altra a 54 km de distància respecte la costa) i davant del municipi català anomenat Vilanova i la Geltrú (se n’ha fet, també, una extracció a 8-10 km i una altra a 30-40 km de distància respecte la costa). D’aquestes mostres, obtingudes per perforació, se n’han analitzat el primer i segon centímetres. S’han quantificat els hidrocarburs aromàtics policíclics (PAHs), els bifenils policlorats (PCBs) i els compostos organoclorats (OCPs) utilitzats antigament com a pesticides. S’ha posat de manifest que en les zones més properes a la costa, les concertacions COPs són més elevades a la regió més meridional, tot i estar davant de la desembocadura del riu Besòs. Segurament això és degut a la influència de la deriva litoral (corrent costaner marí en direcció NE-SW). Finalment, l’índex Phytane/Pristane, l’índex de preferència de carboni o, en anglès Carbon Preference Index (CPI) i la barreja complexa sense resoldre o, en anglès, Unresolved Complex Mixture (UCM) apunten a la conclusió que l’origen dels hidrocarburs analitzats (n-alcans) podria ser petrogènic.

Application of compositional data analysis to geochemical data of marine sediments

In an earlier investigation (Burger et al., 2000) five sediment cores near the RodriguesTriple Junction in the Indian Ocean were studied applying classical statistical methods(fuzzy c-means clustering, linear mixing model, principal component analysis) for theextraction of endmembers and evaluating the spatial and temporal variation ofgeochemical signals. Three main factors of sedimentation were expected by the marinegeologists: a volcano-genetic, a hydro-hydrothermal and an ultra-basic factor. Thedisplay of fuzzy membership values and/or factor scores versus depth providedconsistent results for two factors only; the ultra-basic component could not beidentified. The reason for this may be that only traditional statistical methods wereapplied, i.e. the untransformed components were used and the cosine-theta coefficient assimilarity measure.During the last decade considerable progress in compositional data analysis was madeand many case studies were published using new tools for exploratory analysis of thesedata. Therefore it makes sense to check if the application of suitable data transformations,reduction of the D-part simplex to two or three factors and visualinterpretation of the factor scores would lead to a revision of earlier results and toanswers to open questions . In this paper we follow the lines of a paper of R. Tolosana-Delgado et al. (2005) starting with a problem-oriented interpretation of the biplotscattergram, extracting compositional factors, ilr-transformation of the components andvisualization of the factor scores in a spatial context: The compositional factors will beplotted versus depth (time) of the core samples in order to facilitate the identification ofthe expected sources of the sedimentary process.Kew words: compositional data analysis, biplot, deep sea sediments

Interactions between grain size and composition of sediments: two examples

Two contrasting case studies of sediment and detrital mineral composition are investigated in order to outline interactions between chemical composition and grain size. Modern glacial sediments exhibit a strong dependence of the two parameters due to the preferential enrichment of mafic minerals, especially biotite, in the fine-grained fractions. On the other hand, the composition of detrital heavy minerals (here: rutile) appears to be not systematically related to grain-size, but is strongly controlled by location, i.e. the petrology of the source rocks of detrital grains. This supports the use of rutile as a well-suited tracer mineral for provenance studies. The results further suggest that (i) interpretations derived from whole-rock sediment geochemistry should be flanked by grain-size observations, and (ii) a more sound statistical evaluation of these interactions require the development of new tailor-made statistical tools to deal with such so-called two-way compositions

A Log-linear model of grain size influence on the geochemistry of sediments

Sediment composition is mainly controlled by the nature of the source rock(s), and chemical (weathering) and physical processes (mechanical crushing, abrasion, hydrodynamic sorting) during alteration and transport. Although the factors controlling these processes are conceptually well understood, detailed quantification of compositional changes induced by a single process are rare, as are examples where the effects of several processes can be distinguished. The present study was designed to characterize the role of mechanical crushing and sorting in the absence of chemical weathering. Twenty sediment samples were taken from Alpine glaciers that erode almost pure granitoid lithologies. For each sample, 11 grain-size fractions from granules to clay (ø grades &-1 to &9) were separated, and each fraction was analysed for its chemical composition.The presence of clear steps in the box-plots of all parts (in adequate ilr and clr scales) against ø is assumed to be explained by typical crystal size ranges for the relevant mineral phases. These scatter plots and the biplot suggest a splitting of the full grain size range into three groups: coarser than ø=4 (comparatively rich in SiO2, Na2O, K2O, Al2O3, and dominated by “felsic” minerals like quartz and feldspar), finer than ø=8 (comparatively rich in TiO2, MnO, MgO, Fe2O3, mostly related to “mafic” sheet silicates like biotite and chlorite), and intermediate grains sizes (4≤ø &8; comparatively rich in P2O5 and CaO, related to apatite, some feldspar).To further test the absence of chemical weathering, the observed compositions were regressed against three explanatory variables: a trend on grain size in ø scale, a step function for ø≥4, and another for ø≥8. The original hypothesis was that the trend could be identified with weathering effects, whereas each step function would highlight those minerals with biggest characteristic size at its lower end. Results suggest that this assumption is reasonable for the step function, but that besides weathering some other factors (different mechanical behavior of minerals) have also an important contribution to the trend.Key words: sediment, geochemistry, grain size, regression, step function

Oscil.lacions del nivell del mar i sediments associats durant l'Holocè a la Costa Brava Meridional (Girona)

Several marine deposits in the southern Costa Brava shoreline have been studied. They appear at different heights above and below the present sea level. Three groups are defined in relation to their origin: conglomerate levels at the bottom of the cliffs, not-cementedemerged beaches and cemented submerged beaches. The age of the emerged beaches has been accurately determined by means of the ceramic content and radiocarbon dating. Chronological succession of the deposits and their stratigraphic and paleontological characteristics allow to define a sequence of the sea level changes during the latest stages of the versiliane transgression in the studied area

Sediments antics del litoral del Baix Empodà entre es Forn (Begur) i Vall-presona (Santa Cristina d'Aro)

A la Costa Brava hi ha, en comparació amb altres àrees mediterrànies, pocs testimonis de sediments litorals antics. El domini manifest dels processosd'erosió n'és la causa principal. Tanmateix, hi ha alguns dipòsits litorals fòssils, que se situen uns decimetres per sobre i per sota del nivell del mar actual. L'estudi detallat dels diferents nivells localitzats fins ara ha permès caracteritzar-los des d'un punt de vista estratigràfic. Així, s'ha pogut constatar que es tracta d'acumulacions de blocs aplegats al peu de penya-segats, de platges emergides sense cimentar, i de platges submergides que han patit un procés de cimentació. La seva edat és molt recent, en termes geològics, i es remunta a començaments de l'era cristiana

Flux and composition of settling particles across the continental margin of the Gulf of Lion: the role of dense shelf water cascading

Settling particles were collected using sediment traps deployed along three transects in the Lacaze-Duthiers and Cap de Creus canyons and the adjacent southern open slope from October 2005 to October 2006. The settling material was analyzed to obtain total mass fluxes and main constituent contents (organic matter, opal, calcium carbonate, and siliciclastics). Cascades of dense shelf water from the continental shelf edge to the lower continental slope occurred from January to March 2006. They were traced through strong negative near-bottom temperature anomalies and increased current speeds, and generated two intense pulses of mass fluxes in January and March 2006. This oceanographic phenomenon appeared as the major physical forcing of settling particles at almost all stations, and caused both high seasonal variability in mass fluxes and important qualitative changes in settling material. Fluxes during the dense shelf water cascading (DSWC) event ranged from 90.1 g m(-2) d(-1) at the middle Cap de Creus canyon (1000 m) to 3.2 g m(-2) d(-1) at the canyon mouth (1900 m). Fractions of organic matter, opal and calcium carbonate components increased seaward, thus diminishing the siliciclastic fraction. Temporal variability of the major components was larger in the canyon mouth and open slope sites, due to the mixed impact of dense shelf water cascading processes and the pelagic biological production. Results indicate that the cascading event remobilized and homogenized large amounts of material down canyon and southwardly along the continental slope contributing to a better understanding of the off-shelf particle transport and the internal dynamics of DSWC events.

Estudi palinologic dels sediments de les mels de Xixona (Alacant)

Anàlisi pol.línica dels sediments de dotze mostres de mei recollides al terme municipal de Xixona (Alacant). Utilitzant els resultats fern una classificació qualitativa de les mels segons el seu origen floral i una de quantitativa aplicant els críteris de MAURIZIO, 1939.

Precisions sobre la determinació de la fracció argila a sediments i sòls arenosos

Es proposen uns milloraments en la metodologia classica de determinació qualitativa dels minerals de la fraccio argila en sediments i sbls sorrencs. L'extraccioconstade: garbellament de la mostra amb un garbelladorde2 mmde pas; eliminacio de la materia organica amb aigua oxigenada; centnfugacio a 6.000 r. p. m.; garbellament en humit per 0,2 mm, agitamenc dispersio amb calgon; decantacio i sifonat; centrifugació i desecacio. Nova dispersio per a la preparacio d'agregats onentats i sedimentacio sobre els «portes» dins de plaques de Petri. Aixi queden a punt d'obtenir els diagrames roentgen. Per I'espectroscbpia de raigs infrarojos, es dispersen les mostres i, a més de les mostres «normals», es tracten amb malaquita o bencidina. Diferents exemples il.lustren el treball.

External forcings, oceanographic processes and particle flux dynamics in Cap de Creus submarine canyon, NW Mediterranean Sea

Particle fluxes (including major components and grain size), and oceanographic parameters (near-bottom water temperature, current speed and suspended sediment concentration) were measured along the Cap de Creus submarine canyon in the Gulf of Lions (GoL; NW Mediterranean Sea) during two consecutive winter-spring periods (2009 2010 and 2010 2011). The comparison of data obtained with the measurements of meteorological and hydrological parameters (wind speed, turbulent heat flux, river discharge) have shown the important role of atmospheric forcings in transporting particulate matter through the submarine canyon and towards the deep sea. Indeed, atmospheric forcing during 2009 2010 and 2010 2011 winter months showed differences in both intensity and persistence that led to distinct oceanographic responses. Persistent dry northern winds caused strong heat losses (14.2 × 103 W m−2) in winter 2009 2010 that triggered a pronounced sea surface cooling compared to winter 2010 2011 (1.6 × 103 W m−2 lower). As a consequence, a large volume of dense shelf water formed in winter 2009 2010, which cascaded at high speed (up to ∼1 m s−1) down Cap de Creus Canyon as measured by a current-meter in the head of the canyon. The lower heat losses recorded in winter 2010 2011, together with an increased river discharge, resulted in lowered density waters over the shelf, thus preventing the formation and downslope transport of dense shelf water. High total mass fluxes (up to 84.9 g m−2 d−1) recorded in winter-spring 2009 2010 indicate that dense shelf water cascading resuspended and transported sediments at least down to the middle canyon. Sediment fluxes were lower (28.9 g m−2 d−1) under the quieter conditions of winter 2010 2011. The dominance of the lithogenic fraction in mass fluxes during the two winter-spring periods points to a resuspension origin for most of the particles transported down canyon. The variability in organic matter and opal contents relates to seasonally controlled inputs associated with the plankton spring bloom during March and April of both years.

Influence on present-day coastal dynamics and evolution of a relict subaqueous delta lobe: Sol de Riu lobe, Ebro Delta. Continental Shelf Research, 74: 94-104. doi:10.1016/j.csr.2013.11.021

We used high-resolution swath-bathymetry data to characterise the morphology of the abandoned subaqueous Sol de Riu delta lobe in the Ebro Delta, Western Mediterranean Sea. This study aims to assess the influence of an abandoned delta lobe on present-day coastal dynamics in a micro-tidal environment. Detailed mapping of the relict Sol de Riu lobe also showed a set of bedforms interpreted as footprints of human activities: seasonal V-shaped depressions on the middle shoreface due to boat anchoring and old trawling marks between 16 and 18 m water depth. Estimations of the mobility of bottom sediment showed that the shallowest shoreface (i.e. less than 7 m depth) is the most dynamic part of the relict lobe, while the middle shoreface experienced significant morphological changes since the lobe was abandoned. The deepest shoreface (i.e. water depth in excess of 15 m), which corresponds to the front of the lobe, is defined by a very small potential for morphological change. Simulations showed that while the relict lobe does not significantly affect the typical short period waves (Tp ≈4 s) in the study area, it does interfere with the most energetic wave conditions (Tp ≥ 7 s) acting as a shoal leading to the concentration of wave energy along the shoreline northwest of the lobe. The consequence of such modification of the high-energy wave propagation pattern by the relict lobe is an alteration of the wave-induced littoral sediment dynamics with respect to a situation without the lobe.

Reexposure and advection of C-14-depleted organic carbon from old deposits at the upper continental slope

Outcrops of old strata at the shelf edge resulting from erosive gravity-driven flows have been globally described on continental margins. The reexposure of old strata allows for the reintroduction of aged organic carbon (OC), sequestered in marine sediments for thousands of years, into the modern carbon cycle. This pool of reworked material represents an additional source of C-14-depleted organic carbon supplied to the ocean, in parallel with the weathering of fossil organic carbon delivered by rivers from land. To understand the dynamics and implications of this reexposure at the shelf edge, a biogeochemical study was carried out in the Gulf of Lions (Mediterranean Sea) where erosive processes, driven by shelf dense water cascading, are currently shaping the seafloor at the canyon heads. Mooring lines equipped with sediment traps and current meters were deployed during the cascading season in the southwestern canyon heads, whereas sediment cores were collected along the sediment dispersal system from the prodelta regions down to the canyon heads. Evidence from grain-size, X-radiographs and Pb-210 activity indicate the presence in the upper slope of a shelly-coarse surface stratum overlying a consolidated deposit. This erosive discontinuity was interpreted as being a result of dense water cascading that is able to generate sufficient shear stress at the canyon heads to mobilize the coarse surface layer, eroding the basal strata. As a result, a pool of aged organic carbon (Delta C-14 = -944.5 +/- 24.7%; mean age 23,650 +/- 3,321 ybp) outcrops at the modern seafloor and is reexposed to the contemporary carbon cycle. This basal deposit was found to have relatively high terrigenous organic carbon (lignin = 1.48 +/- 0.14 mg/100 mg OC), suggesting that this material was deposited during the last low sea-level stand. A few sediment trap samples showed anomalously depleted radiocarbon concentrations (Delta C-14 = -704.4 +/- 62.5%) relative to inner shelf (Delta C-14 = -293.4 +/- 134.0%), mid-shelf (Delta C-14 = -366.6 +/- 51.1%), and outer shelf (Delta C-14 = -384 +/- 47.8%) surface sediments. Therefore, although the major source of particulate material during the cascading season is resuspended shelf deposits, there is evidence that this aged pool of organic carbon can be eroded and laterally advected downslope.