Le bassin de Cariaco représente un emplacement idéal pour l’étude de la préservation de la matière organique (MO) en particulier la sulfuration naturelle, car il a présenté des conditions euxiniques récurrentes au cours de son histoire. Pour contraindre les processus de préservation de la MO, nous avons étudié les sédiments varvés du bassin de Cariaco sur une période de 130 ka. Nous avons mis au point un protocole basé sur des hydrolyses séquentielles permettant d’isoler des kérogènes libres d'artefacts. Ce protocole a permis de libérer d’importantes quantités de carbohydrates représentant jusqu'à 3% du carbone organique total. Ces carbohydrates d’origine algo-bactérienne présentent une diminution en profondeur lié à des processus de dégradation in situ et/ou à l’incorporation dans la matrice macromoléculaire. L’étude des marqueurs moléculaires présents dans les extraits organiques corrobore l’origine principalement autochtone de la MO. Cependant la contribution des végétaux terrestres a été mise en évidence dans les échantillons correspondant aux périodes glaciaires. Le processus de sulfuration naturelle a un rôle important dans la préservation de la MO à Cariaco. La sulfuration intramoléculaire est indiquée par la présence des thiophènes et thiolanes à l’état libre. La désulfuration au nickel de Raney et la pyrolyse des kérogènes révèlent également une sulfuration intermoléculaire. La sulfuration ne présente pas une tendance générale à l’augmentation dans l’intervalle étudié. Le processus se révèle sensible aux variations climatiques, et facteurs tels que les conditions redox du milieu et la disponibilité et réactivité des précurseurs moléculaires. / The Cariaco basin provide an ideal location to study the organic matter (OM) preservation processes in particular the natural sulfurization, since it has presented recurrent euxinic conditions along its history. To better understand the OM preservation processes, we have studied the varved sediments of Cariaco in a time interval of 130 ky. In this study, we have employed an artifact free method based on stepwise hydrolysis for the isolation of kerogen. This method permitted to obtain important amounts of monomeric carbohydrates, accounting for up to 3% of the total organic carbon. Those algal/bacterial-derived carbohydrates present a decrease with depth related to in situ degradation and/or incorporation to the macromolecular matrix. The investigation of the organic extracted biomarkers corroborate the authochtonous origin of the OM. Nevertheless, an important contribution of terrestrial OM was observed in the samples from glacials periods. The natural sulfurization process have an important role in the preservation of OM in Cariaco basin. The intramolecular sulfurization was revealed by the presence of free alkylthiophenes and thiolanes. Raney nickel desulfurization and kerogen pyrolysis also revealed intermolecular sulfurization. The natural sulfurization does not present a global increase in the time interval studied. This process respond to variations in climatic conditions, redox conditions in the water column and sediments and also to the reactivity and availability of the molecular precursors.

The Intertropical Convergence Zone (ITCZ) is a feature that results from the ocean-atmosphere interactions in the tropics around the world. The ITCZ is characterized by surface wind convergence, tall storm clouds, and it forms a belt of high time-averaged precipitation around the globe. The ITCZ undergoes seasonal migrations between 5°S and 15°N roughly following the subsolar point on Earth with the seasons, with a mean annual position located slightly above the Equator, between 2° and 5°N. This study tested the hypothesis that there was a northward shift in the median position of the ITCZ in the first decade of the 2000’s relative to the 1900’s. This hypothesis has been posed in the literature given a weakening in the intensity of the Trade Winds observed in the southern Caribbean Sea during the first decade of the 2000’s, with concomitant ecological impacts due to weakening in coastal wind-driven upwelling. The hypothesis was tested by analyzing variations in the monthly latitudinal position of the ITCZ over the Atlantic Ocean relative to the median position computed for the period 1987-2011. The position of the ITCZ was derived from satellite-derived ocean surface wind measurements collected from 1987 to 2011. A Mann-Kendall analysis and a Monte Carlo simulation were used to test for trends in the median cross-basin latitudinal position of the ITCZ. The study included an analysis of regional changes across the tropical central Atlantic (50°W to 15°W), the Western Atlantic (50°W to 30°W), and the Eastern Atlantic (30°W to 15°W) within the tropics. The results show a slight southward trend in the median position of the ITCZ over the central Atlantic and also in the Eastern Atlantic in the first decade of the 2000’s relative to the 1990’s. While this trend is barely significant, it is likely simply due to interannual variation in the average annual position of the ITCZ. The data were also examined for the timing and persistence of a double ITCZ in the Atlantic. The double ITCZ over the Atlantic appeared every year in February or March, with the largest separation between the northern and southern branches of the ITCZ observed in June and July. The possible effects of changes in the average latitudinal position of the ITCZ on the upwelling in the Cariaco Basin (southeastern Caribbean Sea off Venezuela) were also examined. Anomalies of the median of the latitudinal position of the ITCZ in the Atlantic were compared with anomalies of in-situ temperature collected during the 1990’s and the first decade of the 2000’s by the CARIACO Ocean Time-Series program and with anomalies of satellite SST (from the Advanced Very High Resolution Radiometer satellite; AVHRR) from 1995 to 2016. Correlation analysis were performed between anomalies of water temperatures at various depths and anomalies of satellite SST with anomalies of the monthly mean ITCZ position with lags up to 3 months for the time series, and also just for the Cariaco basin upwelling months (December-April). For the whole Cariaco time series there were no significant correlations between the anomalies of the ITCZ position and anomalies in subsurface temperatures in the Cariaco Basin. However, during the upwelling period, the central Atlantic and Western Atlantic ITCZ position anomalies were directly correlated with Cariaco Basin temperature anomalies with no-lag (r = 0.20), and the central and Eastern Atlantic ITCZ position anomalies were inversely correlated with Cariaco Basin temperatures (r ~ -0.22 to -0.28) with ITCZ leading Cariaco temperatures by 3 months. However, these correlations were low, indicating that other factors than the position of ITCZ latitudinal position play bigger role on the Cariaco basin upwelling variability. Interannual variability in oceanographic and meteorological characteristics of the Atlantic Ocean are expected as a result of large-scale changes in other regions of the world, including due to changes such as the El Niño Southern Oscillation (ENSO) and the Atlantic Multidecadal Oscillation (AMO). Six oceanic-atmospheric variables are used to monitor ENSO over the tropical Pacific, while the AMO is determined by monitoring SST over the Atlantic. Correlations with lags of up to ± 6 months were conducted with those climate indices and the anomalies of the median monthly latitudinal position of the ITCZ. Significant direct correlations with ENSO (Multivariate ENSO Index) were seen in the Atlantic and Western Atlantic (r = 0.15), with ENSO leading the position of the ITCZ anomalies by 3 months. This implies that within three months after an El Niño event (warm ENSO anomaly in the Pacific) the ITCZ over the mid-Atlantic and Western Atlantic Ocean tends to shift to a more northerly position. The AMO also had a direct influence on the anomalies of the ITCZ position (r = 0.13) in the Central and the Western Atlantic, with the AMO leading ITCZ anomalies by 1 month (i.e. a warming of the North Atlantic led to a northward shift in the ITCZ one month later). Correlations between AMO and the ITCZ anomalies in the Eastern Atlantic were also direct but with no lag. Although significant, these correlations were low. An inverse correlation (~ -0.35) was found between ENSO and anomalies of water temperature of the Cariaco Basin. ENSO lagged ocean temperature anomalies by 3 to 4 months for both the whole Cariaco time series and for the upwelling months of CARIACO data. Correlations with AMO were direct (~ 0.4); for the whole time series AMO led Cariaco temperature anomalies by 3 months, but for the upwelling months AMO lagged Cariaco temperature anomalies by one month.

The aim of this dissertation was to understand lithogenic suspended sediment transport mechanisms and distribution in two river-influenced margins: The Cariaco Basin, Venezuela, and the Amazon Shelf, Brazil. Lithogenic sediment input in the Cariaco Basin is controlled by small mountainous rivers (SMR), while in the Amazon Shelf it is dominated by the Amazon River, the largest river in the world in terms of freshwater discharge (~20% of global riverine discharge). Optical transmissometer measurements were coupled with particulate organic matter (POM) observations to understand changes in the geochemical composition of suspended sediment and spatial/temporal distributions over the two regions of interest. In the Cariaco Basin sampling was conducted during the rainy seasons of September 2003, 2006 and 2008, and during the upwelling period (dry season) of 2009. Our results suggest that bottom nepheloid layers (BNL) originating at the mouth of the SMR discharging into the Cariaco Basin are a major delivery mechanism of terrigenous sediments to the basin's interior year-round. Intermediate nepheloid layers (INL) were also observed near the shelf break (~100m) and appear to effectively carry terrigenous material laterally from the shelf to deep waters, thereby providing a plausible supply mechanism of the terrestrial material observed in sediment traps, deployed >70 km offshore as part of the CARIACO Ocean Time-Series. These findings highlight the importance of small, local rivers in the Cariaco Basin as sources of terrestrial material. Indeed, the low isotopic composition of particulate organic carbon (δ13Corg, ~-30 - -24 ‰) carried by the BNL suggests that this material was continentally derived. BNL δ13Corg also changed with season, indicating that the geochemical composition of BNL reflects particle source. These nepheloid layers contained relatively low POM concentrations (average of 10%), agreeing well with published data, yet the fine sediment of the BNL may serve as mineral ballast, enhancing the sinking velocities of POC and thus increasing the efficiency of the biological pump in Cariaco. We suggest that during the transition between the upwelling and rainy season BNL deliver sediment to the deep Cariaco Basin in pulses. During upwelling, BNL are retained on the inner shelf by onshore Ekman transport associated with upwelling. The nepheloid layers are later released as the upwelling subsides; this, coupled with high river discharge rates, may explain the seasonal pulse of sediment observed at the end of the upwelling period (May) in the sediment trap array. The SMR in Cariaco also have the capacity to deliver large amounts of sediment to the Cariaco Basin during episodic events, such as earthquakes and floods. During September 2008 a sediment density flow was observed in the eastern Cariaco Basin, likely triggered by a magnitude 5.2 earthquake that occurred on August 11, 2008 off the city of Cumaná. Elevated suspended sediments near the bottom were observed at the mouth of the Manzanares Canyon (> 90 g m-2, over a depth of 165 m) and decreased to ~11 g m-2 (over a depth of 40 m) 42 Km away from the canyon's mouth at the CARIACO Ocean Time-Series site (10.5° N, 64.67° W). The sediment flux associated with this single event was ~ 10% of the total annual sediment flux that typically reaches the Cariaco Basin deep seafloor. Average carbon to nitrogen atomic ratios (C/N) as well as C and N isotopic composition confirm that most of the organic matter transferred by the sediment flow was of continental origin (C/N ratios of ~19.3, δ13C of -27.04 ‰, and δ15N of 6.83 ‰). The Manzanares River mouth is located at the head of the canyon, and likely supplies most of the fine grained sediments and fresh organic carbon that accumulate in the upper part of the canyon. This suggests that the canyon is an active depositional center, and its proximity to the Manzanares River and Cariaco Basin is critical for sediment supply offshore, which in turn can have a significant impact on the long-term sequestration of carbon into the deep basin. The nutrient and sediment biogeochemistry of the outer Amazon Shelf was studied in February-March 2010 to replicate observations made by the AmasSeds study in 1989-1991. These transects roughly corresponded to the AmasSeds Open Shelf (OS) and River Mouth (RM) transects. Onshore winds (~6 m s-1) contained the Amazon plume within ~120 Km of the coast; the plume was visible only in the mid-shelf stations located closest to the coast in the OS transect. Within the river plume, surface dissolved inorganic nutrient concentrations were near zero, except for silicates (4-6 μM). Coupled with oxygen supersaturation (AOU < 1), this suggested complete biological uptake of the major dissolved inorganic nutrients (N, P). Dissolved organic carbon (DOC) was also highest within the plume (average of 116 μM), decreasing to ~73 μM in oceanic waters. Total suspended solids (TSS) in surface waters within the plume were ~1-1.5 mg l-1, decreasing to ~0.2-0.3 mg l-1 in all other sampled stations both over the shelf and in deeper waters. TSS were highest within BNL (22-33 mg l-1) observed over the inner shelf; BNL were not observed outside the area of the Amazon plume. Suspended particulate organic carbon (POCsusp) showed a depleted δ13C isotopic signal (~-25 ‰ to -28 ‰) in surface and bottom waters, suggesting terrestrial provenance. Within the BNL, %POC was low (0.6-0.9%, as compared to 7-18% in surface waters), showing extensive and rapid decomposition of organic matter over the shelf. Atomic C/N ratios in particulate organic matter both in surface waters and within BNL were relatively close to Redfield's (8-14) and relatively stable over the area sampled. Particulate atomic organic carbon vs. particulate organic phosphorous (POC/POP) ratios were also low within the BNL (~110) and increased offshore (>500), suggesting a direct input of particulate P from the Amazon River or from reworked surface sediments. The fraction of POC in surface sediments was also low (0.73 ±; 0.56%; N = 5) and relatively uniform across the region sampled. We estimated instantaneous fluxes of 38.7 metric tons TSS s-1, 0.24 metric tons POC s-1 and 6.42 x 10-3 metric tons POP s-1 northwestward over an area extending between ~50 Km and 120 Km offshore. Our TSS estimates are 30% lower than those calculated by Nittrouer et al. (1986) during peak discharge of the Amazon. We also calculated that some 1.50 Tg yr-1 of DOC were being flushed northwestward along the outer shelf annually, which represent ~6% of the total DOC transported by the Amazon. By analyzing these two geographical settings it was possible to compare and contrast transport mechanisms of continentally-derived material and establish the relative importance of each mechanism in their different environment. There is still much to be understood regarding BNL in the Cariaco Basin, such as their role within the Manzanares Submarine Canyon with regards to sediment contribution and deposition. Additionally, during the last 30 years, anthropogenic influences on the small rivers around the Basin have significantly altered the drainage and sediment loads, yet reliable data to quantify the level of influence and change over time are not available. We need a better understanding of the natural variability of these small, tropical fluvial systems, trends and impact of episodic events, to better interpret the climate record stored at the bottom of the basin and predict future ecosystem changes in the region. In the Amazon Shelf, more accurate estimates of DOC, POC and POP fluxes northwestward are warranted. The magnitude of the Amazon River discharge dampens changes that have occurred in the last 20 years within the Amazon Basin, suggesting that historic Amazon Shelf sediment and carbon estimates are still valid. The data presented here adds to the growing body of literature that highlights the significance of river-influenced continental margins as sites of organic carbon deposition, remineralization export and sequestration.

The Southern Caribbean Sea experiences a strong upwelling process along the coast from about 61°W to 75.5°W and 10-13°N. In this dissertation three aspects of this upwelling system are examined: (A) A mid-year secondary upwelling that was previously observed in the southeastern Caribbean Sea between June-July, when land based stations show a decrease in wind speed. The presence and effects of this upwelling along the whole southern Caribbean upwelling system were evaluated, as well as the relative forcing contribution of alongshore winds (Ekman Transport, ET) and wind-curl (Ekman Pumping, EP). (B) Stronger upwelling occurs in two particular regions, namely the eastern (63-65°W) and western (70-73°W) upwelling areas. However, the eastern area has higher fish biomass than the western area (78% and 18%, respectively, of the total small pelagic biomass of the southern Caribbean upwelling system). The upwelling dynamics along the southern Caribbean margin was studied to understand those regional variations on fish biomass. (C) The most important fishery in the eastern upwelling area off Venezuela is the Spanish sardine (Sardinella aurita). The sardine artisanal fishery is protected and only takes place up to ~10 km offshore. The effects of the upwelling cycle on the spatial distribution of S. aurita were studied. The main sources of data were satellite observations of sea surface temperature (SST), chlorophyll-a (Chl) and wind (ET and EP), in situ observations from the CARIACO Ocean Time-Series program, sardine biomass from 8 hydroacoustics surveys (1995-1998), and temperature profiles from the World Ocean Atlas 2005 used to calculate the depth of the Subtropical Underwater core (traced by the 22°C isotherm). The most important results of the study were as follows: (A) The entire upwelling system has a mid-year upwelling event between June-August, besides the primary upwelling process of December-April. This secondary event is short-lived (~5 weeks) and ~1.5°C warmer than the primary upwelling. Together, both upwelling events lead to about 8 months of cooler waters (-3, averaged from the coast to 100 km offshore) in the region. Satellite nearshore wind (~25 km offshore) remained high in the eastern upwelling area (> 6 m s-1) and had a maximum in the western area (~10 m s-1) producing high offshore ET during the mid-year upwelling (vertical transport of 2.4 - 3.8 m3 s-1 per meter of coastline, for the eastern and western areas, respectively). Total coastal upwelling transport was mainly caused by ET (~90%). However, at a regional scale, there was intensification of the wind curl during June as well; as a result open-sea upwelling due to EP causes isopycnal shoaling of deeper waters enhancing the coastal upwelling. (B) The eastern and western upwelling areas had upwelling favorable winds all year round. Minimum / maximum offshore ET (from weekly climatologies) were 1.52 / 4.36 m3 s-1 per meter, for the western upwelling area; and 1.23 / 2.63 m3 s-1 per meter, for the eastern area. The eastern and western upwelling areas showed important variations in their upwelling dynamics. Annual averages in the eastern area showed moderate wind speeds (6.12 m s-1), shallow 22°C isotherm (85 m), cool SSTs (25.24°C), and phytoplankton biomass of 1.65 mg m-3. The western area has on average stronger wind speeds (8.23 m s-1) but a deeper 22°C isotherm (115 m), leading to slightly warmer SSTs (25.53°C) and slightly lower phytoplankton biomass (1.15 mg m-3). We hypothesize that the factors that most inhibits fish production in the western upwelling area are the high level of wind-induced turbulence and the strong offshore ET. (C) Hydroacoustics values of Sardinella aurita biomass (sAsardine) and the number of small pelagics schools collected in the eastern upwelling region off northeast Venezuela were compared with environmental variables (satellite products of SST, SST gradients, and Chl -for the last two cruises-) and spatial variables (distance to upwelling foci and longitude-latitude). These data were examined using Generalized Additive Models. During the strongest upwelling season (February-March) sAsardine was widely distributed in the cooler, Chl rich upwelling plumes over the wide (~70km) continental shelf. During the weakest upwelling season (September-October) sAsardine was collocated with the higher Chl (1-3 mg m-3) found within the first 10 km from the upwelling foci; this increases Spanish sardine availability (and possibly the catchability) for the artisanal fishery. These results imply that during prolonged periods of weak upwelling the environmentally stressed (due to food scarceness) Spanish sardine population would be closer to the coast and more available to the fishery, which could easily turn into overfishing. After two consecutive years of weak upwelling (2004-2005) Spanish sardine fishery crashed and as of 2011 has not recovered to previous yield; however during 2004 a historical capture peak occurred. We hypothesize that this Spanish sardine collapse was caused by a combination of sustained stressful environmental conditions and of overfishing, due to the increased catchability of the stock caused by aggregation of the fish in the cooler coastal upwelling cells during the anomalous warm upwelling season.