949 resultados para OXYGEN-UPTAKE KINETICS


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Without doubt, global climate change is directly linked to the anthropogenic release of greenhouse gases such as carbon dioxide (CO2) and methane (UN IPCC-Report 2007). Therefore, research efforts to comprehend the global carbon cycle have increased during the last years. In the context of the observed changes, it is of particular interest to decipher the role of the hydro-, bio- and atmospheres and how the different compartments of the earth system are affected by the increase of atmospheric CO2. Due to its huge carbon inventory, the marine carbon cycle represents the most important component in this respect. Numerous findings suggest that the Southern Ocean plays a key role in terms of oceanic CO2 uptake. However, an exact quantification of such fluxes of material is hard to achieve for large areas, not least on account of the inaccessibility of this remote region. In particular, there exist so far only few accurate data for benthic carbon fluxes. The latter can be derived from high resolution pore water oxygen profiles, as one possible method. However the ex situ flux determinations carried out on sediment cores, tend to suffer from temperature and pressure artefacts. Alternatively, oxygen microprofiles can be measured in situ, i.e. at the seafloor. Until now, no such data have been published for the Southern Ocean. During the Antarctic Expedition ANT-XXI/4, within the framework of this thesis, in situ and ex situ oxygen profiles were measured and used to derive benthic organic carbon fluxes. Having both types of measurements from the same locations, it was possible to establish a depth-related correction function which was applied subsequently to revise published and additional unpublished carbon fluxes to the seafloor. This resulted in a consistent data base of benthic carbon inputs covering many important sub-regions of the Southern Ocean including the Amundsen and Bellingshausen Seas (southern Pacific), Scotia and Weddell Seas (southern South Atlantic) as well as the Crozet Basin (southern Indian Ocean). Including additional locations on the Antarctic Shelf, there are now 134 new and revised measurement locations, covering almost 180° of the Southern Ocean, for which benthic organic carbon fluxes and sedimentary oxygen penetration depth values are available. Further, benthic carbon fluxes were empirically related to dominant diatom distributions in surface sediments as well as to long-term remotely sensed chlorophyll-a estimates. The comparison of these results with benthic carbon fluxes of the entire Atlantic Ocean reveals significantly higher export efficiencies for the Southern Ocean than have previously been assumed, especially for the area of the opal belt.

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Thesis (Ph.D.)--University of Washington, 2016-05

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Research techniques and a methodology have been developed that enable the reduction kinetics of molten lead smelting slags with solid carbon to be studied. The rates of reduction of PbO-FeO-Fe2O3-CaO-SiO2 slags with carbon have been measured for a range of slag compositions for PbO concentrations between 3 and 100 weight percent, and temperatures between 1423 and 1573 K. The reduction rates were determined for both graphite and coke. Within the range of process conditions examined, it has been shown that the reaction rates are almost independent of carbon reactivity, SiO2/CaO and SiO2/Fe ratio in the range of compositions investigated and are not influenced by the presence of sulphur in the slag.The apparent first order rate constants for oxygen removal increase with increasing PbO concentration and oxygen activity in the slag. The data indicate that the rate limiting reaction step for the reduction of lead slags with solid carbon is the chemical reaction at the gas/slag interface.

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The ingress of water and Kokubo simulated body fluid (SBF) into poly (2-hydroxyethyl methacrylate) (PHEMA), and its co-polymers with tetrahydrofurduryl methacrylate (THFMA), loaded with either one of two model drugs, vitamin 1312 or aspirin, was studied by mass uptake over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 wt% or 10 wt% of the drugs. From DSC studies it was observed that vitamin B-12 behaved as a physical cross-linker restricting chain segmental mobility, and so had a small anti-plasticisation effect on PHEMA and the co-polymers rich in HEMA, but almost no effect on the T-g of co-polymers rich in THFMA. On the other hand, aspirin exhibited a plasticising effect on PHEMA and the copolymers. All of the polymers were found to absorb water and SBF according to a Fickian diffusion mechanism. The polymers were all found to swell to a greater extent in SBF than in water, which was attributed to the presence of Tris buffer in the SBF. The sorptions of the two penetrants were found to follow Fickian kinetics in all cases and the diffusion coefficients at 310 K for SBF were found to be smaller than those for water, except for the polymers containing aspirin where the diffusion coefficients were higher than for the other systems. For example, for sorption into PHEMA the diffusion coefficient for water was 1.41 X 10(-11) m(2)/s and for SBF was 0.79 x 10-11 m(2)/s, but in the presence of 5 wt% aspirin the corresponding values were 1.27 x 10(-1)1 m(2)/s and 1.25 x 10(-11) m(2)/s, respectively. The corresponding values for PHEMA loaded with 5 wt% B-12 were 1.25 x 10(-11) m(2)/s and 0.74 x 10(-11) m(2)/s, respectively.

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Setf-supported asymmetric hollow-fiber membranes of mixed oxygen-ionic and electronic conducting perovskite Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) were prepared by a combined phase-inversion and sintering technique. The starting inorganic powder was synthesized by combined EDTA-citrate complexing process followed by thermal treatment at 600 degrees C. The powder was dispersed in a polymer solution and then extruded into hollow-fiber precursors through a spinneret. ne fiber precursors were sintered at elevated temperatures to form gastight membranes, which were characterized by SEM and gas permeation tests. Performance of the hollow fibers in air separation was both experimentally and theoretically studied at various conditions. The results reveal that the oxygen permeation process was controlled by the slow oxygen surface exchange kinetics under the investigated conditions. The porous inner surface of the prepared perovskite hollow-fiber membranes considerably favored the oxygen permeation. The maximum oxygen flux measured was 0.031 mol-m(-2).s(-1) at 950 degrees C with the sweep gas flow rate of 0.522 mol(.)m(-2).s(-1). To improve the oxygen flux of BSCF perovskite membranes, future work should be focused on surface modification rather than reduction of the membrane thickness. (c) 2006 American Institute of Chemical Engineers.

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Hypoxia is a stress condition in which tissues are deprived of an adequate O2 supply; this may trigger cell death with pathological consequences in cardiovascular or neurodegenerative disease. Reperfusion is the restoration of an oxygenated blood supply to hypoxic tissue and can cause more cell injury. The kinetics and consequences of reactive oxygen and nitrogen species (ROS/RNS) production in cardiomyoblasts are poorly understood. The present study describes the systematic characterization of the kinetics of ROS/RNS production and their roles in cell survival and associated protection during hypoxia and hypoxia/reperfusion. H9C2 cells showed a significant loss of viability under 2% O2 for 30min hypoxia and cell death; associated with an increase in protein oxidation. After 4h, apoptosis induction under 2% O2 and 10% O2 was dependent on the production of mitochondrial superoxide (O2-•) and nitric oxide (•NO), partly from nitric oxide synthase (NOS). Both apoptotic and necrotic cell death during 2% O2 for 4h could be rescued by the mitochondrial complex I inhibitor; rotenone and NOS inhibitor; L-NAME. Both L-NAME and the NOX (NADPH oxidase) inhibitor; apocynin reduced apoptosis under 10% O2 for 4h hypoxia. The mitochondrial uncoupler; FCCP significantly reduced cell death via a O2-• dependent mechanism during 2% O2, 30min hypoxia. During hypoxia (2% O2, 4h)/ reperfusion (21% O2, 2h), metabolic activity was significantly reduced with increased production of O2-• and •NO, during hypoxia but, partially restored during reperfusion. O2-• generation during hypoxia/reperfusion was mitochondrial and NOX- dependent, whereas •NO generation depended on both NOS and non-enzymatic sources. Inhibition of NOS worsened metabolic activity during reperfusion, but did not effect this during sustained hypoxia. Nrf2 activation during 2% O2, a sustained hypoxia and reperfusion was O2-•/•NO dependent. Inhibition of NF-?B activation aggravated metabolic activity during 2% O2, 4h hypoxia. In conclusion, mitochondrial O2-•, but, not ATP depletion is the major cause of apoptotic and necrotic cell death in cardiomyoblasts under 2% O2, 4h hypoxia, whereas apoptotic cell death under 10% O2, 4h, is due to NOS-dependent •NO. The management of ROS/RNS rather than ATP is required for improved survival during hypoxia. O2-• production from mitochondria and NOS is cardiotoxic during hypoxia/reperfusion. NF-?B activation during hypoxia and NOS activation during reperfusion is cardiomyoblast protective.

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The purpose of this study was to determine the seasonal water use patterns of dominant macrophytes coexisting in the coastal Everglades ecotone. We measured the stable isotope signatures in plant xylem water of Rhizophora mangle, Cladium jamaicense, and Sesuvium portulacastrum during the dry (DS) and wet (WS) seasons in the estuarine ecotone along Taylor River in Everglades National Park, FL, USA. Shallow soilwater and deeper groundwater salinity was also measured to extrapolate the salinity encountered by plants at their rooting zone. Average soil water oxygen isotope ratios (δ 18O) was enriched (4.8 ± 0.2‰) in the DS relative to the WS (0.0 ± 0.1‰), but groundwater δ 18O remained constant between seasons (DS: 2.2 ± 0.4‰; WS: 2.1 ± 0.1‰). There was an inversion in interstitial salinity patterns across the soil profile between seasons. In the DS, shallow water was euhaline [i.e., 43 practical salinity units (PSU)] while groundwater was less saline (18 PSU). In the WS, however, shallow water was fresh (i.e., 0 PSU) but groundwater remained brackish (14 PSU). All plants utilized 100% (shallow) freshwater during the WS, but in the DS R. mangle switched to a soil–groundwater mix (δ 55% groundwater) while C. jamaicense and S. portulacastrum continued to use euhaline shallow water. In the DS, based on δ 18O data, the roots of R. mangle roots were exposed to salinities of 25.4 ± 1.4 PSU, less saline than either C. jamaicense(39.1 ± 2.2 PSU) or S. portulacastrum (38.6 ± 2.5 PSU). Although the salinity tolerance of C. jamaicense is not known, it is unlikely that long-term exposure to high salinity is conducive to the persistence of this freshwater marsh sedge. This study increases our ecological understanding of how water uptake patterns of individual plants can contribute to ecosystem levels changes, not only in the southeast saline Everglades, but also in estuaries in general in response to global sea level rise and human-induced changes in freshwater flows.

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Schinus terebinthifolius Raddi (Schinus) is one of the most widely found woody exotic species in South Florida. This exotic is distributed across environments with different hydrologic regimes, from upland pine forests to the edges of sawgrass marshes and into saline mangrove forests. To determine if this invasive exotic had different physiological attributes compared to native species in a coastal habitat, we measured predawn xylem water potentials (Ψ), oxygen stable isotope signatures (δ18O), and sodium (Na+) and potassium (K+) contents of sap water from plants within: (1) a transition zone (between a mangrove forest and upland pineland) and (2) an upland pineland in Southwest Florida. Under dynamic salinity and hydrologic conditions, Ψ of Schinus appeared less subject to fluctuations caused by seasonality when compared with native species. Although stem water δ18O values could not be used to distinguish the depth of Schinus and native species' water uptake in the transition zone, Ψ and sap Na+/K+ patterns showed that Schinus was less of a salt excluder relative to the native upland species during the dry season. This exotic also exhibited Na+/K+ ratios similar to the mangrove species, indicating some salinity tolerance. In the upland pineland, Schinus water uptake patterns were not significantly different from those of native species. Differences between Schinus and native upland species, however, may provide this exotic an advantage over native species within mangrove transition zones.

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Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.

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The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

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The rapid development of nanotechnology and wider applications of engineered nanomaterials (ENMs) in the last few decades have generated concerns regarding their environmental and health risks. After release into the environment, ENMs undergo aggregation, transformation, and, for metal-based nanomaterials, dissolution processes, which together determine their fate, bioavailability and toxicity to living organisms in the ecosystems. The rates of these processes are dependent on nanomaterial characteristics as well as complex environmental factors, including natural organic matter (NOM). As a ubiquitous component of aquatic systems, NOM plays a key role in the aggregation, dissolution and transformation of metal-based nanomaterials and colloids in aquatic environments.

The goal of this dissertation work is to investigate how NOM fractions with different chemical and molecular properties affect the dissolution kinetics of metal oxide ENMs, such as zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs), and consequently their bioavailability to aquatic vertebrate, with Gulf killifish (Fundulus grandis) embryos as model organisms.

ZnO NPs are known to dissolve at relatively fast rates, and the rate of dissolution is influenced by water chemistry, including the presence of Zn-chelating ligands. A challenge, however, remains in quantifying the dissolution of ZnO NPs, particularly for time scales that are short enough to determine rates. This dissertation assessed the application of anodic stripping voltammetry (ASV) with a hanging mercury drop electrode to directly measure the concentration of dissolved Zn in ZnO NP suspensions, without separation of the ZnO NPs from the aqueous phase. Dissolved zinc concentration measured by ASV ([Zn]ASV) was compared with that measured by inductively coupled plasma mass spectrometry (ICP-MS) after ultracentrifugation ([Zn]ICP-MS), for four types of ZnO NPs with different coatings and primary particle diameters. For small ZnO NPs (4-5 nm), [Zn]ASV was 20% higher than [Zn]ICP-MS, suggesting that these small NPs contributed to the voltammetric measurement. For larger ZnO NPs (approximately 20 nm), [Zn]ASV was (79±19)% of [Zn]ICP-MS, despite the high concentrations of ZnO NPs in suspension, suggesting that ASV can be used to accurately measure the dissolution kinetics of ZnO NPs of this primary particle size.

Using the ASV technique to directly measure dissolved zinc concentration, we examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L-1) for Suwannee River humic acid (SRHA), Suwannee River fulvic acid and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. NOM isolates with higher SUVA were also more effective at enhancing the colloidal stability of the NPs; however, the NOM-promoted dissolution was likely due to enhanced interactions between surface metal ions and NOM rather than smaller aggregate size.

Based on the above results, we designed experiments to quantitatively link the dissolution kinetics and bioavailability of CuO NPs to Gulf killifish embryos under the influence of NOM. The CuO NPs dissolved to varying degrees and at different rates in diluted 5‰ artificial seawater buffered to different pH (6.3-7.5), with or without selected NOM isolates at various concentrations (0.1-10 mg-C L-1). NOM isolates with higher SUVA and aromatic carbon content (such as SRHA) were more effective at promoting the dissolution of CuO NPs, as with ZnO NPs, especially at higher NOM concentrations. On the other hand, the presence of NOM decreased the bioavailability of dissolved Cu ions, with the uptake rate constant negatively correlated to dissolved organic carbon concentration ([DOC]) multiplied by SUVA, a combined parameter indicative of aromatic carbon concentration in the media. When the embryos were exposed to CuO NP suspension, changes in their Cu content were due to the uptake of both dissolved Cu ions and nanoparticulate CuO. The uptake rate constant of nanoparticulate CuO was also negatively correlated to [DOC]×SUVA, in a fashion roughly proportional to changes in dissolved Cu uptake rate constant. Thus, the ratio of uptake rate constants from dissolved Cu and nanoparticulate CuO (ranging from 12 to 22, on average 17±4) were insensitive to NOM type or concentration. Instead, the relative contributions of these two Cu forms were largely determined by the percentage of CuO NP that was dissolved.

Overall, this dissertation elucidated the important role that dissolved NOM plays in affecting the environmental fate and bioavailability of soluble metal-based nanomaterials. This dissertation work identified aromatic carbon content and its indicator SUVA as key NOM properties that influence the dissolution, aggregation and biouptake kinetics of metal oxide NPs and highlighted dissolution rate as a useful functional assay for assessing the relative contributions of dissolved and nanoparticulate forms to metal bioavailability. Findings of this dissertation work will be helpful for predicting the environmental risks of engineered nanomaterials.

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The effects of ocean acidification and elevated seawater temperature on coral calcification and photosynthesis have been extensively investigated over the last two decades, whereas they are still unknown on nutrient uptake, despite their importance for coral energetics. We therefore studied the separate and combined impacts of increases in temperature and pCO2 on phosphate, ammonium, and nitrate uptake rates by the scleractinian coral S. pistillata. Three experiments were performed, during 10 days i) at three pHT conditions (8.1, 7.8, and 7.5) and normal temperature (26°C), ii) at three temperature conditions (26°, 29°C, and 33°C) and normal pHT(8.1), and iii) at three pHT conditions (8.1, 7.8, and 7.5) and elevated temperature (33°C). After 10 days of incubation, corals had not bleached, as protein, chlorophyll, and zooxanthellae contents were the same in all treatments. However, photosynthetic rates significantly decreased at 33°C, and were further reduced for the pHT 7.5. The photosynthetic efficiency of PSII was only decreased by elevated temperature. Nutrient uptake rates were not affected by a change in pH alone. Conversely, elevated temperature (33°C) alone induced an increase in phosphate uptake but a severe decrease in nitrate and ammonium uptake rates, even leading to a release of nitrogen into seawater. Combination of high temperature (33°C) and low pHT(7.5) resulted in a significant decrease in phosphate and nitrate uptake rates compared to control corals (26°C, pHT = 8.1). These results indicate that both inorganic nitrogen and phosphorus metabolism may be negatively affected by the cumulative effects of ocean warming and acidification.

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Site 723 is located in a water depth of 808 m at the center of the oxygen minimum zone and the middle part of the main thermocline on the Oman Margin. Oxygen isotope curves of planktonic delta18OP and benthic delta18OB can be traced back continuously to Stage 23 with high resolution measurements. A tentative correlation to Stage 53 has been tried using oxygen isotope stratigraphy. The amplitudes of the fluctuations of the benthic delta18OB curve are small, compared with the planktonic delta18OP curve. The delays of benthic oxygen isotopes delta18OB related to the planktonic delta18OP appear in the transgressive stages. Carbon isotopes of benthic delta13CB and planktonic delta13CP generally show an inverse correlation with oxygen isotope values delta18OB and delta18OB and delta18OP, however, the changes of delta13C are more gradual than those of delta18O during transgressive stages in spite of the synchronized changes of delta13C with those of delta18O during regressive stages. The difference of oxygen isotope between benthic and planktonic foraminifers represents the degree of pushing up the thermocline by upwelling, and the difference of carbon isotope represents the relative amount of upwelling Sigma[CO2] to the biological uptake in the surface water. These isotopic differences can be used as indicators of upwelling and show strong upwelling in the interglacial and weak upwelling in the glacial stages. The organic carbon content is correlated with the isotopic upwelling indicators, and higher content is correlated with the isotopic upwelling indicators and higher content appears in the interglacial stages. The calculated rate of sedimentation based on oxygen isotope stratigraphy in glacial stages is significantly high, two to four times that of interglacial stages, and the absolute flux of fluvial sediments with variability of lithofacies increased in the glacial stage. The present glacial-interglacial cycle with the fluctuation of upwelling relating to the southwest monsoon can be traced back to Stage 8, 250 ka. From Stage 8 to 12, 250-450 ka, the upwelling indicator of oxygen isotope difference did not show such distinct cyclicity. For Stages 12-15, 450-600 ka, the upwelling can be estimated as strong as in interglacial stage of the present cycles, with slightly weak upwelling in the glacial stage. This upwelling and climate can be traced back to the late Pliocene. The strongest upwelling can be estimated in the Pliocene-Pleistocene time by the isotopic indicators and the high organic carbon content.

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The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.