Oxygen In Surface Layer Research Articles

The Impact of Progressive Buildup of Trapped Gas Bubbles on the Performance of Oxygen Evolution Reaction Electrodes during Alkaline Water Electrolysis

Hydroxide exchange membrane electrolyzers (HEMELs) stand to be an effective means of achieving low-cost green hydrogen. However, HEMEL durability remains a substantial barrier to realizing this goal. The United States Department of Energy has set a durability target of a voltage increase of 2 µV/hr1. We have previously demonstrated constant current degradation rates of 1810 and 560 µV/hr with applied current densities of 500 and 200 mA/cm2, respectively, thus illustrating the substantial gap between our current achievable HEMEL durability and our target durability2.Gaseous products are formed at both electrodes in a HEMEL; by manipulating the wettability of the electrodes, recent studies have shown that the failure of gas bubbles to detach from the electrode surface leads to overpotentials associated with the loss of accessible reaction sites and exacerbated mass transport to those sites that remain accessible3,4. While these studies have demonstrated the impact of gas bubbles on acute water electrolyzer performance, we have found little work to investigate the impact of trapped gas bubbles from a durability perspective.Here we find that electrode wettability can change throughout the lifetime of a device. We investigate the durability of an FexNiyOOH – nF anode catalyst supported on nickel felt in a three-electrode setup with 1M KOH. We find that at a moderately low current density of 50 mA/cm2 the performance of this catalyst degrades by tens of mV over several hundred hours and that this performance loss is recoverable with the removal of oxygen bubbles adhered to the anode surface at open circuit. Moreover, when we resume the passage of current, the surface layer of oxygen (and associated performance loss) evolves more rapidly – suggesting that the wettability of the anode has decreased throughout the experiment. This is further supported by contact angle measurements of pre- and post-mortem anodes. Finally, we investigate whether the introduction of hydrophilic ion-conducting polymers can mitigate the emergent hydrophobicity of the anode catalyst layer. Technical Targets for Proton Exchange Membrane Electrolysis, Hydrogen and Fuel Cell Technologies Office. https://www.energy.gov/eere/fuelcells/technical-targets-proton-exchange-membrane-electrolysis. J. Xiao et al., ACS Catal., 11, 264-270 (2021). R. Iwata et al., Joule, 5(4), 887-900 (2021). Z. Kang et al., Electrochimica Acta, 354 (2020).

Surface water oxygenation and low bioproductivity during deposition of iron formation of the Jacadigo Group (Brazil): Insights from combined cadmium – Chromium isotopes

The Banda Alta Formation (Urucum district, Mato Grosso do Sul, Brazil) comprises ∼600 Ma Fe and Mn deposits, which are among the world's youngest and largest Neoproterozoic sedimentary Fe and Mn formations (IF; MnF). These have been deposited in a redox-stratified, marine sub-basin (Jacadigo Basin), which was strongly influenced by glacial advance/retraction cycles with temporary influx of continental freshwater and upwelling of metal-enriched deep anoxic seawater. Cr and Cd isotopes measured on meticulously separated hematite mesobands from drill core samples are relatively homogenous throughout the ca. 325 m thick sequence sampled in the Banda Alta Fm., with average authigenic δ53Cr values of +0.93 ± 0.24 ‰ (2σ; n = 23) and δ114Cd values of −0.14 ± 0.14 ‰ (2σ; n = 15). The significant enrichment of Cr, in parallel with the strong enrichments of other redox sensitive elements (U, Mo), attests for effective and efficient reduction removal processes in the surface waters during cycles where upwelling Fe2+-rich waters reached the oxygenated surface layer exposed to the atmosphere during episodic glacier retreat stages. Assuming a similar quantitative and efficient removal pathway of dissolved Cd by iron oxyhydroxides, the so-inferred average δ114Cd signature of −0.14 ± 0.14 ‰ in the Jacadigo Basin surface water is significantly lower than signatures of modern ocean surface waters with a range of δ114Cd of ca. ∼0.4 to ∼1 ‰ and even lower than the signature of modern ocean deep waters with δ114Cd of ∼0.3 ‰. It possibly attests to reduced primary production levels and lower nutrient utilization rates during deposition of the Late Neoproterozoic Jacadigo Group, compared to today. This despite the inferred oxidized surface water layer that must have prevailed during this time, as implied by the strongly positively fractionated Cr isotope signatures and pronouncedly negative Ce-anomalies recorded in the seawater-like, shale-normalized Rare Earth Element and Yttrium (REY) patterns exhibited by the hematite mesobands. Data presented herein speak for: (1) a stable, isotopically heavy Cr input to the Jacadigo Basin at the time of deposition, implying high atmospheric O2 levels in the Late Neoproterozoic (2) likely quantitative, reductive incorporation / adsorption processes of dissolved Cr and Cd, respectively, into/onto precipitating iron oxyhydroxides, and (3) the prevalence of low nutrient concentrations and utilization rates in the Jacadigo Basin during glacier retreat cycles. Banded iron formations are considered suitable archives for reconstructing redox and bioproductivity levels in past marine depositional basin, including those prevalent in Neoproterozoic glacial conditions, via employing the CrCd isotope double tracer to iron-rich mesobands.

A shift in redox conditions near the Ediacaran/Cambrian transition and its possible influence on early animal evolution, Corumbá Group, Brazil

The Ediacaran–Cambrian transition witnessed some of the most important biological, tectonic, climatic and geochemical changes in Earth’s history. Of utmost importance for early animal evolution is the likely shift in redox conditions of bottom waters, which might have taken place in distinct pulses during the late Ediacaran and early Paleozoic. To track redox changes during this transition, we present new trace element, total organic carbon and both inorganic and organic carbon isotopes, and the first iron speciation data on the Tamengo and Guaicurus formations of the Corumbá Group in western Brazil, which record important paleobiological changes between 555 Ma to < 541 Ma. The stratigraphically older Tamengo Formation is composed mainly of limestone with interbedded marls and mudrocks, and bears fragments of upper Ediacaran biomineralized fossils such as Cloudina lucianoi and Corumbella werneri. The younger Guaicurus Formation represents a regional transgression of the shallow carbonate platform and is composed of a homogeneous fine-grained siliciclastic succession, bearing meiofaunal bilateral burrows. The new iron speciation data reveal predominantly anoxic and ferruginous (non-sulfidic) bottom water conditions during deposition of the Tamengo Formation, with FeHR/FeT around 0.8 and FePy/FeHR below 0.7. The transition from the Tamengo to the Guaicurus Formation is marked by a stratigraphically rapid drop in FeHR/FeT to below 0.2, recording a shift to likely oxic bottom waters, which persist upsection. Redox-sensitive element (RSE) concentrations are muted in both formations, but consistent with non-sulfidic bottom water conditions throughout. We interpret the collected data to reflect a transition between two distinct paleoenvironmental settings. The Tamengo Formation represents an environment with anoxic bottom waters, with fragments of biomineralized organisms that lived on shallower, probably mildly oxygenated surficial waters, and that were then transported down-slope. Similar to coeval successions (e.g., the Nama Group in Namibia), our data support the hypothesis that late Ediacaran biomineralized organisms lived in a thin oxygenated surface layer above a relatively shallow chemocline. The Guaicurus Formation, on the other hand, records the expansion of oxic conditions to deeper waters during a sea level rise. Although the relationship between global biogeochemical changes and the activities of early bioturbators remains complex, these results demonstrate an unequivocal synchronous relationship between oxygenation of the Corumbá basin and the local appearance of meiofaunal bioturbators.

A Tale of Two Seasons: Distinct Seasonal Viral Communities in a Thermokarst Lake

Thermokarst lakes are important features of subarctic landscapes and are a substantial source of greenhouse gases, although the extent of gas produced varies seasonally. Microbial communities are responsible for the production of methane and CO2 but the "top down" forces that influence microbial dynamics (i.e., grazers and viruses) and how they vary temporally within these lakes are still poorly understood. The aim of this study was to examine viral diversity over time to elucidate the seasonal structure of the viral communities in thermokarst lakes. We produced virus-enriched metagenomes from a subarctic peatland thermokarst lake in the summer and winter over three years. The vast majority of vOTUs assigned to viral families belonged to Caudovirales (Caudoviricetes), notably the morphological groups myovirus, siphovirus and podovirus. We identified two distinct communities: a dynamic, seasonal community in the oxygenated surface layer during the summer and a stable community found in the anoxic water layer at the bottom of the lake in summer and throughout much of the water column in winter. Comparison with other permafrost and northern lake metagenomes highlighted the distinct composition of viral communities in this permafrost thaw lake ecosystem.

Two dimensional NbSe2/Nb2O5 metal-semiconductor heterostructure-based photoelectrochemical photodetector with fast response and high flexibility.

Two dimensional (2D) metal-semiconductor heterostructures are promising for high-performance optoelectronic devices due to fast carrier separation and transportation. Considering the superior metallic characteristics accompanied by high electrical conductivity in NbSe2, surface oxidation provides a facile way to form NbSe2/Nb2O5 metal-semiconductor heterostructures. Herein, size-dependent NbSe2/Nb2O5 nanosheets were achieved by a liquid phase exfoliation method and a gradient centrifugation strategy. These NbSe2/Nb2O5 heterostructure-based photodetectors show high responsivity with 23.21 μA W-1, fast response time of millisecond magnitude, and wide band detection ability in the UV-Vis region. It is noticeable that the photocurrent density is sensitive to the surface oxygen layer due to the oxygen-sensitized photoconduction mechanism. The flexible testing of the NbSe2/Nb2O5 heterostructure-based PEC-type photodetectors exhibits high photodetection performance even after bending and twisting. Beyond that, the solid-state PEC-type NbSe2/Nb2O5 photodetector also achieves relatively stable photodetection and high stability. This work promotes the application of 2D NbSe2/Nb2O5 metal-semiconductor heterostructures in flexible optoelectronic devices.

Fluorine‐Doping Strategy To Improve the Surface and Electrochemical Properties of LiNi0.6Co0.2Mn0.2O2 Cathodes for Use in Lithium‐Ion Batteries

AbstractThis study sought to achieve fluorine doping into the surface structure of LiNi0.6Co0.2Mn0.2O2 (NCM622) cathodes for use in lithium‐ion batteries by the atomic layer deposition method to improve structural stability and electrochemical performance. Thin‐film electrodes were used to clearly understand the fundamental effects of surface properties. Based on our observations, the oxygen vacancy that basically exists in the surface of the NCM622 thin‐film electrode triggers the additional formation of oxygen derivatives with a spinel‐like phase, leading to poor cycling stability and severe deterioration of the surface structure. Contrary, the fluorinated NCM622 thin‐film electrode exhibits improved electrochemical properties including satisfactory cycling stability, which benefits from the higher binding energy of fluorine that positively influences the stability of the surface oxygen layer by being doped into the unstable oxygen site, and thus the formation of oxygen derivative phases is successfully suppressed during electrochemical reactions.

Effect of oxygen in surface layers formed during sliding wear of Ni–ZrO2 coatings

Nickel-based coatings with different content of zirconia were deposited on steel by short-pulse laser melting of powder mixtures of pure components. High temperatures during laser short-pulse melting lead to dissolution of the zirconia in the nickel-zirconia melt. Ultrafast cooling of the melt fixes in the solid state the supersaturated solid solution of zirconia in the nickel matrix. The short-pulse laser processing allows the precise amount of zirconia to be dissolved in the metal matrix, therefore the main objective of this research is to study the effect of the oxide content on tribological properties of the coatings. Nickel-zirconia coatings with low zirconia content show a steep decrease in the coefficient of friction (COF) down to 0.03 during wear tests in boundary lubrication conditions. The structure and composition of tribolayers formed both on coated disks and counterfaces, made of cast iron, have been determined and described as mechanically alloyed layers. The main feature of the tribolayers is their almost unoxidized state after wear tests, which was verified by XPS characterization. The results reveal the influence of the dissolved zirconia in the coatings on resistance to oxidation and adhesion of the rubbed surfaces in contact during severe sliding friction.

Diurnal Changes in Hypoxia Shape Predator-Prey Interaction in a Bird-Fish System

Animals often face changing environments, and behavioral flexibility allows them to rapidly and adaptively respond to abiotic factors that vary more or less regularly. However, abiotic factors that affect prey species do not necessarily affect their predators. Still, the prey’s response might affect the predator indirectly, yet evidence from the wild for such a classical bottom-up effect of abiotic factors shaping several trophic levels remains sparse. In many aquatic environments, daily changes in oxygen concentrations occur frequently. When oxygen levels drop to hypoxic levels, many fishes respond with aquatic surface respiration (ASR), during which they obtain oxygen by skimming the upper, oxygenated surface layer. By increasing time at the surface, fish become more vulnerable to fish-eating birds. We explored these cascading effects in a sulfidic spring system that harbors the endemic sulphur molly (Poecilia sulphuraria) as prey species and several fish-eating bird species. Sulfide-rich springs pose harsh conditions as hydrogen sulfide (H2S) is lethal to most metazoans and reduces dissolved oxygen (DO). Field sampling during three daytimes indicated that water temperatures rose from morning to (after)noon, resulting in the already low DO levels to decrease further, while H2S levels showed no diurnal changes. The drop in DO levels was associated with a decrease in time spent diving in sulphur mollies, which corresponded with an increase in ASR. Interestingly, the laboratory-estimated threshold at which the majority of sulphur mollies initiate ASR (ASR50: &amp;lt;1.7 mg/L DO) was independent of temperature and this value was exceeded daily when hypoxic stress became more severe toward noon. As fish performed ASR, large aggregations built up at the water surface over the course of the day. As a possible consequence of fish spending more time at the surface, we found high activity levels of fish-eating birds at noon and in the afternoon. Our study reveals that daily fluctuations in water’s oxygen levels have the potential to alter predator-prey interactions profoundly and thus highlights the joined actions of abiotic and biotic factors shaping the evolution of a prey species.

Climate-driven deoxygenation elevates fishing vulnerability for the ocean's widest ranging shark

Climate-driven expansions of ocean hypoxic zones are predicted to concentrate pelagic fish in oxygenated surface layers, but how expanding hypoxia and fisheries will interact to affect threatened pelagic sharks remains unknown. Here, analysis of satellite-tracked blue sharks and environmental modelling in the eastern tropical Atlantic oxygen minimum zone (OMZ) shows shark maximum dive depths decreased due to combined effects of decreasing dissolved oxygen (DO) at depth, high sea surface temperatures, and increased surface-layer net primary production. Multiple factors associated with climate-driven deoxygenation contributed to blue shark vertical habitat compression, potentially increasing their vulnerability to surface fisheries. Greater intensity of longline fishing effort occurred above the OMZ compared to adjacent waters. Higher shark catches were associated with strong DO gradients, suggesting potential aggregation along suitable DO gradients contributed to habitat compression and higher fishing-induced mortality. Fisheries controls to counteract deoxygenation effects on shark catches will be needed as oceans continue warming.

Simulations of field emission from copper electrodes with inclusion of oxygen surface layer and work function changes based on first-principles calculations

Analysis of field emission requires the inclusion of the internal potentials that shape the electronic wavefunctions and tunneling probabilities; details of the work function that are dependent on material quality and defects; and the role of the density of states (DOS) that influences the electronic supply. Here, these factors are collectively included on the basis of density functional theory to obtain predictions of field-dependent electron tunneling current densities. Results are obtained in copper for three different orientations. The DOS is predicted to be broadened by an externally applied electric field. The (100) copper is shown to yield the largest current density, and the (111) orientation is the lowest. The presence of an oxide surface monolayer is shown to increase the work function, leading to the emission of current reductions. The technique is general and can be applied to other materials (e.g., carbon fibers) that have shown promise as cathode emitters.

High temperature fatigue and oxidation characteristics of forged steel piston materials

Abstract In order to study the fatigue characteristics and oxidation characteristics of 38MnVS6 and 42CrMo4, two kinds of forging steel piston materials, under high temperature and high load conditions, the temperature field, fatigue safety coefficient and distribution of surface oxygen layer were compared and analyzed by means of material characteristics detection, calculation of finite element numerical simulation and bench test and so on. Results showed that forging fiber lines of both two kinds of forged steel pistons could meet the process requirements. However, as for the basic characteristic values, the 42CrMo4 piston was better than the 38MnVS6 piston, increasing by 10% approximately on performance values. Besides, the maximum of temperature of the two pistons both appeared around the corner on the top of combustion chamber, and the temperature of the 38MnVS6 piston was even higher. After combining the basic characteristic, the average fatigue safety coefficient of the 42CrMo4 piston in the combustion chamber and the cooling gallery was more important than that of the 38MnVS6 piston, increasing by 3.6–7%. In addition, under the action of high temperature and pressure, obvious surface oxidation was produced on the top of the pistons. Meanwhile, a certain carbon deposit was also formed on the top of cooling galleries. In general, due to the difference of temperature distribution and thermal conductivity, the oxidation and carbon deposition phenomenon of the 42CrMo4 piston was significantly weaker than that of the 38MnVS6 piston the maximum optimization value of which even reached 90%.

Seasonal Variation of Thermocline Depth: Consequence on Nutrient Availability in the Ivorian Coastal Zone

Faced with the threat of overfishing in Africa, this study was initiated in the coastal zone of Côte d'Ivoire to understand the nutrients availability as function of variation in the depth of thermocline. Data from the ocean bank, World Ocean Atlas (WOA), were used in the ODV software during the twelve months of 2009 taken at 5.5°W/4.5°N (station coordinates). ODV software has allowed to make seasonal analysis, from vertical profiles and latitudinal analysis from the coast toward the sea through some parameters such as temperature, nitrate, phosphate and oxygen. The depth of thermocline, nitracline, phosphacline and oxycline was determined by the seasonal analysis. To evaluate the enrichment intensity of coast towards the sea, latitudinal analysis was investigated using the section profiles (1°S/5°N coordinates). The main results have shown not only the variation in the depth of the thermocline, but also the variation of nitracline, phosphacline and oxycline at different marine seasons. During the cold season, there was an ascent of the thermocline over the surface of water and a strong enrichment from the coast to the sea especially in August. While in hot season, the thermocline was lower and its stability has favoured the stratification of the water column, which prevents the enrichment of the oxygenated surface layer. Analysis of relationships shows that nutrient elements and oxygen change polynomially with temperature.

Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

AbstractO2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self‐consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10−7 to 5 × 10−3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long‐standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an ~30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low‐energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1–6) × 10−3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

Effect of Charges on the Interaction of a Water Molecule with the Fe2O3(0001) Surface

Electronic charges can play a significant role in interaction between water and oxide surfaces, but not much is known about it. In this work, the interaction of a single water molecule with the Fe2O3(0001) surface was studied by DFT+U calculations. To simulate the charged slabs we have used two different methodologies: directly changing the total number of electrons in the supercell, while using a background charge to keep the whole slab neutral; and including guest atoms that act as donors/acceptors. We find that both approaches give similar qualitative and quantitative results, with the added electron being localized on a single Fe atom, while the hole is delocalized mainly on the surface oxygen layer. In addition, we obtain that a water molecule binds more strongly to the negatively charged surfaces when compared to the neutral case. This reduces the energy barrier and increases the enthalpy gains for water dissociation, while a hole reduces this interaction’s strength and also inhibits water dissociation.

Acidification increases sensitivity to hypoxia in important forage fishes

Hypoxia (low dissolved oxygen [DO]) and CO2-induced acidification are important aquatic stressors that are exacerbated by anthropogenic nutrient inputs and are expected to increase in severity with increasing atmospheric CO2 and higher global temperatures. Understanding how species respond to changes in DO and pH is critical to predicting how climate change will affect estuarine ecosystems, including the extreme shallow margins of these systems, where factors such as respiration, photosynthesis, and tides create daily fluctuations of DO and pH, and strong correlations between the 2 stressors. To determine how acidification affects the sensitivity to hypoxia of 2 im portant forage fishes, the silversides Menidia menidia and M. beryllina, we recorded opercula ventilation rates, aquatic surface respiration (ASR, where fish breathe in the oxygenated surface layer during hypoxic events), and mortality as we lowered either DO or both DO and pH simultaneously. Fish subjected to low DO and low pH in the laboratory performed ASR and died at higher DO concentrations than fish subjected only to hypoxia. Additionally, fish beat their opercula slower, which may have contributed to the differences in ASR and mortality that we saw. These results indicate acidification can increase mortality under hypoxia not only directly but also indirectly by increasing vulnerability to predation during increased use of ASR.

Dead zone or oasis in the open ocean? Zooplankton distribution and migration in low-oxygen modewater eddies

Abstract. The eastern tropical North Atlantic (ETNA) features a mesopelagic oxygen minimum zone (OMZ) at approximately 300–600 m depth. Here, oxygen concentrations rarely fall below 40 µmol O2 kg−1, but are expected to decline under future projections of global warming. The recent discovery of mesoscale eddies that harbour a shallow suboxic (&lt; 5 µmol O2 kg−1) OMZ just below the mixed layer could serve to identify zooplankton groups that may be negatively or positively affected by ongoing ocean deoxygenation. In spring 2014, a detailed survey of a suboxic anticyclonic modewater eddy (ACME) was carried out near the Cape Verde Ocean Observatory (CVOO), combining acoustic and optical profiling methods with stratified multinet hauls and hydrography. The multinet data revealed that the eddy was characterized by an approximately 1.5-fold increase in total area-integrated zooplankton abundance. At nighttime, when a large proportion of acoustic scatterers is ascending into the upper 150 m, a drastic reduction in mean volume backscattering (Sv) at 75 kHz (shipboard acoustic Doppler current profiler, ADCP) within the shallow OMZ of the eddy was evident compared to the nighttime distribution outside the eddy. Acoustic scatterers avoided the depth range between approximately 85 to 120 m, where oxygen concentrations were lower than approximately 20 µmol O2 kg−1, indicating habitat compression to the oxygenated surface layer. This observation is confirmed by time series observations of a moored ADCP (upward looking, 300 kHz) during an ACME transit at the CVOO mooring in 2010. Nevertheless, part of the diurnal vertical migration (DVM) from the surface layer to the mesopelagic continued through the shallow OMZ. Based upon vertically stratified multinet hauls, Underwater Vision Profiler (UVP5) and ADCP data, four strategies followed by zooplankton in response to in response to the eddy OMZ have been identified: (i) shallow OMZ avoidance and compression at the surface (e.g. most calanoid copepods, euphausiids); (ii) migration to the shallow OMZ core during daytime, but paying O2 debt at the surface at nighttime (e.g. siphonophores, Oncaea spp., eucalanoid copepods); (iii) residing in the shallow OMZ day and night (e.g. ostracods, polychaetes); and (iv) DVM through the shallow OMZ from deeper oxygenated depths to the surface and back. For strategy (i), (ii) and (iv), compression of the habitable volume in the surface may increase prey–predator encounter rates, rendering zooplankton and micronekton more vulnerable to predation and potentially making the eddy surface a foraging hotspot for higher trophic levels. With respect to long-term effects of ocean deoxygenation, we expect avoidance of the mesopelagic OMZ to set in if oxygen levels decline below approximately 20 µmol O2 kg−1. This may result in a positive feedback on the OMZ oxygen consumption rates, since zooplankton and micronekton respiration within the OMZ as well as active flux of dissolved and particulate organic matter into the OMZ will decline.

Spatial and seasonal patterns of fine-scale to mesoscale upper ocean dynamics in an Eastern Boundary Current System

The physical forcing of the ocean surface includes a variety of energetic processes, ranging from internal wave (IW) to submesoscale and mesoscale, associated with characteristic horizontal scales. While the description of mesoscale ocean dynamics has greatly benefited from the availability of satellite data, observations of finer scale patterns remain scarce. Recent studies showed that the vertical displacements of the oxycline depth, which separates the well-mixed oxygenated surface layer from the less oxygenated deeper ocean, estimated by acoustics, provide a robust proxy of isopycnal displacements over a wide range of horizontal scales. Using a high-resolution and wide-range acoustic data set in the Northern Humboldt Current System (NHCS) off Peru, the spatial and temporal patterns of fine-scale-to-mesoscale upper ocean dynamics are investigated. The spectral content of oxycline/pycnocline profiles presents patterns characteristic of turbulent flows, from the mesoscale to the fine scale, and an energization at the IW scale (2km–200m). On the basis of a typology performed on 35,000 structures we characterized six classes of physical structures according to their shape and scale range. The analysis reveals the existence of distinct features for the fine-scale range below ∼2–3km, and clearly indicates the existence of intense IW and submesoscale activity over the entire NHCS region. Structures at scales smaller than ∼2km were more numerous and energetic in spring than in summer. Their spatiotemporal variability supports the interpretation that these processes likely relate to IW generation by interactions between tidal flows, stratification and the continental slope. Given the impact of the physical forcing on the biogeochemical and ecological dynamics in EBUS, these processes should be further considered in future ecosystem studies based on observations and models. The intensification of upper ocean stratification resulting from climate change makes such high-resolution analyses even more critical.

The Effect of Temperature on Wear Mechanism of the AlCrN Coated Components

The aim of the paper was to investigate the temperature effect on the wear mechanism of AlCrN coated components. The coating was deposited by Physical Vapour Deposition process (PVD) on WC/Co substrate. Tribological tests were performed in sliding conditions using high temperature T‑21 tribotester, produced by ITeE-PIB Radom. The tests were performed in a ball-on-disc configuration (Si3N4 ceramic ball), under dry friction conditions at room temperature, 600°C and 750°C. An optical microscope, interferometer, and scanning electron microscope were used to analyse the worn surfaces. Following this study, it was found that wear resistance of the coating AlCrN tribosystem depended on the temperature. The biggest wear was reported at room temperature. At 600°C the intensity of wear of the coating was 4-fold lower, and at 750°C wear was 6-fold lower that at room temperature. High temperature wear resistance of AlCrN coating involves creating protective oxide layer. Performed analysis of structure the surface layer, showed a much higher content of oxygen in wear scar than outside. At high temperatures, friction additional intensified oxidation process thus the amount of oxygen in surface layer increased with temperature. Oxide layer, Al2O3 and Cr2O3 probably, created at high temperature was a barrier to further oxidation of the coating and had very high wear resistance at high temperature.

Long-term Variations of Water Quality Parameters in Lake Kyoungpo

In order to identify long-term trends of water quality parameters in Lake Kyeongpo, Mann- Kendall test, Sen``s slope estimator and linear regression were applied on data, with 15 parameters from three different sites and rainfall, monitored once in every two months from March to November during 1998~2013. Seasonal variation analysis only used Mann-Kendall test and Sen``s slope estimator. Analysis result showed that salinity, transparency and nutrient variables (total phosphorus, dissolved inorganic phosphorus, total nitrogen, nitrate nitrogen, ammonia nitrogen) were only parameters having statistically significant trend. In linear regression analysis, salinity (surface and bottom layer of all sites) and transparency (only at site 1), were figured out with statistically significant increasing trend, while in non-parametric statistical method, salinity and transparency in all sites (surface, middle, deep) were figured out with statistically significant increasing trend. Water quality parameters showing statistically significant decreasing trends were dissolved oxygen (surface layer of site 1 and bottom layer of sites 2 and 3), total phosphorus (sites 1 and 2), dissolved inorganic phosphorus, total nitrogen, nitrate nitrogen and ammonia nitrogen in the linear regression analysis and, dissolved oxygen (bottom layer of all sites), total phosphorus, dissolved inorganic phosphorus, total nitrogen, nitrate nitrogen and ammonia nitrogen in the non-parametric method. Seasonal trend analysis result showed that salinity, turbidity, transparency and suspended solids in spring, salinity, transparency, nitrate nitrogen and suspended solids in summer and temperature, salinity, transparency and suspended solids in fall were the variables depending on the season with increasing trends. In general, rainfall during the research period showed decreasing trend. The significant reduction trends of nutrients in Lake Kyeongpo were believed to be related to lagoon restoration and water management project run by Gangneung city and under-water wear removal, but further detailed studies are needed to know the exact causes.

Egg production and hatching success of Calanus chilensis and Acartia tonsa in the northern Chile upwelling zone (23°S), Humboldt Current System

Oxygen Minimum Zones (OMZ's) are expanding and intensifying as result of climate change, affecting Eastern Boundary Upwelling Systems. Local effects of vertical movements of OMZ's that result from changes in upwelling intensity could reduce or expand the oxygenated surface layer that most zooplanktonic species inhabit in coastal areas. Using the copepods Calanus chilensis and Acartia tonsa as model organisms, an experimental test of the impact of different dissolved oxygen (DO) concentrations (between 0.5 and 5mlL−1) on egg production and hatching success was carried out and compared with field estimations of egg production, female and egg abundance in Mejillones Bay (23°S). Abundance of C. chilensis was highly variability and no consistent pattern in egg production and hatching success was found across DO levels, whereas A. tonsa egg production had maximum values between 2.6 and 4.7ml O2 L−1 and hatching success was positively correlated with DO (r=0.75). In the field, temperature was the main factor controlling the dynamics of both species, while Chl-a and DO were also correlated with C. chilensis and A. tonsa, respectively. Principal Component Analysis showed that abundances of both copepods were controlled by temperature, stratification, OMZ depth, and Ekman transport, which together explained more than 70% of the total variance and were the main factors that modulated the populations of C. chilensis and A. tonsa in the upwelling zone of northern Chile (23°S). The differential responses of C. chilensis and A. tonsa to changes in DO concentrations associated with vertical movements of the OMZ suggest that C. chilensis may be better adapted to hypoxic conditions than A. tonsa, however both species are successful and persistent all year-round. We suggest that physiological responses of copepods could be used to evaluate population dynamics affected by the shoaling of OMZ's and the repercussions to trophic food webs of eastern boundary current systems.