Surface Oxygen Levels Research Articles

Convergent evolution of giant size in eurypterids.

Eurypterids-Palaeozoic marine and freshwater arthropods commonly known as sea scorpions-repeatedly evolved to remarkable sizes (over 0.5 m in length) and colonized continental aquatic habitats multiple times. We compiled data on the majority of eurypterid species and explored several previously proposed explanations for the evolution of giant size in the group, including the potential role of habitat, sea surface temperature and dissolved sea surface oxygen levels, using a phylogenetic comparative approach with a new tip-dated tree. There is no compelling evidence that the evolution of giant size was driven by temperature or oxygen levels, nor that it was coupled with the invasion of continental aquatic environments, latitude or local faunal diversity. Eurypterid body size evolution is best characterized by rapid bursts of change that occurred independently of habitat or environmental conditions. Intrinsic factors played a major role in determining the convergent origin of gigantism in eurypterids.

(Invited) Universal Alignment of Surface and Bulk Oxygen Levels in Semiconductors

Lattices of most semiconductors have a large density of intrinsic and extrinsic defects which gives rise to effects such as surface Fermi level (EF) pinning, dopant compensation, asymmetrical p versus n-doping, and device degradation. Oxygen and hydrogen are the two most important impurities in semiconductors because of their ubiquitous presence in growth and device processing environments and consequently their incorporation strongly influences electronic and electrical properties. Therefore, a deeper understanding of the interaction of these species with the semiconductor surface and bulk defects is necessary for enabling the development of devices based on them such as photovoltaic and photocatalytic systems, fuel cells, and many others. Analysis of the reported surface work function values and the substitutional bulk O-defect energies show that the surface Fermi level of position in a broad range of group IV, III-V, II-VI, and I-III-VI2 semiconductors with physisorbed O2 lies universally at approximately -5.1 eV below the vacuum level. Similarly, results show that the energy of the bulk substitutional O-related amphoteric defects incorporated during crystal growth also has a universal energy of ~ -5.0 eV with respect to the vacuum level for most of the investigated semiconductors. It is shown that the process of ‘surface transfer doping’ that involves an adsorbed nanoscale water film on the semiconductor surface is likely responsible for the universal alignment of oxygen levels. Figure 1

Universal alignment of surface and bulk oxygen levels in semiconductors

Oxygen and hydrogen are the two most important impurities in semiconductors because of their ubiquitous presence in growth and device processing environments, and consequently, their incorporation strongly influences electronic and electrical properties. Therefore, a deeper understanding of the interaction of these species with the semiconductor surface and bulk defects is necessary for enabling the development of devices based on them, such as photovoltaic and photocatalytic systems and fuel cells. It is shown here, through the analysis of the reported surface work function values and substitutional bulk O-defect energies, that the surface Fermi level of semiconductors with physisorbed O2 lies universally at approximately −5.1 eV below the vacuum level. Similarly, the results show that the energy of substitutional bulk O-related amphoteric defects incorporated during the crystal growth also has a universal energy of ∼−5.0 eV with respect to the vacuum level for most semiconductors investigated. It is shown that the process of “surface transfer doping” involving an adsorbed water film on the semiconductor surface is likely responsible for the universal alignment of oxygen levels.

Chromium isotope systematics and the diagenesis of marine carbonates

Stable chromium (Cr) isotopes have emerged as a new tool for tracking broad-scale changes in Earth's surface oxygen levels. Carbonates are one proposed sedimentary Cr isotope archive. In order to contribute to the development of a robust framework for interpreting carbonate Cr isotopic compositions and evaluating their ability to record the global redox state, we explored Cr isotope systematics of modern and Archean carbonate successions—representing end member oxic and anoxic Earth system states. We generated new data from carbonate platform sediments from the Great Bahama Bank with variable post-depositional histories to better understand the effects of diagenetic alteration on carbonate-bound Cr and its isotopic composition in a modern well-oxygenated ocean-atmosphere system. More specifically, we investigated the effects of dolomitization and aragonite-to-calcite neomorphism in marine and meteoric fluids. We also present δ53Cr values from three carbonate successions, the ∼3.0 Ga Chobeni Formation (South Africa), ∼2.8 Ga Mosher Carbonate Formation (Canada), and ∼2.65 Ga Cheshire Formation (Zimbabwe), that were deposited under an anoxic atmosphere. We find that modern Bahamian carbonates have a large range of almost exclusively positive δ53Cr values (from −0.04 to 2.88‰). The δ53Cr values appear to be altered during both meteoric diagenesis and dolomitization but there may also be instances of rock-buffered conditions that may best preserve depositional δ53Cr values. These observations provide a baseline for carbonate Cr isotope behavior in a well-oxygenated ocean-atmosphere system. Our Archean carbonate successions contain both positively fractionated and crustal δ53Cr values, ranging between −0.37 and 0.89‰. The Cr isotope fractionation observed in Archean strata is most plausibly linked to either non-redox dependent Cr isotope fractionation, local Cr redox cycling, late-stage diagenetic alteration, or some combination thereof. Given the significant effects of post-depositional alteration on the isotopic composition of carbonate-bound Cr, we suggest that Cr isotope values from ancient carbonate sediments should be generally interpreted with caution and cannot be straightforwardly linked to changes in atmospheric oxygen abundance.

Episodic ferruginous conditions associated with submarine volcanism led to the deposition of a Late Carboniferous iron formation

Iron formations (IFs) are iron-rich chemical sediments that were widespread throughout the Precambrian. The deposition of IFs has provided key evidence about the prevalence of anoxic and ferruginous marine conditions throughout Earth’s history. Here, we describe the Shikebutai IF, hosted in a Late Carboniferous volcano-sedimentary sequence in the Western Tianshan region of northwest China. The IF is largely composed of hematite, jasper, and siderite. The chemical composition of the Shikebutai IF is dominated by Fe2O3 and SiO2, and very low concentrations of Al2O3, TiO2, Th, Nb, and Sc were observed, indicative of an authigenic origin. High Fe/Ti, Fe/Al, Co/Zn, and Ni/Zn ratios, along with positive Eu anomalies and εNd(t) values point to a significant submarine volcanic and hydrothermal contribution. The absence of negative Ce anomalies and heterogeneous δ56Fe values suggest progressive oxidation of hydrothermally sourced Fe(II) and deposition in an anoxic to low oxygen basin. Low P/Fe ratios in the Shikebutai IF, comparable to those found in the Precambrian, are consistent with Si inhibition of P sorption and P drawdown with high hydrothermal inputs. The intimate association of this Late Carboniferous IF with submarine volcanic activity suggests an origin that is analogous to Precambrian Algoma-type IFs. Further, the Shikebutai IF provides evidence for an episode of basin-scale anoxic, ferruginous conditions coinciding with the generally well-oxygenated deep oceans of the Phanerozoic, with deposition driven by enhanced submarine volcanic and hydrothermal activity in the Western Tianshan region during the Late Carboniferous. This demonstrates how, even with near modern surface oxygen levels, enhanced hydrothermal activity can shape the marine redox landscape and cause the development of ferruginous conditions without quantitative sulfate drawdown.

On the co-evolution of surface oxygen levels and animals.

Few topics in geobiology have been as extensively debated as the role of Earth's oxygenation in controlling when and why animals emerged and diversified. All currently described animals require oxygen for at least a portion of their life cycle. Therefore, the transition to an oxygenated planet was a prerequisite for the emergence of animals. Yet, our understanding of Earth's oxygenation and the environmental requirements of animal habitability and ecological success is currently limited; estimates for the timing of the appearance of environments sufficiently oxygenated to support ecologically stable populations of animals span a wide range, from billions of years to only a few million years before animals appear in the fossil record. In this light, the extent to which oxygen played an important role in controlling when animals appeared remains a topic of debate. When animals originated and when they diversified are separate questions, meaning either one or both of these phenomena could have been decoupled from oxygenation. Here, we present views from across this interpretive spectrum-in a point-counterpoint format-regarding crucial aspects of the potential links between animals and surface oxygen levels. We highlight areas where the standard discourse on this topic requires a change of course and note that several traditional arguments in this "life versus environment" debate are poorly founded. We also identify a clear need for basic research across a range of fields to disentangle the relationships between oxygen availability and emergence and diversification of animal life.

The impact of marine nutrient abundance on early eukaryotic ecosystems.

The rise of eukaryotes to ecological prominence represents one of the most dramatic shifts in the history of Earth's biosphere. However, there is an enigmatic temporal lag between the emergence of eukaryotic organisms in the fossil record and their much later ecological expansion. In parallel, there is evidence for a secular increase in the availability of the key macronutrient phosphorus (P) in Earth's oceans. Here, we use an Earth system model equipped with a size-structured marine ecosystem to explore relationships between plankton size, trophic complexity, and the availability of marine nutrients. We find a strong dependence of planktonic ecosystem structure on ocean nutrient abundance, with a larger ocean nutrient inventory leading to greater overall biomass, broader size spectra, and increasing abundance of large Zooplankton. If existing estimates of Proterozoic marine nutrient levels are correct, our results suggest that increases in the ecological impact of eukaryotic algae and trophic complexity in eukaryotic ecosystems were directly linked to restructuring of the global P cycle associated with the protracted rise of surface oxygen levels. Our results thus suggest an indirect but potentially important mechanism by which ocean oxygenation may have acted to shape marine ecological function during late Proterozoic time.

Mesoproterozoic oxygenated deep seawater recorded by early diagenetic carbonate concretions from the Member IV of the Xiamaling Formation, North China

Oxygen availability is crucial for the evolution of eukaryotes in geological history. However, the evolution of mid-Proterozoic oceanic–atmospheric redox conditions remains heavily debated, e.g., [O2] <0.1–1% PAL vs. >4–8% PAL (present atmospheric level). In order to further constrain the surface oxygen levels during Mesoproterozoic, an investigation on the I/(Ca + Mg) ratios of deep-water (>100 m) early diagenetic carbonate concretions from the shale-predominated Member IV of the Xiamaling Formation (~1.4 Ga) in three sections of the North China Platform was conducted. The results show that more than half (36/47) of the I/(Ca + Mg) values obtained from the concretions are higher than 0.5 μmol/mol (avg. 0.68), indicating non-negligible iodate retained in the porewaters where the concretions were formed. Compared with the iodine redox cycle and oxygen transportation pathway from bottom seawater to surface sediments in modern oceans, the oxygen concentration of the bottom seawater was estimated to be higher than 16–22 μM, and the minimal atmospheric oxygen level should be higher than 6–9% PAL. This result differs from the previous estimation that the atmospheric oxygen level is lower than 0.1–1% PAL, but is consistent with the estimation of >4–8% PAL at ~1.4 Ga.

Effect of aging process on some properties of conventional and multilayered translucent zirconia for monolithic restorations

The purpose of this study was to evaluate the surface characteristics and optical and mechanical properties of materials through hydrothermal aging using different types of translucent monolithic zirconia.Three conventional materials (LT, KT, and ET) and three multilayered materials (LM, KM, and EM) of translucent monolithic zirconia were investigated. 45 bar-shaped specimens in each group were fabricated for the measurement of surface characteristics and mechanical properties and were randomly divided into 3 subgroups. 10 plate-shaped specimens in each group were fabricated for the measurement of optical properties. All specimens were autoclaved for 0, 5, and 10 h, respectively. The various properties of translucent monolithic zirconia, such as phase distribution, surface roughness, surface texture, elemental analysis, total transmittance (Tt), contrast ratio (CR), three point flexural strength (TFS), nanoindentation hardness (NH), and Young's modulus (YM), were measured through different tests. Statistical analyses were performed with one-way ANOVA, Tukey HSD post hoc test, independent sample t-test, paired sample t-test, and two-way ANOVA (α = 0.05).After aging, the monoclinic phase of all groups increased relative to the tetragonal phase. All groups exhibited an increase in the surface roughness and oxygen levels, but exhibited a decrease in the zirconium and yttrium levels (P < .05). All groups had increased microcracks and grain push-out. Tt increased and CR decreased in the LT, KT, and ET groups. However, Tt decreased and CR increased in the LM, KM, and EM groups (P < .05). The TFS, NH, and YM showed a decreasing tendency, but there were no significant difference in several materials (P > .05).Alterations in the surface characteristics were found on the surfaces of translucent monolithic zirconia after aging. The aging process caused conventional materials to become more translucent, but multilayered materials were more opaque. The various properties of translucent monolithic zirconia were affected by the materials fabricated with different types after aging.

A case for low atmospheric oxygen levels during Earth's middle history.

The oxygenation of the atmosphere - one of the most fundamental transformations in Earth's history - dramatically altered the chemical composition of the oceans and provides a compelling example of how life can reshape planetary surface environments. Furthermore, it is commonly proposed that surface oxygen levels played a key role in controlling the timing and tempo of the origin and early diversification of animals. Although oxygen levels were likely more dynamic than previously imagined, we make a case here that emerging records provide evidence for low atmospheric oxygen levels for the majority of Earth's history. Specifically, we review records and present a conceptual framework that suggest that background oxygen levels were below 1% of the present atmospheric level during the billon years leading up to the diversification of early animals. Evidence for low background oxygen levels through much of the Proterozoic bolsters the case that environmental conditions were a critical factor in controlling the structure of ecosystems through Earth's history.

Costs of epibionts on Antarctic sea spiders

Nearly all marine animals harbor epibionts, organisms living on their body surfaces. The positive or negative effects that epibionts have on their hosts depend on many factors, including the size and location of the epibionts on their host. The present study examined the effects of epibionts on gas exchange, locomotion, and drag of three species of Antarctic sea spiders (pycnogonids). Sea spiders are a cosmopolitan group of marine arthropods that lack gills and rely instead on the diffusion of oxygen directly across their cuticle. Encrusting epibionts, such as bryozoans and algae, had only minor effects on surface oxygen levels, but they reduced the functional diffusion coefficient of oxygen through the cuticle by about half. Although these effects are significant locally and may be severe in individuals with high coverage by epibionts, the total coverage on most individuals was not high enough to significantly alter oxygen fluxes into the animal. Macroepibionts, such as barnacles, had no effect on host walking speeds, but they increased by two-to-threefold the drag experienced by host sea spiders. This likely increases the energetic costs of walking and increases the chance of being dislodged by high currents. These results suggest that epibionts can impose diverse costs to their hosts but only in subtle ways that depend on total epibiont coverage of the host and rates of water flow.

Geochemistry of Paleoproterozoic Gunflint Formation carbonate: Implications for hydrosphere-atmosphere evolution

The ∼1880Ma Gunflint Formation has played a critical role in shaping our view of the evolution of the Precambrian biosphere and the redox state of Earth’s early oceans. Herein we present a study of the petrology and geochemistry of calcic grainstones and stromatolitic limestones present at the very top of the Gunflint Formation and compare them with underlying ankeritic grainstones that dominate the shore-proximal portion of the basin. Meteoric calcite cements in the upper limestones formed prior to the unit being brecciated and/or buried by debris carried by the blast cloud from the 1850Ma Sudbury impact event. The intraclastic grains and cements in the limestone are highly enriched in V, Cr, U and REEs, with REE patterns similar to those of modern groundwater. Cr isotopes have a distinctly positive signature in most samples indicating formation of oxidized, hexavalent Cr during subaerial weathering. These redox-sensitive metals were transported in oxygenated groundwater and precipitated where the fluid encountered reducing conditions. In contrast, the underlying ankeritic marine grainstones have REE patterns similar to those of some modern-day venting hydrothermal fluids and earliest Paleoproterozoic seawater. This work suggests that significant levels of oxygen existed in the atmosphere at the time, whereas, even shallow areas of the world ocean remained very oxygen-deficient or that there were strong temporal variations in surface oxygen levels. The contrast in redox state of anoxic shallow-marine water versus oxic groundwater may have been linked to strong sub-seafloor hydrothermal circulation and extensive upwelling onto shallow shelves, which could have sustained widespread marine anoxia. More broadly, our study highlights the importance of investigating and understanding lateral geochemical gradients, and the flux rates that control them, in shallow paleomarine settings.

Earth’s oxygen cycle and the evolution of animal life

The emergence and expansion of complex eukaryotic life on Earth is linked at a basic level to the secular evolution of surface oxygen levels. However, the role that planetary redox evolution has played in controlling the timing of metazoan (animal) emergence and diversification, if any, has been intensely debated. Discussion has gravitated toward threshold levels of environmental free oxygen (O2) necessary for early evolving animals to survive under controlled conditions. However, defining such thresholds in practice is not straightforward, and environmental O2 levels can potentially constrain animal life in ways distinct from threshold O2 tolerance. Herein, we quantitatively explore one aspect of the evolutionary coupling between animal life and Earth's oxygen cycle-the influence of spatial and temporal variability in surface ocean O2 levels on the ecology of early metazoan organisms. Through the application of a series of quantitative biogeochemical models, we find that large spatiotemporal variations in surface ocean O2 levels and pervasive benthic anoxia are expected in a world with much lower atmospheric pO2 than at present, resulting in severe ecological constraints and a challenging evolutionary landscape for early metazoan life. We argue that these effects, when considered in the light of synergistic interactions with other environmental parameters and variable O2 demand throughout an organism's life history, would have resulted in long-term evolutionary and ecological inhibition of animal life on Earth for much of Middle Proterozoic time (∼1.8-0.8 billion years ago).

A shale-hosted Cr isotope record of low atmospheric oxygen during the Proterozoic

Abstract The emergence and expansion of animal life on Earth represents a dramatic shift in the structure and complexity of the biosphere. A lack of firm constraints on surface oxygen levels during the mid-Proterozoic has resulted in heated debate as to whether the rise and earliest diversification of animals was directly linked to a change in environmental oxygen levels or, instead, simply reflects the timing of innovations in gene expression and developmental regulation and was independent of a direct environmental trigger. Here, we present chromium (Cr) isotope data from marine black shales that provide evidence for minimal Cr oxidation throughout the mid-Proterozoic leading up to the diversification of eukaryotes and the rise of animals during the late Neoproterozoic. This observation requires very low background oxygen levels (&amp;lt;1% of present atmospheric levels). Accepting previously proposed estimates of pO2 levels needed to induce Cr isotope fractionation, our data provide support for the persistence of an Earth system in which baseline atmospheric pO2 would have been low enough to inhibit the diversification of animals until ca. 800 Ma. More generally, evidence for a delayed rise of atmospheric oxygen strongly suggests that environmental factors have played a fundamental role in controlling the emergence and expansion of complex life on Earth.

Ediacaran Marine Redox Heterogeneity and Early Animal Ecosystems.

Oxygenation has widely been viewed as a major factor driving the emergence and diversification of animals. However, links between early animal evolution and shifts in surface oxygen levels have largely been limited to extrapolation of paleoredox conditions reconstructed from unfossiliferous strata to settings in which contemporaneous fossils were preserved. Herein, we present a multi-proxy paleoredox study of late Ediacaran (ca. 560-551 Ma) shales hosting the Miaohe Konservat-Lagerstätte of South China and, for comparison, equivalent non-fossil-bearing shales at adjacent sections. For the fossiliferous strata at Miaohe there is geochemical evidence for anoxic conditions, but paleontological evidence for at least episodically oxic conditions. An oxygen-stressed environment is consistent with the low diversity and simple morphology of Miaohe Biota macrofossils. However, there is no evidence for euxinic (anoxic and sulphidic) conditions for the fossiliferous strata at Miaohe, in contrast to adjacent unfossiliferous sections. Our results indicate that Ediacaran marine redox chemistry was highly heterogeneous, even at the kilometre-scale. Therefore, our study provides direct—rather than inferred—evidence that anoxia played a role in shaping a landmark Ediacaran ecosystem. If the anoxic conditions characteristic of the studied sections were widespread in the late Neoproterozoic, environmental stress would have hindered the development of complex ecosystems.

Large-scale fluctuations in Precambrian atmospheric and oceanic oxygen levels from the record of U in shales

The atmosphere–ocean system experienced a progressive change from anoxic to more oxidizing conditions through time. This oxidation is traditionally envisaged to have occurred as two stepwise increases in atmospheric oxygen at the beginning and end of the Proterozoic Eon. Here, we present a study of the redox-sensitive element, uranium, in organic-rich shales to track the history of Earth's surface oxidation at an unprecedented temporal resolution. Fluctuations in the degree of uranium enrichment in organic-rich shales suggest that the initial rise of atmospheric oxygen ~2.4billionyr ago was followed by a decline to less oxidizing conditions during the mid-Proterozoic. This redox state persisted for almost 1billionyr, ending with a second oxygenation event in the latest Neoproterozoic. The U record tracks major fluctuations in surface oxygen level and challenges conventional models that suggest the Earth underwent a unidirectional rise in atmospheric oxygen during the Precambrian.

Effect of UV and electrochemical surface treatments on the adsorption and reaction of linear alcohols on non-porous carbon fibre

The adsorption properties of untreated, electrochemically treated and ultra-violet/ozone treated polyacrylonitrile based carbon fibres were investigated using temperature programmed desorption (TPD) on a series of linear alcohols as probes in order to understand its surface properties. Surface uptake was found to be sensitive to both the surface treatment and the nature of the adsorbates. Surface coverage increased with increasing alcohol chain due to the increase in their polarizability. It also increased with the level of surface oxygen of the fibres most likely because it facilitates the OH bond dissociation of the alcohol functional group. In addition, the desorption temperature (during TPD) tracked the surface oxygen levels (as determined from XPS O1s signal) suggesting increasing in the adsorption energy. The reactions of C1–C4 linear alcohols were also investigated on the surface of the fibre carbon. The main reaction was dehydrogenation to the corresponding aldehydes; the dehydration reaction to olefins was not observed. The dehydrogenation reaction was sensitive to the length of the alky chain. It was highest for methanol (to formaldehyde) and decreased with increasing the carbon number. Overall TPD of linear alcohols was shown to be a promising method for quantifying the level and strength of bonding occurring on carbon fibre surfaces.

Studies of isolated global brain ischaemia: III. Influence of pulsatile flow during cerebral perfusion and its link to consistent full neurological recovery with controlled reperfusion following 30 min of global brain ischaemia

Brain damage is universal in the rare survivor of unwitnessed cardiac arrest. Non-pulsatile-controlled cerebral reperfusion offsets this damage, but may simultaneously cause brain oedema when delivered at the required the high mean perfusion pressure. This study analyses pulsatile perfusion first in control pigs and then using controlled reperfusion after prolonged normothermic brain ischaemia (simulating unwitnessed arrest) to determine if it might provide a better method of delivery for brain reperfusion. Initial baseline studies during isolated brain perfusion in 12 pigs (six non-pulsatile and six pulsatile) examined high (750 cc/min) then low (450 cc/min) fixed flow before and after transient (30 s) ischaemia, while measuring brain vascular resistance and oxygen metabolism. Twelve subsequent pigs underwent 30 min of normothermic global brain ischaemia followed by either uncontrolled reperfusion with regular blood (n = 6) or pulsatile-controlled reperfusion (n = 6) before unclamping brain inflow vessels. Functional neurological deficit score (NDS; score: 0, normal; 500, brain death) was evaluated 24 h post-reperfusion. High baseline flow rates with pulsatile and non-pulsatile perfusion before and after transient ischaemia maintained normal arterial pressures (90-100 mmHg), surface oxygen levels IN Vivo Optical Spectroscopy (INVOS) and oxygen uptake. In contrast, oxygen uptake fell after 30 s ischaemia at 450 cc/min non-pulsatile flow, but improved following pulsatile perfusion, despite its delivery at lower mean cerebral pressure. Uncontrolled (normal blood) reperfusion after 30 min of prolonged ischaemia, caused negligible INVOS O(2) uptake (<10-15%), raised conjugated dienes (CD; 1.75 ± 0.15 A(233 mn)), one early death, multiple seizures, high NDS (243 ± 16) and extensive cerebral infarcts (2,3,5-triphenyl tetrazolium chloride stain) and oedema (84.1 ± 0.6%). Conversely, pulsatile-controlled reperfusion pigs exhibited normal O(2) uptake, low CD levels (1.31 ± 0.07 A(233 mn); P < 0.01 versus uncontrolled reperfusion), no seizures and a low NDS (32 ± 14; P < 0.001 versus uncontrolled reperfusion); three showed complete recovery (NDS = 0) and all could sit and eat. Post-mortem brain oedema was minimal (81.1 ± 0.5; P < 0.001 versus uncontrolled reperfusion) and no infarctions occurred. Pulsatile perfusion lowers cerebral vascular resistance and improves global O(2) uptake to potentially offset post-ischaemic oedema following high-pressure reperfusion. The irreversible functional and anatomic damage that followed uncontrolled reperfusion after a 30-min warm global brain ischaemia interval was reversed by pulsatile-controlled reperfusion, as its delivery resulted in consistent near complete neurological recovery and absent brain infarction.

Surface studies of hydroxylated multi-wall carbon nanotubes

CVD grown MWCNTs, of typical diameter 5 to 50nm and with approximately 15–20 concentric graphene layers in the multi-walls, have been surface functionalised using the Fenton hydroxylation reaction. HRTEM reveals little physical difference between the treated and untreated materials; images from both exhibit similar multi-wall structure and contain evidence for some low-level disruption of the very outermost layers. Raman spectra from the two types of nanotubes are almost identical displaying the disorder (D) peaks at approximately 1350cm−1 and graphite (G) peaks at approximately 1580cm−1, characteristic of graphene-based carbon materials, in approximately equal intensity ratios. Equilibrium adsorption data for nitrogen at 77K leads to BET surface areas of 60.4m2g−1 for the untreated and 71.8m2g−1 for the hydroxylated samples; the increase in area being due to separation of the tube-bundles during functionalization. This is accompanied by a decrease in measured porosity, mostly at high relative pressures of nitrogen, i.e. where larger (meso 2–5nm and macro >5nm) pores are being filled, which is consistent with an attendant loss of inter-tube capillarity. X-ray photoelectron spectroscopy (XPS) shows that hydroxylation increases the nanotube surface oxygen level from 4.3at.% to 22.3at.%; chemical shift data indicate that approximately 75% of that oxygen is present as hydroxyl (–OH) groups. Water vapour adsorption by the hydroxylated surfaces leads to Type II isotherms which are characteristic of relatively high numbers of hydrogen bonding interactions compared to the untreated materials which exhibit Type III curves. This difference in polar surface energy is confirmed by calorimetric enthalpies of immersion in water which are −54mJm−2 for the untreated and −192mJm−2 for the hydroxylated materials. The treated materials therefore have significantly increased water wettability/dispersivity and a greater potential for cross-linking with matrix compounds. The mechanism by which hydroxylation occurs i.e. free radical (OH) attack and subsequent electrophilic addition at CC bonds in the graphene basal planes, is discussed.

Heterogeneity of Skin Surface Oxygen Level of Wrist in Relation to Acupuncture Point

The distribution of partial oxygen pressure (pO2) is analyzed for the anterior aspect of the left wrist with an amperometric oxygen microsensor composed of a small planar Pt disk-sensing area (diameter = 25 μm). The pO2 levels vary depending on the measurement location over the wrist skin, and they are systematically monitored in the analysis for both one-dimensional single line (along the wrist transverse crease) and two-dimensional square area of the wrist region. Relatively higher pO2 values are observed at certain area in close proximity to the position of acupuncture points with statistical significance, indicating strong relationship between oxygen and acupuncture point. The used oxygen microsensor is sensitive enough to detect the pO2 variation depending on the location. This study may provide information helpful to understand possible physiological roles of the acupuncture points.