Mercury and amino acid content relations in northern pike (Esox lucius) in subarctic lakes along a climate-productivity gradient.

Mercury is a highly toxic element for consumers, but its relation to amino acids and physiology of wild fish is not well known. The main aim of this study was to evaluate how total mercury content (THg) of northern pike (Esox lucius) is related to amino acids and potentially important environmental and biological factors along a climate-productivity gradient of ten subarctic lakes. Linear regression between THg and sixteen amino acids content [nmol mg-1 dry weight] from white dorsal muscle of pike from these lakes were tested. Lastly, a general linear model (GLM) for age-corrected THg was used to test which factors are significantly related to mercury content of pike. There was a positive relationship between THg and proline. Seven out of sixteen analysed amino acids (histidine, threonine, arginine, serine, glutamic acid, glycine, and aspartic acid) were significantly negatively related to warmer and more productive lakes, while THg showed a positive relationship. GLM model indicated higher THg was found in higher trophic level pike with lower cysteine content and inhabiting warmer and more productive lakes with larger catchment containing substantial proportion of peatland area. In general, THg was not only related to the biological and environmental variables but also to amino acid content.

Distance decay 2.0 - A global synthesis of taxonomic and functional turnover in ecological communities.

Aim: Understanding the variation in community composition and species abundances (i.e., ß-diversity) is at the heart of community ecology. A common approach to examine ß-diversity is to evaluate directional variation in community composition by measuring the decay in the similarity among pairs of communities along spatial or environmental distance. We provide the first global synthesis of taxonomic and functional distance decay along spatial and environmental distance by analysing 148 datasets comprising different types of organisms and environments. Location: Global. Time period: 1990 to present. Major taxa studied: From diatoms to mammals. Method: We measured the strength of the decay using ranked Mantel tests (Mantel r) and the rate of distance decay as the slope of an exponential fit using generalized linear models. We used null models to test whether functional similarity decays faster or slower than expected given the taxonomic decay along the spatial and environmental distance. We also unveiled the factors driving the rate of decay across the datasets, including latitude, spatial extent, realm and organismal features. Results: Taxonomic distance decay was stronger than functional distance decay along both spatial and environmental distance. Functional distance decay was random given the taxonomic distance decay. The rate of taxonomic and functional spatial distance decay was fastest in the datasets from mid-latitudes. Overall, datasets covering larger spatial extents showed a lower rate of decay along spatial distance but a higher rate of decay along environmental distance. Marine ecosystems had the slowest rate of decay along environmental distances. Main conclusions: In general, taxonomic distance decay is a useful tool for biogeographical research because it reflects dispersal-related factors in addition to species responses to climatic and environmental variables. Moreover, functional distance decay might be a cost-effective option for investigating community changes in heterogeneous environments.

Comparative trophic ecology of microhabitat-associated guilds of reef fishes in the Adriatic Sea.

Reef ecosystems are characterized by highly heterogenous habitats and functionally diverse fish communities. Few studies have examined how functional diversity differs among habitats within these communities, i.e., species associated with a specific habitat may have similar trophic ecologies meaning that the functional diversity within the community is driven by habitat diversity or, conversely, high functional diversity within each habitat would indicate that resource segregation also occurs at the habitat level. We used stable isotope ratios of carbon and nitrogen to estimate trophic position, resource use and ontogenetic niche shifts of 15 reef fishes associated with four distinct habitat types (cryptobenthic, epibenthic sand, epibenthic rock and hyperbenthic) on the Croatian coast of the Adriatic Sea. Trophic ecology was quite similar across fish assemblages, but there was strong evidence of niche segregation among fish species within each assemblage showing high functional diversity within each microhabitat. The sampled fish community contained benthic and pelagic resource users, along with multiple intermediate generalists. Consumer stable isotope ratios revealed considerable interspecific variation in resource use among fishes within each habitat type. The cryptobenthic fishes were a notable exception to this trend with the narrow range of resource use values, indicating reliance of these species on a single resource. The greatest diversity of trophic positions within a guild was observed in cryptobenthic and rock-associated epibenthic fishes. The majority of observed ontogenetic variation in studied fish species reflected an increase in benthic resource use and trophic position. However, the degree of ontogenetic variation in trophic ecology of studied species, if present, was generally low, showing no dramatic change in the ecology of any species. The size structuring among guilds was considerable, with cryptobenthic fishes the smallest on average and hyperbenthic fishes the largest, despite guilds having similar ranges of trophic positions.

Winter ecology of specialist and generalist morphs of European whitefish, Coregonus lavaretus, in subarctic northern Europe.

European whitefish is a model species for adaptive radiation of fishes in temperate and subarctic lakes. In northern Europe the most commonly observed morphotypes are a generalist (LSR) morph and a pelagic specialist (DR) morph. The evolution of a pelagic specialist morph is something of an enigma, however, as this region is characterized by long, dark winters with pelagic primary production limited to a brief window in late summer. We conducted the first winter-based study of polymorphic whitefish populations to determine the winter ecology of both morphs, and we combined seasonal diet and stable isotope analysis with several proxies of condition in three polymorphic whitefish populations. The generalist LSR morph fed on benthic and pelagic prey in summer but was solely reliant on benthic prey in winter. This was associated with a noticeable but moderate reduction in condition, lipid content and stomach fullness in winter relative to summer. In contrast, the DR whitefish occupied a strict pelagic niche in both seasons. A significant reduction in pelagic prey during winter resulted in severe decrease in condition, lipid content and stomach fullness in DR whitefish in winter relative to summer, with the pelagic morph apparently approaching starvation in winter. We suggest that this divergent approach to seasonal foraging is associated with the divergent life-history traits of both morphs.

Season and species influence stable isotope ratios between lethally and non-lethally sampled tissues in freshwater fish.

The field of stable isotope ecology is moving away from lethal sampling (internal organs and muscle) towards non-lethal sampling (fins, scales and epidermal mucus). Lethally and non-lethally sampled tissues often differ in their stable isotope ratios due to differences in metabolic turnover rate and isotopic routing. If not accounted for when using non-lethal tissues, these differences may result in inaccurate estimates of resource use and trophic position derived from stable isotopes. To address this, the authors tested whether tissue type, season and their interaction influence the carbon and nitrogen stable isotope ratios of fishes and whether estimates of species trophic position and resource use are affected by tissue type, season and their interaction. This study developed linear conversion relationships between two fin types and dorsal muscle, accounting for seasonal variation. The authors focused on three common temperate freshwater fishes: northern pike Esox lucius, yellow perch Perca flavescens and lake whitefish Coregonus clupeaformis. They found that fins were enriched in 13 C and depleted in 15 N compared to muscle in all three species, but the effect of season and the interaction between tissue type and season were species and isotope dependent. The estimates of littoral resource use based on fin isotope ratios were between 13% and 36% greater than those based on muscle across species. Season affected this difference for some species, suggesting the potential importance of using season-specific conversions when working with non-lethal tissues. Fin and muscle stable isotopes produced similar estimates of trophic position for northern pike and yellow perch, but fin-based estimates were 0.2-0.4 trophic positions higher than muscle-based estimates for lake whitefish. The effect of season was negligible for estimates of trophic position in all species. Strong correlations existed between fin and muscle δ13 C and δ15 N values for all three species; thus, linear conversion relationships were developed. The results of this study support the use of non-lethal sampling in stable isotope studies of fishes. The authors suggest that researchers use tissue conversion relationships and account for seasonal variation in these relationships when differences between non-lethal tissues and muscle, and seasonal effects on those differences, are large relative to the scale of isotope values under investigation and/or the trophic discrimination factors under use.

Increasing temperature and productivity change biomass, trophic pyramids and community-level omega-3 fatty acid content in subarctic lake food webs.

Climate change in the Arctic is outpacing the global average and land-use is intensifying due to exploitation of previously inaccessible or unprofitable natural resources. A comprehensive understanding of how the joint effects of changing climate and productivity modify lake food web structure, biomass, trophic pyramid shape and abundance of physiologically essential biomolecules (omega-3 fatty acids) in the biotic community is lacking. We conducted a space-for-time study in 20 subarctic lakes spanning a climatic (+3.2°C and precipitation: +30%) and chemical (dissolved organic carbon: +10 mg/L, total phosphorus: +45 µg/L and total nitrogen: +1,000 µg/L) gradient to test how temperature and productivity jointly affect the structure, biomass and community fatty acid content (eicosapentaenoic acid [EPA] and docosahexaenoic acid [DHA]) of whole food webs. Increasing temperature and productivity shifted lake communities towards dominance of warmer, murky-water-adapted taxa, with a general increase in the biomass of primary producers, and secondary and tertiary consumers, while primary invertebrate consumers did not show equally clear trends. This process altered various trophic pyramid structures towards an hour glass shape in the warmest and most productive lakes. Increasing temperature and productivity had negative fatty acid content trends (mg EPA + DHA/g dry weight) in primary producers and primary consumers, but not in secondary nor tertiary fish consumers. The massive biomass increment of fish led to increasing areal fatty acid content (kg EPA + DHA/ha) towards increasingly warmer, more productive lakes, but there were no significant trends in other trophic levels. Increasing temperature and productivity are shifting subarctic lake communities towards systems characterized by increasing dominance of cyanobacteria and cyprinid fish, although decreasing quality in terms of EPA + DHA content was observed only in phytoplankton, zooplankton and profundal benthos.

An arithmetic correction for the effect of lipid on carbon stable isotope ratios in muscle and digestive glands of the American lobster (Homarus americanus).

RATIONALE: Lipid correction models use elemental carbon-to-nitrogen ratios to estimate the effect of lipids on δ13 C values and provide a fast and inexpensive alternative to chemically removing lipids. However, the performance of these models varies, especially in whole-body invertebrate samples. The generation of tissue-specific lipid correction models for American lobsters, both an ecologically and an economically important species in eastern North America, will aid ecological research of this species and our understanding of the function of these models in invertebrates. METHOD: We determined the δ13 C and δ15 N values before and after lipid extraction in muscle and digestive glands of juvenile and adult lobster. We assessed the performance of four commonly used models (nonlinear, linear, natural logarithm (LN) and generalized linear model (GLM)) at estimating lipid-free δ13 C values based on the non-lipid-extracted δ13 C values and elemental C:N ratios. The accuracy of model predictions was tested using paired t-tests, and the performance of the different models was compared using the Akaike information criterion score. RESULTS: Lipid correction models accurately estimated post-lipid-extraction δ13 C values in both tissues. The nonlinear model was the least accurate for both tissues. In muscle, the three other models performed well, and in digestive glands, the LN model provided the most accurate estimates throughout the range of C:N values. In both tissues, the GLM estimates were not independent of the post-lipid-extraction δ13 C values, thus reducing their transferability to other datasets. CONCLUSIONS: Whereas previous work found that whole-body models poorly estimated the effect of lipids in invertebrates, we show that tissue-specific lipid correction models can generate accurate and precise estimates of lipid-free δ13 C values in lobster. We suggest that the tissue-specific logarithmic models presented here are the preferred models for accounting for the effect of lipid on lobster isotope ratios.

Acid treatment of Atlantic salmon (Salmo salar) scales prior to analysis has negligible effects on δ13C and δ15N isotope ratios.

There is debate in the literature as to whether scales of fishes require acidification to remove inorganic carbonates prior to stable isotope analysis. Acid-treated and untreated scales from 208 Atlantic salmon from nine locations on both sides of the Atlantic were analysed for δ13C and δ15N. Linear mixed-effect models determined the effect of acid treatment to be statistically significant. However, the mean difference was small (δ13C 0.1 ± 0.2‰, δ15N -0.1 ± 0.2‰) and not of biological relevance. This study concludes that Atlantic salmon scales do not need to be acidified prior to stable isotope analysis.

Fruit of the forest - larval sea lamprey Petromyzon marinus are fuelled by allochthonous resources.

We used stable isotopes of carbon, hydrogen and nitrogen to quantify the trophic position and resource use of larval sea lamprey Petromyzon marinus, four benthic macroinvertebrate functional feeding guilds (scraper, shredder, collector and predator) and other fishes in three rivers in eastern Canada. Larval lamprey and most invertebrate guilds foraged as primary consumers in all rivers whereas all other fishes predominantly foraged as secondary consumers. Larval lamprey obtained 75-85% of their resources from allochthonous derived material. This level exceeded all invertebrate guilds, which assimilated approximately 50% allochthonous and 50% autochthonous materials and fishes, which predominantly assimilated between 25% and 60% allochthonous material. Larval lamprey occupied a unique position within the river food webs analysed and show remarkable fidelity to a trophic niche specialising on terrestrially derived detritus.

Compositionally controlled plasmonics in amorphous semiconductor metasurfaces.

Amorphous bismuth telluride (Bi:Te) provides a composition-dependent, CMOS-compatible alternative material platform for plasmonics in the ultraviolet-visible spectral range. Thin films of the chalcogenide semiconductor are found, using high-throughput physical vapor deposition and characterization techniques, to exhibit a plasmonic response (a negative value of the real part of relative permittivity) over a band of wavelengths extending from ~250 nm to between 530 and 978 nm, depending on alloy composition (Bi:Te at% ratio). The plasmonic response is illustrated via the fabrication of subwavelength period nano-grating metasurfaces, which present strong, period-dependent plasmonic absorption resonances in the visible range, manifested in the perceived color of the nanostructured domains in reflection.

Ecology under lake ice.

Winter conditions are rapidly changing in temperate ecosystems, particularly for those that experience periods of snow and ice cover. Relatively little is known of winter ecology in these systems, due to a historical research focus on summer 'growing seasons'. We executed the first global quantitative synthesis on under-ice lake ecology, including 36 abiotic and biotic variables from 42 research groups and 101 lakes, examining seasonal differences and connections as well as how seasonal differences vary with geophysical factors. Plankton were more abundant under ice than expected; mean winter values were 43.2% of summer values for chlorophyll a, 15.8% of summer phytoplankton biovolume and 25.3% of summer zooplankton density. Dissolved nitrogen concentrations were typically higher during winter, and these differences were exaggerated in smaller lakes. Lake size also influenced winter-summer patterns for dissolved organic carbon (DOC), with higher winter DOC in smaller lakes. At coarse levels of taxonomic aggregation, phytoplankton and zooplankton community composition showed few systematic differences between seasons, although literature suggests that seasonal differences are frequently lake-specific, species-specific, or occur at the level of functional group. Within the subset of lakes that had longer time series, winter influenced the subsequent summer for some nutrient variables and zooplankton biomass.

Particle size and support effects in electrocatalysis.

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.

Lake morphometry and resource polymorphism determine niche segregation between cool- and cold-water-adapted fish.

Climate change is increasing ambient temperatures in Arctic and subarctic regions, facilitating latitudinal range expansions of freshwater fishes adapted to warmer water temperatures. The relative roles of resource availability and interspecific interactions between resident and invading species in determining the outcomes of such expansions has not been adequately evaluated. Ecological interactions between a cool-water adapted fish, the perch (Perca fluviatilis), and the cold-water adapted European whitefish (Coregonus lavaretus), were studied in both shallow and deep lakes with fish communities dominated by (1) monomorphic whitefish, (2) monomorphic whitefish and perch, and (3) polymorphic whitefish and perch. A combination of stomach content, stable-isotope, and invertebrate prey availability data were used to identify resource use and niche overlap among perch, the trophic generalist large sparsely rakered (LSR) whitefish morph, and the pelagic specialist densely rakered (DR) whitefish morph in 10 subarctic lakes at the contemporary distribution limit of perch in northern Scandinavia. Perch utilized its putative preferred littoral niche in all lakes. LSR whitefish utilized both littoral and pelagic resources in monomorphic whitefish-dominated lakes. When found in sympatry with perch, LSR whitefish exclusively utilized pelagic prey in deep lakes, but displayed niche overlap with perch in shallow littoral lakes. DR whitefish was a specialist zooplanktivore, relegating LSR whitefish from pelagic habitats, leading to an increase in niche overlap between LSR whitefish and perch in deep lakes. Our results highlight how resource availability (lake depth and fish community) governs ecological interactions between native and invading species, leading to different outcomes even at the same latitudes. These findings suggest that lake morphometry and fish community structure data should be included in bioclimate envelope-based models of species distribution shifts following predicted climate change.

Dual fuels: intra-annual variation in the relative importance of benthic and pelagic resources to maintenance, growth and reproduction in a generalist salmonid fish.

Ecological systems are often characterized as stable entities. However, basal productivity in most ecosystems varies between seasons, particularly in subarctic and polar areas. How this variability affects higher trophic levels or entire food webs remains largely unknown, especially in these high-latitude regions. We undertook a year-long study of benthic (macroinvertebrate) and pelagic (zooplankton) resource availability, along with short (day/days: stomach content)-, medium (month: liver δ(13)C and δ(15)N isotopes)- and long-term (season: muscle δ(13)C and δ(15)N isotopes) assessments of resource use by a generalist fish, the European whitefish, in a deep, oligotrophic, subarctic lake in northern Europe. Due to the long ice-covered winter period, we expected to find general benthic reliance throughout the year, but also a seasonal importance of zooplankton to the diet, somatic growth and gonadal development of whitefish. Benthic and pelagic resource availability varied between seasons: peak littoral benthic macroinvertebrate density occurred in mid-winter, whereas maximum zooplankton density was observed in summer. Whitefish stomach content revealed a reliance on benthic prey items during winter and pelagic prey in summer. A seasonal shift from benthic to pelagic prey was evident in liver isotope ratios, but muscle isotope ratios indicated a year-round reliance on benthic macroinvertebrates. Whitefish activity levels as well as somatic and gonadal growth all peaked during the summer, coinciding with the zooplankton peak and the warmest water temperature. Stable isotopes of muscle consistently depicted the most important resource, benthic macroinvertebrates, whereas short-term indicators, that is, diet and stable isotopes of liver, revealed the seasonal significance of pelagic zooplankton for somatic growth and gonad development. Seasonal variability in resource availability strongly influences consumer growth and reproduction and may also be important in other ecosystems facing pronounced annual weather fluctuations.

Environmental and biological factors are joint drivers of mercury biomagnification in subarctic lake food webs along a climate and productivity gradient.

Subarctic lakes are getting warmer and more productive due to the joint effects of climate change and intensive land-use practices (e.g. forest clear-cutting and peatland ditching), processes that potentially increase leaching of peat- and soil-stored mercury into lake ecosystems. We sampled biotic communities from primary producers (algae) to top consumers (piscivorous fish), in 19 subarctic lakes situated on a latitudinal (69.0-66.5° N), climatic (+3.2 °C temperature and +30% precipitation from north to south) and catchment land-use (pristine to intensive forestry areas) gradient. We first tested how the joint effects of climate and productivity influence mercury biomagnification in food webs focusing on the trophic magnification slope (TMS) and mercury baseline (THg baseline) level, both derived from linear regression between total mercury (log10THg) and organism trophic level (TL). We examined a suite of environmental and biotic variables thought to explain THg baseline and TMS with stepwise generalized multiple regression models. Finally, we assessed how climate and lake productivity affect the THg content of top predators in subarctic lakes. We found biomagnification of mercury in all studied lakes, but with variable TMS and THg baseline values. In stepwise multiple regression models, TMS was best explained by negative relationships with food chain length, climate-productivity gradient, catchment properties, and elemental C:N ratio of the top predator (full model R2 = 0.90, p < 0.001). The model examining variation in THg baseline values included the same variables with positive relationships (R2 = 0.69, p = 0.014). Mass-standardized THg content of a common top predator (1 kg northern pike, Esox lucius) increased towards warmer and more productive lakes. Results indicate that increasing eutrophication via forestry-related land-use activities increase the THg levels at the base of the food web and in top predators, suggesting that the sources of nutrients and mercury should be considered in future bioaccumulation and biomagnification studies.

Predator community and resource use jointly modulate the inducible defense response in body height of crucian carp.

Phenotypic plasticity can be expressed as changes in body shape in response to environmental variability. Crucian carp (Carassius carassius), a widespread cyprinid, displays remarkable plasticity in body morphology and increases body depth when exposed to cues from predators, suggesting the triggering of an antipredator defense mechanism. However, these morphological changes could also be related to resource use and foraging behavior, as an indirect effect of predator presence. In order to determine whether phenotypic plasticity in crucian carp is driven by a direct or indirect response to predation threat, we compared twelve fish communities inhabiting small lakes in southeast Norway grouped by four categories of predation regimes: no predator fish, or brown trout (Salmo trutta), perch (Perca fluviatilis), or pike (Esox lucius) as main piscivores. We predicted the body shape of crucian carp to be associated with the species composition of predator communities and that the presence of efficient piscivores would result in a deeper body shape. We use stable isotope analyses to test whether this variation in body shape was related to a shift in individual resource use-that is, littoral rather than pelagic resource use would favor the development of a specific body shape-or other environmental characteristics. The results showed that increasingly efficient predator communities induced progressively deeper body shape, larger body size, and lower population densities. Predator maximum gape size and individual trophic position were the best variables explaining crucian carp variation in body depth among predation categories, while littoral resource use did not have a clear effect. The gradient in predation pressure also corresponded to a shift in lake productivity. These results indicate that crucian carp have a fine-tuned morphological defense mechanism against predation risk, triggered by the combined effect of predator presence and resource availability.

Hybridisation between two cyprinid fishes in a novel habitat: genetics, morphology and life-history traits.

BACKGROUND: The potential role hybridisation in adaptive radiation and the evolution of new lineages has received much recent attention. Hybridisation between roach (Rutilus rutilus L.) and bream (Abramis brama L.) is well documented throughout Europe, however hybrids in Ireland occur at an unprecedented frequency, often exceeding that of both parental species. Utilising an integrated approach, which incorporates geometric morphometrics, life history and molecular genetic analyses we identify the levels and processes of hybridisation present, while also determining the direction of hybridisation, through the analysis of mitochondrial DNA. RESULTS: The presence of F2 hybrids was found to be unlikely from the studied populations, although significant levels of backcrossing, involving both parental taxa was observed in some lakes. Hybridisation represents a viable conduit for introgression of genes between roach and bream. The vast majority of hybrids in all populations studied exhibited bream mitochondrial DNA, indicating that bream are maternal in the majority of crosses. CONCLUSIONS: The success of roach x bream hybrids in Ireland is not due to a successful self reproducing lineage. The potential causes of widespread hybridisation between both species, along with the considerations regarding the role of hybridisation in evolution and conservation, are also discussed.

The Hydrogen Evolution Reaction and Hydrogen Oxidation Reaction on thin film PdAu alloy surfaces.

A high throughput synthetic and screening methodology has been applied to the study of the Hydrogen Evolution Reaction (HER) and Hydrogen Oxidation Reaction (HOR) activities of PdAu thin film alloy surfaces. A compositional gradient method has been used to produce non-equilibrium surfaces of PdAu solid solution alloys. XPS shows surface compositions for these un-annealed alloys to be the same as the bulk, in contrast to the observed and expected behaviour of annealed alloys. The surface redox behaviour of the alloys provides direct evidence for the existence of Pd ensembles with distinctive surface chemistry dominating the oxygen interaction at intermediate alloy compositions. CO stripping voltammetry indicates that alloying of Pd with Au results in a strong poisoning of CO adsorption with the exception of CO adsorbed on Pd monomers. The compositional dependence of the HER and HOR activities is strongly correlated on the alloy surfaces, with a maximum in geometric activity observed at 60 at% Au, corresponding to a maximum in specific activity at 70 at% Au, for both reactions. This activity is associated with Pd poor ensembles. There is some evidence that while the Pd monomer catalyses the HER, HOR is not sustained at compositions where the monomer is present.

The influence of support and particle size on the platinum catalysed oxygen reduction reaction.

A range of platinum deposits, equivalent thicknesses (delta) 0.2-2.5 nm, have been synthesised on carbon and reduced titania (TiO(x)) supports using physical vapour deposition on (10 x 10) arrays of electrodes. For delta < 1.0 nm, discrete platinum centres are formed and the TiO(x) supported platinum show two distinct characteristics: (a) a strong positive shift in the potential for the oxidation of monolayers of CO with decreasing loading of Pt leading to an inability to oxidise the CO on the lowest loadings and (b) a strong negative shift in the potential for the reduction of oxygen. Both observations can be understood in terms of an increase in the irreversibility of the Pt/PtO couple at such surfaces. The same trends, although significantly weaker, are seen with the carbon supported platinum, delta < 1.0 nm, and it is suggested that the Pt/PtO couple on carbon shows intermediate kinetics between Pt on TiO(x) and bulk Pt. These results have significant implications for understanding the mechanism of oxygen reduction on supported Pt catalysts and hence for the search for alternative supports to platinum for ORR electrocatalysts.