The anatomy of Last Glacial Maximum climate variations in south Westland, New Zealand, derived from pollen records

We present pollen records from three sites in south Westland, New Zealand, that document past vegetation and inferred climate change between approximately 30,000 and 15,000 cal. yr BP. Detailed radiocarbon dating of the enclosing sediments at one of those sites, Galway tarn, provides a more robust chronology for the structure and timing of climate-induced vegetation change than has previously been possible in this region. The Kawakawa/Oruanui tephra, a key isochronous marker, affords a precise stratigraphic link across all three pollen records, while other tie points are provided by key pollen-stratigraphic changes which appear to be synchronous across all three sites. Collectively, the records show three episodes in which grassland, interpreted as indicating mostly cold subalpine to alpine conditions, was prevalent in lowland south Westland, separated by phases dominated by subalpine shrubs and montane-lowland trees, indicating milder interstadial conditions. Dating, expressed as a Bayesian-estimated single 'best' age followed in parentheses by younger/older bounds of the 95% confidence modelled age range, indicates that a cold stadial episode, whose onset was marked by replacement of woodland by grassland, occurred between 28,730 (29,390-28,500) and 25,470 (26,090-25,270) cal. yr BP (years before AD, 1950), prior to the deposition of the Kawakawa/Oruanui tephra. Milder interstadial conditions prevailed between 25,470 (26,090-25,270) and 24,400 (24,840-24,120) cal. yr BP and between 22,630 (22,930-22,340) and 21,980 (22,210-21,580) cal. yr BP, separated by a return to cold stadial conditions between 24,400 and 22,630 cal. yr BP. A final episode of grass-dominated vegetation, indicating cold stadial conditions, occurred from 21,980 (22,210-21,580) to 18,490 (18,670-17,950) cal. yr BP. The decline in grass pollen, indicating progressive climate amelioration, was well advanced by 17,370 (17,730-17,110) cal. yr BP, indicating that the onset of the termination in south Westland occurred sometime between ca 18,490 and ca 17,370 cal. yr BP. A similar general pattern of stadials and interstadials is seen, to varying degrees of resolution but generally with lesser chronological control, in many other paleoclimate proxy records from the New Zealand region. This highly resolved chronology of vegetation changes from southwestern New Zealand contributes to the examination of past climate variations in the southwest Pacific region. The stadial and interstadial episodes defined by south Westland pollen records represent notable climate variability during the latter part of the Last Glaciation. Similar climatic patterns recorded farther afield, for example from Antarctica and the Southern Ocean, imply that climate variations during the latter part of the Last Glaciation and the transition to the Holocene interglacial were inter-regionally extensive in the Southern Hemisphere and thus important to understand in detail and to place into a global context. © 2013 Elsevier Ltd. All rights reserved.

Electrocatalytic activity of Ru-modified Pt(111) electrodes toward CO oxidation

The electrochemical deposition of Ru on Pt(111) electrodes has been investigated by electron diffraction, Auger spectroscopy, and cyclic voltammetry in a closed UHV transfer system. At small coverages Ru formed a monatomic commensurate layer, at higher coverage mostly small islands with a bilayer height were detected. When the Pt was almost completely covered by Ru, three-dimensional clusters developed. The island structure of Ru changed upon electrooxidation of CO, reflecting an enhanced mobility of Ru. Adsorption and electrooxidation of CO have been studied on such Ru-modified Pt(111) electrodes using cyclic voltammetry and in situ FTIR spectroscopy. Compared to the pure metals, the Ru-CO bond is weakened, the Pt-CO bond strengthened on the modified electrodes. The catalytic activity of the Ru/Pt(111) electrode toward CO adlayer oxidation is higher than that of pure Ru and a PtRu alloy (50:50). It is concluded that the electrooxidation of CO takes place preferentially at the Ru islands, while CO adsorbed on Pt migrates to them. © 1999 American Chemical Society.

Preparation and characterization of new anodes based on Ti mesh for direct methanol fuel cells

A novel anode structure based on Ti mesh for the direct methanol fuel cell (DMFC) has been prepared by thermal deposition of ~5 µm PtRuO2 catalyst layer on ~50 µm Ti mesh. The preparation procedures and the main characteristics of the anode were studied by half-cell testing, scanning electron microscopy analysis, energy-dispersive X-ray measurement, and single-cell testing. The optimum calcination temperature is 450°C, calcination time is 90- 120 min, PtRuO2 catalyst loading is 5.0 mg cm-2, Pt precursor concentration range of solution is 0.14- 0.4 M, and solution aging time is 1 day. The performances of the anodes prepared using the solution kept within 20 days showed no significant difference. When it was used in DMFC feed with low-concentration methanol solution at 90°C, this new anode shows better performance than that of the conventional anode, because its thin hydrophilic structure is a benefit to the transport of methanol and carbon dioxide. However, due to its opening structure, when higher concentration methanol was employed, the performance of the cell with new anode became worse. © 2006 The Electrochemical Society. All rights reserved.

Ti mesh anodes prepared by electrochemical deposition for the direct methanol fuel cell

An anode structure based on Ti mesh has been developed for the direct methanol fuel cell (DMFC). This new anode was prepared by electrochemical deposition of a ~ 3 µ m PtRu catalyst layer on ~ 50 µ m Ti mesh. It has a thinner structure compared to that of a porous carbon-based conventional anode. The Ti mesh anode shows a performance comparable to, and exceeding that, of the conventional anode in a DMFC operating with 0.25 or 0.5 M methanol solution and atmosphere oxygen at 90 C. However, it shows a lower performance of the cell when higher concentrations of methanol was employed. This may be attributed to its thin and open structure, which could facilitate the transport of methanol from the flow field to the anode catalyst layer and carbon dioxide in the opposite direction. © 2006 International Association for Hydrogen Energy.

Modeling target bulk heating resulting from ultra-intense short pulse laser irradiation of solid density targets

Isochoric heating of solid-density matter up to a few tens of eV is of interest for investigating astrophysical or inertial fusion scenarios. Such ultra-fast heating can be achieved via the energy deposition of short-pulse laser generated electrons. Here, we report on experimental measurements of this process by means of time-and space-resolved optical interferometry. Our results are found in reasonable agreement with a simple numerical model of fast electron-induced heating. (C) 2013 AIP Publishing LLC.

A Late Pleistocene record of climate and environmental change from the northern and southern Kelabit Highlands of Sarawak, Malaysian Borneo

A late Pleistocene vegetation record is presented, using multi-proxy analysis from three palaeochannels in the northern (Bario) and southern (Pa'Dalih) Kelabit Highlands of Sarawak, Malaysian Borneo. Before 50 000 cal a BP and until approximate to 47 700 cal a BP [marine isotope stage 3 (MIS3)], two of the sites were probably being influenced by energetic fluvial deposition, possibly associated with strong seasonality. Fluvial activity declines between 47 700 and 30 000 cal a BP (MIS3), and may be associated with a reduction in seasonality with overall stability in precipitation. The pollen record between 47 700 and 30 000 cal a BP generally shows much higher representation of upper-montane taxa compared with the Holocene, indicating often significantly reduced temperatures. After 35 000-30 000 cal a BP and until the mid-Holocene, hiatuses appear in two of the records, which could be linked to fluvial down-cutting during the late/mid Holocene. Despite the jump in ages, a pronounced representation of Ericaceae and upper-montane taxa, represented both at Bario and at Pa'Dalih, corresponds to a further lowering of temperatures during the Last Glacial Maximum (MIS2). Thick charcoal bands in the PDH 210 record also suggest periods of extreme aridity between 30 200 and 12 700 cal a BP. This is followed by energetic fluvial deposition of sands and gravels, and may reflect a significant increase in seasonality.

Detection of Low-Concentration Contaminants in Solution by Exploiting Chemical Derivatization in Surface-Enhanced Raman Spectroscopy

Testing the cause of the Sphagnum austinii (Sull. ex Aust.) decline: Multiproxy evidence from a raised bog in Northern Ireland

We use a multiproxy palaeoecological dataset from Dead Island bog in Northern Ireland to examine the cause of the Sphagnum austinii (Sphagnum imbricatum) decline. The disappearance of this species from the peat record occurred just after the ‘AD 860’ tephra layer and is coeval with a rapid increase in bog surface wetness and increased mineral dust and charcoal abundance. Although it is difficult to identify one specific cause of the decline, the evidence for increased soil-derived dust is apparent and is supported by regional tephra-dated pollen diagrams that reveal extensive landscape changes due to agricultural intensification in early Medieval Ireland. As the decline of S. austinii occurred much later (~ AD 1860) in Fallahogy bog (~ 1.2 km away), we suggest that the decline of S. austinii at Dead Island was caused by a combination of fire and the deposition of soil-derived dust. We suggest that future studies should consider the use of multiple cores from each site to examine the within-site variability of the decline of S. austinii.

Cyclic nanoindentation and nano-impact fatigue characterisation of functionally graded TiN/TiNi shape memory film

This paper investigates the mechanism of nanoscale fatigue of functionally graded TiN/TiNi films using nano-impact and multiple-loading-cycle nanoindentation tests. The functionally graded films were deposited on silicon substrate, in which TiNi films maintain shape memory and pseudo elastic behavior, while a modified TiN surface layer provides tribological and anti-corrosion properties. Nanomechanical tests were performed to comprehend the localized film performance and failure modes of the functionally graded film using NanoTestTM equipped with Berkovich and conical indenter between 100 μN to 500 mN loads. The loading mechanism and load history are critical to define film failure modes (i.e. backward depth deviation) including the shape memory effect of the functionally graded layer. The results are sensitive to the applied load, loading type (e.g. semi-static, dynamic) and probe geometry. Based on indentation force-depth profiles, depth-time data and post-test surface observations of films, it is concluded that the shape of the nanoindenter is critical in inducing the localized indentation stress and film failure, including shape recovery at the lower load range. Elastic-plastic finite element (FE) simulation during nanoindentation loading indicated that the location of subsurface maximum stress near the interface influences the backward depth deviation type of film failure. A standalone, molecular dynamics simulation was performed with the help of a long range potential energy function to simulate the tensile test of TiN nanowire with two different aspect ratios to investigate the theory of its failure mechanism.

First comprehensive peat depositional records for tin, lead and copper associated with the antiquity of Europe's largest cassiterite deposits

Tin, as a constituent of bronze, was central to the technological development of early societies, but cassiterite (SnO2) deposits were scarce and located distantly from the centres of Mediterranean civilizations. As Britain had the largest workable ore deposits in the ancient Western world, this has led to much historical speculation and myth regarding the long-distance trading of tin from the Bronze Age onwards. Here we establish the first detailed chronology for tin, along with lead and copper deposition, into undisturbed ombrotrophic (rain-fed) peat bogs located at Bodmin Moor and Dartmoor in the centre of the British tin ore fields. Sustained elevated tin deposition is demonstrated clearly, with peaks occurring at 100-400 and 700-1000 calendar years AD - contemporaneous with the Roman and Anglo-Saxon periods respectively. While pre-Roman Iron Age tin exploitation undoubtedly took place, it was on a scale that did not result in convincingly enhanced deposition of the metal. The deposition of lead in the peat record provides evidence of a pre-Roman metal-based economy in southwest Britain. Emerging in the 4th century BC, this was centred on copper and lead ore processing that expanded exponentially and then collapsed upon Roman colonization during the 1st century AD. (C) 2011 Elsevier Ltd. All rights reserved.

Sequence stratigraphy related distribution of diagenetic alterations In Miocene deltaic and shoreface arenites, the Suez Rift, EGYPT.

The distribution of eogenetic alterations in shoreface-offshore and coarse-grained deltaic, calcarenite to hybrid arenites of the Mheiherrat Formation (lower Rudeis), Early Miocene, the Gulf of Suez, Egypt) can be constrained within a sequence stratigraphic framework. The bioclast-rich, shoreface (trangressive systems tract; TST) and shoreface (highstand systems tract; HST) arenites, particularly those below the parasequence boundaries and maximum flooding surface, are cemented by grain-coating microcrystalline, circumgranular isopacheous acicular and columnar, and coarse-crystalline calcite (δ18OVPDB = -3.6 to -0.3 ‰; δ13CVPDB = -2.3 to -0.7 ‰), non-Ferro an dolomite (δ18OVPDB = -3.9 to +0.9‰; δ13CVPDB = -2.5 ‰ to -0.7 ‰), and pyrite. Zeolite, palygorskite and gypsum occur in the HST shoreface arenites, being enhanced by aird climatic condations. The coarse-grained deltaic LST deposits are pervasively cemented by coarse-crystalline, pore-filling calcite and small amounts of microcrystalline calcite (δ18OVPDB = -4.4 to -2.3 ‰; δ13CVPDB = -2.8 to -1.3 ‰) and non-ferroan dolomite (δ18OVPDB = -4.8 to -2.5 ‰; δ13CVPDB = -3.3 to -1.5 ‰). Thus, this study demonstrates that changes in pore-water chemistry, which induced changes in the texture, composition and extent of cementation in the Miocene arenites was controlled by changes in the relative sea level and by the paleo-climatic conditions during deposition of the HST arenites.

Sequence stratigraphy related distribution of diagenetic alterations In Miocene deltaic and shoreface arenites, the Suez Rift, EGYPT.. Available from: https://www.researchgate.net/publication/264545153_Sequence_stratigraphy_related_distribution_of_diagenetic_alterations_In_Miocene_deltaic_and_shoreface_arenites_the_Suez_Rift_EGYPT [accessed Apr 15, 2015].

Suspension plasma sprayed coatings using dilute hydrothermally produced titania feedstocks for photocatalytic applications

Titanium dioxide coatings have potential applications including photocatalysts for solar assisted hydrogen production, solar water disinfection and self-cleaning windows. Herein, we report the use of suspension plasma spraying (SPS) for the deposition of conformal titanium dioxide coatings. The process utilises a nanoparticle slurry of TiO2 (ca. 6 and 12 nm respectively) in water, which is fed into a high temperature plasma jet (ca. 7000-20 000 K). This facilitated the deposition of adherent coatings of nanostructured titanium dioxide with predominantly anatase crystal structure. In this study, suspensions of nano-titanium dioxide, made via continuous hydrothermal flow synthesis (CHFS), were used directly as a feedstock for the SPS process. Coatings were produced by varying the feedstock crystallite size, spray distance and plasma conditions. The coatings produced exhibited ca. 90-100% anatase phase content with the remainder being rutile (demonstrated by XRD). Phase distribution was homogenous throughout the coatings as determined by micro-Raman spectroscopy. The coatings had a granular surface, with a high specific surface area and consisted of densely packed agglomerates interspersed with some melted material. All of the coatings were shown to be photoactive by means of a sacrificial hydrogen evolution test under UV radiation and compared favourably with reported values for CVD coatings and compressed discs of P25.

Action Spectra of P25 TiO2 and a visible light absorbing, carbon-modified titania in the photocatalytic degradation of stearic acid

The photonic efficiencies of films of Evonik (formerly Degussa) P25 TiO2 and carbon-modified TiO2 Kronos VLP 7000 samples are reported as a function of excitation wavelength (300–430 nm; FWHM ∼ 7.5 nm), i.e. the action spectra, for the degradation of stearic acid, a model organic for the photocatalytic destruction of solid surface organic pollutants. For each of these semiconductor photocatalysts, at 365 nm (FWHM = 18 nm), the dependence of the rate of degradation of stearic acid, upon the irradiance, I, is determined and the rate is found to be proportional to I0.65 and I0.82 for P25 and Kronos titania, respectively. Assuming this relationship holds at all wavelengths, the action spectra for two different semiconductor photocatalysts is modified by plotting, (RSA (rate of stearic acid destruction, units: molecules cm−2 s−1)/Iθ) vs. wavelength of excitation (λexcit), and both differ noticeably from those of the original (unmodified) action spectra, which are plots of (RSA/I = photonic efficiency, ξ) vs. λexcit. The shape of the modified action spectrum for P25 TiO2 is consistent with that reported by others for other organic mineralisation reactions and correlates well with diffuse reflectance data for P25 TiO2 (Kubelka–Munk plot), although there is some evidence that the active phase, in the photodegradation of stearic acid, is the anatase form present in P25. The unmodified and modified action spectra of the beige Kronos VLP 7000 TiO2 compound exhibits little or no activity in the visible i.e. (λexcit > 400 nm) and a peak at 350 nm. The Kronos powder contains a yellow/brown conjugated, extractable, organic sensitiser which has been identified by others as the species responsible for its reported photocatalytic visible light activity. But, irradiation of the Kronos powder film, with and without a stearic acid coating, in air, using UVA or visible light, bleaches rapidly (<60 min) most, if not all, of the little colour exhibited by the original Kronos powder. The photobleached form of the Kronos has a similar action spectrum to that of the unbleached form, which, in turn, appears very similar to that of P25 titania, at wavelengths >350 nm. It is proposed that the difference between the Kronos and P25 powder films at wavelengths <350 nm is due to a photodegradation-resistant, previously unidentified (but extractable using MeCN) UV-absorbing organic species in the former which screens the titania particles at these lower wavelengths. The implications of these observations are discussed briefly.

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≅0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants. © 2003 Elsevier Science Ltd. All rights reserved.

Recent Developments in the Analysis of the Black Mat Layer and Cosmic Impact at 12.8ka

Recent analyses of sediment samples from "black mat" sites in South America and Europe support previous interpretations of an ET impact event that reversed the Late Glacial demise of LGM ice during the Bølling Allerød warming, resulting in a resurgence of ice termed the Younger Dryas (YD) cooling episode. The breakup or impact of a cosmic vehicle at the YD boundary coincides with the onset of a 1-kyr long interval of glacial resurgence, one of the most studied events of the Late Pleistocene. New analytical databases reveal a corpus of data indicating that the cosmic impact was a real event, most possibly a cosmic airburst from Earth's encounter with the Taurid Complex comet or unknown asteroid, an event that led to cosmic fragments exploding interhemispherically over widely dispersed areas, including the northern Andes of Venezuela and the Alps on the Italian/French frontier. While the databases in the two areas differ somewhat, the overall interpretation is that microtextural evidence in weathering rinds and in sands of associated paleosols and glaciofluvial deposits carry undeniable attributes of melted glassy carbon and Fe spherules, planar deformation features, shock-melted and contorted quartz, occasional transition and platinum metals, and brecciated and impacted minerals of diverse lithologies. In concert with other black mat localities in the Western USA, the Netherlands, coastal France, Syria, Central Asia, Peru, Argentina and Mexico, it appears that a widespread cosmic impact by an asteroid or comet is responsible for deposition of the black mat at the onset of the YD glacial event. Whether or not the impact caused a 1-kyr interval of glacial climate depends upon whether or not the Earth had multiple centuries-long episodic encounters with the Taurid Complex or asteroid remnants; impact-related changes in microclimates sustained climatic forcing sufficient to maintain positive mass balances in the reformed ice; and/or inertia in the Atlantic thermohaline circulation system persisted for 1kyr.