Anodic behavior of InP: film growth, porous structures and current oscillations.

We review our recent work on the anodization of InP in KOH electrolytes. The anodic oxidation processes are shown to be remarkably different in different concentrations of KOH. Anodization in 2 - 5 mol dm-3 KOH electrolytes results in the formation of porous InP layers but, under similar conditions in a 1 mol dm-3 KOH, no porous structure is evident. Rather, the InP electrode is covered with a thin, compact surface film at lower potentials and, at higher potentials, a highly porous surface film is formed which cracks on drying. Anodization of electrodes in 2 - 5 mol dm-3 KOH results in the formation of porous InP under both potential sweep and constant potential conditions. The porosity is estimated at ~65%. A thin layer (~ 30 nm) close to the surface appears to be unmodified. It is observed that this dense, near-surface layer is penetrated by a low density of pores which appear to connected it to the electrolyte. Well-defined oscillations are observed when InP is anodized in both the KOH and (NH4)2S. The charge per cycle remains constant at 0.32 C cm-2 in (NH4)2S but increases linearly with potential in KOH. Although the characteristics of the oscillations in the two systems differ, both show reproducible and well-behaved values of charge per cycle.

Formation and characterization of porous InP layers in KOH Solutions

Porous InP layers were formed electrochemically on (100) oriented n-InP substrates in various concentrations of aqueous KOH under dark conditions. In KOH concentrations from 2 mol dm-3 to 5 mol dm-3, a porous layer is obtained underneath a dense near-surface layer. The pores within the porous layer appear to propagate from holes through the near-surface layer. Transmission electron microscopy studies of the porous layers formed under both potentiodynamic and potentiostatic conditions show that both the thickness of the porous layer and the mean pore diameter decrease with increasing KOH concentration. The degree of porosity, estimated to be 65%, was found to remain relatively constant for all the porous layers studied.

Elucidating the Space-Time Structure of Low Level Warm Season Precipitation Processes in the Southern Appalachian Mountains Using Models and Observations

Light rainfall is the baseline input to the annual water budget in mountainous landscapes through the tropics and at mid-latitudes. In the Southern Appalachians, the contribution from light rainfall ranges from 50-60% during wet years to 80-90% during dry years, with convective activity and tropical cyclone input providing most of the interannual variability. The Southern Appalachians is a region characterized by rich biodiversity that is vulnerable to land use/land cover changes due to its proximity to a rapidly growing population. Persistent near surface moisture and associated microclimates observed in this region has been well documented since the colonization of the area in terms of species health, fire frequency, and overall biodiversity. The overarching objective of this research is to elucidate the microphysics of light rainfall and the dynamics of low level moisture in the inner region of the Southern Appalachians during the warm season, with a focus on orographically mediated processes. The overarching research hypothesis is that physical processes leading to and governing the life cycle of orographic fog, low level clouds, and precipitation, and their interactions, are strongly tied to landform, land cover, and the diurnal cycles of flow patterns, radiative forcing, and surface fluxes at the ridge-valley scale. The following science questions will be addressed specifically: 1) How do orographic clouds and fog affect the hydrometeorological regime from event to annual scale and as a function of terrain characteristics and land cover?; 2) What are the source areas, governing processes, and relevant time-scales of near surface moisture convergence patterns in the region?; and 3) What are the four dimensional microphysical and dynamical characteristics, including variability and controlling factors and processes, of fog and light rainfall? The research was conducted with two major components: 1) ground-based high-quality observations using multi-sensor platforms and 2) interpretive numerical modeling guided by the analysis of the in situ data collection. Findings illuminate a high level of spatial – down to the ridge scale - and temporal – from event to annual scale - heterogeneity in observations, and a significant impact on the hydrological regime as a result of seeder-feeder interactions among fog, low level clouds, and stratiform rainfall that enhance coalescence efficiency and lead to significantly higher rainfall rates at the land surface. Specifically, results show that enhancement of an event up to one order of magnitude in short-term accumulation can occur as a result of concurrent fog presence. Results also show that events are modulated strongly by terrain characteristics including elevation, slope, geometry, and land cover. These factors produce interactions between highly localized flows and gradients of temperature and moisture with larger scale circulations. Resulting observations of DSD and rainfall patterns are stratified by region and altitude and exhibit clear diurnal and seasonal cycles.

Le processus de thermo-érosion du pergélisol dans la zone de pergélisol continu

Les polygones à coin de glace sont très répandus dans la zone du pergélisol continu. Lorsque le ruissellement d’eau de fonte nivale s’infiltre de façon concentrée dans une cavité, il peut initier le processus de thermo-érosion du pergélisol (notamment des coins de glace) pouvant mener à la formation de ravins. Dans la vallée de Qalikturvik sur l’Ile Bylot (NU, Canada), le développement de ravins de thermo-érosion dans un milieu de polygones à coins de glace entraîne comme impact : i. la réorganisation des réseaux de drainage impliquant un assèchement des milieux humides en marge des chenaux d’érosion, ii. des variations dans le régime thermique et de l’humidité de proche-surface et iii. la prise en charge et le déplacement des sédiments vers l’extérieur du bassin-versant. L’objectif de cette thèse vise à approfondir les connaissances géomorphologiques propres au ravinement par thermo-érosion, d’examiner, caractériser et quantifier les impacts du ravinement (tel que sus-mentionné en i. ii. iii.) et le rôle de celui-ci dans une optique d’évolution du paysage périglaciaire à l’échelle temporelle de l’année à la décennie. Les ravins sont dynamiques : un ravin en particulier déclenché en 1999 et étudié depuis s’érodait à une vitesse de 38 à 50 m/a durant sa première décennie d’existence, pour atteindre une longueur totale de ~750 m et une surface érodée de ~25 000 m² en 2009. Des puits sont localisés près des zones de ravinement actives ; des levées alluviale, mares et polygones effondrés dans les zones stabilisées post-perturbation. Sur la terrasse de polygones recouvrant le plancher de la vallée au site à l’étude, 35 ravins furent identifiés et 1401 polygones furent perturbés avec 200 000 m³ de sols transportés. Une amélioration du drainage, une dégradation de la capacité de rétention de l’humidité, une transition d’un écoulement de ruissellement vers un écoulement canalisé caractérise les aires ravinées et leurs environs. Les polygones intacts sont homogènes d’un à l’autre et dans leurs centres ; les polygones perturbés ont une réponse hétérogène (flore, humidité et régime thermique). Les milieux érodés hétérogènes succèdent aux milieux homogènes et deviennent le nouvel état d’équilibre pour plusieurs décennies.

Stable oxygen and carbon isotopic composition of foraminifera and sea water from the Arctic Ocean

O18/O16 data on a depth profile of water samples from the Arctic Ocean reveal that near surface water is depleted in O18 by about 4 per mil, but water at depths greater than 350 meters reaches near normal open ocean water composition. The O18 profile very closely follows the salinity profile, with deltaO18 changing by about 0.8 per mil per 1 per mil salinity change. The results of deltaO18 measurements on the pelagic species Globigerina pachyderma from a composite core show that the deltaO18 value has not changed since the latter part of the last glacial period. This constancy we take to indicate that the temperature and the deltaO18 value of the water in which these foraminifera grew have not changed significantly since that time. Such a conclusion seems to imply that the present ice coverage in the Arctic Ocean has remained unchanged during the last 25,000 years. However, the deltaO18 value of benthonic foraminifera shows a shift of 1.2 per mil between the end of the last glacial period and the present warm period. This shift is consistent with the idea that the deep water mass of the Arctic Ocean is formed outside the Arctic basin. The information on the deltaO18 value of the benthonic foraminifera from the top of the core was used in conjunction with the data on deltaO18 and temperature of the bottom water to establish the constant in the empirical equation relating deltaO18 values to temperature for the preparation procedure used in our laboratory. Based on this calibration, the data confirm A. W. H. Bé's contention (personal communication, 1960) that G. pachyderma incorporates about one-half of its CaCO3 below 300 meters.

(Table 1) Active-layer thickness as measured by the Biocomplexity Experiment (BE) for the flooded, drained and control sections in Barrow, Alaska

A continuous time series of annual soil thaw records, extending from 1994 to 2009, is available for comparison with the records of thaw obtained from the Biocomplexity Experiment (BE) for the period 2006-2009. Discontinuous records of thaw at Barrow from wet tundra sites date back to the 1960s. Comparisons between the longer records with the BE observations reveal strong similarities. Records of permafrost temperature, reflecting changes in the annual surface energy exchange, are available from the 1950s for comparison with results from measurement programs begun in 2002. The long-term systematic geocryological investigations at Barrow indicate an increase in permafrost temperature, especially during the last several years. The increase in near-surface permafrost temperature is most pronounced in winter. Marked trends are not apparent in the active-layer record, although subsidence measurements on the North Slope indicate that penetration into the ice-rich layer at the top of permafrost has occurred over the past decade. Active-layer thickness values from the 1960s are generally higher than those from the 1990s, and are very similar to those of the 2000s. Analysis of spatial active-layer observations at representative locations demonstrates significant variations in active-layer thickness between different landscape types, reflecting the influence of vegetation, substrate, microtopography, and, especially, soil moisture. Landscape-specific differences exist in the response of active-layer thickness to climatic forcing. These differences are attributable to the existence of localized controls related to combinations of surface and subsurface characteristics. The geocryological records at Barrow illustrate the importance and effectiveness of sustained, well organized monitoring efforts to document long-term trends.

Meteorological observations and eddy covariance raw data from polygonal tundra in the Lena River Delta, Siberia

We present the first ecosystem-scale methane flux data from a northern Siberian tundra ecosystem covering the entire snow-free period from spring thaw until initial freeze-back. Eddy covariance measurements of methane emission were carried out from the beginning of June until the end of September in the southern central part of the Lena River Delta (72°22' N, 126°30' E). The study site is located in the zone of continuous permafrost and is characterized by Arctic continental climate with very low precipitation and a mean annual temperature of -14.7°C. We found relatively low fluxes of on average 18.7 mg/m**2/d, which we consider to be because of (1) extremely cold permafrost, (2) substrate limitation of the methanogenic archaea, and (3) a relatively high surface coverage of noninundated, moderately moist areas. Near-surface turbulence as measured by the eddy covariance system in 4 m above the ground surface was identified as the most important control on ecosystem-scale methane emission and explained about 60% of the variance in emissions, while soil temperature explained only 8%. In addition, atmospheric pressure was found to significantly improve an exponential model based on turbulence and soil temperature. Ebullition from waterlogged areas triggered by decreasing atmospheric pressure and near-surface turbulence is thought to be an important pathway that warrants more attention in future studies. The close coupling of methane fluxes and atmospheric parameters demonstrated here raises questions regarding the reliability of enclosure-based measurements, which inherently exclude these parameters.

(Table 1) Mean annual ground temperatures and description of permafrost boreholes in Russia

The results of the International Permafrost Association's International Polar Year Thermal State of Permafrost (TSP) project are presented based on field measurements from Russia during the IPY years (2007-09) and collected historical data. Most ground temperatures measured in existing and new boreholes show a substantial warming during the last 20 to 30 years. The magnitude of the warming varied with location, but was typically from 0.5°C to 2°C at the depth of zero annual amplitude. Thawing of Little Ice Age permafrost is ongoing at many locations. There are some indications that the late Holocene permafrost has begun to thaw at some undisturbed locations in northeastern Europe and northwest Siberia. Thawing of permafrost is most noticeable within the discontinuous permafrost domain. However, permafrost in Russia is also starting to thaw at some limited locations in the continuous permafrost zone. As a result, a northward displacement of the boundary between continuous and discontinuous permafrost zones was observed. This data set will serve as a baseline against which to measure changes of near-surface permafrost temperatures and permafrost boundaries, to validate climate model scenarios, and for temperature reanalysis.

(Table 1) Stable carbon isotope ratios of methane and carbon dioxide from ODP Leg 169S holes

Sites 1033 and 1034 of ODP Leg 169S in Saanich Inlet have an unusual diagenetic system, that has the appearance of being depth reversed, i.e. a bacterial methane accumulation zone underlain by a sulphate reduction zone. During the late Pleistocene grey, undifferentiated, glacio-marine clays were deposited with low Corg contents (<0.4 wt.%), and interstitial fluids replete in SO4 (ca. 27 mM), devoid of CH4 and low in nutrients. This indicates oxic conditions are present, reflecting the open exchange of waters with Haro Strait during the Pleistocene before the Saanich Peninsula emerged. In the earliest Holocene (ca. 11,000 years BP) the inlet was formed, severely restricting water circulation, and leading to the presence of anoxic bottom waters. The sediments are laminated and show a dramatic rise to high Corg, Norg and Stot contents (up to 2.5, 0.4, 1.4 wt.%, respectively) over a period of ca. 1000 years. The nutrient concentrations are especially high (TA, NH4, PO4 up to 115 meq/l, 20 mM and 400 µM, respectively), SO4 is exhausted and CH4 is prolific. Stable carbon isotope ratio measurements of CH4 and co-existing CO2 indicate that methanogenesis is via carbonate reduction (delta13C-CH4 ca. -60 to - 70 per mil, delta13C-CO2 ca. +10 per mil). At the sulphate-methane interfaces, both at the near-surface and at 50 mbsf (Site 1033) and 80 mbsf (Site 1034) methane consumption by sulphate reducing bacteria is intensive.

Gas hydrate investigation at the Amsterdam mud volcano

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.

(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

(Table 1) Age control and temporal resolution of paleoceanographic records of the North Atlantic

Short-term changes in sea surface conditions controlling the thermohaline circulation in the northern North Atlantic are expected to be especially efficient in perturbing global climate stability. Here we assess past variability of sea surface temperature (SST) in the northeast Atlantic and Norwegian Sea during Marine Isotope Stage (MIS) 2 and, in particular, during the Last Glacial Maximum (LGM). Five high-resolution SST records were established on a meridional transect (53°N-72°N) to trace centennial-scale oscillations in SST and sea-ice cover. We used three independent computational techniques (SIMMAX modern analogue technique, Artificial Neural Networks (ANN), and Revised Analog Method (RAM)) to reconstruct SST from planktonic foraminifer census counts. SIMMAX and ANN reproduced short-term SST oscillations of similar magnitude and absolute levels, while RAM, owing to a restrictive analog selection, appears less suitable for reconstructing "cold end" SST. The SIMMAX and ANN SST reconstructions support the existence of a weak paleo-Norwegian Current during Dansgaard-Oeschger (DO) interstadials number 4, 3, 2, and 1. During the LGM, two warm incursions of 7°C water to occurred in the northern North Atlantic but ended north of the Iceland Faroe Ridge. A rough numerical estimate shows that the near-surface poleward heat transfer from 53° across the Iceland-Faroe Ridge up to to 72° N dropped to less than 60% of the modern value during DO interstadials and to almost zero during DO stadials. Summer sea ice was generally confined to the area north of 70°N and only rarely expanded southward along the margins of continental ice sheets. Internal LGM variability of North Atlantic (>40°N) SST in the GLAMAP 2000 compilation (Sarnthein et al., 2003, doi:10.1029/2002PA000771; Pflaumann et al., 2003, doi:10.1029/2002PA000774) indicates maximum instability in the glacial subpolar gyre and at the Iberian Margin, while in the Nordic Seas, SST was continuously low.

(Table 1) Experimental details and results

Factor-of-safety analyses of submarine slope failure depend critically on the shear strength of the slope material, which is often evaluated with residual strength values and for normally consolidated sediments. Here, we report on direct measurements of both shear strength and cohesion for a quartz-clay mixture over a wide range of overconsolidation ratios (OCRs). For normally consolidated sediment at low stresses, cohesion is the dominant source of shear strength compared to friction. Significant increases in peak shear strength occur for OCR > 4, and the primary source of this strength increase is due to increased cohesion, rather than friction. The proportion of added shear strength due to cohesion depends log-linearly on the OCR. We show that at shallow depths where OCR values can be high, overconsolidated clays can be stronger than pure or nearly pure quartz sediments, which are cohesionless under near-surface conditions. Our data also suggest that areas which have experienced significant unroofing due to previous mass movements are less likely to experience subsequent failure at shallow depths due to increased peak strength, and if failure occurs it is expected to be deeper where the OCR is lower. In seismically active areas, this is one potential explanation for the general observation of lower slope failure recurrence compared to rates expected from triggering due to local earthquakes.

Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

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

Ground ice hydrochemical composition of permafrost core ICDP5011-3

The continuous sediment record from Lake El'gygytgyn in the northeastern Eurasian Arctic spans the last 3.6 Ma and for much of this time permafrost dynamics and lake level changes have likely played a crucial role for sediment delivery to the lake. Changes in the ground-ice hydrochemical composition (d18O, dD, pH, electrical conductivity, Na+, Mg2+, Ca2+, K+, HCO3-, Cl-, SO4-) of a 141 m long permafrost record from the western crater plain are examined to reconstruct repeated periods of freeze and thaw at the lake edge. Stable water isotope and major ion records of ground ice in the permafrost reflect both a synsedimentary palaeo-precipitation signal preserved in the near-surface permafrost (0.0-9.1 m core depth) and a post-depositional record of thawing and refreezing in deeper layers of the core (9.1-141.0 m core depth). These lake marginal permafrost dynamics were controlled by lake level changes that episodically flooded the surfaces and induced thaw in the underlying frozen ground. During times of lake level fall these layers froze over again. At least three cycles of freeze and thaw are identified and the hydrochemical data point to a vertical and horizontal talik refreezing through time. Past permafrost thaw and freeze may have destabilised the basin slopes of Lake El'gygytgyn and this has probably promoted the release of mass movements from the lake edge to the deeper basin as known from frequently occurring turbidite layers in the lake sediment column.