Wet chemistry synthesis towards nanostructures of thermoelectric antimonides

Die vorliegende Arbeit befasst sich mit der Synthese von nanostrukturierten Antimoniden, wobei die folgenden beiden Themen bearbeitet wurden: rnAus chemischer Sicht wurden neue Synthesewege entwickelt, um Nanopartikel der Verbindungen in den binären Systemen Zn-Sb und Fe-Sb herzustellen (Zn4Sb3, ZnSb, FeSb2, Fe1+xSb). Anders als in konventionellen Festkörperreaktionen, die auf die Synthese von Bulk-Materialien oder Einkristallen zielen, muss die Synthese von Nanopartikeln Agglomerate und Ostwald-Wachstum vermeiden. Daher benötigen annehmbare Reaktionszeiten und vergleichsweise tiefe Reaktionstemperaturen kurze Diffusionswege und tiefe Aktivierungsbarrieren. Demzufolge bedient sich die Synthese der Reaktion von Antimon-Nanopartikeln und geeigneten molekularen oder nanopartikulären Edukten der entsprechenden Übergangsmetalle. Zusätzlich wurden anisotrope ZnSb Strukturen synthetisiert, indem eine Templat-Synthese mit Hilfe von anodisierten Aluminiumoxid- oder Polycarbonat-Membranen angewandt wurde. rnDie erhaltenen Produkte wurden hauptsächlich durch Röntgen-Diffraktion und Elektronenmikroskopie untersucht. Die Auswertung der Pulver Röntgendiffraktions-Daten stellte eine Herausforderung dar, da die Nanostrukturierung und die Anwesenheit von mehreren Phasen zu verbreiterten und überlagernden Reflexen führen. Zusätzliche Fe-Mößbauer Messungen wurden im Falle der Fe-Sb Produkte vorgenommen, um detailliertere Informationen über die genaue Zusammensetzung zu erhalten. Die erstmals hergestellte Phase Zn1+xSb wurde einer detaillierten Kristallstrukturanalyse unterzogen, die mit Hilfe einer neuen Diffraktionsmethode, der automatisierten Elektronen Diffraktions Tomographie, durchgeführt wurde.rnrnAus physikalischer Sicht sind Zn4Sb3, ZnSb und FeSb2 interessante thermoelektrische Materialien, die aufgrund ihrer Fähigkeit thermische in elektrische Energie umzuwandeln, großes Interesse geweckt haben. Nanostrukturierte thermoelektrische Materialien zeigen dabei eine höhere Umwandlungseffizienz zu erhöhen, da deren thermische Leitfähigkeit herabgesetzt ist. Da thermoelektrische Bauteile aus dichten Bulk-Materialien gefertigt werden, spielte die Verfestigung der synthetisierten nanopartikulären Pulver eine große Rolle. Die als „Spark Plasma Sintering“ bezeichnete Methode wurde eingesetzt, um die Proben zu pressen. Dies ermöglicht schnelles Heizen und Abkühlen der Probe und kann so das bei klassischen Heißpress-Methoden unvermeidliche Kristallitwachstum verringern. Die optimalen Bedingungen für das Spark Plasma Sintern zu finden, ist Inhalt von bestehender und weiterführender Forschung. rnEin Problem stellt die Stabilität der Proben während des Sinterns dar. Trotz des schnellen Pressens wurde eine teilweise Zersetzung im Falle des Zn1+xSb beobachtet, wie mit Hilfe von Synchrotrondiffraktionsuntersuchungen aufgedeckt wurde. Morphologie und Dichte der verschiedenen verfestigten Materialien wurden mittels Rasterelektronenmikroskopie und Lasermikroskopie bestimmt. Die Gitterdynamik wurde mit Hilfe von Wärmekapazitätsmessungen- und inelastischer Kern-Streuung untersucht. Die Wärmeleitfähigkeit der nanostrukturierten Materialien ist im Vergleich zu den Festkörpern ist drastisch reduziert - im Falle des FeSb2 um mehr als zwei Größenordnungen. Abhängig von der Zusammensetzung und mechanischen Härte wurden für einen Teil der verfestigten Nanomaterialien die thermoelektrische Eigenschaften, wie Seebeck Koeffizient, elektrische und Wärmeleitfähigkeit, gemessen.rn

Seawater carbonate chemistry near the Island of Ischia, Italy, 2008

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7.41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms.

Seawater carbonate chemistry and calcification rate in flume experiment

Ocean acidification (OA) poses a severe threat to tropical coral reefs, yet much of what is know about these effects comes from individual corals and algae incubated in isolation under high pCO2. Studies of similar effects on coral reef communities are scarce. To investigate the response of coral reef communities to OA, we used large outdoor flumes in which communities composed of calcified algae, corals, and sediment were combined to match the percentage cover of benthic communities in the shallow back reef of Moorea, French Polynesia. Reef communities in the flumes were exposed to ambient (400 ?atm) and high pCO2 (1300 ?atm) for 8 weeks, and calcification rates measured for the constructed communities including the sediments. Community calcification was reduced by 59% under high pCO2, with sediment dissolution explaining ~ 50% of this decrease; net calcification of corals and calcified algae remained positive but was reduced by 29% under elevated pCO2. These results show that, despite the capacity of coral reef calcifiers to maintain positive net accretion of calcium carbonate under OA conditions, reef communities might transition to net dissolution as pCO2 increases, particularly at night, due to enhanced sediment dissolution.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Physical properties nd chemistry of igneous rocks from the Pigafetta and East Mariana Basins

Physical properties of basalts from Ocean Drilling Program Sites 800 and 801 in the Pigafetta Basin and Site 802 in the East Mariana Basin, including porosity, wet-bulk density, grain density, compressional wave velocity, and thermal conductivity, were measured aboard JOIDES Resolution during Leg 129. The ranges for the properties are large, as typified by the velocity, which varies from 3.46 to 6.59 km/s. Extensively altered basalts immediately above and below a silicified hydrothermal deposit (60-69 m sub-basement depth) at Site 801 display the highest porosity, and lowest bulk density, velocity, and thermal conductivity, whereas the slightly altered rocks from Site 802 and the lowermost part of Site 801 represent the other extreme in physical properties variations. In order to better establish the relationship between physical properties and alteration of the rocks, the compressional wave velocities were compared with results from major and trace elemental analyses and petrographic examination of select samples. For the Leg 129 basalts, velocity displays a generally consistent decrease with increasing K2O, H2O+, loss on ignition, and Rb contents and the value of Fe3+/FeT and decreasing concentrations of SiO2, FeOT, CaO, MgO, and MnO. These trends are consistent with trends documented for the progressive alteration of oceanic crust and indicate that on a laboratory sample scale, basalt alteration is largely responsible for the variation of the physical properties of basalts sampled at Sites 800, 801, and 802.

Borehole temperature, submarine permafrost methane concentrations and pore water chemistry measured on borehole BK2, central Laptev Sea shelf

Submarine permafrost degradation has been invoked as a cause for recent observations of methane emissions from the seabed to the water column and atmosphere of the East Siberian shelf. Sediment drilled 52 m down from the sea ice in Buor Khaya Bay, central Laptev Sea revealed unfrozen sediment overlying ice-bonded permafrost. Methane concentrations in the overlying unfrozen sediment were low (mean 20 µM) but higher in the underlying ice-bonded submarine permafrost (mean 380 µM). In contrast, sulfate concentrations were substantially higher in the unfrozen sediment (mean 2.5 mM) than in the underlying submarine permafrost (mean 0.1 mM). Using deduced permafrost degradation rates, we calculate potential mean methane efflux from degrading permafrost of 120 mg/m**2 per year at this site. However, a drop of methane concentrations from 190 µM to 19 µM and a concomitant increase of methane d13C from -63 per mil to -35 per mil directly above the ice-bonded permafrost suggest that methane is effectively oxidized within the overlying unfrozen sediment before it reaches the water column. High rates of methane ebullition into the water column observed elsewhere are thus unlikely to have ice-bonded permafrost as their source.

Environmental characteristics, and growth traits and leaf chemistry of tundra plants in a warming experiment at Alexandra Fiord

Understanding plant trait responses to elevated temperatures in the Arctic is critical in light of recent and continuing climate change, especially because these traits act as key mechanisms in climate-vegetation feedbacks. Since 1992, we have artificially warmed three plant communities at Alexandra Fiord, Nunavut, Canada (79°N). In each of the communities, we used open-top chambers (OTCs) to passively warm vegetation by 1-2 °C. In the summer of 2008, we investigated the intraspecific trait responses of five key species to 16 years of continuous warming. We examined eight traits that quantify different aspects of plant performance: leaf size, specific leaf area (SLA), leaf dry matter content (LDMC), plant height, leaf carbon concentration, leaf nitrogen concentration, leaf carbon isotope discrimination (LCID), and leaf d15N. Long-term artificial warming affected five traits, including at least one trait in every species studied. The evergreen shrub Cassiope tetragona responded most frequently (increased leaf size and plant height/decreased SLA, leaf carbon concentration, and LCID), followed by the deciduous shrub Salix arctica (increased leaf size and plant height/decreased SLA) and the evergreen shrub Dryas integrifolia (increased leaf size and plant height/decreased LCID), the forb Oxyria digyna (increased leaf size and plant height), and the sedge Eriophorum angustifolium spp. triste (decreased leaf carbon concentration). Warming did not affect d15N, leaf nitrogen concentration, or LDMC. Overall, growth traits were more sensitive to warming than leaf chemistry traits. Notably, we found that responses to warming were sustained, even after many years of treatment. Our work suggests that tundra plants in the High Arctic will show a multifaceted response to warming, often including taller shoots with larger leaves.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

Interstitial-water chemistry of ODP Leg 119 sites

Ocean Drilling Program inorganic geochemistry procedures routinely overlook more than 99% of the sediment column. Present and past biogeochemical reactions alter the sediment record; however, most of these reaction zones are bypassed by the normal methods where samples are collected every 30 m. A new approach to increase resolution was introduced during Leg 119. Ten milliliters of sediment provided interstitial-water samples for ammonia, silica, sulfate, magnesium, and calcium analyses. The new method introduced some systematic differences in concentrations, as well as some decrease in precision. A number of advantages, however, may warrant using the method in some instances. In cases where routine interstitial-water data showed anomalous results, core sections were retrieved from the storage facility and resampled. The new high-resolution procedure was used to provide water samples in cases were water contents were low and routine squeezing could not recover pore water.

Carbonate chemistry, community metabolism, PAR, temperature and salinity of One Tree Island reef

There are few in situ studies showing how net community calcification (Gnet) of coral reefs is related to carbonate chemistry, and the studies to date have demonstrated different predicted rates of change. In this study, we measured net community production (Pnet), Gnet, and carbonate chemistry of a reef flat at One Tree Island, Great Barrier Reef. Diurnal pCO2 variability of 289-724 µatm was driven primarily by photosynthesis and respiration. The reef flat was found to be net autotrophic, with daily production of ? 35 mmol C/m**2/d and net calcification of ? 33 mmol C/m**2/d . Gnet was strongly related to Pnet, which drove a hysteresis pattern in the relationship between Gnet and aragonite saturation state (Omega ar). Although Pnet was the main driver of Gnet, Omega ar was still an important factor, where 95% of the variance in Gnet could be described by Pnet and Omega ar. Based on the observed in situ relationship, Gnet would be expected to reach zero when Omega ar is 2.5. It is unknown what proportion of a decline in Gnet would be through reduced calcification and what would occur through increased dissolution, but the results here support predictions that overall calcium carbonate production will decline in coral reefs as a result of ocean acidification.