Synthesis, structure, and stability of metal-organic frameworks

Metal-organic frameworks (MOFs) obtained much attention because of their unusual structures and properties as well as their potential applications. This dissertation research was focused on (1) the effects of synthesis conditions on the structures of MOFs, (2) the thermal stability of MOFs, (3) pressure-induced amorphization, and (4) the effect of high-valent ions on the structure of a MOF. This research demonstrated that the crystal structure of MOF-5 could be controlled by drying solvents. If the vacuum solvent is dimethylformamide (DMF), the crystal structure of MOF-5 is tetragonal. In contrast, if the DMF is displaced by CH2Cl2 before the vacuum, the obtained MOF-5 occupies a cubic structure. Furthermore, it was found that the tetragonal MOF-5 exhibited a mediate surface area (300-1000 m2/g). The surface area of tetragonal MOF-5 is also dependent on Zn(NO3)2/H2BDC (H2BDC: terephthalic acid) molar ratios used for its synthesis. The optimum ratio is 1.38, at which synthesized tetragonal MOF-5 exhibits the highest crystallinity and surface area (1297 m2/g). The thermal stability and decomposition of MOF-5 were systematically investigated. The thermal decomposition of cubic and tetragonal MOF-5s resulted in the same products: CO2, benzene, amorphous carbon, and crystal ZnO. The thermal decomposition is due to breaking carboxylic bridges between benzene rings and Zn4O clusters. Identifying structural relationships between crystalline and noncrystalline states is of fundamental interest in materials research. Currently, amorphization of solid materials at ambient temperature requires an ultra-high pressure (several GPa). However, this research demonstrated that MOF-5 and IRMOF-8 can be irreversibly amorphized at ambient temperature by employing a low compressing pressure of 3.5 MPa, which is 100 times lower than that required for amorphization of other solids. Furthermore, the pressure-induced amorphization (PIA) of MOFs is strongly dependent on the changeability of bond angles. If the geometric structure of a MOF can allow bond angles to be changed without breaking bonds, it can easily be amorphized by compression. This can explain why MOF-5 and IRMOF-8 can easily be amorphized via compression than Cu-BTC. It is generally recognized that zeolitic imidazolate frameworks (ZIFs) occupy much higher stability than other types of MOFs. The representative of ZIFs is Zn(2-methylimidazole)2 (ZIF-8) exhibiting high-decomposition temperature and high chemical resistance to various solvents. However, so far, it is still unknown whether the high stability of ZIF-8 can be challenged by ions, which is important for its modification by doping ions. In this research, we performed aqueous salt solution treatment on ZIF-8, and the results showed that anions (Cl¯ and NO3¯) in a solution exhibited no effect on the crystal structure of ZIF-8. However, the effect of cations (in a solution) on structure of ZIF-8 strongly depends on the cation valences. The univalent metal cations showed no effect on the structure of ZIF-8, whereas the bivalent or higher-valent metal cations caused the collapse of ZIF-8 crystal structure. Therefore, structure stability of ZIF-8 is considered when it is subjected to the application, in which high-valent metal cations are involved.

Geochemistry and Stable Isotopes of Surface Water and Groundwater in the Continental Pit in Butte, Montana, USA

The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

Coupling of eastern and western subpolar North Atlantic: salt transport in the Irminger Current

Salt transport in the Irminger Current and thus the coupling between eastern and western subpolar North Atlantic plays an important role for climate variability across a wide range of time scales. High-resolution ocean modeling and observations indicate that 5 salinities in the eastern subpolar North Atlantic decrease with enhanced circulation of the North Atlantic subpolar gyre (SPG). This has led to the perception that a stronger SPG also transports less salt westward. In this study, we analyze a regional ocean model and a comprehensive global coupled climate model, and show that a stronger SPG transports more salt in the Irminger Current irrespective of lower salinities in its 10 source region. The additional salt converges in the Labrador Sea and the Irminger Basin by eddy transports, increases surface salinity in the western SPG, and favors more intense deep convection. This is part of a positive feedback mechanism with potentially large implications for climate variability and predictability.

Stabilizing Lead Cathodes with Diammonium Salt Additives in the Deoxygenation of Aromatic Amides

Lead is efficiently protected against cathodic corrosion by the addition of diammonium salts in the electrolyte. The cationic coating of the cathode allows the efficient electroreduction of benzamides to benzylamines. The electrochemical deoxygenation of the amide is achieved without the use of oxophilic agents or sacrificial anodes. The surface of the lead cathode stays smooth and the cathode can be reused for multiple runs, providing <2.5 ppm of the crude product. Cyclic voltammetry studies reveal a shift in the onset potential of the hydrogen evolution reaction by −157 mV.

Quantitative component analysis of the coarse fraction of surface sediments from the Persian Gulf

In the Persian Gulf and the Gulf of Oman marl forms the primary sediment cover, particularly on the Iranian side. A detailed quantitative description of the sediment components > 63 µ has been attempted in order to establish the regional distribution of the most important constituents as well as the criteria governing marl sedimentation in general. During the course of the analysis, the sand fraction from about 160 bottom-surface samples was split into 5 phi° fractions and 500 to 800 grains were counted in each individual fraction. The grains were cataloged in up to 40 grain type catagories. The gravel fraction was counted separately and the values calculated as weight percent. Basic for understanding the mode of formation of the marl sediment is the "rule" of independent availability of component groups. It states that the sedimentation of different component groups takes place independently, and that variation in the quantity of one component is independent of the presence or absence of other components. This means, for example, that different grain size spectrums are not necessarily developed through transport sorting. In the Persian Gulf they are more likely the result of differences in the amount of clay-rich fine sediment brought in to the restricted mouth areas of the Iranian rivers. These local increases in clayey sediment dilute the autochthonous, for the most part carbonate, coarse fraction. This also explains the frequent facies changes from carbonate to clayey marl. The main constituent groups of the coarse fraction are faecal pellets and lumps, the non carbonate mineral components, the Pleistocene relict sediment, the benthonic biogene components and the plankton. Faecal pellets and lumps are formed through grain size transformation of fine sediment. Higher percentages of these components can be correlated to large amounts of fine sediment and organic C. No discernable change takes place in carbonate minerals as a result of digestion and faecal pellet formation. The non-carbonate sand components originate from several unrelated sources and can be distinguished by their different grain size spectrum; as well as by other characteristics. The Iranian rivers supply the greatest amounts (well sorted fine sand). Their quantitative variations can be used to trace fine sediment transport directions. Similar mineral maxima in the sediment of the Gulf of Oman mark the path of the Persian Gulf outflow water. Far out from the coast, the basin bottoms in places contain abundant relict minerals (poorly sorted medium sand) and localized areas of reworked salt dome material (medium sand to gravel). Wind transport produces only a minimal "background value" of mineral components (very fine sand). Biogenic and non-biogenic relict sediments can be placed in separate component groups with the help of several petrographic criteria. Part of the relict sediment (well sorted fine sand) is allochthonous and was derived from the terrigenous sediment of river mouths. The main part (coarse, poorly sorted sediment), however, was derived from the late Pleistocene and forms a quasi-autochthonous cover over wide areas which receive little recent sedimentation. Bioturbation results in a mixing of the relict sediment with the overlying younger sediment. Resulting vertical sediment displacement of more than 2.5 m has been observed. This vertical mixing of relict sediment is also partially responsible for the present day grain size anomalies (coarse sediment in deep water) found in the Persian Gulf. The mainly aragonitic components forming the relict sediment show a finely subdivided facies pattern reflecting the paleogeography of carbonate tidal flats dating from the post Pleistocene transgression. Standstill periods are reflected at 110 -125m (shelf break), 64-61 m and 53-41 m (e.g. coare grained quartz and oolite concentrations), and at 25-30m. Comparing these depths to similar occurrences on other shelf regions (e. g. Timor Sea) leads to the conclusion that at this time minimal tectonic activity was taking place in the Persian Gulf. The Pleistocene climate, as evidenced by the absence of Iranian river sediment, was probably drier than the present day Persian Gulf climate. Foremost among the benthonic biogene components are the foraminifera and mollusks. When a ratio is set up between the two, it can be seen that each group is very sensitive to bottom type, i.e., the production of benthonic mollusca increases when a stable (hard) bottom is present whereas the foraminifera favour a soft bottom. In this way, regardless of the grain size, areas with high and low rates of recent sedimentation can be sharply defined. The almost complete absence of mollusks in water deeper than 200 to 300 m gives a rough sedimentologic water depth indicator. The sum of the benthonic foraminifera and mollusca was used as a relative constant reference value for the investigation of many other sediment components. The ratio between arenaceous foraminifera and those with carbonate shells shows a direct relationship to the amount of coarse grained material in the sediment as the frequence of arenaceous foraminifera depends heavily on the availability of sand grains. The nearness of "open" coasts (Iranian river mouths) is directly reflected in the high percentage of plant remains, and indirectly by the increased numbers of ostracods and vertebrates. Plant fragments do not reach their ultimate point of deposition in a free swimming state, but are transported along with the remainder of the terrigenous fine sediment. The echinoderms (mainly echinoids in the West Basin and ophiuroids in the Central Basin) attain their maximum development at the greatest depth reached by the action of the largest waves. This depth varies, depending on the exposure of the slope to the waves, between 12 to 14 and 30 to 35 m. Corals and bryozoans have proved to be good indicators of stable unchanging bottom conditions. Although bryozoans and alcyonarian spiculae are independent of water depth, scleractinians thrive only above 25 to 30 m. The beginning of recent reef growth (restricted by low winter temperatures) was seen only in one single area - on a shoal under 16 m of water. The coarse plankton fraction was studied primarily through the use of a plankton-benthos ratio. The increase in planktonic foraminifera with increasing water depth is here heavily masked by the "Adjacent sea effect" of the Persian Gulf: for the most part the foraminifera have drifted in from the Gulf of Oman. In contrast, the planktonic mollusks are able to colonize the entire Persian Gulf water body. Their amount in the plankton-benthos ratio always increases with water depth and thereby gives a reliable picture of local water depth variations. This holds true to a depth of around 400 m (corresponding to 80-90 % plankton). This water depth effect can be removed by graphical analysis, allowing the percentage of planktonic mollusks per total sample to be used as a reference base for relative sedimentation rate (sedimentation index). These values vary between 1 and > 1000 and thereby agree well with all the other lines of evidence. The "pteropod ooze" facies is then markedly dependent on the sedimentation rate and can theoretically develop at any depth greater than 65 m (proven at 80 m). It should certainly no longer be thought of as "deep sea" sediment. Based on the component distribution diagrams, grain size and carbonate content, the sediments of the Persian Gulf and the Gulf of Oman can be grouped into 5 provisional facies divisions (Chapt.19). Particularly noteworthy among these are first, the fine grained clayey marl facies occupying the 9 narrow outflow areas of rivers, and second, the coarse grained, high-carbonate marl facies rich in relict sediment which covers wide sediment-poor areas of the basin bottoms. Sediment transport is for the most part restricted to grain sizes < 150 µ and in shallow water is largely coast-parallel due to wave action at times supplemented by tidal currents. Below the wave base gravity transport prevails. The only current capable of moving sediment is the Persian Gulf outflow water in the Gulf of Oman.

Geochemical composition of surface snow, ice and debris from glaciers in Norway, Nepal and New Zealand

Alpine glacier samples were collected in four contrasting regions to measure supraglacial dust and debris geochemical composition. A total of 70 surface glacier ice, snow and debris samples were collected in 2009 and 2010 in Svalbard, Norway, Nepal and New Zealand. Trace elemental abundances in snow and ice samples were measured via inductively coupled plasma mass spectrometry (ICP-MS). Supraglacial debris mineral, bulk oxide and trace element composition were determined via X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF). A total of 45 elements and 10 oxide compound abundances are reported. The uniform data collection procedure, analytical measurement methods and geochemical comparison techniques are used to evaluate supraglacial dust and debris composition variability in the contrasting glacier study regions. Elemental abundances revealed sea salt aerosol and metal enrichment in Svalbard, low levels of crustal dust and marine influences to southern Norway, high crustal dust and anthropogenic enrichment in the Khumbu Himalayas, and sulfur and metals attributed to quiescent degassing and volcanic activity in northern New Zealand. Rare earth element and Al/Ti elemental ratios demonstrated distinct provenance of particulates in each study region. Ca/S elemental ratio data showed seasonal denudation in Svalbard and Norway. Ablation season atmospheric particulate transport trajectories were mapped in each of the study regions and suggest provenance pathways. The in situ data presented provides first order glacier surface geochemical variability as measured from four diverse alpine glacier regions. This geochemical surface glacier data is relevant to glaciologic ablation rate understanding as well as satellite atmospheric and land-surface mapping techniques currently in development.

Sea surface temperature and salinity reconstruction of sediment core GeoB3129-1

A sediment core from the western tropical Atlantic covering the last 21,000 yr has been analysed for centennial scale reconstruction of sea surface temperature (SST) and ice volume-corrected oxygen isotopic composition of sea water (delta18O(ivc-sw)) using Mg / Ca and delta18O of the shallow dwelling planktonic foraminifer Globigerinoides ruber (white). At a period between 15.5 and 17.5 kyr BP, the Mg / Ca SST and delta18O(ivc-sw), a proxy for sea surface salinity (SSS), reveals a warming of around 2.5 °C along with an increase in salinity. A second period of pronounced warming and SSS increase occurred between 11.6 and 13.5 kyr BP. Within age model uncertainties, both warming intervals were synchronous with air temperature increase over Antarctica and ice retreat in the southern South Atlantic and terminated with abrupt centennial scale SSS decrease and slight SST cooling in conjunction with interglacial reactivation of the meridional overturning circulation (MOC). We suggest that during these warm intervals, production of saline and warm water of the North Brazil Current resulted in pronounced heat and salt accumulation, and was associated with warming in the southern Atlantic, southward displacement of the intertropical convergence zone and weakened MOC. At the termination of the Younger Dryas and Heinrich event 1, intensification of cross-equatorial heat and salt transport caused centennial scale cooling and freshening of the western tropical Atlantic surface water. This study shows that the western tropical Atlantic served as a heat and salt reservoir during deglaciation. The sudden release of accumulated heat and salt at the end of Younger Drays and Heinrich event 1 may have contributed to the rapid reinvigoration of the Atlantic MOC.

Wave height (regular and irregular waves) reduction in 2m water depth over a 40-m-long salt marsh test section in a large scale laboratory flume

Coastal communities around the world face increasing risk from flooding as a result of rising sea level, increasing storminess, and land subsidence. Salt marshes can act as natural buffer zones, providing protection from waves during storms. However, the effectiveness of marshes in protecting the coastline during extreme events when water levels and waves are highest is poorly understood. Here, we experimentally assess wave dissipation under storm surge conditions in a 300-m-long wave flume that contains a transplanted section of natural salt marsh. We find that the presence of marsh vegetation causes considerable wave attenuation, even when water levels and waves are high. From a comparison with experiments without vegetation, we estimate that up to 60% of observed wave reduction is attributed to vegetation. We also find that although waves progressively flatten and break vegetation stems and thereby reduce dissipation, the marsh substrate remained remarkably stable and resistant to surface erosion under all conditions.The effectiveness of storm wave dissipation and the resilience of tidal marshes even at extreme conditions suggest that salt marsh ecosystems can be a valuable component of coastal protection schemes.

NDT for concrete under accelerated freeze/thaw tests and surface scaling

Freezing of water or salt solution in concrete pores is a main cause for severe damage and significant reduction of the service life. Most of the freeze-thaw (F-T) accelerated tests measure the scaling of concrete by weighting. This paper presents complementary procedures based on the use of strain gages and ultrasonic pulse velocity (UPV) for measuring the deterioration of concrete due to freezing and thawing. These non-destructive testing (NDT) procedures are applied to two types of concretes, one susceptible to F-T damage and the other does not. The results show a good correlation between scaling and the measurements obtained with NDT. Showing NDT the advantage to detect before the damage and to perform continuous measurement

The breaking of axisymmetric slender liquid bridges

Liquids held by surface tension forces can bridge the gap between two solid bodies placed not too far apart from each other. The equilibrium conditions and stability criteria for static, cylindrical liquid bridges are well known. However, the behaviour of an unstable liquid bridge, regarding both its transition toward breaking and the resulting configuration, is a matter for discussion. The dynamical problem of axisymmetric rupture of a long liquid bridge anchored at two equal coaxial disks is treated in this paper through the adoption of one-dimensional theories which are widely used in capillary jet problems

Stability of slender, axisymmetric liquid bridges between unequal disks

The stability of slender, axisymmetric liquid bridges held by surface tension forces between two coaxial, parallel solid disks having different radii is studied by using standard perturbation techniques. The results obtained show that the behaviour of such configurations becomes similar to that of liquid bridges between equal disks when subject to small axial gravity forces.

On the use of liquid bridges as accelerometers

The shape of the interface of a drop of liquid held by surface tension forces between two solid disks,a liquid bridge, depends on the geometry of the supporting disks, the volume of liquid and the external forces acting on the drop. Therefore, once the geometry of the supporting disks and the volume of liquid are fixed, and assuming that the value of the surface tension is known, a way to measure such external forces could be by measuring the deformation of the liquid bridge interface.