Hydrothermal Instability Of Thermocapillary Convection In Large-Prandtl-Number Liquid Bridges Under Microgravity

Linear stability analysis was performed to study the mechanism of transition of thermocapillary convection in liquid bridges with liquid volume ratios ranging from 0.4 to 1.2, aspect ratio of 0.75 and Prandtl number of 100. 2-D governing equations were solved to obtain the steady axi-symmetric basic flow and temperature distributions. 3-D perturbation equations were discretized at the collocation grid points using the Chebyshev-collocation method. Eigenvalues and eigenfunctions were obtained by using the Q-R. method. The predicted critical Marangoni numbers and critical frequencies were compared with data from space experiments. The disturbance of the temperature distribution on the free surface causes the onset of oscillatory convection. It is shown that the origin of instability is related to the hydrothermal origin for convections in large-Prandtl-number liquid bridges. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

A comparison of seafloor habitats and associated benthic fauna in areas open and closed to bottom trawling along the central California Continental Shelf

Executive Summary: A number of studies have shown that mobile, bottom-contact fishing gear (such as otter trawls) can alter seafloor habitats and associated biota. Considerably less is known about the recovery of these resources following such disturbances, though this information is critical for successful management. In part, this paucity of information can be attributed to the lack of access to adequate control sites – areas of the seafloor that are closed to fishing activity. Recent closures along the coast of central California provide an excellent opportunity to track the recovery of historically trawled areas and to compare recovery rates to adjacent areas that continue to be trawled. In June 2006 we initiated a multi-year study of the recovery of seafloor microhabitats and associated benthic fauna inside and outside two new Essential Fish Habitat (EFH) closures within the Cordell Bank and Gulf of the Farallones National Marine Sanctuaries. Study sites inside the EFH closure at Cordell Bank were located in historically active areas of fishing effort, which had not been trawled since 2003. Sites outside the EFH closure in the Gulf of Farallones were located in an area that continues to be actively trawled. All sites were located in unconsolidated sands at equivalent water depths. Video and still photographic data collected via a remotely operated vehicle (ROV) were used to quantify the abundance, richness, and diversity of microhabitats and epifaunal macro-invertebrates at recovering and actively trawled sites, while bottom grabs and conductivity/temperature/depth (CTD) casts were used to quantify infaunal diversity and to characterize local environmental conditions. Analysis of still photos found differences in common seafloor microhabitats between the recovering and actively trawled areas, while analysis of videographic data indicated that biogenic mound and biogenic depression microhabitats were significantly less abundant at trawled sites. Each of these features provides structure with which demersal fishes, across a wide range of size classes, have been observed to associate. Epifaunal macro-invertebrates were sparsely distributed and occurred in low numbers in both treatments. However, their total abundance was significantly different between treatments, which was attributable to lower densities at trawled sites. In addition, the dominant taxa were different between the two sites. Patchily-distributed buried brittle stars dominated the recovering site, and sea whips (Halipteris cf. willemoesi) were most numerous at the trawled site though they occurred in only five of ten transects. Numerical classification (cluster analysis) of the infaunal samples also revealed a clear difference between benthic assemblages in the recovering vs. trawled areas due to differences in the relative abundances of component species. There were no major differences in infaunal species richness, H′ diversity, or J′ evenness between recovering vs. trawled site groups. However, total infaunal abundance showed a significant difference attributable to much lower densities at trawled sites. This pattern was driven largely by the small oweniid polychaete Myriochele gracilis, which was the most abundant species in the overall study region though significantly less abundant at trawled sites. Other taxa that were significantly less abundant at trawled sites included the polychaete M. olgae and the polychaete family Terebellidae. In contrast, the thyasirid bivalve Axinopsida serricata and the polychaetes Spiophanes spp. (mostly S. duplex), Prionospio spp., and Scoloplos armiger all had significantly to near significantly higher abundances at trawled sites. As a result of such contrasting species patterns, there also was a significant difference in the overall dominance structure of infaunal assemblages between the two treatments. It is suggested that the observed biological patterns were the result of trawling impacts and varying levels of recovery due to the difference in trawling status between the two areas. The EFH closure was established in June 2006, within a month of when sampling was conducted for the present study, however, the stations within this closure area are at sites that actually have experienced little trawling since 2003, based on National Marine Fishery Service trawl records. Thus, the three-year period would be sufficient time for some post-trawling changes to have occurred. Other results from this study (e.g., similarly moderate numbers of infaunal species in both areas that are lower than values recorded elsewhere in comparable habitats along the California continental shelf) also indicate that recovery within the closure area is not yet complete. Additional sampling is needed to evaluate subsequent recovery trends and persistence of effects. Furthermore, to date, the study has been limited to unconsolidated substrates. Ultimately, the goal of this project is to characterize the recovery trajectories of a wide spectrum of seafloor habitats and communities and to link that recovery to the dynamics of exploited marine fishes. (PDF has 48 pages.)

Automated, objective texture segmentation of multibeam echosounder data - Seafloor survey and substrate maps from James Island to Ozette Lake, Washington Outer Coast

Without knowledge of basic seafloor characteristics, the ability to address any number of critical marine and/or coastal management issues is diminished. For example, management and conservation of essential fish habitat (EFH), a requirement mandated by federally guided fishery management plans (FMPs), requires among other things a description of habitats for federally managed species. Although the list of attributes important to habitat are numerous, the ability to efficiently and effectively describe many, and especially at the scales required, does not exist with the tools currently available. However, several characteristics of seafloor morphology are readily obtainable at multiple scales and can serve as useful descriptors of habitat. Recent advancements in acoustic technology, such as multibeam echosounding (MBES), can provide remote indication of surficial sediment properties such as texture, hardness, or roughness, and further permit highly detailed renderings of seafloor morphology. With acoustic-based surveys providing a relatively efficient method for data acquisition, there exists a need for efficient and reproducible automated segmentation routines to process the data. Using MBES data collected by the Olympic Coast National Marine Sanctuary (OCNMS), and through a contracted seafloor survey, we expanded on the techniques of Cutter et al. (2003) to describe an objective repeatable process that uses parameterized local Fourier histogram (LFH) texture features to automate segmentation of surficial sediments from acoustic imagery using a maximum likelihood decision rule. Sonar signatures and classification performance were evaluated using video imagery obtained from a towed camera sled. Segmented raster images were converted to polygon features and attributed using a hierarchical deep-water marine benthic classification scheme (Greene et al. 1999) for use in a geographical information system (GIS). (PDF contains 41 pages.)

Developing alternatives for optimal representation of seafloor habitats and associated communities in Stellwagen Bank National Marine Sanctuary

The implementation of various types of marine protected areas is one of several management tools available for conserving representative examples of the biological diversity within marine ecosystems in general and National Marine Sanctuaries in particular. However, deciding where and how many sites to establish within a given area is frequently hampered by incomplete knowledge of the distribution of organisms and an understanding of the potential tradeoffs that would allow planners to address frequently competing interests in an objective manner. Fortunately, this is beginning to change. Recent studies on the continental shelf of the northeastern United States suggest that substrate and water mass characteristics are highly correlated with the composition of benthic communities and may therefore, serve as proxies for the distribution of biological biodiversity. A detailed geo-referenced interpretative map of major sediment types within Stellwagen Bank National Marine Sanctuary (SBNMS) has recently been developed, and computer-aided decision support tools have reached new levels of sophistication. We demonstrate the use of simulated annealing, a type of mathematical optimization, to identify suites of potential conservation sites within SBNMS that equally represent 1) all major sediment types and 2) derived habitat types based on both sediment and depth in the smallest amount of space. The Sanctuary was divided into 3610 0.5 min2 sampling units. Simulations incorporated constraints on the physical dispersion of sampling units to varying degrees such that solutions included between one and four site clusters. Target representation goals were set at 5, 10, 15, 20, and 25 percent of each sediment type, and 10 and 20 percent of each habitat type. Simulations consisted of 100 runs, from which we identified the best solution (i.e., smallest total area) and four nearoptimal alternates. We also plotted total instances in which each sampling unit occurred in solution sets of the 100 runs as a means of gauging the variety of spatial configurations available under each scenario. Results suggested that the total combined area needed to represent each of the sediment types in equal proportions was equal to the percent representation level sought. Slightly larger areas were required to represent all habitat types at the same representation levels. Total boundary length increased in direct proportion to the number of sites at all levels of representation for simulations involving sediment and habitat classes, but increased more rapidly with number of sites at higher representation levels. There were a large number of alternate spatial configurations at all representation levels, although generally fewer among one and two versus three- and four-site solutions. These differences were less pronounced among simulations targeting habitat representation, suggesting that a similar degree of flexibility is inherent in the spatial arrangement of potential protected area systems containing one versus several sites for similar levels of habitat representation. We attribute these results to the distribution of sediment and depth zones within the Sanctuary, and to the fact that even levels of representation were sought in each scenario. (PDF contains 33 pages.)

Acoustic signatures of the seafloor: Tools for predicting grouper habitat

Groupers are important components of commercial and recreational fisheries. Current methods of diver-based grouper census surveys could potentially benefit from development of remotely sensed methods of seabed classification. The goal of the present study was to determine if areas of high grouper abundance have characteristic acoustic signatures. A commercial acoustic seabed mapping system, QTC View Series V, was used to survey an area near Carysfort Reef, Florida Keys. Acoustic data were clustered using QTC IMPACT software, resulting in three main acoustic classes covering 94% of the area surveyed. Diver-based data indicate that one of the acoustic classes corresponded to hard substrate and the other two represented sediment. A new measurement of seabed heterogeneity, designated acoustic variability, was also computed from the acoustic survey data in order to more fully characterize the acoustic response (i.e., the signature) of the seafloor. When compared with diver-based grouper census data, both acoustic classification and acoustic variability were significantly different at sites with and without groupers. Sites with groupers were characterized by hard bottom substrate and high acoustic variability. Thus, the acoustic signature of a site, as measured by acoustic classification or acoustic variability, is a potentially useful tool for stratifying diver sampling effort for grouper census.

Reactivity of titanocene methylidene with metal halides, alkene sulfides, and alkene oxides

Titanocene metallacyclobutanes show a wide variety of reactivites with organic and inorganic reagents. Their reactions include methylene transfer to organic carbonyls, formation of enolates, electron transfer from activated alkyl chlorides, olefin metathesis, ring opening polymerization. Recently, preparations of heterobinuclear µ-methylene complexes were reported. In this thesis, mechanistic, synthetic, and structural studies of the heterobinuclear µ-methylene complexes will be described. Also, the reaction of titanocene methylidene trimethylphosphine complex with alkene sulfide and styrene sulfide will be presented.

Heterobinuclear µ-methylene-µ-methyl complexes C_(p2)Ti(µ-CH_2)( µ-CH_3)M(1,5-COD) have been prepared (M = Rh, Ir). X-ray crystallography showed that the methyl group of the complex was bonded to the rhodium and bridges to the titanium through an agostic bond. The ^(1)H,^(13)CNMR, IR spectra along with partial deuteration studies supported the structure in both solution and solid state. Activation of the agostic bond is demonstrated by the equilibration of the µ-CH_3 and µ-CH_2 groups. A nonlinear Arrhenius plot, an unusually large kinetic isotope effect (24(5)), and a large negative activation entropy (-64(3)eu) can be explained by the quantum-mechanical tunneling. Calculated rate constants with Bell-type barrier fitted well with the observed one. This equilibration was best explained by a 4e-4c mechanism (or σ bond metathesis) with the character of quantum-mechanical tunneling.

Heterobinuclear µ-methylene-µ-phenyl complexes were synthesized. Structural study of C_(p2)Ti(µ-CH_(2))(µ-p-Me_(2)NC_(6)H_(4))Rh(l,5-COD) showed that the two metal atoms are bridged by the methylene carbon and the ipso carbon of the p-N,N-dimethylarninophenyl group. The analogous structure of C_(p2))Ti(µ-CH_(2))(µ-o-MeOC_(6)H_(4))Rh(1,5-COD) has been verified by the differential NOE. The aromaticity of the phenyl group observed by ^(1)H NMR, was confirmed by the comparison of the C-C bond lengths in the crystallographic structure. The unusual downfield shifts of the ipso carbon in the ^(13)C NMR are assumed to be an indication of the interaction between the ipso carbon and electron-deficient titanium.

Titanium-platinum heterobinuclear µ-methylene complexes C_(p2)Ti(µ-CH_(2))(µ -X)Pt(Me)(PM_(2)Ph) have been prepared (X= Cl, Me). Structural studies indicate the following:(1) the Ti-CH2 bond possesses residual double bond character, (2) there is a dative Pt→Ti interaction which may be regarded as a π back donation from the platinum atom to the 'Ti=CH_(2)'' group, and (3) the µ-CH_3 group is bound to the titanium atom through a three-center, two-electron agostic bond.

Titanocene (η^(2)-thioformaldehyde)•PMe_3 was prepared from C_(p2)Ti=CH_(2)•PMe_3 and sulfur-containing organic compounds (e.g. alkene sulfide, triphenylphosphine sulfide) including elemental sulfur. Mechanistic studies utilizing trans-styrene sulfide-d_1 suggested the stepwise reaction to explain equimolar mixture of trans- and cis-styrene-d_1 as by-products. The product reacted with methyl iodide to produce cationic titanocene (η_(2)-thiomethoxymethyl) complex. Complexes having less coordinating anion like BF_4 or BPh_4 could be obtained through metathesis. Together with structural analyses, the further reactivities of the complexes have been explored.

The complex C_(p2)TiOCH_(2)CH(Ph)CH_2 was prepared from the compound C_(p2)Ti=CH_(2)-PMe_3 and styrene oxide. The product was characterized with ^(1)H-^(1)H correlated 2-dimensional NMR, selective decoupling of ^(1)H NMR, and differential NOE. Stereospecificity of deuterium in the product was lost when trans-styrene oxide-d_1 was allowed to react. Relative rates of the reaction were measured with varying substituents on the phenyl ring. Better linearity (r = -0.98, p^(+) = -0.79) was observed with σ_(p)^(+)than σ(r = -0.87, p = -1.26). The small magnitude of p^+ value and stereospecificity loss during the formation of product were best explained by the generation of biradicals, but partial generation of charge cannot be excluded. Carbonylation of the product followed by exposure to iodine yields the corresponding β-phenyl γ-lactone.

Mechanism of mass transfer in the formation of hydrothermal deposits of sulphides [Translation from: Trudy Inst.Geol.rudn.Mesterozh. 16, 80 [pages 44-46 ”Solubility of sulphides of iron” only], 1958]

This partial translation of the original paper provides the summary of this study of the mechanism of mass transfer in the formation of hydrothermal deposits of sulphides. For determining the solubility of sulphides of iron, the radioactive isotope Fe59 was used. The solubility of two sulphides was determined.

Hydrothermal experiments on the thermal stability of amino substances in sediments

Aspartic acid, threonine, serine and other thermally unstable amino acids have been found in fine-grained elastic sediments of advanced geologic age. The presence of these compounds in ancient sediments conflicts with experimental data determined for their simple thermal decomposition.

Recent and Late Miocene sediments and their humic acid extracts, known to contain essentially complete suites of amino acids, were heated with H₂O in a bomb at temperatures up to 500°C in order to compare the thermal decomposition characteristics of the sedimentary amino compounds.

Most of the amino acids found in protein hydrolyzates are obtained from the Miocene rock in amounts 10 to 100 times less than from the Recent sediment. The two unheated humic acids are rather similar despite their great age difference. The Miocene rock appears uncontaminated by Recent carbon.

Yields of amino acids generally decline in the heated Recent sediment. Some amino compounds apparently increase with heating time in the Miocene rock.

Relative thermal stabilities of the amino acids in sediments are generally similar to those determined using pure aqueous solutions. The relative thermal stabilities of glutamic acid, glycine, and phenylalanine vary in the Recent sediment but are uniform in the Miocene rock.

Amino acids may occur in both proteins and humic complexes in the Recent sediment, while they are probably only present in stabilized organic substances in the Miocene rock. Thermal decomposition of protein amino acids may be affected by surface catalysis in the Recent sediment. The apparent activation energy for the decomposition of alanine in this sediment is 8400 calories per mole. Yields of amino compounds from the heated sediments are not affected by thermal decomposition only.

Amino acids in sediments may only be useful for geothermometry in a very general way.

A better picture of the amino acid content of older sedimentary rocks may be obtained if these sediments are heated in a bomb with H₂O at temperatures around 150°C prior to HCl hydrolysis.

Leucine-isoleucine ratios may prove to be useful as indicators of amino acid sources or for evaluating the fractionation of these substances during diagenesis. Leucine-isoleucine ratios of the Recent and Miocene sediments and humic acids are identical. The humic acids may have a continental source.

The carbon-nitrogen and carbon-hydrogen ratios of sediments and humic acids increase with heating time and temperature. Ratios comparable to those in some kerogens are found in the severely heated Miocene sediment and humic acid.

Growth of composite sapphire/Ti : sapphire by the hydrothermal method

Composite sapphire/Ti:sapphire crystals for high-power laser application were grown by the hydrothermal method. The results of the X-ray rocking curve analysis indicate high crystalline quality of the surface Al2O3 material. The strong bonding between the overgrown Al2O3 and seed Ti:Al2O3 crystals is indispensable for withstanding high thermal stresses produced by intense optical pumping. The optical loss at the boundary of the composite crystal is considerably low, indicating the lack of scattering centers. (c) 2005 Elsevier B.V. All rights reserved.

Low-temperature hydrothermal growth of oriented [0001] ZnO film

Well-aligned ZnO films have been successfully prepared by using low-temperature hydrothermal approach on (0001) sapphire substrates that were pre-coated with a ZnO nano-layer by dip-coating. The characterizations of scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicate that the ZnO films consist of hexagonal rods that grow along the c axis based on the sapphire substrates. It is found that the size of ZnO rods can be adjusted by an aqueous solution with some methenamine. (c) 2006 Elsevier B.V. All rights reserved.

Hydrothermal growth and characterization of ZnO crystals

ZnO crystals with dimensions of 30 x 38 x 8 turn 3 have been grown by the hydrothermal method using a mixed solution of KOH, LiOH and H2O2. The growing rates for +c(0001) and -c(000 (1) over bar) were 0.17 and 0.09 mm/day, respectively. The crystal color was very light green for +c sector and dark brown for -c sector. For the +c sector, the resistivity at room temperature was 80 0 cm, the carrier concentration was about 10(4)/cm(3), and the mobility was about 100 cm(2)/Vs. The full-width at half-maximum (FWHM) of double axis X-ray rocking curve for the polished Zn face cut from +c sector was 45 arcsec. The photoluminescence (PL) spectrum and the absorption spectrum of +c part of the crystals at room temperature were also reported and discussed in this paper. (c) 2008 Elsevier B.V. All rights reserved.

Effective herding of flatfish by cables with minimal seafloor contact

Otter trawls are very effective at capturing flatfish, but they can affect the seaf loor ecosystems where they are used. Alaska f latf ish trawlers have very long cables (called sweeps) between doors and net to herd fish into the path of the trawl. These sweeps, which ride on and can disturb the seaf loor, account for most of the area affected by these trawls and hence a large proportion of the potential for damage to seaf loor organisms. We examined modifications to otter trawls, such that disk clusters were installed at 9-m intervals to raise trawl sweeps small distances above the seafloor, greatly reducing the area of direct seafloor contact. A critical consideration was whether flatfish would still be herded effectively by these sweeps. We compared conventional and modified sweeps using a twin trawl system and analyzed the volume and composition of the resulting catches. We tested sweeps raised 5, 7.5, and 10 cm and observed no significant losses of flatfish catch until sweeps were raised 10 cm, and those losses were relatively small (5–10%). No size composition changes were detected in the flatfish catches. Alaska pollock (Theragra chalcogramma) were captured at higher rates with two versions of the modified sweeps. Sonar observations of the sweeps in operation and the seaf loor after passage confirmed that the area of direct seafloor contact was greatly reduced by the modified sweep

Comparison of echogram measurements against data expectations and assumptions for distinguishing seafloor substrates

Defining types of seafloor substrate and relating them to the distribution of fish and invertebrates is an important but difficult goal. An examination of the processing steps of a commercial acoustics analyzing software program, as well as the data values produced by the proprietary first echo measurements, revealed potential benef its and drawbacks for distinguishing acoustically distinct seafloor substrates. The positive aspects were convenient processing steps such as gain adjustment, accurate bottom picking, ease of bad data exclusion, and the ability to average across successive pings in order to increase the signal-to-noise ratio. A noteworthy drawback with the processing was the potential for accidental inclusion of a second echo as if it were part of the first echo. Detailed examination of the echogram measurements quantified the amount of collinearity, revealed the lack of standardization (subtraction of mean, division by standard deviation) before principal components analysis (PCA), and showed correlations of individual echogram measurements with depth and seafloor slope. Despite the facility of the software, these previously unknown processing pitfalls and echogram measurement characteristics may have created data artifacts that generated user-derived substrate classifications, rather than actual seafloor substrate types.

Vanadyl arsenates as catalysts for selective oxidation of organic sulfides and alkenes

artículo científico (postprint)

Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint