Oxygen concentration at time series station DYNAPROC

Continuous measurements between 0 and 200 m depth were performed every 2 h over two separate periods of four days at a station in the open northwestern Mediterranean Sea (Dyfamed Station) during the Dynaproc cruise in May 1995. Estimates of the daily variations in profiles of temperature, partial pressure of CO2, oxygen, chlorophyll a and nutrients were obtained. The distributions of the various physical and chemical properties were clearly different during the two time series, which were separated by a period of 11 days during which a wind event occurred. The mean daily utilization or production due to biological processes of dissolved inorganic carbon (DIC), nitrate+nitrite and oxygen were calculated along isopycnals using a vertical diffusion model. Between the surface and about 20 m depth, DIC was consumed and O2 released during the two time series while the nitrate+nitrite concentrations as well as supplies were zero. After the wind event, the O2 : C : N ratios of consumption (or production) were, on average, near the Redfield ratios, but during the first time series, the C : N utilization ratio between 20 and 35 m was two to three times that of Redfield stoichiometry and the oxygen release was low. The integrated net community production (NCP) in terms of carbon was equivalent during the two time series, whereas the chlorophyll a biomass was twice as high, on average, during the first time series but did decrease. These results imply that the production systems were different during the two periods. The first time series corresponds to a period at the end of production, due to the nutrient depletion in the euphotic layer. The formation of degradation products of the living material in dissolved organic form is probably important as indicated by the high C : N utilization ratios. The second time series corresponds to a reactivation of the primary production due to the upward shift of nutrients after the wind event.

Comparative analysis for the assessment of restoration treatments on stone material from the roman theater of Merida (Spain)

The overall goal of the project is the study of effects of conservation treatments applied on stone material from archaeological sites, i n terms of superficial changes, effectiveness and durability. In this sense, one of the first premises is characterize the surface of the treated and untreated material in order to determine changes in physical and chemical properties.

Interaction of two arginine residues in lactate oxidase with the enzyme flavin: Conversion of FMN to 8-formyl-FMN

Two arginine residues, Arg-181 and Arg-268, are conserved throughout the known family of FMN-containing enzymes that catalyze the oxidation of α-hydroxyacids. In the lactate oxidase from Aerococcus viridans, these residues have been changed to lysine in two single mutations and in a double mutant form. In addition, Arg-181 has been replaced by methionine to determine the effect of removing the positive charge on the residue. The effects of these replacements on the kinetic and thermodynamic properties are reported. With all mutant forms, there are only small effects on the reactivity of the reduced flavin with oxygen. On the other hand, the efficiency of reduction of the oxidized flavin by l-lactate is greatly reduced, particularly with the R268K mutant forms. The results demonstrate the importance of the two arginine residues in the binding of substrate and its interaction with the flavin, and are consistent with a previous hypothesis that they also play a role of charge neutralization in the transition state of substrate dehydrogenation. The replacement of Arg-268 by lysine also results in a slow conversion of the 8-CH3- substituent of FMN to yield 8-formyl-FMN, still tightly bound to the enzyme, and with significantly different physical and chemical properties from those of the FMN-enzyme.

Protein–RNA interactions: a structural analysis

A detailed computational analysis of 32 protein–RNA complexes is presented. A number of physical and chemical properties of the intermolecular interfaces are calculated and compared with those observed in protein–double-stranded DNA and protein–single-stranded DNA complexes. The interface properties of the protein–RNA complexes reveal the diverse nature of the binding sites. van der Waals contacts played a more prevalent role than hydrogen bond contacts, and preferential binding to guanine and uracil was observed. The positively charged residue, arginine, and the single aromatic residues, phenylalanine and tyrosine, all played key roles in the RNA binding sites. A comparison between protein–RNA and protein–DNA complexes showed that whilst base and backbone contacts (both hydrogen bonding and van der Waals) were observed with equal frequency in the protein–RNA complexes, backbone contacts were more dominant in the protein–DNA complexes. Although similar modes of secondary structure interactions have been observed in RNA and DNA binding proteins, the current analysis emphasises the differences that exist between the two types of nucleic acid binding protein at the atomic contact level.

Climatic evolution of eastern South America during the last deglaciation: a paleoceanographic approach

Para dar suporte ao atual debate sobre as consequências climáticas da liberação antropogênica de CO2 na atmosfera, o refinamento do conhecimento sobre mudanças climáticas e oceanográficas no passado é necessário. A Circulação de Revolvimento Meridional do Atlântico (CRMA) tem papel fundamental na oceanografia e clima das áreas sob influência do Oceano Atlântico, controlando diretamente a estratificação e distribuição de massas d\'água, a quantidade de calor transportada pelo oceano e os ciclo e armazenamento de compostos químicos, como o CO2 em mar profundo. A formação e circulação da Água Intermediária Antártica (AIA), envolvida no transporte de calor e sal para o giro subtropical do Hemisfério Sul e nas teleconexões climáticas entre altas e baixas latitudes, é componente importante do ramo superior da CRMA. A reconstrução de propriedades de massas de água intermediárias é, portanto, importante para a compreensão dos sistemas de retroalimentação entre oceano-clima. No entanto, informações quanto a evolução da AIA continuam limitadas. Oscilações da CRMA e consequentes mudanças na distribuição de calor tem implicações importantes para o clima Sul Americano, influenciando a disponibilidade de umidade para o Sistema de Monções Sul Americano (SMSA), via temperatura da superfície marinha e posicionamento da Zona de Convergência Intertropical. Neste trabalho nós reconstruímos a assinatura isotópica da AIA durante os estágios isotópicos marinhos 2 e 3 (41-12 cal ka AP) usando isótopos de carbono e oxigênio de foraminíferos bentônicos (gêneros Cibicidoides e Uvigerina) de um testemunho de sedimentos marinhos datados por radiocarbono (1100 m de profundidade e a 20°S na costa do Brasil). Concluímos que propriedades físicas e químicas da AIA mudaram durante os estadiais Heinrich 3 e 4, provavelmente como consequência de enfraquecimento da CRMA durante estes períodos. Também reconstruímos as condições continentais do leste brasileiro entre o último máximo glacial e a deglaciação (23-12 cal ka AP) baseadas em razões Ti/Ca de nosso testemunho de sedimentos marinhos como indicadoras de aporte terrígeno do Rio Doce. A maior parte da chuva que cai na Bacia do Rio Doce está relacionada a atividade do SMAS. Nosso registro de Ti/Ca em conjunto com \'\'delta\' POT.18\'O de espeleotemas da Caverna Lapa Sem Fim, também no leste do Brasil, sugere diminuição marcante da chuva durante o interestadial Bølling-Allerød, provavelmente relacionada a enfraquecimento do SMAS. Ademais comparamos as razões de Ti/Ca com dados de saída da rodada SYNTRACE do modelo climático CCSM3 com forçantes transientes para a última deglaciação. Os registros geoquímicos e a saída do modelo mostram resultados consistentes entre si e sugerem que o leste da América do Sul passou pelo seu período mais seco de toda a última deglaciação durante o interestadial Bølling-Allerød, provavelmente relacionado ao enfraquecimento do SMAS.

Influência da substituição de matérias primas nas propriedades dos fluxantes para lingotamento contínuo de aços médio carbono

O fluxante é uma escória sintética que influencia na qualidade superficial do aço e na estabilidade do processo de lingotamento contínuo. Este produto é aplicado diretamente sobre o aço líquido na região do molde de cobre refrigerado a água e atua diretamente no resfriamento primário do aço. O fluxante tem as propriedades físico-químicas adaptadas para cada tipo de aço e também para as condições de lingotamento. Na superfície do aço líquido, o fluxante funde e forma uma poça líquida, atuando como isolante térmico, protegendo o aço da reoxidação e absorvendo inclusões principalmente de Al2O3. A poça líquida escoa, lubrificando e controlando a transferência de calor na interface entre o molde e a pele de aço em solidificação. O problema de qualidade superficial do aço, quando relacionado ao fluxante, se resume a alarmes de colamento, trincas de quina, marcas de oscilação profundas e trincas longitudinais, sendo este último um problema particular do aço médio carbono. Neste trabalho, foram analisados diferentes fluxantes baseados inicialmente no fluxante comercial aplicado no lingotamento contínuo de placas de aço médio carbono. Todos os fluxantes foram desenvolvidos com composições químicas similares. O objetivo foi avaliar o impacto da substituição de fontes de matérias-primas em diferentes composições de modo a avaliar as propriedades físico-químicas com base no fluxante comercial de referência. Como resultado, de todas as propriedades físico-químicas, foi a temperatura de cristalização que sofreu a alteração mais significativa.

Sedimentology at the continental margin of the southern Weddell Sea

During four expeditions with RV "Polarstern" at the continental margin of the southern Weddell Sea, profiling and geological sampling were carried out. A detailed bathymetric map was constructed from echo-sounding data. Sub-bottom profiles, classified into nine echotypes, have been mapped and interpreted. Sedimentological analyses were carried out on 32 undisturbed box grab surface samples, as well as on sediment cores from 9 sites. Apart from the description of the sediments and the investigation of sedimentary structures on X-radiographs the following characteristics were determined: grain-size distributions; carbonate and Corg content; component distibutions in different grain-size fractions; stable oxygen and carbon isotopes in planktic and, partly, in benthic foraminifers; and physical properties. The stratigraphy is based On 14C-dating, oxygen isotope Stages and, at one site, On paleomagnetic measurements and 230Th-analyses The sediments represent the period of deposition from the last glacial maximum until recent time. They are composed predominantly of terrigenous components. The formation of the sediments was controlled by glaciological, hydrographical and gravitational processes. Variations in the sea-ice coverage influenced biogenic production. The ice sheet and icebergs were important media for sediment transport; their grounding caused compaction and erosion of glacial marine sediments on the outer continental shelf. The circulation and the physical and chemical properties of the water masses controlled the transport of fine-grained material, biogenic production and its preservation. Gravitational transport processes were the inain mode of sediment movements on the continental slope. The continental ice sheet advanced to the shelf edge and grounded On the sea-floor, presumably later than 31,000 y.B.P. This ice movement was linked with erosion of shelf sediments and a very high sediment supply to the upper continental slope from the adiacent southern shelf. The erosional surface On the shelf is documented in the sub-bottom profiles as a regular, acoustically hard reflector. Dense sea-ice coverage above the lower and middle continental slope resulted in the almost total breakdown of biogenic production. Immediately in front of the ice sheet, above the upper continental slope, a <50 km broad coastal polynya existed at least periodically. Biogenic production was much higher in this polynya than elsewhere. Intense sea-ice formation in the polynya probably led to the development of a high salinity and, consequently, dense water mass, which flowed as a stream near bottom across the continental slope into the deep sea, possibly contributing to bottom water formation. The current velocities of this water mass presumably had seasonal variations. The near-bottom flow of the dense water mass, in combination with the gravity transport processes that arose from the high rates of sediment accumulation, probably led to erosion that progressed laterally from east to West along a SW to NE-trending, 200 to 400 m high morphological step at the continental slope. During the period 14,000 to 13,000 y.B.P., during the postglacial temperature and sea-level rise, intense changes in the environmental conditions occured. Primarily, the ice masses on the outer continental shelf started to float. Intense calving processes resulted in a rapid retreat of the ice edge to the south. A consequence of this retreat was, that the source area of the ice-rafted debris changed from the adjacent southern shelf to the eastern Weddell Sea. As the ice retreated, the gravitational transport processes On the continental slope ceased. Soon after the beginning of the ice retreat, the sea-ice coverage in the whole research area decreased. Simultaneously, the formation of the high salinity dense bottom water ceased, and the sediment composition at the continental slope then became influenced by the water masses of the Weddell Gyre. The formation of very cold Ice Shelf Water (ISW) started beneath the southward retreating Filchner-Ronne Ice Shelf somewhat later than 12,000 y.B.P. The ISW streamed primarily with lower velocities than those of today across the continental slope, and was conducted along the erosional step on the slope into the deep sea. At 7,500 y.B.P., the grounding line of the ice masses had retreated > 400 km to the south. A progressive retreat by additional 200 to 300 km probably led to the development of an Open water column beneath the ice south of Berkner Island at about 4,000 y.B.P. This in turn may have led to an additional ISW, which had formed beneath the Ronne Ice Shelf, to flow towards the Filcher Ice Shelf. As a result, increased flow of ISW took place over the continental margin, possibly enabling the ISW to spill over the erosional step On the upper continental slope towards the West. Since that time, there is no longer any documentation of the ISW in the sedimentary Parameters on the lower continental slope. There, recent sediments reflect the lower water masses of the Weddell Gyre. The sea-ice coverage in early Holocene time was again so dense that biogenic production was significantly restricted.

Molecular mixed-valence cyanide bridged Co-III-Fe-II complexes

Cyano-bridged mixed-valence compounds have been known for a long time, i.e., Prussian Blue polymeric solids. Nevertheless, the interest in discrete complexes having a well-defined molecular nuclearity has emerged more recently. There are numerous examples of cyano-bridged mixed-valence complexes in the recent literature, as they show promising and useful applications in electrochromism, molecular magnetism and molecular electronics. In this paper, the reactivity, synthetic and structural chemistry, as well as some physical and chemical properties, of a series of discrete dinuclear mixed-valence cyano-bridged complexes of general formulae [LnCoIII(mu NC)Fe-II(CN)(5)](-) (L = pentadentate macrocyclic ligand) are reviewed. Special emphasis is given to the synthetic strategy, redox properties and metal-to-metal-charge-transfer (MMCT) band energy. Tuning the MMCT transition energy has been possible by changing the redox potential of the metal centers, both through structural and outer-sphere changes. The redox processes that involve the appearance and disappearance of these MMCT bands in the visible region have been dealt with in relation to the possible uses of the complexes. (c) 2004 Elsevier B.V. All rights reserved.

Using nitrogen stable isotope ratios ( d15N) of macroalgae to monitor changes in the extent of sewage impacts in Moreton Bay, Australia

During the past decade the use of stable isotopes to investigate transport pathways of nutrients in aquatic ecosystems has contributed new understanding and knowledge to many aspects of ecology; from the trophic structure of food webs to the spatial extent of nutrient discharges. At the same time aquatic monitoring programs around the world have become more interested in quantifying ecosystem health rather than simply measuring the physical and chemical properties of water (nutrients, pH, temperature and turbidity). A novel technique was initiated in 1998 as part of the development of the Ecosystem Health Monitoring Program in S.E. Queensland Australia (EHMP) using changes in the 15N value of the red macroalgae Catenella nipae, to indicate regions impacted by sewage nitrogen. Sewage plume mapping, using the 15N of C. nipae, has demonstrated that over the past 5 years there has been a large reduction in the magnitude and spatial extent of 15N enrichment at sites close to sewage treatment plants (STPs) discharging into Moreton Bay. This presentation will discuss how the 15N signatures of the C. nipae in the plume at the mouth of the Brisbane River have declined since it was first sampled in 1998 and will evaluate causes that may be responsible for these variations. A series of laboratory experiments were conducted to investigate how environmental conditions influence the 15N signature of C, nipae over the incubation period. These data will be used to discuss the observed in situ decline in 15N in an attempt to determine if the reduction can be attributed solely to improvements in the wastewater discharge.

Interactions at the head-tape interface of a linear tape system

Many of the recent improvements in the capacity of data cartridge systems have been achieved through the use of narrower tracks, higher linear densities and continuous servo tracking with multi-channel heads. These changes have produced new tribological problems at the head/tape interface. It is crucial that the tribology of such systems is understood and this will continue since increasing storage capacities and faster transfer rates are constantly being sought. Chemical changes in the surface of single and dual layer MP tape have been correlated to signal performance. An accelerated tape tester, consisting of a custom made cycler ("loop tester"), was used to ascertain if results could be produced that were representative of a real tape drive system. A second set of experiments used a modified tape drive (Georgens cycler), which allowed the effects of the tape transport system on the tape surface to be studied. To isolate any effects on the tape surface due to the head/tape interface, read/write heads were not fitted to the cycler. Two further sets of experiments were conducted which included a head in the tape path. This allowed the effects of the head/tape interface on the physical and chemical properties of the head and tape surfaces to be investigated. It was during the final set of experiments that the effect on the head/tape interface, of an energised MR element, was investigated. The effect of operating each cycler at extreme relative humidity and temperature was investigated through the use of an environmental chamber. Extensive use was made of surface specific analytical techniques such as XPS, AFM, AES, and SEM to study the physical and chemical changes that occur at the head/tape interface. Results showed that cycling improved the signal performance of all the tapes tested. The data cartridge drive belt had an effect on the chemical properties of the tape surface on which it was in contact. Also binder degradation occurred for each tape and appeared to be greater at higher humidity. Lubricant was generally seen to migrate to the tape surface with cycling. Any surface changes likely to affect signal output occurred at the head surface rather than the tape.

Use of colour image analysis for assessment of fire damaged concrete

The aim of this project was to carry out a fundamental study to assess the potential of colour image analysis for use in investigations of fire damaged concrete. This involved:(a) Quantification (rather than purely visual assessment) of colour change as an indicator of the thermal history of concrete.(b) Quantification of the nature and intensity of crack development as an indication of the thermal history of concrete, supporting and in addition to, colour change observations.(c) Further understanding of changes in the physical and chemical properties of aggregate and mortar matrix after heating.(d) An indication of the relationship between cracking and non-destructive methods of testing e.g. UPV or Schmidt hammer. Results showed that colour image analysis could be used to quantify the colour changes found when concrete is heated. Development of red colour coincided with significant reduction in compressive strength. Such measurements may be used to determine the thermal history of concrete by providing information regarding the temperature distribution that existed at the height of a fire. The actual colours observed depended on the types of cement and aggregate that were used to make the concrete. With some aggregates it may be more appropriate to only analyse the mortar matrix. Petrographic techniques may also be used to determine the nature and density of cracks developing at elevated temperatures and values of crack density correlate well with measurements of residual compressive strength. Small differences in crack density were observed with different cements and aggregates, although good correlations were always found with the residual compressive strength. Taken together these two techniques can provide further useful information for the evaluation of fire damaged concrete. This is especially so since petrographic analysis can also provide information on the quality of the original concrete such as cement content and water / cement ratio. Concretes made with blended cements tended to produce small differences in physical and chemical properties compared to those made with unblended cements. There is some evidence to suggest that a coarsening of pore structure in blended cements may lead to onset of cracking at lower temperatures. The use of DTA/TGA was of little use in assessing the thermal history of concrete made with blended cements. Corner spalling and sloughing off, as observed in columns, was effectively reproduced in tests on small scale specimens and the crack distributions measured. Relationships between compressive strength/cracking and non-destructive methods of testing are discussed and an outline procedure for site investigations of fire damaged concrete is described.

The performance of cement stabilised minestone

This study is concerned with the durability of cement stabilised minestone (CSM). Minestone is dominated by the clay-bearing mudrocks and shales of the Coal Measures. Consequently, engineering problems are often encountered due to the likelihood of these rocks undergoing volume change and degradation when exposed to fluctuations in moisture content. In addition, iron sulphides (chiefly pyrite) are frequently present in minestone as diagenetic minerals which on excavation have the potential to oxidise forming sulphate minerals. The oxidation of sulphides may in itself contribute to volume increase in pyritic rocks and sulphate minerals may combine with the products of cement hydration to produce further expansion. The physical and chemical properties of a wide range of minestones are determined and attempts are made to correlate these with the engineering performance of cement stabilised specimens subjected to short-term immersion in water. Criteria, based on these raw material indices are proposed with a view to eliminating minestones which are unsuitable. A long-term durability study is also described. In this, the geochemical stability of pyrite in CSM was examined together with the role played by the sulphur bearing mineralogy in determining the engineering performance of CSM's exposed to conditions of increased moisture availability. The nature of a number of disrupted CSM pavements which have been examined are also discussed.

Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder compression ignition engine

Digestate from the anaerobic digestion conversion process is widely used as a farm land fertiliser. This study proposes an alternative use as a source of energy. Dried digestate was pyrolysed and the resulting oil was blended with waste cooking oil and butanol (10, 20 and 30 vol.%). The physical and chemical properties of the pyrolysis oil blends were measured and compared with pure fossil diesel and waste cooking oil. The blends were tested in a multi-cylinder indirect injection compression ignition engine.Engine combustion, exhaust gas emissions and performance parameters were measured and compared with pure fossil diesel operation. The ASTM copper corrosion values for 20% and 30% pyrolysis blends were 2c, compared to 1b for fossil diesel. The kinematic viscosities of the blends at 40 C were 5–7 times higher than that of fossil diesel. Digested pyrolysis oil blends produced lower in-cylinder peak pressures than fossil diesel and waste cooking oil operation. The maximum heat release rates of the blends were approximately 8% higher than with fossil diesel. The ignition delay periods of the blends were higher; pyrolysis oil blends started to combust late and once combustion started burnt quicker than fossil diesel. The total burning duration of the 20% and 30% blends were decreased by 12% and 3% compared to fossil diesel. At full engine load, the brake thermal efficiencies of the blends were decreased by about 3–7% when compared to fossil diesel. The pyrolysis blends gave lower smoke levels; at full engine load, smoke level of the 20% blend was 44% lower than fossil diesel. In comparison to fossil diesel and at full load, the brake specific fuel consumption (wt.) of the 30% and 20% blends were approximately 32% and 15% higher. At full engine load, the CO emission of the 20% and 30% blends were decreased by 39% and 66% with respect to the fossil diesel. Blends CO2 emissions were similar to that of fossil diesel; at full engine load, 30% blend produced approximately 5% higher CO2 emission than fossil diesel. The study concludes that on the basis of short term engine experiment up to 30% blend of pyrolysis oil from digestate of arable crops can be used in a compression ignition engine.

Fatigue in metallic alloys containing non-metallic particles

This paper examines the effects of non-metallic particles on fatigue performance and, in particular, their influence on fatigue crack propagation at high ΔK (Kmax) levels. The nature and properties of a number of common non-metallic particles found in Fe- and Al- based alloys are described, and consideration is given to the consequences of mismatch of physical and chemical properties between particle and matrix. Effects of particles on fatigue in conventional alloys are illustrated and compared with the behaviour of Al/SiCp MMC. The problems associated with developing particulate reinforced MMC with adequate fatigue crack growth resistance and toughness for structural applications are discussed. © 1991.

Mechanisms of action of microbicides

This chapter describes the sites and mechanisms of action of the major groups of microbicides, relating their physical and chemical properties to interactions with microbial structures. It considers the physical, cellular and molecular methods for studying the mechanisms of action of chemical microbicides. These range from the uptake, binding and penetration of microbial cells, to the interaction with microbial structures, including the cell wall, membrane, nucleic acids, cytoplasm and enzymes. Key features of the mechanisms of action of the major groups of microbicides are described covering oxidizing agents, alkylating agents, metal ion-binding agents, nucleic acid-binding agents, protein denaturants and agents that interact with lipids. © 2013 Blackwell Publishing Ltd.