Bulk and surface switching in Mn-Fe-based Prussian blue analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.

Heavy ion irradiation effects in zirconium nitride

Polycrystalline zirconium nitride (ZrN) samples were irradiated with He +, Kr ++, and Xe ++ ions to high (>1·10 16 ions/cm 2) fluences at ∼100 K. Following ion irradiation, transmission electron microscopy (TEM) and grazing incidence X-ray diffraction (GIXRD) were used to analyze the microstructure and crystal structure of the post-irradiated material. For ion doses equivalent to approximately 200 displacements per atom (dpa), ZrN was found to resist any amorphization transformation, based on TEM observations. At very high displacement damage doses, GIXRD measurements revealed tetragonal splitting of some of the diffraction maxima (maxima which are associated with cubic ZrN prior to irradiation). In addition to TEM and GIXRD, mechanical property changes were characterized using nanoindentation. Nanoindentation revealed no change in elastic modulus of ZrN with increasing ion dose, while the hardness of the irradiated ZrN was found to increase significantly with ion dose. Finally, He + ion implanted ZrN samples were annealed to examine He gas retention properties of ZrN as a function of annealing temperature. He gas release was measured using a residual gas analysis (RGA) spectrometer. RGA measurements were performed on He-implanted ZrN samples and on ZrN samples that had also been irradiated with Xe ++ ions, in order to introduce high levels of displacive radiation damage into the matrix. He evolution studies revealed that ZrN samples with high levels of displacement damage due to Xe implantation, show a lower temperature threshold for He release than do pristine ZrN samples.

Measuring employee innovation:a review of existing scales and the development of the innovative behavior and innovation support inventories across cultures

Purpose - The paper develops a model of employee innovative behavior conceptualizing it as distinct from innovation outputs and as a multi-faceted behavior rather than a simple count of ‘innovative acts’ by employees. It understands individual employee innovative behaviors as a micro-foundation of firm intrapreneurship that is embedded in and influenced by contextual factors such as managerial, organizational and cultural support for innovation. Building from a review of existing employee innovative behavior scales and theoretical considerations we develop and validate the Innovative Behavior Inventory (IBI) and the Innovation Support Inventory (ISI). Design/methodology/approach – Two pilot studies, a third validation study in the Czech Republic and a fourth cross-cultural validation study using population representative samples from Switzerland, Germany, Italy and the Czech Republic (N=2812 employees and 450 entrepreneurs) were conducted. Findings - Both inventories were reliable and showed factorial, criterion, convergent and discriminant validity as well as cross-cultural equivalence. Employee innovative behavior was supported as comprising of idea generation, idea search, idea communication, implementation starting activities, involving others and overcoming obstacles. Managerial support was the most proximal contextual influence on innovative behavior and mediated the effect of organizational support and national culture. Originality/value - The paper advances our understanding of employee innovative behavior as a multi-faceted phenomenon and the contextual factors influencing it. Where past research typically focuses on convenience samples within a particular country, we offer first robust evidence that our model of employee innovative behavior generalizes across cultures and types of samples. Our model and the IBI and ISI inventories enable researchers to build a deeper understanding of the important micro-foundation underpinning intrapreneurial behavior in organizations and allow practitioners to identify their organizations’ strengths and weaknesses related to intrapreneurship.

Stability of Ampelometric Characteristics of Vitis vinifera L. cv. 'Syrah' and 'Sauvignon blanc' Leaves: Impact of Within-vineyard Variability and Pruning Method/Bud Load

Historically, grapevine (Vitis vinifera L.) leaf characterisation has been a driving force in the identification of cultivars. In this study, ampelometric (foliometric) analysis was done on leaf samples collected from hand-pruned, mechanically pruned and minimally pruned ‘Sauvignon blanc’ and ‘Syrah’ vines to estimate the impact of within-vineyard variability and a change in bud load on the stability of leaf properties. The results showed that within-vineyard variability of ampelometric characteristics was high within a cultivar, irrespective of bud load. In terms of the O.I.V. coding system, zero to four class differences were observed between minimum and maximum values of each characteristic. The value of variability of each characteristic was different between the three levels of bud load and the two cultivars. With respect to bud load, the number of shoots per vine had a significant effect on the characteristics of the leaf laminae. Single leaf area and lengths of veins changed significantly for both cultivars, irrespective of treatment, while angle between veins proved to be a stable characteristic. A large number of biometric data can be recorded on a single leaf; the data measured on several leaves, however, are not necessarily unique for a specific cultivar. The leaf characteristics analysed in this study can be divided into two groups according to the response to a change in bud load, i.e. stable (angles between the veins, depths of sinuses) and variable (length of the veins, length of the petiole, single leaf area). The variable characteristics are not recommended to be used in cultivar identification, unless the pruning method/bud load is known.

Spatial and seasonal variability in elemental content, δ13C, and δ15N ofThalassia testudinum from South Florida and its implications for ecosystem studies

Elemental and isotopic composition of leaves of the seagrassThalassia testudinum was highly variable across the 10,000 km2 and 8 years of this study. The data reported herein expand the reported range in carbon:nitrogen (C:N) and carbon:phosphorus (C:P) ratios and δ13C and δ15N values reported for this species worldwide; 13.2–38.6 for C:N and 411–2,041 for C:P. The 981 determinations in this study generated a range of −13.5‰ to −5.2‰ for δ13C and −4.3‰ to 9.4‰ for δ15N. The elemental and isotope ratios displayed marked seasonality, and the seasonal patterns could be described with a simple sine wave model. C:N, C:P, δ13C, and δ15N values all had maxima in the summer and minima in the winter. Spatial patterns in the summer maxima of these quantities suggest there are large differences in the relative availability of N and P across the study area and that there are differences in the processing and the isotopic composition of C and N. This work calls into question the interpretation of studies about nutrient cycling and food webs in estuaries based on few samples collected at one time, since we document natural variability greater than the signal often used to imply changes in the structure or function of ecosystems. The data and patterns presented in this paper make it clear that there is no threshold δ15N value for marine plants that can be used as an unambiguous indicator of human sewage pollution without a thorough understanding of local temporal and spatial variability.

Annotated record and chemical composition of ferromanganese concretions and crusts sampled from the lakes and streams of Norway

The main objective of the project was to develop a geochemical method for exploration of ores associated with granitic rocks. Fe and Mn oxidates were sampled in streambeds and lakes from 129 localities in Southeastern Norway. 65 of these localities are situated in the northern Oslo Graben. The samples were examined mineralogically and chemically by a variety of methods. Geochemical maps of the element content in oxidates show regional distribution patterns for several elements. Sampling and analysis of oxidates can be used in exploration for mineralizations such as the Skrukkelia Mo-deposit in the northern Oslo Graben. New anomalies (especially for Zn and W) have been detected. Appendix I contains a description of samples, chemical and mineralogical determinations performed on the samples, backscattered electron image-, X-ray image- and scanning electron image pictures of the oxidate preparates. Appendix II contains spectral plots, point analysis with the microprobe, X-ray diffractograms, analytical results, correlation coefficient matrix, scatterplots, frequency distributions and information on data storage. Appendix III containS maps of the element content in oxidates.

(Table 1, page 1376) Chemical analyses of manganese nodules and crusts from the Pacific Ocean

A compilation of chemical analyses of Pacific Ocean nodules using an x-ray fluorescence technique. The equipment used was a General Electric XRD-5 with a tungsten tube. Lithium fluoride was used as the diffraction element in assaying for all elements above calcium in the atomic table and EDDT was used in conjunction with a helium path for all elements with an atomic number less than calcium. Flow counters were used in conjunction with a pulse height analyzer to eliminate x-ray lines of different but integral orders in gathering count data. The stability of the equipment was found to be excellent by the author. The equipment was calibrated by the use of standard ores made from pure oxide forms of the elements in the nodules and carefully mixed in proportion to the amounts of these elements generally found in the manganese nodules. Chemically analyzed standards of the nodules themselves were also used. As a final check, a known amount of the element in question was added to selected samples of the nodules and careful counts were taken on these samples before and after the addition of the extra amount of the element. The method involved the determination and subsequent use of absorption and activation factors for the lines of the various elements. All the absorption and activation factors were carefully determined using the standard ores. The chemically analyzed samples of the nodules by these methods yielded an accuracy to at least three significant figures.

Obtenção e conservação de espermatozoides de cutia (Dasyprocta leporina Linneaus, 1753) do semiárido brasileiro

The general objective of this thesis was to stablish protocols to obtain and conserve agouti (Dasyprocta leporina) sperm bred in captivity in the Brazilian semi-arid, aiming its sustainable production. The thesis was divided in three experiments. In the first one, we studied the influence of the interaction between two probes (quadratics and sine waves) and two stimulation protocols (continuous and in series) on the agouti sperm collection by electroejaculation efficiency. The most efficient interaction on this obtainment was the one with probes with rings associated with stimuli in series (4/7; 57%, P<0.05). In the second experiment we compared the cryoprotectant effects of different substances (glycerol, ethyleneglycol, dimethylsulfoxide, dimethylformamide) on epididymis sperm cryopreservation. The highest values on motility (39.5±4.6%), vigor (2.9±0.2) and membrane integrity (30.6±4.5%) were observed on the samples cryopreserved using glycerol when compared to those with ethyleneglycol and dimethylformamide, but there was no difference (P>0.05) when compared to the samples cryopreserved with dimethylsulfoxide. At last, we studied the effects of the methods to obtain sperm (electroejaculation vs epididymal collection) on post thawing sperm quality. The samples obtained by epididymal retrograde flushing showed values for motility of 25.0±10.9% and vigor 2.4±0.8, and those obtained by electroejaculation had 31.2±14.2% of motility and vigor of 2.2±0.7, however, without statistical difference (P>0.05), which shows the possibility to successfully use the epididymal sperm cryopreservation protocol on agouti ejaculated sperm. In conclusion, significant advances on obtainment and processing of agouti sperm were made, allowing the establishment of germplasm banks from sperm samples obtained from the epididymis or by electroejaculation.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

(Table 2) Radiocarbon dates of sediment cores obtained during Bio Hespérides cruise SVAIS and OGS Explora cruise EGLACOM between 2007-2008

A high-resolution paleomagnetic and rock magnetic study has been carried out on sediment cores collected in glaciomarine silty-clay sequences from the continental shelf and slope of the southern Storfjorden trough-mouth fan, on the northwestern Barents Sea continental margin. The Storfjorden sedimentary system was investigated during the SVAIS and EGLACOM cruises, when 10 gravity cores, with a variable length from 1.03 m to 6.41 m, were retrieved. Accelerator mass spectrometry (AMS) 14C analyses on 24 samples indicate that the cores span a time interval that includes the Holocene, the last deglaciation phase and in some cores the last glacial maximum. The sediments carry a well-defined characteristic remanent magnetization and have a valuable potential to reconstruct the paleosecular variation (PSV) of the geomagnetic field, including relative paleointensity (RPI) variations. The paleomagnetic data allow reconstruction of past dynamics and amplitude of the geomagnetic field variations at high northern latitudes (75°-76° N). At the same time, the rock magnetic and paleomagnetic data allow a high-resolution correlation of the sedimentary sequences and a refinement of their preliminary age models. The Holocene PSV and RPI records appear particularly sound, since they are consistent between cores and they can be correlated to the closest regional stacking curves (UK PSV, FENNOSTACK and FENNORPIS) and global geomagnetic model for the last 7 ka (CALS7k.2). The computed amplitude of secular variation is lower than that outlined by some geomagnetic field models, suggesting that it has been almost independent from latitude during the Holocene.

(Table 1, page 754) Estimated concentrations of various elements in nineteen manganese nodules

Using spectrochemical techniques Fe, Si, Mg, Co, Ni, Cu, V, Mo, Ti and Tl have been estimated in nineteen manganese nodules, eight from the Atlantic ocean, seven from the Pacific ocean and four from the Indian ocean. Though data on more samples are required before firm and detailed conclusions can be made about the distribution of elements in manganese nodules, several distinct features appear when the data on the nineteen samples are examined. Certain elements appear to enrich more strongly than others. For example, relative to igneous rocks Mo is much more strongly enriched than V. For several elements (Ni, Cu and particularly Co and Tl) the degree of enrichment in two Fe-low nodules is far smaller than in the other nodules. The magnitude of dispersion of concentration appears to vary considerably for different elements; thus, whereas variation of concentration of V is relatively small, that of Ni, Cu, Co and Tl is far larger. The statistical nature of the distribution of Fe in manganese nodules appears to be characteristic and different from that of the other elements studied so far. Of the possible inter-element relationships examined that of Ni-Cu appears to be the most strongly developed.

Nd and Sm isotopic record from fossil fish teeth recovered from ODP Site 177-1090

Neodymium (Nd) isotopes were measured on 181 samples of fossil fish teeth recovered from Oligocene to Miocene sections at Ocean Drilling Program Site 1090 (3700 m water depth) on Agulhas Ridge in the Atlantic sector of the Southern Ocean. A long-term decreasing trend toward less radiogenic Nd isotope compositions dominates the record. This trend is interrupted by shifts toward more radiogenic compositions near the early/late Oligocene boundary and the Oligocene/Miocene boundary. Overall, epsilon-Nd values at Agulhas Ridge are more radiogenic than at other Atlantic locations, and are similar to those at Indian Ocean locations. The pattern of variability is remarkably similar to Nd isotope results from Walvis Ridge (South Atlantic) and Ninetyeast Ridge (Indian Ocean). In contrast, Agulhas Ridge and Maud Rise Nd isotope records do not show similar patterns over this interval. Results from this study indicate that deep water in the Atlantic flowed predominantly from north to south during the Oligocene and Miocene, and that export of Northern Component Water (NCW) to the Southern Ocean increased in the late Oligocene. There is also evidence for efficient exchange of deep waters between the Atlantic sector of the Southern Ocean and the Indian Ocean, although the direction of deep water flow is not entirely clear from these data. The shifts to more radiogenic Nd isotopic compositions most likely represent increases in the flux of Pacific waters through Drake Passage, and the timing of these events reflect development of a mature Antarctic Circumpolar Current (ACC). The relative timing of increased NCW export and ACC maturation support hypotheses that link deep water formation in the North Atlantic to the opening of Drake Passage.

Stable carbon and oxygen isotope ratios of foraminifera from Cretaceous and Paleocene sediments

Detailed analysis of over 200 samples of uppermost Cretaceous and Paleocene sediments from Atlantic Ocean DSDP Sites 384, 86, 95, 152, 144, 20C, 21, 356, 357, and 329 provides new information on the temperature stratification of Paleocene planktonic foraminifera, the temperature and carbon isotopic changes across the Cretaceous/Tertiary boundary, and the fluctuating temperature and carbon isotopic records through the Paleocene ~64.5-54 m.y.). There was a significant temperature rise across the Cretaceous/Tertiary boundary both at the surface and in deep waters of the Atlantic Ocean. This temperature rise occurred before the basal Tertiary 'Globigerina' eugubina Zone, so that in the oldest Paleocene sample yet analyzed from the deep sea (Site 356) temperatures are already three degrees higher at the bottom and at the surface than in the Cretaceous. The temperature rise across the boundaryis more pronounced on the bottom and in samples from higher latitudes. Accompanying the temperature rise across the boundary there is a significant shift in the carbon isotope profile. In the basal Paleocene the foraminifera of the surface zone demonstrate very negative carbon isotope values (unlike in the Cretaceous of today's ocean), while deeper dwelling species have more positive values which then decrease to the bottom. The unusual carbon isotope gradients persist through the first three million years of the Paleocene until towards the top of planktonic foraminiferal Zone P.1 (G. trinidadensis Zone) the foraminifera record a profile more positive at the surface and decreasing towards the bottom (as in today's ocean). During the Paleocene there are two noteworthy rises in surface water temperature; the first around 62-61 m.y. (G. trinidadensis Zone), and the second near the base of the Globorotalia angulata Zone, 60-59 m.y. At this time surface temperatures at low to mid latitudes reached values near 25°C, while at mid-latitude Site 384 temperature highs near 22°C were registered. At a sample spacing of around one per million years, we have only produced some of the detail of these temperature fluctuations. The later Paleocene is generally cooler and there do not seem to be any large variations either through time or latitude. Middle-latitude sites average temperatures near 15°C at the surface, while high lower latitude site temperatures range near 18°C. The most salient feature of the bottom temperature record (based on multispecific samples) through the Paleocene is its lack of fluctuations. There is an overall temperature range of 5°C at these intermediate depth sites (paleodepth estimates between 1500 and 3000 m). Higher values near 13°C accompany the surface temperature peaks around 62 and 60 m.y., while low values near 8°C occur in Zone P.2 (61-60 m.y.). We detected no change in bottom temperature across the paleocene/Eocene boundary in the few samples studied so far. While there are several fluctuations in the carbon isotope values through the early Paleocene, the general trend is one of increasingly positive values at the surface and at depth. This trend culminates in the late Paleocene (upper Zone P.4, about 56-57 m.y.) with a major excursion in the carbon isotope values. At low latitudes the range between the surface and the deepest planktonic foraminifera is a delta13C of 4 per mil as compared with a range of 2 per mil today. The carbon values drop off slightly, but remain strongly positive through the remainder of the Paleocene at most sites. Accompanying the carbon isotope excursion at Site 384 is a productivity increase and a proposed rise in the CCD.

Nd- and Sr- isotope ratios of oceanic basalts

143Nd/144Nd ratios have been determined on 37 samples of oceanic basalt, with a typical precision of +/- 2-3 * 10**-5 (2 sigma). Ocean island and dredged and cored submarine basalts are included for which reliable measurements of 87Sr/86Sr ratios exist in the literature or have been measured as part of this study. A strong negative correlation exists between 143Nd/144Nd and 87Sr/86Sr ratios in basalts from Iceland and the Reykjanes Ridge, but such a clear correlation does not exist for samples from the Hawaiian Islands. However, when other ocean island basalts from the Atlantic are included there is an overall correlation between these two parameters. Increases and decreases in Rb/Sr in oceanic basalt source regions have in general been accompanied by decreases and increases respectively in Sm/Nd ratios. The compatibility of the data with single-stage models is assessed and it is concluded that enrichment and depletion events, which are consistent with transfer of silicate melts, are responsible for the observed variation.

Trace element composition of IODP Site 304-U1309 and 305-U1309 (Table A2)

IODP Site U1309 was drilled at Atlantis Massif, an oceanic core complex, at 30°N on the Mid-Atlantic Ridge (MAR). We present the results of a bulk rock geochemical study (major and trace elements) carried out on 228 samples representative of the different lithologies sampled at this location. Over 96% of Hole U1309D is made up of gabbroic rocks. Diabases and basalts cross-cut the upper part of the section; they have depleted MORB compositions similar to basalts sampled at MAR 30°N. Relics of mantle were recovered at shallow depth. Mantle peridotites show petrographic and geochemical evidence of extensive melt-rock interactions. Gabbroic rocks comprise: olivine-rich troctolites (> 70% modal olivine) and troctolites having high Mg# (82-89), high Ni (up to 2300 ppm) and depleted trace element compositions (Yb 0.06-0.8 ppm); olivine gabbros and gabbros (including gabbronorites) with Mg# of 60-86 and low trace element contents (Yb 0.125-2.5 ppm); and oxide gabbros and leucocratic dykes with low Mg# (< 50), low Ni (~65 ppm) and high trace element contents (Yb up to 26 ppm). Troctolites and gabbros are amongst the most primitive and depleted oceanic gabbroic rocks. The main geochemical characteristics of Site U1309 gabbroic rocks are consistent with a formation as a cumulate sequence after a common parental MORB melt, although (lack of systematic) downhole variations indicate that the gabbroic series were built by multiple magma injections. In detail, textural and geochemical variations in olivine-rich troctolites and gabbronorites suggest chemical interaction (assimilation?) between the parental melt and the intruded lithosphere. Site U1309 gabbroic rocks do not represent the complementary magmatic product of 30°N volcanics, although they sample the same mantle source. The bulk trace element composition of Site U1309 gabbroic rocks is similar to primitive MORB melt compositions; this implies that there was no large scale removal of melts from this gabbro section. The occurrence of such a large magmatic sequence implies that a high magmatic activity is associated with the formation of Atlantis Massif. Our results suggest that almost all melts feeding this magmatic system stays trapped into the intruded lithosphere.