Transport of chromium and selenium in a pristine sand and gravel aquifer: Role of adsorption processes

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Anderson, L.C.D.; Rea, B.A.

1995-01-01

Field transport experiments were conducted in an oxic sand and gravel aquifer using Br (bromide ion), Cr (chromium, injected as Cr(VI)), Se (selenium, injected as Se(VI)), and other tracers. The aquifer has mildly acidic pH values and low concentrations of dissolved salts. Within analytical errors, all mobile Cr was present as Cr(VI). All mobile Se was probably present as Se(VI). Adsorption of Cr and Se onto aquifer sediments caused retardation of both tracers. Breakthrough curves for Cr and Se had extensive tails, which caused large decreases in their maximum concentrations relative to the nonreactive Br tracer after only 2.0 m of transport. A surface complexation model was applied to the results of laboratory studies of Cr(VI) adsorption on aquifer solids from the site based on adsorption onto hydrous ferric oxide. The modeling results suggested that the dominant adsorbents in the aquifer solids have lower affinities for anion adsorption than pure hydrous ferric oxide. The steep rising limbs and extensive tails observed in most of the breakthrough curves are qualitatively consistent with the equilibrium surface complexation model; however, slow rates of adsorption and desorption may have contributed to these features. Variations during transport in the concentrations of Cr, Se, and other anions competing for adsorption sites likely gave rise to variations in the extent of adsorption. Adequate description of the observed retardation of Cr and Se would require a coupled transport-adsorption model that can account for these effects. Companion experiments in the mildly reducing zone of the aquifer (Kent et al., 1994) showed a loss of Cr mass, probably resulting from reduction to Cr(III), and little retardation of mobile Cr and Se during transport; this contrast illustrates the influence of aquifer chemistry on the transport of redox-sensitive solutes.

Evaluation of flow properties in the weldments of vanadium alloys using a novel indentation technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gubbi, A.N.; Rowcliffe, A.F.; Lee, E.H.

1996-10-01

Automated Ball Indentation (ABI) testing, was successfully employed to determine the flow properties of the fusion zone, heat affected zone (HAZ), and base metal of the gas tungsten arc (GTA) and electron beam (EB) welds of the V-4Cr-4Ti (large heat no. 832665) and the V-5Cr-5Ti (heat 832394) alloys. ABI test results showed a clear distinction among the properties of the fusion zone, HAZ, and base metal in both GTA and EB welds of the two alloys. GTA and EB welds of both V-4Cr-4Ti and V-5Cr-5Ti alloys show strengthening of both the fusion zone and the HAZ (compared to base metal)more » with the fusion zone having higher strength than the HAZ. These data correlate well with the Brinell hardness. On the other hand, GTA welds of both alloys, after a post-weld heat treatment of 950{degrees}C for 2 h, show a recovery of the properties to base metal values with V-5Cr-5Ti showing a higher degree of recovery compared to V-4Cr-4Ti. These measurements correlate with the reported recovery of the Charpy impact properties.« less

Frictional and structural characterization of ion-nitrided low and high chromium steels

NASA Technical Reports Server (NTRS)

Spalvins, T.

1985-01-01

Low Cr steels AISI 41410, AISI 4340, and high Cr austenitic stainless steels AISI 304, AISI 316 were ion nitrided in a dc glow discharge plasma consisting of a 75 percent H2 - 25 percent N2 mixture. Surface compound layer phases were identified, and compound layer microhardness and diffusion zone microhardness profiles were established. Distinct differences in surface compound layer hardness and diffusion zone profiles were determined between the low and high Cr alloy steels. The high Cr stainless steels after ion nitriding displayed a hard compound layer and an abrupt diffusion zone. The compound layers of the high Cr stainless steels had a columnar structure which accounts for brittleness when layers are exposed to contact stresses. The ion nitrided surfaces of high and low Cr steels displayed a low coefficient of friction with respect to the untreated surfaces when examined in a pin and disk tribotester.

Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

PubMed

Matczak, W; Chmielnicka, J

1993-03-01

For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr VI). Total Cr content of fumes varied from 0.1 to 7.4%. The distribution of particular Cr compounds was: 52.6% soluble Cr (including 50.7% Cr VI), 65.5% total Cr VI, and 11.4% insoluble Cr VI. The results obtained indicate that MMA/SS welding is a process that could be highly hazardous to human health. Evaluation of occupational exposure has shown that MMA/SS welders may exceed the admissible concentrations of soluble and insoluble Cr VI forms as well as of Mn and Ni. In the plants investigated the sum of the ratios of concentrations of particular welding fumes in the breathing zone of welders exceeded corresponding maximum allowable concentration values by 24 times (including 17 times for total Cr VI). Due to the variety and changeability of particular parameters occurring in the working environment, the composition of MMA/SS welding fumes (in the welder's breathing zone) is so variable that it is not possible to assess the exposure by means of one universal exposure indicator (maximum additive hygienic limit value). The evaluation should be based on the results of measurements of concentrations of particular elements in welding fumes.

Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

PubMed Central

Matczak, W; Chmielnicka, J

1993-01-01

For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr VI). Total Cr content of fumes varied from 0.1 to 7.4%. The distribution of particular Cr compounds was: 52.6% soluble Cr (including 50.7% Cr VI), 65.5% total Cr VI, and 11.4% insoluble Cr VI. The results obtained indicate that MMA/SS welding is a process that could be highly hazardous to human health. Evaluation of occupational exposure has shown that MMA/SS welders may exceed the admissible concentrations of soluble and insoluble Cr VI forms as well as of Mn and Ni. In the plants investigated the sum of the ratios of concentrations of particular welding fumes in the breathing zone of welders exceeded corresponding maximum allowable concentration values by 24 times (including 17 times for total Cr VI). Due to the variety and changeability of particular parameters occurring in the working environment, the composition of MMA/SS welding fumes (in the welder's breathing zone) is so variable that it is not possible to assess the exposure by means of one universal exposure indicator (maximum additive hygienic limit value). The evaluation should be based on the results of measurements of concentrations of particular elements in welding fumes. PMID:8457491

Phase Evolution and Properties of Al2CrFeNiMo x High-Entropy Alloys Coatings by Laser Cladding

NASA Astrophysics Data System (ADS)

Wu, Wei; Jiang, Li; Jiang, Hui; Pan, Xuemin; Cao, Zhiqiang; Deng, Dewei; Wang, Tongmin; Li, Tingju

2015-10-01

A series of Al2CrFeNiMo x ( x = 0 to 2.0 at.%) high-entropy alloys coatings was synthesized on stainless steel by laser cladding. The effect of Mo content on the microstructures and mechanical properties of Al2CrFeNiMo x coatings was studied. The results show that the laser clad layer consists of the cladding zone, bonding zone, and heat-affected zone. The Al2CrFeNiMo x coatings are composed of two simple body-center cubic phases and the cladding zone is mainly composed of equiaxed grains. When the content of Mo reaches 2 at.%, a eutectic structure is found in the interdendritic regions. The surface microhardness of the Al2CrFeNiMo2 coating is 678 HV, which is about three times higher than that of the substrate (243 HV). Compared with stainless steel, the wear resistance of the coatings has been improved greatly. The wear mass loss of the Al2CrFeNiMo alloy is 9.8 mg, which is much less than that of the substrate (18.9 mg) and its wear scar width is the lowest among the Al2CrFeNiMo x coatings, indicating that the wear resistance of the Al2CrFeNiMo is the best.

The ZONMET thermodynamic and kinetic model of metal condensation

NASA Astrophysics Data System (ADS)

Petaev, Michail I.; Wood, John A.; Meibom, Anders; Krot, Alexander N.; Keil, Klaus

2003-05-01

The ZONMET model of metal condensation is a FORTRAN computer code that calculates condensation with partial isolation-type equilibrium partitioning of the 19 most abundant elements among 203 gaseous and 488 condensed phases and growth in the nebula of a zoned metal grain by condensation from the nebular gas accompanied by diffusional redistribution of Ni, Co, and Cr. Of five input parameters of the ZONMET model (chemical composition of the system expressed as the dust/gas [ D/ G] ratio, nebular pressure [ Ptot], isolation degree [ξ], cooling rate ( CR), and seed size), only two—the D/ G ratio and the CR of the nebular source region of a zoned Fe,Ni grain—are important in determining the grain radius and Ni, Co, and Cr zoning profiles. We found no evidence for the supercooling during condensation of Fe,Ni metal that is predicted by the homogeneous nucleation theory. The model allows estimates to be made of physicochemical parameters in the CH chondrite nebular source regions. Modeling growth and simultaneous diffusional redistribution of Ni, Co, and Cr in the zoned metal grains of CH chondrites reveals that the condensation zoning profiles were substantially modified by diffusion while the grains were growing in the nebula. This means that previous estimates of the physicochemical conditions in the nebular source regions of CH and CB chondrites, based on measured zoning profiles of Ni, Co, Cr, and platinum group elements in Fe,Ni metal grains, need to be corrected. The two zoned metal grains in the PAT 91456 and NWA 470 CH chondrites studied so far require nebular source regions with different chemical compositions ( D/ G = 1 and D/ G = 4, respectively) and thermal histories characterized by variable cooling rates ( CR = 0.011 + 0.0022 × Δ T K/h and CR = 0.05 + 0.0035 × Δ T K/h, respectively). It appears that the metal grains of the CH chondrites were formed in multiple nebular source regions or in different events within the same source region as the CB chondrite metal grains were formed.

Ca ISOTOPE EFFECTS IN ORGUEIL LEACHATES AND THE IMPLICATIONS FOR THE CARRIER PHASES OF {sup 54}Cr ANOMALIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moynier, Frederic; Podosek, Frank A.; Brannon, Joyce

Primitive meteorites contain small {sup 40}Ca excesses, in addition to rare anomalies in {sup 48}Ca. Refractory inclusions from Vigarano and Allende have larger {sup 40}Ca and resolvable {sup 48}Ca anomalies. These results imply that Ca isotopic heterogeneities were still present in the early solar system at both the mineral and whole-rock scale. The absence of correlated Ca isotope anomalies in leachates from the CI1 chondrite Orgueil containing large {sup 54}Cr anomalies has implications on the origin of the Cr anomalies. {sup 54}Cr has to be produced either in massive stars during s-process nucleosynthesis without accompanying {sup 48}Ca or in particularmore » zones in the rare Type Ia supernovae. In the latter case, {sup 54}Cr has been produced in a zone predominantly enriched in Cr and {sup 54}Cr and not mixed with other zones, or {sup 54}Cr has been produced together with other neutron-rich nuclides and there has been subsequent decoupling of this material in the star, in the solar system, or in the laboratory.« less

The effects of thermomechanical processing and annealing on the microstructural evolution and stress corrosion cracking of alloy 690

NASA Astrophysics Data System (ADS)

Miller, Cody A.

The effects of short-range order (SRO), long-range order (LRO), and plastic strain on the microstructure and stress corrosion cracking (SCC) susceptibility of Ni-Cr-Fe Alloy 690 have been investigated in detail. First, the presence of 1/3{422} and 1/2{311} diffuse intensities in B=[111] and B=[112] selected area diffraction patterns (SADPs), previously believed to indicate the presence of SRO, has been examined in Alloy 690, a Ni-Cr binary alloy, and a number of FCC materials in an effort to determine their source. It is shown that these intensities are not due to SRO, although their source remains somewhat unclear. However, an experiment was conducted that tracked the strong {111} reflections in a B=[112] SADP as the sample was tilted (19°) towards a B=[111] zone axis. Significantly, it was noted that the {111} intensities never fully disappear and that they fall in the 1/3{422} positions within the B=[111] SADP. This indicates that these diffuse intensities are related to reflections that lie in the first order Laue zone (FOLZ) when the zone is aligned along B=[111], although theoretical calculations indicate scattering from these planes into the zero order Laue zone used to form the SADP should not occur. Thus, while calculations are inconsistent with the behavior expected, the diffuse intensities observed in a number of high index zones are consistent with projections of higher order Laue zone reflections into the zero layer, suggesting that the theory is in need of reassessment. Second, the stability of the gamma'-Ni2Cr LRO phase present on the Ni-Cr phase diagram was examined in a Ni-55Cr binary alloy. The results indicate that the gamma'-Ni2Cr phase is indeed metastable, and that the two-phase gamma-Ni + alpha-Cr phase field extends all the way to room temperature. Likewise, the sluggish formation of the gamma'-Ni 2Cr phase appears to occur only over a narrow composition and temperature range. It is speculated that this important phase in more complex alloys is also metastable and its metastability should be considered in applications involving long-term, high temperature exposures. Third, the effects of thermomechanical processing and long-term aging on the microstructural evolution and SCC susceptibility of Alloy 690 were examined in detail. It is shown that cold working and subsequent aging have large impacts on the microstructures observed and on the mechanical properties, and it is these changes that are related to the differences in SCC behavior. Most importantly, it is shown that the very high work hardening in Alloy 690 leads to large increases in yield strength that appear to overshadow the more subtle variations in carbide distributions at grain boundaries and prior coherent twin boundaries, and that SCC initiation is difficult if not impossible under static loading conditions. Based on these observations, it is concluded that the long-term concerns by industry of SCC initiation in Alloy 690 in the thermally-treated condition can probably be ignored unless there are regions where the alloy has been significantly hardened mechanically and the material will undergo some type of dynamic loading.

Microstructure and Thermal History of Metal Particles in CH Chondrites

NASA Technical Reports Server (NTRS)

Goldstein, J. I.; Jones, R. H.; Kotula, P. G.; Michael, J. R.

2005-01-01

Fe-Ni metal particles with smooth Ni, Co, and Cr zoning patterns, 8-13 wt.% Ni in the center of the particle to 3-5 wt% Ni at the rim, have been identified in several CR-clan (CH, Bencubbinlike, and CR) chondrites. These zoning patterns are broadly consistent with an origin by gas-solid condensation in the solar nebula at temperatures between approximately 1500 to 1300 K and fast cooling rates, 2 to 25 K/day. Apparently, this condensate metal was not melted during chondrule formation or affected significantly in the solid-state by alteration during parent body processing. Consideration of diffusional redistribution of Ni, Co, Cr and siderophile elements have further constrained the calculated condensation temperatures and cooling rates of the zoned condensates. These condensate metals have irregular shapes and vary in size from 50 to 350 m as revealed in some detail by optical and SEM techniques. In addition to zoned condensate particles, other types of metal particles have been observed. These include zoned condensates with exsolution-precipitates, unzoned homogeneous metal with no exsolution precipitates, unzoned metal exhibiting exsolution precipitates and high Ni metal grains.

[Mechanical properties of weld area soldered by lasers and structural changes in hot reaction zone].

PubMed

Wu, H; Cui, Y; Mu, W

2001-05-01

To analyse and measure the welding depths and strengths of three kinds of welding materials under different laser welding conditions as well as the structural changes of the heat affected zone. Under different voltages and pulse duration three kinds of measuring sticks, including Co-Cr alloy, Ni-Cr alloy and pure titanium were welded and their strengths were compared with that of control group. At the same time, the structure of the heat-affected zone was analysed by means of the gold-phase method. The welding depth and strength of Co-Cr alloy were in direct proportion to the setting voltage, with averages of 335MPa (250V) to 573MPa(330V). At the heat-affected zone, the crystal particle was small and the end point of welding by laser bean presented the shape of the mountain peak and the interval of finger shape. The center of measuring sticks had a black zone with the circle shape. The setting voltage was in direct proportion to the welding depth of pure titanium and in inverse proportion to the welding strength with averages of 221MPa(250V) to 154MPa (330V). The crystal particle in the heat affected zone grew large and the solid phase expanded, the interval of the crystal oxidised, and the structure showed honeycomb changes. The laser welding is favourable to the welding properties of Co-Cr and Ni-Cr alloys, but its effect on the welding properties of pure titanium needs further discussion.

Laboratory investigations of the effects of nitrification-induced acidification on Cr cycling in vadose zone material partially derived from ultramafic rocks

USGS Publications Warehouse

Mills, Christopher T.; Goldhaber, Martin B.

2012-01-01

Sacramento Valley (California, USA) soils and sediments have high concentrations of Cr(III) because they are partially derived from ultramafic material. Some Cr(III) is oxidized to more toxic and mobile Cr(VI) by soil Mn oxides. Valley soils typically have neutral to alkaline pH at which Cr(III) is highly immobile. Much of the valley is under cultivation and is both fertilized and irrigated. A series of laboratory incubation experiments were conducted to assess how cultivation might impact Cr cycling in shallow vadose zone material from the valley. The first experiments employed low (7.1 mmol N per kg soil) and high (35 mmol N kg− 1) concentrations of applied (NH4)2SO4. Initially, Cr(VI) concentrations were up to 45 and 60% greater than controls in low and high incubations, respectively. After microbially-mediated oxidation of all NH4+, Cr(VI) concentrations dropped below control values. Increased nitrifying bacterial populations (estimated by measurement of phospholipid fatty acids) may have increased the Cr(VI) reduction capacity of the vadose zone material resulting in the observed decreases in Cr(VI). Another series of incubations employed vadose zone material from a different location to which low (45 meq kg− 1) and high (128 meq kg− 1) amounts of NH4Cl, KCl, and CaCl2 were applied. All treatments, except high concentration KCl, resulted in mean soil Cr(VI) concentrations that were greater than the control. High concentrations of water-leachable Ba2 + (mean 38 μmol kg− 1) in this treatment may have limited Cr(VI) solubility. A final set of incubations were amended with low (7.1 mmol N kg− 1) and high (35 mmol N kg− 1) concentrations of commercial liquid ammonium polyphosphate (APP) fertilizer which contained high concentrations of Cr(III). Soil Cr(VI) in the low APP incubations increased to a concentration of 1.8 μmol kg− 1 (5 × control) over 109 days suggesting that Cr(III) added with the APP fertilizer was more reactive than naturally-occurring soil Cr(III).

Compositional and mineralogical zoning by inward crystallization of mafic magma: evidence from the Guwoon hornblende gabbro-diorite Complex, Hwacheon, Korea.

NASA Astrophysics Data System (ADS)

Park, Y.-R.; Kim, G.-Y.

2009-04-01

The small body, ca. 1.3 by 1.6km, of a hot-air ballon shape hornblende gabbro - diorite Complex, in Gowoonri, Hwacheon, Korea consists of marginal diorite and central hornblende gabbro. The volumetrically dominant hornblende gabbro in the core of the Complex shows a zoned distribution with three layers distinguished by different dominant mafic mineral phases. From the margin toward the core of the hornblende gabbro body, the domintant mafic minerals change from amphibole phenocryst of nearly rounded shape in cross section with pyroxene pseudomorph through prismatic shape of amphibole to polycrystalline biotite aggregates. Systematic variations in geochemical characteristics among three distinct zones of hornblende gabbro body are also observed. From the outer zone toward the core, major oxides such as MnO, MgO, and CaO show a decreasing tendency, whereas total FeO/(total FeO + MgO) value shows an increasing tendency. Concentrations of trace elements also show systematic variations. Where incompatible elements such as Ba and Th increase, compatible elements like Cr and Sc decrease from the margin toward the core. The zonal distribution divided by change in dominant mafic mineral phase from pyroxene through amphibole to biotite, and systematic compositional changes in both major and trace elements from the outer zone toward the core of the hornblende gabbro body suggest that an inward crystallization mechanism played a major role in the formation of the hornblende gabbro in Guwoonri, Hwacheon, Korea.

Cortisol, Testosterone, and Prospective Risk for War-zone Stress-Evoked Depression.

PubMed

Cobb, Adam R; Josephs, Robert A; Lancaster, Cynthia L; Lee, Han-Joo; Telch, Michael J

2018-04-27

The major challenges of efforts to reveal biological risk factors and biomarkers of depression include the complexity of underlying systems, interactions with other systems, and contextual factors governing their expression. Altered endocrine function is believed to be a central contributor to depressive illness, but across studies, evidence for a link between endocrine markers and depression has been mixed, inconclusive, or conditional in nature. In the present study, we evaluated basal testosterone (T), cortisol (C), and CO2 inhalation-stress-reactivity measures of these hormones (TR, CR) as pre-deployment moderators of the later impact of war-zone stressors on depression symptoms in-theater. At pre-deployment, U.S. soldiers (N = 120) completed demographic, clinical and hormone measures, and during deployment, they completed monthly, web-based assessments of war-zone stressors and depression symptoms (N = 533 observations). Mixed effects models estimated the effects of the pre-deployment hormone profiles in moderating war-zone stressors' impact on in-theater depression. Models also tested whether hormonally linked risk for later stress-evoked depression depends on pre-existing depression. Controlling for pre-deployment depression, high T was protective; whereas TR had depressogenic effects that were amplified by pre-deployment depression. Further, high C was protective, but heightened CR was depressogenic, but only among those with elevated pre-deployment depression. Findings highlight the importance of examining basal and reactivity measures of endocrine function, and use of prospective, longitudinal models to test hypothesized causal pathways associated with depression vulnerability in the war-zone. Results also suggest that pre-existing depression and cortisol may work in tandem to increase vulnerability for later stress-evoked depression in the war-zone.

Thermobarometric constraints on mid-Cretaceous to late Cretaceous metamorphic events in the western metamorphic belt of the Coast Mountains complex near Petersburg, southeastern Alaska

USGS Publications Warehouse

Himmelberg, Glen R.; Brew, David A.

2005-01-01

The western metamorphic belt is part of the Coast Mountains Complex of southeastern Alaska and western Canada. This complex formed as a result of mid-Cretaceous through middle Eocene crustal shortening between the previously amalgamated Wrangellia and Alexander terranes (Insular superterrane) and previously accreted terranes of the North American continental margin (Intermontane superterrane). The western metamorphic belt, which ranges from a few kilometers to several tens of kilometers in width, records a complex sequence of contact-metamorphic and regional metamorphic events, the most significant of which are designated M1R, M2C-R, and M3R. The M1R regional metamorphic event ranged in grade from subgreenschist to greenschist facies and was overprinted by the M2C-R and M3R metamorphic events. The M2C-R metamorphic event is recorded in discrete contact-metamorphic aureoles and regional metamorphic-mineral assemblages related to tonalite-granodiorite plutons of the Admiralty-Revillagigedo plutonic belt. The M3R metamorphic belt, which is adjacent to the M2C-R belt, is characterized by regional Barrovian isograds of garnet, staurolite, kyanite, and sillimanite. Using the THERMOCALC program, pressure-temperature (P-T) conditions for the M2C-R metamorphic event are estimated to be in the ranges 5.3-7.5 kbars and 525-640 deg.C and for the M3R metamorphic event in the ranges 9.4-12.6 kbars and 730-895 deg.C. The M2C-R metamorphic event occurred at approximately 90 Ma, but the timing of the M3R metamorphic event is poorly documented and uncertain. On the basis of an 40Ar/39Ar age on actinolitic amphibole and a Sm-Nd age on garnet core, the timing of metamorphism might be constrained between 90+/-1 and 80+/-9 Ma, although the Sm-Nd age of 80+/-9 m.y. possibly reflects postpeak growth. Thermobarometric data suggest that the two events occurred at different crustal levels and followed different P-T paths. No evidence exists that M2C-R metamorphic-mineral assemblages were overprinted by the M3R metamorphic event, as proposed by some workers. Juxtaposition of the two belts of rocks probably occurred along the Coast shear zone during uplift and exhumation of the Coast Mountains.

Chromium-rich lawsonite in high-Cr eclogites from the Făgăras Massif (South Carpathians)

NASA Astrophysics Data System (ADS)

Negulescu, E.; Săbău, G.

2012-12-01

Lawsonite is a relatively rare phase in natural rocks, because of its thermal decomposition during exhumation, and Cr-bearing lawsonite being restricted to only a few occurrences worldwide. Here we report Cr-lawsonite in eclogites hosted in a medium-grade metamorphic complex. Several high-Cr eclogite lenses occur in the Topolog Complex (Făgăras Massif) of dominantly gneissic-amphibolitic composition. High Cr contents are the result of emerald-green mm-sized nodules containing Cr-rich minerals, embedded in a gray-green matrix of kyanite, clinopyroxene, garnet, amphibole, zoisite, and rutile. Garnets occur as porphyroblasts or in coronas around clinopyroxene aggregates probably replacing former magmatic pyroxene. Relict gabbroic textures (sometimes pegmatoid) and whole rock geochemistry indicate a gabbroic cumulate origin. The REE pattern, displaying a slight positive Eu anomaly and a tea spoon-shaped LREE depletion is also indicative of a cumulate origin, as also noted by Pe Piper & Piper (2002) for the Othrys gabbro (as well as others in the Vourinos and Pindos ophiolitic suites) with the same unusual REE-pattern. The emerald-green Cr-rich nodules are unevenly distributed in the rock, and always enclosed in Cr-rich clinopyroxenes (up to 5.46% Cr2O3) which may exhibit Cr-diffusion haloes towards normal Cr-free matrix pyroxene. The nodules consist of diablastic chromite, rutile and Cr-rich kyanite of up to 15.67 wt% Cr2O3, Cr-bearing epidote, to which Cr-rich staurolite (up to 10.45% Cr2O3; XMg up to 0.68) and Cr-rich lawsonite (up to 9.17% Cr2O3) may exceptionally associate. Cr concentrations in kyanite and lawsonite are, to our knowledge, the highest reported so far. Cr-lawsonite was identified in a single sample, as small single phase inclusions armoured in Cr-kyanite. Equilibrium PT-conditions of 2.6 GPa and 610o C were derived from the garnet-mantled clinopyroxene aggregates using multi-equilibria calculation with the PTGIBBS routine of Brandelik & Massonne (2004). These conditions fall still inside the stability field of lawsonite, below the thermal breakdown of this phase (Pawley, 1994), and consistent with its metastable persistence as armoured relics, during a near-isobaric late stage heating episode recorded in eclogites from the same structural setting (Săbău & Negulescu, 2006). Acknowledgements Financial support by grant PN-II-ID-PCE-2011-3-0030 Romanian Executive Unit for Financing Higher Education, Research, Development and Innovation. Prof. Hans-Joachim Masonne kindly provided access to the analytical facilities at Institut für Mineralogie und Kristallchemie in Stuttgart. References Brandelik, A., Massonne, H.-J. (2004). PTGIBBS - an Excel™ Visual Basic program for computing and visualizing thermodynamic functions and equilibria of rock-forming minerals. Computers and Geosciences 30, 909-923. Pawley, A. (1994) The pressure and temperature stability limits of lawsonite: Implication for H2O recycling in subduction zones. Contrib. Mineral. Petrol. 118, 99-108. Săbău, G., Negulescu, E. (2006) Metamorphic forming and evolution conditions of the eclogites in the Topolog Complex, Făgăras Mountains. Romanian Journal of Petrology 78, 39-46.

Stratification of welding fumes and grinding particles in a large factory hall equipped with displacement ventilation.

PubMed

Niemelä, R; Koskela, H; Engström, K

2001-08-01

The purpose of the study was to investigate the performance of displacement ventilation in a large factory hall where large components of stainless steel for paper, pulp and chemical industries were manufactured. The performance of displacement ventilation was evaluated in terms of concentration distributions of welding fumes and grinding particles, flow field of the supply air and temperature distributions. Large differences in vertical stratification patterns between hexavalent chromium (Cr(VI)) and other particulate contaminants were observed. The concentration of Cr(VI) was notably lower in the zone of occupancy than in the upper part of the factory hall, whereas the concentrations of total airborne particles and trivalent chromium (Cr(III)) were higher in the occupied zone than in the upper zone. The stratification of Cr(VI) had the same tendency as the air temperature stratification caused by the displacement flow field.

Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: a potential source of geogenic Cr(VI) to groundwater

USGS Publications Warehouse

Mills, Christopher T.; Morrison, Jean M.; Goldhaber, Martin B.; Ellefsen, Karl J.

2011-01-01

Concentrations of geogenic Cr(VI) in groundwater that exceed the World Health Organization’s maximum contaminant level for drinking water (50 μg L−1) occur in several locations globally. The major mechanism for mobilization of this Cr(VI) at these sites is the weathering of Cr(III) from ultramafic rocks and its subsequent oxidation on Mn oxides. This process may be occurring in the southern Sacramento Valley of California where Cr(VI) concentrations in groundwater can approach or exceed 50 μg L−1. To characterize Cr geochemistry in the area, samples from several soil auger cores (approximately 4 m deep) and drill cores (approximately 25 m deep) were analyzed for total concentrations of 44 major, minor and trace elements, Cr associated with labile Mn and Fe oxides, and Cr(VI). Total concentrations of Cr in these samples ranged from 140 to 2220 mg per kg soil. Between 9 and 70 mg per kg soil was released by selective extractions that target Fe oxides, but essentially no Cr was associated with the abundant reactive Mn oxides (up to ~1000 mg hydroxylamine-reducible Mn per kg soil was present). Both borehole magnetic susceptibility surveys performed at some of the drill core sites and relative differences between Cr released in a 4-acid digestion versus total Cr (lithium metaborate fusion digestion) suggest that the majority of total Cr in the samples is present in refractory chromite minerals transported from ultramafic exposures in the Coast Range Mountains. Chromium(VI) in the samples studied ranged from 0 to 42 μg kg−1, representing a minute fraction of total Cr. Chromium(VI) content was typically below detection in surface soils (top 10 cm) where soil organic matter was high, and increased with increasing depth in the soil auger cores as organic matter decreased. Maximum concentrations of Cr(VI) were up to 3 times greater in the deeper drill core samples than the shallow auger cores. Although Cr(VI) in these vadose zone soils and sediments was only a very small fraction of the total solid phase Cr, they are a potentially important source for Cr(VI) to groundwater. Enhanced groundwater recharge through the vadose zone due to irrigation could carry Cr(VI) from the vadose zone to the groundwater and may be the mechanism responsible for the correlation observed between elevated Cr(VI) and NO3- source concentrations in previously published data for valley groundwaters. Incubation of a valley subsoil showed a Cr(VI) production rate of 24 μg kg−1 a−1 suggesting that field Cr(VI) concentrations could be regenerated annually. Increased Cr(VI) production rates in H+-amended soil incubations indicate that soil acidification processes such as nitrification of ammonium in fertilizers could potentially increase the occurrence of geogenic Cr(VI) in groundwater. Thus, despite the natural origin of the Cr, Cr(VI) generation in the Sacramento Valley soils and sediments has the potential to be influenced by human activities.

Geochemistry and petrogenesis of serpentinite from the Ingalls ophiolite complex, central Cascades, Washington

NASA Astrophysics Data System (ADS)

MacDonald, J. H., Jr.; Milliken, S. H.; Zalud, K. M.

2017-12-01

The Jurassic Ingalls ophiolite complex is located in the central Cascades, Washington State. This ophiolite predominantly consists of three variably serpentinized mantle units. Serpentinite occurs as massive replacing peridotite, or as highly sheared fault zones cutting other rocks. Mylonitic serpentinite forms a large-scale mélange in the middle of the ophiolite, and is interpreted as a fracture zone. Whole-rock and mineral geochemistry of the massive serpentinite was done to understand the metasomatic process and identify the possible protoliths of these rocks. Whole-rock major and trace elements of the massive serpentinite are similar to modern peridotites. The majority of samples analyzed are strongly serpentinized, while a few were moderately to weakly altered. Ca, Mg, and Al suggest these rocks formed from serpentinized harzburgite and dunite with minor lherzolite. All samples have positive Eu/Eu*. Serpentinites plot in fields defined by modern abyssal and forearc peridotites. Trace elements suggests the protoliths underwent variable amounts of mantel depletion (5-20%). Serpentine and relic igneous minerals were analyzed by EPMA at the Florida Center for Analytical Electron Microscopy. The serpentine dose not chemically display brucite mixing, has minor substitution of Fe, Ni, and Cr for Mg, and minor Al substitution for Si. Bastites have higher Ni than replaced olivine. Mineral chemistry, high LOI, and X-ray diffraction suggest lizardite is the primary serpentine polymorph, with minor chrysotile also occurring. Relic Al-chromite and Cr-spinel commonly have Cr-magnetite rims. These relic cores have little SiO2 and Fe3+, suggesting the spinels are well preserved. Most spinels plot in overlap fields defined by abyssal and arc peridotite, while two samples plot entirely in arc fields. Relic olivine have Fo90 to Fo92 and plot along the mantle array. Relic pyroxene are primarily enstatite, with lesser high-Ca varieties. Relic minerals plot near fields defined by harzburgite, dunite, and lherzolite from unaltered Ingalls peridotite. The massive serpentinite likely formed by low T (< 300°C), and possibly low pressure, hydrothermal alteration of harzburgite, dunite and lherzolite. The protoliths were variably depleted mantle residues from a possible supra-subduction zone setting.

Chromium(IV)–Peroxo Complex Formation and Its Nitric Oxide Dioxygenase Reactivity

PubMed Central

Yokoyama, Atsutoshi; Han, Jung Eun; Cho, Jaeheung; Kubo, Minoru; Ogura, Takashi; Siegler, Maxime A.; Karlin, Kenneth D.; Nam, Wonwoo

2012-01-01

The O2 and NO reactivity of a Cr(II) complex bearing a 12-membered tetraazamacrocyclic TMC ligand, [CrII(12-TMC)(Cl)]+ (1), and the NO reactivity of its peroxo derivative, [CrIV(12-TMC)(O2)(Cl)]+ (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [CrIII(14-TMC)(O2)(Cl)]+, a Cr(IV)-peroxo complex (2) is formed in the reaction of 1 and O2. Full spectroscopic and X-ray analysis reveals that 2 possesses a side-on η2-peroxo ligation. A quantitative reaction of 2 with NO affords a reduction in Cr oxidation state and production of a Cr(III)-nitrato complex, [CrIII(12-TMC)(NO3)(Cl)]+ (3). The latter is suggested to form via a Cr(III)-peroxynitrite intermediate. A Cr(II)-nitrosyl complex, [CrII(12-TMC)(NO)(Cl)]+ (4), derived from 1 andNO could also be synthesized; however, it does not react with O2. PMID:22950528

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Hot Ductility Behaviors in the Weld Heat-Affected Zone of Nitrogen-Alloyed Fe-18Cr-10Mn Austenitic Stainless Steels

NASA Astrophysics Data System (ADS)

Moon, Joonoh; Lee, Tae-Ho; Hong, Hyun-Uk

2015-04-01

Hot ductility behaviors in the weld heat-affected zone (HAZ) of nitrogen-alloyed Fe-18Cr-10Mn austenitic stainless steels with different nitrogen contents were evaluated through hot tension tests using Gleeble simulator. The results of Gleeble simulations indicated that hot ductility in the HAZs deteriorated due to the formation of δ-ferrite and intergranular Cr2N particles. In addition, the amount of hot ductility degradation was strongly affected by the fraction of δ-ferrite.

Reactions of a Chromium(III)-Superoxo Complex and Nitric Oxide That Lead to the Formation of Chromium(IV)-Oxo and Chromium(III)-Nitrito Complexes

PubMed Central

Yokoyama, Atsutoshi; Cho, Kyung-Bin

2013-01-01

The reaction of an end-on Cr(III)-superoxo complex bearing a 14-membered tetraazamacrocyclic TMC ligand, [CrIII(14-TMC)(O2)(Cl)]+, with nitric oxide (NO) resulted in the generation of a stable Cr(IV)-oxo species, [CrIV(14-TMC)(O)(Cl)]+, via the formation of a Cr(III)-peroxynitrite intermediate and homolytic O-O bond cleavage of the peroxynitrite ligand. Evidence for the latter comes from EPR spectroscopy, computational chemistry, and the observation of phenol nitration chemistry. The Cr(IV)-oxo complex does not react with nitrogen dioxide (NO2), but reacts with NO to afford a Cr(III)-nitrito complex, [CrIII(14-TMC)(NO2)(Cl)]+. The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally. PMID:24066924

Chromium distribution in an Amazonian river exposed to tannery effluent.

PubMed

de Sousa, Eduardo Araujo; Luz, Cleber Calado; de Carvalho, Dario Pires; Dorea, Caetano Chang; de Holanda, Igor Bruno Barbosa; Manzatto, Ângelo Gilberto; Bastos, Wanderley Rodrigues

2016-11-01

This study aims to evaluate the Cr concentrations in surface water, suspended particles, and bottom sediments exposed to tannery effluent releases in the Candeias River. Cr concentrations were compared in relation to environmental thresholds imposed by United States Environmental Protection Agency (USEPA) and the Brazilian Environmental Council (CONAMA), and the geoaccumulation index (Igeo) was calculated in bottom sediment. Samples were collected in flood and dry seasons. Cr extraction was done by an acid extraction and quantified by flame atomic absorption spectrometry. Most samples were found to be below the environmental thresholds imposed by CONAMA and USEPA, except in the one from the discharge zone sampled during the dry season, showing values 1.5 and 6.1 higher than CONAMA in water and bottom sediment, respectively. Cr concentrations were significantly higher (P < 0.001) in suspended particles during dry season than flood season. Surface water and bottom sediment did not show significant differences between the seasons. The Igeo revealed an enrichment of Cr in bottom sediments after discharge zone, indicating that the effluent may be contributing to metal accumulation in the sediment. Apparently, the Candeias River shows a wash behavior on the river bottom, leaching the accumulated metal deposited on the riverbed to other areas during the flood pulses, which decreases Cr concentration in the discharge zone during dry seasons. Thus, this behavior can promote Cr dispersion to unpolluted areas.

Complexation humic substances of soils with metal ions as the main way migration of matals from soil to water

NASA Astrophysics Data System (ADS)

Dinu, Marina

2013-04-01

Organic matter (OM) of natural waters can bind with the ions metals (IM) entering the system, thus reducing their toxic properties. OM in water consists predominantly (up to 80%) of humic acids (HA), represented by highmolecular, dyed, polyfunctional compounds. The natural-climatic zones feature various ratios of fulvic (FA) and humic acids. An important specific feature of metals as contamination elements is the fact that when they occur in the environment, their potential toxicity and bioavailability depend significantly on their speciation. In recent years, lakes have been continuously enriched in hazardous elements such as Pb, Cd, Al, and Cr on a global (regional) basis. The most important organic ligands are humic matter (HM) washed out from soils in water and metals occur in natural waters as free ions, simple complexes with inorganic and organic ligands, and mineral and organic particles of molecules and ions sorbed on the surface. The occurrence of soluble metal forms in natural waters depends on the presence of organic and inorganic anions. However, direct determinations are rather difficult. The goal was the calculation and analysis of the forms of metals in the system catchment basin, based on the chemical composition of the water body and the structural features of soil humic substances (HS).We used the following analytical techniques - leaching of humic substances from soil and sample preparation (Orlov DS, 1985), the functional characteristics of humic substances - spectral analysis methods, the definition of conditional stability constants of complexes - electrochemical methods of analysis. Our results show thet HAs of selected soil types are different in functions, and these differences effect substantially the complexing process. When analyzing the results obtained in the course of spectrometric investigation of HMs in selected soil types, we determined the following main HA characteristics: (1) predominance of oxygen bearing groups in HM of the northern taiga soils; (2) similar amounts of oxygen bearing fragments, hydrocarbon constituents, and nitrogen bearing components in the mixed forest zones; (3) occurrence of aromatic and aliphatic hydrocarbons in HM of steppe soils. The HM functional characteristics influence substantially the stability constants of complexes with metal ions and complex stoichiometry: Fe(III)>Cu(II)>Pb(II)>Al(III)>Co(II)>Ni(II)>Cd(II)>Zn(II)>Cr(III)>Mg(II)>Sr(II)>Ca(II)>Mn(II) - northern taiga soils; Cu(II)>Fe(III)>Al(III)>Ni(II)>Zn(II)>Pb(II)>Co(II)>Cd(II)>Sr(II)>Mn(II)>Cr(III)>Ca(II)>Mg(II) - mixed forest zones; Fe(III)>Cu(II)>Al(III)>Pb(II)>Ni(II)>Zn(II)>Co(II)>Ca(II)>Cd(II)>Sr(II)>Mg(II)>Cr(III)>Mn(II) - steppe soils. 1. T.I. Moiseenko, L.P. Kudryavtseva, and N.A. Gashkina, Scattered Element in Surface Land Waters: Technophility, Bioaccumulation, and Ecotoxicology (Nauka, Moscow, 2006) 2. G. M. Varshal, Ext. Abstr. Doct. Dis. Chem. (Inst. Geokh. Analit. Khim. RAN, Moscow, 1994).. 4. D.S. Orlov, Humic Acids (MGU, Moscow, 1986) 5. D.V. Kovalevsky, Ext. Abstr. Cand. Dis. Chem. (MGU, Moscow, 1998). 6. I.A. Linnik and B. I. Nabivanets, Metal Migration Forms in Surface Fresh Waters (Gidrometizdat, Leningrad, 1985) 7. Hartley, F., Burgess, C., and Alcoc, R., Solution Equilibria (Ellis Horwood, Chichester (UK), 1980). 8. Yu. Yu. Lur'e, Reference Book of Physicochemical Values (Nauka, Moscow, 2000)

Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franz, Robert, E-mail: robert.franz@unileoben.ac.at; Mendez Martin, Francisca; Hawranek, Gerhard

2016-03-15

Al{sub x}Cr{sub 1−x} composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N{sub 2}, and O{sub 2} atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N{sub 2} and O{sub 2} atmospheres were nonuniform as a resultmore » of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes.« less

A case of Alzheimer's disease in magmatic crystals

NASA Astrophysics Data System (ADS)

Costa Rodriguez, F.; Bouvet de Maisonneuve, C.

2012-12-01

The reequilibration of chemical zoning in crystals from volcanic rocks is increasingly used to determine the duration of the processes involved in their origin, residence and transport. There now exist a good number of determinations of diffusion coefficients in olivine (Fe-Mg, Mn, Ca, Ni, Cr), plagioclase (CaAl-NaSi, Mg, Sr, Ba, REE), pyroxenes (Fe-Mg, Mn, Ca, REE) and quartz (Ti), but most studies have used a single element or component in a single mineral group. Although this is a good approach, it can only access a limited range of time scales, typically the short-term memory of the crystal. In other words, for process durations that are longer than the combination of the diffusivity and diffusion distance (and for a constant boundary), the long-term memory of the crystal might have been lost. This could explain why most time determinations of magmatic processes from volcanic rocks give times of about < 100 years, and why these are shorter than the thousands of years obtained from U-Th series disequilibrium isotopes. We have done a series of numerical calculations and natural observation to determine the time windows that can be accessed with different elements and minerals, and how they may affect the time scales and interpretations of processes that the crystals might be recording. We have looked at two end-members representative of mafic and silicic magmas by changing the temperature and mineral compositions. 3 dimensional calculations of diffusion reequilibration at the center of a 1 x 0.5 x 0.5 mm crystal and using a constant boundary as first case. We find that for mafic magma and olivine, 90 % of equilibration of Fe-Mg, Mn, and Ni occurs in a few decades, but gradients in Ca and Cr persist for a few thousand years. These results can for example explain the large ranges of Ca and Cr contents at a given Fe/Mg of olivine, and why apparently contradictory times can be obtained from elements with different diffusivities in the same crystal. At the same time these findings also highlight that there is a long-term memory of the crystal that is typically not accessed by current studies. However, unraveling this memory is more complex because it seems unrealistic to assume a constant composition at the boundary for hundreds or thousands of years, and because crystals can be growing and dissolving multiple times. Additional models considering growth and a variable boundary show that a significant part of the memory is lost by multiple changes in concentration being superimposed at the crystal rim. Here we also report a case where accessing the older history of the crystals might be possible by a combination of X-Ray element maps plus multiple element zoning traverses (Fe-Mg, Ca, Mn, Ni, Al, P, Cr) in olivine from Llaima volcano (Chile). Element distributions reveal that the crystals had an early history of fast growth. The delicate structures of P zoning have been used to recognize any crystal dissolution. Cr, Fe-Mg, Ni, Mn are zoned but the times obtained from Cr are 4 x longer than those of the other elements. Our interpretation is that the Cr zoning records the older memory of the crystal since eruption but that of Fe-Mg has lost part of the memory due to multiple changes at the rim or complete homogenization of the crystal. Thus using multiple elements and minerals allow accessing the long and short term memory of the crystals and associated magma.

Mineralogy, composition and PGM of chromitites from Pefki, Pindos ophiolite complex (NW Greece): evidence for progressively elevated fAs conditions in the upper mantle sequence

NASA Astrophysics Data System (ADS)

Kapsiotis, Argirios; Grammatikopoulos, Tassos A.; Tsikouras, Basilios; Hatzipanagiotou, Konstantin; Zaccarini, Federica; Garuti, Giorgio

2011-01-01

The Pindos ophiolite complex, located in the northwestern part of continental Greece, hosts various chromite deposits of both metallurgical (high-Cr) and refractory (high-Al) type. The Pefki chromitites are banded and sub-concordant to the surrounding serpentinized dunites. The Cr# [Cr/(Cr + Al)] of magnesiochromite varies between 0.75 and 0.79. The total PGE grade ranges from 105.9 up to 300.0 ppb. IPGE are higher than PPGE, typical of mantle hosted ophiolitic chromitites. The PGM assemblage in chromitites comprises anduoite, ruarsite, laurite, irarsite, sperrylite, hollingworthite, Os-Ru-Ir alloys including osmium and rutheniridosmine, Ru-bearing oxides, braggite, paolovite, platarsite, cooperite, vysotskite, and palladodymite. Iridarsenite and omeiite were also observed as exsolutions in other PGM. Rare electrum and native Ag are recovered in concentrates. This PGM assemblage is of great petrogenetic importance because it is significantly different from that commonly observed in podiform mantle-hosted and banded crustal-hosted ophiolitic chromitites. PGE chalcogenides of As and S are primary, and possibly crystallized directly from a progressively enriched in As boninitic melt before or during magnesiochromite precipitation. The presence of Ru-bearing oxides implies simultaneous desulfurization and dearsenication processes. Chemically zoned laurite and composite paolovite-electrum intergrowths are indicative of the relatively high mobility of certain PGE at low temperatures under locally oxidizing conditions. The PGM assemblage and chemistry, in conjunction with geological and petrologic data of the studied chromitites, indicate that it is characteristic of chromitites found within or close to the petrologic Moho. Furthermore, the strikingly different PGM assemblages between the high-Cr chromitites within the Pindos massif is suggestive of non-homogeneous group of ores.

Redox transformation and reductive immobilization of Cr(VI) in the Columbia River hyporheic zone sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Fen; Liu, Yuanyuan; Zachara, John

An experimental and modeling study was conducted to investigate the redox transformation and reductive immobilization of groundwater contaminant Cr in hyporheic zone (HZ) sediments from U.S. Department of Energy’s Hanford site, where groundwater Cr(VI) is migrating and discharging to the nearby Columbia River. Experimental results revealed that Cr(VI) can be reduced to immobile reduced Cr by the HZ sediments in the presence/absence of O2. Anaerobic pre-incubation of the sediments increased the effective rate of Cr reduction that was correlated with the increase in HCl-extractable Fe(II) content in the sediments. The reduced Cr was stable in exposure to O2 under field-relevantmore » pH (~7.5) and Mn-containing (~0.02% w/w) conditions. The Cr(VI) reduction rate showed a multi-rate behavior, apparently reflecting the presence of reductants with different reactivity in the sediments. The results from this study indicated that the HZ sediments can reductively immobilize Cr and the sediment redox capacity can be recharged through microbial activities. The results implied that HZ can play a role as a natural permeable redox barrier for removing groundwater Cr before it discharges into a river system.« less

Redox transformation and reductive immobilization of Cr(VI) in the Columbia River hyporheic zone sediments

NASA Astrophysics Data System (ADS)

Xu, Fen; Liu, Yuanyuan; Zachara, John; Bowden, Mark; Kennedy, David; Plymale, Andrew E.; Liu, Chongxuan

2017-12-01

An experimental and modeling study was conducted to investigate the redox transformation and reductive immobilization of groundwater contaminant Cr in hyporheic zone (HZ) sediments from U.S. DOE's Hanford Site, where groundwater Cr(VI) is migrating and discharging to the nearby Columbia River. Experimental results revealed that Cr(VI) can be reduced and immobilized by the HZ sediments in the presence/absence of O2. Anaerobic pre-incubation of the sediments increased the effective rate of Cr reduction that was correlated with the increase in HCl-extractable Fe(II) content in the sediments. The reduced Cr was stable when exposed to O2 under field-relevant pH (7.5) with and without dissolved Mn(II), which might be oxidized to form Mn(III/IV) oxides that may oxidize reduced Cr. The Cr(VI) reduction rate showed a multi-rate behavior, apparently reflecting the presence of reductants with different reactivity in the sediments. The results from this study indicated that the HZ sediments can reductively immobilize Cr and the sediment redox capacity can be recharged through microbial activities. The results implied that HZ can play a role as a natural permeable redox barrier for removing groundwater Cr before it discharges into a river system.

An investigation of passivity and breakdown of amorphous chromium-bromine thin films for surface modification of metallic biomaterials

NASA Astrophysics Data System (ADS)

Cormier, Lyne Mercedes

1998-12-01

The objectives of this investigation of amorphous Cr-B thin films as prospective coatings for biomaterials applications were to (i) produce and characterize an amorphous Cr-B thin film coating by magnetron sputtering, (ii) evaluate its corrosion resistance in physiologically relevant electrolytes, and (iii) propose a mechanism for the formation/dissolution of the passive film formed on amorphous Cr-B in chloride-containing near-neutral salt electrolytes. Dense (zone T) amorphous Cr75B25 thin films produced by DC magnetron sputtering were found to be better corrosion barriers than nanoczystalline or porous (zone 1) amorphous Cr75B25 thin films. The growth morphology and microstructure were a function of the sputtering pressure and substrate temperature, in agreement with the structure zone model of Thornton. The passivity/loss of passivity of amorphous Cr 75B25 in near-neutral salt solutions was explained using a modified bipolar layer model. The chromate ions identified by X-Ray Photoelectron Spectroscopy (XPS) in the outer layer of the passive film were found to play a determinant role in the passive behaviour of amorphous Cr75B 25 thin films in salt solutions. In near-neutral salt solutions of pH = 5 to 7, a decrease in pH combined with an increase in chloride concentration resulted in less dissolution of the Cr75B25 thin films. The apparent breakdown potential at 240 mV (SCE) obtained by Cyclic Potentiodynamic Anodic Polarization (CPAP) was associated with oxidation of species within the passive film, but not to dissolution leading to immediate loss of passivity. Pit Propagation Rate (PPR) testing evaluated the stable pitting potential to be between 600 and 650 mV. Amorphous Cr75B25 thin films ranked the best among other Cr-based materials such as 316L stainless steel, CrB2 and Cr investigated in this study for general corrosion behaviour in NaCl and Hanks solutions by CPAP testing. In terms of corrosion resistance, amorphous Cr75B25 thin films were recognized as a promising material for surface modification of biomaterials.

Comparing anti-hyperglycemic activity and acute oral toxicity of three different trivalent chromium complexes in mice.

PubMed

Li, Fang; Wu, Xiangyang; Zou, Yanmin; Zhao, Ting; Zhang, Min; Feng, Weiwei; Yang, Liuqing

2012-05-01

Three different ligands (rutin, folate and stachyose) of chromium(III) complexes were compared to examine whether they have similar effect on anti-hyperglycemic activity as well as the acute toxicity status. Anti-hyperglycemic activities of chromium rutin complex (CrRC), chromium folate complex (CrFC) and chromium stachyose complex (CrSC) were examined in alloxan-induced diabetic mice with daily oral gavage for a period of 2 weeks at the dose of 0.5-3.0 mg Cr/kg. Acute toxicities of CrRC and CrFC were tested using ICR mice at the dose of 1.0-5.0 g/kg with a single oral gavage and observed for a period of 2 weeks. Biological activities results indicated that only CrRC and CrFC could decrease blood glucose level, reduce the activities of aspartate transaminase, alanine transaminase, alkaline phosphatase, and increase liver glycogen level. In acute toxicity study, LD(50) values for both CrRC and CrFC were above 5.0 g/kg. The minimum lethal dose for CrFC was above 5.0 g/kg, while that for CrRC was 1.0 g/kg. Anti-diabetic activity of those chromium complexes was not similar and their acute toxicities were also different. CrFC represent an optimal chromium supplement among those chromium complexes with potential therapeutic value to control blood glucose in diabetes and non-toxicity in acute toxicity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Heavy metal contamination and ecological risk assessment in the surface sediments of the coastal area surrounding the industrial complex of Gabes city, Gulf of Gabes, SE Tunisia.

PubMed

El Zrelli, Radhouan; Courjault-Radé, Pierre; Rabaoui, Lotfi; Castet, Sylvie; Michel, Sylvain; Bejaoui, Nejla

2015-12-30

In the present study, the concentrations of 6 trace metals (Hg, Cd, Cu, Pb, Cr and Zn) were assessed in the surface sediments of the central coastal area of Gabes Gulf to determine their contamination status, source, spatial distribution and ecological risks. The ranking of metal contents was found to be Zn>Cd>Cr>Pb>Cu>Hg. Correlation analysis indicated that Cd and Zn derived mainly from the Tunisian Chemical Group phosphogypsum. The other pollutants may originate from other industrial wastes. Metallic contamination was detected in the south of chemical complex, especially in the inter-harbor zone, where the ecological risk of surface sediments is the highest, implying potential negative impacts of industrial pollutants. The spatial distribution of pollutants seems to be due to the effect of harbor installations and coastal currents. The metallic pollution status of surface sediments of Gabes Gulf is obvious, very worrying and requires rapid intervention. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cryptic trace-element alteration of Anorthosite, Stillwater complex, Montana

USGS Publications Warehouse

Czamanske, G.K.; Loferski, P.J.

1996-01-01

Evidence of cryptic alteration and correlations among K, Ba, and LREE concentrations indicate that a post-cumulus, low-density aqueous fluid phase significantly modified the trace-element contents of samples from Anorthosite zones I and II of the Stillwater Complex, Montana. Concentrations of Ba, Ca, Co, Cr, Cu, Fe, Hf, K, Li, Mg, Mn, Na, Ni, Sc, Sr, Th, Zn, and the rare-earth elements (REE) were measured in whole rocks and plagioclase separates from five traverses across the two main plagioclase cumulate (anorthosite) zones and the contiguous cumulates of the Stillwater Complex in an attempt to better understand the origin and solidification of the anorthosites. However, nearly the entire observed compositional range for many trace elements can be duplicated at a single locality by discriminating between samples rich in oikocrystic pyroxene and those which are composed almost entirely of plagioclase and show anhedral-granular texture. Plagioclase separates with high trace-element contents were obtained from the pyroxene-poor samples, for which maps of K concentration show plagioclase grains to contain numerous fractures hosting a fine-grained, K-rich phase, presumed to be sericite. Secondary processes in layered intrusions have the potential to cause cryptic disturbance, and the utmost care must be taken to ensure that samples provide information about primary processes. Although plagioclase from Anorthosite zones I and II shows significant compositional variation, there are no systematic changes in the major- or trace-element compositions of plagioclase over as much as 630 m of anorthosite thickness or 18 km of strike length. Plagioclase in the two major anorthosite zones shows little distinction in trace-element concentrations from plagioclase in the cumulates immediately below, between, and above these zones.

Orthopyroxene as a recorder of primitive achondrite petrogenesis: Major-, minor-, and trace-element systematics of orthopyroxene in Lodran. [Abstract only

NASA Technical Reports Server (NTRS)

Papike, J. J.; Spilde, M. N.; Fowler, G. W.; Shearer, C. K.

1994-01-01

Considerable attention has been paid recently to the primitive achondrites because they may form a link between chondrites and more differentiated achondrite meteorites. A recent paper by Miyamoto and Takeda addresses the thermal history of lodranites Yamato 74357 and MAC 88177 as inferred from chemical zoning of pyroxene and olivine determined by electron microprobe analyses. Their results suggested that interstitial melt was present and then extracted. We have taken the analysis of Lodran-type meteorites one step further by incorporating the techniques of Electromagnetic Pulse/Wavelength Dispersive Spectroscopy (EMP/WDS) compositional imaging and scanning ion mass spectroscopy (SIMS) analysis. Orthopyroxene in Lodran is strongly zoned in CaO, Al2O3, TiO2, and Cr2O3 within the last 10-30 microns from the grain boundaries. The rims are reversely zoned in Mg-Fe, exhibiting Mg enrichment, and compositions change from a fairly uniform Wo3En94 within the grains to Wo1En96 at the rims. CaO drops from 1.6 to 0.6 wt% and Al2O3, TiO2, and Cr2O3 exhibit similar depletions. MnO is fairly uniform throughout the grains at around 0.5 wt%. Olivine is also reversely zoned with respect to not only grain boundaries but also to fractures within the grains, giving many olivine grains a complex, patchy zoning pattern. Some of the core-rim trace-element systematics for orthopyroxene are illustrated. Because of the rather narrow zoned rims in Lodran orthopyroxene and the low trace-element abundances, it is difficult to clearly resolve the trace-element systematics. Nevertheless it is evident that the cores are enriched in the incompatible trace elements Ce, Nd, Dy, Er, Yb, Y, and Zr relative to the rims.

A bis(amido) ligand set that supports two-coordinate chromium in the +1, +2, and +3 oxidation states†

PubMed Central

Cai, Irene C.; Lipschutz, Michael I.

2014-01-01

The amido ligand –N(SiiPr3)DIPP (DIPP = 2,6-diisopropylphenyl) has been used to prepare two-coordinate complexes of CrI, CrII, and CrIII. The two-coordinate CrII complex has also been used to prepare a three-coordinate CrIII iodide complex, which can be used to access a stable CrIII methyl species. PMID:25222516

Anion-exchange high-performance liquid chromatography of water-soluble chromium (VI) and chromium (III) complexes in biological materials.

PubMed

Suzuki, Y

1987-04-10

A high-performance anion-exchange liquid chromatograph coupled to visible-range (370 nm) and UV (280 nm) detectors and an atomic-absorption spectrometer allowed the rapid determination of CrVI and/or complexes of CrIII in rat plasma, erythrocyte lysate and liver supernatant treated with CrVI or CrIII in vitro. CrVI in the eluates was determined using both the visible-range detector and atomic-absorption spectrometer (AAS). The detection limits of CrVI in standard solutions using these methods were 2 and 5 ng (signal-to-noise ratio = 2), respectively. Separations of the biological components and of CrIII complexes were monitored by UV and AAS analyses, respectively. Time-related decreases of CrVI accompanied by increases in CrIII complexes were observed, indicating the reduction of CrVI by some of the biological components. The reduction rates were considerably higher in the liver supernatant and erythrocyte lysate than in the plasma. These results indicate that the anion-exchange high-performance liquid chromatographic system is useful for simultaneous determination of CrVI and CrIII complexes in biological materials.

First-Principles Calculations for Chemical Reaction between Sodium Diethyldithiocarbamate and Transition-Metal (Cr) atom to Produce Cr(DDC)3 and Cr(DDC)2ODDC

NASA Astrophysics Data System (ADS)

Setiyanto, Henry; Muhida, Rifki; Kishi, Tomoya; Rempillo, Ofelia; Rahman, Mahmudur; Dipojono, Hermawan Kresno; Di\\ {n}o, Wilson Agerico; Matsumoto, Shigeno; Kasai, Hideaki

2006-10-01

We investigate the chemical reaction between a Cr transition-metal atom and sodium diethyldithiocarbamate (NaDDC), a complexing agent used to detect and extract Cr in human blood samples. Using density-functional-theory-based calculations, we determine their stable structures of Cr(DDC)2ODDC and Cr(DDC)3 complexes and obtain their dissociation energies. We found dissociation energies of -10.66 and -3.24 eV for Cr(DDC)2ODDC and Cr(DDC)3 complexes, respectively. Hence, on the basis of dissociation energies, we have verified that the reaction of NaDDC with Cr produces Cr(DDC)2ODDC as a major product.

Assessment of Trace Metals Concentration in Tree Barks as Indicator of Atmospheric Pollution within Ibadan City, South-West, Nigeria

PubMed Central

Ejidike, Ikechukwu P.; Onianwa, Percy C.

2015-01-01

Tree bark species were randomly collected from 65 sites having different anthropogenic activities, such as industrial, high traffic commercial, residential high and residential low traffic volume areas of Ibadan City, Nigeria. Levels of Cd, Cu, Pb, Zn, Co, and Cr of the dry-ashed bark samples were determined by AAS. The mean metal concentrations (mg kg−1) in samples from industrial zone were found as Pb: 3.67 ± 1.97, Cd: 0.10 ± 0.07, Zn: 30.96 ± 32.05, Cu: 7.29 ± 5.17, Co: 0.91 ± 0.58, and Cr: 2.61 ± 1.84. The trend of mean trace metal concentrations at high traffic commercial zone follows the order: Zn > Pb > Cu > Cr > Co > Cd. Residential high traffic and low traffic zones revealed the same trend as Cd < Co < Cr < Pb < Cu < Zn. Relatively strong positive correlation between the heavy metals at ρ < 0.05, such as Zn versus Cu (r = 0.79) and Co versus Cu (r = 0.77), was observed. The results of the study suggest that tree bark samples could potentially serve as bioindicators for Cu, Pb, Zn, Cr, and possibly Co and Cd. Furthermore, interspecies variation of heavy metal concentrations in plants barks is recommended. PMID:26605104

Element mixing distribution and structure feature of fusion zone in laser welding between different alloys and pure titanium.

PubMed

Wu, Haishu; Liu, Jihong; Liu, Xuecheng; Li, Changyi; Yu, Zhiwei

2002-07-01

To study micro morphology and element-mixing distribution of different alloys welded in laser and analyze the feasibility of laser welding different alloys. Alloys and titanium were matched into 4 groups: Au-Pt with Ni-Cr; Au-Pt with pure Ti; pure Ti with Ni-Cr; Ni-Cr with Co-Cr. They were welded in laser. Changes in metallography after hybridization of crystalline grain, ranges of heat-affected zone and pores were observed through SEM with ultra-thin windowed X-ray energy atlas. Meanwhile 10 testing points were chosen with area of 300 micro m x 900 micro m along the welding surface from the side A alloy to the side B alloy, than the element mixing distribution and tendency were analyzed with X-ray energy atlas. 1. Hybridization of different alloys: (l) in the group of Au-Pt with Ti, there was titanium element mixing into Au-Pt tissue gradually and evenly on the Au-Pt side of the interface without clear boundary and increasing in size of crystalline grain. However, there was titanium crystalline grain increasing in size, irregular morphology and small sacks on the titanium side with clear boundary. (2) in the group of Ni-Cr with Ti, there was mixing regularly, slow transition and interlocks between crystalline grains on the Ni-Cr side of the in terface. Poor transition, clear boundary and small cracks were observed on titanium side. (3) in the group of Co-Cr with Ni-Cr, there was good transition, obscure boundary on both sides resulting from network, cylinder and branch structure growing. 2. Element-mixing distribution of different alloys. In fusion zone, the metal elements in matched groups mixed well and hybridized into new alloys except titanium blocks. The location of wave peak depended on the composition of alloys. Most of elements were from the alloy far from the fusion zone. The hybridization between pure titanium and any other alloys is not good The effect of laser welding different alloys is ideal except with pure titanium.

Zoned Cr, Fe-spinel from the La Perouse layered gabbro, Fairweather Range, Alaska

USGS Publications Warehouse

Czamanske, G.K.; Himmelberg, G.R.; Goff, F.E.

1976-01-01

Zoned spinel of unusual composition and morphology has been found in massive pyrrhotite-chalcopyrite-pent-landite ore from the La Perouse layered gabbro intrusion in the Fairweather Range, southeastern Alaska. The spinel grains show continuous zoning from cores with up to 53 wt.% Cr2O3 to rims with less than 11 wt.% Cr2O3. Their composition is exceptional because they contain less than 0.32 wt.% MgO and less than 0.10 wt.% Al2O3 and TiO2. Also notable are the concentrations of MnO and V2O3, which reach 4.73 and 4.50 wt.%, respectively, in the cores. The spinel is thought to have crystallized at low oxygen fugacity and at temperatures above 900??C, directly from a sulfide melt that separated by immiscibility from the gabbroic parental magma. ?? 1976.

Phosphorus zoning in olivine of Kilauea Iki lava lake, Hawaii

NASA Astrophysics Data System (ADS)

Fabbrizio, Alessandro; Beckett, John R.; Baker, Michael B.; Stolper, Edward M.

2010-05-01

Kilauea Iki lava lake was formed when the lavas of the 1959 summit eruption of Kilauea volcano ponded in Kilauea Iki pit crater, as described by [1]. The main chamber of this lake has been drilled repeatedly from 1960 to 1981 as the lake has cooled and crystallized and partial descriptions of core can be found in [2-7]. The bulk of the core consists of a gray, olivine-phyric basalt matrix [3]. Rapid diffusion of divalent cations through olivine at magmatic temperatures can delete information on early-formed zoning and thus information on early magmatic history, recorded in olivine during its growth, is often largely lost [8-11]. In the last years many studies [8-11] have shown that natural olivine, terrestrial and extraterrestrial, from several localities and rock types can preserve a complex zoning in P (sometimes associated with Cr and Al). Simple crystallization experiments conducted by [10] and [11] were able to replicate these features (i.e., sector and oscillatory zoning). Here, we describe P, Cr and Al zoning in olivine from the 1981 drilling of Kilauea Iki lava lake hole #1 (KI81-1) [6]. Kα X-ray intensity maps and major and minor element quantitative analyses were obtained using the Caltech JEOL JXA-8200 electron microprobe. We acquired P, Cr, Al, Fe and Ti X-ray maps simultaneously at 15 kV and 400 nA, a beam diameter of 1 μm, pixel spacing of 1-2 μm, and count times of 420-1500 msec/step were used depending on the dimension of the crystal. 15 kV and 40 nA with a beam diameter of 1 μm were used to collect quantitative analyses. P2O5 contents of the Iki olivines range from below detection limit to 0.30 wt%. Zoning in phosphorus, based on X-ray intensity maps, was observed in all olivines we examined. The P zoning patterns of the olivines display several styles. P shows oscillatory zoning comparable to that seen in terrestrial and extraterrestrial igneous olivines and in experimentally grown olivine [8-11]; high P regions, inside the crystals, outline low P chambers and P enriched zones were also observed; near the margins of the crystals is possible to find the presence of discontinuous sets of P-enriched bands that generally outline euhedral crystal forms; some crystals are characterized by P-enriched ghosts of relict crystals in their interior that are associated with probable undercooling and/or with an initial pulse of rapid crystal growth [8, 10]. Phenocrysts and microphenocrysts are frequently unzoned in major and minor divalent cations (Fe, Mg, Mn, Ca, Ni), but all are zoned in P. Variations in Cr and Al correlate spatially with P but are much fainter or absents, in some crystal the P-enriched bands are superimposed with small crystals of chromite (≤1 μm) aligned along the P zoning. Probably these chromites were formed by precipitation from the original Cr and Al bands. In no case was observed Ti zoning. [1] Richter D.H. et al. (1970) US Geol Surv Prof Pap 537-E, 73 p. [2] Richter D.H., Moore J.G. (1966) US Geol Surv Prof Pap 537-B, 26 p. [3] Helz R.T. (1980) Bull Volcanol 43-4, 675-701. [4] Helz R.T. et al. (1984) US Geol Surv Open File Rep 84-484, 72 p. [5] Hardee H.C. et al. (1981) Geophys Res Lett 8, 1211-1214. [6] Helz R.T., Wright T.L. (1983) US Geol Surv Open File Rep 83-326, 66 p. [7] Helz R.T. (1987) Geochem Soc Spec Pub 1, 241-258. [8] Beckett J.R. et al. (2008) LPSC abs. 1726. [9] Mccanta M.C. et al. (2008) LPSC abs. 1807. [10] Milmann-Barris M.S. et al. (2008) CMP 155, 739-765. [11] Mccanta M.C. et al. (2008) GCA 72-12, S1, A610.

Partition of heavy metals in a tropical river system impacted by municipal waste.

PubMed

Duc, Trinh Anh; Loi, Vu Duc; Thao, Ta Thi

2013-02-01

A research program was established to identify the governing factors for the partition coefficient (K(D)) of heavy metals between suspended particulate and dissolved phases in the Day River system a tropical, highly alluvial aquatic system, in Vietnam. The targeted river system, draining an urbanized-industrialized catchment where discharged wastewater is mostly untreated, could be separated into the least impacted, pristine area, and the most impacted, polluted area. Organic matter degradation was shown to govern the variation of parameters like total organic carbon, biochemical oxygen demand, chemical oxygen demand, nutrients, conductivity, or redox potential. Heavy metals in both dissolved and particulate phases were enriched in severely polluted area because of wastewater inflow that contains concentrated metals and intensification of metal influx from sediment. Results show log K(D) in the order Mn < As < Zn < Hg < Ni < Cu < Cd < Co < Pb < Cr < Fe and As < Zn < Ni < Mn < Cr < Cu < Co < Fe in the polluted zone and the pristine zone, respectively. A decreasing tendency of partition coefficients of 11 heavy metals considered from the pristine to the impacted zones was observed. Three explanations for the difference are: (1) increase of solubility of most heavy metals in low redox potential, (2) competition for the binding sites with major and minor cations, and (3) complexation with dissolved organic matter concentrated in municipal waste impacted water. Apart from domestic waste impact, statistical analysis has contributed to identify the influence of climate condition and hydrological regime to the partition of heavy metals in the area.

Microstructure and Oxidation of a MAX Phase/Superalloy Hybrid Interface

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita

2014-01-01

Corrosion resistant, strain tolerant MAX phase coatings are of interest for turbine applications. Thin Cr2AlC MAX phase wafers were vacuum diffusion bonded to an advanced turbine disk alloy, LSHR, at 1100 C. The interface, examined by optical and scanning electron microscopy, revealed a primary diffusion zone consisting of 10 micrometers of beta-Ni(Co)Al, decorated with various NiCoCrAl, MC and M3B2 precipitates. On the Cr2AlC side, an additional 40 micrometers Al-depletion zone of Cr7C3 formed in an interconnected network with the beta-Ni(Co)Al. Oxidation of an exposed edge at 800 C for 100 h produced a fine-grained lenticular alumina scale over Cr2AlC and beta-Ni(Co)Al, with coarser chromia granules over the Cr7C3 regions. Subsequent growth of the diffusion layers was only 5 micrometers in total. A residual stress of 500 MPa was estimated for the MAX phase layer, but no interfacial damage was observed. Subsequent tests for 1000 h reveal similar results.

Factors Affecting Impact Toughness in Stabilized Intermediate Purity 21Cr Ferritic Stainless Steels and Their Simulated Heat-Affected Zones

NASA Astrophysics Data System (ADS)

Anttila, Severi; Alatarvas, Tuomas; Porter, David A.

2017-12-01

The correlation between simulated weld heat-affected zone microstructures and toughness parameters has been investigated in four intermediate purity 21Cr ferritic stainless steels stabilized with titanium and niobium either separately or in combination. Extensive Charpy V impact toughness testing was carried out followed by metallography including particle analysis using electron microscopy. The results confirmed that the grain size and the number density of particle clusters rich in titanium nitride and carbide with an equivalent circular diameter of 2 µm or more are statistically the most critical factors influencing the ductile-to-brittle transition temperature. Other inclusions and particle clusters, as well as grain boundary precipitates, are shown to be relatively harmless. Stabilization with niobium avoids large titanium-rich inclusions and also suppresses excessive grain growth in the heat-affected zone when reasonable heat inputs are used. Thus, in order to maximize the limited heat-affected zone impact toughness of 21Cr ferritic stainless steels containing 380 to 450 mass ppm of interstitials, the stabilization should be either titanium free or the levels of titanium and nitrogen should be moderated.

Mechanical characteristics of heterogeneous structures obtained by high-temperature brazing of corrosion-resistant steels with rapidly quenched non-boron nickel-based alloys

NASA Astrophysics Data System (ADS)

Kalin, B.; Penyaz, M.; Ivannikov, A.; Sevryukov, O.; Bachurina, D.; Fedotov, I.; Voennov, A.; Abramov, E.

2018-01-01

Recently, the use rapidly quenched boron-containing nickel filler metals for high temperature brazing corrosion resistance steels different classes is perspective. The use of these alloys leads to the formation of a complex heterogeneous structure in the diffusion zone that contains separations of intermediate phases such as silicides and borides. This structure negatively affects the strength characteristics of the joint, especially under dynamic loads and in corrosive environment. The use of non-boron filler metals based on the Ni-Si-Be system is proposed to eliminate this structure in the brazed seam. Widely used austenitic 12Cr18Ni10Ti and ferrite-martensitic 16Cr12MoSiWNiVNb reactor steels were selected for research and brazing was carried out. The mechanical characteristics of brazed joints were determined using uniaxial tensile and impact toughness tests, and fractography was investigated by electron microscopy.

Percolation of isotopically heterogeneous interstitial melts in the crystal mush of the Rum layered intrusion, NW Scotland

NASA Astrophysics Data System (ADS)

O'Driscoll, B.; Hepworth, L. N.; Daly, J. S.; Gertisser, R.; Emeleus, C. H.

2017-12-01

The cumulate stratigraphy of layered intrusions offers a means of interrogating the replenishment and solidification histories of mafic magma chambers. Cumulates comprise cumulus minerals, which accumulate to form a silicate framework, and intercumulus minerals, which represent melt crystallised within the crystal mush. This fundamental textural distinction lies at the heart of cumulus theory and underpins some of the classic models of crystal-liquid differentiation that are based on layered intrusions. In order to shed further light on the importance of postcumulus processes in layered intrusions, and to demonstrate that crystal mushes may behave as open-systems during the crystallisation of cumulates, we investigated mineral-scale textural and geochemical heterogeneity in Unit 10 of the 60 Ma Rum layered intrusion. Numerous ( 1 mm thick) Cr-spinel seams occur throughout the 65 m Unit 10 peridotite stratigraphy. Unusually, intercumulus plagioclase and clinopyroxene crystals in the peridotite several centimetres above and below these seams exhibit complex optical and major element zoning. Sampling of individual intra-crystal zones in these phases was carried out using a New Wave Micromill, for analysis of their 87Sr/86Sr compositions to be measured on unspiked samples by TIMS. Both minerals reveal intra-crystalline isotopic heterogeneity. The maximum range (with 2σ uncertainties) of 87Sr/86Sr in the Unit 10 plagioclase is 0.704026±17-0.704591±8 and in clinopyroxene is 0.703533±23-0.704517±17. Within a single, oscillatory-zoned plagioclase, three discrete zones yield 87Sr/86Sr values of 0.704337±20, 0.704095±20 and 0.704052±11. A complex patchily-zoned clinopyroxene yields a 87Sr/86Sr range of 0.703533±23-0.703894±23. The new data demonstrate that multiple generations of isotopically distinct melts percolated through the Unit 10 crystal mush, suggesting solidification from cumulates that underwent repeated cycles of resorption and recrystallisation at the postcumulus stage. The cumulate products of layered intrusions may therefore form from magma addition within the crystal mush, and such a process might be especially relevant for precious metal enrichment, given the association between isotopic disequilibrium and the locations of Cr-spinel seams observed here.

Diversity, distribution and quantification of antibiotic resistance genes in goat and lamb slaughterhouse surfaces and meat products.

PubMed

Lavilla Lerma, Leyre; Benomar, Nabil; Knapp, Charles W; Correa Galeote, David; Gálvez, Antonio; Abriouel, Hikmate

2014-01-01

The distribution and quantification of tetracycline, sulfonamide and beta-lactam resistance genes were assessed in slaughterhouse zones throughout meat chain production and the meat products; this study represents the first to report quantitatively monitor antibiotic resistance genes (ARG) in goat and lamb slaughterhouse using a culture independent approach, since most studies focused on individual bacterial species and their specific resistance types. Quantitative PCR (qPCR) revealed a high prevalence of tetracycline resistance genes tetA and tetB in almost all slaughterhouse zones. Sulfonamide resistance genes were largely distributed, while beta-lactam resistance genes were less predominant. Statistical analysis revealed that resistant bacteria, in most cases, were spread by the same route in almost all slaughterhouse zones, except for tetB, blaCTX and blaTEM genes, which occurred in few zones as isolated 'hot spots.' The sum of all analyzed ARG indicated that slaughterhouse surfaces and end products act as reservoirs of ARG, mainly tet genes, which were more prevalent in slaughtering room (SR), cutting room (CR) and commercial meat products (MP). Resistance gene patterns suggest they were disseminated throughout slaughterhouse zones being also detected in commercial meat products, with significant correlations between different sampling zones/end products and total resistance in SR, CR and white room (WR) zones, and also refrigerator 4 (F4) and MP were observed. Strategically controlling key zones in slaughterhouse (SR, CR and WR) by adequate disinfection methods could strategically reduce the risks of ARG transmission and minimize the issues of food safety and environment contamination.

Diversity, Distribution and Quantification of Antibiotic Resistance Genes in Goat and Lamb Slaughterhouse Surfaces and Meat Products

PubMed Central

Lavilla Lerma, Leyre; Benomar, Nabil; Knapp, Charles W.; Correa Galeote, David; Gálvez, Antonio; Abriouel, Hikmate

2014-01-01

The distribution and quantification of tetracycline, sulfonamide and beta-lactam resistance genes were assessed in slaughterhouse zones throughout meat chain production and the meat products; this study represents the first to report quantitatively monitor antibiotic resistance genes (ARG) in goat and lamb slaughterhouse using a culture independent approach, since most studies focused on individual bacterial species and their specific resistance types. Quantitative PCR (qPCR) revealed a high prevalence of tetracycline resistance genes tetA and tetB in almost all slaughterhouse zones. Sulfonamide resistance genes were largely distributed, while beta-lactam resistance genes were less predominant. Statistical analysis revealed that resistant bacteria, in most cases, were spread by the same route in almost all slaughterhouse zones, except for tetB, blaCTX and blaTEM genes, which occurred in few zones as isolated ‘hot spots.’ The sum of all analyzed ARG indicated that slaughterhouse surfaces and end products act as reservoirs of ARG, mainly tet genes, which were more prevalent in slaughtering room (SR), cutting room (CR) and commercial meat products (MP). Resistance gene patterns suggest they were disseminated throughout slaughterhouse zones being also detected in commercial meat products, with significant correlations between different sampling zones/end products and total resistance in SR, CR and white room (WR) zones, and also refrigerator 4 (F4) and MP were observed. Strategically controlling key zones in slaughterhouse (SR, CR and WR) by adequate disinfection methods could strategically reduce the risks of ARG transmission and minimize the issues of food safety and environment contamination. PMID:25479100

Microstructure Evolution During Continuous Cooling in AISI 5140 Steel Processed by Induction Heating Chromizing

NASA Astrophysics Data System (ADS)

Hu, Jianjun; Ma, Chaoping; Yang, Xian; Xu, Hongbin; Guo, Ning; Yu, Hongbing

2017-11-01

In this study, induction heating chromizing (IHC) and box-type furnace heating chromizing (BFHC) were conducted on commercial AISI 5140 steels, respectively. Microstructure, microhardness and wear resistance of the chromized samples were characterized. The results show that the IHC samples have thicker Cr coating layer and stronger interface bond due to pre-compressive stress among the packed powders. Three kinds of microstructures including alloyed cementite (AC-layer), fine pearlite zone (FP-zone) and carbon-poor zone (CP-zone) are formed near the interface in the IHC samples. The main reason given for this is that different contents of Cr and C have different effects on pearlite phase and morphology. The IHC sample shows better wear properties due to its stronger interface bonding strength than that of the BFHC sample. The formation mechanism of CP-zone and its influences on microhardness and wear resistance are also discussed.

Application of Precipitate Free Zone Growth Kinetics to the β-Phase Depletion Behavior in a CoNiCrAlY Coating Alloy: An Analytical Approach

NASA Astrophysics Data System (ADS)

Chen, H.

2018-06-01

This paper concerns the β-phase depletion kinetics of a thermally sprayed free-standing CoNiCrAlY (Co-31.7 pct Ni-20.8 pct Cr-8.1 pct Al-0.5 pct Y, all in wt pct) coating alloy. An analytical β-phase depletion model based on the precipitate free zone growth kinetics was developed to calculate the β-phase depletion kinetics during isothermal oxidation. This approach, which accounts for the molar volume of the alloy, the interfacial energy of the γ/ β interface, and the Al concentration at γ/ γ + β boundary, requires the Al concentrations in the β-phase depletion zone as the input rather than the oxidation kinetics at the oxide/coating interface. The calculated β-phase depletion zones derived from the current model were compared with experimental results. It is shown that the calculated β-phase depletion zones using the current model are in reasonable agreement with those obtained experimentally. The constant compositional terms used in the model are likely to cause the discrepancies between the model predictions and experimental results. This analytical approach, which shows a reasonable correlation with experimental results, demonstrates a good reliability in the fast evaluation on lifetime prediction of MCrAlY coatings.

Application of Precipitate Free Zone Growth Kinetics to the β-Phase Depletion Behavior in a CoNiCrAlY Coating Alloy: An Analytical Approach

NASA Astrophysics Data System (ADS)

Chen, H.

2018-03-01

This paper concerns the β-phase depletion kinetics of a thermally sprayed free-standing CoNiCrAlY (Co-31.7 pct Ni-20.8 pct Cr-8.1 pct Al-0.5 pct Y, all in wt pct) coating alloy. An analytical β-phase depletion model based on the precipitate free zone growth kinetics was developed to calculate the β-phase depletion kinetics during isothermal oxidation. This approach, which accounts for the molar volume of the alloy, the interfacial energy of the γ/β interface, and the Al concentration at γ/γ + β boundary, requires the Al concentrations in the β-phase depletion zone as the input rather than the oxidation kinetics at the oxide/coating interface. The calculated β-phase depletion zones derived from the current model were compared with experimental results. It is shown that the calculated β-phase depletion zones using the current model are in reasonable agreement with those obtained experimentally. The constant compositional terms used in the model are likely to cause the discrepancies between the model predictions and experimental results. This analytical approach, which shows a reasonable correlation with experimental results, demonstrates a good reliability in the fast evaluation on lifetime prediction of MCrAlY coatings.

Safety of trivalent chromium complexes: no evidence for DNA damage in human HaCaT keratinocytes.

PubMed

Hininger, Isabelle; Benaraba, Rachida; Osman, Mireille; Faure, Henri; Marie Roussel, Anne; Anderson, Richard A

2007-06-15

Several studies have demonstrated beneficial effects of supplemental trivalent Cr in subjects with reduced insulin sensitivity with no documented signs of toxicity. However, recent studies have questioned the safety of supplemental trivalent Cr complexes. The objective of this study was to evaluate the cytotoxic and genotoxic potential of the Cr(III) complexes (histidinate, picolinate, and chloride) used as nutrient supplements compared with Cr(VI) dichromate. The cytotoxic and genotoxic effects of the Cr complexes were assessed in human HaCaT keratinocytes. The concentrations of Cr required to decrease cell viability were assessed by determining the ability of a keratinocyte cell line (HaCaT) to reduce tetrazolium dye, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide. DNA damage using the Comet assay and the production of 8-hydroxy-2'-deoxyguanosine were also determined with and without hydrogen peroxide-induced stress. The LC50 for human cultured HaCaT keratinocytes was 50 microM for hexavalent sodium dichromate and more than 120-fold higher for Cr chloride (6 mM) and Cr histidinate (10 mM). For Cr picolinate at saturating concentration (120 microM) the LC50 was not attained. High Cr(III) concentrations, 250 microM Cr as Cr chloride and Cr histidinate and 120 microM Cr picolinate (highest amount soluble in the system), not only did not result in oxidative DNA damage but exhibited protective antioxidant effects when cells were exposed to hydrogen peroxide-induced oxidative stress. These data further support the low toxicity of trivalent Cr complexes used in nutrient supplements.

Chromium Isotopic Monitoring of HRC-Stimulated Bio-containment at the 100H Test Site, Hanford, Washington

NASA Astrophysics Data System (ADS)

Christensen, J. N.; Brown, S. T.; Brodie, E. L.; Chakraborty, R.; Conrad, M. E.; Long, P. E.; Faybishenko, B.; Hazen, T. C.

2007-12-01

Hexavalent Cr (Cr(VI)) groundwater contamination is a common problem in the U.S. associated with industrial activity (e.g. electroplating, tanning, paints, anti-corrosion). In the particular case of the Hanford Site, Washington, chromate was used primarily to inhibit corrosion in nuclear reactor cooling systems. During the active operation of the Hanford Site, disposal of waste water bearing chromate, and accidental releases to the vadose zone resulted in significant groundwater contamination with local concentrations near the Columbia river reaching over 1000 ppb Cr(VI). In an effort to test an effective bio-containment strategy for groundwater Cr(VI), a site was selected between the 100D and 100H reactor areas with modest concentrations (~100 ppb Cr(VI) over the past two decades). A slow-release 13C labeled polylactate amendment (HRCTM, Regenesis, Ltd.) was injected into groundwater within a sandy formation to stimulate bacterial activity in order to produce conditions that promote the reduction of dissolved Cr(VI) to insoluble Cr(III) complexes [1]. Since the injection of HRCTM in August 2004, groundwater Cr(VI) concentration has been locally below 1 ppb, and reducing conditions have been maintained to at least the present time. The isotopic composition of Cr can be fractionated during reduction from Cr(VI) to Cr(III) and so has the potential to be used as a monitor of hexavalent Cr reduction [2, 3]. This would provide a direct signature of Cr(VI) reduction, discernable from simple attenuation by dilution. In order to explore the use of Cr isotopic measurements for evaluating processes of Cr(VI) reduction, we have analyzed a series of samples in space and time for Cr isotopic composition (δ53Cr, permil deviation of sample 53Cr/52Cr from that of SRM970). Groundwater samples came from the HRC injection well, from multiple depths of three down-gradient wells, and from an up-gradient well. Samples from down-gradient wells have Cr that is isotopically fractionated relative to samples from the up-gradient well. Taken together, samples from a single sampling campaign yield an apparent fractionation of 2.2 ‰. Cr isotopic measurements of the latest samples (June, 2007) confirm continued reduction of Cr(VI) nearly three years after the introduction of HRCTM, suggesting the long-term effectiveness of this bio-stimulated containment strategy. [1] http://esd.lbl.gov/ERT/hanford100h/ [2] Ellis, AS, Johnson, TM and Bohlen, TD (2002) Science. 295:2060-2062. [3] Johnson, TM and Bohlen, TD (2004) Reviews in Mineralogy and Geochemistry, Vol. 55, p.289-317.

Redox and complexation chemistry of the CrVI/CrV-D-glucaric acid system.

PubMed

Mangiameli, María Florencia; González, Juan Carlos; Bellú, Sebastián; Bertoni, Fernando; Sala, Luis F

2014-06-28

When an excess of uronic acid over Cr(VI) is used, the oxidation of D-glucaric acid (Glucar) by Cr(VI) yields D-arabinaric acid, CO2 and Cr(III)-Glucar complex as final redox products. The redox reaction involves the formation of intermediate Cr(IV) and Cr(V) species. The reaction rate increases with [H(+)] and [substrate]. The experimental results indicated that Cr(IV) and Cr(V) are very reactive intermediates since their disappearance rates are much faster than Cr(VI). Cr(IV) and Cr(V) intermediates are involved in fast steps and do not accumulate in the redox reaction of the mixture Cr(VI)-Glucar. Kinetic studies show that the redox reaction between Glucar and Cr(VI) proceeds through a mechanism combining one- and two-electron pathways: Cr(VI) → Cr(IV) → Cr(II) and Cr(VI) → Cr(IV) → Cr(III). After the redox reaction, results show a slow hydrolysis of the Cr(III)-Glucar complex into [Cr(OH2)6](3+). The proposed mechanism is supported by the observation of free radicals, CrO2(2+) (superoxo-Cr(III) ion) and oxo-Cr(V)-Glucar species as reaction intermediates. The continuous-wave electron paramagnetic resonance, CW-EPR, spectra show that five-coordinate oxo-Cr(V) bischelates are formed at pH ≤ 4 with the aldaric acid bound to oxo-Cr(V) through the carboxylate and the α-OH group. A different oxo-Cr(V) species with Glucar was detected at pH 6.0. The high g(iso) value for the last species suggests a mixed coordination species, a five-coordinated oxo-Cr(V) bischelate with one molecule of Glucar acting as a bi-dentate ligand, using the 2-hydroxycarboxylate group, and a second molecule of Glucar with any vic-diolate sites. At pH 7.5 only a very weak EPR signal was observed, which may point to instability of these complexes. This behaviour contrasts with oxo-Cr(V)-uronic species, and must thus be related to the Glucar acyclic structure. In vitro, our studies on the chemistry of oxo-Cr(V)-Glucar complexes can provide information on the nature of the species that are likely to be stabilized in vivo.

Apoptosis of lymphocytes in the presence of Cr(V) complexes: role in Cr(VI)-induced toxicity.

PubMed

Vasant, C; Balamurugan, K; Rajaram, R; Ramasami, T

2001-08-03

Cr(VI) compounds have been declared as a potent occupational carcinogen by IARC (1990) through epidemiological studies among workers in chrome plating, stainless-steel, and pigment industries. Studies relating to the role of intermediate oxidation states such as Cr(V) and Cr(IV) in Cr(VI)-induced carcinogenicity are gaining importance. In this study, issues relating to toxicity elicited by Cr(V) have been addressed and comparisons made with those relating to Cr(VI) employing human peripheral blood lymphocytes. Lymphocytes have been isolated from heparinized blood by Ficoll-Hypaque density gradient centrifugation and exposed to Cr(V) complexes viz. sodium bis(2-ethyl-2-hydroxybutyrato)oxochromate(V), Na[Cr(V)O(ehba)(2)], 1 and sodium bis(2-hydroxy-2-methylbutyrato)oxochromate(V), Na[Cr(V)O(hmba)(2)], 2 and Cr(VI). The phytohemagglutinin (PHA)-induced proliferation of lymphocytes has been found to be inhibited by the two complexes of Cr(V) and chromate Cr(VI) in a time- and concentration-dependent manner. Viability of cells decreases in the presence of Cr(V). Apoptosis appears to be the mode of cell death in the presence of both Cr(V) and Cr(VI). Pretreatment of cells with antioxidants before exposure to chromium(V) complexes reverse apoptosis partially. Possibility for the formation and implication of reactive oxygen species in Cr(V)-induced apoptosis of human lymphocyte cells has been indicated in this investigation. The intermediates of Cr(V) and radical species in the biotoxic pathways elicited by Cr(VI) seems feasible. Copyright 2001 Academic Press.

Preparation of multilayered nanocrystalline thin films with composition-modulated interfaces

NASA Astrophysics Data System (ADS)

Biro, D.; Barna, P. B.; Székely, L.; Geszti, O.; Hattori, T.; Devenyi, A.

2008-06-01

The properties of multilayer thin film structures depend on the morphology and structure of interfaces. A broad interface, in which the composition is varying, can enhance, e.g., the hardness of multilayer thin films. In the present experiments multilayers of TiAlN and CrN as well as TiAlN, CrN and MoS 2 were studied by using unbalanced magnetron sputter sources. The sputter sources were arranged side by side on an arc. This arrangement permits development of a transition zone between the layers, where the composition changes continuously. The multilayer system was deposited by one-fold oscillating movement of substrates in front of sputter sources. Thicknesses of layers could be changed both by oscillation frequency and by the power applied to sputter sources. Ti/Al: 50/50 at%, pure chromium and MoS 2 targets were used in the sputter sources. The depositions were performed in an Ar-N 2 mixture at 0.22 Pa working pressure. The sputtering power of the TiAl source was feed-back adjusted in fuzzy-logic mode in order to avoid fluctuation of the TiAl target sputter rate due to poisoning of the target surface. Structure characterization of films deposited on <1 0 0> Si wafers covered by thermally grown SiO 2 was performed by cross-sectional transmission electron microscopy. At first a 100 nm thick Cr base layer was deposited on the substrate to improve adhesion, which was followed by a CrN transition layer. The CrN transition layer was followed by a 100 nm thick TiAlN/CrN multilayer system. The TiAlN/CrN/MoS 2 multilayer system was deposited on the surface of this underlayer system. The underlayer systems Cr, CrN and TiAlN/CrN were crystalline with columnar structure according to the morphology of zone T of the structure zone models. The column boundaries contained segregated phases showing up in the under-focused TEM images. The surface of the underlayer system was wavy due to dome-shaped columns. The nanometer-scaled TiAlN/CrN/MoS 2 multilayer system followed this waviness. Crystallinity of the TiAlN and CrN layers in the multilayer system decreases with increasing thickness of the MoS 2 layer.

Effect of alkaline precipitation on Cr species of Cr(III)-bearing complexes typically used in the tannery industry.

PubMed

Wang, Dandan; Ye, Yuxuan; Liu, Hui; Ma, Hongrui; Zhang, Weiming

2018-02-01

Various organic compounds extensively used in the leather industry could influence the performance of alkaline precipitation with Cr(III). This study focused on two typical Cr(III)-bearing complexes (Cr(III)-collagen and Cr(III)-citrate) ubiquitous in tannery effluent yet with distinct treatment efficiencies, as Cr(III) was much more difficult to remove in the Cr(III)-citrate solution. Comprehensive analytical methods were employed to explore the intrinsic mechanism. It was found that a lower removal efficiency towards Cr(III) was significantly associated with higher oligomers. The molecular size of the Cr(III)-citrate complex continued to increase with rising pH, making it larger overall than Cr(III)-collagen species. The growing oligomer moiety of dissolved Cr(III)-complex species could persist in the stronger basic pH range, leading to the large amount of residual Cr(III) in the Cr(III)-citrate system. Combining this result with potentiometric titration and X-ray photoelectron spectroscopy data, it was believed that the polymeric species other than monomers facilitated resisting the attack from hydroxide ions, and the postulated Cr(III)-citrate species towards higher oligomers were discovered. Beyond that, both charge neutralization and sweeping effects were presented among the gradually emerging flocs in the Cr(III)-collagen system together with the electric double layer compression effect derived from salinity, thus resulting in a larger floc size and higher Cr(III) removal efficiency in saline solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of a two-domain binding site for the urokinase-type plasminogen activator-plasminogen activator inhibitor-1 complex in low-density-lipoprotein-receptor-related protein.

PubMed

Andersen, O M; Petersen, H H; Jacobsen, C; Moestrup, S K; Etzerodt, M; Andreasen, P A; Thøgersen, H C

2001-07-01

The low-density-lipoprotein-receptor (LDLR)-related protein (LRP) is composed of several classes of domains, including complement-type repeats (CR), which occur in clusters that contain binding sites for a multitude of different ligands. Each approximately 40-residue CR domain contains three conserved disulphide linkages and an octahedral Ca(2+) cage. LRP is a scavenging receptor for ligands from extracellular fluids, e.g. alpha(2)-macroglobulin (alpha(2)M)-proteinase complexes, lipoprotein-containing particles and serine proteinase-inhibitor complexes, like the complex between urokinase-type plasminogen activator (uPA) and the plasminogen activator inhibitor-1 (PAI-1). In the present study we analysed the interaction of the uPA-PAI-1 complex with an ensemble of fragments representing a complete overlapping set of two-domain fragments accounting for the ligand-binding cluster II (CR3-CR10) of LRP. By ligand blotting, solid-state competition analysis and surface-plasmon-resonance analysis, we demonstrate binding to multiple CR domains, but show a preferential interaction between the uPA-PAI-1 complex and a two-domain fragment comprising CR domains 5 and 6 of LRP. We demonstrate that surface-exposed aspartic acid and tryptophan residues at identical positions in the two homologous domains, CR5 and CR6 (Asp(958,CR5), Asp(999,CR6), Trp(953,CR5) and Trp(994,CR6)), are critical for the binding of the complex as well as for the binding of the receptor-associated protein (RAP) - the folding chaperone/escort protein required for transport of LRP to the cell surface. Accordingly, the present work provides (1) an identification of a preferred binding site within LRP CR cluster II; (2) evidence that the uPA-PAI-1 binding site involves residues from two adjacent protein domains; and (3) direct evidence identifying specific residues as important for the binding of uPA-PAI-1 as well as for the binding of RAP.

Deformation behavior of laser welds in high temperature oxidation resistant Fe-Cr-Al alloys for fuel cladding applications

NASA Astrophysics Data System (ADS)

Field, Kevin G.; Gussev, Maxim N.; Yamamoto, Yukinori; Snead, Lance L.

2014-11-01

Ferritic-structured Fe-Cr-Al alloys are being developed and show promise as oxidation resistant accident tolerant light water reactor fuel cladding. This study focuses on investigating the weldability and post-weld mechanical behavior of three model alloys in a range of Fe-(13-17.5)Cr-(3-4.4)Al (wt.%) with a minor addition of yttrium using modern laser-welding techniques. A detailed study on the mechanical performance of bead-on-plate welds using sub-sized, flat dog-bone tensile specimens and digital image correlation (DIC) has been carried out to determine the performance of welds as a function of alloy composition. Results indicated a reduction in the yield strength within the fusion zone compared to the base metal. Yield strength reduction was found to be primarily constrained to the fusion zone due to grain coarsening with a less severe reduction in the heat affected zone. For all proposed alloys, laser welding resulted in a defect free weld devoid of cracking or inclusions.

Effect of the Platinum Electroplated Layer Thickness on the Coatings' Microstructure

NASA Astrophysics Data System (ADS)

Zagula-Yavorska, Maryana; Gancarczyk, Kamil; Sieniawski, Jan

2017-03-01

CMSX 4 and Inconel 625 superalloys were coated by platinum layers (3 and 7 μm thick) in the electroplating process. The heat treatment of platinum layers (at 1,050 ˚C for 2 h) was performed to increase platinum adherence to the superalloys substrate. The diffusion zone obtained on CMSX 4 superalloy (3 and 7 μm platinum thick before heat treatment) consisted of two phases: γ-Ni(Al, Cr) and (Al0.25Pt0.75)Ni3. The diffusion zone obtained on Inconel 625 superalloy (3 μm platinum thick before heat treatment) consisted of the α-Pt(Ni, Cr, Al) phase. Moreover, γ-Ni(Cr, Al) phase was identified. The X-ray diffraction (XRD) results revealed the presence of platinum in the diffusion zone of the heat-treated coating (7 μm platinum thick) on Inconel 625 superalloy. The surface roughness parameter Ra of heat-treated coatings increased with the increase of platinum layers thickness. This was due to the unequal mass flow of platinum and nickel.

Detrital Cr-spinel in the Šambron-Kamenica Zone (Slovakia): evidence for an ocean-spreading zone in the Northern Vardar suture?

NASA Astrophysics Data System (ADS)

Lenaz, Davide; Mazzoli, Claudio; Spišiak, Jan; Princivalle, Francesco; Maritan, Lara

2009-03-01

The Šambron-Kamenica Zone is situated on the northern margin of the Levočské vrchy mountains and Šarišskà vrchovina Highland, where the Central Carpathian Paleogene joins the Pieniny Klippen Belt. Sandstone outcrops in this area. From Cretaceous to Late Oligocene in age, these sediments suggest transport directions from S and SE. The heavy mineral assemblages of this sandstone include Cr-spinel grains, mainly displaying types II and III alpine-peridotite affinities, and are representative of Ocean Island Basalt volcanism. A sample from Upper Eocene sediments at Vit’az shows a clear change in Cr-spinel composition, which turns out to have types I and II peridotite affinities, and to derive from arc and Middle Ocean Ridge Basalt volcanism, with sediment transport directions from SW and WSW. These data indicate major variations in the Upper Eocene tectonic setting, giving constraints to paleogeographic reconstruction of the Slovak Central Carpathians.

The decay of triple systems

NASA Astrophysics Data System (ADS)

Martynova, A. I.; Orlov, V. V.

2014-10-01

Numerical simulations have been carried out in the general three-body problem with equal masses with zero initial velocities, to investigate the distribution of the decay times T based on a representative sample of initial conditions. The distribution has a power-law character on long time scales, f( T) ∝ T - α , with α = 1.74. Over small times T < 30 T cr ( T cr is the mean crossing time for a component of the triple system), a series of local maxima separated by about 1.0 T cr is observed in the decay-time distribution. These local peaks correspond to zones of decay after one or a few triple encounters. Figures showing the arrangement of these zones in the domain of the initial conditions are presented.

Addition of DNA to CrVI and Cytochrome b5 Containing Proteoliposomes Leads to Generation of DNA Strand Breaks and CrIII Complexes

PubMed Central

Borthiry, Griselda R.; Antholine, William E.; Myers, Judith M.; Myers, Charles R.

2009-01-01

Chromium (Cr) is a cytotoxic metal that can be associated with a variety of types of DNA damage, including Cr-DNA adducts and strand breaks. Prior studies with purified human cytochrome b5 and NADPH :P450 reductase in reconstituted proteoliposomes (PLs) demonstrated rapid reduction of CrVI (hexavalent chromium, as CrO42− ), and the generation of CrV, superoxide (O2·−) , and hydroxyl radical (HO˙). Studies reported here examined the potential for the species produced by this system to interact with DNA. Strand breaks of purified plasmid DNA increased over time aerobically, but were not observed in the absence of O2. CrV is formed under both conditions, so the breaks are not mediated directly by CrV. The aerobic strand breaks were significantly prevented by catalase and EtOH, but not by the metal chelator diethylenetriaminepentaacetic acid (DTPA), suggesting that they are largely due to HO˙ from Cr-mediated redox cycling. EPR was used to assess the formation of Cr-DNA complexes. Following a 10-min incubation of PLs, CrO42− , and plasmid DNA, intense EPR signals at g = 5.7and g = 5.0 were observed. These signals are attributed to specific CrIII complexes with large zero field splitting (ZFS). Without DNA, the signals in the g = 5 region were weak. The large ZFS signals were not seen, when CrIIICl3 was incubated with DNA, suggesting that the CrIII–DNA interactions are different when generated by the PLs. After 24 h, a broad signal at g = 2 is attributed to CrIII complexes with a small ZFS. This g = 2 signal was observed without DNA, but it was different from that seen with plasmid. It is concluded that EPR can detect specific CrIII complexes that depend on the presence of plasmid DNA and the manner in which the CrIII is formed. PMID:18729091

Morphology and composition of spinel in Pu'u 'O'o lava (1996-1998), Kilauea volcano, Hawaii

USGS Publications Warehouse

Roeder, P.L.; Thornber, C.; Poustovetov, Alexei; Grant, A.

2003-01-01

The morphology and composition of spinel in rapidly quenched Pu'u 'O'o vent and lava tube samples are described. These samples contain glass, olivine phenocrysts (3-5 vol.%) and microphenocrysts of spinel (~0.05 vol.%). The spinel surrounded by glass occurs as idiomorphic octahedra 5-50 μm in diameter and as chains of octahedra that are oriented with respect to each other. Spinel enclosed by olivine phenocrysts is sometimes rounded and does not generally form chains. The temperature before quenching was calculated from the MgO content of the glass and ranges from 1150oC to 1180oC. The oxygen fugacity before quenching was calculated by two independent methods and the log f O2 ranged from -9.2 to -9.9 (delta QFM=-1). The spinel in the Pu'u'O'o samples has a narrow range in composition with Cr/(Cr+Al)=0.61 to 0.73 and Fe2+/(Fe2++Mg) =0.46 to 0.56. The lower the calculated temperature for the samples, the higher the average Fe2+/(Fe2++Mg), Fe3+ and Ti in the spinel. Most zoned spinel crystals decrease in Cr/(Cr+Al) from core to rim and, in the chains, the Cr/(Cr+Al) is greater in the core of larger crystals than in the core of smaller crystals. The occurrence of chains and hopper crystals and the presence of Cr/(Cr+Al) zoning from core to rim of the spinel suggest diffusion-controlled growth of the crystals. Some of the spinel crystals may have grown rapidly under the turbulent conditions of the summit reservoir and in the flowing lava, and the crystals may have remained in suspension for a considerable period. The rapid growth may have caused very local (μm) gradients of Cr in the melt ahead of the spinel crystal faces. The crystals seem to have retained the Cr/(Cr+Al) ratio that developed during the original growth of the crystal, but the Fe2+/(Fe2++Mg) ratio may have equilibrated fairly rapidly with the changing melt composition due to olivine crystallization. Six of the samples were collected on the same day at various locations along a 10-km lava tube and the calculated pre-collection temperatures of the samples show a 5oC drop with distance from the vent. The average Fe2+/(Fe2++Mg) of the spinel in these samples shows a weak positive correlation with decreasing MgO in the glass of these samples. The range in Cr2O3 (0.041-0.045 wt.%) of the glass for these six samples is too small to distinguish a consistent change along the lava tube. The spinel in the Pu'u 'O'o samples shows a zoning trend in a Cr-Al-Fe3+ diagram almost directly away from the Cr apex. This compares with a zoning trend in rapidly quenched MORB samples away from Cr coupled with decreasing Fe3+. The trend away from Cr displayed by spinel in rapidly quenched samples is in marked contrast to the trend of increasing Fe3+ shown by spinel in slowly cooled lava. 

Chromium isotope fractionation in ferruginous sediments

NASA Astrophysics Data System (ADS)

Bauer, Kohen W.; Gueguen, Bleuenn; Cole, Devon B.; Francois, Roger; Kallmeyer, Jens; Planavsky, Noah; Crowe, Sean A.

2018-02-01

Ferrous Fe is a potent reductant of Cr(VI), and while a number of laboratory studies have characterized Cr isotope fractionation associated with Cr(VI) reduction by ferrous iron, the expression of this fractionation in real-world ferrous Fe-rich environments remains unconstrained. Here we determine the isotope fractionation associated with Cr(VI) reduction in modern ferrous Fe-rich sediments obtained from the previously well studied Lake Matano, Indonesia. Whole core incubations demonstrate that reduction of Cr(VI) within ferruginous sediments provides a sink for Cr(VI) leading to Cr(VI) concentration gradients and diffusive Cr(VI) fluxes across the sediment water interface. As reduction proceeded, Cr(VI) remaining in the overlying lake water became progressively enriched in the heavy isotope (53Cr), increasing δ53Cr by 2.0 ± 0.1‰ at the end of the incubation. Rayleigh distillation modelling of the evolution of Cr isotope ratios and Cr(VI) concentrations in the overlying water yields an effective isotope fractionation of εeff = 1.1 ± 0.2‰ (53Cr/52Cr), whereas more detailed diagenetic modelling implies an intrinsic isotope fractionation of εint = 1.80 ± 0.04‰. Parallel slurry experiments performed using anoxic ferruginous sediment yield an intrinsic isotope fractionation of εint = 2.2 ± 0.1‰. These modelled isotope fractionations are corroborated by direct measurement of the δ53Cr composition on the upper 0.5 cm of Lake Matano sediment, revealing an isotopic offset from the lake water of Δ53Cr = 0.21-1.81‰. The data and models reveal that effective isotope fractionations depend on the depth at which Cr(VI) reduction takes place below the sediment water interface-the deeper the oxic non-reactive zone, the smaller the effective fractionation relative to the intrinsic fractionation. Based on the geochemistry of the sediment we suggest the electron donors responsible for reduction are a combination of dissolved Fe(II) and 0.5 M HCl extractable (solid phase) Fe(II). Our results are in line with the range of intrinsic fractionation factors observed for such phases in previous laboratory studies. We suggest that intrinsic isotope fractionations of around 1.8‰, may be broadly characteristic of ferruginous environments, but we note that the partitioning of ferrous Fe between dissolved and solid phases may modulate this value. These results indicate that seawater δ53Cr is only captured with high-fidelity by ferruginous sediments when oxygen penetration, and therefore the upper boundary of the zone of Cr(VI) reduction, extends to more than 10 cm below the sediment-water-interface, as can be the case in sediments deposited below oligotrophic waters. In more productive regions, with thinner oxic zones, ferruginous sediments would record δ53Cr as much as 1.8‰ lower than seawater δ53Cr. This implies that a range of sediment δ53Cr compositions, that include that of the igneous silicate earth (ISE), are possible even when seawater is isotopically heavier than the ISE.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Density Functional Study for Chemical Reaction between Cr and Fe with Sodium Diethyldithiocarbamate (NaDDC)

NASA Astrophysics Data System (ADS)

Setiyanto, Henry; Muhida, Rifki; Kishi, Tomoya; Rahman, Md. Mahmudur; Dipojono, Hermawan K.; Diño, Wilson A.; Matsumoto, Shigeno; Kasai, Hideaki

Analytical chemistry in the perspective of ab initio molecular orbital calculation is introduced by investigating the chemical reaction between transition metals Cr and Fe with sodium diethyldithiocarbamate (NaDDC), a complexing agent to detect and extract Cr in human blood sample. Using density functional theory—based calculations, we determine the stable structure of the Cr-DDC and Fe-DDC complexes and obtain its dissociation energies. We found dissociation energy values of -3.24 and -2.67 eV for Cr and Fe complexes, respectively; and hence the formation of the former complex is more favorable than the formation of the latter.

Evidence of the impacting body of the Ries crater - the discovery of Fe-Cr-Ni veinlets below the crater bottom

USGS Publications Warehouse

El, Goresy A.; Chao, E.C.T.

1976-01-01

Fe-Cr-Ni particles and veinlets have been discovered in the top 15 m of the compressed zone with abundant shatter cones below the bottom of the Ries crater. The metallic particles are less than a few microns across. They occur in various minerals along healed intergranular and locally in intragranular microfractures in quartz diorite, amphibolite and chloritized granite of the basement crystalline rocks. The particles consist of major Fe, Cr, and Ni with minor Si and Ca. Origin due to contamination is absolutely ruled out. We believe that these Fe-Cr-Ni particles are probably condensed from the vaporized impacting body which produced the Ries crater. These particles were injected with high velocity into microfractures near the top of the compressed zone, implanted in and across various minerals before these microfractures were resealed. The presence of Si and Ca as well as the fact that the Cr content is nearly twice that of Ni, led us to conclude that the Ries impacting body is very likely not an iron meteorite but a stony meteorite. ?? 1976.

Anion Photoelectron Spectroscopic Studies of NbCr(CO)_n- (n = 2,3) Heterobimetallic Carbonyl Complexes

NASA Astrophysics Data System (ADS)

Baudhuin, Melissa A.; Boopalachandran, Praveenkumar; Leopold, Doreen

2015-06-01

Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)2- and NbCr(CO)3- complexes prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities (± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr-, which have formal bond orders of 5.5 (2Δ) and 6 (1σ+), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950–1050°C

DOE PAGES

Jalowicka, A.; Duan, R.; Huczkowski, P.; ...

2015-09-25

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni–Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950–1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. In the case of oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbidemore » and nitride but also of the Ni-W rich M 6C. The width of the M 6C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M 23C 6 in the specimen core. Moreover, with increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.« less

Cr(VI) Occurrence and Geochemistry in Water From Public-Supply Wells in California

DOE PAGES

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.; ...

2015-08-18

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950-1050°C

NASA Astrophysics Data System (ADS)

Jalowicka, A.; Duan, R.; Huczkowski, P.; Chyrkin, A.; Grüner, D.; Pint, B. A.; Unocic, K. A.; Quadakkers, W. J.

2015-11-01

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni-Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950-1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. The oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbide and nitride but also of the Ni-W rich M6C. The width of the M6C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M23C6 in the specimen core. With increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.

Cr(VI) occurrence and geochemistry in water from public-supply wells in California

USGS Publications Warehouse

Izbicki, John; Wright, Michael; Seymour, Whitney A.; McCleskey, R. Blaine; Fram, Miranda S.; Belitz, Kenneth; Esser, Bradley K.

2015-01-01

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH ≥ 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.

Photodynamic therapy and fluorescent diagnostics of head and neck cancer with second-generation photosensitizers

NASA Astrophysics Data System (ADS)

Vakulovskaya, Elena G.

2005-08-01

Photodynamic Therapy (PDT) and fluorescent diagnostics (FD) using Photosense was provided in 50 patients with head and neck cancer T1-3 stage, in 89 patients with skin cancer, using Radaclorine (RC) in 42 patients with T1-4 stage basal cell carcinoma (BCC),in 6 patients with oral cancer. Detection of borders of tumor, intensity of accumulation of photosensitizers in tumor, normal tissues were done by Spectral-fluorescent Complex. We"ve got fluorescence o fa 11 tumors and additional fluorescence zones were found with cytological verification. We used semiconductive lasers: Milon - h = 660+2nm, light dose 200 - 300 J/cm2 and Biospec (h=672+2nm), multiple laser surface and interstitial irradiation with total 1 ight d ose till 4 00-600 Ji cm2. A fter P DT with P S in head and neck cancer we"ve had complete response (CR) in 66.0% and partial response (PR) in 30.0%, with RC CR in BCC T1- 2NOMO - 92.9%, in recurrrencies CR - 60,6%, PR - 39,4%. The efficacy of PDT with PS was higher (CR - 86.7%, PR - 13,3%) and the recurrence rate in 6 months lower. Our experience show pronounced efficacy of PDT for head and neck tumors of different localization and histology, FD is providing diagnostically significant information, demonstrated high sensitivity and specificity.

Neutral complexes as oxidants for the reduced form of parsley (Petroselinum crispum) [2Fe--2S] ferredoxin. Evidence for partial blocking by redox-inactive Cr(III) complexes.

PubMed Central

Adzamli, I K; Kim, H O; Sykes, A G

1982-01-01

The 1 : 1 reactions of three neutral Co(III) oxidants, Co(acac)3, Co(NH3)3(NO2)3 and Co(acac)2(NH3)(NO2), with reduced parsley (Petroselinum crispum) [2Fe--2S] ferredoxin (which carries a substantial negative charge), have been studied at 25 degrees C, pH 8.0 (Tris/HCl), I0.10 (NaCl). Whereas it has previously been demonstrated that with Co(NH3)6+ as oxidant the reaction if completely blocked by redox-inactive Cr(NH3)63+, the neutral oxidants are only partially blocked by this same complex. The effects of three Cr(III) complexes, Cr(NH3)63+%, Cr(en)33+ and (en)2Cr . mu(OH,O2CCH3) . CR(en)24+ have been investigated. Kinetic data for the response of 3+, neutral, as well as 1--oxidants to the presence of 3+ (and 4+) Cr(III) complexes can now be rationalized in terms of a single functional site on the protein for electron transfer. Electrostatics have a significant influence on association at this site. PMID:7115307

Metal ion complex formation in small lakes of the Western Siberian Arctic zone

NASA Astrophysics Data System (ADS)

Kremleva, Tatiana; Dinu, Marina

2017-04-01

The paper is based on joint investigation of the Tyumen State University (Russia, Tyumen) and the Geochemistry and Analytical Chemistry Vernadsky Institute of Russian Academy of Sciences (Moscow, Russia) during 2012-2014 period. It presents the results of research of chemical composition of about 70 small lakes located in the area of tundra and northern taiga of West Siberia (Russia, Yamal-Nenets and Khanty-Mansi Autonomous Districts of the Tyumen region). The investigation includes determination of different parameters of natural water samples: • content of trace elements (Al, Fe, Mn, Cr, Cu, Ni, Zn, Cd, Co, Pb, etc., total more than 60 elements) by emission method with an inductively coupled plasma (ICP-MS) using mass spektrometrometre Element 2 equipment; • content of inorganic and total carbon (TIC and TC) by elemental analysis and the difference between the total and inorganic carbon gives the organic carbon content (TOC); • pH value by potentiometric method; • content of basic ions (Na+, Ca2+, K+, Mg2+, NH4+, Cl-, SO42-, NO3-, PO43-) by ion chromatography. Determination of the chemical composition of samples was conducted in the accredited laboratory according to standard procedures with regular quality control of results. Heavy metals in natural waters can exist in various forms: free (hydrated) ions bound in complexes with organic or inorganic ligands, as well as in the form of suspensions. The form of metal existence has a significant influence on their availability to transport in aquatic organisms. Metal ions associated in stable complexes with organic substances are considered less toxic. From the previous investigations state that the most stable complexes are ligands with organic ions Fe3+, Al3+. The main conclusion of the present research states that if the total content of aluminum, iron and manganese ions (meq/dm3) is equal to or greater than the concentration of dissolved organic carbon (TOC, mg/dm3) in lakes water other heavy metals will be predominantly in free, ionic or bound form with inorganic ligands. This state means paradox consequence that the increase of dissolved Fe content will lead to toxicity rise of other elements having less affinity to organic material. For surface waters of Western Siberian Arctic zone this situation is quite common. The total concentration of iron and aluminum ions in most lakes of tundra and northern taiga zones is approximately equal to water complexing ability. From the other side humic substances participation in inactivation of other more toxic metals (Cu, Pb, Cd, Cr, Ni et al.) will be poor. Arctic part of Western Siberia undergoes significant anthropogenic load due to extensive oil and gas recovery in this zone. Surface waters of Western Siberia are characterized by high natural content of iron, aluminum and copper ions and anthropogenic load of heavy metals makes the situation more serious.

The Wenquan ultramafic rocks in the Central East Kunlun Fault zone, Qinghai-Tibet Plateau—crustal relics of the Paleo-Tethys ocean

NASA Astrophysics Data System (ADS)

Jia, Lihui; Meng, Fancong; Feng, Huibin

2018-06-01

The Wenquan ultramafic rocks, located in the East Kunlun Orogenic belt in the northeastern part of the Qinghai-Tibet Plateau, consist of dunite, wehrlite, olivine-clinopyroxenite and clinopyroxenite, and exhibit cumulate textures. Olivine from dunite has high Fo (forsterite, 90.0-91.8 wt%) and NiO content (0.15-0.42 wt%). Cr-spinels from all of the rocks in this suite are characterized by high Cr# (100×[Cr/(Cr + Al)], 67-91), low Mg# (100×[Mg/(Mg + Fe2+)], 17-35) and low TiO2 contents (mostly < 0.5 wt%). Clinopyroxene displays high Mg# (92-98) and low TiO2 content (0.002-0.099 wt%), similar to those in ophiolitic cumulates. Geochemically, the Wenquan ultramafic rocks show enrichment of LILE, Sr, and Ba, and depletion of Nb and Th. High-Mg# (mostly > 80) and low-CaO (< 0.08 wt%) olivine, high-Cr# (up to 91) spinel, and low Ti contents of clinopyroxene and Cr-spinel indicate that the Wenquan cumulates were generated by high-degree partial melting of a depleted oceanic lithosphere mantle. The ultramafic intrusion most likely evolved from high-Mg basaltic magmas (Mg# = 77.5) that underwent fractional crystallization and crustal contamination. Zircon grains from clinopyroxenites yield a U-Pb weighted mean age of 331 ± 2 Ma, which is nearly coeval with the formation age of the A'nyemaqen ophiolites. The Wenquan Carboniferous ophiolites are confirmed to exist in the Central East Kunlun Fault zone, whereas previous studies have considered them to be the Proterozoic ophiolites. The Wenquan ophiolite might be a relict of the Paleotethyan ocean, indicating that there were two cycles of oceanic-continental evolution along the Central East Kunlun Fault zone.

A plutonic view of explosive volcanism: the shatter zone of the Cadillac Mountain granite, Maine

NASA Astrophysics Data System (ADS)

Wiebe, R.

2013-12-01

The Silurian Cadillac Mountain granite (CMG) is about 15 km in diameter. It is underlain on its deeper western margin by layered gabbro-diorite (GD) up to 3 km thick and on its eastern and southern margins by an intrusive breccia (the 'shatter zone' (SZ)), up to 1 km wide. Coeval rhyolite tuffs, ignimbrites and lavas occur near the southern margin of the granite. The more shallow eastern part of the SZ can be divided into three zones: (SZA) An outer zone against country rock (CR) consists of strongly broken up, deformed sedimentary rocks and angular blocks of diabase invaded by thin irregular veins of aphanitic felsite. All CR fragments are tightly packed with less than ~ 15% matrix, which coarsens inward to vfg quartz, feldspar and biotite. (SZB) A central zone contains abundant sedimentary and scarce rhyolite blocks (typically < 1 m) and larger diabase blocks (from < 1 m to 10s of meters). This zone has 20 to 60% fg to mg matrix with quartz, two feldspars, biotite and abundant pieces of CR down to a few mm. It typically has a strong flow fabric around CR blocks. (SZC) The inner zone has only large (10-80 m) blocks of sedimentary rock, diabase and rhyolite (flows and ignimbrite). The mg granitic matrix (>60%) has blocky hypersolvus feldspar, interstitial to equant quartz, Fe-cpx, Fe-hornblende, two oxides and scarce fayalite. Feldspar in this zone consistently has a sequence of zones consisting of: (1) a homogeneous core of ~ An10Ab80Or10, (2) a transition up to 1 mm wide with 10-15 Or-Ab oscillations (e.g. from Or10 to Or30), each from 20 to 100 microns in width, and (3) a nearly homogeneous rim of variable width averaging about An3Ab70Or27. The occurrence of crystals with such distinctive zoning over such a great distance (18 km) suggests that the zoning was produced by an intensive parameter and not by magma mixing. Because the crystals are restricted to the SZ matrix, processes that produced the shatter zone probably also influenced feldspar zoning. Analysis of clast size distribution of CR fragments in SZA and SZB suggests an extremely high-energy environment consistent with a pyroclastic eruption from the CMG magma chamber (Roy et al. 2012). If such an eruption did occur, one expected effect would be episodic, sudden drops in pressure during degassing and eruptive events. Since the lower part of the chamber was apparently relatively dry (hypersolvus alkali feldspar with ternary feldspar occurs in CMG immediately above the GD), the drop in pressure would lower H2O activity so that the Ab-rich loop of the alkali feldspar phase diagram would shift to higher T, causing the melt to fall below the liquidus and shift the equilibrium solid feldspar to higher Or values. This matches the initial oscillatory zone to higher Or on the homogeneous cores. Because the SZ terminates at the top of the GD, it is likely that mafic input contributed to the eruption. The large inward increase in the crystallization T of the matrix from SZA to SZC probably records initial escape of a cooler felsic cap and upwelling of deep, hot hypersolvus magma along with partial collapse of the chamber roof.

A chilled margin of komatiite and Mg-rich basaltic andesite in the western Bushveld Complex, South Africa

NASA Astrophysics Data System (ADS)

Maier, W. D.; Barnes, S.-J.; Karykowski, B. T.

2016-06-01

A chill sequence at the base of the Lower Zone of the western Bushveld Complex at Union Section, South Africa, contains aphanitic Mg-rich basaltic andesite and spinifex-textured komatiite. The basaltic andesite has an average composition of 15.2 % MgO, 52.8 % SiO2, 1205 ppm Cr, and 361 ppm Ni, whereas the komatiite has 18.7 % MgO, 1515 ppm Cr, and 410 ppm Ni. Both rock types have very low concentrations of immobile incompatible elements (0.14-0.72 ppm Nb, 7-31 ppm Zr, 0.34-0.69 ppm Th, 0.23-0.27 wt% TiO2), but high PGE contents (19-23 ppb Pt, 15-16 ppb Pd) and Pt/Pd ratios (Pt/Pd 1.4). Strontium and S isotopes show enriched signatures relative to most other Lower Zone rocks. The rocks could represent a ~20 % partial melt of subcontinental lithospheric mantle. This would match the PGE content of the rocks. However, this model is inconsistent with the high SiO2, Fe, and Na2O contents and, in particular, the low K2O, Zr, Hf, Nb, Ta, Th, LREE, Rb, and Ba contents of the rocks. Alternatively, the chills could represent a komatiitic magma derived from the asthenosphere that underwent assimilation of the quartzitic floor accompanied by crystallization of olivine and chromite. This model is consistent with the lithophile elements and the elevated Sr and S isotopic signatures of the rocks. However, in order to account for the high Pt and Pd contents of the magma, the mantle must have been twice as rich in PGE as the current estimate for PUM, possibly due to a component of incompletely equilibrated late veneer.

The reduction mechanism of a natural chromite at 1416 °C

NASA Astrophysics Data System (ADS)

Soykan, O.; Eric, R. H.; King, R. P.

1991-02-01

The behavior of a natural chromite from the Bushveld Complex, Transvaal, South Africa, during reduction at 1416 °C by graphite was studied by means of thermogravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis. Experimental runs were allowed to proceed up to 120 minutes, resulting in 99 pct reduction. The specific objective of this study was to delineate the reduction mechanism of chromite by graphite. Zoning was observed in partially reduced chromites with degrees of reduction of up to about 70 pct. The inner cores were rich in iron, while the outer cores were depleted of iron. Energy-dispersive X-ray analysis revealed that Fe2+ and Cr3+ ions had diffused outward, whereas Cr2+, Al3+, and Mg2+ ions had diffused inward. The following mechanism of reduction, which is based on the assumption that the composition of the spinel phase remains stoichiometric with increasing degree of reduction, is proposed, (a) Initially, Fe3+ and Fe2+ ions at the surface of the chromite particle are reduced to the metallic state. This is followed immediately by the reduction of Cr3+ ions to the divalent state, (b) Cr2+ ions diffusing toward the center of the particle reduce the Fe3+ ions in the spinel under the surface of the particle to Fe2+ at the interface between the inner and outer cores. Fe2+ ions diffuse toward the surface, where they are reduced to metallic iron, (c) After the iron has been completely reduced, Cr3+ and any Cr2+ that is present are reduced to the metallic state, leaving an iron- and chromium-free spinel, MgAl2O4.

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA

2008-05-12

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of themore » most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.« less

The Redox-Active Chromium Phthalocyanine System: Isolation of Five Oxidation States from Pc4- CrI to Pc2- CrIII.

PubMed

Zhou, Wen; Thompson, John R; Leznoff, Clifford C; Leznoff, Daniel B

2017-02-16

The preparation and structural characterization of a series of chromium phthalocyanine complexes with multiple metal and ring oxidation states were achieved using PcCr II (1) (Pc=phthalocyanine) or PcCr II (THF) 2 (1⋅THF 2 ) as starting materials. The reaction of soluble 1⋅THF 2 with Br 2 or I 2 gave the PcCr III halide complexes PcCrX(THF) (X=I/I 3 , Br; 3, 4, respectively). Treatment of 1 with 0.5 equivalent of PhIO or air generated the dinuclear [PcCr(THF)] 2 (μ-O) (5), whereas the addition of one equivalent of AgSbF 6 to 1 resulted in oxidation to THF-solvated octahedral [PcCr III (THF) 2 ]SbF 6 (6). The reduction of 1 with three sequential equivalents of KEt 3 BH resulted in the isolation of [K(DME) 4 ][Pc 3- Cr II ] (7), [K(DME) 4 ] 2 [Pc 4- Cr II ] (8) and [K 6 (DME) 4 ][Pc 4- Cr I ] 2 (9), respectively. The reduced products are deep purple in colour, with visible absorption maxima between 500-580 nm. The ring-reduced complexes 7 and 8 are monomeric, whereas 9 is a 1D chain of dinuclear [PcCr] 2 units with intercalated K + cations and supported by Cr-Cr interactions of 2.988(2) Å. Addition of four equivalents of KC 8 resulted in the demetallated product PcK 2 (DME) 4 (10), which has a 1D chain structure. The isolation and structural characterization of new PcCr complexes spanning five oxidation states, including rare examples of crystalline reduced Pc-ring species emphasizes the broad redox activity and stability of phthalocyanine-based complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Current status of new SAGE project with 51Cr neutrino source

DOE PAGES

Gavrin, V.; Cleveland, B.; Danshin, S.; ...

2015-03-15

A very short-baseline neutrino oscillation experiment with an intense 51Cr neutrino source is currently under construction at the Baksan Neutrino Observatory of the Institute for Nuclear Research RAS (BNO). The experiment, which is based on the existing SAGE experiment, will use an upgraded Gallium-Germanium Neutrino Telescope (GGNT) and an artificial 51Cr neutrino source with activity ~3 MCi to search for transitions of active neutrinos to sterile states with Δm 2 ~1 eV 2. The neutrino source will be placed in the center of a liquid Ga metal target that is divided into two concentric zones, internal and external. The averagemore » path length of neutrinos in each zone will be the same and the neutrino capture rate will be measured separately in each zone. The oscillation signature, which comes from the ratio of events in the near and far gallium volumes, will be largely free of systematic errors, such as may occur from cross section and source strength uncertainties, and will provide a clean signal of electron neutrino disappearance into a sterile state at baselines of about 0.6 and 2.0 m. The sensitivity to the disappearance of electron neutrinos is expected to be a few percent. Construction of this set of new facilities, including a two-zone tank for irradiation of 50 tons of Ga metal with the intense 51Cr source, as well as additional modules of the GGNT counting and extraction systems, is close to completion. In order to check the new facilities they will first be used for SAGE solar neutrino measurements.« less

Current status of new SAGE project with 51Cr neutrino source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavrin, V.; Cleveland, B.; Danshin, S.

A very short-baseline neutrino oscillation experiment with an intense 51Cr neutrino source is currently under construction at the Baksan Neutrino Observatory of the Institute for Nuclear Research RAS (BNO). The experiment, which is based on the existing SAGE experiment, will use an upgraded Gallium-Germanium Neutrino Telescope (GGNT) and an artificial 51Cr neutrino source with activity ~3 MCi to search for transitions of active neutrinos to sterile states with Δm 2 ~1 eV 2. The neutrino source will be placed in the center of a liquid Ga metal target that is divided into two concentric zones, internal and external. The averagemore » path length of neutrinos in each zone will be the same and the neutrino capture rate will be measured separately in each zone. The oscillation signature, which comes from the ratio of events in the near and far gallium volumes, will be largely free of systematic errors, such as may occur from cross section and source strength uncertainties, and will provide a clean signal of electron neutrino disappearance into a sterile state at baselines of about 0.6 and 2.0 m. The sensitivity to the disappearance of electron neutrinos is expected to be a few percent. Construction of this set of new facilities, including a two-zone tank for irradiation of 50 tons of Ga metal with the intense 51Cr source, as well as additional modules of the GGNT counting and extraction systems, is close to completion. In order to check the new facilities they will first be used for SAGE solar neutrino measurements.« less

Altered stoichiometry Escherichia coli Cascade complexes with shortened CRISPR RNA spacers are capable of interference and primed adaptation

DOE PAGES

Kuznedelov, Konstantin; Mekler, Vladimir; Lemak, Sofia; ...

2016-10-13

The Escherichia coli type I-E CRISPR-Cas system Cascade effector is a multisubunit complex that binds CRISPR RNA (crRNA). Through its 32-nucleotide spacer sequence, Cascade-bound crRNA recognizes protospacers in foreign DNA, causing its destruction during CRISPR interference or acquisition of additional spacers in CRISPR array during primed CRISPR adaptation. Within Cascade, the crRNA spacer interacts with a hexamer of Cas7 subunits. We show that crRNAs with a spacer length reduced to 14 nucleotides cause primed adaptation, while crRNAs with spacer lengths of more than 20 nucleotides cause both primed adaptation and target interference in vivo. Shortened crRNAs assemble into altered-stoichiometry Cascademore » effector complexes containing less than the normal amount of Cas7 subunits. The results show that Cascade assembly is driven by crRNA and suggest that multi-subunit type I CRISPR effectors may have evolved from much simpler ancestral complexes.« less

Altered stoichiometry Escherichia coli Cascade complexes with shortened CRISPR RNA spacers are capable of interference and primed adaptation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuznedelov, Konstantin; Mekler, Vladimir; Lemak, Sofia

The Escherichia coli type I-E CRISPR-Cas system Cascade effector is a multisubunit complex that binds CRISPR RNA (crRNA). Through its 32-nucleotide spacer sequence, Cascade-bound crRNA recognizes protospacers in foreign DNA, causing its destruction during CRISPR interference or acquisition of additional spacers in CRISPR array during primed CRISPR adaptation. Within Cascade, the crRNA spacer interacts with a hexamer of Cas7 subunits. We show that crRNAs with a spacer length reduced to 14 nucleotides cause primed adaptation, while crRNAs with spacer lengths of more than 20 nucleotides cause both primed adaptation and target interference in vivo. Shortened crRNAs assemble into altered-stoichiometry Cascademore » effector complexes containing less than the normal amount of Cas7 subunits. The results show that Cascade assembly is driven by crRNA and suggest that multi-subunit type I CRISPR effectors may have evolved from much simpler ancestral complexes.« less

Investigation on Microstructure and Impact Toughness of Different Zones in Duplex Stainless Steel Welding Joint

NASA Astrophysics Data System (ADS)

Zhang, Zhiqiang; Jing, Hongyang; Xu, Lianyong; Han, Yongdian; Li, Guolu; Zhao, Lei

2017-01-01

This paper investigated on microstructure and impact toughness of different zones in duplex stainless steel welding joint. High-temperature heat-affected zone (HTHAZ) contained coarse ferrite grains and secondary precipitates such as secondary austenite, Cr2N, and sigma. Intergranular secondary austenite was prone to precipitation in low-temperature heat-affected zone (LTHAZ). Both in weld metal (WM) and in HTHAZ, the austenite consisted of different primary and secondary austenite. The ferrite grains in base metal (BM) presented typical rolling texture, while the austenite grains showed random orientation. Both in the HTHAZ and in the LTHAZ, the ferrite grains maintained same texture as the ferrite in the BM. The secondary austenite had higher Ni but lower Cr and Mo than the primary austenite. Furthermore, the WM exhibited the highest toughness because of sufficient ductile austenite and unapparent ferrite texture. The HTHAZ had the lowest toughness because of insufficient austenite formation in addition to brittle sigma and Cr2N precipitation. The LTHAZ toughness was higher than the BM due to secondary austenite precipitation. In addition, the WM fracture was dominated by the dimple, while the cleavage was main fracture mode of the HTHAZ. Both BM and LTHAZ exhibited a mixed fracture mode of the dimple and quasi-cleavage.

Effect of Heat Treatment on Microstructure and Hot Impact Toughness of Various Zones of P91 Welded Pipes

NASA Astrophysics Data System (ADS)

Pandey, C.; Mahapatra, M. M.

2016-06-01

The new generation super critical thermal power plants are required to operate at enhanced thermal efficiency of over 50% to reduce the fuel consumption and environmental pollution. Creep strength-enhanced ferritic steels, commonly known as Cr-Mo alloys such as P91 (X10CrMoVNb 9-1) are such material of choice for the next generation power plants. The operating requirement of these next generation power plants is that steam temperature of around 650 °C is maintained. For such high-temperature application, creep strength of material is the primary consideration together with adequate weld heat-affected zone (HAZ) toughness. Present work deals with the effect of high service temperature on impact toughness of P91 (X10CrMoVNb 9-1) base material, weld fusion zone, and HAZ. The impact toughness of HAZ for conventional weld groove design and narrow weld groove design has been evaluated experimentally in as-welded and at different post-weld heat treatment conditions. Fractography of the impact toughness specimens of base metal, weld fusion zone, and HAZ was carried out using scanning electron microscope. The effects of heat treatment schemes on the percentage of element present at the fracture surface were also studied.

Delta-Ferrite Distribution in a Continuous Casting Slab of Fe-Cr-Mn Austenitic Stainless Steel

NASA Astrophysics Data System (ADS)

Chen, Chao; Cheng, Guoguang

2017-10-01

The delta-ferrite distribution in a continuous casting slab of Fe-Cr-Mn stainless steel grade (200 series J4) was analyzed. The results showed that the ferrite fraction was less than 3 pct. The "M" type distribution was observed in the thickness direction. For the distribution at the centerline, the maximum ferrite content was found in the triangular zone of the macrostructure. In addition, in this zone, the carbon and sulfur were severely segregated. Furthermore, an equilibrium solidification calculation by Thermo-Calc® software indicates that the solidification mode of the composition in this triangular zone is the same as the solidification mode of the averaged composition, i.e., the FA (ferrite-austenite) mode. None of the nickel-chromium equivalent formulas combined with the Schaeffler-type diagram could predict the ferrite fraction of the Cr-Mn stainless steel grade in a reasonable manner. The authors propose that more attention should be paid to the development of prediction models for the ferrite fraction of stainless steels under continuous casting conditions.

Mechanism study of humic acid functional groups for Cr(VI) retention: Two-dimensional FTIR and 13C CP/MAS NMR correlation spectroscopic analysis.

PubMed

Zhang, Jia; Chen, Linpeng; Yin, Huilin; Jin, Song; Liu, Fei; Chen, Honghan

2017-06-01

Undissolved humic acid (HA) is known to substantially effect the migration and transformation of hexavalent chromium [Cr(VI)] in soils. The mechanisms of Cr(VI) retention in soils by undissolved HA have been reported; however, past studies are inconclusive about the types of HA functional groups that are involved in Cr(VI) retention and the retention mechanisms. Utilizing a two-dimensional correlation spectroscopy (2DCOS) analysis for FTIR and 13 C CP/MAS NMR, this study investigated the variations of HA function groups and molecular structures after reactions with aqueous Cr(VI) under different pH conditions. Based on the changing sequence of functional groups interpreted from the 2DCOS results, a four-step mechanism for Cr(VI) retention was determined as follows: (1) electrostatic adsorption of Cr(VI) to HA surface, (2) complexation of adsorbed Cr(VI) by carboxyl and ester, (3) reduction of complexed Cr(VI) to Cr(III) by phenol and polysaccharide, and (4) complexation of reduced Cr(III) by carboxylic groups. These functional groups that are involved in Cr(VI) retention were determined to occur in aromatic domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

Creep behavior and in-depth microstructural characterization of dissimilar joints

PubMed Central

Kauffmann, F; Klein, T; Klenk, A; Maile, K

2013-01-01

The 700 °C power plants currently under development will utilize Ni-base alloys such as alloy 617 for components to be operated at temperatures >650 °C. Due to economic reasons for components or parts of components which are subjected to temperatures <650 °C, 2% Cr or 9–12% Cr steels is used, depending on the required mechanical properties. This makes the dissimilar joining of Ni-base alloys and Cr steels a necessity in these plants. Experimental investigations show that these joints have to be identified as weak points with regard to damage development under creep and creep-fatigue loading. The present investigation focuses on welds between the alloy 617 and 2% Cr steel. Under creep load the fracture occurs near the fusion line between the 2% Cr steel base metal and alloy 617 weld metal. To explain the reasons for this fracture location, the microstructure of this fusion line was investigated using TEM and FIB techniques after welding and after creep loading. The TEM investigations have shown a small zone in the weld metal near the fusion line exhibiting chromium depletion and clearly reduced amounts of chromium carbides, leading to a weakening of this zone. PMID:27877551

Calorimetric investigation of precipitation kinetics in Al-Mg-Si-X(Cr,Be) alloys

NASA Astrophysics Data System (ADS)

Woo, K. D.; Lee, J. S.; Kim, S. W.

1999-07-01

This study has been carried out by differential scanning calorimetry (DSC) to study the kinetics of precipitation and the dissolution of metastable and stable phases in Al-Mg-Si-(Cr,Be) alloys which were heat treated by T6, two-step aging and RRA (retrogression and reaging) treatment. The heat flow variations by phase transformation in the as-quenched specimen were calculated from DSC thermograms obtained from heating rates of 5, 10, 15 and 20°C/min. Four exothermic peaks may be attributed to the precipitation of G.P.I zone, G.P.II zone(β″), β' and β (Mg2Si) phases, and three endothermic peaks may be attributed to the dissolution of G.P.I zone, β″ and the β' phases, respectively. The kinetic equation (dY/dt)=f(Y)koexp(-Q*/RT) can be used to study the precipitation kinetics of Ai-Mg-Si-(Cr, Be) alloys, where Q*, ko, and f(Y)are the activation energy, frequency factors and the function of Y, respectively. The kinetic parameters measured from DSC curves can be used to interpret the transformation kinetics.The formation rate of β″ phase in the Al-Mg-Si alloy increased by the small addition of Be. This is because Be increases the nucleating rate of the β″ phase due to the decrease of the matrix/β″ interface energy. By the addition of Be or Cr and Be in Al-Mg-Si alloy, G.P. zone was easily decomposed during retrogression treatment at 225°C for 3 min. Therefore, maximum hardness can be obtained by RRA (150°C/20 min→225°C/3 min→ 180°C/3O min) in Al-0.8%Mg-1.0%Si-0.05% Be and Al-0.8% Mg-l.0% Si-0.l% Cr-0.05% Be alloys owing to the high density of β″ and β' precipitates.

RESULTS FROM RECENT SCIENCE AND TECHNOLOGY INVESTIGATIONS TARGETING CHROMIUM IN THE 100D AREA HANFORD SITE WASHINGTON USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

PETERSEN SW; THOMPSON KM; TONKIN MJ

2009-12-03

Sodium dichromate was used in Hanford's 100D Area during the reactor operations period of 1950 to 1964 to retard corrosion in the reactor cooling systems. Some of the sodium dichromate was released to the environment by spills and/or leaks from pipelines used to deliver the chemical to water treatment plants in the area. As a result, hexavalent chromium [Cr(VI)] has migrated through the vadose zone to the groundwater and contaminated nearly 1 km{sup 2} of groundwater to above the drinking water standard of 48 {micro}g/L. Three technology tests have recently been completed in this area to characterize the source areamore » of the plumes and evaluate alternative methods to remove Cr(VI) from groundwater. These are (1) refine the source area of the southern plume; (2) test electrocoagulation as an alternative groundwater treatment technology; and (3) test the ability to repair a permeable reactive barrier by injecting micron or nanometer-size zero-valent iron (ZVI). The projects were funded by the US Department of Energy as part of a program to interject new technologies and accelerate active cleanup. Groundwater monitoring over the past 10 years has shown that Cr(VI) concentrations in the southern plume have not significantly diminished, strongly indicating a continuing source. Eleven groundwater wells were installed in 2007 and 2008 near a suspected source area and monitored for Cr(VI) and groundwater levels. Interpretation of these data has led to refinement of the source area location to an area of less than 1 hectare (ha, 2.5 acres). Vadose zone soil samples collected during drilling did not discover significant concentrations of Cr(VI), indicating the source is localized, with a narrow wetted path from the surface to the water table. Electrocoagulation was evaluated through a pilot-scale treatability test. Over 8 million liters of groundwater were treated to Cr(VI) concentrations of {le}20 {micro}g/L. The test determined that this technology has the potential to treat Cr(VI) to these low levels, but system reliability and operational complexity rendered electrocoagulation less cost effective than the baseline technology of ion exchange. Laboratory and field tests were conducted to evaluate the practicality of injecting ZVI into the aquifer to increase the lifespan and effectiveness of an existing permeable reactive barrier. From a database of 30 ZVI materials, 6 were chosen and tested in the laboratory to determine their geochemical and physical performance under simulated 100D aquifer conditions. The best-performing ZVI was injected into the aquifer and met the primary goals of communicating the iron at least 7 meters from the injection point and reducing the aquifer to transform mobile Cr(VI) to trivalent chromium Cr(III), which is effectively immobile in the aquifer.« less

Microstructural evolution and precipitation behavior in heat affected zone of Inconel 625 and AISI 904L dissimilar welds

NASA Astrophysics Data System (ADS)

Senthur Prabu, S.; Devendranath Ramkumar, K.; Arivazhagan, N.

2017-11-01

In the present investigation an attempt has been made to join the dissimilar combination of Inconel 625 super alloy and super austenitic stainless steel (AISI 904L) using manual multi-pass continuous current gas tungsten arc (CCGTA) welding processes. Two different filler wires such as ERNiCrMo-4 and ERNiCrCoMo-1 have been used to compare the metallurgical properties of these welded joints. Both optical microscopy and scanning electron microscopy techniques were adopted to disseminate the microstructure traits of these weldments. Formation of secondary phases at the HAZ and weld interface of AISI 904L was witnessed while using the ERNiCrCoMo-1 filler, along with Solidification Grain Boundary (SGB) and Migrated Grain Boundary (MGB) were also observed at the weld zone.

Differential impact of ionic and coordinate covalent chromium (Cr)-DNA binding on DNA replication.

PubMed

Fornsaglio, Jamie L; O'Brien, Travis J; Patierno, Steven R

2005-11-01

The reactive species produced by the reduction of Cr(VI), particularly Cr(III), can form both ionic and coordinate covalent complexes with DNA. These Cr(III)-DNA interactions consist of Cr-DNA monoadducts, Cr-DNA ternary adducts, and Cr-DNA interstrand cross-links (Cr-ICLs), the latter of which are DNA polymerase arresting lesions (PALs). We sought to determine the impact of Cr-DNA interactions on the formation of replication blocking lesions in S. cerevisiae using a PCR-based method. We found that target sequence (TS) amplification using DNA isolated from Cr(VI)-treated yeast actually increased as a function of Cr(VI) concentration. Moreover, the enhanced TS amplification was reproduced in vitro using Cr(III)-treated DNA. In contrast, PCR amplification of TS from DNA isolated from yeast exposed to equitoxic doses of the inorganic DNA cross-linking agent cisplatin (CDDP), was decreased in a concentration-dependent manner. This paradox suggested that a specific Cr-DNA interaction, such as an ionic Cr-DNA complex, was responsible for the enhanced TS amplification, thereby masking the replication-blocking effect of certain ternary Cr-DNA adducts (i.e. interstrand cross-links). To test this possibility, we removed ionically associated Cr from the DNA using salt extraction prior to PCR analysis. This procedure obviated the increased amplification and revealed a dose-dependent decrease in TS amplification and an increase in Cr-PALs. These data from DNA analyzed ex vivo after treatment of intact cells indicate that ionic interactions of Cr with DNA result in increased DNA amplification whereas coordinate-covalent Cr-DNA complexes lead to formation of Cr-PALs. Thus, these results suggest that treatment of living cells with Cr(VI) leads to two modes of Cr-binding, which may have conflicting effects on DNA replication.

Chromium complexes for luminescence, solar cells, photoredox catalysis, upconversion, and phototriggered NO release

PubMed Central

Büldt, Laura A.

2017-01-01

Some complexes of Cr(iii) and Cr(0) have long been known to exhibit interesting photophysical and photochemical properties, but in the past few years important conceptual progress was made. This Perspective focuses on the recent developments of Cr(iii) complexes as luminophores and dyes for solar cells, their application in photoredox catalysis, their use as sensitizers in upconversion processes, and their performance as photochemical nitric oxide sources. The example of a luminescent Cr(0) isocyanide complex illustrates the possibility of obtaining photoactive analogues of d6 metal complexes that are commonly made from precious metals such as Ru(ii) or Ir(iii). The studies highlighted herein illustrate the favorable excited-state properties of robust first-row transition metal complexes with broad application potential. PMID:29163886

Chromium complexes for luminescence, solar cells, photoredox catalysis, upconversion, and phototriggered NO release.

PubMed

Büldt, Laura A; Wenger, Oliver S

2017-11-01

Some complexes of Cr(iii) and Cr(0) have long been known to exhibit interesting photophysical and photochemical properties, but in the past few years important conceptual progress was made. This Perspective focuses on the recent developments of Cr(iii) complexes as luminophores and dyes for solar cells, their application in photoredox catalysis, their use as sensitizers in upconversion processes, and their performance as photochemical nitric oxide sources. The example of a luminescent Cr(0) isocyanide complex illustrates the possibility of obtaining photoactive analogues of d 6 metal complexes that are commonly made from precious metals such as Ru(ii) or Ir(iii). The studies highlighted herein illustrate the favorable excited-state properties of robust first-row transition metal complexes with broad application potential.

Clinical and imaging features in different inner border-zone infarct patterns.

PubMed

Wang, Yujie; Wang, Jian

2015-03-01

The clinical and imaging features of different inner border-zone infarct patterns, corona radiata (CR) and centrum semiovale (CSO), is not quiet clear. Both are mostly reported together in previous studies. We intended to observe their clinical and imaging features. We observed 83 patients-47 cases with CR infarct lesion pattern and 36 cases with CSO. The lesion patterns were determined by diffusion-weighted imaging. Basic, clinical and radiologic features were compared between the patients with CR and CSO infarct lesion patterns. There was no significant difference between CR and CSO infarct patterns in terms of risk factors. However, patients with CR infarct had a higher initial National Institutes of Health Stroke Scale (NIHSS) score at admission (5.2 ± 2.3) than with CSO (3.9 ± 2.0, p = 0.009). Early clinical deterioration (OR, 2.42; 95% CI, 1.12-5.21; p = 0.024) and middle cerebral artery (MCA) stenosis (OR, 10.31; 95% CI, 3.30-32.19; p < 0.0001) were independently associated with the CR infarct lesion pattern. Partial infarct lesion shape (OR, 5.95; 95% CI, 1.40-25.33; p = 0.016) and internal carotid artery (ICA) stenosis (OR, 5.28; 95% CI, 1.92-14.51; p = 0.001) were independently correlated with the CSO infarct lesion pattern. Although CR and CSO infarct patterns might share common etiology and mechanisms, their clinical and imaging features are different.

Slow Magnetic Relaxation and Single-Molecule Toroidal Behaviour in a Family of Heptanuclear {CrIII LnIII6 } (Ln=Tb, Ho, Er) Complexes.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Swain, Abinash; Moubaraki, Boujemaa; Damjanović, Marko; Wernsdorfer, Wolfgang; Rajaraman, Gopalan; Murray, Keith S

2018-01-15

The synthesis, magnetic properties, and theoretical studies of three heterometallic {Cr III Ln III 6 } (Ln=Tb, Ho, Er) complexes, each containing a metal topology consisting of two Ln 3 triangles connected via a Cr III linker, are reported. The {CrTb 6 } and {CrEr 6 } analogues display slow relaxation of magnetization in a 3000 Oe static magnetic field. Single-crystal measurements reveal opening up of the hysteresis loop for {CrTb 6 } and {CrHo 6 } molecules at low temperatures. Ab initio calculations predict toroidal magnetic moments in the two Ln 3 triangles, which are found to couple, stabilizing a con-rotating ferrotoroidal ground state in Tb and Ho examples and extend the possibility of observing toroidal behaviour in non Dy III complexes for the first time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two binuclear cyanide-bridged Cr(III)-Mn(III) complexes based-on [Cr(2,2'-bipy)(CN)4]- building block: synthesis, crystal structures and magnetic properties.

PubMed

Zhanga, Daopeng; Kong, Lingqian; Zhang, Hongyan

2015-01-01

Tetracyanide building block [Cr(2,2'-bipy)(CN)(4)]- and two bicompartimental Schiff-base based manganese(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in two cyanide-bridged CrIII-MnIII complexes: [Mn(L(1))(H(2)O)][Cr(2,2'-bipy)(CN)(4)]·CH(3)OH·2.5H(2)O (1) and [Mn(L(2))(H(2)O)][Cr(2,2'-bipy)(CN)(4)]·CH(3)OH·(3)H(2)O (2) (L1 = N,N'-(1,3-propylene)-bis(3-methoxysalicylideneiminate), L2 = N,N'-ethylene-bis(3-ethoxysalicylideneiminate)). Single X-ray diffraction analysis shows their similar cyanide-bridged binuclear structures, in which the cyanide precursor acting as monodentate ligand connects the manganese(III) ion. The binuclear complexes are self-complementary through coordinated aqua ligand and the free O4 compartment from the neighboring complex, giving H-bond linking dimer structure. Investigation over magnetic properties reveals the antiferromagnetic magnetic coupling between the cyanide-bridged Cr(III) and Mn(III) ions. A best-fit to the magnetic susceptibilities of these two complexes leads to the magnetic coupling constants J = -5.95 cm(-1), j = -0.61 cm(-1) (1) and J = -4.15 cm(-1), j = -0.57 cm(-1) (2), respectively.

Observation of changes in the metallurgical characteristics of Ni-Cr alloys using Nd:YAG laser welding

PubMed Central

Choi, SM

2014-01-01

This study aimed to determine the effect of hardness change according to penetration depth in the laser fusing zone and observed the correlation of the microstructure as an Nd:YAG laser was irradiated to Ni-Cr alloy for dental use by setting the spot diameter size to various conditions. In all groups, the hardness depth profiles in the laser fusing zone and heat-affected zone (HAZ) had larger values than those of the base metal. In addition, the hardness values in places beyond the fusing zone and the HAZ were measured as being quantitatively lower. The observation result of the diffusion of the constituent elements and microstructure using field emission scanning electron microscopy, energy-dispersive spectroscopy, and electron probe microanalyzer showed that the fusing zone revealed a much finer dendritic form than the base metal due to the self-quenching effect after welding, while no change in constituent elements was found although some evaporation of the main elements was observed. In addition, Mo- and Si-combined intermetallic compounds were formed on the interdendritic area. Through this study, the laser fusing zone had better hardenability due to the intermetallic compound and grain refinement effect. PMID:25342985

Genetic variations in two seahorse species (Hippocampus mohnikei and Hippocampus trimaculatus): evidence for middle Pleistocene population expansion.

PubMed

Zhang, Yanhong; Pham, Nancy Kim; Zhang, Huixian; Lin, Junda; Lin, Qiang

2014-01-01

Population genetic of seahorses is confidently influenced by their species-specific ecological requirements and life-history traits. In the present study, partial sequences of mitochondrial cytochrome b (cytb) and control region (CR) were obtained from 50 Hippocampus mohnikei and 92 H. trimaculatus from four zoogeographical zones. A total of 780 base pairs of cytb gene were sequenced to characterize mitochondrial DNA (mtDNA) diversity. The mtDNA marker revealed high haplotype diversity, low nucleotide diversity, and a lack of population structure across both populations of H. mohnikei and H. trimaculatus. A neighbour-joining (NJ) tree of cytb gene sequences showed that H. mohnikei haplotypes formed one cluster. A maximum likelihood (ML) tree of cytb gene sequences showed that H. trimaculatus belonged to one lineage. The star-like pattern median-joining network of cytb and CR markers indicated a previous demographic expansion of H. mohnikei and H. trimaculatus. The cytb and CR data sets exhibited a unimodal mismatch distribution, which may have resulted from population expansion. Mismatch analysis suggested that the expansion was initiated about 276,000 years ago for H. mohnikei and about 230,000 years ago for H. trimaculatus during the middle Pleistocene period. This study indicates a possible signature of genetic variation and population expansion in two seahorses under complex marine environments.

Bulk and surface properties of liquid Al-Cr and Cr-Ni alloys.

PubMed

Novakovic, R

2011-06-15

The energetics of mixing and structural arrangement in liquid Al-Cr and Cr-Ni alloys has been analysed through the study of surface properties (surface tension and surface segregation), dynamic properties (chemical diffusion) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of statistical mechanical theory in conjunction with quasi-lattice theory. The Al-Cr phase diagram exhibits the existence of different intermetallic compounds in the solid state, while that of Cr-Ni is a simple eutectic-type phase diagram at high temperatures and includes the low-temperature peritectoid reaction in the range near a CrNi(2) composition. Accordingly, the mixing behaviour in Al-Cr and Cr-Ni alloy melts was studied using the complex formation model in the weak interaction approximation and by postulating Al(8)Cr(5) and CrNi(2) chemical complexes, respectively, as energetically favoured.

IN SITU ABIOTIC DETOXIFICATION AND IMMOBILIZATION OF HEXAVALENT CHROMIUM IN THE CAPILLARY FRINGE ZONE

EPA Science Inventory

Detailed site characterization data from the former electroplating shop at the U.S. Coast Guard Air Support Center, Elizabeth City, North Carolina suggested that the elevated Cr(VI) in the capillary fringe area had contaminated the ground water at the site. Most of the mobile Cr(...

Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals.

PubMed

Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

2016-02-16

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Mechanical Properties and Microstructure of Dissimilar Friction Stir Welds of 11Cr-Ferritic/Martensitic Steel to 316 Stainless Steel

NASA Astrophysics Data System (ADS)

Sato, Yutaka S.; Kokawa, Hiroyuki; Fujii, Hiromichi T.; Yano, Yasuhide; Sekio, Yoshihiro

2015-12-01

Dissimilar joints between ferritic and austenitic steels are of interest for selected applications in next generation fast reactors. In this study, dissimilar friction-stir welding of an 11 pct Cr ferritic/martensitic steel to a 316 austenitic stainless steel was attempted and the mechanical properties and microstructure of the resulting welds were examined. Friction-stir welding produces a stir zone without macroscopic weld-defects, but the two dissimilar steels are not intermixed. The two dissimilar steels are interleaved along a sharp zigzagging interface in the stir zone. During small-sized tensile testing of the stir zone, this sharp interface did not act as a fracture site. Furthermore, the microstructure of the stir zone was refined in both the ferritic/martensitic steel and the 316 stainless steel resulting in improved mechanical properties over the adjacent base material regions. This study demonstrates that friction-stir welding can produce welds between dissimilar steels that contain no macroscopic weld-defects and display suitable mechanical properties.

Drilling the Bushveld Complex- the world's largest layered mafic intrusion

NASA Astrophysics Data System (ADS)

Ashwal, L. D.; Webb, S. J.; Trumbull, R. B.

2013-12-01

The fact that surprising new discoveries can be made in layered mafic intrusions (e.g., subtle 100-150 m cyclicity in apparently homogeneous cumulates over 1000s of m) means that we are still in the first-order characterization phase of understanding these objects. Accordingly, we have secured funding from ICDP for a planning workshop to be held in Johannesburg in early 2014, aimed at scientific drilling of the Bushveld Complex, the world's largest layered mafic intrusion. Science objectives include, but are not limited to: 1. Magma chamber processes & melt evolution. How many melts/magmas/mushes were involved, what were their compositions and how did they interact? What, if anything, is missing from the Complex, and where did it go? Did Bushveld magmatism have an effect upon Earth's atmosphere at 2 Ga? 2. Crust-mantle interactions & origin of Bushveld granitoids. Are Bushveld granites & rhyolites crustal melts, differentiates from the mafic magmas or products of immiscibility? How can the evolved isotopic signatures in the mafic rocks (e.g., epsilon Nd to -8) be understood? 3. Origin of ore deposits. What were the relative roles of gravity settling, magma mixing, immiscibility and hydrothermal fluid transport in producing the PGE, Cr and V deposits? We have identified 3 potential drilling targets representing a total of ~12 km of drill core. Exact locations of drill sites are to be discussed at the workshop. Target A- East-Central Bushveld Complex. We propose 3 overlapping 3 km boreholes that will provide the first roof-to-floor continuous coverage of the Rustenburg Layered Suite. These boreholes will represent a curated, internationally available reference collection of Bushveld material for present and future research. Target B- Southeastern Bushveld Complex. We propose a single borehole of ~2 km depth, collared in Rooiberg felsite, and positioned to intersect the Roof Zone, Upper Zone, Main Zone and floor of the Complex. Amongst other things, this site will evaluate the latest differentiates of the Complex: are they represented by felsic Rooiberg lavas (Van Tongeren & Mathez, 2012 J. Petrol. 51, 1891), or a newly-discovered sequence of hornblende quartz monzonites (Cawthorn, 2013, J. Petrol., in press)? Target C- Northern Lobe of Bushveld Complex. We propose 2 shorter ~500 m boreholes sited to (a) fill in missing stratigraphy of 2 existing deep cores (Bellevue & Moordkopje) including the unique 200 m thick troctolitic horizon in the Main Zone, and (b) to study the transgressive Main Zone - Upper Zone boundary several km north of the Bellevue/Moordkopje sites. All boreholes are intended to provide continuous down-hole geophysical measurements including magnetic susceptibility, density, electrical conductivity and radiometric data. There is also potential to obtain deep fluids and gases for biogeochemical and other studies. All interested geoscientists are welcome to attend the workshop. Watch the ICDP website for announcements (www.icdp-online.org).

On the positronium spin conversion reactions caused by some macrocyclic Co II complexes

NASA Astrophysics Data System (ADS)

Fantola-Lazzarini, Anna L.; Lazzarini, Ennio

2002-08-01

The rate constants, kCR, of ortho- into para-positronium ( o-Ps→ p-Ps) spin conversion reactions, CR, caused by the high-spin [Co IIsep] 2+, [Co IIdinosar] 2+ and [Co IIdiamsar] 2+ macrocyclic complexes and also by high-spin [Co II sen] 2+ tripod complex were measured at several temperatures. The delocalizations, β, of Co II unpaired electrons, promoted by the mentioned ligands, were determined by using the previously established correlations between kCR and the electron delocalization β of unpaired metal electrons. β is given by the ratio between the Racah inter-electronic repulsion parameters of complexes, B, and that of the free ions, B0. The β values are compared with those of the Co II complexes with en (1,2-ethanediamine), pn (1,2 propanediamine) and dien (2,2' diamino diethylamine) ligands. The kCR rate constants are also compared with those of the Ps oxidation reactions, OR, promoted by the corresponding Co III complexes. It is concluded that, unlike OR's, the CR's do not occur by formation of hepta-coordinate adducts with Ps atoms.

[Transfer characteristic and source identification of soil heavy metals from water-level-fluctuating zone along Xiangxi River, three-Gorges Reservoir area].

PubMed

Xu, Tao; Wang, Fei; Guo, Qiang; Nie, Xiao-Qian; Huang, Ying-Ping; Chen, Jun

2014-04-01

Transfer characteristics of heavy metals and their evaluation of potential risk were studied based on determining concentration of heavy metal in soils from water-level-fluctuating zone (altitude:145-175 m) and bank (altitude: 175-185 m) along Xiangxi River, Three Gorges Reservoir area. Factor analysis-multiple linear regression (FA-MLR) was employed for heavy metal source identification and source apportionment. Results demonstrate that, during exposing season, the concentration of soil heavy metals in water-level-fluctuation zone and bank showed the variation, and the concentration of soil heavy metals reduced in shallow soil, but increased in deep soil at water-level-fluctuation zone. However, the concentration of soil heavy metals reduced in both shallow and deep soil at bank during the same period. According to the geoaccumulation index,the pollution extent of heavy metals followed the order: Cd > Pb > Cu > Cr, Cd is the primary pollutant. FA and FA-MLR reveal that in soils from water-level-fluctuation zone, 75.60% of Pb originates from traffic, 62.03% of Cd is from agriculture, 64.71% of Cu and 75.36% of Cr are from natural rock. In soils from bank, 82.26% of Pb originates from traffic, 68.63% of Cd is from agriculture, 65.72% of Cu and 69.33% of Cr are from natural rock. In conclusion, FA-MLR can successfully identify source of heavy metal and compute source apportionment of heavy metals, meanwhile the transfer characteristic is revealed. All these information can be a reference for heavy metal pollution control.

Trace metals in suspended particles, sediments and Asiatic clams (Corbicula fluminea) of the Río de la Plata Estuary, Argentina.

PubMed

Bilos, C; Colombo, J C; Presa, M J

1998-01-01

Suspended particulate matter (SPM), sandy sediments and Asiatic clams were collected at seven sites along 150 km of the Río de la Plata coast to assess the magnitude of trace metal pollution in the area. Metal concentrations in SPM (Cu: 7.4-109; Cr: 75-408; Mn: 525-1341 microg(-1)), sediments (Cr: 16-27; Zn: 26-99; Mn: 221-489 microg(-1)) and bivalves (Cd: 0.5-1.9; Ni: 1.3-6.4; Cr: 1.3-11; Mn: 15-81; Cu: 28-89; Zn: 118-316 microg g(-1)) are comparable to those reported for other moderately polluted world rivers. Cu levels in Asiatic clams are among the highest, similar to those reported for heavily polluted sites. SPM Cu and Cr concentrations displayed a clear geographical trend with values increasing with proximity to major urban centers. Sediments showed a less clear pattern possibly due to their coarse nature (>98% sand) and higher proportion of mineral-associated residual metals. The clams showed a complex pattern due to the variability introduced by size-related factors and the natural dynamics of SPM in the estuary. Cr and Mn showed an apparent reverse industrial trend with higher concentrations in clams collected at distant stations near the turbidity maximum zone, possibly reflecting enhanced particle retention. Cu, Cd and Ni showed no clear geographical pattern, whereas Zn increased in the clams collected in the most industrialized area. A significant relationship with clam size was observed for Cu (positive) and Zn (negative) suggesting different physiological requirements for both metals with age. A principal component analysis confirmed these geographical and size-related trends.

Unusual Oxidative Limitations for Al-MAX Phases

NASA Technical Reports Server (NTRS)

Smialek, James L.

2017-01-01

Alumina-forming MAX phases are well-known for their excellent oxidation resistance, rivaling many metallic NiAl, NiCrAl, and FeCrAl counterparts and with upper temperature capability possible to approximately1400C. However a number of limitations have been emerging that need to be acknowledged to permit robust performance in demanding applications. Ti2AlC and Ti3AlC2 possess excellent scale adhesion, cyclic oxidation/moisture/volatility resistance, and TBC compatibility. However they are very sensitive to Al content and flux in order to maintain an exclusive Al2O3 scale without runaway oxidation of ubiquitous TiO2 transient scales. Accelerated oxidation has been shown to occur for Al-depleted, damaged, or roughened surfaces at temperatures less than 1200C. Conversely, Cr2AlC is less sensitive to transients, but exhibits volatile losses at 1200C or above if common Cr7C3 impurity phases are present. Poor scale adhesion is exhibited after oxidation at 1150C or above, where spallation occurs at the Cr7C3 (depletion zone) interface. Delayed spallation is significant and suggests a moisture-induced phenomenon similar to non-adherent metallic systems. Re-oxidation of this surface does not reproduce the initial pure Al2O3 behavior, but initiates a less-protective scale. Cr2AlC has also been shown to have good long term bonding with superalloys at 800C, but exhibits significant Beta-NiAl + Cr7C3 diffusion zones at 1100C and above. This may set limits on Cr2AlC as a high temperature TBC bond coat on Ni-based superalloys, while improving corrosion resistance in lower temperature applications.

Effect of substituent groups (R= sbnd CH3, sbnd Br and sbnd CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes

NASA Astrophysics Data System (ADS)

Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2017-12-01

Complexes [Cr(3-CH3-pic)2(H2O)2]NO3·H2O (1), [Cr(5-Br-pic)2(H2O)2]NO3·H2O (2) and [Cr(5-CF3-pic)2(H2O)2]NO3·H2O (3) were synthesized (pic = pyridine-2-carboxylic acid) and characterized by X-ray crystal diffraction. Crystal structure indicates that two bidentate ligands occupy equatorial position and two H2O occupy axial positions in trans-configuration. (i) Decomposition of complexes 1, 2 and 3 in different medium (phosphate buffered saline (PBS), apo-ovotransferrin (apootf) and EDTA) indicates that decomposition rate constants of these complexes follow the sequence of 1 < 2 < 3. (ii) The redox potential of Cr(III)/Cr(II) by cyclic voltammetry follows the sequence of 1 (-1.20 V) > 3 (-1.29 V) > 2 (-1.31 V). (iii) In addition, ·OH-generation of the new synthesized complexes was determined by Fenton-like reaction in comparison with Cr(pic)3, and it may be related to the reduction potential of the complexes. (iv) Moreover, Hammett substituent constants σp (inductive) and σm (resonance) (R = 3-CH3, 5-Br, 5-CF3) were introduced to evaluate the impact of substituent groups on the bond length and decomposition kinetics. The substituent group on the ligand has great effect on the properties of the complexes.

Removal combined with reduction of hexavalent chromium from aqueous solution by Fe-ethylene glycol complex microspheres

NASA Astrophysics Data System (ADS)

Zhang, Yong-Xing; Jia, Yong

2016-12-01

Three-dimensional Fe-ethylene glycol (Fe-EG) complex microspheres were synthesized by a facile hydrothermal method, and were characterized by field emission scanning electron microscopy and transmission electron microscopy. The adsorption as well as reduction properties of the obtained Fe-EG complex microspheres towards Cr(VI) ions were studied. The experiment data of adsorption kinetic and isotherm were fitted by nonlinear regression approach. In neutral condition, the maximum adsorption capacity was 49.78 mg g-1 at room temperature, and was increased with the increasing of temperature. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy revealed that adsorption of Cr(VI) was a feasible, spontaneous and endothermic process. Spectroscopic analysis revealed the adsorption of Cr(VI) was a physical adsorption process. The adsorbed CrO42- ions were partly reduced to Cr(OH)3 by Fe(II) ions and the organic groups in the Fe-EG complex.

A Complex of Cas Proteins 5, 6, and 7 Is Required for the Biogenesis and Stability of Clustered Regularly Interspaced Short Palindromic Repeats (CRISPR)-derived RNAs (crRNAs) in Haloferax volcanii*

PubMed Central

Brendel, Jutta; Stoll, Britta; Lange, Sita J.; Sharma, Kundan; Lenz, Christof; Stachler, Aris-Edda; Maier, Lisa-Katharina; Richter, Hagen; Nickel, Lisa; Schmitz, Ruth A.; Randau, Lennart; Allers, Thorsten; Urlaub, Henning; Backofen, Rolf; Marchfelder, Anita

2014-01-01

The clustered regularly interspaced short palindromic repeats/CRISPR-associated (CRISPR-Cas) system is a prokaryotic defense mechanism against foreign genetic elements. A plethora of CRISPR-Cas versions exist, with more than 40 different Cas protein families and several different molecular approaches to fight the invading DNA. One of the key players in the system is the CRISPR-derived RNA (crRNA), which directs the invader-degrading Cas protein complex to the invader. The CRISPR-Cas types I and III use the Cas6 protein to generate mature crRNAs. Here, we show that the Cas6 protein is necessary for crRNA production but that additional Cas proteins that form a CRISPR-associated complex for antiviral defense (Cascade)-like complex are needed for crRNA stability in the CRISPR-Cas type I-B system in Haloferax volcanii in vivo. Deletion of the cas6 gene results in the loss of mature crRNAs and interference. However, cells that have the complete cas gene cluster (cas1–8b) removed and are transformed with the cas6 gene are not able to produce and stably maintain mature crRNAs. crRNA production and stability is rescued only if cas5, -6, and -7 are present. Mutational analysis of the cas6 gene reveals three amino acids (His-41, Gly-256, and Gly-258) that are essential for pre-crRNA cleavage, whereas the mutation of two amino acids (Ser-115 and Ser-224) leads to an increase of crRNA amounts. This is the first systematic in vivo analysis of Cas6 protein variants. In addition, we show that the H. volcanii I-B system contains a Cascade-like complex with a Cas7, Cas5, and Cas6 core that protects the crRNA. PMID:24459147

Use of a Ferrous Sulfate - Sodium Dithionite Blend to Treat a Dissolved Phase Cr(VI) Plume

EPA Science Inventory

A field study was conducted to evaluate the use of a combination of sodium dithionite and ferrous sulfate in creating an in situ redox zone for treatment of a dissolved phase Cr(VI) plume at a former industrial site. The reductant blend was injected into the path of a dissolved ...

Mineral potential for nickel, copper, platinum group elements(PGE), and chromium deposits hosted in ultramafic rocks in the Islamic Republic of Mauritania (phase V, deliverable 67): Chapter G in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Marsh, Erin; Anderson, Eric D.

2015-01-01

PRISM-I summary documents mention the presence of mafic-ultramafic igneous intrusive rocks in several areas of Mauritania and a number of chromium (Cr) and copper-nickel (Cu-Ni (±Co, Au)) occurrences associated with them. Permissive geologic settings generally include greenstone belts of any age, layered mafic-ultramafic and unlayered gabbro-anorthosite intrusive complexes in cratonic settings, ophiolite complexes, flood basalt provinces, and fluid-rich shear zones cutting accumulations of mafic-ultramafic rocks. Regions of Mauritania having these characteristics that are discussed in PRISM-I texts include the Mesoarchean greenstone belts of the TasiastTijirit terrane in the southwestern Rgueïbat Shield, two separate layered ultramafic complexes in the Amsaga Complex west of Atar, serpentinized metadunites in Mesoarchean rocks of the Rgueïbat Shield in the Zednes map sheet, several lateritized annular mafic-ultramafic complexes in the Paleoproterozoic northwestern portion of the Rgueïbat Shield, and the serpentinized ophiolitic segments of the Gorgol Noir Complex in the axial portion of the southern Mauritanides. Bureau de Recherches Géologiques et Minières (BRGM) work in the “Extreme Sud” zone also suggests that small copper occurrences associated with the extensive Jurassic microgabbroic intrusive rocks in the Taoudeni Basin of southeastern Mauritania could have potential for magmatic Cu-Ni (PGE, Co, Au) sulfide mineralization. Similarly, Jurassic mafic intrusive rocks in the northeastern Taoudeni Basin may be permissive. Known magmatic Cu-Ni deposits of these types in Mauritania are few in number and some uncertainty exists as to the nature of several of the more important ones.

Optimization of operator and physical parameters for laser welding of dental materials.

PubMed

Bertrand, C; le Petitcorps, Y; Albingre, L; Dupuis, V

2004-04-10

Interactions between lasers and materials are very complex phenomena. The success of laser welding procedures in dental metals depends on the operator's control of many parameters. The aims of this study were to evaluate factors relating to the operator's dexterity and the choice of the welding parameters (power, pulse duration and therefore energy), which are recognized determinants of weld quality. In vitro laboratory study. FeNiCr dental drawn wires were chosen for these experiments because their properties are well known. Different diameters of wires were laser welded, then tested in tension and compared to the control material as extruded, in order to evaluate the quality of the welding. Scanning electron microscopy of the fractured zone and micrograph observations perpendicular and parallel to the wire axis were also conducted in order to analyse the depth penetration and the quality of the microstructure. Additionally, the micro-hardness (Vickers type) was measured both in the welded and the heat-affected zones and then compared to the non-welded alloy. Adequate combination of energy and pulse duration with the power set in the range between 0.8 to 1 kW appears to improve penetration depth of the laser beam and success of the welding procedure. Operator skill is also an important variable. The variation in laser weld quality in dental FeNiCr wires attributable to operator skill can be minimized by optimization of the physical welding parameters.

Chemical properties and biotoxicity of several chromium picolinate derivatives.

PubMed

Liu, Bin; Liu, Yanfei; Chai, Jie; Hu, Xiangquan; Wu, Duoming; Yang, Binsheng

2016-11-01

As a man-made additive, chromium picolinate Cr(pic) 3 has become a popular dietary supplement worldwide. In this paper Cr(pic) 3 and its new derivatives Cr(6-CH 3 -pic) 3 (1), [Cr(6-NH 2 -pic) 2 (H 2 O) 2 ]NO 3 (2) and Cr(3-NH 2 -pic) 3 (3) were synthesized, and complexes 1 and 2 were characterized by X-ray crystal structure (where pic=2-carboxypyridine). The relationship between the chemical properties and biotoxicity of these complexes was fully discussed: (1) The dynamics stability of chromium picolinate complexes mainly depends on the CrN bonds length. (2) There is a positive correlation between the dynamics stability, electrochemical potentials and generation of reactive oxygen species through Fenton-like reaction. (3) However, no biological toxicity was observed through MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) and sub-chronic oral toxicity study for these chromium picolinate compounds. Together, our findings establish a framework for understanding the structure-property-toxicity relationships of the chromium picolinate complexes. Copyright © 2016 Elsevier Inc. All rights reserved.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate.

PubMed

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-02-04

In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. The results have shown that the reaction is first order with respect to both [IO4(-)] and the complex concentration, and the rate increases over the pH range 2.62 - 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 x 10(-3) s(-1)), is greater than the value of k1 (1.22 x 10(-3) s(-1)) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0 degrees C and I = 0.20 mol dm(-3). It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4(-) to chromium(III). The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between DeltaH* and DeltaS* values for these reactions.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate

PubMed Central

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-01-01

Background In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. Results The results have shown that the reaction is first order with respect to both [IO4-] and the complex concentration, and the rate increases over the pH range 2.62 – 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 × 10-3 s-1), is greater than the value of k1 (1.22 × 10-3 s-1) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0°C and I = 0.20 mol dm-3. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4- to chromium(III). Conclusion The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions. PMID:19193241

Redox Equilibria Involving Chromium Minerals in Aqueous Fluids in the Deep Earth - Implications for Diamond Formation

NASA Astrophysics Data System (ADS)

Huang, J.; Huang, F.; Hao, J.; Sverjensky, D. A.

2017-12-01

Diamonds are often associated with inclusions of garnet that are characteristically Cr-rich and Ca-poor, suggesting metasomatic reactions involving fluids [1]. To investigate these reactions, we developed a thermodynamic characterization of Cr-bearing minerals and integrated it with our database for the thermodynamic properties of aqueous Cr-species [2]. We retrieved thermodynamic properties of picrochromite (MgCr2O4), and knorringite (Mg3Cr2Si3O12) consistent with minerals in the Berman (1988) using calorimetric data and experimental phase equilibria involving the reactions: MgCr2O4 + SiO2 = Cr2O3 + MgSiO3 [2] and MgCr2O4 + 4MgSiO3 = Mg3Cr2Si3O12 + Mg2SiO4 [3], respectively.At high temperatures and pressures, neutral pH and FMQ, the predicted solubilities of eskolaite and knorringite equilibrium with Cr2+ in a pure water system are very low. However, we found that complexes of Cr2+ and Cl- could increase the solubilities of chromium minerals significantly. At 500°C and 0.2 - 1.0 GPa, we retrieved the CrCl(OH)0 neutral complex from experiments on the solubility of Cr2O3 in HCl solutions [4]. At 1,000°C and 4.0 GPa, we retrieved the properties of a CrCl3- complex from experiments on the solubility of Cr2O3 in KCl solutions [5]. The predicted solubility of a garnet containing 23 mole% of knorringite in equilibrium with CrCl3- in a peridotitic diamond-forming fluid is 22 millimolal (1,144 ppm). This result suggests that a redox reaction relating to diamond formation might involveMg3Al2Si3O12 + 0.5CO2(aq) + 2 CrCl3- + 2H+ = Mg3Cr2Si3O12 + 0.5C-Diamond + 2Al3+ + 6Cl-. In this way, high temperature and pressure fluids containing Cr(II)-complexes might promote the mobility of chromium and be involved in metasomatic reactions and diamond formation.[1]Boyd et al. (1993)[2] Hao et al. (submitted to Geochem. Persp. Letters)[3] Berman (1988)[4] Klemme et al. (2000)[5] Klemme et al. (2004)[6] Watenphul et al. (2014)[7] Klein-BenDavid et al. (2011)

Selective and sensitive speciation analysis of Cr(VI) and Cr(III), at sub-μgL-1 levels in water samples by electrothermal atomic absorption spectrometry after electromembrane extraction.

PubMed

Tahmasebi, Zeinab; Davarani, Saied Saeed Hosseiny

2016-12-01

In this work, electromembrane extraction in combination with electrothermal atomic absorption spectrometry (ET-AAS) was investigated for speciation, preconcentration and quantification of Cr(VI) and Cr(III) in water samples through the selective complexation of Cr(VI) with 1,5-diphenylcarbazide (DPC) as a complexing agent. DPC reduces Cr(VI) to Cr(III) ions and then Cr(III) species are extracted based on electrokinetic migration of their cationic complex (Cr(III)-DPC) toward the negative electrode placed in the hollow fiber. Also, once oxidized to Cr(VI), Cr(III) ions in initial sample were determined by this procedure. The influence of extraction parameters such as pH, type of organic solvent, chelating agent concentration, stirring rate, extraction time and applied voltage were evaluated following a one-at-a-time optimization approach. Under optimized conditions, the extracted analyte was quantified by ETAAS, with an acceptable linearity in the range of 0.05-5ngmL -1 (R 2 value=0.996), and a repeatability (%RSD) between 3.7% and 12.2% (n=4) for 5.0 and 1.0ngmL -1 of Cr(VI), respectively. Also, we obtained an enrichment factor of 110 that corresponded to the recovery of 66%. The detection limit (S/N ratio of 3:1) was 0.02ngmL -1 . Finally, this new method was successfully employed to determine Cr(III) and Cr(VI) species in real water samples. Copyright © 2016. Published by Elsevier B.V.

Effects of Sex, Strain, and Energy Intake on Hallmarks of Aging in Mice.

PubMed

Mitchell, Sarah J; Madrigal-Matute, Julio; Scheibye-Knudsen, Morten; Fang, Evandro; Aon, Miguel; González-Reyes, José A; Cortassa, Sonia; Kaushik, Susmita; Gonzalez-Freire, Marta; Patel, Bindi; Wahl, Devin; Ali, Ahmed; Calvo-Rubio, Miguel; Burón, María I; Guiterrez, Vincent; Ward, Theresa M; Palacios, Hector H; Cai, Huan; Frederick, David W; Hine, Christopher; Broeskamp, Filomena; Habering, Lukas; Dawson, John; Beasley, T Mark; Wan, Junxiang; Ikeno, Yuji; Hubbard, Gene; Becker, Kevin G; Zhang, Yongqing; Bohr, Vilhelm A; Longo, Dan L; Navas, Placido; Ferrucci, Luigi; Sinclair, David A; Cohen, Pinchas; Egan, Josephine M; Mitchell, James R; Baur, Joseph A; Allison, David B; Anson, R Michael; Villalba, José M; Madeo, Frank; Cuervo, Ana Maria; Pearson, Kevin J; Ingram, Donald K; Bernier, Michel; de Cabo, Rafael

2016-06-14

Calorie restriction (CR) is the most robust non-genetic intervention to delay aging. However, there are a number of emerging experimental variables that alter CR responses. We investigated the role of sex, strain, and level of CR on health and survival in mice. CR did not always correlate with lifespan extension, although it consistently improved health across strains and sexes. Transcriptional and metabolomics changes driven by CR in liver indicated anaplerotic filling of the Krebs cycle together with fatty acid fueling of mitochondria. CR prevented age-associated decline in the liver proteostasis network while increasing mitochondrial number, preserving mitochondrial ultrastructure and function with age. Abrogation of mitochondrial function negated life-prolonging effects of CR in yeast and worms. Our data illustrate the complexity of CR in the context of aging, with a clear separation of outcomes related to health and survival, highlighting complexities of translation of CR into human interventions. Published by Elsevier Inc.

Metasomatized and hybrid rocks associated with a Palaeoarchaean layered ultramafic intrusion on the Johannesburg Dome, South Africa

NASA Astrophysics Data System (ADS)

Anhaeusser, Carl R.

2015-02-01

The Johannesburg Dome occurs as an inlier of Palaeoarchaean-Mesoarchaean granitic rocks, gneisses and greenstones in the central part of the Kaapvaal Craton, South Africa. In the west-central part of the dome a large greenstone remnant is surrounded and intruded by ca. 3114 Ma porphyritic granodiorites. Referred to locally as the Zandspruit greenstone remnant, it consists of a shallow-dipping ultramafic complex comprised of a number of alternating layers of harzburgite and pyroxenite. The ultramafic rocks are metamorphosed to greenschist grade and have largely been altered to serpentinite and amphibolite (tremolite-actinolite). In the granite-greenstone contact areas the porphyritic granodiorite has partially assimilated the greenstones producing a variety of hybrid rocks of dioritic composition. The hybrid rocks contain enclaves or xenoliths of greenstone and, in places, orbicular granite structures. Particularly noteworthy is an unusual zone of potash-metasomatized rock, occurring adjacent to the porphyritic granodiorite, consisting dominantly of biotite and lesser amounts of carbonate, quartz and sericite. Large potash-feldspar megacrysts and blotchy aggregated feldspar clusters give the rocks a unique texture. An interpretation placed on these rocks is that they represent metasomatized metapyroxenites of the layered ultramafic complex. Field relationships and geochemical data suggest that the rocks were influenced by hydrothermal fluids emanating from the intrusive porphyritic granodiorite. The adjacent greenstones were most likely transformed largely by the process of infiltration metasomatism, rather than simple diffusion, as CO2, H2O as well as dissolved components were added to the greenstones. Element mobility appears to have been complex as those generally regarded as being immobile, such as Ti, Y, Zr, Hf, Ta, Nb, Th, Sc, Ni, Cr, V, and Co, have undergone addition or depletion from the greenstones. Relative to all the rocks analyzed from the greenstones, the surrounding granitoids, and the hybrid rocks, those from the Zandspruit metasomatized zone show prominent enrichment of K2O, TiO2, Al2O3, Rb, Y, Zr, Nb, Ba, Th and U and depletion in MgO, FeOt, CaO, Cr, Co and Ni.

η6-Cycloparaphenylene transition metal complexes: synthesis, structure, photophysical properties, and application to the selective monofunctionalization of cycloparaphenylenes.

PubMed

Kubota, Natsumi; Segawa, Yasutomo; Itami, Kenichiro

2015-01-28

The synthesis, structure, photophysical properties, and reactivity of cycloparaphenylenes (CPPs) coordinated to group 6 transition metal fragments are described. The η(6)-coordination of [9]CPP or [12]CPP with M(CO)6 (M = Cr, Mo, W) afforded the corresponding [n]CPP-M(CO)3 complexes (n = 9, 12; M = Cr, Mo, W). In the (1)H NMR spectra of these complexes, characteristic upfield-shifted singlet signals corresponding to the four hydrogen atoms attached to the coordinated C6H4 ring of the CPPs were observed at 5.4-5.9 ppm. The complex [9]CPP-Cr(CO)3 could be successfully isolated in spite of its instability. X-ray crystallographic analysis and computational studies of [9]CPP-Cr(CO)3 revealed that chromium-CPP coordination occurs at the convex surface of [9]CPP both in the solid state and in solution. TD-DFT calculations suggested that the emerging high-wavenumber absorption peak upon coordination of [9]CPP to Cr(CO)3 should be assigned to a weak HOMO-LUMO transition. Moreover, by using the complex [9]CPP-Cr(CO)3, a rapid and highly monoselective CPP functionalization has been achieved. The established one-pot method, consisting of complexation, deprotonation, nucleophilic substitution, and decomplexation steps, yielded silyl-, boryl-, and methoxycarbonyl-substituted CPPs in up to 93% yield relative to reacted starting material.

Fluid-related modifications of Cr-spinel and olivine from ophiolitic peridotites by contact metamorphism of granitic intrusions in the Ablah area, Saudi Arabia

NASA Astrophysics Data System (ADS)

Ahmed, Ahmed Hassan; Surour, Adel Abdullah

2016-05-01

The Ablah serpentinized peridotites and overlying layered metagabbros represent an allochthonous piece of a dismembered ophiolite in the southern Hijaz terrane that belongs to the Neoproterozoic Arabian Shield in Saudi Arabia. On both sides, the ophiolite is bounded by wider domains of granitic intrusions and volcano-sedimentary successions, all together follow a N-S trend. The protolith of the Ablah serpentinized peridotites is mainly harzburgite which is partly or totally serpentinized. Carbonate veins of variable sizes invade and hydrate the serpentinized peridotites. Away from the contact with the granitic intrusions, fresh primary (igneous) olivine and Cr-spinel are preserved in the partly serpentinized peridotites. These relict primary minerals are used to infer their tectonic setting of formation as a nascent spreading center rock association of mid-ocean ridge or back-arc basin setting. Based on the re-distribution of elements related to different thermal effects, three patterns of Cr-spinel modification can be defined. The first pattern can be followed in the partly serpentinized peridotites where Cr-spinel displays simple zoning that is characterized by sharp contact between primary Al-rich cores and secondary Fe3+-rich rims. These cores and rims are homogeneous and show progressive decrease in Mg, Al and Cr, but with remarkable increase in Fe3+ and Fe2+ toward the rims. Mineral assemblage in equilibrium with this type of Cr-spinel is primary olivine + antigorite + chlorite ± talc ± chrysotile. The second pattern of Cr-spinel modification is represented by homogeneous weakly zoned Cr-rich spinel with no distinct sharp contacts between Cr-rich cores and magnetite rims. Cr-spinel cores of this type are rich in Cr and Fe2+, and poor in Mg, Al and Fe3+. The mineral assemblage in equilibrium with this Cr-spinel type is Fe-rich olivine + antigorite + enstatite + chlorite + tremolite + anthophyllite ± talc. The third pattern is defined by pervasive heterogeneous modification in which the alteration starts from the cores outwards forming a very characteristic "atoll" textured SiO2- and Cr-rich porous spinel. This type is characterized by core-to-rim increase in Cr, Fe3+, Si, Mn, Ni and Ti, and decrease in Mg, Al and Fe2+. The mineral assemblage in equilibrium with this pattern is chlorite + carbonates + lizardite/chrysotile ± antigorite. The first modification pattern is suggested to form under nearly solid-state conditions in the distal part from the granitic intrusion. The second pattern could be formed under reducing conditions with high temperature and fluid/rock ratio near the contact zone. The peak metamorphic temperature of this stage ranges from 500 to 650 °C that indicate upper amphibolite facies conditions. During retrograde metamorphism, the hydrothermal fluids are cooler and oxidizing which lead to the precipitation of thick marble-like carbonate veins within the serpentinized peridotites. In such a case, the aqueous fluids attack the Al- and Mg-rich cores, which are less resistant and replicable than the Fe-rich rims, and form the third chemical modification pattern of porous SiO2-rich spinel. The high SiO2 content in Cr-spinel is most probably attributed to the formation of Mg- and Al-rich silicates within the sub-microscopic pores of altered Cr-spinel.

Microscale characterization of metallic coatings for a high strength high conductivity copper alloy

NASA Astrophysics Data System (ADS)

Jain, Piyush

NiCrAlY overlay coatings are being considered by NASA's Glenn Research Center to prevent blanching and reduce thermo-mechanical fatigue of rocket engine combustion chamber liners made of GRCop-84 (Cu-8%Cr-4%Nb) for reusable launch vehicles (RLVs). However, their successful application depends upon their integrity to the GRCop-84 during multiple firings of rocket engines. This study focuses on determining the adhesion of NiCrAlY coatings and their microstructural stability on GRCop-84 as a function of thermal cycling. Specimens were prepared by depositing NiCrAlY top coat on GRCop-84 by vacuum plasma spaying with a thin layer of Cu-26Cr as a bond coat. A thermal cycling rig was built to thermally cycle the NiCrAlY/Cu-26Cr/GRCop-84 specimens from RT to 600°C in an argon environment, with 10 minutes hold at 600°C, and 4 minutes hold at RT. Samples were cut from the coupons in as-received condition (AR), after 100 thermal cycles (TC-100), and after 300 thermal cycles (TC-300) for characterization. A newly developed interfacial microsample testing technique was employed to determine the adhesion of the coatings on GRCop-84, where bowtie shaped microsamples having interfaces normal to the tensile axis were tested. Interfacial microsamples of NiCrAlY/Cu-26Cr/GRCop-84 in all the conditions (AR, TC-100, and TC-300) failed cohesively in the substrate at a UTS of 380+/-5 MPa and their interfaces remained intact. The microstructural characterization revealed that microstructure of the NiCrAlY/Cu-26Cr/GRCop-84 specimens does not degrade as a function of thermal cycling. Constitutive properties of NiCrAlY, Cu-26Cr, and GRCop-84 were measured by testing monolithic samples and were used to build the finite element model (FEM) of the interfacial microsamples. The FE model analyzed the local stress-strain in the interfacial microsamples during the testing and confirmed the strength of the interfaces to be higher than 380+/-5 MPa. Depleted zones, devoid of Cr2Nb particles, were observed in the substrate near the interface, which has been attributed to uncontrolled processing parameters during the coating deposition. The interfacial microsamples containing depleted zones, failed at 335+/-25 MPa in AR condition exhibiting cohesive-adhesive failure, and at 360+/-15 MPa in TC-300 condition exhibiting adhesive failure. All these results suggested that the presence of depleted zone decreases the adhesion of the coating and should be avoided in future coatings deposition. Adhesion of two top coats, NiCrAlY (with the Cu-26Cr bond coat) and the Cu-26Cr (without any bond coat), were found to be lower on the grit blasted GRCop-84 than on the polished GRCop-84. The adhesion of both the top coats on polished GRCop-84 was measured to be 380+/-5 MPa with cohesive failure in the substrate, while the adhesion of NiCrAlY top coat on the grit blasted GRCop-84 was measured to be 142+/-35 MPa with cohesive failure in the Cu-26Cr bond coat, and the adhesion of Cu-26Cr top coat on the grit blasted GRCop-84 was measured to be 360+/-25 MPa with cohesive failure in the Cu-26Cr top coat. The microstructural characterization revealed that the reason of lower strength of top coats on the grit blasted GRCop-84 was the porosity present in the coatings on the grit blasted GRCop-84, while the coatings on the polished GRCop-84 did not have any measurable porosity.

Has irrigated water from Mahaweli River contributed to the kidney disease of uncertain etiology in the dry zone of Sri Lanka?

PubMed

Diyabalanage, Saranga; Abekoon, Sumith; Watanabe, Izumi; Watai, Chie; Ono, Yuko; Wijesekara, Saman; Guruge, Keerthi S; Chandrajith, Rohana

2016-06-01

The Mahaweli is the largest river basin in Sri Lanka that provides water to the dry zone region through multipurpose irrigation schemes . Selenium, arsenic, cadmium, and other bioimportant trace elements in surface waters of the upper Mahaweli River were measured using ICP-MS. Trace element levels were then compared with water from two other rivers (Maha Oya, Kalu Ganga) and from six dry zone irrigation reservoirs. Results showed that the trace metal concentrations in the Mahaweli upper catchment were detected in the order of Fe > Cu > Zn > Se > Cr > Mn > As > Ni > Co > Mo. Remarkably high levels of Ca, Cr, Co, Ni, Cu, As, and Se were observed in the Mahaweli Basin compared to other study rivers. Considerably high levels of Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Se were found in upstream tributaries of the Mahaweli River. Such metals possibly originated from phosphate and organic fertilizers that are heavily applied for tea and vegetable cultivations within the drainage basin. Cadmium that is often attributed to the etiology of unknown chronic kidney diseases in certain parts of the dry zone is much lower than previously reported levels. Decrease in these metals in the lower part of the Mahaweli River could be due to adsorption of trace metals onto sediment and consequent deposition in reservoirs.

Probing chromium(III) from chromium(VI) in cells by a fluorescent sensor

NASA Astrophysics Data System (ADS)

Hu, Xiangquan; Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2016-01-01

Cellular uptake of Cr(VI), followed by its reduction to Cr(III) with the formation of kinetically inert Cr(III) complexes, is a complex process. To better understand its physiological and pathological functions, efficient methods for the monitoring of Cr(VI) are desired. In this paper a selective fluorescent probe L, rhodamine hydrazide bearing a benzo[b]furan-2-carboxaldehyde group, was demonstrated as a red chemosensor for Cr(III) at about 586 nm. This probe has been used to probe Cr(III) which is reduced from Cr(VI) by reductants such as glutathione (GSH), vitamin C, cysteine (Cys), H2O2 and Dithiothreitol (DTT) by fluorescence spectra. Cr(VI) metabolism in vivo is primarily driven by Vc and GSH. Vc could reduce CrO42 - to Cr(III) in a faster rate than GSH. The indirectly detection limit for Cr(VI) by L + GSH system was determined to be 0.06 μM at pH = 6.2. Moreover, the confocal microscopy image experiments indicated that Cr(VI) can be reduced to Cr(III) inside cells rapidly and the resulted Cr(III) can be captured and imaged timely by L.

New group 6 metal carbonyl complexes with 4,5-dimethyl-N,N-bis(pyridine-2-yl-methylene)benzene-1,2-diimine Schiff base: synthesis, spectral, cyclic voltammetry and biological activity studies.

PubMed

Mohamed, Rania G; Elantabli, Fatma M; Helal, Nadia H; El-Medani, Samir M

2015-04-15

Thermal reaction of M(CO)6 (M=Cr, Mo or W) with a Schiff base (DMPA) derived from the condensation of 4,5-dimethyl-1,2-phenylenediamine and pyridine-2-carboxaldehyde in THF in absence and presence of a secondary ligand; 2-aminobenzimidazole (Abz), thiourea (Tu) or 2-(2'-pyridyl)benzimidazole (pybz) were studied. The reaction of Cr(CO)6 gave the four complexes Cr2(CO)2(DMPA)2; 1, Cr(DMPA)2(Abz)2; 2, Cr2(CO)4(DMPA)2(Tu)2; 3 and Cr(DMPA)2(Pybz); 4, while the thermal reaction of Mo(CO)6 resulted in the formation of the two complexes Mo2(O)6(DMPA)2; 5, and Mo2(O)2(CO)2(DMPA)2(Tu)2; 6. Thermal reaction of W(CO)6 and the Schiff base DMPA gave the complex W(O)2(DMPA)2; 7. The ligand DMPA and its metal complexes have been reported and characterized based on elemental analyses, IR, (1)H NMR, magnetic measurements, and thermal analysis. Cyclic voltammetry and biological activity were also investigated. Copyright © 2015 Elsevier B.V. All rights reserved.

A complex of Cas proteins 5, 6, and 7 is required for the biogenesis and stability of clustered regularly interspaced short palindromic repeats (crispr)-derived rnas (crrnas) in Haloferax volcanii.

PubMed

Brendel, Jutta; Stoll, Britta; Lange, Sita J; Sharma, Kundan; Lenz, Christof; Stachler, Aris-Edda; Maier, Lisa-Katharina; Richter, Hagen; Nickel, Lisa; Schmitz, Ruth A; Randau, Lennart; Allers, Thorsten; Urlaub, Henning; Backofen, Rolf; Marchfelder, Anita

2014-03-07

The clustered regularly interspaced short palindromic repeats/CRISPR-associated (CRISPR-Cas) system is a prokaryotic defense mechanism against foreign genetic elements. A plethora of CRISPR-Cas versions exist, with more than 40 different Cas protein families and several different molecular approaches to fight the invading DNA. One of the key players in the system is the CRISPR-derived RNA (crRNA), which directs the invader-degrading Cas protein complex to the invader. The CRISPR-Cas types I and III use the Cas6 protein to generate mature crRNAs. Here, we show that the Cas6 protein is necessary for crRNA production but that additional Cas proteins that form a CRISPR-associated complex for antiviral defense (Cascade)-like complex are needed for crRNA stability in the CRISPR-Cas type I-B system in Haloferax volcanii in vivo. Deletion of the cas6 gene results in the loss of mature crRNAs and interference. However, cells that have the complete cas gene cluster (cas1-8b) removed and are transformed with the cas6 gene are not able to produce and stably maintain mature crRNAs. crRNA production and stability is rescued only if cas5, -6, and -7 are present. Mutational analysis of the cas6 gene reveals three amino acids (His-41, Gly-256, and Gly-258) that are essential for pre-crRNA cleavage, whereas the mutation of two amino acids (Ser-115 and Ser-224) leads to an increase of crRNA amounts. This is the first systematic in vivo analysis of Cas6 protein variants. In addition, we show that the H. volcanii I-B system contains a Cascade-like complex with a Cas7, Cas5, and Cas6 core that protects the crRNA.

LA-ICP-MS trace element mapping: insights into the crystallisation history of a metamorphic garnet population

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2017-04-01

In comparison to our understanding of major element zoning, relatively little is known about the incorporation of trace elements into metamorphic garnet. Given their extremely slow diffusivities and sensitivity to changing mineral assemblages, the analysis of the distribution of trace elements in garnet has the potential to yield a wealth of information pertaining to interfacial attachment mechanisms during garnet crystallisation, the mobility of trace elements in both garnet and the matrix, and trace element geochronology. Due to advances in the spatial resolution and analytical precision of modern microbeam techniques, small-scale trace element variations can increasingly be documented and used to inform models of metamorphic crystallisation. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in particular, can be used to rapidly quantify a wide range of elemental masses as a series of laser rasters, producing large volumes of spatially constrained trace element data. In this study, we present LA-ICP-MS maps of trace element concentrations from numerous centrally-sectioned garnets representative of the crystal size-distribution of a single sample's population. The study sample originates from the garnet-grade Barrovian zone of the Lesser Himalayan Sequence in Sikkim, northeast India, and has been shown to have crystallised garnet within a single assemblage between 515 ˚C and 565˚C, with no evidence for accessory phase reaction over the duration of garnet growth. Previous models have indicated that the duration of garnet crystallisation was extremely rapid (<1 Myr), with negligible diffusional homogenisation of major divalent cations. Consequently, the trace element record likely documents the primary zonation generated during garnet growth. In spite of straightforward (i.e. concentrically-zoned) major element garnet zonation, trace elements maps are characterised by significant complexity and variability. Y and the heavy rare earth elements are strongly enriched in crystal cores, where there is overprinting of the observed internal fabric, and exhibit numerous concentric annuli towards crystal rims. Conversely, the medium rare earth elements (e.g. Gd, Eu and Sm) exhibit bowl-shaped zoning from core to rim, with no annuli, and core and rim compositions of the medium rare earth elements are the same throughout the population within crystals of differing size. Cr exhibits pronounced spiral zoning, and the average Cr content increases towards garnet rims. In all cases, spirals are centered on the geometric core of the crystals. These LA-ICP-MS maps highlight the complexity of garnet growth over a single prograde event, and indicate that there is still much to be learnt from the analysis of garnet using ever-improving analytical methods. We explore the potential causes of the variations in the distribution of trace elements in garnet, and assess how these zoning patterns may be used to refine our understanding of the intricacies of garnet crystallisation and the spatial and temporal degree of trace element equilibration during metamorphism.

Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O 2 activation by non-adiabatic oxidative addition to a single metal center

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

2015-10-16

A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp tBu,MeCr V(O) 2] (Tp tBu,Me=hydrotris(3- tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp tBu,MeCr III(S 2)]. The transformation of the putative peroxo intermediate [Tp tBu,MeCr III(O 2)] (S= 3/ 2) into [Tp tBu,MeCr V(O) 2] (S= 1/ 2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(Tp tBu,MeCr) 2(μ-O) 2] exists, mechanistic experiments suggest that O 2 activation occurs on a single metal center, by an oxidativemore » addition on the quartet surface followed by crossover to the doublet surface.« less

Primitive andesites from the Taupo Volcanic Zone formed by magma mixing

NASA Astrophysics Data System (ADS)

Beier, Christoph; Haase, Karsten M.; Brandl, Philipp A.; Krumm, Stefan H.

2017-05-01

Andesites with Mg# >45 erupted at subduction zones form either by partial melting of metasomatized mantle or by mixing and assimilation processes during melt ascent. Primitive whole rock basaltic andesites from the Pukeonake vent in the Tongariro Volcanic Centre in New Zealand's Taupo Volcanic Zone contain olivine, clino- and orthopyroxene, and plagioclase xeno- and antecrysts in a partly glassy matrix. Glass pools interstitial between minerals and glass inclusions in clinopyroxene, orthopyroxene and plagioclase as well as matrix glasses are rhyolitic to dacitic indicating that the melts were more evolved than their andesitic bulk host rock analyses indicate. Olivine xenocrysts have high Fo contents up to 94%, δ18O(SMOW) of +5.1‰, and contain Cr-spinel inclusions, all of which imply an origin in equilibrium with primitive mantle-derived melts. Mineral zoning in olivine, clinopyroxene and plagioclase suggest that fractional crystallization occurred. Elevated O isotope ratios in clinopyroxene and glass indicate that the lavas assimilated sedimentary rocks during stagnation in the crust. Thus, the Pukeonake andesites formed by a combination of fractional crystallization, assimilation of crustal rocks, and mixing of dacite liquid with mantle-derived minerals in a complex crustal magma system. The disequilibrium textures and O isotope compositions of the minerals indicate mixing processes on timescales of less than a year prior to eruption. Similar processes may occur in other subduction zones and require careful study of the lavas to determine the origin of andesite magmas in arc volcanoes situated on continental crust.

Method for the determination of chromium in feed matrix by HPLC.

PubMed

Umesh, Balakrishnan; Rajendran, Rajendra Moorthy; Manoharan, Muthu Tamizh

2015-11-01

An improved method for the chromatographic separation and determination of chromium (III) and (VI) [ CRIII AND CRVI: ] in mineral mixtures and feed samples has been developed. The method uses precolumn derivatization using ammonium pyrrolidinedithiocarbamate ( APD: ) followed by reversed-phase liquid chromatography to separate the chromium ions. Both Cr(III) and Cr(VI) species are chelated with ammonium pyrrolidinedithiocarbamate prior to separation by mixing with acetonitrile and 0.5 mmol acetate buffer (pH 4.5). Optimum chromatographic separations were obtained with a polymer-based reversed-phase column (Kinetex, 5 μ, 250 × 4.5 mm, Phenomenex, Torrance, CA) and a mobile phase containing acetonitrile and water (7:3). Both Cr(III) and Cr(VI) ion concentrations were directly determined from the corresponding areas in the chromatogram. The effect of analytical parameters, including pH, concentration of ligand, incubation temperature, and mobile phase, was optimized for both chromium complexes. The range of the procedure was found to be linear for Cr(III) and Cr(VI) concentrations between 0.125 and 4 μg/mL (r² = 0.9926) and 0.1 and 3.0 μg/mL (r² = 0.9983), respectively. Precision was evaluated by replicate analysis in which the percentage relative standard deviation values for chromium complex were found to be below 4.0. The recoveries obtained (85-115%) for both Cr(III) and Cr(VI) complexes indicated the accuracy of the developed method. The degradation products, as well as the excipients, were well resolved from the chromium complex peak in the chromatogram. Finally, the new method proved to be suitable for routine analysis of Cr(III) and Cr(VI) species in raw materials, mineral mixtures, and feed samples. © 2015 Poultry Science Association Inc.

Removal of Cr(VI) from Aqueous Environments Using Micelle-Clay Adsorption

PubMed Central

Qurie, Mohannad; Khamis, Mustafa; Manassra, Adnan; Ayyad, Ibrahim; Nir, Shlomo; Scrano, Laura; Bufo, Sabino A.; Karaman, Rafik

2013-01-01

Removal of Cr(VI) from aqueous solutions under different conditions was investigated using either clay (montmorillonite) or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI) from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI) removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI) from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques. PMID:24222757

United States Coast Guard Antisubmarine Warfare (ASW) in the Maritime Defense Zone (MDZ) - A Strategic Approach

DTIC Science & Technology

1989-03-01

RIC ILE COPY AIR WAR COLLGE REEAC R~pCR UNITED STATES COAST GUARD ANTISUBMARINE WARFARE (ASW) IN THE MARITIME DEFENSE ZONE (MDZ) -A STRATEGIC...going to perform in these MDZs. Those tasks identified so far include: port and coastal physical security & preventive safety, mine warfare

Microstructure characteristics of Ni/WC composite cladding coatings

NASA Astrophysics Data System (ADS)

Yang, Gui-rong; Huang, Chao-peng; Song, Wen-ming; Li, Jian; Lu, Jin-jun; Ma, Ying; Hao, Yuan

2016-02-01

A multilayer tungsten carbide particle (WCp)-reinforced Ni-based alloy coating was fabricated on a steel substrate using vacuum cladding technology. The morphology, microstructure, and formation mechanism of the coating were studied and discussed in different zones. The microstructure morphology and phase composition were investigated by scanning electron microscopy, optical microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. In the results, the coating presents a dense and homogeneous microstructure with few pores and is free from cracks. The whole coating shows a multilayer structure, including composite, transition, fusion, and diffusion-affected layers. Metallurgical bonding was achieved between the coating and substrate because of the formation of the fusion and diffusion-affected layers. The Ni-based alloy is mainly composed of γ-Ni solid solution with finely dispersed Cr7C3/Cr23C6, CrB, and Ni+Ni3Si. WC particles in the composite layer distribute evenly in areas among initial Ni-based alloying particles, forming a special three-dimensional reticular microstructure. The macrohardness of the coating is HRC 55, which is remarkably improved compared to that of the substrate. The microhardness increases gradually from the substrate to the composite zone, whereas the microhardness remains almost unchanged in the transition and composite zones.

Genetic Variations in Two Seahorse Species (Hippocampus mohnikei and Hippocampus trimaculatus): Evidence for Middle Pleistocene Population Expansion

PubMed Central

Zhang, Yanhong; Pham, Nancy Kim; Zhang, Huixian; Lin, Junda; Lin, Qiang

2014-01-01

Population genetic of seahorses is confidently influenced by their species-specific ecological requirements and life-history traits. In the present study, partial sequences of mitochondrial cytochrome b (cytb) and control region (CR) were obtained from 50 Hippocampus mohnikei and 92 H. trimaculatus from four zoogeographical zones. A total of 780 base pairs of cytb gene were sequenced to characterize mitochondrial DNA (mtDNA) diversity. The mtDNA marker revealed high haplotype diversity, low nucleotide diversity, and a lack of population structure across both populations of H. mohnikei and H. trimaculatus. A neighbour-joining (NJ) tree of cytb gene sequences showed that H. mohnikei haplotypes formed one cluster. A maximum likelihood (ML) tree of cytb gene sequences showed that H. trimaculatus belonged to one lineage. The star-like pattern median-joining network of cytb and CR markers indicated a previous demographic expansion of H. mohnikei and H. trimaculatus. The cytb and CR data sets exhibited a unimodal mismatch distribution, which may have resulted from population expansion. Mismatch analysis suggested that the expansion was initiated about 276,000 years ago for H. mohnikei and about 230,000 years ago for H. trimaculatus during the middle Pleistocene period. This study indicates a possible signature of genetic variation and population expansion in two seahorses under complex marine environments. PMID:25144384

Impacts and Policy Implications of Metals Effluent Discharge into Rivers within Industrial Zones: A Sub-Saharan Perspective from Ethiopia

NASA Astrophysics Data System (ADS)

Zinabu, E.; Kelderman, P.; van der Kwast, J.; Irvine, K.

2018-04-01

Kombolcha, a city in Ethiopia, exemplifies the challenges and problems of the sub-Saharan countries where industrialization is growing fast but monitoring resources are poor and information on pollution unknown. This study monitored metals Cr, Cu, Zn, and Pb concentrations in five factories' effluents, and in the effluent mixing zones of two rivers receiving discharges during the rainy seasons of 2013 and 2014. The results indicate that median concentrations of Cr in the tannery effluents and Zn in the steel processing effluents were as high as 26,600 and 155,750 µg/L, respectively, much exceeding both the USEPA and Ethiopian emission guidelines. Cu concentrations were low in all effluents. Pb concentrations were high in the tannery effluent, but did not exceed emission guidelines. As expected, no metal emission guidelines were exceeded for the brewery, textile and meat processing effluents. Median Cr and Zn concentrations in the Leyole river in the effluent mixing zones downstream of the tannery and steel processing plant increased by factors of 52 (2660 compared with 51 µg Cr/L) and 5 (520 compared with 110 µg Zn/L), respectively, compared with stations further upstream. This poses substantial ecological risks downstream. Comparison with emission guidelines indicates poor environmental management by industries and regulating institutions. Despite appropriate legislation, no clear measures have yet been taken to control industrial discharges, with apparent mismatch between environmental enforcement and investment policies. Effluent management, treatment technologies and operational capacity of environmental institutions were identified as key improvement areas to adopt progressive sustainable development.

Short-period oscillations in photoemission from thin films of Cr(100)

NASA Astrophysics Data System (ADS)

Vyalikh, Denis V.; Zahn, Peter; Richter, Manuel; Dedkov, Yu. S.; Molodtsov, S. L.

2005-07-01

Angle-resolved photoemission (PE) study of thin films of Cr grown on Fe(100) reveals thickness-dependent short-period oscillations of the PE intensity close to the Fermi energy at k‖˜0 . The oscillations are assigned to quantum-well states (QWS) caused by the nesting between the Fermi-surface sheets around the Γ and the X points in the Brillouin zone of antiferromagnetic Cr. The experimental data are confirmed by density-functional calculations applying a screened Korringa-Kohn-Rostoker Green’s function method. The period of the experimentally observed QWS oscillations amounts to about 2.6 monolayers and is larger than the fundamental 2-monolayer period of antiferromagnetic coupling in Cr.

Corrosion behaviours of the dental magnetic keeper complexes made by different alloys and methods.

PubMed

Wu, Min-Ke; Song, Ning; Liu, Fei; Kou, Liang; Lu, Xiao-Wen; Wang, Min; Wang, Hang; Shen, Jie-Fei

2016-09-29

The keeper and cast dowel-coping, as a primary component for a magnetic attachment, is easily subjected to corrosion in a wet environment, such as the oral cavity, which contains electrolyte-rich saliva, complex microflora and chewing behaviour and so on. The objective of this in vitro study was to examine the corrosion resistance of a dowel and coping-keeper complex fabricated by finish keeper and three alloys (cobalt-chromium, CoCr; silver-palladium-gold, PdAu; gold-platinum, AuPt) using a laser-welding process and a casting technique. The surface morphology characteristics and microstructures of the samples were examined by means of metallographic microscope and scanning electron microscope (SEM). Energy-dispersive spectroscopy (EDS) with SEM provided elements analysis information for the test samples after 10% oxalic acid solution etching test. Tafel polarization curve recordings demonstrated parameter values indicating corrosion of the samples when subjected to electrochemical testing. This study has suggested that massive oxides are attached to the surface of the CoCr-keeper complex but not to the AuPt-keeper complex. Only the keeper area of cast CoCr-keeper complex displayed obvious intergranular corrosion and changes in the Fe and Co elements. Both cast and laser-welded AuPt-keeper complexes had the highest free corrosion potential, followed by the PdAu-keeper complex. We concluded that although the corrosion resistance of the CoCr-keeper complex was worst, the keeper surface passive film was actually preserved to its maximum extent. The laser-welded CoCr- and PdAu-keeper complexes possessed superior corrosion resistance as compared with their cast specimens, but no significant difference was found between the cast and laser-welded AuPt-keeper complexes. The Fe-poor and Cr-rich band, appearing on the edge of the keeper when casting, has been proven to be a corrosion-prone area.

Natural Cr3+-rich ettringite: occurrence, properties, and crystal structure

NASA Astrophysics Data System (ADS)

Seryotkin, Yurii V.; Sokol, Ella V.; Kokh, Svetlana N.; Murashko, Mikhail N.

2017-08-01

Cr3+-rich ettringite with Cr3+→Al substitution and Cr/(Cr + Al) ratios up to 0.40-0.50 was found in mineral assemblages of the Ma'aleh Adumim area of Mottled Zone (Judean Desert). The Cr3+-rich compositions were the latest in the thaumasite → ettringite-thaumasite solid solution → ettringite → ettringite-bentorite solid solution series. The mineral-forming solution was enriched in Cr3+ and had a pH buffered by afwillite at 11-12. Chromium was inherited from larnite rocks produced by high-temperature combustion metamorphic alteration of bioproductive calcareous sediments. The Cr/(Cr + Al) ratios are within 0.10-0.15 in most of the analysed crystals. This degree of substitution imparts pink colouration to the crystals, but does not affect their habit (a combination of monohedra and a prism). The habit changes to pyramid faces in coarse and later Cr3+-bearing crystals as Cr/(Cr + Al) ratios increase abruptly to 0.40-0.50. Single-crystal XRD analysis of one Cr-free and two Cr3+-rich samples and their structure determination and refinement indicate that the Cr-rich crystals (with Cr/(Cr + Al) to 0.3) preserve the symmetry and metrics of ettringite. The Ca-O bonding network undergoes differentiation with increase of Cr3+ concentration at octahedral M sites. The compression of Ca2 and expansion of Ca1 polyhedra sub-networks correlates with the degree of Cr3+→Al substitution.

Ti-48Al-2Cr-2Nb Evaluated Under Fretting Conditions

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Lerch, Bradley A.; Draper, Susan L.; Raj, Sai V.

2002-01-01

Material parameters govern many of the design decisions in any engineering task. When two materials are in contact and microscopically small, relative motions (either vibratory or creeping) occur, and fretting fatigue can result. Fretting fatigue is a material response influenced by the materials in contact as well as by such variables as loading and vibratory conditions. Fretting produces fresh, clean interacting surfaces and induces adhesion, galling, and wear in the contact zone. Time, money, and materials are unnecessarily wasted when galling and wear result in excessive fretting fatigue that leads to poorly performing, unreliable mechanical systems. Fretting fatigue is a complex problem of significant interest to aircraft engine manufacturers. It can occur in a variety of engine components. Numerous approaches, depending on the component and the operating conditions, have been taken to address the fretting problems. The components of interest in this investigation were the low-pressure turbine blades and disks. The blades in this case were titanium aluminide, Ti-48Al-2Cr- 2Nb, and the disk was a nickel-base superalloy, Inconel 718 (IN 718). A concern for these airfoils is the fretting in fitted interfaces at the dovetail where the blade and disk are connected. Careful design can reduce fretting in most cases, but not completely eliminate it, because the airfoils frequently have a skewed (angled) blade-disk dovetail attachment, which leads to a complex stress state. Furthermore, the local stress state becomes more complex when the influence of the metal-metal contact and the edge of contact are considered.

Hydrogen bond assisted interaction of glutamine with chromium (III) complex of 8-hydroxyquinoline: Experimental and theoretical studies

NASA Astrophysics Data System (ADS)

Narayanan, Jayanthi; Carlos-Alberto, Aguilar H.; Arturo, Lazarini M.; Höpfl, Herbert; Enrique-Fernando, Velazquez C.; Fernando, Rocha A.; Fernando-Toyohiko, Wakida K.; Velazquez-Lopez, José E.; Lesli, Arroyo O.

2018-03-01

Chromium (III) complex [Cr (hq)3;C2H5OH] of 8-hydroxyquinoline (hq) was prepared and its structure was resolved by X-ray diffraction analysis at low-temperature, showing that Cr3+ ion presents in distorted octahedral geometry, and it is consistent with the DFT optimized structure. It was observed that solvent ethanol is involved a hydrogen bond with 8-hydroxyquinoline anion. Furthermore, the molecular orbital contributions to spectral bands observed for the complex were determined by TD-DFT. The interaction of [Cr (hq)3;C2H5OH] with glutamine (Gln) or asparagine (Asn) shows that the complex binds effectively with glutamine through hydrogen bonding (H2N+-HṡṡṡOethanol) to form a possible stable adduct [Cr (hq)3;C2H5OH)Gln], yielding its binding constant 10,000 times greater (1.4315 M-1) than that for Asn (5.0 × 10-4 M-1). This is apparently due to the formation of stable secondary coordination sphere through the hydrogen bond between the metal complex with Gln. This observation is good agreement with the total molecular energy as well as with the molecular orbital study, i.e. in the DFT calculation, a lower total molecular energy (-8299,549.441 kcal/mmol) for [Cr (hq)3;C2H5OH) Gln] was obtained than that resulted for [Cr (hq)3;C2H5OH)Asn] (-8194,799.867 kcal/mmol), establishing ethanol effectively stabilizes the interaction between glutamine and the complex. Finally, antibacterial properties of [Cr (hq)3;C2H5OH] against Gram positive Bacillus cereus and Gram negative Escherichia coli was also studied, and compared its bacterial growths for its adducts of glutamine or of asparagine.

Intracellular versus extracellular accumulation of Hexavalent chromium reduction products by Geobacter sulfurreducens PCA.

PubMed

Gong, Yufeng; Werth, Charles J; He, Yaxue; Su, Yiming; Zhang, Yalei; Zhou, Xuefei

2018-05-10

Hexavalent chromium (Cr(VI)) reduction by Geobacter sulfurreducens PCA was evaluated in batch experiments, and the form and amounts of intracellular and extra-cellular Cr(VI) reduction products were determined over time. The first-order Cr(VI) reduction rate per unit mass of cells was consistent for different initial cell concentrations, and approximately equal to (2.065 ± 0.389) x 10 -9  mL CFU -1 h -1 . A portion of the reduced Cr(VI) products precipitated on Geobacter cell walls as Cr(III) and was bound via carboxylate functional groups, a portion accumulated inside Geobacter cells, and another portion existed as soluble Cr(III) or organo-Cr(III) released to solution. A mass balance analysis of total chromium in aqueous media, on cell walls, and inside cells was determined as a function of time, and with different initial cell concentrations. Mass balances were between 92% and 98%, and indicated Cr(VI) reduction products accumulate more on cell walls and inside cells with time and with increasing initial cell concentration, as opposed to particulates in aqueous solution. Reduced Cr(VI) products both in solution and on cell surfaces appear to form organo-Cr(III) complexes, and our results suggest that such complexes are more stable to reoxidation than aqueous Cr(III) or Cr(OH) 3 . Chromium inside cells is also likely more stable to reoxidation, both because it can form organic complexes, and it is separated by the cell membrane from solution conditions. Hence, Cr(VI) reduction products in groundwater during bioremediation may become more stable against re-oxidation, and may pose a lower risk to human health, over time and with greater initial biomass densities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Zircon U-Pb ages and petrogenesis of a tonalite-trondhjemite-granodiorite (TTG) complex in the northern Sanandaj-Sirjan zone, northwest Iran: Evidence for Late Jurassic arc-continent collision

NASA Astrophysics Data System (ADS)

Azizi, Hossein; Zanjefili-Beiranvand, Mina; Asahara, Yoshihiro

2015-02-01

The Ghalaylan Igneous Complex is located in the northern part of the Sanandaj-Sirjan zone (SSZ) in northwest Iran. At the surface, the complex is ellipsoidal or ring-shaped. The igneous rocks, which are medium- to fine-grained, were intruded into a Jurassic metamorphic complex and are cut by younger dikes. Zircon U-Pb ages indicate that the crystallization of the main body occurred from 157.9 ± 1.6 to 155.6 ± 5.6 Ma. The igneous complex includes granodiorite, tonalite, and quartz monzonite, as well as subvolcanic to volcanic rocks such as dacite and rhyolite. The rocks have high concentrations of Al2O3 (15-19 wt.%), SiO2 (65-70 wt.%), and Sr (700-1100 ppm), high (La/Yb)N ratios (15-40), and very low concentrations of MgO (< 0.83 wt.%), Ni (< 7 ppm), and Cr (usually < 50 ppm). There is a lack of negative Eu anomalies. These geochemical features show that the rocks are similar to high-silica adakites and Archaean tonalite-trondhjemite-granodiorite (TTG) rocks. The initial ratios of 87Sr/86Sr and 143Nd/144Nd vary from 0.70430 to 0.70476 and from 0.51240 to 0.51261, respectively, values that are similar to those of primitive mantle and the bulk Earth. The chemical compositions of the igneous rocks of the complex, and their isotope ratios, differ from those of neighboring granitic bodies in the northern SSZ. Based on our results, we suggest a new geodynamic model for the development of this complex, as follows. During the generation of the Songhor-Ghorveh island arc in the Neotethys Ocean, an extensional basin, such as a back-arc, developed between the island arc and the Sanandaj-Sirjan zone (SSZ). As a consequence, basaltic magma was injected from the asthenosphere without the development of a mature oceanic crust. During arc-continent collision in the Late Jurassic, hot basaltic rocks were present beneath the SSZ at depths of 30-50 km, and the partial melting of these rocks led to the development of TTG-type magmas, forming the source of the Ghalaylan Igneous Complex.

Cr(III) solubility in aqueous fluids at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Watenphul, Anke; Schmidt, Christian; Jahn, Sandro

2014-02-01

Trivalent chromium is generally considered relatively insoluble in aqueous fluids and melts. However, numerous counterexamples in nature indicate Cr(III) mobilization by aqueous fluids during metamorphism or hydrothermal alteration of chromite-bearing rocks, or by pegmatite melts. So far, very little is known about the chromium concentrations and speciation in such fluids. In this study, the solubility of eskolaite (Cr2O3) in 1.6-4.2 m aqueous HCl solutions was determined in situ at elevated pressures up to 1 GPa and temperatures ranging between 400 and 700 °C using synchrotron micro-X-ray fluorescence spectroscopy (μ-XRF). Determined concentrations of dissolved Cr ranged between about 900-18,000 ppm, with the highest concentrations found at 500 °C and 861 MPa. The Cr(III) solubility in aqueous HCl fluids is retrograde in the studied temperature range and increases with pressure. In addition, Cr(III) complexation in these fluids was explored by Raman spectroscopy on a 12.3 mass% HCl fluid in equilibrium with eskolaite at 400 and 600 °C, 0.3-1.6 GPa. All spectra show two prominent Cr-Cl stretching bands at about 275 and 325 cm-1, which display some fine structure, and in some spectra weak bands in the region between 380 and 500 cm-1. The sum of the integrated intensities of the two dominant bands reveals qualitatively the same changes with temperature along an isochore, with pressure at constant temperature, and with the time required for equilibration as the Cr(III) concentrations in the fluid determined by μ-XRF. Complementary ab initio molecular dynamics simulations of a 4 m HCl solution at two different densities (0.8 and 0.97 g/cm3) and temperatures (427 and 727 °C) were performed to investigate the vibrational properties of various(O)y3-x and (O)y(OH)z3-x-z complexes with 3⩽x+z⩽4 and 0⩽y⩽2. Quasi-normal mode analysis reveals that both the tetrahedral symmetric and antisymmetric Cr-Cl stretching vibrations of CrCl4(H2O)0-2- have characteristic frequencies in the range of the two strongest experimentally observed Raman bands, whereas Cr-O stretching vibrations of hydroxy-chloride complexes occur at wavenumbers above 400 cm-1. Solubility and complexation of Cr(III) depend strongly on the activities of Cl- and H+. At high H+ and Cl- activity, the results are consistent with CrCl(H2O)0-2-1-0 complexes as major Cr(III) species, the Cr coordination number of which increases with pressure by becoming more aquated. At low Cl- activity, i.e. in our study at high-temperature low-pressure conditions, the data indicate mixed CrClx((OH)z3-x-z complexes with Cl-Cr ratios less than three. In situ μ-XRF solubility experiments conducted with eskolaite + (H2O + 29 mass% Na2CO3) and kosmochlor + (H2O + 44 mass% Na2Si3O7) resulted in dissolved Cr concentrations at or below the detection limit of 500 ppm. Thus, acidic chloridic fluids seem to be more efficient agents for Cr(III) mobilization and transport at crustal conditions than aqueous alkali carbonate or silicate solutions.

IN SITU SOURCE TREATMENT OF CR(VI) USING A FE(II)-BASED REDUCTANT BLEND: LONG-TERM MONITORING AND EVALUATION

EPA Science Inventory

The long-term effectiveness of a FeSO4 + Na2S2O4 reductant solution blend for in situ saturated zone treatment of dissolved and solid phase Cr(VI) in a high pH chromite ore processing solid waste (COPSW) fill material was investigated. Two field pilot injection studies were cond...

Molecular structure and biological studies on Cr(III), Mn(II) and Fe(III) complexes of heterocyclic carbohydrazone ligand.

PubMed

Abu El-Reash, G M; El-Gammal, O A; Radwan, A H

2014-01-01

The chelating behavior of the ligand (H2APC) based on carbohydrazone core modified with pyridine end towards Cr(III), Mn(II) and Fe(III) ions have been examined. The (1)H NMR and IR data for H2APC revealed the presence of two stereoisomers syn and anti in both solid state and in solution in addition to the tautomeric versatility based on the flexible nature of the hydrazone linkage leading to varied coordination modes. The spectroscopic data confirmed that the ligand behaves as a monobasic tridentate in Cr(III) and Fe(III) complexes and as neutral tetradentate in Mn(II) complex. The electronic spectra as well as the magnetic measurements confirmed the octahedral geometry for all complexes. The bond length and angles were evaluated by DFT method using material studio program for all complexes. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and cytotoxic activities of the compounds have been screened. Cr(III) complex and H2APC showed the highest antioxidant activity using ABTS and DPPH methods. With respect to in vitro Ehrlich ascites assay, H2APC exhibited the potent activity followed by Fe(III) and Cr(III)complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

Mechanism-based design of labile precursors for chromium(I) chemistry

DOE PAGES

Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

2015-08-27

Here, we report that dinitrogen complexes of the type Tp R,RCr–N 2–CrTp R,R are not the most labile precursors for Cr(I) chemistry, as they are sterically protected from obligatory associative ligand substitution. A mononuclear alkyne complex – Tp tBu,MeCr(η 2-C 2(SiMe 3) 2) – proved to be much more reactive.

Structural Basis for Dual-Inhibition Mechanism of a Non-Classical Kazal-Type Serine Protease Inhibitor from Horseshoe Crab in Complex with Subtilisin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shenoy, Rajesh T.; Thangamani, Saravanan; Velazquez-Campoy, Adrian

2011-04-26

Serine proteases play a crucial role in host-pathogen interactions. In the innate immune system of invertebrates, multi-domain protease inhibitors are important for the regulation of host-pathogen interactions and antimicrobial activities. Serine protease inhibitors, 9.3-kDa CrSPI isoforms 1 and 2, have been identified from the hepatopancreas of the horseshoe crab, Carcinoscorpius rotundicauda. The CrSPIs were biochemically active, especially CrSPI-1, which potently inhibited subtilisin (Ki=1.43 nM). CrSPI has been grouped with the non-classical Kazal-type inhibitors due to its unusual cysteine distribution. Here we report the crystal structure of CrSPI-1 in complex with subtilisin at 2.6 Å resolution and the results of biophysicalmore » interaction studies. The CrSPI-1 molecule has two domains arranged in an extended conformation. These two domains act as heads that independently interact with two separate subtilisin molecules, resulting in the inhibition of subtilisin activity at a ratio of 1:2 (inhibitor to protease). Each subtilisin molecule interacts with the reactive site loop from each domain of CrSPI-1 through a standard canonical binding mode and forms a single ternary complex. In addition, we propose the substrate preferences of each domain of CrSPI-1. Domain 2 is specific towards the bacterial protease subtilisin, while domain 1 is likely to interact with the host protease, Furin. Elucidation of the structure of the CrSPI-1: subtilisin (1:2) ternary complex increases our understanding of host-pathogen interactions in the innate immune system at the molecular level and provides new strategies for immunomodulation.« less

Occurrence and Speciation of Polymeric Chromium(III), Monomeric Chromium(III) and Chromium(VI) in Environmental Samples

PubMed Central

HU, LIGANG; CAI, YONG; JIANG, GUIBIN

2016-01-01

Laboratory experiments suggest that polymeric Cr(III) could exist in aqueous solution for a relative long period of time. However, the occurrence of polymeric Cr(III) has not been reported in environmental media due partially to the lack of method for speciating polymeric Cr. We observed an unknown Cr species during the course of study on speciation of Cr in the leachates of chromated-copper-arsenate (CCA)-treated wood. Efforts were made to identify structure of the unknown Cr species. Considering the forms of Cr existed in the CCA-treated woods, we mainly focused our efforts to determine if the unknown species were polymeric Cr(III), complex of Cr/As or complex of Cr with dissolved organic matter (DOM). In order to evaluate whether polymeric Cr(III) largely exist in wood leachates, high performance liquid chromatography coupled with inductively coupled mass spectrometry (HPLC-ICPMS was used) for simultaneous speciation of monomeric Cr(III), polymeric Cr(III), and Cr(VI). In addition to wood leachates where polymeric Cr (III) ranged from 39.1 to 67.4 %, occurrence of the unknown Cr species in other environmental matrices, including surface waters, tap and waste waters, was also investigated. It was found that polymeric Cr(III) could exist in environmental samples containing μg/L level of Cr, at a level up to 60% of total Cr, suggesting that polymeric Cr(III) could significantly exist in natural environments. Failure in quantifying polymeric Cr(III) would lead to the underestimation of total Cr and bias in Cr speciation. The environmental implication of the presence of polymeric Cr(III) species in the environment deserves further study. PMID:27156211

Theoretical study of the magnetic exchange coupling behavior substituting Cr(III) with Mo(III) in cyano-bridged transition metal complexes

NASA Astrophysics Data System (ADS)

Zhang, Yi-Quan; Luo, Cheng-Lin

Molecular magnetism in a series of cyano-bridged first and second transition metal complexes has been investigated using density functional theory (DFT) combined with the broken-symmetry (BS) approach. Several exchange-correlation (XC) functionals in the ADF package were used to investigate complexes I [-(Me3tacn)2(cyclam)NiMo2(CN)6]2+, II [-(Me3tacn)2(cyclam)Ni-Cr2(CN)6]2+, III [(Me3tacn)6MnMo6(CN)18]2+, and IV [(Me3tacn)6MnCr6(CN)18]2+ (Me3tacn = N,N?,N‴-trimethyl-1,4,7-triazacyclononane). For models A (the molded structure of complex I) and B (the modeled structure of complex II), all the XCs given qualitatively reasonable results and predict ferromagnetic coupling character between M (M = MoIII for A or CrIII for B) and NiII in coincidence with the experimental results (see Tables and ). The calculated using Operdew, OPBE, O3LYP, and B3LYP functionals and experimental J values show that substituting CrIII with MoIII will enhance the ferromagnetic exchange coupling interactions. But VWN, PW91, PBE, VSXC, and tau-HCTH functionals have no way to differentiate the relative strength of the intramolecular magnetic exchange coupling interactions of A and B correctly. For models C (the modeled structure of complex III) and D (the modeled structure of complex IV), all the XCs in ADF and B3LYP in Gaussian 03 with several basis sets show that substituting CrIII with MoIII will enhance the antiferromagnetic exchange coupling interactions. From the above calculations, the substitution of CrIII by MoIII will enhance the magnetic coupling interactions, whether the magnetic coupling interactions are ferro- or antiferromagnetic. Moreover, Kahn's model was applied to investigate the above facts.

Mechanical characteristics and microstructure of weld joint of high-temperature martensitic steel containing 9% Cr

NASA Astrophysics Data System (ADS)

Shakhova, Ya. E.; Belyakov, A. N.; Kaibyshev, R. O.

2016-04-01

The structure and mechanical characteristics of a weld joint of 10Kh9K3V2MFBR steel (0.097 C, 0.17.Si, 0.54 Mn, 8.75 Cr, 0.21 Ni, 0.51 Mo, 0.07 Nb, 0.23 V, 0.004 N, 0.003 B, 1.6 W, 0.15 Cu, and Fe for balance, wt %) have been studied; the joint was produced by hand welding in an argon atmosphere using 03Kh20N45M7G6B welding wire (0.3 C, 20 Cr, 45 Ni, 7 Mo, 6 Mn, and 1 Nb, wt %). The weld joint is divided into the zone of the base metal, a thermal effect zone, which consists of zones that contain fine and coarse original austenitic grains, and the zone of seam metal. It has been shown that the weld joint of 10Kh9K3V2MFBR steel possesses high strength characteristics at the room temperature under static loading and a satisfactorily impact toughness, which has the minimum value of 30 J/cm2 in the zone of the seam metal and does not depend on the temperature. With a decrease in the temperature from the room temperature to 253 K, a ductile-brittle transition occurs in the thermal effect zone. Creep tests carried out at the temperature of 923 K have shown that the long-term strength of the weld seam is lower than that of the base material in the entire stress range being tested. At stresses of 140 MPa or higher, the acceleration of creep in the weld seam is observed, while at low stresses of about 120 MPa, the rates of creep in the weld seam and in the base metal remain similar until the transition to the stage of accelerated fracture occurs. The difference in the values of the long-term strength is due to premature fracture, which occurs in the thermal effect zone with the finegrained structure.

ESR spectrum of Cr(V) with 2,3-dioxynaphthalene in a liquid crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Novosadov, N.A.; Mukhtarov, A.S.; Usmanov, Z.I.

1987-01-01

Research has previously been reported on the complex formed by Cr(V) with 2,3-dioxynaphthalene (I) in solution in DMFA. An open question remaining is the mutual orientation of the molecular symmetry axes and the magnetic ones. The authors give results on the complex formed by Cr(V) with I obtained by ESR in 4-methoxy-benzylidene-n-4'-butylaniline (MBBA). The ESR spectrum of Cr(V) with I in the nematic phase of MBBA is a strong line due to /sup 52/Cr with g = 1.978 and four weak lines due to /sup 53/Cr at the natural content with HFI constant a* = 11.8 x 10/sup -4/ T;more » when the MBBA is converted to the isotropic phase, the observed HFI constant from /sup 53/Cr increases to 18 x 10/sup -4/ T, while the g factor is unaltered.« less

Computationally Efficient Power Allocation Algorithm in Multicarrier-Based Cognitive Radio Networks: OFDM and FBMC Systems

NASA Astrophysics Data System (ADS)

Shaat, Musbah; Bader, Faouzi

2010-12-01

Cognitive Radio (CR) systems have been proposed to increase the spectrum utilization by opportunistically access the unused spectrum. Multicarrier communication systems are promising candidates for CR systems. Due to its high spectral efficiency, filter bank multicarrier (FBMC) can be considered as an alternative to conventional orthogonal frequency division multiplexing (OFDM) for transmission over the CR networks. This paper addresses the problem of resource allocation in multicarrier-based CR networks. The objective is to maximize the downlink capacity of the network under both total power and interference introduced to the primary users (PUs) constraints. The optimal solution has high computational complexity which makes it unsuitable for practical applications and hence a low complexity suboptimal solution is proposed. The proposed algorithm utilizes the spectrum holes in PUs bands as well as active PU bands. The performance of the proposed algorithm is investigated for OFDM and FBMC based CR systems. Simulation results illustrate that the proposed resource allocation algorithm with low computational complexity achieves near optimal performance and proves the efficiency of using FBMC in CR context.

Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) ions: synthesis, structural characterization and biological activity studies.

PubMed

Abd el-Halim, Hanan F; Mohamed, Gehad G; el-Dessouky, Maher M I; Mahmoud, Walaa H

2011-11-01

Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, (1)H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25±1°C and at 0.1 M KNO(3) ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO(2)(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H(2)O)(4)]·Cl(2) and [Zn(LFX)(H(2)O)(4)]·Cl(2) were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had been found to be inactive at lower concentration than 100 μg/ml. Copyright © 2011 Elsevier B.V. All rights reserved.

Effects of cooling time and alloying elements on the microstructure of the gleeble-simulated heat-affected zone of 22% Cr duplex stainless steels

NASA Astrophysics Data System (ADS)

Hsieh, Rong-Iuan; Liou, Horng-Yih; Pan, Yeong-Tsuen

2001-10-01

The effects of austenite stabilizers, such as nitrogen, nickel, and manganese, and cooling time on the microstructure of the Gleeble simulated heat-affected zone (HAZ) of 22% Cr duplex stainless steels were investigated. The submerged are welding was performed for comparison purposes. Optical microscopy (OM) and transmission electron microscopy (TEM) were used for microscopic studies. The amount of Cr2N precipitates in the simulated HAZ was determined using the potentiostatic electrolysis method. The experimental results indicate that an increase in the nitrogen and nickel contents raised the δ to transformation temperature and also markedly increased the amount of austenite in the HAZ. The lengthened cooling time promotes the reformation of austenite. An increase in the austenite content reduces the supersaturation of nitrogen in ferrite matrix as well as the precipitation tendency of Cr2N. The optimum cooling time from 800 to 500 °C (Δ t 8/5) obtained from the Gleeble simulation is between 30 and 60 s, which ensures the austenite content in HAZ not falling below 25% and superior pitting and stress corrosion cracking resistance for the steels. The effect of manganese on the formation of austenite can be negligible.

The effect of organic compounds in the oxidation kinetics of Cr(III) by H 2O 2

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; Gennari, Francesca; Campanella, Luigi; Millero, Frank J.

2008-12-01

The oxidation of Cr(III) has been studied in NaCl solutions in the presence of two siderophore models, acetohydroxamic acid (Aha) and benzohydroxamic acid (Bha), the natural siderophore Desferal (DFOB) and the synthetic aminocarboxilate (ethylenedinitrilo)-tetra-acetic acid (EDTA) as a function of pH (8-9), ionic strength (0.01-2 M) and temperature (10-50 °C), at different Cr(III)-organic compound ratios. The addition of Aha and Bha caused the rates to increase at low ligand/Cr(III) ratios and decrease at high ratios. The variation of the pseudo first order rate constant ( k1) as a function of the ligand concentration has been attributed to the formation of three Cr(III)-organo species (1:1, 1:2, 1:3), which can form in the presence of monohydroxamic acids. A kinetic model has been developed that gives a value of 600 (min -1) for the pseudo first order rate constant k and values approaching zero for k and k. These kinetic results demonstrate that these monohydroxamic acids are able to bind with Cr(III) under experimental conditions that may occur in natural waters and can increase the oxidation rates of Cr(III) with H 2O 2 by a factor of 3.5 at an Aha/Cr(III) ratio of about 50-100. The monohydroxamic acids also affect the rates on aged products of Cr(III), suggesting that these ligands are able to affect the oxidation rates by releasing reactive Cr(III). DFOB and EDTA do not have a great effect on the oxidation of Cr(III) with H 2O 2. This is thought to be due to the much longer times they need to form complexes with Cr(III) compared to Aha and Bha. The rates for the formation of DFOB and EDTA complexes with Cr(III) are not competitive with the rates of the formation of aged Cr(III). After allowing Cr(III) and DFOB to react for 5 days to form the complex, reaction rates of Cr(III) with H 2O 2 appear to be lowered probably because of steric hindrance of the chelated Cr(III).

Field method for the determination of hexavalent chromium by ultrasonication and strong anion-exchange solid-phase extraction.

PubMed

Wang, J; Ashley, K; Marlow, D; England, E C; Carlton, G

1999-03-01

A simple, fast, sensitive, and economical field method was developed and evaluated for the determination of hexavalent chromium (CrVI) in environmental and workplace air samples. By means of ultrasonic extraction in combination with a strong anion-exchange solid-phase extraction (SAE-SPE) technique, the filtration, isolation, and determination of CrVI in the presence of trivalent chromium (CrIII) and potential interferents was achieved. The method entails (1) ultrasonication in basic ammonium buffer solution to extract CrVI from environmental matrixes; (2) SAE-SPE to separate CrVI from CrIII and interferences; (3) elution/acidification of the eluate; (4) complexation of chromium with 1,5-diphenylcarbazide; and (5) spectrophotometric determination of the colored chromium-diphenylcarbazone complex. Several critical parameters were optimized in order to effect the extraction of both soluble (K2CrO4) and insoluble (PbCrO4) forms of CrVI without inducing CrIII oxidation or CrVI reduction. The method allowed for the dissolution and purification of CrVI from environmental and workplace air sample matrixes for up to 24 samples simultaneously in less than 90 min (including ultrasonication). The results demonstrated that the method was simple, fast, quantitative, and sufficiently sensitive for the determination of occupational exposures of CrVI. The method is applicable for on-site monitoring of CrVI in environmental and industrial hygiene samples.

Sensitivity of a global climate model to the critical Richardson number in the boundary layer parameterization

DOE PAGES

Zhang, Ning; Liu, Yangang; Gao, Zhiqiu; ...

2015-04-27

The critical bulk Richardson number (Ri cr) is an important parameter in planetary boundary layer (PBL) parameterization schemes used in many climate models. This paper examines the sensitivity of a Global Climate Model, the Beijing Climate Center Atmospheric General Circulation Model, BCC_AGCM to Ri cr. The results show that the simulated global average of PBL height increases nearly linearly with Ri cr, with a change of about 114 m for a change of 0.5 in Ri cr. The surface sensible (latent) heat flux decreases (increases) as Ri cr increases. The influence of Ri cr on surface air temperature and specificmore » humidity is not significant. The increasing Ri cr may affect the location of the Westerly Belt in the Southern Hemisphere. Further diagnosis reveals that changes in Ri cr affect stratiform and convective precipitations differently. Increasing Ri cr leads to an increase in the stratiform precipitation but a decrease in the convective precipitation. Significant changes of convective precipitation occur over the inter-tropical convergence zone, while changes of stratiform precipitation mostly appear over arid land such as North Africa and Middle East.« less

Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study.

PubMed

Kapre, Ruta R; Bothe, Eberhard; Weyhermüller, Thomas; George, Serena Debeer; Muresan, Nicoleta; Wieghardt, Karl

2007-09-17

From the reaction mixture of 3,6-di-tert-butylcatechol, H2[3,6L(cat)], [CrCl3(thf)3], and NEt3 in CH3CN in the presence of air, the neutral complex [CrIII(3,6L*(sq))3] (S = 0) (1) was isolated. Reduction of 1 with [Co(Cp)2] in CH2Cl2 yielded microcrystals of [Co(Cp)2][CrIII(3,6L*(sq))2(3,6L(cat))] (S = 1/2) (2) where (3,6L*(sq)(1-) is the pi-radical monoanionic o-semiquinonate of the catecholate dianion (3,6Lcat)(2-). Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O)]z (z = 0, 1-, 2-, 3-). The corresponding tris(benzo-1,2-dithiolato)chromium complex [N(n-Bu)4][CrIII(3,5L*S,S)2(3,5LS,S)] (S = 1/2) (3) has also been isolated; (3,5LS,S)(2-) represents the closed-shell dianion 3,5-di-tert-butylbenzene-1,2-dithiolate(2-), and (3,5L*S,S)(1-) is its monoanionic pi radical. Complex 3 is a member of the electron-transfer series [Cr(3,5L(S,S))3]z (z = 0, 1-, 2-, 3-). It is shown by Cr K-edge and S K-edge X-ray absorption, UV-vis, and EPR spectroscopies, as well as X-ray crystallography, of 1 and 3 that the oxidation state of the central Cr ion in each member of both electron-transfer series remains the same (+III) and that all redox processes are ligand-based. These experimental results have been corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.

Gravimetric and analytical evaluation of welding fume in an automobile part manufacturing factory.

PubMed

Mansouri, N; Atbi, F; Moharamnezhad, N; Rahbaran, D A; Alahiari, M

2008-12-28

Welding is one of the most exercised industrial processes which welders are exposed to chemical and physical Hazardous agents. This study was conducted to evaluate occupational and environmental exposures to aerosols generated by welding processes in a factory. A total of 28 samples of aerosols were collected at 4 different locations including indoor, outdoor, source of welding and the stacks using a high volume pump with a volumetric flow rate of 112 lit/min calibrated with a dry gas meter. The samples were collected on round 110 mm fiber glass filters, measured gravimetrically, extracted using nitric acid and analyzed with atomic absorption spectroscopy method for heavy metals including Fe, Mn, Ni, Cr3+, Cr+6, Co, and Zn. Gravimetric measuring has shown the mean values of indoor air: 1.33 mg/m3, breathing zone of the welders using coated electrodes and CO2: 7.25 mg/m3 and 6.45 mg/m3 respectively and in ventilation exhausts: 95.07 mg/m3. The mean values of Fe, Mn, and Ni were 0.8, 0.041, and 0.00 mg/m3 in indoor air, 2.7, 0.18, and 0.15 mg/m3 in breathing zone of welders used coated electrodes, and 1.75, 0.08, and 0.22 mg/m3 in breathing zone of welders used CO2 welding respectively. The concentrations of Cr3+, Cr+6, Co, and Zn were too low to be detected. The welders were exposed to high concentration of metallic fumes, which raise the risk of pulmonary dysfunction and other health disorders. Using suitable respiratory masks and Appling the effective local ventilation system may improve the working condition.

Biomechanical comparison of the strength of adhesion of polymethylmethacrylate cement to zirconia ceramic and cobalt-chromium alloy components in a total knee arthroplasty.

PubMed

Kumahashi, Nobuyuki; Uchio, Yuji; Kitamura, Nobuto; Satake, Shigeru; Iwamoto, Mikio; Yasuda, Kazunori

2014-11-01

The purpose of this study was to clarify the biomechanical characteristics of cement-material interfaces for the zirconia ceramic and cobalt-chromium (Co-Cr) alloy femoral components used for total knee arthroplasty. In the first sub-study, we compared the strength of adhesion of the cement to flat plates, by tensile testing under dry and moistened conditions. In the second sub-study, we compared the maximum load of the cement-component complex by tensile testing. In the third sub-study, we compared the fatigue characteristics of the cement-component complex by use of a dynamic tensile testing machine. Under dry conditions, the maximum strength of adhesion to the zirconia ceramic plate was the same as that to the Co-Cr alloy plate. Under moistened conditions, however, the strength of adhesion to the zirconia ceramic plate was significantly lower (p = 0.0017) whereas the strength of adhesion to the Co-Cr alloy plate was not reduced. Maximum load for the cement-component complexes for zirconia ceramic and Co-Cr alloy was no different under both dry and moistened conditions. Fatigue testing showed that cement-zirconia adhesion was stronger than cement-Co-Cr alloy adhesion (p = 0.0161). The strength of adhesion of cement to zirconia ceramic is substantially weaker under wet conditions than under dry conditions. The mechanical properties of cement-zirconia ceramic component complexes and cement-Co-Cr alloy component complexes are equivalent.

FTIR investigation of the H2, N2, and C2H4 molecular complexes formed on the Cr(II) sites in the Phillips catalyst: a preliminary step in the understanding of a complex system.

PubMed

Groppo, E; Lamberti, C; Bordiga, S; Spoto, G; Damin, A; Zecchina, A

2005-08-11

This work reports the first complete FTIR characterization of H2, N2 and C2H4 molecular complexes formed on the Cr(II) sites in the Phillips catalyst. The use of a silica aerogel as support for Cr(II) sites, substituting the conventional aerosil material, allowed us to obtain a remarkable increase in the signal-to-noise ratio of the IR spectra of adsorbed species. The improvement is directly related to an increase of the surface area of the support (approximately 700 m2 g(-1)) and to an almost complete absence of scattering [Groppo et al., Chem. Mater. 2005, 17, 2019-2027]. The use of this support and the adoption of suitable experimental conditions results, for the first time, in the clear observation of H2 and N2 adducts formed on two different types of Cr(II) sites, thus yielding important information on the coordinative state of the Cr(II) ions, which well agrees with the evidences provided in the past by other probe molecules. Furthermore, we report the first complete characterization of the C2H4 pi-complexes formed on Cr(II) sites. These results are particularly important in the view of the understanding of the polymerization mechanism, since the C2H4 coordination and the formation of pi-bonded complexes are the first steps of the reaction.

Carbon Isotope Composition of Nighttime Leaf-Respired CO2 in the Agricultural-Pastoral Zone of the Songnen Plain, Northeast China

PubMed Central

Cui, Haiying; Wang, Yunbo; Jiang, Qi; Chen, Shiping; Ma, Jian-Ying; Sun, Wei

2015-01-01

Variations in the carbon isotope signature of leaf dark-respired CO2 (δ13CR) within a single night is a widely observed phenomenon. However, it is unclear whether there are plant functional type differences with regard to the amplitude of the nighttime variation in δ13CR. These differences, if present, would be important for interpreting the short-term variations in the stable carbon signature of ecosystem respiration and the partitioning of carbon fluxes. To assess the plant functional type differences relating to the magnitude of the nighttime variation in δ13CR and the respiratory apparent fractionation, we measured the δ13CR, the leaf gas exchange, and the δ13C of the respiratory substrates of 22 species present in the agricultural-pastoral zone of the Songnen Plain, northeast China. The species studied were grouped into C3 and C4 plants, trees, grasses, and herbs. A significant nocturnal shift in δ13CR was detected in 20 of the studied species, with the magnitude of the shift ranging from 1‰ to 5.8‰. The magnitude of the nighttime variation in δ13CR was strongly correlated with the daytime cumulative carbon assimilation, which suggests that variation in δ13CR were influenced, to some extent, by changes in the contribution of malate decarboxylation to total respiratory CO2 flux. There were no differences in the magnitude of the nighttime variation in δ13CR between the C3 and C4 plants, as well as among the woody plants, herbs and graminoids. Leaf respired CO2 was enriched in 13C compared to biomass, soluble carbohydrates and lipids; however the magnitude of enrichment differed between 8 pm and 4 am, which were mainly caused by the changes in δ13CR. We also detected the plant functional type differences in respiratory apparent fractionation relative to biomass at 4 am, which suggests that caution should be exercised when using the δ13C of bulk leaf material as a proxy for the δ13C of leaf-respired CO2. PMID:26356083

A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

PubMed

Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

2014-09-21

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

Experimental Monitoring of Cr(VI) Bio-reduction Using Electrochemical Geophysics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Birsen Canan; Gary R. Olhoeft; William A. Smith

2007-09-01

Many Department of Energy (DOE) sites are contaminated with highly carcinogenic hexavalent chromium (Cr(VI)). In this research, we explore the feasibility of applying complex resistivity to the detection and monitoring of microbially-induced reduction of hexavalent chromium (Cr(VI)) to a less toxic form (Cr(III)). We hope to measure the change in ionic concentration that occurs during this reduction reaction. This form of reduction promises to be an attractive alternative to more expensive remedial treatment methods. The specific goal of this research is to define the minimum and maximum concentration of the chemical and biological compounds in contaminated samples for which themore » Cr(VI) - Cr(III) reduction processes could be detected via complex resistivity. There are three sets of experiments, each comprised of three sample columns. The first experiment compares three concentrations of Cr(VI) at the same bacterial cell concentration. The second experiment establishes background samples with, and without, Cr(VI) and bacterial cells. The third experiment examines the influence of three different bacterial cell counts on the same concentration of Cr(VI). A polarization relaxation mechanism was observed between 10 and 50 Hz. The polarization mechanism, unfortunately, was not unique to bio-chemically active samples. Spectral analysis of complex resistivity data, however, showed that the frequency where the phase minimum occurred was not constant for bio-chemically active samples throughout the experiment. A significant shifts in phase minima occurred between 10 to 20 Hz from the initiation to completion of Cr(VI) reduction. This phenomena was quantified using the Cole-Cole model and the Marquardt-Levenberg nonlinear least square minimization method. The data suggests that the relaxation time and the time constant of this relaxation are the Cole-Cole parameters most sensitive to changes in biologically-induced reduction of Cr(VI).« less

78 FR 17341 - Fisheries of the Exclusive Economic Zone Off Alaska; Bering Sea and Aleutian Islands Crab...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-21

.... 120806311-3213-01] RIN 0648-BC25 Fisheries of the Exclusive Economic Zone Off Alaska; Bering Sea and... Bering Sea/Aleutian Islands King and Tanner Crabs (FMP). If approved, these regulations would revise the... of the CR Program were analyzed in the Bering Sea/Aleutian Islands Crab Fisheries Final EIS. Due to...

The CRISPR RNA-guided surveillance complex in Escherichia coli accommodates extended RNA spacers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Michelle L.; Jackson, Ryan N.; Denny, Steven R.

Bacteria and archaea acquire resistance to foreign genetic elements by integrating fragments of foreign DNA into CRISPR (clustered regularly interspaced short palindromic repeats) loci. In Escherichia coli, CRISPR-derived RNAs (crRNAs) assemble with Cas proteins into a multi-subunit surveillance complex called Cascade (CRISPR-associated complex for antiviral defense). Cascade recognizes DNA targets via protein-mediated recognition of a protospacer adjacent motif and complementary base pairing between the crRNA spacer and the DNA target. Previously determined structures of Cascade showed that the crRNA is stretched along an oligomeric protein assembly, leading us to ask how crRNA length impacts the assembly and function of thismore » complex. We found that extending the spacer portion of the crRNA resulted in larger Cascade complexes with altered stoichiometry and preserved in vitro binding affinity for target DNA. Longer spacers also preserved the in vivo ability of Cascade to repress target gene expression and to recruit the Cas3 endonuclease for target degradation. Lastly, longer spacers exhibited enhanced silencing at particular target locations and were sensitive to mismatches within the extended region. These findings demonstrate the flexibility of the Type I-E CRISPR machinery and suggest that spacer length can be modified to fine-tune Cascade activity.« less

The CRISPR RNA-guided surveillance complex in Escherichia coli accommodates extended RNA spacers

DOE PAGES

Luo, Michelle L.; Jackson, Ryan N.; Denny, Steven R.; ...

2016-05-12

Bacteria and archaea acquire resistance to foreign genetic elements by integrating fragments of foreign DNA into CRISPR (clustered regularly interspaced short palindromic repeats) loci. In Escherichia coli, CRISPR-derived RNAs (crRNAs) assemble with Cas proteins into a multi-subunit surveillance complex called Cascade (CRISPR-associated complex for antiviral defense). Cascade recognizes DNA targets via protein-mediated recognition of a protospacer adjacent motif and complementary base pairing between the crRNA spacer and the DNA target. Previously determined structures of Cascade showed that the crRNA is stretched along an oligomeric protein assembly, leading us to ask how crRNA length impacts the assembly and function of thismore » complex. We found that extending the spacer portion of the crRNA resulted in larger Cascade complexes with altered stoichiometry and preserved in vitro binding affinity for target DNA. Longer spacers also preserved the in vivo ability of Cascade to repress target gene expression and to recruit the Cas3 endonuclease for target degradation. Lastly, longer spacers exhibited enhanced silencing at particular target locations and were sensitive to mismatches within the extended region. These findings demonstrate the flexibility of the Type I-E CRISPR machinery and suggest that spacer length can be modified to fine-tune Cascade activity.« less

Crystallization and preliminary X-ray diffraction analysis of the CRISPR-Cas RNA-silencing Cmr complex.

PubMed

Osawa, Takuo; Inanaga, Hideko; Numata, Tomoyuki

2015-06-01

Clustered regularly interspaced short palindromic repeat (CRISPR)-derived RNA (crRNA) and CRISPR-associated (Cas) proteins constitute a prokaryotic adaptive immune system (CRISPR-Cas system) that targets and degrades invading genetic elements. The type III-B CRISPR-Cas Cmr complex, composed of the six Cas proteins (Cmr1-Cmr6) and a crRNA, captures and cleaves RNA complementary to the crRNA guide sequence. Here, a Cmr1-deficient functional Cmr (CmrΔ1) complex composed of Pyrococcus furiosus Cmr2-Cmr3, Archaeoglobus fulgidus Cmr4-Cmr5-Cmr6 and the 39-mer P. furiosus 7.01-crRNA was prepared. The CmrΔ1 complex was cocrystallized with single-stranded DNA (ssDNA) complementary to the crRNA guide by the vapour-diffusion method. The crystals diffracted to 2.1 Å resolution using synchrotron radiation at the Photon Factory. The crystals belonged to the triclinic space group P1, with unit-cell parameters a = 75.5, b = 76.2, c = 139.2 Å, α = 90.3, β = 104.8, γ = 118.6°. The asymmetric unit of the crystals is expected to contain one CmrΔ1-ssDNA complex, with a Matthews coefficient of 2.03 Å(3) Da(-1) and a solvent content of 39.5%.

Spectrophotometric Determination of Cr(III) and Pb(II) Using Their Complexes with 5,11,17,23-Tetra[(2-ethyl acetoethoxyphenyl)(azo)phenyl]calix[4]arene

PubMed Central

Van Tan, Le; Quang Hieu, Tran; Van Cuong, Nguyen

2015-01-01

New complexes of 5,11,17,23-tetra[(2-ethyl acetoethoxyphenyl)(azo)phenyl]calix[4]arene (TEAC) with Pb(II) and Cr(III) were prepared in basic solution with a mixture of MeOH and H2O as solvent. The ratio of TEAC and metal ion in complexes was found to be 1 : 1 under investigated condition. The complex formation constants (based on Benesi-Hildebrand method) for TEAC-Pb(II) and TEAC-Cr(III) were 4.03 × 104 and 1.2 × 104, respectively. Additionally, the molar extinction coefficients were 5 × 104 and 1.42 × 104 for TEAC-Pb(II) and TEAC-Cr(III), respectively. The H-Point Standard Addition Method (HPSAM) has been applied for simultaneous determination of complexes formation of Cr(III)/Pb(II) and TEAC with concentration from 2 : 1 to 1 : 20 (w/w). The proposed method was successfully utilized to invest lead and chromium contents in plating wastewater samples. The results for several analyzed samples were found to be in satisfied agreement with those acquired by using the inductively coupled plasma mass spectrometry (ICP-MS) technique. PMID:25984379

Minor Elements in Nakhlite Pyroxenes: Cr in MIL00346

NASA Technical Reports Server (NTRS)

McKay, G. A.; Schwandt, C.; Le, L.; Makishima, J.; Kurihara, T.

2006-01-01

Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998

Characteristics comparison of weld metal zones welded to cast and forged steels for piston crown material

NASA Astrophysics Data System (ADS)

Moon, Kyung-Man; Kim, Yun-Hae; Lee, Myeong-Hoon; Baek, Tae-Sil

2015-03-01

An optimum repair welding for the piston crown which is one of the engine parts exposed to the combustion chamber is considered to be very important to prolong the engine lifetime from an economical point of view. In this study, two types of filler metals such as 1.25Cr-0.5Mo, 0.5Mo were welded with SMAW method and the other two types of filler metals such as Inconel 625 and 718 were welded with GTAW method, respectively, and the used base metals were the cast and forged steels of the piston crown material. The weld metal zones welded with Inconel 625 and 718 filler metals exhibited higher corrosion resistance compared to 1.25Cr-0.5Mo and 0.5Mo filler metals. In particular, the weld metal zone welded with Inconel 718 and 0.5Mo, filler metals indicated the best and worst corrosion resistance, respectively. Consequently, it is suggested that the corrosion resistance of the weld metal zone surely depends on the chemical components of each filler metal and welding method irrespective of the types of piston crown material.

Lattice relations and solidification of the complex regular eutectic (Cr,Fe)-(Cr,Fe)23C6

NASA Astrophysics Data System (ADS)

Lai, Hsuan-Han; Hsieh, Chih-Chun; Lin, Chi-Ming; Wu, Weite

2017-05-01

The eutectic (Cr,Fe)-(Cr,Fe)23C6 showed a triaxial fishbone structure and could be categorized as a "complex regular structure". In this study, the lattice relations of the fishbone (Cr,Fe)23C6 were examined and the solidification process was observed using a transmission electron microscope and a confocal laser scanning microscope. For one of the three fish bones in a eutectic cell, parallel (Cr,Fe)23C6 lamellas at one side of the spine had the same lattice direction, as did those in the (Cr,Fe) phase. The lattices of neighboring (Cr,Fe)23C6 and (Cr,Fe) phases were not coherent. Lamellar (Cr,Fe)23C6 on opposite sides of a spine had different lattice directions, and their lattice boundary was in the spine. By using the confocal laser scanning microscope, the solidification of lamellar eutectic structure could be observed. At the low cooling rate of 5 o C·min-1, parallel lamellas would grow thick blocks instead of thin plates. To obtain a thin lamellar eutectic structure, the cooling rate should be higher, like the rate in welding.

Dispersion of single-wall carbon nanotubes with supramolecular Congo red - properties of the complexes and mechanism of the interaction.

PubMed

Jagusiak, Anna; Piekarska, Barbara; Pańczyk, Tomasz; Jemioła-Rzemińska, Małgorzata; Bielańska, Elżbieta; Stopa, Barbara; Zemanek, Grzegorz; Rybarska, Janina; Roterman, Irena; Konieczny, Leszek

2017-01-01

A method of dispersion of single-wall carbon nanotubes (SWNTs) in aqueous media using Congo red (CR) is proposed. Nanotubes covered with CR constitute the high capacity system that provides the possibility of binding and targeted delivery of different drugs, which can intercalate into the supramolecular, ribbon-like CR structure. The study revealed the presence of strong interactions between CR and the surface of SWNTs. The aim of the study was to explain the mechanism of this interaction. The interaction of CR and carbon nanotubes was studied using spectral analysis of the SWNT-CR complex, dynamic light scattering (DLS), differential scanning calorimetry (DSC) and microscopic methods: atomic force microscopy (AFM), transmission (TEM), scanning (SEM) and optical microscopy. The results indicate that the binding of supramolecular CR structures to the surface of the nanotubes is based on the "face to face stacking". CR molecules attached directly to the surface of the nanotubes can bind further, parallel-oriented molecules and form supramolecular and protruding structures. This explains the high CR binding capacity of carbon nanotubes. The presented system - containing SWNTs covered with CR - offers a wide range of biomedical applications.

A ruler protein in a complex for antiviral defense determines the length of small interfering CRISPR RNAs.

PubMed

Hatoum-Aslan, Asma; Samai, Poulami; Maniv, Inbal; Jiang, Wenyan; Marraffini, Luciano A

2013-09-27

Small RNAs undergo maturation events that precisely determine the length and structure required for their function. CRISPRs (clustered regularly interspaced short palindromic repeats) encode small RNAs (crRNAs) that together with CRISPR-associated (cas) genes constitute a sequence-specific prokaryotic immune system for anti-viral and anti-plasmid defense. crRNAs are subject to multiple processing events during their biogenesis, and little is known about the mechanism of the final maturation step. We show that in the Staphylococcus epidermidis type III CRISPR-Cas system, mature crRNAs are measured in a Cas10·Csm ribonucleoprotein complex to yield discrete lengths that differ by 6-nucleotide increments. We looked for mutants that impact this crRNA size pattern and found that an alanine substitution of a conserved aspartate residue of Csm3 eliminates the 6-nucleotide increments in the length of crRNAs. In vitro, recombinant Csm3 binds RNA molecules at multiple sites, producing gel-shift patterns that suggest that each protein binds 6 nucleotides of substrate. In vivo, changes in the levels of Csm3 modulate the crRNA size distribution without disrupting the 6-nucleotide periodicity. Our data support a model in which multiple Csm3 molecules within the Cas10·Csm complex bind the crRNA with a 6-nucleotide periodicity to function as a ruler that measures the extent of crRNA maturation.

Determination of hexavalent chromium in exhaled breath condensate and environmental air among chrome plating workers.

PubMed

Goldoni, Matteo; Caglieri, Andrea; Poli, Diana; Vettori, Maria Vittoria; Corradi, Massimo; Apostoli, Pietro; Mutti, Antonio

2006-03-15

Chromium speciation has attracted attention because of the different toxicity of Cr(III), which is considered relatively non-toxic, and Cr(VI), which can cross cell membranes mainly as a chromate anion and has been classified as a class I human carcinogen. The aims of the present study were to measure soluble Cr(VI) levels in environmental samples, to develop a simple method of quantifying Cr(VI) in exhaled breath condensate (EBC), and to follow the kinetics of EBC Cr(VI) in chrome plating workers.Personal air samples were collected from 10 chrome platers; EBC was collected from the same workers immediately after the work shift on Tuesday and before the work shift on the following Wednesday. Environmental and EBC Cr(VI) levels were determined by means of colorimetry and electrothermal absorption atomic spectrometry, respectively.The method of detecting Cr(VI) in environmental air was based on the extraction of the Cr(VI)-diphenylcarbazide (Cr(VI)-DPC) complex in 1-butanol, whereas EBC Cr(VI) was determined using a solvent extraction of Cr(VI) as an ion pair with tetrabutylammonium ion, and subsequent direct determination of the complex (Cr(VI)-DPC) in EBC.Kinetic data showed that airborne Cr(VI) was reduced by 50% in airway lining fluid sampled at the end of exposure and that there was a further 50% reduction after about 15 h. The persistence of Cr(VI) in EBC supports the use of EBC in assessing target tissue levels of Cr(VI).

Spin exchange effects on the physicochemical properties of tetraoxolene-bridged bimetallic complexes.

PubMed

Guo, Dong; McCusker, James K

2007-04-16

The synthesis, physical, and spectroscopic properties of a series of metal complexes bridged by the redox-active chloranilate ligand are described. Compounds containing the (CAcat,cat)4- ligand, where (CAcat,cat)4- represents the fully reduced aromatic form of chloranilate, have been prepared by two different routes from H2CA and H4CA starting materials; the corresponding (CAsq,cat)3- analogue was obtained by one-electron oxidation with decamethylferrocenium tetrafluoroborate. Homo- and heterobimetallic complexes containing CrIII and GaIII with chloranilate have been prepared, yielding the following six complexes: [Ga2(tren)2(CAcat,cat)](BPh4)2 (1), [Ga2(tren)2(CAsq,cat)](BPh4)2(BF4) (2), [GaCr(tren)2(CAcat,cat)](BPh4)2 (3), [GaCr(tren)2(CAsq,cat)](BPh4)2(BF4) (4), [Cr2(tren)2(CAcat,cat)] (BPh4)2 (5), and [Cr2(tren)2(CAsq,cat)](BPh4)2(BF4) (6) (where tren is tris(2-aminoethyl)amine). Single-crystal X-ray structures have been obtained for complexes 1, 3, and 5; nearly identical C-C bond distances within the quinoidal ligand confirm the aromatic character of the bridge in each case. Complex 2 exhibits a temperature-independent magnetic moment of microeff = 1.64 +/- 0.04 microB in the solid state between 4 and 350 K, consistent with the CAsq,cat formulation of the ligand and an S = 1/2 ground state for complex 2. Complex 3 exhibits a value of microeff = 3.44 +/- 0.09 microB that is also temperature-independent, indicating an S = 3/2 ground state. Complexes 4-6 are all influenced by Heisenberg spin exchange. The temperature-independent behavior of complexes 4 and 6 indicate the presence of strong antiferromagnetic exchange between the CrIII and the (sq,cat) bridging radical yielding well-isolated ground states of S = 1 and 5/2 for 4 and 6, respectively. In contrast, complex 5 exhibits a weak intramolecular antiferromagnetic exchange interaction between the two CrIII centers (J = -2 cm-1 for H = -2Jŝ1.ŝ2) via superexchange through the diamagnetic CAcat,cat bridge. The absorption spectra of the CAsq,cat-containing complexes exhibit a number of sharp, relatively intense features in fluid solution. Group theoretical arguments coupled with a qualitative ligand-field analysis including the effects of Heisenberg spin exchange suggest that several of the observed transitions are a consequence of exchange interactions in both the ground- and excited-state manifolds of the compounds.

Spectrophotometric Method for the Determination of Atmospheric Cr Pollution as a Factor to Accelerated Corrosion.

PubMed

Homa, Dereje; Haile, Ermias; Washe, Alemayehu P

2017-01-01

The effect of Cr(VI) pollution on the corrosion rate of corrugated iron roof samples collected from tanning industry areas was investigated through simulated laboratory exposure and spectrophotometric detection of Cr(III) deposit as a product of the reaction. The total level of Cr detected in the samples ranged from 113.892 ± 0.17 ppm to 53.05 ± 0.243 ppm and showed increasing trend as sampling sites get closer to the tannery and in the direction of tannery effluent stream. The laboratory exposure of a newly manufactured material to a simulated condition showed a relatively faster corrosion rate in the presence of Cr(VI) with concomitant deposition of Cr(III) under pH control. A significant ( P = 0.05) increase in the corrosion rate was also recorded when exposing scratched or stress cracked samples. A coupled redox process where Cr(VI) is reduced to a stable, immobile, and insoluble Cr(III) accompanying corrosion of the iron is proposed as a possible mechanism leading to the elevated deposition of the latter on the materials. In conclusion, the increased deposits of Cr detected in the corrugated iron roof samples collected from tanning industry zones suggested possible atmospheric Cr pollution as a factor to the accelerated corrosion of the materials.

Spectrophotometric Method for the Determination of Atmospheric Cr Pollution as a Factor to Accelerated Corrosion

PubMed Central

Homa, Dereje; Haile, Ermias

2017-01-01

The effect of Cr(VI) pollution on the corrosion rate of corrugated iron roof samples collected from tanning industry areas was investigated through simulated laboratory exposure and spectrophotometric detection of Cr(III) deposit as a product of the reaction. The total level of Cr detected in the samples ranged from 113.892 ± 0.17 ppm to 53.05 ± 0.243 ppm and showed increasing trend as sampling sites get closer to the tannery and in the direction of tannery effluent stream. The laboratory exposure of a newly manufactured material to a simulated condition showed a relatively faster corrosion rate in the presence of Cr(VI) with concomitant deposition of Cr(III) under pH control. A significant (P = 0.05) increase in the corrosion rate was also recorded when exposing scratched or stress cracked samples. A coupled redox process where Cr(VI) is reduced to a stable, immobile, and insoluble Cr(III) accompanying corrosion of the iron is proposed as a possible mechanism leading to the elevated deposition of the latter on the materials. In conclusion, the increased deposits of Cr detected in the corrugated iron roof samples collected from tanning industry zones suggested possible atmospheric Cr pollution as a factor to the accelerated corrosion of the materials. PMID:28469950

High-Temperature Behavior of a NiCr-Coated T91 Boiler Steel in the Platen Superheater of Coal-Fired Boiler

NASA Astrophysics Data System (ADS)

Chatha, Sukhpal Singh; Sidhu, Hazoor S.; Sidhu, Buta S.

2013-06-01

Ni-20Cr coating was deposited on T91 boiler tube steel by high-velocity oxy-fuel (HVOF) process to enhance high-temperature oxidation resistance. High-temperature performance of bare, as well as HVOF-coated steel specimens was evaluated for 1500 h under in the platen superheater zone of coal-fired boiler, where the temperature was around 900 °C. Experiments were carried out for 15 cycles, each of 100-h duration followed by 1-h cooling at ambient temperature. The extent of degradation of the specimens was assessed by the thickness loss and depth of internal corrosion attack. Ni-20Cr-coated steel performed better than the uncoated steel in actual boiler environment. The improved degradation resistance of Ni-20Cr coating can be attributed to the presence of Cr2O3 in the top oxide scale and dense microstructure.

Simultaneous determination of Cr(III) and Cr(VI) in tannery wastewater using low pressure ion chromatography combined with flow injection spectrophotometry

NASA Astrophysics Data System (ADS)

Chen, Shujuan; Zhang, Xinshen; Yu, Lingyun; Wang, Li; Li, Hui

2012-03-01

Trivalent and hexavalent chromium have been successfully separated and determined using low pressure ion chromatography combined with flow injection spectrophotometric analysis (LPIC-FIA). A column packed with crosslinking starch microspheres was used for on-line separation of Cr(III) from Cr(VI) in a flow-injection system because of its absorptive effect on Cr(III). To determine the concentration of Cr(III) and Cr(VI) in samples, we used 3.0 mmol/L nitric acid to elute adsorbed Cr(III) from the column and then used ceric sulfate-sulfuric acid as oxidant to convert all Cr(III) into Cr(VI). Then, Cr(VI) directly came from the samples and Cr(VI) came from Cr(III) successively formed a amaranthine complex with diphenycarbazide and the complex shows a maximum absorption at 530 nm. Analytical parameters including the concentration of eluent and oxidant solution, oxidizing temperature, length of oxidizing reaction coil, reaction coil and injection coil, interfering effects, etc., were optimized. The limit of detection was 1.25 μg/L for Cr(VI) and 3.76 μg/L for Cr(III). The linear relationship between absorption with the concentration of Cr(VI) and Cr(III) was 0.001-1.000 mg/L and 0.030-1.000 mg/L with correlation coefficients of 0.9995 and 0.9994, respectively. The relative standard deviation of Cr(VI) and Cr(III) was 1.21% and 1.66%, respectively (n = 10). Major cations and anions did not show any interference. We validated this method through certified reference materials and through measuring the recovery in tannery wastewater.

Features of radiation damage of vanadium and its alloys at a temperature of 330-340°C

NASA Astrophysics Data System (ADS)

Kazakov, V. A.; Ostrovsky, Z.; Goncharenko, Yu; Chakin, V.

2000-12-01

Microstructural changes of vanadium alloys after irradiation at 340°C to 12 dpa in the BOR-60 reactor in 7Li environment is analyzed. Materials are vanadium and its alloys V-3Ti, V-3Fe, V-6Cr, V-4Cr-4Ti, V-5Cr-10Ti, V-6Cr-1Zr-0.1C. Void formation was observed in the binary alloys V-3Fe, V-3Ti and V-6Cr. It is shown that three-four-fold increase in V-4Cr-4Ti yield stress is produced by the formation of dislocation loops (DLs) and fine radiation-induced precipitates (RIPs) with a density of 1.7×1017 cm-3. It is expected that embrittlement of the welds will be worse because density of DLs and RIPs is 1.4-1.6 times higher. Besides, invisible coherent or semi-coherent RIPs are formed in the fusion zone. Elemental maps of the rupture surface of irradiated V-4Cr-4Ti are presented.

Cas5d Protein Processes Pre-crRNA and Assembles into a Cascade-like Interference Complex in Subtype I-C/Dvulg CRISPR-Cas System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nam, Ki Hyun; Haitjema, Charles; Liu, Xueqi

Clustered regularly interspaced short palindromic repeats (CRISPRs), together with an operon of CRISPR-associated (Cas) proteins, form an RNA-based prokaryotic immune system against exogenous genetic elements. Cas5 family proteins are found in several type I CRISPR-Cas systems. Here, we report the molecular function of subtype I-C/Dvulg Cas5d from Bacillus halodurans. We show that Cas5d cleaves pre-crRNA into unit length by recognizing both the hairpin structure and the 3 single stranded sequence in the CRISPR repeat region. Cas5d structure reveals a ferredoxin domain-based architecture and a catalytic triad formed by Y46, K116, and H117 residues. We further show that after pre-crRNA processing,more » Cas5d assembles with crRNA, Csd1, and Csd2 proteins to form a multi-sub-unit interference complex similar to Escherichia coli Cascade (CRISPR-associated complex for antiviral defense) in architecture. Our results suggest that formation of a crRNA-presenting Cascade-like complex is likely a common theme among type I CRISPR subtypes.« less

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride-carbonate fluids

NASA Astrophysics Data System (ADS)

Kanitpanyacharoen, W.; Boudreau, A. E.

2013-02-01

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe3O4) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride-carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.

Adaptation and micro-structure of Co-Cr alloy maxillary complete denture base plates fabricated by selective laser melting technique.

PubMed

Ye, Ye; Jiao, Ting; Zhu, Jiarui; Sun, Jian

2018-01-24

The purpose of the study was to evaluate the adaptation and micro-structure of Co-Cr alloy maxillary complete denture base plates fabricated by the selective laser melting (SLM) technique. Twenty pairs of edentulous casts were randomly and evenly divided into two groups, and manufacturing of the Co-Cr alloy maxillary complete denture base was conducted either by the SLM technique or by the conventional method. The base-cast sets were transversally sectioned into three sections at the distal canines, mesial of the first molars and the posterior palatal zone. The gap between the metal base and cast was measured in these three sections with a stereoscopic microscope, and the data were analysed using t tests. A total of five specimens of 5 mm diameter were fabricated with the Co-Cr alloy by SLM and the traditional casting technology. A scanning electron microscope (SEM) was used to evaluate the differences in microstructure between these specimens. There was no statistical difference between the three sections in all four groups (P > 0.05). At the region of the canines, the clearance value for the SLM Co-Cr alloy group was larger than that of the conventional method group (P < 0.05). At the mesial of the first molar region and the posterior palatal zone, there was no statistical difference between the gaps observed in the two groups (P > 0.05). The SLM Co-Cr alloy has a denser microstructure behaviour and less casting defect than the cast Co-Cr alloy. The SLM technique showed initial feasibility for the manufacture of dental bases of complete dentures, but large sample studies are needed to prove its reliability in clinical applications. The mechanical properties and microstructure of the denture frameworks prepared by selective laser melting indicate that these dentures are appropriate for clinical use.

Microstructure characterization of heat affected zone after welding in Mod.9Cr–1Mo steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sawada, K., E-mail: sawada.kota@nims.go.jp; Hara, T.; Tabuchi, M.

2015-03-15

The microstructure of the heat affected zone after welding was investigated in Mod.9Cr–1Mo steel, using TEM and STEM-EDX. The microstructure of thin foil was observed at the fusion line, and at the positions of 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm and 3.5 mm to the base metal side of the fusion line. Martensite structure with very fine lath and high dislocation density was confirmed at all positions. Twins with a twin plane of (112) were locally observed at all positions. Elemental mapping was obtained for all positions by means of STEM-EDX. Inclusions of mainlymore » Si were formed at the fusion line but not at the other positions. No precipitates could be detected at the fusion line or at the position of 0.5 mm. On the other hand, MX particles were observed at the positions of 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm and 3.5 mm even after welding. M{sub 23}C{sub 6} particles were also confirmed at the positions of 2.0 mm, 2.5 mm, 3.0 mm and 3.5 mm. Very fine equiaxed grains were locally observed at the positions of 2.0 mm and 2.5 mm. The Cr content of the equiaxed grains was about 12 mass%, although the martensite area included about 8 mass% Cr. - Graphical abstract: Display Omitted - Highlights: • Nonequilibrium microstructure of heat affected zone was observed after welding in Mod.9Cr–1Mo steel. • Inclusions containing Si were detected at the fusion line. • Undissolved M{sub 23}C{sub 6} and MX particles were confirmed in heat affected zone. • Twins with a twin plane of (112) were locally observed at all positions. • Very fine ferrite grains with high Cr content were observed in fine grained heat affected zone.« less

Assessment of expected breeding values for fertility traits of Murrah buffaloes under subtropical climate.

PubMed

Dash, Soumya; Chakravarty, A K; Singh, Avtar; Shivahre, Pushp Raj; Upadhyay, Arpan; Sah, Vaishali; Singh, K Mahesh

2015-03-01

The aim of the present study was to assess the influence of temperature and humidity prevalent under subtropical climate on the breeding values for fertility traits viz. service period (SP), pregnancy rate (PR) and conception rate (CR) of Murrah buffaloes in National Dairy Research Institute (NDRI) herd. Fertility data on 1379 records of 581 Murrah buffaloes spread over four lactations and climatic parameters viz. dry bulb temperature and relative humidity (RH) spanned over 20 years (1993-2012) were collected from NDRI and Central Soil and Salinity Research Institute, Karnal, India. Monthly average temperature humidity index (THI) values were estimated. Threshold THI value affecting fertility traits was identified by fixed least-squares model analysis. Three zones of non-heat stress, heat stress and critical heat stress zones were developed in a year. The genetic parameters heritability (h(2)) and repeatability (r) of each fertility trait were estimated. Genetic evaluation of Murrah buffaloes was performed in each zone with respect to their expected breeding values (EBV) for fertility traits. Effect of THI was found significant (p<0.001) on all fertility traits with threshold THI value identified as 75. Based on THI values, a year was classified into three zones: Non heat stress zone(THI 56.71-73.21), HSZ (THI 75.39-81.60) and critical HSZ (THI 80.27-81.60). The EBVfor SP, PR, CR were estimated as 138.57 days, 0.362 and 69.02% in non-HSZ while in HSZ EBV were found as 139.62 days, 0.358 and 68.81%, respectively. EBV for SP was increased to 140.92 days and for PR and CR, it was declined to 0.357 and 68.71% in critical HSZ. The negative effect of THI was observed on EBV of fertility traits under the non-HSZ and critical HSZ Thus, the influence of THI should be adjusted before estimating the breeding values for fertility traits in Murrah buffaloes.

Uncovering the Roles of Oxygen in Cr(III) Photoredox Catalysis.

PubMed

Higgins, Robert F; Fatur, Steven M; Shepard, Samuel G; Stevenson, Susan M; Boston, David J; Ferreira, Eric M; Damrauer, Niels H; Rappé, Anthony K; Shores, Matthew P

2016-04-27

A combined experimental and theoretical investigation aims to elucidate the necessary roles of oxygen in photoredox catalysis of radical cation based Diels-Alder cycloadditions mediated by the first-row transition metal complex [Cr(Ph2phen)3](3+), where Ph2phen = bathophenanthroline. We employ a diverse array of techniques, including catalysis screening, electrochemistry, time-resolved spectroscopy, and computational analyses of reaction thermodynamics. Our key finding is that oxygen acts as a renewable energy and electron shuttle following photoexcitation of the Cr(III) catalyst. First, oxygen quenches the excited Cr(3+)* complex; this energy transfer process protects the catalyst from decomposition while preserving a synthetically useful 13 μs excited state and produces singlet oxygen. Second, singlet oxygen returns the reduced catalyst to the Cr(III) ground state, forming superoxide. Third, the superoxide species reduces the Diels-Alder cycloadduct radical cation to the final product and reforms oxygen. We compare the results of these studies with those from cycloadditions mediated by related Ru(II)-containing complexes and find that the distinct reaction pathways are likely part of a unified mechanistic framework where the photophysical and photochemical properties of the catalyst species lead to oxygen-mediated photocatalysis for the Cr-containing complex but radical chain initiation for the Ru congener. These results provide insight into how oxygen can participate as a sustainable reagent in photocatalysis.

Vegetative and Atmospheric Controls on the Bouchet-Morton Complementary Relationship Hypothesis

NASA Astrophysics Data System (ADS)

Pettijohn, J. C.; Salvucci, G. D.; Phillips, N. G.; Daley, M. J.

2006-12-01

The Bouchet-Morton Complementary Relationship (CR) hypothesis is a potentially-powerful analytic tool to help understand the feedback between evapotranspiring land surfaces and the atmospheric boundary layer (ABL), and how potential evaporation reflects this coupling on multiple time and length scales. In spite of advances in our ability to measure and model these processes, the heuristic CR hypothesis remains an unsolved, first-order problem. The leading theoretical models, i.e., Morton, Granger, and Szilagyi, of the coupled land surface atmosphere mechanisms responsible for CR focus primarily on vertical humidity (vapor pressure) profiles while assuming that vegetative and/or atmospheric diffusivities play an insignificant role in regulating CR. Further, whereas Granger and Szilagyi assume almost opposite vertical temperature profile boundary conditions, both derivations appear to validate CR. Contrary to these multiple working hypotheses' assumptions, our recent CR evaluation of 147 days (1987-1989) at the FIFE temperate grassland discovered that canopy conductance was an essential forcing variable in complementarity, and thus improved CR in application when included in the definition of potential evaporation. To isolate the exact forcing mechanisms of canopy and ABL conductances to complementarity, we evaluated CR in a mixed-deciduous forest at Harvard Forest (summers 2005-2006) by comparing daily averaged water-stressed (non-irrigated, regionally stressed soil moisture) and water-unstressed (irrigated, `potential') transpiration. Root-zone soil moisture of a red maple (Acer rubrum L.) sample set was elevated using a pulse-irrigation system. Whole-tree transpiration of the `potential` (water-unstressed) and a reference (water-stressed) set of maples was monitored at high frequency using heat-dissipation Granier-type sap flux sensors. To isolate physiological and/or atmospheric forcing of CR, we estimated isothermal Penman-Monteith transpiration models of both irrigated and non-irrigated time series using a Jarvis type multiplicative stress model of scaled canopy conductance to water vapor transport. Poorly-constrained model parameters (e.g., environmental stress boundary conditions) were estimated using a grid search routine; further, parameter confidence limits were inferred using bootstrap replacement sampling. Preliminary results suggest the following: (1) the absence of an unstressed canopy conductance in the Penman equation results in violation of fundamental CR assumptions (similar to FIFE); and (2) unlimited root-zone water availability does not reduce the leaf-level stomatal resistance enough to yield complementarity, i.e., the typical CR potential signal is also a function of other environmental stresses, e.g., vapor pressure deficit. In summary, our results yield valuable insight into the role of vertical atmospheric and vegetative conductances in CR.

Corrosion-resistant amorphous metallic films of Mo49Cr33B18 alloy

NASA Technical Reports Server (NTRS)

Ramesham, R.; Distefano, S.; Fitzgerald, D.; Thakoor, A. P.; Khanna, S. K.

1987-01-01

Corrosion-resistant amorphous metallic alloy films of Mo49Cr33B18 with a crystallization temperature of 590 C were deposited onto glass and quartz substrates by magnetron sputter-quench technique. The amorphous nature of the films was confirmed by their diffuse X-ray diffraction patterns. The deposited films are densely packed (zone T) and exhibit low stress and good adhesion to the substrate. Corrosion current of as-deposited coating of MoCrB amorphous metallic alloy is approximately three orders of magnitude less than the corrosion current of 304 stainless steel in 1N H2SO4 solution.

Speciation of chromium using reversed phase-high performance liquid chromatography coupled to different spectrometric detection methods

NASA Astrophysics Data System (ADS)

Andrle, C. M.; Jakubowski, N.; Broekaert, J. A. C.

1997-02-01

Speciation of Cr(III) and Cr(VI) based on the formation of different complexes with ammonium-pyrrolidinedithioate (APDC) in a continuous flow technique and their preconcentration using solid phase extraction (SPE) have been elaborated and applied to the analysis of waste waters from the galvanic industry. The Cr complexes were separated and determined using reversed phase-high performance liquid chromatography (RP-HPLC) coupled to different detection methods, namely UV-detection, graphite furnace-atomic absorption spectrometry (GF-AAS) and inductively coupled plasma mass spectrometry with hydraulic high pressure nebulization (HHPN/ICP-MS). After optimization the detection limits for Cr(III) and Cr(VI) of all methods are at the μg 1 -1 level and the precision in terms of RSD is 5% ( cCr = 100 μg 1 -1, N = 10). The procedure was applied to the determination of Cr(III) and Cr(VI) at the μg 1 -1 level in galvanic waste waters, and its accuracy was approved by comparing the results with those of independent methods.

Corrosion behavior in high heat input welded heat-affected zone of Ni-free high-nitrogen Fe–18Cr–10Mn–N austenitic stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moon, Joonoh, E-mail: mjo99@kims.re.kr; Ha, Heon-Young; Lee, Tae-Ho

2013-08-15

The pitting corrosion and interphase corrosion behaviors in high heat input welded heat-affected zone (HAZ) of a metastable high-nitrogen Fe–18Cr–10Mn–N austenitic stainless steel were explored through electrochemical tests. The HAZs were simulated using Gleeble simulator with high heat input welding condition of 300 kJ/cm and the peak temperature of the HAZs was changed from 1200 °C to 1350 °C, aiming to examine the effect of δ-ferrite formation on corrosion behavior. The electrochemical test results show that both pitting corrosion resistance and interphase corrosion resistance were seriously deteriorated by δ-ferrite formation in the HAZ and their aspects were different with increasingmore » δ-ferrite fraction. The pitting corrosion resistance was decreased by the formation of Cr-depleted zone along δ-ferrite/austenite (γ) interphase resulting from δ-ferrite formation; however it didn't depend on δ-ferrite fraction. The interphase corrosion resistance depends on the total amount of Cr-depleted zone as well as ferrite area and thus continuously decreased with increasing δ-ferrite fraction. The different effects of δ-ferrite fraction on pitting corrosion and interphase corrosion were carefully discussed in terms of alloying elements partitioning in the HAZ based on thermodynamic consideration. - Highlights: • Corrosion behavior in the weld HAZ of high-nitrogen austenitic alloy was studied. • Cr{sub 2}N particle was not precipitated in high heat input welded HAZ of tested alloy. • Pitting corrosion and interphase corrosion show a different behavior. • Pitting corrosion resistance was affected by whether or not δ-ferrite forms. • Interphase corrosion resistance was affected by the total amount of δ-ferrite.« less

Specific Reactions of Different Striatal Neuron Types in Morphology Induced by Quinolinic Acid in Rats

PubMed Central

Mu, Shuhua; Wu, Jiajia; Chen, Si; OuYang, Lisi; Lei, Wanlong

2014-01-01

Huntington's disease (HD) is a neurological degenerative disease and quinolinic acid (QA) has been used to establish HD model in animals through the mechanism of excitotoxicity. Yet the specific pathological changes and the underlying mechanisms are not fully elucidated. We aimed to reveal the specific morphological changes of different striatal neurons in the HD model. Sprague-Dawley (SD) rats were subjected to unilaterally intrastriatal injections of QA to mimic the HD model. Behavioral tests, histochemical and immunhistochemical stainings as well as Western blots were applied in the present study. The results showed that QA-treated rats had obvious motor and cognitive impairments when compared with the control group. Immunohistochemical detection showed a great loss of NeuN+ neurons and Darpp32+ projection neurons in the transition zone in the QA group when compared with the control group. The numbers of parvalbumin (Parv)+ and neuropeptide Y (NPY)+ interneurons were both significantly reduced while those of calretinin (Cr)+ and choline acetyltransferase (ChAT)+ were not changed notably in the transition zone in the QA group when compared to the controls. Parv+, NPY+ and ChAT+ interneurons were not significantly increased in fiber density while Cr+ neurons displayed an obvious increase in fiber density in the transition zone in QA-treated rats. The varicosity densities of Parv+, Cr+ and NPY+ interneurons were all raised in the transition zone after QA treatment. In conclusion, the present study revealed that QA induced obvious behavioral changes as well as a general loss of striatal projection neurons and specific morphological changes in different striatal interneurons, which may help further explain the underlying mechanisms and the specific functions of various striatal neurons in the pathological process of HD. PMID:24632560

Heavy metals in oysters, mussels and clams collected from coastal sites along the Pearl River Delta, South China.

PubMed

Fang, Zhan-Qiang; Cheung, R Y H; Wong, M H

2003-01-01

Concentrations of 8 heavy metals: cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), chromium (Cr), antimony (Sb) and tin (Sn) were examined in 3 species of bivalves ( Perna viridis, Crassostrea rivularis and Ruditapes philippinarum) collected from 25 sites along the Pearl River Delta coastal waters in the South China Sea from July to August 1996. In general, Cd, Cu, Zn and Sn concentrations in the three bivalve species collected from the Estuarine Zone were significantly higher than those collected from the Western and Eastern Zones of the Pearl River Delta, which are related to the existence of various anthropogenic activities in the catchment of the Pearl River Delta. The Western Estuarine Zone is mainly impacted hy Cr, Ni and Cu contamination. In Victoria Harbor, heavy metal contamination is mainly due to Cu and Pb, Cd, Cu and Zn concentrations in oysters were significantly higher than those in mussels and clams. This could be explained by the fact that oysters live mainly in the Estuarine Zone of the Pearl River Delta which receives most of the polluting discharges from the catchment of the Delta. During turbid condition, heavy metals( soluble or adsorbed on suspended particulates) discharged from the Delta are filtered from the water column and subsequently accumulated into the soft body tissues of oysters. Heavy metal concentrations in the three bivalve species were compared with the maximum permissible levels of heavy metals in seafood regulated by the Public Health and Municipal Services Ordinance, Laws of Hong Kong, and it was revealed that Cd and Cr concentrations in the three bivalve species exceeded the upper limits. At certain hotspots in the Delta, the maximum acceptable daily load for Cd was also exceeded.

CrIII as an alternative to RuII in metallo-supramolecular chemistry.

PubMed

Zare, Davood; Doistau, Benjamin; Nozary, Homayoun; Besnard, Céline; Guénée, Laure; Suffren, Yan; Pelé, Anne-Laure; Hauser, Andreas; Piguet, Claude

2017-07-18

Compared to divalent ruthenium coordination complexes, which are widely exploited as parts of multi-component photonic devices, optically active trivalent chromium complexes are under-represented in multi-metallic supramolecular architectures performing energy conversion mainly because of the tricky preparation of stable heteroleptic Cr III building blocks. We herein propose some improvements with the synthesis of a novel family of kinetically inert heteroleptic bis-terdentate mononuclear complexes, which can be incorporated into dinuclear rod-like dyads as a proof-of-concept. The mechanism and magnitude of intermetallic CrCr communication have been unraveled by a combination of magnetic, photophysical and thermodynamic investigations. Alternated aromatic/alkyne connectors provided by Sonogashira coupling reactions emerge as the most efficient wires for long-distance communication between two chromium centres bridged by Janus-type back-to-back bis-terdentate receptors.

Applications of several spectral techniques to characterize coordination compounds derived from 2,6-diacetylpyridine derivative

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Sharma, Amit Kumar

2009-09-01

The coordination compounds of Cr III, Mn II and Co II metal ions derived from quinquedentate 2,6-diacetylpyridine derivative have been synthesized and characterized by using the various physicochemical studies like stoichiometric, molar conductivity and magnetic, and spectral techniques like IR, NMR, mass, UV and EPR. The general stoichiometries of the complexes are found to be [Cr(H 2L)X] and [M(HL)X], where M = Mn(II) and Co(II); H 2L = dideprotonated ligand, HL = monodeprotonated ligand and X = NO 3-, Cl - and OAc -. The studies reveal that the complexes possess monomeric compositions with six coordinated octahedral geometry (Cr III and Mn II complexes) and six coordinated tetragonal geometry (Co II complexes).

Monitored Natural Recovery at Contaminated Sediment Sites

DTIC Science & Technology

2009-05-01

Cr(VI)  hexavalent  chromium   Cr(III)  trivalent   chromium   CSM  conceptual site model  DBT  dibutyltin  DELT  deformities, eroded fins, lesions, and...nickel sulfide complexes in Foundry Cove, NY (USEPA 2005c).  Hexavalent chromium (Cr(VI)) reduction, subsequent precipitation as trivalent chromium (Cr...established scientific findings—such as the reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in reduced environments (Martello et

Effect of nitroso complexes of some transition metals on the activity of soluble guanylate cyclase.

PubMed

Severina, I S; Bussygina, O G; Grigorjev, N B

1992-03-01

Effects of nitroso complexes of some transition metals (Fe, Co, Cr), differing in the character of NO oxidation on the activity of human and rat platelet guanylate cyclase were studied. 3 types of nitroso complexes were used: (1) NO group carries a positive charge--a nitrosonium cation (Na2[FeNO + (CN)5]-nitroprusside); (2) NO is neutral--(K3[CrNO(CN)5 and [CoNO(NH3)5]SO4) and (3) NO is coordinated as anion NO- (K3[CoNO-(CN)5]. It is shown that the highest stimulatory effect is produced by sodium nitroprusside, whose activating action is due to the interaction of its NO group with the guanylate cyclase heme. Nitroso complexes (Co and Cr) the NO group of which is neutral stimulated guanylate cyclase activity insignificantly and this activation was not guanylate cyclase heme directed. Nitroso complex (Co) with NO coordinated as anion NO(-)--is a guanylate cyclase inhibitor. In contrast to nitroprusside, the nitroso complexes used (Co and Cr) have no hypotensive effect. It was concluded that the essential requirement for the realization of the hypotensive effect of transition metals' nitroso complexes is the ability of these compounds to activate soluble guanylate cyclase solely by the heme-dependent mechanism.

Microanalyzing Metasomatism: Correlative Microanalysis of Trace Elements and Oxygen Isotopes in the Franciscan

NASA Astrophysics Data System (ADS)

Goltz, A. E.; Hoover, W. F.; Page, F. Z.; Moreira, H.; Storey, C.; Kitajima, K.; Valley, J. W.

2017-12-01

Mélange fluids play a vital role in metamorphic processes; however, because of the complexity of the mélange, the fluid signals are hard to isolate. Microanalysis of Heavy Rare Earth Elements (HREE) in garnet has the potential to be a powerful tool in understanding the nature of these fluids. When coupled to oxygen isotope analysis, HREE signals may be attributed to an internal or external fluid source. This study pairs microanalysis of HREE and oxygen isotopes in garnet to reveal the origin of HREE enrichment events in two rocks (02WC1 and 02WC4) from the Ward Creek area of the Franciscan Complex. 02WC1 is an intergrown epidote-blueschist and eclogite, with the assemblage omph + ep + glc + gt + sph ± rt ± ab. Its whole-rock major element composition is similar to altered oceanic crust. Two generations of epidote are evident: the first Mn-rich, the other Mn-poor. Garnets have prograde zoning profiles with high spessartine contents ( 40%) in their cores, are unzoned in oxygen isotopes from core (9.6±0.4‰, 2SD, VSMOW) to rim (9.8±0.4‰), and have HREE peaks in their mantles. 02WC4 is also banded with zones of differing epidote content and overall assemblage ep + gt + hbl + omph + sph ± phg ± chl. The whole rock composition of 02WC4 is unusual; it is broadly basaltic but is also SiO2 poor (41.95%) and Cr and Ni rich (675 and 182 ppm, respectively). Epidote shows two generations with higher (cores) and lower (rims) Mn content. Garnet cores are high in spessartine ( 50%), and some garnet mantles have pronounced Mn and Fe plateaux. Garnets are zoned in oxygen isotopes from core (10.2±0.6‰) to rim (6.9±0.4‰). There is one HREE peak in the mantle, coincident with high values of δ18O and one in the rims corresponding to lower values of δ18O. The HREE peaks that occur in high δ18O areas throughout 02WC1 and 02WC4 are likely internally derived within the sample. Mn annuli in garnets and dissolution textures in epidote cores implicate epidote dehydration as the cause of HREE transfer in this case. On the other hand, HREE peaks in lower δ18O regimes are probably externally derived. In addition to δ18O and HREE zoning in the rims of garnets, the enrichment of Cr and Ni and depletion of SiO2 suggest a late-stage mantle metasomatic event in the rock. Correlated HREE and δ18O analysis in garnet provides a powerful new technique to unravel complicated fluid histories in rocks.

CASPT2 study of inverse sandwich-type dinuclear Cr(I) and Fe(I) complexes of the dinitrogen molecule: significant differences in spin multiplicity and coordination structure between these two complexes.

PubMed

Nakagaki, Masayuki; Sakaki, Shigeyoshi

2014-02-20

Inverse sandwich-type complexes (ISTCs), (μ-N2)[M(AIP)]2 (AIPH = (Z)-1-amino-3-imino-prop-1-ene; M = Cr and Fe), were investigated with the CASPT2 method. In the ISTC of Cr, the ground state takes a singlet spin multiplicity. However, the singlet to nonet spin states are close in energy to each other. The thermal average of effective magnetic moments (μeff) of these spin multiplicities is close to the experimental value. The η(2)-side-on coordination structure of N2 is calculated to be more stable than the η(1)-end-on coordination one. This is because the d-orbital of Cr forms a strong dπ-π* bonding interaction with the π* orbital of N2 in molecular plane. In the ISTC of Fe, on the other hand, the ground state takes a septet spin multiplicity, which agrees well with the experimentally reported μeff value. The η(1)-end-on structure of N2 is more stable than the η(2)-side-on structure. In the η(1)-end-on structure, two doubly occupied d-orbitals of Fe can form two dπ-π* bonding interactions. The negative spin density is found on the bridging N2 ligand in the Fe complex but is not in the Cr complex. All these interesting differences between ISTCs of Cr and Fe are discussed on the basis of the electronic structure and bonding nature.

Electrostatic Steering Accelerates C3d:CR2 Association.

PubMed

Mohan, Rohith R; Huber, Gary A; Morikis, Dimitrios

2016-08-25

Electrostatic effects are ubiquitous in protein interactions and are found to be pervasive in the complement system as well. The interaction between complement fragment C3d and complement receptor 2 (CR2) has evolved to become a link between innate and adaptive immunity. Electrostatic interactions have been suggested to be the driving factor for the association of the C3d:CR2 complex. In this study, we investigate the effects of ionic strength and mutagenesis on the association of C3d:CR2 through Brownian dynamics simulations. We demonstrate that the formation of the C3d:CR2 complex is ionic strength-dependent, suggesting the presence of long-range electrostatic steering that accelerates the complex formation. Electrostatic steering occurs through the interaction of an acidic surface patch in C3d and the positively charged CR2 and is supported by the effects of mutations within the acidic patch of C3d that slow or diminish association. Our data are in agreement with previous experimental mutagenesis and binding studies and computational studies. Although the C3d acidic patch may be locally destabilizing because of unfavorable Coulombic interactions of like charges, it contributes to the acceleration of association. Therefore, acceleration of function through electrostatic steering takes precedence to stability. The site of interaction between C3d and CR2 has been the target for delivery of CR2-bound nanoparticle, antibody, and small molecule biomarkers, as well as potential therapeutics. A detailed knowledge of the physicochemical basis of C3d:CR2 association may be necessary to accelerate biomarker and drug discovery efforts.

Synthesis, structure, and magnetic characterization of Cr{sub 4}US{sub 8}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Matthew D.; Chan, Ian Y.; Malliakas, Christos D.

The compound Cr{sub 4}US{sub 8} has been synthesized at 1073 K and its crystal structure has been determined at 100 K. The structure is modulated with a two-fold commensurate supercell. The subcell may be indexed in an orthorhombic cell but weak supercell reflections lead to the monoclinic superspace group P2{sub 1}/c(α0γ)0s with two Cr sites, one U site, and four S sites. The structure comprises a three-dimensional framework of CrS{sub 6} octahedra with channels that are partially occupied by U atoms. Each U atom in these channels is coordinated by eight S atoms in a bicapped trigonal-prismatic arrangement. The magneticmore » behavior of Cr{sub 4}US{sub 8} is complex. At temperatures above ~120 K at all measured fields, there is little difference between field-cooled and zero field-cooled data and χ(T) decreases monotonously with temperature, which is reminiscent of the Curie–Weiss law. At lower temperatures, the temperature dependence of χ(T) is complex and strongly dependent on the magnetic field strength. - Graphical abstract: Structure of Cr{sub 4}US{sub 8} viewed down the a axis. - Highlights: • At 1073 K Cr{sub 4}US{sub 8} was synthesized and at 100 K its crystal structure was determined. • The 3D structure comprises CrS{sub 6} octahedra with channels partially occupied by U. • The magnetic behavior of Cr{sub 4}US{sub 8} is complex.« less

Minor Elements in Nakhlite Pyroxenes: Does Cr Record Changes in REDOX Conditions during Crystallization?

NASA Technical Reports Server (NTRS)

McKay, G.; Schwandt, C.; Le, L.; Mikouchi, T.

2007-01-01

Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998

Mineralogical and geochemical characteristics of BERYL (AQUAMARINE) from the Erongo Volcanic Complex, Namibia

NASA Astrophysics Data System (ADS)

Lum, Jullieta Enone; Viljoen, Fanus; Cairncross, Bruce; Frei, Dirk

2016-12-01

The granite hosted pegmatites of the Erongo Volcanic Complex in central Namibia are well known for the wide variety of minerals present, of considerable interest to mineral collectors. These include (amongst others) often spectacular, museum quality examples of beryl, schorl, jeremejevite, fluorite, quartz, goethite and cassiterite. The locality is particularly recognized for hosting a variety of beryl types, including green, yellow (heliodor), colorless (goshenite) and blue/greenish blue (aquamarine) variants. Comprehensive geochemical studies of the Erongo beryls are very limited. The present contribution serves to document the visual characteristics (colour, colour zoning, inclusion content) as well as the major and trace element chemistry of 42 blue, two green and one colorless beryl from Erongo, and to compare these with other localities worldwide. The beryls from Erongo are generally subhedral to euhedral with a well-formed prismatic habit. Idiomorphic crystals, characterised by strong hexagonal prisms, are common. Beryl is commonly associated with schorl, quartz, muscovite, alkali feldspar, plagioclase feldspar, iron oxides, foitite, rossmanite and cassiterite. Aquamarines range from pale blue to deep blue or greenish blue, with marked colour zoning seen in a number of samples. One of the two green beryls examined is of a medium green colour, and is heavily included, while the other specimen has a pale yellowish green colour. The goshenite sample is colourless, clear, and transparent. Numerous cracks are present in the samples examined, and these are usually filled by iron oxides. Inclusions species encountered in the beryl samples are schorl, quartz, muscovite, feldspar, iron oxides and cassiterite, clearly reflective of the host pegmatite mineralogy. Aquamarine and green beryl contain iron as the main chromophore while goshenite is devoid of chromophores. Fe contents in beryl increase with colour intensity, consistent with the known chromatic effects of Fe in blue, yellow and green beryl. Consistently low Cr contents in all studied beryls do not concur with Cr being a chromophore element for green beryl. Marked compositional zoning is present, with variable Fe (0.79-3.19 wt% FeOT), Na (0.09-0.35 wt% Na2O), Al (15.99-18.18 wt% Al2O3) in aquamarine. Zoning patterns range from simple core-to-rim transitions, to more complex sector and/or oscillatory zoning. Trace element contents vary amongst the beryl types examined, with the highest contents and most extreme variations observed in the aquamarines. This is probably partly due to sampling bias relating to the size of the sample set examined. Octahedral cation substitution is dominant, with Na incorporated (over Cs) at the channels, in order to maintain charge balance. Inferences based on charge balance arguments suggest that tetrahedral Be-Li substitution in these beryls may also be present. Cs, Sc, Ga and Mn are positively correlated with Rb, consistent with the incorporation of these elements at the octahedral site (Sc, Mn and minor Ga) or the channel site (Cs, Rb), in order to preserve charge balance. In contrast, Ca, Zn and Ti do not correlate with Rb, nor with Cs. This is unexpected, as Ti and Ca are known to substitute at the octahedral site in beryl, while Ca may also enter the 2a channel site of beryl. The major and trace element chemistry of the beryls are generally similar to other worldwide beryl deposits of similar colour and do not serve to distinguish beryls from Erongo.

Determination of hexavalent chromium in exhaled breath condensate and environmental air among chrome plating workers

PubMed Central

Goldoni, Matteo; Caglieri, Andrea; Poli, Diana; Vettori, Maria Vittoria; Corradi, Massimo; Apostoli, Pietro; Mutti, Antonio

2006-01-01

Chromium speciation has attracted attention because of the different toxicity of Cr(III), which is considered relatively non-toxic, and Cr(VI), which can cross cell membranes mainly as a chromate anion and has been classified as a class I human carcinogen. The aims of the present study were to measure soluble Cr(VI) levels in environmental samples, to develop a simple method of quantifying Cr(VI) in exhaled breath condensate (EBC), and to follow the kinetics of EBC Cr(VI) in chrome plating workers. Personal air samples were collected from 10 chrome platers; EBC was collected from the same workers immediately after the work shift on Tuesday and before the work shift on the following Wednesday. Environmental and EBC Cr(VI) levels were determined by means of colorimetry and electrothermal absorption atomic spectrometry, respectively. The method of detecting Cr(VI) in environmental air was based on the extraction of the Cr(VI)-diphenylcarbazide (Cr(VI)–DPC) complex in 1-butanol, whereas EBC Cr(VI) was determined using a solvent extraction of Cr(VI) as an ion pair with tetrabutylammonium ion, and subsequent direct determination of the complex (Cr(VI)–DPC) in EBC. Kinetic data showed that airborne Cr(VI) was reduced by 50% in airway lining fluid sampled at the end of exposure and that there was a further 50% reduction after about 15 h. The persistence of Cr(VI) in EBC supports the use of EBC in assessing target tissue levels of Cr(VI). PMID:17047732

Cytotoxic and genotoxic potential of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA complex in human hepatoma (HepG2) cells.

PubMed

Novotnik, Breda; Ščančar, Janez; Milačič, Radmila; Filipič, Metka; Žegura, Bojana

2016-07-01

Chromium (Cr) and ethylenediaminetetraacetate (EDTA) are common environmental pollutants and can be present in high concentrations in surface waters at the same time. Therefore, chelation of Cr with EDTA can occur and thereby stable Cr(III)-EDTA complex is formed. Since there are no literature data on Cr(III)-EDTA toxicity, the aim of our work was to evaluate and compare Cr(III)-EDTA cytotoxic and genotoxic activity with those of Cr(VI) and Cr(III)-nitrate in human hepatoma (HepG2) cell line. First the effect of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on cell viability was studied in the concentration range from 0.04 μg mL(-1) to 25 μg mL(-1) after 24 h exposure. Further the influence of non-cytotoxic concentrations of Cr(VI), Cr(III)-nitrate and Cr(III)-EDTA on DNA damage and genomic stability was determined with the comet assay and cytokinesis block micronucleus cytome assay, respectively. Cell viability was decreased only by Cr(VI) at concentrations above 1.0 μg mL(-1). Cr(VI) at ≥0.2 μg mL(-1) and Cr(III) at ≥1.0 μg mL(-1) induced DNA damage, while after Cr(III)-EDTA exposure no formation DNA strand breaks was determined. Statistically significant formation of micronuclei was induced only by Cr(VI) at ≥0.2 μg mL(-1), while no influence on the frequency of nuclear buds nor nucleoplasmic bridges was observed at any exposure. This study provides the first evidence that Cr(III)-EDTA did not induce DNA damage and had no influence on the genomic stability of HepG2 cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Ruler Protein in a Complex for Antiviral Defense Determines the Length of Small Interfering CRISPR RNAs

PubMed Central

Hatoum-Aslan, Asma; Samai, Poulami; Maniv, Inbal; Jiang, Wenyan; Marraffini, Luciano A.

2013-01-01

Small RNAs undergo maturation events that precisely determine the length and structure required for their function. CRISPRs (clustered regularly interspaced short palindromic repeats) encode small RNAs (crRNAs) that together with CRISPR-associated (cas) genes constitute a sequence-specific prokaryotic immune system for anti-viral and anti-plasmid defense. crRNAs are subject to multiple processing events during their biogenesis, and little is known about the mechanism of the final maturation step. We show that in the Staphylococcus epidermidis type III CRISPR-Cas system, mature crRNAs are measured in a Cas10·Csm ribonucleoprotein complex to yield discrete lengths that differ by 6-nucleotide increments. We looked for mutants that impact this crRNA size pattern and found that an alanine substitution of a conserved aspartate residue of Csm3 eliminates the 6-nucleotide increments in the length of crRNAs. In vitro, recombinant Csm3 binds RNA molecules at multiple sites, producing gel-shift patterns that suggest that each protein binds 6 nucleotides of substrate. In vivo, changes in the levels of Csm3 modulate the crRNA size distribution without disrupting the 6-nucleotide periodicity. Our data support a model in which multiple Csm3 molecules within the Cas10·Csm complex bind the crRNA with a 6-nucleotide periodicity to function as a ruler that measures the extent of crRNA maturation. PMID:23935102

Synthesis, spectroscopic characterization, thermal studies, catalytic epoxidation and biological activity of chromium and molybdenum hexacarbonyl bound to a novel N 2O 2 Schiff base

NASA Astrophysics Data System (ADS)

Abdel Aziz, Ayman A.

2010-08-01

Complexes of M(CO) 6 (M = Cr and Mo) with novel Schiff base N,N'-bis(salicylidene)4,5-dichloro-1,2-phenylenediamine (H 2L) were prepared in benzene in two different conditions: (i) under reduced pressure resulting the dicarbonyl precursors [Cr(CO) 2(H 2L)] and [Mo(CO) 2(L)] and (ii) in air resulting the oxo complex [Cr(O)(L)] and the dioxo complex [Mo(O) 2(L)]. The complexes were characterized by elemental analysis, IR, 1H NMR, mass spectrometry, and magnetic measurement. Thermal behaviors of the complexes were also studied by using thermogravimetric analysis (TGA). The catalytic activity of the novel complexes in the epoxidation of cyclooctene, cyclohexene, 1-octene and 1-hexene with tert-butyl-hydroperoxide (TBHP) in methylene chloride was investigated. The antimicrobial activities of the ligand and their complexes have been screened against various strains of bacteria and fungi and the results have been compared with some known antibiotics.

Microstructure and mechanical properties of NiCoCrAlYTa alloy processed by press and sintering route

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereira, J.C., E-mail: jpereira@uc.edu.ve; Centro de Investigaciones en Mecánica, Facultad de Ingeniería, Universidad de Carabobo; Zambrano, J.C.

2015-03-15

Nickel-based superalloys such as NiCoCrAlY are widely used in high-temperature applications, such as gas turbine components in the energy and aerospace industries, due to their strength, high elastic modulus, and high-temperature oxidation resistance. However, the processing of these alloys is complex and costly, and the alloys are currently used as a bond coat in thermal barrier coatings. In this work, the effect of cold press and sintering processing parameters on the microstructure and mechanical properties of NiCoCrAlY alloy were studied using the powder metallurgy route as a new way to obtain NiCoCrAlYTa samples from a gas atomized prealloyed powder feedstock.more » High mechanical strength and adequate densification up to 98% were achieved. The most suitable compaction pressure and sintering temperature were determined for NiCoCrAlYTa alloy through microstructure characterization. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive spectroscopy microanalysis (EDS) were performed to confirm the expected γ-Ni matrix and β-NiAl phase distribution. Additionally, the results demonstrated the unexpected presence of carbides and Ni–Y-rich zones in the microstructure due to the powder metallurgy processing parameters used. Thus, microhardness, nanoindentation and uniaxial compression tests were conducted to correlate the microstructure of the alloy samples with their mechanical properties under the different studied conditions. The results show that the compaction pressure did not significantly affect the mechanical properties of the alloy samples. In this work, the compaction pressures of 400, 700 and 1000 MPa were used. The sintering temperature of 1200 °C for NiCoCrAlYTa alloy was preferred; above this temperature, the improvement in mechanical properties is not significant due to grain coarsening, whereas a lower temperature produces a decrease in mechanical properties due to high porosity and poor solid-state diffusion. - Graphical abstract: Display Omitted - Highlights: • We made NiCoCrAlYTa alloy by a conventional powder metallurgy route. • High densification and adequate strength were observed. • The presence of unexpected carbides found along γ/γ and γ/β grain boundaries was detected. • The effect of cold press and sintering processing parameters on the microstructure and mechanical properties were studied.« less

Expression of Cry1Ac toxin-binding region in Plutella xyllostella cadherin-like receptor and studying their interaction mode by molecular docking and site-directed mutagenesis.

PubMed

Hu, Xiaodan; Zhang, Xiao; Zhong, Jianfeng; Liu, Yuan; Zhang, Cunzheng; Xie, Yajing; Lin, Manman; Xu, Chongxin; Lu, Lina; Zhu, Qing; Liu, Xianjin

2018-05-01

Cadherin-like protein has been identified as the primary Bacillus thuringiensis (Bt) Cry toxin receptor in Lepidoptera pests and plays a key role in Cry toxin insecticidal. In this study, we successfully expressed the putative Cry1Ac toxin-binding region (CR7-CR11) of Plutella xylostella cadherin-like in Escherichia coli BL21 (DE3). The expressed CR7-CR11 fragment showed binding ability to Cry1Ac toxin under denaturing (Ligand blot) and non-denaturing (ELISA) conditions. The three-dimensional structure of CR7-CR11 was constructed by homology modeling. Molecular docking results of CR7-CR11 and Cry1Ac showed that domain II and domain III of Cry1Ac were taking part in binding to CR7-CR11, while CR7-CR8 was the region of CR7-CR11 in interacting with Cry1Ac. The interaction of toxin-receptor complex was found to arise from hydrogen bond and hydrophobic interaction. Through the computer-aided alanine mutation scanning, amino acid residues of Cry1Ac (Met341, Asn442 and Ser486) and CR7-CR11 (Asp32, Arg101 and Arg127) were predicted as the hot spot residues involved in the interaction of the toxin-receptor complex. At last, we verified the importance role of these key amino acid residues by binding assay. These results will lay a foundation for further elucidating the insecticidal mechanism of Cry toxin and enhancing Cry toxin insecticidal activity by molecular modification. Copyright © 2018 Elsevier B.V. All rights reserved.

Distribution of heavy metals in riverine soils and sediments of the Turia River basin.

NASA Astrophysics Data System (ADS)

Andreu, Vicente; Gimeno-García, Eugenia; Pascual, Juan Antonio

2014-05-01

Water is a scarce and contested good, and a primary need for the population all over. Rivers are one of the mainsources of freshwater to people but, in the same way, receive both point source and difuse pollution, usually frorm wastewaters and agriculture. However, they are not independent bodies but they influence different associated ecosystems that compound the catchment. Soils of the river banks often acts as the last phase of the diffuse contamination pathways, favouring the contaminants input to the river waters. In this sense, the fluvial sedimentary phase usually acts as a sink of pollutants. Sediments can work as resevoirs that accumulate contaminants fixing them or allowing their decomposition or metabolization. However, environmental or human induced, such as variations in water pH, increases in the turbulence or intensity of the water flow, etc.could favour their release to the environment. In this work, the incidence and distribution of seven heavy metals was monitored in riverine soils and sediments of the Turia River. Along the river course, 22 zones were selected for sampling according different lithologies, land uses, size of populations and the proximity to waste waters treatment plants (WWTPs), from the headwaters to the mouth. The selected metals (Cd, Co, Cr, Cu, Pb, Ni and Zn) were analysed to determine its total and extractable contents in the sediments. Total content of metals was extracted by microwave acid digestion and the extractable fraction by treatment with EDTA. Atomic Absorption Spectrometry, using graphite furnace when necessary, was used for the determination of all metals. Highest values for sediments were mainly observed in zones 10 and 22, close to urban areas, reaching values of 172.86 mg/kg for Pb, or 58.34 mg/kg for Cr. However, zone 2 near in the headwaters of the Alfambra River and supposedly of reference for the River authorities shows the highest values of zinc with 96.96 mg/kg. Regarding the available/extractable fraction of the metals, Cd, Co and Cr were under the detection limitswith maximum values in zone 22 too, reching in the case of Pb 59.60 mg/kg. The percentage of available metal in the sediments of the studied zones vary between 15 and 40% for Cu, Pb and Zn, being the higher than 60% for Pb and Zn in zone 8 near the city of Teruel. Regarding soils, the higest levels of total and extractable Cd, Co, Cr and Ni were determined in the zones 11 and 12, near the Benageber reservoir where an important forest fires occurred a year ago. In the same way that was observed for sediments high lvels of metals, mainly Cr and Zn, appeared in the reference zone of the Alfambra River. The organic matter content of soils and sediments is the parameter most strongly related with all the forms of metals, mainly for Cu, Ni, Pb and Zn, and is a key factor in the availability of them. It has to be noted that the textural distribution of the sediments, particularly the clay content, also influences this last factor in the case of Ni. A strong tendency towards enrichment of the sediments in heavy metals is observed in the Turia River from North to South, from the headwater to the stuary, with the exception of the possible existence of a contamination source in zone 2. Acknowledgements This work has been supported by the Spanish Ministry of Science and Innovation and the European Regional Development Funds (ERDF) through the coordinating project MEFTURIA (CGL2011-29703-C02-00), and its subprojects EFAMED and EMEFOR (CGL2011-29703-C02-02), and the project CONSOLIDER-INGENIO 2010 (CSD2009), and for the Generalitat Valenciana (ACOMP/2013/037).

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites.

PubMed

Farmer, John G; Thomas, Rhodri P; Graham, Margaret C; Geelhoed, Jeanine S; Lumsdon, David G; Paterson, Edward

2002-04-01

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.

EFFECT OF STRENGTHENING AT EXPECTED DAMAGING ZONE OF A RC MEMBER WITH DAMAGED ANCHORAGE

NASA Astrophysics Data System (ADS)

Chijiwa, Nobuhiro; Kawanaka, Isao; Maekawa, Koichi

When a reinforced concrete member having cracks at the anchorage zones is loaded, diagonal crack is formed from the tip of the exsisting crack, and it lead s to brittle shaer failure. A reinforced concrete beam containing corrosion cracks at the anchorage zone were strengthened with sheets at the expected damaging zones, and tested in 3-point loading. Th e test result shows that the load capacity of the strengthened beam was the same to that of the repli cate beam with no damage at the anchorage zones and contained enough shear reinforcement to develop flexural failure. It means that strenghtneing at the expected damaging zone with keeping corrosion cr acks along to the tensile reinforcements at the anchorage zones may improve the load capacity of the damaged reinforced concrete.

Synthesis, structure, and magnetic characterization of a C3-symmetric Mn(III)3Cr(III) assembly: molecular recognition between a trinuclear Mn(III) triplesalen complex and a fac-triscyano Cr(III) complex.

PubMed

Freiherr von Richthofen, Carl-Georg; Stammler, Anja; Bögge, Hartmut; DeGroot, Marty W; Long, Jeffrey R; Glaser, Thorsten

2009-11-02

The reaction of the tris(tetradentate) triplesalen ligand H(6)talen(t-Bu(2)), which provides three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone, with Mn(II) salts under aerobic conditions, affords, in situ, the trinuclear Mn(III) triplesalen complex [(talen(t-Bu(2))){Mn(III)(solv)(n)}(3)](3+). This species then reacts with [(Me(3)tacn)Cr(CN)(3)] to form the tetranuclear complex [{(talen(t-Bu(2)))Mn(III)(3)}{(Me(3)tacn)Cr(CN)(3)}](3+) ([Mn(III)(3)Cr(III)](3+)). The regular ligand folding observed in the trinuclear triplesalen complex preorganizes the three metal ions for the reaction with three facially coordinated nitrogen atoms of [(Me(3)tacn)Cr(CN)(3)]. [{(talen(t-Bu(2)))(Mn(III)(MeOH))(3)}{(Me(3)tacn)Cr(CN)(3)}](ClO(4))(3) (1) was characterized by infrared spectroscopy, elemental analysis, mass spectrometry, electron absorption spectroscopy, and magnetic measurements. The molecular structure was established for the acetate-substituted derivative [{(talen(t-Bu(2)))(Mn(III)(MeOH))(2)(Mn(III)(OAc))}{(Me(3)tacn)Cr(CN)(3)}](ClO(4))(2) (2) by single-crystal X-ray diffraction. Variable-temperature-variable-field and mu(eff) versus T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian, consisting of isotropic exchange, zero-field splitting, and Zeeman interaction components. Satisfactory reproduction of the experimental data has been obtained for the parameters J(Mn-Cr) = -0.12 +/- 0.04 cm(-1), J(Mn-Mn) = -0.70 +/- 0.03 cm(-1), and D(Mn) = -3.0 +/- 0.4 cm(-1). These generate a triply degenerate pseudo S(t) = 7/2 spin manifold, which cannot be appropriately described by a giant spin model and which exhibits a weak easy-axis magnetic anisotropy. This is corroborated by the onset of a frequency-dependent chi'' signal at low temperatures, demonstrating a slow relaxation of the magnetization indicative of 1 being a single-molecule magnet. Comparing the properties to those of the heptanuclear analogue [{(talen(t-Bu(2)))Mn(III)(3)}(2){Cr(III)(CN)(6)}](3+) ([Mn(III)(6)Cr(III)](3+)) formed by the reaction of 2 equiv of [(talen(t-Bu(2))){Mn(III)(solv)(n)}(3)](3+) with 1 equiv of [Cr(CN)(6)](3-) [Glaser, T.; Heidemeier, M.; Weyhermüller, T.; Hoffmann, R.-D.; Rupp, H.; Müller, P. Angew. Chem. Int. Ed., 2006, 45, 6033-6037] demonstrates a lower driving force for formation, a strongly reduced J(Mn-Cr) exchange, a slightly reduced J(Mn-Mn) exchange, and a significantly longer Mn-N(N[triple bond]C) bond length in [Mn(III)(3)Cr(III)](3+). Taking into account magneto-structural correlations establishes a supramolecular interaction between the two [(talen(t-Bu(2)))Mn(III)(3)](3+) subunits in [Mn(III)(6)Cr(III)](3+) responsible for the structural distortion and the short Mn-N(N[triple bond]C) distance which results in a strong J(Mn-Cr) exchange and thus [Mn(III)(6)Cr(III)](3+) being a single-molecule magnet with a relatively high effective anisotropy barrier of 25.4 K.

Environmental radiation and potential ecological risk levels in the intertidal zone of southern region of Tamil Nadu coast (HBRAs), India.

PubMed

Punniyakotti, J; Ponnusamy, V

2018-02-01

Natural radioactivity content and heavy metal concentration in the intertidal zone sand samples from the southern region of Tamil Nadu coast, India, have been analyzed using gamma ray spectrometer and ICP-OES, respectively. From gamma spectral analysis, the average radioactivity contents of 238 U, 232 Th, and 40 K in the intertidal zone sand samples are 12.13±4.21, 59.03±4.26, and 197.03±26.24Bq/kg, respectively. The average radioactivity content of 232 Th alone is higher than the world average value. From the heavy metal analysis, the average Cd, Cr, Cu, Ni, Pb, and Zn concentrations are 3.1, 80.24, 82.84, 23.66, 91.67, and 137.07ppm, respectively. The average Cr and Ni concentrations are lower, whereas other four metal (Cd, Cu, Pb, and Zn) concentrations are higher than world surface rock average values. From pollution assessment parameter values, the pollution level is "uncontaminated to moderately contaminated" in the study area. Copyright © 2017 Elsevier Ltd. All rights reserved.

3D cinematic rendering of the calvarium, maxillofacial structures, and skull base: preliminary observations.

PubMed

Rowe, Steven P; Zinreich, S James; Fishman, Elliot K

2018-06-01

Three-dimensional (3D) visualizations of volumetric data from CT have gained widespread clinical acceptance and are an important method for evaluating complex anatomy and pathology. Recently, cinematic rendering (CR), a new 3D visualization methodology, has become available. CR utilizes a lighting model that allows for the production of photorealistic images from isotropic voxel data. Given how new this technique is, studies to evaluate its clinical utility and any potential advantages or disadvantages relative to other 3D methods such as volume rendering have yet to be published. In this pictorial review, we provide examples of normal calvarial, maxillofacial, and skull base anatomy and pathological conditions that highlight the potential for CR images to aid in patient evaluation and treatment planning. The highly detailed images and nuanced shadowing that are intrinsic to CR are well suited to the display of the complex anatomy in this region of the body. We look forward to studies with CR that will ascertain the ultimate value of this methodology to evaluate calvarium, maxillofacial, and skull base morphology as well as other complex anatomic structures.

A trimetallic strategy towards ZnDyCr and ZnDyCo single-ion magnets.

PubMed

Hu, Kong-Qiu; Jiang, Xiang; Wu, Shu-Qi; Liu, Cai-Ming; Cui, Ai-Li; Kou, Hui-Zhong

2015-09-21

Two cyano- and phenoxo-bridged octanuclear complexes ZnDyCo (complex ) and ZnDyCr (complex ) with diamagnetic Zn(ii) and Co(iii) are reported. Dy(iii) is surrounded by nine oxygen atoms of two [Zn(Me2valpn)] (Me2valpn(2-) = dianion of N,N'-2,2-dimethylpropylenebis(3-methoxysalicylideneimine)) and one water molecule. Magnetic studies reveal that both exhibit single-ion magnet (SIM) behavior with the energy barrier of 85.9 K for complex and 100.9 K for complex .

Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

2014-06-01

Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (<1 vol.%), NWA 3109 (<1 vol.%) and HaH 064 (<1 vol.%) as subhedral to anhedral grains comparable in size (∼30 μm to 1 mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe# = 0.55-0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine-chromite equilibration temperatures of ∼1040-1050 °C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ∼1200 to 1300 °C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ∼0.4 → 0.28); (2) Outer zones showing further reduction of FeO (fe# ∼0.28 → 0.15) and containing abundant laths of eskolaite-corundum (Cr2O3-Al2O3); (3) Outermost zones showing extreme reduction of both FeO (fe# <0.15) and Cr2O3 (Cr# as low as 0.2). The grains are surrounded by rims of Si-Al-rich glass, graphite, Fe, Cr-carbides ([Fe,Cr]3C and [Fe,Cr]7C3), Cr-rich sulfides (daubréelite and brezinaite) and Cr-rich symplectic bands on adjacent silicates. Chromite is inferred to have been reduced by graphite, forming eskolaite-corundum and carbides as byproducts, during impact excavation. This event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to <700 °C) at 1-20 °C/h. The kinetics of reduction of chromite is consistent with this scenario. The reduction was facilitated by silicate melt surrounding the chromites, which was partly generated by shock-melting of pyroxenes. Symplectic bands, consisting of fine-scale intergrowths of Ca-pyroxene, chromite and glass, formed by reaction between the Cr-enriched melt and adjacent silicates. Early chromite also occurs in a melt inclusion in olivine in HaH 064 and in a metallic spherule in olivine in LAP 02382. LAP 03587 and CMS 04048 contain ⩽μm-sized chromite + pyroxene symplectic exsolutions in olivine, indicating high Cr valence in the primary olivine. EET 96328 contains a round grain of chromite that could be a late-crystallizing phase. Tiny chromite grains in melt inclusions in EET 96328 formed in late, closed-system reactions. For 7 of the 8 ureilites we conclude that the relatively oxidizing conditions evidenced by the presence of primary or early chromite pertain to the period of high-T igneous processing. The observation that such conditions are recorded almost exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

Kinetics of oxidation of an organic amine with a Cr(V) salen complex in homogeneous aqueous solution and on the surface of mesoporous silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szajna-Fuller, Ewa; Huang, Yulin; Rapp, Jennifer L.

2009-03-09

A comparative study of catalytic activity under homogeneous and heterogeneous conditions was carried out using the (salen)Cr{sup III}-catalyzed oxidation of tetramethylbenzidine (TMB) with iodosobenzene as a model reaction. Amine-functionalized mesoporous silica nanoparticles (MSN) were synthesized in a co-condensation reaction and functionalized with salen via a covalent Si-C bond. A Cr(III) complex of this supported ligand, MSN-(salen)Cr{sup III}, was prepared and characterized. Data from powder XRD, BET isotherms and BJH pore size distribution all showed that MSN-(salen)Cr{sup III} still had the typical MSN high surface area, narrow pore size distribution, and ordered hexagonal pore structure, which were further confirmed by transmissionmore » electron microscopy (TEM) images. {sup 13}C and {sup 29}Si solid-state NMR data provided structural information about the catalyst and verified successful functionalization of the salen ligand and coordination to Cr(III). No unreacted salen or Cr(III) were observed. The loadings of salen and salen-Cr{sup III} complex were determined via TGA and EDX, respectively. Both measurements indicated that approximately 0.5 mmol/g of catalyst was loaded on the surface of MSN. The oxidation of TMB with iodosobenzene using MSN-(salen)Cr{sup III} as a heterogeneous catalyst exhibited both similarities and differences with the analogous homogeneous reaction using (salen)Cr{sup III}(H{sub 2}O){sup +} as a catalyst in aqueous acetonitrile. In the presence of 0.10 M HClO{sub 4}, the two catalytic reactions proceeded at similar rates and generated the doubly oxidized product TMB{sup 2+}. In the absence of acid, the radical cation TMB{sup +} was produced. The kinetics of the heterogeneous reaction in the absence of added acid responded to concentrations of all three reagents, i.e. (salen)Cr{sup III}, TMB, and PhIO.« less

Structure and Electronic Properties of Nano-complex CCl4…Cr(AcacCl)3 on Evidence Derived from Vibrational Spectroscopy

NASA Astrophysics Data System (ADS)

Slabzhennikov, S. N.; Kuarton, L. A.; Ryabchenko, O. B.

In order to specify influence of intermolecular interaction on IR spectrum of interacting species, an investigation of a process CCl4 + Cr(AcacCl)3 → CCl4…Cr(AcacCl)3 has been performed by means of Hartree-Fock-Roothaan method in MIDI basis set with p- and d- polarization functions. An estimation of intermolecular interaction in geometrical parameters, electron density function both between interacting particles and inside themselves, frequencies and intensities of normal modes has been carried out. Chemical bonds with the most significant shifts of characteristics under formation of nano-complex CCl4…Cr(AcacCl)3 have been noted.

Effect of hexavalent chromium on electron leakage of respiratory chain in mitochondria isolated from rat liver.

PubMed

Xie, Ying; Zhong, Caigao; Zeng, Ming; Guan, Lan; Luo, Lei

2013-01-01

In the present study, we explored reactive axygen species (ROS) production in mitochondria, the mechanism of hexavalent chromium (Cr(VI)) hepatotoxicity, and the role of protection by GSH. Intact mitochondria were isolated from rat liver tissues and mitochondrial basal respiratory rates of NADH and FADH2 respiratory chains were determined. Mitochondria were treated with Cr(VI), GSH and several complex inhibitors. Mitochondria energized by glutamate/malate were separately or jointly treated with Rotenone (Rot), diphenyleneiodonium (DPI) and antimycinA (Ant), while mitochondria energized by succinate were separately or jointly treated with Rot, DPI ' thenoyltrifluoroacetone (TTFA) and Ant. Cr(VI) concentration-dependently induced ROS production in the NADH and FADH2 respiratory chain in liver mitochondria. Basal respiratory rate of the mitochondrial FADH2 respiratory chain was significantly higher than that of NADH respiratory chain. Hepatic mitochondrial electron leakage induced by Cr(VI) from NADH respiratory chain were mainly from ubiquinone binding sites of complex I and complex III. Treatment with 50µM Cr(VI) enhances forward movement of electrons through FADH2 respiratory chain and leaking through the ubiquinone binding site of complex III. Moreover, the protective effect of GSH on liver mitochondria electron leakage is through removing excess H2O2 and reducing total ROS. Copyright © 2013 S. Karger AG, Basel.

Carbon-related platinum defects in silicon: An electron paramagnetic resonance study of high spin states

NASA Astrophysics Data System (ADS)

Scheerer, O.; Höhne, M.; Juda, U.; Riemann, H.

1997-10-01

In this article, we report about complexes in silicon investigated by electron paramagnetic resonance (EPR). In silicon doped with C and Pt we detected two different complexes: cr-1Pt (cr: carbon-related, 1Pt: one Pt atom) and cr-3Pt. The complexes have similar EPR properties. They show a trigonal symmetry with effective g-values geff,⊥=2g⊥≈4 and geff,‖=g‖≈2 (g⊥, g‖ true g-values). The g-values can be explained by a spin Hamiltonian with large fine-structure energy (electron spin S=3/2) and smaller Zeeman interaction. The participation of platinum in the complexes is proved by the hyperfine interaction. From experiments with varying carbon concentration we conclude that the complexes contain carbon. Atomistic models based on the Watkins vacancy-model for substitutional Pt were developed.

Microstructure Evolution and Selective Corrosion Resistance in Underwater Multi-pass 2101 Duplex Stainless Steel Welding Joints

NASA Astrophysics Data System (ADS)

Hu, Yu; Shi, Yonghua; Shen, Xiaoqin; Wang, Zhongmin

2018-05-01

A recently developed promising material, 2101 lean duplex stainless steel, represents an alternative to 304 austenite stainless steel. In this work, multi-pass 2101 weld joints were fabricated using the flux-cored arc welding method in a hyperbaric chamber. The pressure varied from 0 to 0.75 MPa. The evolution of the welding process and microstructure was investigated. γ 2 formation in the reheated zones of the WM and HAZ was not uniform. The closer the reheated zone is to the subsequent heat source, the greater the γ 2 formation in the reheated zone. Sufficient primary austenite transformation inhibited Cr2N precipitation and the subsequent intragranular γ 2 formation in the reheated weld passes of the 0.45 MPa weld metal. The localized corrosion resistance of each zone of the 0.45 MPa DSS joint was measured using non-destructive double-loop electrochemical potentiokinetic reactivation tests. The localized corrosion was induced by γ 2 and Cr2N. The root region of the 0.45 MPa weld metal underwent two subsequent welding thermal cycles, which induced increased γ 2 formation and lower resistance to corrosion because of the decreased pitting resistance value of γ 2. The correlation between microstructure evolution and the distribution of selective corrosion was determined.

Development of a Novel Ni-Fe-Cr-B-Si Interlayer Material for Transient Liquid Phase Bonding of Inconel 718

NASA Astrophysics Data System (ADS)

Tarai, U. K.; Robi, P. S.; Pal, Sukhomay

2018-04-01

A Ni-Cr-Fe-Si-B based interlayer material was developed by mechanical alloying (MA) process in a high-energy planetary ball mill. Equiaxed alloy powders of size 12 µm was obtained after milling for 50 hours. X-ray diffraction analysis of the milled powder revealed that milling of elemental powders initially resulted in microcrystalline alloy powder having face centered cubic structure, which on subsequent milling resulted in nano-crystallice alloy powder with a crystallite size of 3.2 nm. XRD analysis also reveals formation of metastable eutectic alloys resulting in lowering of the melting point of the interlayer material to 1025 °C. IN 718 superalloy samples were joined at 1050°C using the developed interlayer. A homogeneous joint was formed by the newly developed interlayer material. Three different zones were observed at the bond (i) isothermally solidified zone, (ii) diffusion affected zone and (iii) unaffected base metal. In the diffusion-affected zone, boron was present at the grain boundaries of Ni γ matrix in bulky metal borides form. The diffusion of boron from interlayer material into the base material was mechanism of isothermal solidification and bond formation in transient liquid phase bonding of IN 718.

Partially degradable friction-welded pure iron-stainless steel 316L bone pin.

PubMed

Nasution, A K; Murni, N S; Sing, N B; Idris, M H; Hermawan, H

2015-01-01

This article describes the development of a partially degradable metal bone pin, proposed to minimize the occurrence of bone refracture by avoiding the creation of holes in the bone after pin removal procedure. The pin was made by friction welding and composed of two parts: the degradable part that remains in the bone and the nondegradable part that will be removed as usual. Rods of stainless steel 316L (nondegradable) and pure iron (degradable) were friction welded at the optimum parameters: forging pressure = 33.2 kPa, friction time = 25 s, burn-off length = 15 mm, and heat input = 4.58 J/s. The optimum tensile strength and elongation was registered at 666 MPa and 13%, respectively. A spiral defect formation was identified as the cause for the ductile fracture of the weld joint. A 40-µm wide intermetallic zone was identified along the fusion line having a distinct composition of Cr, Ni, and Mo. The corrosion rate of the pin gradually decreased from the undeformed zone of pure iron to the undeformed zone of stainless steel 316L. All metallurgical zones of the pin showed no toxic effect toward normal human osteoblast cells, confirming the ppb level of released Cr and Ni detected in the cell media were tolerable. © 2014 Wiley Periodicals, Inc.

Interaction between macrocyclic nickel complexes and the nucleotides GMP, AMP and ApG.

PubMed

Liu, Yangzhong; Sletten, Einar

2003-01-15

Reactions between the nucleotides GMP, AMP and ApG and the complexes Ni(tren), Ni(cyclam) and NiCR in aqueous solution have been monitored by (1)H, (15)N NMR and UV spectroscopy. The three nickel complexes display different properties in reactions with nucleotides. Ni(tren) which has a pseudo-octahedral coordination geometry was shown to bind to all three nucleotides. Ni(cyclam) and NiCR, both with four nitrogen atoms in a square planar arrangement are not able to bind to nucleotides efficiently because of steric hindrance. Oxidation of Ni(cyclam) by KHSO(5) to produce trivalent Ni(III)(cyclam) improves the coordination capacity, while oxidation of NiCR does not produce a similar effect. The nucleotides interact with trivalent nickel complexes to different extent. Ni(III)CR is seen to oxidize GMP gradually but does not affect AMP significantly. Ni(III)(cyclam), on the other hand, does not oxidize either GMP or AMP at the 1:1 concentration of oxidant used. This result is probably due to the lower redox potential of Ni(cyclam). ApG binds less efficiently to the Ni complexes but is easier oxidized than the mononucleotides.

Electrostatic Steering Accelerates C3d:CR2 Association

PubMed Central

2016-01-01

Electrostatic effects are ubiquitous in protein interactions and are found to be pervasive in the complement system as well. The interaction between complement fragment C3d and complement receptor 2 (CR2) has evolved to become a link between innate and adaptive immunity. Electrostatic interactions have been suggested to be the driving factor for the association of the C3d:CR2 complex. In this study, we investigate the effects of ionic strength and mutagenesis on the association of C3d:CR2 through Brownian dynamics simulations. We demonstrate that the formation of the C3d:CR2 complex is ionic strength-dependent, suggesting the presence of long-range electrostatic steering that accelerates the complex formation. Electrostatic steering occurs through the interaction of an acidic surface patch in C3d and the positively charged CR2 and is supported by the effects of mutations within the acidic patch of C3d that slow or diminish association. Our data are in agreement with previous experimental mutagenesis and binding studies and computational studies. Although the C3d acidic patch may be locally destabilizing because of unfavorable Coulombic interactions of like charges, it contributes to the acceleration of association. Therefore, acceleration of function through electrostatic steering takes precedence to stability. The site of interaction between C3d and CR2 has been the target for delivery of CR2-bound nanoparticle, antibody, and small molecule biomarkers, as well as potential therapeutics. A detailed knowledge of the physicochemical basis of C3d:CR2 association may be necessary to accelerate biomarker and drug discovery efforts. PMID:27092816

Methods for determining soluble and insoluble Cr III and Cr VI compounds in welding fumes.

PubMed

Matczak, W; Chmielnicka, J

1989-01-01

An analytical procedure for simultaneous determination of soluble and insoluble Cr III and Cr VI compounds in welding fumes has been proposed. In the welding fume samples collected on a membrane filter, total chromium was determined with atomic absorption spectrophotometry (AAS). Glass filters with collected samples were divided into two parts. In one part of the sample, soluble and insoluble chromium was determined by means of AAS. The separation of soluble chromium III and VI was carried out on diphenylcarbazide resin. In the second part of the sample total chromium VI was determined by means of the colorimetric method with s-diphenylcarbazide. The difference in the results of these determinations allowed the calculation of the content of total Cr III, Cr III insolub. and Cr VI insolub. The results of determining chromium compounds in welding fumes samples collected in the welder's breathing zone and in experimental chambers are also presented in this paper. The content of total chromium in the fumes determined by AAS (from a membrane filtr) and that calculated from the sum of soluble and insoluble chromium (from a glass filter) were concordant and within the limits of the admissible error for the method. Total chromium content in welding fume samples collected individually was found to range from 2.4-4.2%. The percentage of particular chromium compounds as compared to total chromium (100%) amounted: total Cr III--34%, total Cr VI--66%, soluble chromium--66% and in this Cr III--20% and Cr VI--43%, insoluble chromium--34% and in this: Cr III--14% and Cr VI--20%.

Probing ‘Spin-Forbidden’ Oxygen Atom Transfer: Gas-Phase Reactions of Chromium-Porphyrin Complexes

PubMed Central

Fornarini, Simonetta; Lanucara, Francesco; Warren, Jeffrey J.

2010-01-01

Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a ‘two-state’ reactivity model has been extensively applied especially in iron-porphyrin systems. Herein we explore the gas phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)CrIII]+ (1) and [(TPFPP)CrVO]+ (2). These are an attractive system to examine the effects of spin state change on oxygen atom transfer because the d1 CrV species are doublets while the CrIII complexes have quartet ground states with high-lying doublet excited states. In the gas phase, [(TPFPP)CrIII]+ forms adducts with a variety of neutral donors but O-atom transfer is only observed for NO2. Pyridine N-oxide adducts of 1 do yield 2 upon collision induced dissociation (CID), but the ethylene oxide, DMSO, and TEMPO analogs do not. [(TPFPP)CrVO]+ is shown by its reactivity and by CID experiments to be a terminal metal-oxo with a single vacant coordination site. It also displays limited reaction chemistry, being deoxygenated only by the very potent reductant P(OMe)3. In general, [(TPFPP)CrVO]+ species are much less reactive than the Fe and Mn analogs. Thermochemical analysis of the reactions points towards the involvement of spin issues in the lower observed reactivity of the chromium complexes. PMID:20218631

Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC.

PubMed

Halim, Cheryl E; Short, Stephen A; Scott, Jason A; Amal, Rose; Low, Gary

2005-10-17

A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.

Correlation effect and magnetic moments in Cr2Te3

NASA Astrophysics Data System (ADS)

Youn, S. J.; Kwon, S. K.; Min, B. I.

2007-05-01

The electronic and magnetic structures of Cr2Te3 have been studied theoretically using the linearized muffin-tin orbitals band method. Experimental photoemission spectra and magnetic moments can be described better when the on-site Coulomb correlation U of Cr 3d electrons is considered using the local spin-density approximation+U method. The proper size of U is found to be U ˜1.7eV. The complex magnetic behaviors of Cr2Te3 come from the degeneracy of parallel and antiparallel alignments of CrI spin to CrII and CrIII spins.

Characteristics of Eutectic α(Cr,Fe)-(Cr,Fe)23C6 in the Eutectic Fe-Cr-C Hardfacing Alloy

NASA Astrophysics Data System (ADS)

Lai, Hsuan-Han; Hsieh, Chih-Chun; Lin, Chi-Ming; Wu, Weite

2017-01-01

A specific eutectic (Cr,Fe)-(Cr,Fe)23C6 structure had been previously reported in the research studies of Fe-Cr-C hardfacing alloys. In this study, a close observation and discussion of the eutectic (Cr,Fe)-(Cr,Fe)23C6 were conducted. The eutectic solidification occurred when the chromium content of the alloy exceeded 35 wt pct. The eutectic structure showed a triaxial radial fishbone structure which was the so called "complex regular structure." Lamellar costa plates showed local asymmetry at two sides of a spine. Individual costae were able to combine as one, and spines showed extra branches. Costae that were nearly parallel to the heat flow direction were longer than those that were vertical to the heat flow direction. The triaxial spines preferred to intersect at 120 deg, while the costae preferred to intersect the spine at 90 deg and 35.26 deg due to the lattice relationships. The solidified metal near the fusion boundary showed an irregular structure instead of a complex regular structure. The reason for the irregular morphology was the high growth rate near the fusion boundary.

Phenocrysts and megacrysts of olivines from ultramafic lamprophyres of the Chadobets and Il'bokich uplifts, Southwestern Siberia

NASA Astrophysics Data System (ADS)

Smirnova, Maria; Sazonova, Lyudmila; Nosova, Anna; Kargin, Alexey; Shcherbakov, Vasiliy

2017-04-01

The study of composition and zoning of olivines from ultramafic lamprophyres of the SW Siberian craton allowed us to distinguish their main types (phenocrysts and megacrysts) and to estimate the possible P-T conditions of phenocryst crystallization. The studied rocks occur as sills and dikes in the Chadobets and Il'bokich uplifts of the Irkeneeva-Chadobets trough. The ultramafic lamprophyres of these uplifts are spaced around 80 km apart and differ in age by more than 150 Ma. The rocks of the Il'bokich Uplift are dated at Devonian, while the age of the Chadobets Complex is restricted to the Triassic. The episodes of these complexes formation were separated by the large flood basalt event. According to classification (Tappe et al., 2005), the studied rocks are aillikite and damtjernite. Olivine phenocrysts from the rocks of the Il'bokich and Chadobets complexes are represented by sub- and euhedral grains. They are composed of core, transitional zone, and rim. Olivine cores in the aillikites of the Il'bokich Complex are characterized by Mg# 89; CaO - 0.13-0.14 wt %; TiO2 around 0.03 wt %, Al - 200-380 ppm, and Cr - 130-340 ppm. The cores of phenocrysts from the Chadobets lamprophyres have Mg# 85-87, CaO varying within 0.1-0.2 wt %, and TiO2 - 0.02-0.05 wt %. The megacrysts differ from the phenocrysts of these rocks in the lower Mg# 83-84 and CaO - 0.08-0.14 wt % at higher TiO2 - 0.04-0.05 wt %. Al - 100-700 ppm, Cr - 20-65 ppm. The most striking difference between olivines of the two complexes is observed between their Mg#-Ni relations. The cores of olivine phenocrysts from the Il'bokich lamprophyres are characterized by the high Mg number (Mg# = 89) and Ni content (2800-3000 ppm), whereas olivine cores of the Chadobets aillikites have higher contents of Ni (3000-3500 ppm) at lowered (Mg# = 86-88). These characteristics reflect the compositions of their protolith. The temperature was estimated using monomineral olivine thermometer based on the contents of Cr and Al in olivine (De Hooge et al., 2010). This geothermometer was calibrated for a wide compositional range, including kimberlites, and correspondingly, may be used for alkaline-ultrabasic lamprophyres. At pressures above 4 GPa, olivine phenocrysts fall in the field of olivine-kimberlite melt equilibrium (Girnis et al., 1995). The Il'bokich olivine phenocrysts were formed at higher temperature than the Chadobets phenocrysts: from 1240 to 1340oC for the Il'bokich rocks and from 1080 to 1225oC for the Chadobets rocks. In the P-T diagram showing the geotherm of 40 mV/m2, olivines from the Il'bokich and Chadobets lamprophyres lie to the right of the geotherm, which excludes the presence of xenogenic lithospheric mantle olivine in these rocks. De Hoog J.C.M., Gall L., Cornell D.H. 2010. Trace-element geochemistry of mantle olivine and application to mantle petrogenesis and geothermobarometry // Chem. Geol. 270.1: 196-21. Girnis A.V., Brey G.P., Ryabchikov I.D. 1995. Origin of group 1A kimberlites: fluid-saturated melting experiments at 45-55 kbar // EPSL. 134.3: 283-296. Tappe S., Foley S.F., Jenner G.A. et al. 2006. Genesis of Ultramafic Lamprophyres and Carbonatites at Aillik Bay, Labrador: a Consequence of Incipient Lithospheric Thinning beneath the North Atlantic Craton // J. Petrology. 47 (7). 1261-1315.

Influence of ligand-bridged substitution on the exchange coupling constant of chromium-wheels host complexes: a density functional theory study

NASA Astrophysics Data System (ADS)

Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud

2018-05-01

Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.

Zoned chondrules in Semarkona: Evidence for high-and low-temperature processing

USGS Publications Warehouse

Grossman, J.N.; Alexander, C.M. O'D.; Wang, Jingyuan; Brearley, A.J.

2002-01-01

At least 15% of the low-FeO chondrules in Semarkona (LL3.0) have mesostases that are concentrically zoned in Na, with enrichments near the outer margins. We have studied zoned chondrules using electron microprobe methods (x-ray mapping plus quantitative analysis), ion micropobe analysis for trace elements and hydrogen isotopes, cathodoluminescence imaging, and transmission electron microscopy in order to determine what these objects can tell us about the environment in which chondrules formed and evolved. Mesostases in these chondrules are strongly zoned in all moderately volatile elements and H (interpreted as water). Calcium is depleted in areas of volatile enrichment. Titanium and Cr generally decrease toward the chondrule surfaces, whereas Al and Si may either increase or decrease, generally in opposite directions to one another; Mn follows Na in some chondrules but not in others; Fe and Mg are unzoned. D/H ratios increase in the water-rich areas of zoned chondrules. Mesostasis shows cathodoluminescence zoning in most zoned chondrules, with the brightest yellow color near the outside. Mesostasis in zoned chondrules appears to be glassy, with no evidence for devitrification. Systematic variations in zoning patterns among pyroxene- and olivine-rich chondrules may indicate that fractionation of low- and high-Ca pyroxene played some role in Ti, Cr, Mn, Si, Al, and some Ca zoning. But direct condensation of elements into hot chondrules, secondary melting of late condensates into the outer portions of chondrules, and subsolidus diffusion of elements into warm chondrules cannot account for the sub-parallel zoning profiles of many elements, the presence of H2O, or elemental abundance patterns. Zoning of moderately volatile elements and Ca may have been produced by hydration of chondrule glass without devitrification during aqueous alteration on the parent asteroid. This could have induced structural changes in the glass allowing rapid diffusion and exchange of elements between altered glass and surrounding matrix and rim material. Calcium was mainly lost during this process, and other nonvolatile elements may have been mobile as well. Some unzoned, low-FeO chondrules appear to have fully altered mesostasis.

The cells of cajal-retzius: still a mystery one century after.

PubMed

Soriano, Eduardo; Del Río, José Antonio

2005-05-05

Cajal-Retzius (CR) cells are an enigmatic class of neurons located at the surface of the cerebral cortex, playing a major role in cortical development. In this review, we discuss several distinct features of these neurons and the mechanisms by which they regulate cortical development. Many CR cells likely have extracortical origin and undergo cell death during development. Recent genetic studies report unique patterns of gene expression in CR cells, which may help to explain the developmental processes in which they participate. Moreover, a number of studies indicate that CR cells, and their secreted gene product, reelin, are involved in neuronal migration by acting on two key partners, migrating neurons and radial glial cells. Emerging data show that these neurons are a critical part of an early and complex network of neural activity in layer I, supporting the notion that CR cells modulate cortical maturation. Given these key and complex developmental properties, it is therefore conceivable for CR cells to be implicated in the pathogenesis of a variety of neurological disorders.

[Cr-Ti-Al-N complex coating on titanium to strengthen Ti/porcelain bonding].

PubMed

Zhang, Hui; Guo, Tian-wen; Li, Jun-ming; Pan, Jing-guang; Dang, Yong-gang; Tong, Yu

2006-02-01

To study the feasibility of magnetron sputtering Cr-Ti-Al-N complex coating as an interlayer on titanium to enhance the titanium-ceramic binding strength. With a three-point bending test according to ISO 9693, the binding strength of Duceratin (Degussa) to titanium substrate prepared with 4 different surface treatments (polishing, polishing and megnetron sputtering Cr, Ti, Al, and N complex coating, sandblasting, sandblasting and coating) was evaluated. Ti/porcelain interface and fractured Ti surface were examined using scanning electron microscopy with energy-dispersive spectrometry (EDS). The binding strength of polished and coated titanium/Duceratin was significantly higher than polished titanium group (P<0.05). The binding strength of sandblasted and coated titanium/Duceratin did not differ significantly from that of sandblasted titanium group (P>0.05), and the strength in the two sandblasted titanium groups was significantly higher than that in polished and coated titanium group (P<0.05). Megnetron sputtering Cr-Ti-Al-N complex on polished titanium can increase the titanium/porcelain binding strength. Megnetron sputtering coating is a promising Ti/porcelain interlayer.

Graphite fiber/copper composites prepared by spontaneous infiltration

NASA Astrophysics Data System (ADS)

Wang, Hongbao; Tao, Zechao; Li, Xiangfen; Yan, Xi; Liu, Zhanjun; Guo, Quangui

2018-05-01

The major bottleneck in developing graphite fiber reinforced copper (GF/Cu) composites is the poor wettability of Cu/graphite system. Alloying element of chromium (Cr) is introduced to improve the wettability of liquid copper on graphite. Sessile drop method experiments illustrate that the contact angle of liquid Cu-Cr (1.0 wt.%) alloy on graphite substrate decreases to 43° at 1300 °C. The improvement of wettability is related to the formation of chromium carbide layer at interface zone. Based on the wetting experiment, a spontaneous infiltration method for preparing GF/Cu composites is proposed. Unidirectional GF preforms are infiltrated by Cu-Cr alloys without external pressure in a tubular furnace. Results reveal that the GF preform can be fully infiltrated by Cu-Cr alloy (8 wt.%) spontaneously when fiber volume fraction is 40%. The coefficient of thermal expansion (CTE) of GF/Cu-Cr (8.0 wt.%) composites is 4.68 × 10-6/K along the longitudinal direction.

On dissimilar metal welding of AISI4140 and AISI410 by GTAW

NASA Astrophysics Data System (ADS)

Velu, M.; Dixit, Shantanu; Choure, Shubham

2017-11-01

This paper presents the results of metallurgical and mechanical examinations of Gas Tungsten Arc Welding of dissimilar steels AISI4140 and AISI410. Two different filler materials viz., ERNiCr3 and SS410 were used. The various properties of the weldments made using the fillers were compared to select the most appropriate one to get the sound joint. The ultimate tensile and yield strengths of the weldments of SS410 were greater than those of ERNiCr3. The fracture occurred at the weld in weldments made with ERNiCr3, whereas, in the base metal of AISI410 for weldments made with SS410. Microstructure of fusion zone of ERNiCr3 was fully austenitic. Microhardness values in the weld of SS410 were higher and fluctuating compared to those in the weld of ERNiCr3. From this research work, it shall be concluded that SS410 is the best filler material to weld these base materials.

Dislocation loop formation in model FeCrAl alloys after neutron irradiation below 1 dpa

DOE PAGES

Field, Kevin G.; Briggs, Samuel A.; Sridharan, Kumar; ...

2017-08-01

FeCrAl alloys with varying compositions and microstructures are under consideration for accident-tolerant fuel cladding, but limited details exist on dislocation loop formation and growth for this class of alloys under neutron irradiation. Four model FeCrAl alloys with chromium contents ranging from 10.01 to 17.51 wt % and alunimum contents of 4.78 to 2.93 wt % were neutron irradiated to doses of 0.3–0.8 displacements per atom (dpa) at temperatures of 335–355°C. On-zone STEM imaging revealed a mixed population of black dots and larger dislocation loops with either a/2< 111 > or a< 100 > Burgers vectors. Weak composition dependencies were observedmore » and varied depending on whether the defect size, number density, or ratio of defect types was of interest. Here, the results were found to mirror those of previous studies on FeCrAl and FeCr alloys irradiated under similar conditions, although distinct differences exist.« less

Dislocation loop formation in model FeCrAl alloys after neutron irradiation below 1 dpa

NASA Astrophysics Data System (ADS)

Field, Kevin G.; Briggs, Samuel A.; Sridharan, Kumar; Yamamoto, Yukinori; Howard, Richard H.

2017-11-01

FeCrAl alloys with varying compositions and microstructures are under consideration for accident-tolerant fuel cladding, but limited details exist on dislocation loop formation and growth for this class of alloys under neutron irradiation. Four model FeCrAl alloys with chromium contents ranging from 10.01 to 17.51 wt % and aluminum contents of 4.78 to 2.93 wt % were neutron irradiated to doses of 0.3-0.8 displacements per atom (dpa) at temperatures of 335-355 °C. On-zone STEM imaging revealed a mixed population of black dots and larger dislocation loops with either a / 2 〈 111 〉 or a 〈 100 〉 Burgers vectors. Weak composition dependencies were observed and varied depending on whether the defect size, number density, or ratio of defect types was of interest. Results were found to mirror those of previous studies on FeCrAl and FeCr alloys irradiated under similar conditions, although distinct differences exist.

Characterization of Microstructure and Texture of 13Cr4Ni Martensitic Stainless Steel Weld Before and After Tempering =

NASA Astrophysics Data System (ADS)

Mokhtabad Amrei, Mohsen

13Cr4Ni martensitic stainless steels are known for their outstanding performances in the hydroelectric industry, where they are mainly used in the construction of turbine components. Considering the size and geometry of turbine runners and blades, multi-pass welding procedures are commonly used in the fabrication and repair of such turbines. The final microstructure and mechanical properties of the weld are sensitive to the welding process parameters and thermal history. In the case of 13Cr4Ni steel, the thermal cycles imposed by the multi-pass welding operation have significant effects on the complex weld microstructure. Additionally, post-weld heat treatments are commonly used to reduce weld heterogeneity and improve the material's mechanical properties by tempering the microstructure and by forming a "room-temperature-stable austenite." In the first phase of this research, the microstructures and crystallographic textures of aswelded single-pass and double-pass welds were studied as a basis to studying the more complex multi-pass weld microstructure. This study found that the maximum hardness is obtained in high temperature heat affected zone inside the base metal. In particular, the results showed that the heat cycle exposed by the second pass increases the hardness of the previous pass because it produces a finer martensite microstructure. In areas of heat affected zone, a tempering effect is reported from 3 up to 6 millimeters far from the fusion line. Finding austenite phase in these areas are matter of interest and it can be indicative of the microstructure complexity of multi-pass welds. In the second phase of research, the microstructure of multi-pass welds was found to be more heterogeneous than that of single- and double-pass welds. Any individual pass in a multi-pass weld consists of several regions formed by adjacent weld passes heat cycle. Results showed that former austenite grains modification occurred in areas close to the subsequent weld passes. Furthermore, low angle interface laths were observed inside martensite sub-blocks over different regions. The hardness profile of a multi-pass weld was explained by the overlaying heat effects of surrounding passes. In some regions, a tempered matrix was observed, while in other regions a double-quenched microstructure was found. The final aspect of this study focused on the effects of post-weld heat treatments on reformed austenite and carbide formations, and evolution of hardness. The effects of tempering duration and temperature on microstructure were investigated. The study found that nanometer-sized carbides form at martensite lath interfaces and sub-block boundaries. Additionally, it was determined that for any holding duration, the maximum austenite percentage is achievable by tempering at 610 °C. Similarly, the maximum softening was reported for tempering at 610 °C, for any given holding period.

Mechanisms for Reduction of Natural Waters Technogenic Pollution by Metals due to Complexions with Humus Substances (Zoning: Western Siberia and the European Territory of Russia)

NASA Astrophysics Data System (ADS)

Dinu, M. I.

2017-11-01

The article described the complexation of metal ions with humus substances in natural waters (small lakes). Humus substances as the major biochemical components of natural water have a significant impact on the forms and migration of metals and the toxicity of natural objects. This article presents the results of large-scale chemical experiments: the study of the structural features (zonal aspects) of humus substances extracted from soil and water natural climatic zones (more than 300 objects) in Russia (European Russia and West Siberia); the influence of structural features on the physic-chemical parameters of humus acids and, in particular, on their complexing ability. The functional specifics of humus matter extracted from soils is estimated using spectrometric techniques. The conditional stability constants for Fe(III), Cu(II), Pb(II), Cd(II), Zn(II), Ni(II), Co(II), Mn(II), Cr(III), Ca(II), Mg(II), Sr(II), and Al(III) are experimentally determined with the electrochemical, spectroscopic analysis methods. The activities of metals are classified according to their affinity to humus compounds in soils and water. The determined conditional stability constants of the complexes are tested by model experiments, and it is demonstrated that Fe and Al ions have higher conditional stability constants than the ions of alkali earth metals, Pb, Cu, and Zn. Furthermore, the influence of aluminium ions and iron on the complexation of copper and lead as well as the influence of lead and copper on complexation of cobalt and nickel have been identified. The metal forms in a large number of lakes are calculated basing on the experiments’ results. The main chemical mechanisms of the distribution of metals by forms in the water of the lakes in European Russia and West Siberia are described.

Effects of Welding Parameters on Mechanical Properties in Electron Beam Welded CuCrZr Alloy Plates

NASA Astrophysics Data System (ADS)

Jaypuria, Sanjib; Doshi, Nirav; Pratihar, Dilip Kumar

2018-03-01

CuCrZr alloys are attractive structural materials for plasma-facing components (PFC) and heat sink element in the International Thermonuclear Experimental Reactor (ITER) fusion reactors. This material has gained so much attention because of its high thermal conductivity and fracture toughness, high resistance to radiation damage and stability at elevated temperatures. The objective of this work is to study the effects of electron beam welding parameters on the mechanical strength of the butt welded CuCrZr joint. Taguchi method is used as the design of experiments to optimize the input parameters, such as accelerating voltage, beam current, welding speed, oscillation amplitude and frequency. The joint strength and ductility are the desired responses, which are measured through ultimate tensile strength and percent elongation, respectively. Accelerating voltage and welding speed are found to have significant influence on the strength. A combination of low amplitude and high-frequency oscillation is suggested for the higher joint strength and ductility. There is a close agreement between Taguchi predicted results and experimental ones. Fractographic analysis of joint and weld zone analysis are carried out to study the failure behaviour and microstructural variation in the weld zone, respectively.

Assessment of spatial variability of heavy metals in Metropolitan Zone of Toluca Valley, Mexico, using the biomonitoring technique in mosses and TXRF analysis.

PubMed

Zarazúa-Ortega, Graciela; Poblano-Bata, Josefina; Tejeda-Vega, Samuel; Ávila-Pérez, Pedro; Zepeda-Gómez, Carmen; Ortiz-Oliveros, Huemantzin; Macedo-Miranda, Guadalupe

2013-01-01

This study is aimed at assessing atmospheric deposition of heavy metals using the epiphytic moss genera Fabronia ciliaris collected from six urban sites in the Metropolitan Zone of the Toluca Valley in Mexico. The concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr, and Pb were determined by total reflection X-ray fluorescence technique. Results show that the average metal concentration decrease in the following order: Fe (8207 mg/Kg) > Ca (7315 mg/Kg) > K (3842 mg/Kg) > Ti (387 mg/Kg) > Mn, Zn (191 mg/Kg) > Sr (71 mg/Kg) > Pb (59 mg/Kg) > Cu, V (32 mg/Kg) > Cr (24 mg/Kg) > Rb (13 mg/Kg) > Ni (10 mg/Kg). Enrichment factors show a high enrichment for Cr, Cu, Zn, and Pb which provides an evidence of anthropogenic impact in the industrial and urban areas, mainly due to the intense vehicular traffic and the fossil fuel combustion. Monitoring techniques in mosses have proved to be a powerful tool for determining the deposition of heavy metals coming from diverse point sources of pollution.

Chromium chains as polydentate fluoride ligands for actinides and group IV metals.

PubMed

Leng, Ji-Dong; Kostopoulos, Andreas K; Isherwood, Liam H; Ariciu, Ana-Maria; Tuna, Floriana; Vitórica-Yrezábal, Iñigo J; Pritchard, Robin G; Whitehead, George F S; Timco, Grigore A; Mills, David P; Winpenny, Richard E P

2018-05-08

The reactions of {Cr6} horseshoe chains {[nPr2NH2]3[Cr6F11(O2CtBu)10]}2, 1 and precursors of actinides and group IV metals led to a series of ring complexes [nPr2NH2][Cr7TiF6O2(O2CtBu)16], 2, [nPr2NH2][Cr6Ti2F5O3(O2CtBu)16], 3, [Cr6ThF7(O2CtBu)15 (Me2SO)], 4, [(nPr2NH2)2(Cr6Th2F12(O2CtBu)16)], 5 and [nPr2NH2][Cr6U2O2F8(O2CtBu)16(Me2SO)], 6. X-ray structure studies indicate that the {Cr6} chains maintain their structures in these complexes, acting as polydentate fluoride ligands. Their static magnetic properties were measured and fitted by isotropic exchange Hamiltonian. In accordance with 1, the magnetic exchanges between CrIII are antiferromagnetic, while the exchange interactions can be modified by the tetravalent metals. For compound 6, ferromagnetic exchanges JCr-U and JU-U are obtained. EPR spectra of compounds 2-5 were measured at Q band and were simulated. The spectrum of 2 has the same profile as {Cr7Cd} and {Cr7Zn} rings with a ground state S = 3/2. 3, 4 and 5 give similar EPR spectra with S = 0 ground states.

Constraints on the Amount of deeply subducted Water from numerical Models in comparison with natural Samples

NASA Astrophysics Data System (ADS)

Konrad-Schmolke, M.; Halama, R.

2014-12-01

The subduction of hydrated slab mantle to beyond-arc depths is the most important and yet weakly constrained factor in the quantification of the Earth's deep geologic water cycle. During subduction of hydrated oceanic lithosphere, dehydration reactions in the downgoing plate lead to a partitioning of water between upper and lower plate. Water retained in the slab is recycled into the mantle where it controls its rheology and thus plate tectonic velocities. Hence, quantification of the water partitioning in subduction zones is crucial for the understanding of mass transfer between the Earth's surface and the mantle. Combined thermomechanical and thermodynamic models yield quantitative constraints on the water cycle in subduction zones, but unless model results can be linked to natural observations, the reliability of such models remains speculative. We present combined thermomechanical, thermodynamic and geochemical models of active and paleo-subduction zones, whose results can be tested with independent geochemical features in natural rocks. In active subduction zones, evidence for the validity of our model comes from the agreement between modeled and observed across-arc trends of boron concentrations and isotopic compositions in arc volcanic rocks. In the Kamchatkan subduction zone, for example, the model successfully predicts complex geochemical patterns and the spatial distribution of arc volcanoes. In paleo-subduction zones (e.g. Western Gneiss Region and Western Alps), constraints on the water budget and dehydration behavior of the subducting slab come from trace element zoning patterns in ultra-high pressure (UHP) garnets. Distinct enrichments of Cr, Ni and REE in the UHP zones of the garnets can be reconciled by our models that predict intense rehydration and trace element re-enrichment of the eclogites at UHP conditions by fluids released from the underlying slab mantle. Models of present-day subduction zones indicate the presence of 2.5-6 wt.% of water within the uppermost 15 km of the subducted slab mantle. Depending on hydration depth, between 25 and 90% of this water is recycled into the deeper mantle. The Lower Devonian example from the Western Gneiss Region indicates that subduction of water into the Earth's deeper mantle is an active process at least since the middle Paleozoic.

Transport of chromium and selenium in the suboxic zone of a shallow aquifer: Influence of redox and adsorption reactions

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Anderson, L.C.D.; Rea, B.A.; Waite, T.D.

1994-01-01

Breakthrough of Cr(VI) (chromate), Se(VI) (selenate), and O2 (dissolved oxygen) was observed in tracer tests conducted in a shallow, sand and gravel aquifer with mildly reducing conditions. Loss of Cr, probably due to reduction of Cr(VI) to Cr(III) and irreversible sorption of Cr(III), occurred along with slight retardation of Cr(VI), owing to reversible sorption. Reduction of Se(VI) and O2 was thermodynamically feasible but did not occur, indicating conditions, were unfavorable to microbial reduction. Cr(VI) reduction by constituents of aquifer sediments did not achieve local equilibrium during transport. The reduction rate was probably limited by incomplete contact between Cr(VI) transported along predominant flow paths and reductants located in regions within aquifer sediments of comparatively low permeability. Scatter in the amount of Cr reduction calculated from individual breakthrough curves at identical distances downgradient probably resulted from heterogeneities in the distribution of reductants in the sediments. Predictive modeling of the transport and fate of redox-sensitive solutes cannot be based strictly on thermodynamic considerations; knowledge of reaction rates is critical. Potentially important mass transfer rate limitations between solutes and reactants in sediments as well as heterogeneities in the distribution of redox properties in aquifers complicate determination of limiting rates for use in predictive simulations of the transport of redox-sensitive contaminants in groundwater.

Reactivity of Chromium(III) Nutritional Supplements in Biological Media: An X-Ray Absorption Spectroscopic Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, A.; Mulyani, I.; Levina, A.

2009-05-22

Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3]+ (A), [Cr(pic)3] (pic) = 2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4]+ (CrCl3 {center_dot} 6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of amore » library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].« less

pH-specific synthesis and spectroscopic, structural, and magnetic studies of a chromium(III)-citrate species. Aqueous solution speciation of the binary chromium(III)-citrate system.

PubMed

Gabriel, C; Raptopoulou, C P; Terzis, A; Tangoulis, V; Mateescu, C; Salifoglou, A

2007-04-16

In an attempt to understand the aqueous interactions of Cr(III) with the low-molecular-mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)-citrate system was explored, leading to the complex (NH4)4[Cr(C6H4O7)(C6H5O7)].3H2O (1). 1 crystallizes in the monoclinic space group I2/a, with a = 19.260(10) A, b = 10.006(6) A, c = 23.400(10) A, beta = 100.73(2) degrees , V = 4431(4) A3, and Z = 8. 1 was characterized by elemental analysis and spectroscopic, structural, thermal, and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H4O7)(C6H5O7)]4- complex, optimally present around pH approximately 5.5. The structure of 1 reveals a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. The two citrate ligands have different deprotonation states, thus signifying the importance of the mixed deprotonation state in the coordination sphere of the Cr(III) species in aqueous speciation. The latter reveals the distribution of numerous species, including 1, for which the collective structural, spectroscopic, and magnetic data point out its physicochemical profile in the solid state and in solution. The importance of the synthetic efforts linked to 1 and the potential ramifications of Cr(III) reactivity toward both low- and high-molecular-mass biotargets are discussed in light of (a) the quest for well-characterized soluble Cr(III) species that could be detected and identified in biologically relevant fluids, (b) ongoing efforts to delineate the aqueous speciation of the Cr(III)-citrate system and its link to biotoxic Cr(III) manifestations, and (c) the synthetic utility of convenient Cr(III) precursors in the synthesis of advanced materials.

Tribological Behavior of Al-Cr Coating Obtained by Dgpsm and IIP Composite Technology

NASA Astrophysics Data System (ADS)

Luo, Xixi; Yao, Zhengjun; Zhang, Pingze; Zhou, Keyin; Chen, Yu; Tao, Xuewei

An Al-Cr composite alloyed layer composed of an Al enriched layer, a Cr enriched layer and a transition layer from the surface to the bulk along the cross-section was deposited on a 45# steel substrate by composite technology, where Cr was deposited using double glow plasma surface metallurgy (DGPSM), and Al was then implanted by ion implantation (IIP) to achieve higher micro-hardness and excellent abrasive resistance. The composite alloyed layer is approximately 5μm, and as metallurgical adherence to the substrate. The phases are Al8Cr5, Fe2AlCr, Cr23C6, Cr (Al) and Fe (Cr, Al) solid solution. The wear resistance tests were performed under various rotational speed (i.e. 280, 560 and 840r/min) with silicon nitride balls as the counterface material at ambient temperature. The Al-Cr composite alloyed layer exhibits excellent wear resistance when the speed is 280r/min with a friction coefficient as low as 0.3, which is attributed to Al8Cr5 in the Al implanted layer that withstands abrasive wear. Better wear resistance (friction coefficient: 0.254) at 560r/min is resulted from the formation of a high micro-hardness zone, and an oxidation layer with lubrication capacity. In addition, the composite alloyed layer suffers severe oxidative wear and adhesive wear at 840r/min due to the increment of the frictional heating. When compared to the 45# steel substrate, the enhanced wear resistance of the Al-Cr composite alloyed layer demonstrates the viable method developed in this work.

Multi-stage origin of the Coast Range ophiolite, California: Implications for the life cycle of supra-subduction zone ophiolites

USGS Publications Warehouse

Shervais, J.W.; Kimbrough, D.L.; Renne, P.; Hanan, B.B.; Murchey, B.; Snow, C.A.; Zoglman, Schuman M.M.; Beaman, J.

2004-01-01

The Coast Range ophiolite of California is one of the most extensive ophiolite terranes in North America, extending over 700 km from the northernmost Sacramento Valley to the southern Transverse Ranges in central California. This ophiolite, and other ophiolite remnants with similar mid-Jurassic ages, represent a major but short-lived episode of oceanic crust formation that affected much of western North America. The history of this ophiolite is important for models of the tectonic evolution of western North America during the Mesozoic, and a range of conflicting interpretations have arisen. Current petrologic, geochemical, stratigraphic, and radiometric age data all favor the interpretation that the Coast Range ophiolite formed to a large extent by rapid extension in the forearc region of a nascent subduction zone. Closer inspection of these data, however, along with detailed studies of field relationships at several locales, show that formation of the ophiolite was more complex, and requires several stages of formation. Our work shows that exposures of the Coast Range ophiolite preserve evidence for four stages of magmatic development. The first three stages represent formation of the ophiolite above a nascent subduction zone. Rocks associated with the first stage include ophiolite layered gabbros, a sheeted complex, and volcanic rocks vith arc tholeiitic or (roore rarely) low-K calc-alkaline affinities. The second stage is characterized by intrusive wehrlite-clinopyroxenite complexes, intrusive gabbros, Cr-rich diorites, and volcanic rocks with high-Ca boninitic or tholeiitic ankaramite affinities. The third stage includes diorite and quartz diorite plutons, felsic dike and sill complexes, and calc-alkaline volcanic rocks. The first three stages of ophiolite formation were terminated by the intrusion of mid-ocean ridge basalt dikes, and the eruption of mid-ocean ridge basalt or ocean-island basalt volcanic suites. We interpret this final magmatic event (MORB dikes) to represent the collision of an active spreading ridge. Subsequent reorganization of relative plate motions led to sinistral transpression, along with renewed subduction and accretion of the Franciscan Complex. The latter event resulted in uplift and exhumation of the ophiolite by the process of accretionary uplift. ?? 2004 by V. H. Winston and Son, Inc. All rights reserved.

Nanoindentation of Electropolished FeCrAl Alloy Welds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weaver, Jordan; Aydogan, Eda; Mara, Nathan Allan

The present report summarizes Berkovich nanoindentation modulus and hardness measurements on two candidate FeCrAl alloys (C35M and C37M) on as-received (AR) and welded samples. In addition, spherical nanoindentation stress-strain measurements were performed on individual grains to provide further information and demonstrate the applicability of these protocols to mechanically characterizing welds in FeCrAl alloys. The indentation results are compared against the reported tensile properties for these alloys to provide relationships between nanoindentation and tensile tests and insight into weldsoftening for these FeCrAl alloys. Hardness measurements revealed weld-softening for both alloys in good agreement with tensile test results. C35M showed a largermore » reduction in hardness at the weld center from the AR material compared to C37M; this is also consistent with tensile tests. In general, nanohardness was shown to be a good predictor of tensile yield strength and ultimate tensile stress for FeCrAl alloys. Spherical nanoindentation measurements revealed that the fusion zone (FZ) + heat affected zone (HAZ) has a very low defect density typical of well-annealed metals as indicated by the frequent pop-in events. Spherical nanoindentation yield strength, Berkovich hardness, and tensile yield strength measurements on the welded material all show that the C37M welded material has a higher strength than C35M welded material. From the comparison of nanoindentation and tensile tests, EBSD microstructure analysis, and information on the processing history, it can be deduced that the primary driver for weld-softening is a change in the defect structure at the grain-scale between the AR and welded material. These measurements serve as baseline data for utilizing nanoindentation for studying the effects of radiation damage on these alloys.« less

Crystal structure of fac-tri-chlorido-[tris-(pyridin-2-yl-N)amine]-chromium(III).

PubMed

Yamaguchi-Terasaki, Yukiko; Fujihara, Takashi; Nagasawa, Akira; Kaizaki, Sumio

2015-01-01

In the neutral complex mol-ecule of the title compound, fac-[CrCl3(tpa)] [tpa is tris-(pyridin-2-yl)amine; C15H12N4], the Cr(III) ion is bonded to three N atoms that are constrained to a facial arrangement by the tpa ligand and by three chloride ligands, leading to a distorted octa-hedral coordination sphere. The average Cr-N and Cr-Cl bond lengths are 2.086 (5) and 2.296 (4) Å, respectively. The complex mol-ecule is located on a mirror plane. In the crystal, a combination of C-H⋯N and C-H⋯Cl hydrogen-bonding inter-actions connect the mol-ecules into a three-dimensional network.

Carbonation of Peridotite by CO2-rich Fluids: Insights from Listvenites in the Advocate Ophiolite (Newfoundland)

NASA Astrophysics Data System (ADS)

Menzel, Manuel; Garrido, Carlos J.; Marchesi, Claudio; López Sánchez Vizcaíno, Vicente; Hidas, Károly; Escayola, Monica P.; Jamtveit, Bjørn

2017-04-01

Listvenites are the result of a sequence of reactions of CO2-rich hydrothermal fluids with serpentinite that forms magnesite-quartz rocks in the last reaction step. Listvenites are natural analogues for carbon sequestration by mineral carbonation, fixing large quantities of carbon in relatively small, confined zones of intense reactive fluid flux within serpentinite. The association of listvenite (magnesite-quartz), soapstone (talc-magnesite) and carbonated serpentinite in the mantle section of the Advocate ophiolite complex in Newfoundland (Canada) is an ideal natural example to study the carbonation of serpentinites because the reaction progress is recorded by the differently carbonated assemblages. The Advocate listvenites crop out in a 20-30 m wide zone that can be followed for about 1 km, surrounded by serpentinite and harzburgite. Quartz and magnesite veins are widespread in the central listvenite domain. This mobilization of silica into a vein network is reflected in a depletion of silica in the most carbonated lithologies, whereas most other major elements remain unchanged over a wide range of CO2-contents. Notably, there is a sharp decrease in bulk rock Fe3+/Fetotal from 0.65 - 0.8 in lizardite-chrysotile serpentinites to 0.1 - 0.3 in talc-magnesite rocks and listvenites. High Cr and Ni contents and preserved red-brown Cr-spinel in the carbonated lithologies demonstrate the mantle peridotites provenance of the listvenites. The presence of thin veins of Cr-mica (fuchsite) suggests that Cr was mobilized to some degree. Fine dispersed magnetite trails in magnesite trace serpentine pseudomorphs after olivine, indicating that no deformation occurred in some domains during the carbonation, while deformation was concentrated in talc-rich lithologies. The rheological contrasts of serpentinites, soapstones and listvenites and, in consequence, the formation of veins in response to shear- or extensional fractures may result in a re-opening of pathways for the influx of very CO2-rich fluids that are needed for the formation of listvenites. Carbonated mantle rocks like the Advocate listvenites may represent the best accessible natural analogue for carbonation of serpentinites through bend faulting at the outer rise of trenches, since hydrothermal fluids in those systems may become more CO2-rich due to percolation through overlying sediments, thus allowing for localized intense carbonation. Funding: We acknowledge funding from the People programme (Marie Curie Actions - ITN) of the European Union FP7 under REA Grant Agreement n˚ 608001.

Insights into controls on hexavalent chromium in groundwater provided by environmental tracers, Sacramento Valley, California, USA

USGS Publications Warehouse

Manning, Andrew H.; Mills, Christopher T.; Morrison, Jean M.; Ball, Lyndsay B.

2015-01-01

Environmental tracers are useful for determining groundwater age and recharge source, yet their application in studies of geogenic Cr(VI) in groundwater has been limited. Environmental tracer data from 166 wells located in the Sacramento Valley, northern California, were interpreted and compared to Cr concentrations to determine the origin and age of groundwater with elevated Cr(VI), and better understand where Cr(VI) becomes mobilized and how it evolves along flowpaths. In addition to major ion and trace element concentrations, the dataset includes δ18O, δ2H, 3H concentration, 14C activity (of dissolved inorganic C), δ13C, 3He/4He ratio, and noble gas concentrations (He, Ne, Ar, Kr, Xe). Noble gas recharge temperatures (NGTs) were computed, and age-related tracers were interpreted in combination to constrain the age distribution in samples and sort them into six different age categories spanning from <60 yr old to >10,000 yr old. Nearly all measured Cr is in the form of Cr(IV). Concentrations range from <1 to 46 μg L−1, with 10% exceeding the state of California’s Cr(VI) maximum contaminant level of 10 μg L−1. Two groups with elevated Cr(VI) (⩾5 μg L−1) were identified. Group 1 samples are from the southern part of the valley and contain modern (<60 yr old) water, have elevated NO3− concentrations (>3 mg L−1), and commonly have δ18O values enriched relative to local precipitation. These samples likely contain irrigation water and are elevated due to accelerated mobilization of Cr(VI) in the unsaturated zone (UZ) in irrigated areas. Group 2 samples are from throughout the valley and typically contain water 1000–10,000 yr old, have δ18O values consistent with local precipitation, and have unexpectedly warm NGTs. Chromium(VI) concentrations in Group 2 samples may be elevated for multiple reasons, but the hypothesis most consistent with all available data (notably, the warm NGTs) is a relatively long UZ residence time due to recharge through a deep UZ near the margin of the basin. A possible explanation for why Cr(VI) may be primarily mobilized in the UZ rather than farther along flowpaths in the oxic portion of the saturated zone is more dynamic cycling of Mn in the UZ due to transient moisture and redox conditions.

Characterization of a heterobimetallic nonheme Fe(III)-O-Cr(III) species formed by O2 activation.

PubMed

Zhou, Ang; Kleespies, Scott T; Van Heuvelen, Katherine M; Que, Lawrence

2015-10-01

We report the generation and spectroscopic characterization of a heterobimetallic [(TMC)Fe(III)-O-Cr(III)(OTf)4] species (1) by bubbling O2 into a mixture of Fe(TMC)(OTf)2 and Cr(OTf)2 in NCCH3. Complex 1 also formed quantitatively by adding Cr(OTf)2 to [Fe(IV)(O)(TMC)(NCCH3)](2+). The proposed O2 activation mechanism involves the trapping of a Cr-O2 adduct by Fe(TMC)(OTf)2.

Characterization of a Heterobimetallic Nonheme Fe(III)-O-Cr(III) Species Formed by O2 Activation

PubMed Central

Zhou, Ang; Kleespies, Scott T.; Van Heuvelen, Katherine M.; Que, Lawrence

2015-01-01

We report the generation and spectroscopic characterization of a heterobimetallic [(TMC)FeIII-O-CrIII(OTf)4] species (1) by O2 bubbling into a mixture of Fe(TMC)(OTf)2 and Cr(OTf)2 in NCCH3. Complex 1 also formed quantitatively by adding Cr(OTf)2 to [FeIV(O)(TMC)(NCCH3)]2+. The proposed O2 activation mechanism involves the trapping by a Cr-O2 adduct by Fe(TMC)(OTf)2. PMID:26265081

Platinum group elements in stream sediments of mining zones: The Hex River (Bushveld Igneous Complex, South Africa)

NASA Astrophysics Data System (ADS)

Almécija, Clara; Cobelo-García, Antonio; Wepener, Victor; Prego, Ricardo

2017-05-01

Assessment of the environmental impact of platinum group elements (PGE) and other trace elements from mining activities is essential to prevent potential environmental risks. This study evaluates the concentrations of PGE in stream sediments of the Hex River, which drains the mining area of the Bushveld Igneous Complex (South Africa), at four sampling points. Major, minor and trace elements (Fe, Ca, Al, Mg, Mn, V, Cr, Zn, Cu, As, Co, Ni, Cd, and Pb) were analyzed by FAAS and ETAAS in suspended particulate matter and different sediment fractions (<63, 63-500 and 500-2000 μm), and Pt, Pd, Rh, and Ir were measured by ICP-MS after removal of interfering elements (cation exchange resin 50W-DOWEX-X8). Procedures were blank-corrected and accuracy checked using reference materials. Nickel, Cr, Pt, Pd, Rh and Ir show concentrations 3-, 13- 18-, 28-, 48- and 44- fold the typical upper continental crust levels, respectively, although lower than concentrations reported for the parent rocks. The highest concentrations were observed closer to the mining area, decreasing with distance and in the <63 μm fraction, probably derived from atmospheric deposition and surface runoff of PGE-rich particles released from mining activities. Thus, mining activities are causing some disturbance of the surface PGE geochemical cycle, increasing the presence of PGE in the fine fraction of river sediments. We propose that indicators such as airborne particulate matter, and soil and river sediment quality, should be added to the protocols for evaluating the sustainability of mining activities.

The Effect of Dilution on Microsegregation in AWS ER NiCrMo-14 Alloy Welding Claddings

NASA Astrophysics Data System (ADS)

Miná, Émerson Mendonça; da Silva, Yuri Cruz; Dille, Jean; Silva, Cleiton Carvalho

2016-12-01

Dilution and microsegregation are phenomena inherent to claddings, which, in turn, directly affect their main properties. This study evaluated microsegregation in the fusion zone with different dilution levels. The overlays were welded by the TIG cold wire feed process. Dilution was calculated from the geometric characteristics of the claddings and from the conservation of mass equation using chemical composition measurements. Microsegregation was calculated using energy dispersive X-ray spectroscopy measurements of the dendrites and the chemical composition of the fusion zone. The dilution of the claddings was increased by reducing the wire feed rate. Fe showed potential to be incorporated into the solid phase ( k > 1), and this increased with the increase of dilution. Mo, in turn, was segregated into the liquid phase ( k < 1) and also increased with the increase of dilution. However, Cr and W showed a slight decrease in their partition coefficients ( k) with the increase of dilution.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiming; Li, Baiyan; Wu, Zili

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

DOE PAGES

Zhang, Yiming; Li, Baiyan; Wu, Zili; ...

2015-01-09

The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Changes in complex spike activity during classical conditioning

PubMed Central

Rasmussen, Anders; Jirenhed, Dan-Anders; Wetmore, Daniel Z.; Hesslow, Germund

2014-01-01

The cerebellar cortex is necessary for adaptively timed conditioned responses (CRs) in eyeblink conditioning. During conditioning, Purkinje cells acquire pause responses or “Purkinje cell CRs” to the conditioned stimuli (CS), resulting in disinhibition of the cerebellar nuclei (CN), allowing them to activate motor nuclei that control eyeblinks. This disinhibition also causes inhibition of the inferior olive (IO), via the nucleo-olivary pathway (N-O). Activation of the IO, which relays the unconditional stimulus (US) to the cortex, elicits characteristic complex spikes in Purkinje cells. Although Purkinje cell activity, as well as stimulation of the CN, is known to influence IO activity, much remains to be learned about the way that learned changes in simple spike firing affects the IO. In the present study, we analyzed changes in simple and complex spike firing, in extracellular Purkinje cell records, from the C3 zone, in decerebrate ferrets undergoing training in a conditioning paradigm. In agreement with the N-O feedback hypothesis, acquisition resulted in a gradual decrease in complex spike activity during the conditioned stimulus, with a delay that is consistent with the long N-O latency. Also supporting the feedback hypothesis, training with a short interstimulus interval (ISI), which does not lead to acquisition of a Purkinje cell CR, did not cause a suppression of complex spike activity. In contrast, observations that extinction did not lead to a recovery in complex spike activity and the irregular patterns of simple and complex spike activity after the conditioned stimulus are less conclusive. PMID:25140129

Formation of Ultrafine Metal Particles by Gas-Evaporation VI. Bcc Metals, Fe, V, Nb, Ta, Cr, Mo and W

NASA Astrophysics Data System (ADS)

Saito, Yahachi; Mihama, Kazuhiro; Uyeda, Ryozi

1980-09-01

The crystal structures and habits of bcc metal particles have been investigated systematically by electron microscopy. The habits for the bcc structure are rhombic dodecahedra truncated by six {100} faces with various degrees of truncation from 0 to 100%. The truncation degree for Fe and V particles grown in the intermediate zone of a metal smoke is in good agreement with that for the Wulff polyhedron expected from the surface energies calculated for {110} and {100} faces. Particles of Cr, Mo and W have the A-15 type structure besides the ordinary bcc structure. The present results support the hypothesis that the A-15 type structure is stable when the particle size is small. The habits for the A-15 type structure are rhombic dodecahedra (Cr), {211} icositetrahedra (Cr and Mo) and rounded cubes (Mo and W).

SUMMARY CONCLUSIONS FOR THE PILOT IN-SITU CHROMIUM REDUCTION TEST AT RIVERBANK ARMY AMMUNITIONS PLANT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ridley, M

2007-04-25

A treatability study was conducted at Riverbank Army Ammunition Plant's (RBAAP) Site 17, to evaluate the effectiveness of a permeable reactive barrier (PRB) for the treatment of hexavalent chromium (Cr{sup 6+}). The chromium contamination at Site 17 is hydrologically isolated and unsuitable for standard extraction and treatment (pump and treat). The majority of the chromium contamination at Site 17 is trapped within the fine grain sediments of a clay/slit zone (45 to 63). The PRB was established above and adjacent to the contaminated zone at Site 17 to reduce the hexavalent chromium as it leaches out of the contaminated clay/siltmore » zone separating the A zone from the A zone. Site 17 and the monitoring network are described in the In-Situ Chromium Reduction Treatability Study Work Plan (CH2MHILL, January 2004). The PRB was created by reducing naturally occurring Fe{sup 3+} to Fe{sup 2+} with the injection of a buffered sodium dithionite solution into subsurface chromium source area. The Cr{sup 6+} leaching out of the contaminated clay/silt zone and migrating through the PRB is reduced by Fe{sup 2+} to Cr{sup 3+} and immobilized (Amonette, et al., 1994). The sodium dithionite will also reduce accessible Cr{sup 6+}, however the long-term reductant is the Fe{sup 2+}. Bench scale tests (Appendix A) were conducted to assess the quantity and availability of the naturally occurring iron at Site 17, the ability of the sodium dithionite to reduce the hexavalent chromium and Fe within the sediments, and the by-products produced during the treatment. Appendix A, provides a detailed description of the laboratory treatability tests, and provides background information on the technologies considered as possible treatment options for Site 17. Following the sodium dithionite treatment, groundwater/treatment solution was extracted to remove treatment by-products (sulfate, manganese, and iron). The following sections briefly discuss the current treatment status, future recommendations for Site 17, and future recommendations for the application of sodium dithionite at additional sites. At the completion of the treatability test, none of the wells at Site 17 had detectable hexavalent chromium, but the sulfate, iron, and manganese concentrations were detected and exceeded the CA secondary drinking water standards. The extraction done after the injection of the sodium dithionite solution to remove the sulfate, manganese, and iron has to a large extent negated the effectiveness of the iron reduction. Riverbank's local groundwater is naturally high in dissolved oxygen (concentration range at Site 17: 1.8 to 6.0 mg/l) and moving this type of groundwater through the reduced zone caused oxidation of the Fe2+ within the treatment zone, followed by a new release of hexavalent chromium detected in one of the treatment wells. Additional extraction at Site 17 will continue to degrade the PRB, threatening to release additional Cr{sup 6+} into the groundwater. Sulfate and manganese only exceed the CA secondary drinking water standards in the area immediately surrounding the PRB. It is unlikely that these contaminants will threaten any water supply wells in the area. The chromium concentrations are increasing in IW-17. The current concentration is still only a third of the original concentration. It might be worth investigating some of the new zero valent iron treatments, such as nanoscale zero-valent iron (NZVI) to replace the in-situ naturally occurring iron, which may no longer be available for reduction. The NZVI has been successfully tested at NASA in Florida (O'Hara, 2006), and demonstrated no release of metals from the natural sediments. This might also be a viable option for other sites at RBAAP.« less

Ferromagnetic coupled mu-phenoxo-mu-carboxylato heterodinuclear complexes based on the Cr(salen) moiety: structural and magnetic characterization.

PubMed

Alborés, Pablo; Seeman, Johanna; Rentschler, Eva

2009-10-07

The synthesis, crystal structure, and magneto-chemical characterization of two new unprecedented -phenoxo--carboxylato heterodinuclear complexes based on the Cr(salen) moiety (salen = N,N-bis(salicylidene)ethylenediamine), [MII(O2C(CH3)3)(OH2)2(mu-O2C(CH3)3)(-salen)CrIII(O2C(CH3)3)], M = Ni (2), Co(3) are reported. The dinuclear complexes were obtained starting from the mononuclear trans-[Cr(salen)(CN)2]PPh4 (1), whose crystal structure is also reported. They show a trans arrangement of the Cr(salen) unit, bridging through the phenolate O atoms to a second metal center. An additional 2-O2-carboxylato bridge and a further monodentating carboxylate ligand complete the roughly octahedral Cr(III) coordination sphere. The highly distorted octahedral M(II) coordination environment is completed by two coordinated water molecules and an additional monodentating carboxylate. Variable-temperature solid-state DC magnetization studies were carried out in the 2.0-300 K range. Ferromagnetic isotropic pairwise exchange parameters were found with values of J = 4.1 cm-1 (2) and J = 2.1 cm-1 (3). Additionally, for complex 3, a ZFS parameter, D, was employed to properly fit the experimental data. Magnetization (M) vs. field (H) and temperature (T) data further support the presence of this anisotropic component and confirm ground states S = 5/2 and S = 3 for 2 and 3, respectively. Broken symmetry DFT calculations properly reproduce the experimental J values supporting the ferromagnetic exchange interaction experimentally observed. No out of phase susceptibility signal was observed in 0 DC magnetic field for both complexes. However, in the case of complex 3 a non-zero is observed when a small external field is applied below 3 K, suggesting slow relaxation of the magnetization which at 0 DC field is suppressed, probably due to efficient tunnelling relaxation pathways. The low symmetry of the Co(II) site in complex 3 may lead to the presence of transversal anisotropic components which could be responsible for the enhanced tunnelling pathway.

Mono- and bimetallic zwitterionic chromium(0) and tungsten(0) allenyls.

PubMed

Giner, Elena A; Santiago, Alicia; Gómez-Gallego, Mar; Ramírez de Arellano, Carmen; Poulten, Rebecca C; Whittlesey, Michael K; Sierra, Miguel A

2015-06-01

A series of stable chiral (racemic), formally neutral, zwitterionic mono- and bimetallic M(CO)5[C(OEt)═C═CR(NHC)] (M = Cr, W) σ-allenyls are ready available by the addition of N-heterocyclic carbenes (NHCs) to Cr(0) and W(0) alkynyl Fischer carbene complexes. Different classes of NHCs, (e.g., 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene, and their six- and seven-membered analogues and 1,3-bis(dimethyl)imidazol-2-ylidene) were employed as nucleophiles in these C-C bond-forming reactions yielding the novel complexes in essentially quantitative yields. A systematic experimental and computational study of the electronic properties of the Cr- and W-allenyls shows that their UV-vis spectra are directly influenced by the structure of the heterocyclic moiety derived from the NHC (ring size, substituents on the N atoms) and by the nature of the metal fragment (Cr/W). The electron-releasing nature of these complexes allows them to participate in electron-transfer reactions in the ground state, leading to a type of charged α,β-unsaturated Fischer carbenes that incorporate an NHC fragment in their structure.

Organization of the Zone of Transition between the Pretectum and the Thalamus, with Emphasis on the Pretectothalamic Lamina

PubMed Central

Márquez-Legorreta, Emmanuel; Horta-Júnior, José de Anchieta C.; Berrebi, Albert S.; Saldaña, Enrique

2016-01-01

The zone of transition between the pretectum, derived from prosomere 1, and the thalamus, derived from prosomere 2, is structurally complex and its understanding has been hampered by cytoarchitectural and terminological confusion. Herein, using a battery of complementary morphological approaches, including cytoarchitecture, myeloarchitecture and the expression of molecular markers, we pinpoint the features or combination of features that best characterize each nucleus of the pretectothalamic transitional zone of the rat. Our results reveal useful morphological criteria to identify and delineate, with unprecedented precision, several [mostly auditory] nuclei of the posterior group of the thalamus, namely the pretectothalamic lamina (PTL; formerly known as the posterior limitans nucleus), the medial division of the medial geniculate body (MGBm), the suprageniculate nucleus (SG), and the ethmoid, posterior triangular and posterior nuclei of the thalamus. The PTL is a sparsely-celled and fiber rich flattened nucleus apposed to the lateral surface of the anterior pretectal nucleus (APT) that marks the border between the pretectum and the thalamus; this structure stains selectively with the Wisteria floribunda agglutinin (WFA), and is essentially immunonegative for the calcium binding protein parvalbumin (PV). The MGBm, located medial to the ventral division of the MGB (MGBv), can be unequivocally identified by the large size of many of its neurons, its dark immunostaining for PV, and its rather selective staining for WFA. The SG, which extends for a considerable caudorostral distance and deviates progressively from the MGB, is characterized by its peculiar cytoarchitecture, the paucity of myelinated fibers, and the conspicuous absence of staining for calretinin (CR); indeed, in many CR-stained sections, the SG stands out as a blank spot. Because most of these nuclei are small and show unique anatomical relationships, the information provided in this article will facilitate the interpretation of the results of experimental manipulations aimed at the auditory thalamus and improve the design of future investigations. Moreover, the previously neglected proximity between the MGBm and the caudal region of the scarcely known PTL raises the possibility that certain features or roles traditionally attributed to the MGBm may actually belong to the PTL. PMID:27563286

Month-to-month and year-to-year reproducibility of high frequency QRS ECG signals

NASA Technical Reports Server (NTRS)

Batdorf, Niles J.; Feiveson, Alan H.; Schlegel, Todd T.

2004-01-01

High frequency electrocardiography analyzing the entire QRS complex in the frequency range of 150 to 250 Hz may prove useful in the detection of coronary artery disease, yet the long-term stability of these waveforms has not been fully characterized. Therefore, we prospectively investigated the reproducibility of the root mean squared voltage, kurtosis, and the presence versus absence of reduced amplitude zones in signal averaged 12-lead high frequency QRS recordings acquired in the supine position one month apart in 16 subjects and one year apart in 27 subjects. Reproducibility of root mean squared voltage and kurtosis was excellent over these time intervals in the limb leads, and acceptable in the precordial leads using both the V-lead and CR-lead derivations. The relative error of root mean squared voltage was 12% month-to-month and 16% year-to-year in the serial recordings when averaged over all 12 leads. Reduced amplitude zones were also reproducible up to a rate of 87% and 81%, respectively, for the month-to-month and year-to-year recordings. We conclude that 12-lead high frequency QRS electrocardiograms are sufficiently reproducible for clinical use.

Radical Polymerization of Vinyl Acetate and Methyl Methacrylate Using Organochromium Initiators Complexed with Macrocyclic Polyamines

DTIC Science & Technology

1994-06-30

conversion, the increase was faster than at later stages. and therefore the steric strain enfosced by the 5gn backone dpdson Th efficiency of initation...BPOJ),- 0.25M. Cr(OAc)2jDPO, THF. 200CC IVAclo - SMK [Cr2io - [DPOJ~i 0.25M. (UI - (Cr2+’Jo (LIgl - (Cr2൒ 0 _ In the absence of any liganda, a

Redox reactions of V(III) and Cr(III)picolinate complexes in aqueous solutions

NASA Astrophysics Data System (ADS)

Vinayakumar, C. K.; Dey, G. R.; Kishore, K.; Moorthy, P. N.

1996-12-01

Reactions of e aq-, H-atoms, OH, (CH 3) 2COH, and CO 2- radicals with V(III)picolinate and Cr(III)picolinate have been studied by the pulse radiolysis technique. The spectra of V(II)picolinate, V(IV)picolinate, Cr(II)picolinate, OH adduct of Cr(III)picolinate and Cr(IV)picolinate have been obtained and the rate constants of the reactions of various radicals with V(III) and Cr(III)picolinate have been determined. The implications of these results to the chemical decontamination of nuclear reactor systems are discussed.

Solubility and transport of Cr(III) in a historically contaminated soil - Evidence of a rapidly reacting dimeric Cr(III) organic matter complex.

PubMed

Löv, Åsa; Sjöstedt, Carin; Larsbo, Mats; Persson, Ingmar; Gustafsson, Jon Petter; Cornelis, Geert; Kleja, Dan B

2017-12-01

Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (>65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h -1 ). Extended X-ray absorption fine structure (EXAFS) measurements indicated that Cr(III) associated with colloids and particles, and with the solid phase, mainly existed as dimeric hydrolyzed Cr(III) bound to natural organic matter. Dissolution kinetics of this species were fast (≤1 day) at low pH (<3) and slightly slower (≤5 days) at neutral pH. Furthermore, it proved possible to describe the solubility of the dimeric Cr(III) organic matter complex with a geochemical equilibrium model using only generic binding parameters, opening the way for use of geochemical models in risk assessments of Cr(III)-contaminated sites. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Third-order nonlinear optical properties of soluble Cr(III)-dioxolene complexes

NASA Astrophysics Data System (ADS)

Noro, Shin-ichiro; Sassa, Takafumi; Aoyama, Tetsuya; Chang, Ho-Chol; Kitagawa, Susumu; Wada, Tatsuo

2004-10-01

We synthesized novel ligand-based mixed valence (LBMV) CrIII-dioxolene complexes, [Cr(X4SQ)(X4Cat)(4,4'-di-tert-butyl-2,2'-bpy)] (SQ = semiquinone, Cat = catecohol, 2,2'-bpy = 2,2'-bipyridine; X = Cl (2a) and Br (2b)) and [Cr(X4SQ)(X4Cat)(4,4'-dinonyl-2,2'-bpy)] (X = Cl (3a) and Br (3b)), and prepared thin films for investigating their third-order nonlinear optical (NLO) properties in terms of the mixed valence states. Electronic absorption spectra of these complexes in solution and solid states showed an intervalence charge-transfer (IVCT) band from Cat2- to SQ"- at the IR region, indicating of a coexistence of SQ and Cat ligands, namely, LBMV state of the complexes. These complexes were well soluble in nonpolar organic solvent, which allowed us to prepare thin films by spin coating. The obtained films showed the electronic absorption spectra similar to those in solution and were amorphous because of steric hindrance of halogen and alkyl substituents in o-dioxolene and 2,2'-bpy moieties, respectively. The x(3) values of the films of 3a and 3b with a thickness of 30 ~ 40 nm were determined for 1.0 × 10-12 esu at 1.907 μm.

The reduction mechanism of chromite in the presence of a silica flux

NASA Astrophysics Data System (ADS)

Weber, P.; Eric, R. H.

1993-12-01

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe2+ ions and an inward diffusion of Mg2+ and Cr2+ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr3+ and Fe2+) in the spinel and the dissolved cations (Al3+ and Mg2+) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.

Metal release and speciation of released chromium from a biomedical CoCrMo alloy into simulated physiologically relevant solutions.

PubMed

Hedberg, Yolanda; Odnevall Wallinder, Inger

2014-05-01

The objective of this study was to investigate the extent of released Co, Cr(III), Cr(VI), and Mo from a biomedical high-carbon CoCrMo alloy exposed in phosphate-buffered saline (PBS), without and with the addition of 10 µM H2 O2 (PBS + H2 O2 ), and 10 g L(-1) bovine serum albumin (PBS + BSA) for time periods up to 28 days. Comparative studies were made on AISI 316L for the longest time period. No Cr(VI) release was observed for any of the alloys in either PBS or PBS + H2 O2 at open-circuit potential (no applied potential). However, at applied potentials (0.7 V vs. Ag/AgCl), Cr was primarily released as Cr(VI). Co was preferentially released from the CoCrMo alloy at no applied potential. As a consequence, Cr was enriched in the utmost surface oxide reducing the extent of metal release over time. This passivation effect was accelerated in PBS + H2 O2 . As previously reported for 316L, BSA may also enhance metal release from CoCrMo. However, this was not possible to verify due to the precipitation of metal-protein complexes with reduced metal concentrations in solution as a consequence. This was particularly important for Co-BSA complexes after sufficient time and resulted in an underestimation of metals in solution. Copyright © 2013 Wiley Periodicals, Inc.

Kinetics and thermodynamics of bovine serum albumin interactions with Congo red dye.

PubMed

de Paula, Hauster Maximiler Campos; Coelho, Yara Luiza; Agudelo, Alvaro Javier Patiño; Rezende, Jaqueline de Paula; Ferreira, Gabriel Max Dias; Ferreira, Guilherme Max Dias; Pires, Ana Clarissa Dos Santos; da Silva, Luis Henrique Mendes

2017-11-01

To optimize the therapeutic applications of Congo red (CR), a potential inhibitor of protein aggregation, the kinetics and thermodynamics of the interactions between CR and a model protein need to be understood. We used surface plasmon resonance (SPR) and fluorescence techniques to determine the dynamics and thermodynamic parameters for the formation of complexes between CR and bovine serum albumin (BSA). CR interacts with BSA through a transition complex; the activation energy for association (E act(a) ) was determined to be 35.88kJmol -1 , while the activation enthalpy (ΔH ‡ ), entropy (ΔS ‡ ), and Gibbs free energy (ΔG ‡ ) are 33.41kJmol -1 , 0.18Jmol -1 K -1 , and 33.35kJmol -1 , respectively. When this intermediate transforms into the final CR-BSA complex, the entropy of the system increases and part of the absorbed energy is released; this process is associated with a reverse activation energy (E act(d) ) of 20.17kJmol -1 , and values of ΔH ‡ , ΔS ‡ , and ΔG ‡ of 17.69kJmol -1 , -162.86Jmol -1 K -1 , and 66.25kJmol -1 , respectively. A comparison of the SPR and fluorescence results suggests that there is more than one site where BSA interacts with CR. Copyright © 2017 Elsevier B.V. All rights reserved.

Crystal structure of bis­[trans-di­chlorido­bis(propane-1,3-di­amine-κ2 N,N′)chromium(III)] dichromate from synchrotron data

PubMed Central

Moon, Dohyun; Ryoo, Keon Sang; Choi, Jong-Ha

2016-01-01

The structure of the title compound, [CrCl2(tn)2]2[Cr2O7] (tn = propane-1,3-di­amine; C3H10N2), has been determined from synchrotron data. The asymmetric unit contains one CrIII complex cation and half a [Cr2O7]2− anion. In the complex cation, the CrIII ion is coordinated by the four N atoms of two propane-1,3-di­amine (tn) ligands in the equatorial plane and by two Cl atoms in a trans configuration, displaying a distorted octa­hedral coordination sphere. The two six-membered rings in the complex cation have an anti chair–chair conformation with respect to each other. The mean Cr—N(tn) and Cr—Cl bond lengths are 2.09 (1) and 2.320 (2) Å, respectively. The slightly bent dichromate anion is disordered over two sets of sites (occupancy ratio = 0.7:0.3) and has a staggered conformation. The crystal structure is stabilized by inter­molecular hydrogen bonds involving the NH2 groups of the tn ligands as donors and the O atoms of the [Cr2O7]2− anion and chlorido ligands as acceptors. PMID:27920920

Insulin-sensitizing and cholesterol-lowering effects of chromium (D-Phenylalanine)3.

PubMed

Yang, Xiaoping; Li, Shi-Yan; Dong, Feng; Ren, Jun; Sreejayan, Nair

2006-07-01

Low-molecular weight organic chromium complexes are thought to play a key role in carbohydrate and lipid metabolism and therefore have been gaining popularity as nutritional supplement for patients with diabetes and concomitant lipid disorders. The aim of the present study was to evaluate the effects of a novel synthetic chromium (d-phenylalanine)(3) complex on insulin-sensitivity, plasma lipid-profile and oxidant stress in a mouse model of type II diabetes. Plasma glucose levels following intraperitoneal insulin-challenge (1U/kg) to obese ob/ob(+/+) mice treated with Cr(d-Phe)(3) (150 microg/kg/day for 6 weeks) were significantly lower compared to vehicle-control (control: 175.8+/-43.2mg/dL versus Cr(d-Phe)(3) 115.3+/-18.0mg/dL, p<0.01, n=12). Total serum cholesterol to high-density lipoprotein ratio was significantly reduced following Cr(d-Phe)(3)-treatment (control: 2.19+/-0.08 versus Cr(d-Phe)(3) 1.63+/-0.05; p<0.05). Hepatic oxidant stress, assessed as malondialdehyde equivalents and protein-carbonyl content were significantly attenuated following Cr(d-Phe)(3) treatment. The complex also inhibited lipid-peroxidation in vitro, in a concentration dependent manner. Taken together, these data suggest that Cr(d-Phe)(3) may be of potential value in the therapy or prophylaxis of insulin-resistance and dyslipidemia associated with obesity.

A magnetostructural study of linear NiII MnIII NiII, NiII CrIII NiII and triangular Ni(II)3 species containing (pyridine-2-aldoximato)nickel(II) unit as a building block.

PubMed

Weyhermüller, Thomas; Wagner, Rita; Khanra, Sumit; Chaudhuri, Phalguni

2005-08-07

Three trinuclear complexes, NiII MnIII NiII, NiII CrIII NiII and Ni(II)3 based on (pyridine-2-aldoximato)nickel(II) units are described. Two of them, and , contain metal-centers in linear arrangement, as is revealed by X-ray diffraction. Complex is a homonuclear complex in which the three nickel(II) centers are disposed in a triangular fashion. The compounds were characterized by various physical methods including cyclic voltammetric and variable-temperature (2-290 K) susceptibility measurements. Complexes and display antiferromagnetic exchange coupling of the neighbouring metal centers, while weak ferromagnetic spin exchange between the adjacent Ni II and Cr III ions in is observed. The experimental magnetic data were simulated by using appropriate models.

Use of ATP analogs to inhibit HIV-1 transcription

PubMed Central

Narayanan, Aarthi; Sampey, Gavin; Van Duyne, Rachel; Guendel, Irene; Kehn-Hall, Kylene; Roman, Jessica; Currer, Robert; Galons, Hervé; Oumata, Nassima; Joseph, Benoît; Meijer, Laurent; Caputi, Massimo; Nekhai, Sergei; Kashanchi, Fatah

2012-01-01

Human immunodeficiency virus type 1 (HIV-1) is the etiological agent of AIDS. Chronic persistent infection is an important reason for the presence of “latent cell populations” even after Anti Retroviral Therapy (ART). We have analyzed the effect of ATP analogs in inhibiting cdk9/T1 complex in infected cells. A third generation drug named CR8#13 is an effective inhibitor of Tat activated transcription. Following drug treatment, we observed a decreased loading of cdk9 onto the HIV-1 DNA. We found multiple novel cdk9/T1 complexes present in infected and uninfected cells with one complex being unique to infected cells. This complex is sensitive to CR8#13 in kinase assays. Treatment of PBMC with CR8#13 does not kill infected cells as compared to Flavopiridol. Interestingly, there is a difference in sensitivity of various clades to these analogs. Collectively, these results point to targeting novel complexes for inhibition of cellular proteins that are unique to infected cells. PMID:22771113

Chemical and electrochemical behavior of the Cr(3)/Cr(2) half cell in the NASA Redox Energy Storage System

NASA Technical Reports Server (NTRS)

Johnson, D. A.; Reid, M. A.

1982-01-01

The Cr(III) complexes in the NASA Redox Energy Storage System were isolated and identified as Cr(H2O)6(+3) and Cr(H2O)5Cl(+2) by ion exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles were followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations calculated using Beer's Law. During the charge mode Cr(H2O)5Cl(+2) is reduced to Cr(H2O)5Cl(+) and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(+2). Both electrode reactions occur via a chloride-bridge inner-sphere reaction pathway. Hysteresis effects can be explained by the slow attainment of equilibrium between Cr(H2O)6(+3) and Cr(H2O)5Cl(+2).

21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. 176.160 Section 176.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS...

21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. 176.160 Section 176.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS...

21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. 176.160 Section 176.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS...

21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. 176.160 Section 176.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS...

Spatial distribution of dust-bound trace elements in Pakistan and their implications for human exposure.

PubMed

Eqani, Syed Ali Musstjab Akber Shah; Kanwal, Ayesha; Bhowmik, Avit Kumar; Sohail, Mohammad; Ullah, Rizwan; Ali, Syeda Maria; Alamdar, Ambreen; Ali, Nadeem; Fasola, Mauro; Shen, Heqing

2016-06-01

This study aims to assess the spatial patterns of selected dust-borne trace elements alongside the river Indus Pakistan, their relation with anthropogenic and natural sources, and the potential risk posed to human health. The studied elements were found in descending concentrations: Mn, Zn, Pb, Cu, Ni, Cr, Co, and Cd. The Index of Geo-accumulation indicated that pollution of trace metals were higher in lower Indus plains than on mountain areas. In general, the toxic elements Cr, Mn, Co and Ni exhibited altitudinal trends (P < 0.05). The few exceptions to this trend were the higher values for all studied elements from the northern wet mountainous zone (low lying Himalaya). Spatial PCA/FA highlighted that the sources of different trace elements were zone specific, thus pointing to both geological influences and anthropogenic activities. The Hazard Index for Co and for Mn in children exceeded the value of 1 only in the riverine delta zone and in the southern low lying zone, whereas the Hazard Index for Pb was above the bench mark for both children and adults (with few exceptions) in all regions, thus indicating potential non-carcinogenic health risks. These results will contribute towards the environmental management of trace metal(s) with potential risk for human health throughout Pakistan. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical Properties And Toxicity of Chromium(III) Nutritional Supplements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levina, A.; Lay, P.A.

2009-05-19

The status of Cr(III) as an essential micronutrient for humans is currently under question. No functional Cr(III)-containing biomolecules have been definitively described as yet, and accumulated experience in the use of Cr(III) nutritional supplements (such as [Cr(pic){sub 3}], where pic = 2-pyridinecarboxylato) has shown no measurable benefits for nondiabetic people. Although the use of large doses of Cr(III) supplements may lead to improvements in glucose metabolism for type 2 diabetics, there is a growing concern over the possible genotoxicity of these compounds, particularly of [Cr(pic){sub 3}]. The current perspective discusses chemical transformations of Cr(III) nutritional supplements in biological media, withmore » implications for both beneficial and toxic actions of Cr(III) complexes, which are likely to arise from the same biochemical mechanisms, dependent on concentrations of the reactive species. These species include: (1) partial hydrolysis products of Cr(III) nutritional supplements, which are capable of binding to biological macromolecules and altering their functions; and (2) highly reactive Cr(VI/V/IV) species and organic radicals, formed in reactions of Cr(III) with biological oxidants. Low concentrations of these species are likely to cause alterations in cell signaling (including enhancement of insulin signaling) through interactions with the active centers of regulatory enzymes in the cell membrane or in the cytoplasm, while higher concentrations are likely to produce genotoxic DNA lesions in the cell nucleus. These data suggest that the potential for genotoxic side-effects of Cr(III) complexes may outweigh their possible benefits as insulin enhancers, and that recommendations for their use as either nutritional supplements or antidiabetic drugs need to be reconsidered in light of these recent findings.« less

Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

PubMed

Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

2004-11-15

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

Long term high temperature oxidation characteristics of La and Cu alloyed ferritic stainless steels for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Lee, Young-Su; Kim, Dong-Ik

2016-09-01

To ensure the best performance of solid oxide fuel cell metallic interconnects, the Fe-22 wt.% Cr ferritic stainless steels with various La contents (0.006-0.6 wt.%) and Cu addition (1.57 wt.%), are developed. Long-term isothermal oxidation behavior of these steels is investigated in air at 800 °C, for 2700 h. Chemistry, morphology, and microstructure of the thermally grown oxide scale are examined using XPS, SEM-EDX, and XRD techniques. Broadly, all the steels show a double layer consisting of an inner Cr2O3 and outer (Mn, Cr)3O4. Distinctly, in the La-added steels, binary oxides of Cr, Mn and Ti are found at the oxide scale surface together with (Mn, Cr)3O4. Furthermore, all La-varied steels possess the metallic Fe protrusions along with discontinuous (Mn, Cr)3O4 spinel zones at the oxide scale/metal interface and isolated precipitates of Ti-oxides in the underlying matrix. Increase of La content to 0.6 wt.% is detrimental to the oxidation resistance. For the Cu-added steel, Cu is found to segregate strongly at the oxide scale/metal interface which inhibits the ingress of oxygen thereby suppressing the subscale formation of (Mn, Cr)3O4. Thus, Cu addition to the Fe-22Cr ferritic stainless steels benefits the oxidation resistance.

Constructing CrIII-centered heterometallic complexes: [NiCrIII] and [CoCrIII] wheels.

PubMed

Kakaroni, Foteini E; Collet, Alexandra; Sakellari, Eirini; Tzimopoulos, Demetrios I; Siczek, Milosz; Lis, Tadeusz; Murrie, Mark; Milios, Constantinos J

2017-12-19

The solvothermal reaction between Cr(acac) 3 , MCl 2 ·6H 2 O (M = Ni, Co) and 2-hydroxy-4-methyl-6-phenyl-pyridine-3-amidoxime (H 2 L), under basic conditions, led to the synthesis of the heterometallic heptanuclear clusters [MCr(HL zw ) 6 (HL) 6 ]·3Cl (M = Ni, 1; Co, 2), with the nickel analogue displaying an S = 9/2 spin ground-state.

Influence of Cr and W alloying on the fiber-matrix interfacial shear strength in cast and directionally solidified sapphire NiAl composites

NASA Technical Reports Server (NTRS)

Asthana, R.; Tiwari, R.; Tewari, S. N.

1995-01-01

Sapphire-reinforced NiAl matrix composites with chromium or tungsten as alloying additions were synthesized using casting and zone directional solidification (DS) techniques and characterized by a fiber pushout test as well as by microhardness measurements. The sapphire-NiAl(Cr) specimens exhibited an interlayer of Cr rich eutectic at the fiber-matrix interface and a higher interfacial shear strength compared to unalloyed sapphire-NiAl specimens processed under identical conditions. In contrast, the sapphire-NiAl(W) specimens did not show interfacial excess of tungsten rich phases, although the interfacial shear strength was high and comparable to that of sapphire-NiAl(Cr). The postdebond sliding stress was higher in sapphire-NiAl(Cr) than in sapphire-NiAl(W) due to interface enrichment with chromium particles. The matrix microhardness progressively decreased with increasing distance from the interface in both DS NiAl and NiAl(Cr) specimens. The study highlights the potential of casting and DS techniques to improve the toughness and strength of NiAl by designing dual-phase microstructures in NiAl alloys reinforced with sapphire fibers.

Mineralogical and geochemical characterization of weathering profiles developed on mylonites in the Fodjomekwet-Fotouni section of the Cameroon Shear Zone (CSZ), West Cameroon

NASA Astrophysics Data System (ADS)

Tematio, P.; Tchaptchet, W. T.; Nguetnkam, J. P.; Mbog, M. B.; Yongue Fouateu, R.

2017-07-01

The mineralogical and geochemical investigation of mylonitic weathering profiles in Fodjomekwet-Fotouni was done to better trace the occurrence of minerals and chemical elements in this area. Four representative soil profiles were identified in two geomorphological units (upland and lowland) differentiating three weathering products (organo-mineral, mineral and weathered materials). Weathering of these mylonites led to some minerals association such as vermiculite, kaolinite, goethite, smectite, halloysite, phlogopite and gibbsite. The minerals in a decreasing order of abundance are: quartz (24.2%-54.8%); kaolinite (8.4%-36.0%); phlogopite (5.5%-21.9%); goethite (7.8%-16.1%); vermiculite (6.7%-15.7%); smectite (10.2%-11.9%); gibbsite (9.0%-11.8%) and halloysite (5.6%-11.5%) respectively. Patterns of chemical elements allow highlighting three behaviors (enriched elements, depleted elements and elements with complex behavior), depending on the landscape position of the profiles. In the upland weathering products, K, Cr and REEs are enriched; Ca, Mg, Na, Mn, Rb, S and Sr are depleted while Si, Al, Fe, Ti, Ba, Co, Cu, Ga, Mo, Nb, Ni, Pb, Sc, V, Y, Zn and Zr portray a complex behavior. Contrarily, the lowland weathering profiles enriched elements are Fe, Ti, Co, Cr, Cu, V, Zr, Pr, Sm, Tb, Dy, Er and Yb; while depleted elements are Ca, Mg, K, Na, Mn, Ba, Ga, S, Sr, Y, Zn, La, Ce and Nd; and Si, Al, Mo, Nb, Ni, Pb, Rb, Sc evidenced complex behaviors. In all the studied weathering products, the REEs fractionation was also noticeable with a landscape-position dependency, showing light REEs (LREEs) enrichment in the upland areas and heavy REEs (HREEs) in lowland areas. SiO2, Al2O3 and Fe2O3 are positively correlated with most of the traces and REEs (Co, Cu, Nb, Ni, Mo, Pb, Sc, V, Zn, Zr, La, Ce, Sm, Tb, Dy, Er, Yb), pointing to the fact that they may be incorporated into newly formed clay minerals and oxides. Ba, Cr, Ga, Rb, S, Sr, Y, Pr and Nd behave like alkalis and alkaline earths, and are thus highly mobile during weathering.

Novel polymer anchored Cr(III) Schiff base complexes: Synthesis, characterization and antimicrobial properties

NASA Astrophysics Data System (ADS)

Selvi, Canan; Nartop, Dilek

2012-09-01

New polymer-bound Schiff bases and Cr(III) complexes have been synthesized by the reaction of 4-benzyloxybenzaldehyde, polymer-bound with 2-aminophenol, 2-amino-4-chlorophenol and 2-amino-4-methylphenol. The structure of polymeric-Schiff bases and their Cr(III) complexes have been characterized by elemental analyses, magnetic measurements, IR, UV-Vis, TG-DTA and 1H-NMR. All these compounds have also been investigated for antibacterial activity by the well-diffusion method against Staphylococcus aureus (RSKK-07035), Shigella dysenteria type 10 (RSKK 1036), Listeria monocytogenes 4b(ATCC 19115, Escherichia coli (ATCC 1230), Salmonella typhi H (NCTC 901.8394), Staphylococcus epidermis (ATCC 12228), Brucella abortus (RSKK-03026), Micrococcs luteus (ATCC 93419, Bacillus cereus sp., Pseudomonas putida sp. and for antifungal activity against Candida albicans (Y-1200-NIH).

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

PubMed

Konarev, Dmitri V; Troyanov, Sergey I; Shestakov, Alexander F; Yudanova, Evgeniya I; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-01-23

The reaction of tin(iv) phthalocyanine dichloride {Sn IV Cl 2 (Pc 2- )} with decamethylmetallocenes (Cp* 2 M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces Sn IV Cl 2 (Pc 2- ) to form the (Cp* 2 Co + ){Sn IV Cl 2 (Pc˙ 3- )}˙ - ·2C 6 H 4 Cl 2 (1) complex. The negative charge of {Sn IV Cl 2 (Pc˙ 3- )}˙ - is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μ B at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ 3- macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces Sn IV Cl 2 (Pc 2- ) to form the [(Cp* 2 Cr + ){Sn VI Cl 2 (Pc˙ 3- )}˙ - complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp* 2 Cr by chloride anions originating from {Sn IV Cl 2 (Pc˙ 3- )}˙ - to form the complex {(Cp*CrCl 2 )(Sn IV (μ-Cl)(Pc 2- ))}·C 6 H 4 Cl 2 (2) in which the (Cp*CrCl 2 ) and {Sn IV (Pc 2- )} species are bonded through the μ-bridged Cl - anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp* 2 CrCl)(SnClPc)] complex.

Minerals and melt inclusions as keys to understanding magma reservoir processes during formation of volcanic and plutonic mafic-ultramafic complexes in the Maimecha Kotui Province (Polar Siberia)

NASA Astrophysics Data System (ADS)

Simonov, Vladimir; Vasiliev, Yurii; Kotlyarov, Alexey; Stupakov, Sergey

2016-04-01

Magmatic complexes in the Maimecha Kotui Province (Polar Siberia) attract attention of researchers because they contain ultramafic volcanic rocks - meimechites, being products of crystallization of the ultrabasic deep mantle melts (Sobolev et al., 1991, 2009, 2011; Ryabchikov et al., 2002; Vasiliev, Gora, 2014). Effusive meimechites together with intrusive dunites of the Guli massif form ancient (253-246 Ma) volcanic and plutonic association, in which also pyroxenites and alkaline rocks are situated. Conditions of formation of this association were established with the help of minerals and melt inclusions study. The cumulative structure of the Guli massif dunites consists of rather large (2-4 mm) olivine crystals and dividing them zones (0.5-0.7 mm), filled with fine grains of clinopyroxenes and ore minerals (magnetite, ilmenite and chromite). The extended forms of well faceted pyroxene crystals testify to their fast growth from melt between cumulative olivines. Thus, crystallization of clinopyroxenes and ore minerals leads to formation between olivines ore pyroxenites, which are presented in the Guli massif by independent bodies. Analysis of olivine, Cr-spinel and clinopyroxene compositions testify to similarity of conditions of the Guli massif dunites crystallization on the one hand with formation of platinum-bearing Uralian-Alaskan-type mafic-ultramafic complexes and with another - show participation of meimechite magma. Major element composition of melt inclusions in Cr-spinel has shown that dunites of the Guli massif were crystallized with participation of subalkaline picrite magmatic systems, that are relative to melts, responsible of formation of platinum-bearing mafic-ultramafic complexes and meimechites. Peculiarities of trace and rare-earth elements distribution in melt inclusions in Cr-spinel of dunites are actually similar to inclusions in olivine of meimechites. Overall, data on composition of inclusions directly testify to formation of considered dunites from ultrabasic melt close to meimechite magma. The affinity of melts, forming dunites and meimechites, is confirmed by computer simulations, shown high crystallization temperature of olivines from dunites (1590-1415°C) (Simonov et al., 2014, 2015), actually coinciding with data on olivines from meimechite - 1600-1420°C (Sobolev et al., 1991, 2009). A part of this ultrabasic melts was crystallized in the magma chambers (with formation of cumulative dunites) and another part - came up to a surface with formation of effusive meimechites. Presence in Cr-spinels from Guli massif dunites melt inclusions with rather large (up to 50 μm) well faceted olivine crystals, situated in the quenching fine-grained association of minerals (clinopyroxene, feldspar and nepheline), testifies to change of a quiet mode of crystallization by sharp falling of parameters of magma during olivine cumulation in the magma chamber, that resulted in appearance of alkaline rocks. As a whole, minerals and melt inclusions study testify to formation of volcanic and plutonic complexes in the Maimecha Kotui Province (Polar Siberia) as a result of evolution of primary deep mantle ultrabasic melts (similar by its chemical composition to meimechites) during cumulative processes in the magma chambers.

The recycling of chromitites in ophiolites from southwestern North America

NASA Astrophysics Data System (ADS)

González-Jiménez, José M.; Camprubí, Antoni; Colás, Vanessa; Griffin, William L.; Proenza, Joaquín A.; O'Reilly, Suzanne Y.; Centeno-García, Elena; García-Casco, Antonio; Belousova, Elena; Talavera, Cristina; Farré-de-Pablo, Júlia; Satsukawa, Takako

2017-12-01

Podiform chromitites occur in mantle peridotites of the Late Triassic Puerto Nuevo Ophiolite, Baja California Sur State, Mexico. These are high-Cr chromitites [Cr# (Cr/Cr + Al atomic ratio = 0.61-0.69)] that contain a range of minor- and trace-elements and show whole-rock enrichment in IPGE (Os, Ir, Ru). That are similar to those of high-Cr ophiolitic chromitites crystallised from melts similar to high-Mg island-arc tholeiites (IAT) and boninites in supra-subduction-zone mantle wedges. Crystallisation of these chromitites from S-undersaturated melts is consistent with the presence of abundant inclusions of platinum-group minerals (PGM) such as laurite (RuS2)-erlichmanite (OsS2), osmium and irarsite (IrAsS) in chromite, that yield TMA ≈ TRD model ages peaking at 325 Ma. Thirty-three xenocrystic zircons recovered from mineral concentrates of these chromitites yield ages (2263 ± 44 Ma to 278 ± 4 Ma) and Hf-O compositions [ɛHf(t) = - 18.7 to + 9.1 and 18O values < 12.4‰] that broadly match those of zircons reported in nearby exposed crustal blocks of southwestern North America. We interpret these chromitite zircons as remnants of partly digested continental crust or continent-derived sediments on oceanic crust delivered into the mantle via subduction. They were captured by the parental melts of the chromitites when the latter formed in a supra-subduction zone mantle wedge polluted with crustal material. In addition, the Puerto Nuevo chromites have clinopyroxene lamellae with preferred crystallographic orientation, which we interpret as evidence that chromitites have experienced high-temperature and ultra high-pressure conditions (< 12 GPa and 1600 °C). We propose a tectonic scenario that involves the formation of chromitite in the supra-subduction zone mantle wedge underlying the Vizcaino intra-oceanic arc ca. 250 Ma ago, deep-mantle recycling, and subsequent diapiric exhumation in the intra-oceanic basin (the San Hipólito marginal sea) generated during an extensional stage of the Vizcaino intra-oceanic arc ca. 221 Ma ago. The TRD ages at 325 Ma record a partial melting event in the mantle prior to the construction of the Vizcaino intra-oceanic arc, which is probably related to the Permian continental subduction, dated at 311 Ma.

The onset of metamorphism in ordinary and carbonaceous chondrites

USGS Publications Warehouse

Grossman, J.N.; Brearley, A.J.

2005-01-01

Ordinary and carbonaceous chondrites of the lowest petrologic types were surveyed by X-ray mapping techniques. A variety of metamorphic effects were noted and subjected to detailed analysis using electron microprobe, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and cathodoluminescence (CL) methods. The distribution of Cr in FeO-rich olivine systematically changes as metamorphism increases between type 3.0 and type 3.2. Igneous zoning patterns are replaced by complex ones and Cr-rich coatings develop on all grains. Cr distributions in olivine are controlled by the exsolution of a Cr-rich phase, probably chromite. Cr in olivine may have been partly present as tetrahedrally coordinated Cr3+. Separation of chromite is nearly complete by petrologic type 3.2. The abundance of chondrules showing an inhomogeneous distribution of alkalis in mesostasis also increases with petrologic type. TEM shows this to be the result of crystallization of albite. Residual glass compositions systematically change during metamorphism, becoming increasingly rich in K. Glass in type I chondrules also gains alkalis during metamorphism. Both types of chondrules were open to an exchange of alkalis with opaque matrix and other chondrules. The matrix in the least metamorphosed chondrites is rich in S and Na. The S is lost from the matrix at the earliest stages of metamorphism due to coalescence of minute grains. Progressive heating also results in the loss of sulfides from chondrule rims and increases sulfide abundances in coarse matrix assemblages as well as inside chondrules. Alkalis initially leave the matrix and enter chondrules during early metamorphism. Feldspar subsequently nucleates in the matrix and Na re-enters from chondrules. These metamorphic trends can be used to refine classification schemes for chondrites. Cr distributions in olivine are a highly effective tool for assigning petrologic types to the most primitive meteorites and can be used to subdivide types 3.0 and 3.1 into types 3.00 through 3.15. On this basis, the most primitive ordinary chondrite known is Semarkona, although even this meteorite has experienced a small amount of metamorphism. Allan Hills (ALH) A77307 is the least metamorphosed CO chondrite and shares many properties with the ungrouped carbonaceous chondrite Acfer 094. Analytical problems are significant for glasses in type II chondrules, as Na is easily lost during microprobe analysis. As a result, existing schemes for chondrule classification that are based on the alkali content of glasses need to be revised. ?? The Meteorological Society, 2005.

Simultaneous analysis of Cr(III), Cr(VI), and chromium picolinate in foods using capillary electrophoresis-inductively coupled plasma mass spectrometry.

PubMed

Chen, YiQuan; Chen, JinFa; Xi, Zhiming; Yang, Guidi; Wu, Zujian; Li, JianRong; Fu, FengFu

2015-05-01

We herein reported a method for the simultaneous detection of trace Cr(VI), Cr(III), and chromium(III) picolinate (CrPic) in foods using CE-ICP-MS together with ultrasonic-assisted extraction. The Cr(III) (Cr(3+) ) was chelated with trans-1,2-diaminocyclohexane-N,N,N´,N´-tetraacetic acid (DCTA) to form a single charged Cr-DCTA(-) complex. Then, Cr(VI) (CrO4 (2-) ), Cr-DCTA(-) , and CrPic were separated by CE within 8 min under a separation voltage of -13 KV followed by their monitoring with ICP mass spectrometer (ICP-MS). The proposed method is simple, effective, and sensitive. It has an instrument detection limit of 0.10, 0.18, and 0.20 ngCr/mL for Cr(VI), Cr(III), and CrPic, respectively. With the help of the methods, we have successfully determined Cr(VI), Cr(III), and CrPic in nutritional supplement (CrPic yeast tablet) with an RSD (n = 5) <6% and a recovery of 93-103%. The experimental results showed that CrPic was the main speciation of chromium in the nutritional supplement, with a concentration of 1514.6 μg Cr/g. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ecological risk assessment of a coastal zone in Southern Vietnam: Spatial distribution and content of heavy metals in water and surface sediments of the Thi Vai Estuary and Can Gio Mangrove Forest.

PubMed

Costa-Böddeker, Sandra; Hoelzmann, Philipp; Thuyên, Lê Xuân; Huy, Hoang Duc; Nguyen, Hoang Anh; Richter, Otto; Schwalb, Antje

2017-01-30

Enrichment of heavy metals was assessed in the Thi Vai Estuary and in the Can Gio Mangrove Forest (SE, Vietnam). Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn contents in water and in sediments were measured. Total organic carbon, nitrogen, phosphorus and C/N ratios were determined. Cu and Cr values were higher than threshold effect level of toxicity, while Ni exceeded probable effect level, indicating the risk of probable toxicity effects. Enrichment factors (EF), contamination factor (CF) and Geo-accumulation index (I-geo) were determined. CF reveals moderate to considerable pollution with Cr and Ni. EF suggests anthropogenic sources of Cr, Cu and Ni. I-geo indicates low contamination with Co, Cu and Zn and moderate contamination with Cr and Ni. Overall metal contents were lower than expected for this highly industrialized region, probably due to dilution, suggesting that erosion rates and hydrodynamics may also play a role in metal contents distribution. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metallurgical characterization of new palladium-containing cobalt chromium and nickel chromium alloys

NASA Astrophysics Data System (ADS)

Puri, Raghav

Recently introduced to the market has been an entirely new subclass of casting alloy composition whereby palladium (˜25 wt%) is added to traditional base metal alloys such as CoCr and NiCr. Objectives. The purpose of this study was to evaluate the microstructure and Vickers hardness of two new CoPdCr and one new NiPdCr alloy and compare them to traditional CoCr and NiCr alloys. Methods. The casting alloys investigated were: CoPdCr-A (Noble Crown NF, The Argen Corporation), CoPdCr-I (Callisto CP+, Ivoclar Vivadent), NiPdCr (Noble Crown, Argen), CoCr (Argeloy N.P. Special, Argen), and NiCr (Argeloy N.P. Star, Argen). As-cast cylindrical alloy specimens were mounted in epoxy resin and prepared with standard metallographic procedures, i.e. grinding with successive grades of SiC paper and polishing with alumina suspensions. The alloys were examined with an optical microscope, SEM/EPMA, and XRD to gain insight into their microstructure, composition, and crystal structure. Vickers hardness (VHN) was measured and statistically analyzed by one way ANOVA and Tukey's HSD test (alpha=0.05). Results. Optical microscopy showed a dendritic microstructure for all alloys. The Pd-containing alloys appear to possess a more complex microstructure. SEM/EPMA showed Cr to be rather uniformly distributed in the matrix with palladium tending to be segregated apart from Mo and Ni or Co. Areas of different composition may explain the poor electrochemical results noted in previous studies. XRD suggested the main phase in the Ni-containing solutions was a face centered cubic Ni solid solution, whereas the CoCr exhibited a hexagonal crystal structure that was altered to face centered cubic when Pd was included in the composition. For Vickers hardness, the Co-containing alloys possessed a greater hardness than the Ni-containing alloys. However, the incorporation of Pd in CoCr and NiCr had only a slight effect on microhardness. Conclusion. Overall, the inclusion of palladium increases the microstructural complexity of NiCr and CoCr alloys.

Chemical and electrochemical behavior of the Cr(III)/Cr(II) half-cell in the iron-chromium redox energy storage system

NASA Technical Reports Server (NTRS)

Johnson, D. A.; Reid, M. A.

1985-01-01

The Cr(III) complexes present in the acidified chromium solutions used in the iron-chromium redox energy storage system have been isolated and identified as Cr(H2O)6(3+) and Cr(H2O)5Cl(2+) by ion-exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles have been followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations of the Cr(III) species calculated using Beer's law. During the charge mode, Cr(H2O)5Cl(2+) is reduced to Cr(H2O)5Cl(+), and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(2+). Electrode potential measurements also support this interpretation. Hysteresis effects in the charge-discharge curves can be explained by the slow attainment of equilibrium between Cr(H2O)6(3+) and Cr(H2O)5Cl(2+).

Complex multifractal nature in Mycobacterium tuberculosis genome

PubMed Central

Mandal, Saurav; Roychowdhury, Tanmoy; Chirom, Keilash; Bhattacharya, Alok; Brojen Singh, R. K.

2017-01-01

The mutifractal and long range correlation (C(r)) properties of strings, such as nucleotide sequence can be a useful parameter for identification of underlying patterns and variations. In this study C(r) and multifractal singularity function f(α) have been used to study variations in the genomes of a pathogenic bacteria Mycobacterium tuberculosis. Genomic sequences of M. tuberculosis isolates displayed significant variations in C(r) and f(α) reflecting inherent differences in sequences among isolates. M. tuberculosis isolates can be categorised into different subgroups based on sensitivity to drugs, these are DS (drug sensitive isolates), MDR (multi-drug resistant isolates) and XDR (extremely drug resistant isolates). C(r) follows significantly different scaling rules in different subgroups of isolates, but all the isolates follow one parameter scaling law. The richness in complexity of each subgroup can be quantified by the measures of multifractal parameters displaying a pattern in which XDR isolates have highest value and lowest for drug sensitive isolates. Therefore C(r) and multifractal functions can be useful parameters for analysis of genomic sequences. PMID:28440326

Complex multifractal nature in Mycobacterium tuberculosis genome

NASA Astrophysics Data System (ADS)

Mandal, Saurav; Roychowdhury, Tanmoy; Chirom, Keilash; Bhattacharya, Alok; Brojen Singh, R. K.

2017-04-01

The mutifractal and long range correlation (C(r)) properties of strings, such as nucleotide sequence can be a useful parameter for identification of underlying patterns and variations. In this study C(r) and multifractal singularity function f(α) have been used to study variations in the genomes of a pathogenic bacteria Mycobacterium tuberculosis. Genomic sequences of M. tuberculosis isolates displayed significant variations in C(r) and f(α) reflecting inherent differences in sequences among isolates. M. tuberculosis isolates can be categorised into different subgroups based on sensitivity to drugs, these are DS (drug sensitive isolates), MDR (multi-drug resistant isolates) and XDR (extremely drug resistant isolates). C(r) follows significantly different scaling rules in different subgroups of isolates, but all the isolates follow one parameter scaling law. The richness in complexity of each subgroup can be quantified by the measures of multifractal parameters displaying a pattern in which XDR isolates have highest value and lowest for drug sensitive isolates. Therefore C(r) and multifractal functions can be useful parameters for analysis of genomic sequences.

Paramagnetic 19F NMR and Electrospray Ionization Mass Spectrometric Studies of Substituted Pyridine Complexes of Chromium(III): Models for Potential Use of 19F NMR to Probe Cr(III)-Nucleotide Interaction1

PubMed Central

Rhodes, Nicholas R.; Belmore, Ken; Cassady, Carolyn J.; Vincent, John B.

2013-01-01

The synthesis and characterization of chromium basic carboxylate complexes, [Cr3(O2CR)6L3]+, containing trifluoroacetate, 3-fluoropyridine, 3-trifluoromethylpyridine, and 4-trifluoromethylpyridine are described. The substituted pyridine ligands are used as models of DNA bases to determine whether 19F NMR would be a potentially useful probe of the binding of Cr3+ to DNA. The 19F NMR resonances of the coordinated ligands, while broadened by delocalization of unpaired electron density from the S=3/2 chromic centers, are readily discernable, and the contact shifts are of sufficient magnitude that the signals from coordinated and free ligands can easily be differentiated. Thus, 19F NMR appears to be a potentially useful probe of the binding of Cr3+ to DNA containing F-labeled bases. Additionally, electrospray MS is shown to be a convenient method to establish the identity of chromium basic carboxylate assemblies. PMID:24222929

Assessment of Cyclic Lifetime of NiCoCrAlY/ZrO2-Based EB-PVD TBC Systems via Reactive Element Enrichment in the Mixed Zone of the TGO Scale

NASA Astrophysics Data System (ADS)

Fritscher, Klaus; Braue, Wolfgang; Schulz, Uwe

2013-05-01

The chemical composition of the alumina-zirconia mixed zone (MZ) of an electron beam physical vapor deposited thermal barrier coating (EB-PVD TBC) system is affected by service conditions and by the interdiffusion of elements from the substrate alloy below and the zirconia top coat. Three NiCoCrAlY bond-coated Ni-base substrates with YPSZ or CeSZ EB-PVD TBCs were subjected to a cyclic furnace oxidation test (FCT) at 1373 K (1100 °C) in order to provide experimental evidence of a link between chemistry of the MZ, the substrate alloy, the ceramic top coat, and the time in the FCT. Energy dispersive spectroscopy of the MZ revealed preferred accumulation of Cr, Zr, Y, and Ce. The concentration of the reactive elements (RE = Ce + Y + Zr) was related to the respective average lifetimes of the TBC systems at 1373 K (1100 °C). The RE content in the MZ turned out to be a life-limiting parameter for YPSZ and CeSZ TBC systems which can be utilized to predict their relative lifetimes on the individual substrates. Conversely, the TBC failure mechanisms of YPSZ and CeSZ TBC systems are dissimilar.

Microstructure and mechanical properties of friction stir welded and laser welded high entropy alloy CrMnFeCoNi

NASA Astrophysics Data System (ADS)

Jo, Min-Gu; Kim, Han-Jin; Kang, Minjung; Madakashira, Phaniraj P.; Park, Eun Soo; Suh, Jin-Yoo; Kim, Dong-Ik; Hong, Sung-Tae; Han, Heung Nam

2018-01-01

The high entropy alloy CrMnFeCoNi has been shown to have promising structural properties. For a new alloy to be used in a structural application it should be weldable. In the present study, friction stir welding (FSW) and laser welding (LW) techniques were used to butt weld thin plates of CrMnFeCoNi. The microstructure, chemical homogeneity and mechanical behavior of the welds were characterized and compared with the base metal. The tensile stress-strain behavior of the welded specimens were reasonable when compared with that of the base metal. FSW refined the grain size in the weld region by a factor of ˜14 when compared with the base metal. High-angle annular dark field transmission electron microscopy in combination with energy dispersive X-ray spectroscopy showed chemical inhomogeneity between dendritic and interdendritic regions in the fusion zone of LW. Large fluctuations in composition (up to 15 at%) did not change the crystal structure in the fusion zone. Hardness measurements were carried out in the weld cross section and discussed in view of the grain size, low angle grain boundaries and twin boundaries in FSW specimens and the dendritic microstructure in LW specimens.

21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. 176.160 Section 176.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances for Use Only as Components of...

Automation of liquid-liquid extraction-spectrophotometry using prolonged pseudo-liquid drops and handheld CCD for speciation of Cr(VI) and Cr(III) in water samples.

PubMed

Chen, Wen; Zhong, Guanping; Zhou, Zaide; Wu, Peng; Hou, Xiandeng

2005-10-01

A simple spectrophotometric system, based on a prolonged pseudo-liquid drop device as an optical cell and a handheld charge coupled device (CCD) as a detector, was constructed for automatic liquid-liquid extraction and spectrophotometric speciation of trace Cr(VI) and Cr(III) in water samples. A tungsten halogen lamp was used as the light source, and a laboratory-constructed T-tube with two open ends was used to form the prolonged pseudo-liquid drop inside the tube. In the medium of perchloric acid solution, Cr(VI) reacted with 1,5-diphenylcarbazide (DPC); the formed complex was automatically extracted into n-pentanol, with a preconcentration ratio of about 5. The organic phase with extracted chromium complex was then pumped through the optical cell for absorbance measurement at 548 nm. Under optimal conditions, the calibration curve was linear in the range of 7.5 - 350 microg L(-1), with a correlation coefficient of 0.9993. The limit of detection (3sigma) was 7.5 microg L(-1). That Cr(III) species cannot react with DPC, but can be oxidized to Cr(VI) prior to determination, is the basis of the speciation analysis. The proposed speciation analysis was sensitive, yet simple, labor-effective, and cost-effective. It has been preliminarily applied for the speciation of Cr(VI) and Cr(III) in spiked river and tap water samples. It can also be used for other automatic liquid-liquid extraction-spectrophotometric determinations.

Crystal structure and conformational analysis of s-cis-(acetylacetonato)(ethylenediamine-N,N'-diacetato)-chromium(III): development of vibrationally optimized force field (VOFF).

PubMed

Choi, Jong-Ha; Niketić, Svetozar R; Djordjević, Ivana; Clegg, William; Harrington, Ross W

2012-05-01

The crystal structure of [Cr(edda)(acac)] (edda = ethylediamine-N,N'-diacetate; acac = acetylacetonato) has been determined by a single crystal X-ray diffraction study at 150 K. The chromium ion is in a distorted octahedral environment coordinated by two N and two O atoms of chelating edda and two O atoms of acac, resulting in s-cis configuration. The complex crystallizes in the space group P2(1)/c of the monoclinic system in a cell of dimensions a = 10.2588(9), b = 15.801(3), c = 8.7015(11) Å, β =101.201(9)° and Z = 4. The mean Cr-N(edda), Cr-O(edda) and Cr-O(acac) bond distances are 2.0829(14), 1.9678(11) and 1.9477(11) Å while the angles O-Cr-O of edda and O-Cr-O of acac are 171.47(5) and 92.72(5)°, respectively. The crystal structure is stabilized by N-H···O hydrogen bonds linking [Cr(edda)(acac)] molecules in distinct linear strands. The visible electronic and IR spectroscopic properties are also discussed. An improved, physically more realistic force field, Vibrationally Optimized Force Field (VOFF), capable of reproducing structural and vibrational properties of [Cr(edda)(acac)] was developed and its transferability demonstrated on selected chromium(III) complexes with similar ligands.

Aqueous Cr(VI) reduction by electrodeposited zero-valent iron at neutral pH: acceleration by organic matters.

PubMed

Liu, Junxi; Wang, Chuan; Shi, Jianying; Liu, Hong; Tong, Yexiang

2009-04-15

This work investigated the effect of co-existing organic matters on aqueous Cr(VI) reduction by electrodeposited zero-valent iron (ED Fe(0)) at neutral pH. The ED Fe(0) prepared in a solution containing mixture of saccharin, L-ascorbic acid and sodium dodecyl sulfate showed higher activity in reducing the aqueous Cr(VI) at neutral pH than that prepared without any organic presence. XRD and SEM indicated that the structure of ED Fe(0) was significantly improved to nano-scale by the presence of organic mixture in the preparation solution. Further, the ED Fe(0) activity in the Cr(VI) reduction at neutral pH was increased by the co-existence of citric acid or oxalic acid in the chromate solution. Electrochemical impedance spectroscopy (EIS) demonstrated that the corrosive current increased with the concentration of organic matter in the reaction solution. With the co-existing organic matters in the preparation solution, the ED Fe(0) corroded more rapidly due to its nano-size, thus the Cr(VI) reduction by the ferrous iron was accelerated. With the co-existing organic matters in the reaction solution, the Cr(VI) reduction was accelerated by a Fe(II) complex as the main electron donor, and a prevention of the passivation due to the Fe(III) and Cr(III) complexes also accelerated the Cr(VI) reduction.

Fate of chromium in soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prokisch, J.; Gyori, Z.; Kovacs, B.

The chromium cycle in soil was studied with speciation of chromium. The aim was to look for the possibilities the mobilization of chromium(III) and to measure the rate of chromate reduction in nature and pot and field experiments in Hungarian soils. The authors developed a sensitive and simple method for chromium speciation with a microcolumn connected an inductively coupled plasma atomic emission spectrometer. Detection limits are convenient to measure chromium forms in a 0.01 M CaCl{sub 2} extract of a contaminated soil, but it is not enough to measure that of the uncontaminated soils. CR(VI) as chromate anion is notmore » adsorbed on pH dependent temporary charges of clays but in strongly acidic soil. Therefore CR(VI) can be leached out easily from the top layer of soil and can be transported into the ground water. Chromate ion can be reduced to CR(III) by organic matter of soil in acidic medium. CR(VI) is more stable at higher pH and lower humus content. Thus the reduction much quicker in the upper, weakly acidic top layer. CR(VI) oxidizes the organic matter of soil. The rate of this reaction depends on pH values, the humus content of the soil and temperature. CR(III) leaching in different uncontaminated soils was studied too. There are 3 pathways of mobilization of Cr(III). When pH decreases in soil the CR(III) becomes more soluble, similarly to the aluminium(III) ion. When the soil contains large quantity of water soluble organic ligands, Cr makes complexes with them and complexes formed can be leached out from the top layer. The third possibility is the oxidation of CR(III) to Cr(VI). It could happen on surface of manganese dioxide in the well-aired top layer.« less

Determination of hexavalent chromium in industrial hygiene samples using ultrasonic extraction and flow injection analysis.

PubMed

Wang, J; Ashley, K; Kennedy, E R; Neumeister, C

1997-11-01

A simple, fast, and sensitive method was developed for the determination of hexavalent chromium (CrVI) in workplace samples. Ultrasonic extraction in alkaline solutions with 0.05 M (NH4)2SO4-0.05 M NH3 provided good extraction efficiency of CrVI from the sample and allowed the retention of CrVI on an ion-exchange resin (95%). The CrVI in the sample solution was then separated as an anion from trivalent chromium [CrIII] and other cations by elution from the anion-exchange resin with 0.5 M (NH4)2SO4 in 0.1 M NH3 (pH 8) buffer solution. The eluate was then acidified with hydrochloric acid and complexed with 1,5-diphenylcarbazide reagent prior to flow injection analysis. By analyzing samples with and without oxidation of CrIII to CrVI using CeIV, the method can measure CrVI and total Cr. For optimizing the separation and determination procedure, preliminary trials conducted with two certified reference materials (CRMs 013-050 and NIST 1633a) and three spiked samples (ammonia buffer solution, cellulose ester filters and acid washed sand) indicated that the recovery of CrVI was quantitative (> 90%) with this method. The limit of detection for FIA-UV/VIS determination of the Cr-diphenylcarbazone complex was in the sub-nanogram range (0.11 ng). The technique was also applied successfully to a workplace coal fly ash sample that was collected from a power plant and paint chips that were collected from a heating gas pipe and a university building. The principal advantages of this method are its simplicity, sensitivity, speed and potential portability for field analysis.

Hexavalent chromium targets mitochondrial respiratory chain complex I to induce reactive oxygen species-dependent caspase-3 activation in L-02 hepatocytes.

PubMed

Xiao, Fang; Li, Yanhong; Dai, Lu; Deng, Yuanyuan; Zou, Yue; Li, Peng; Yang, Yuan; Zhong, Caigao

2012-09-01

Hexavalent chromium [Cr(VI)], which is used for various industrial applications, such as leather tanning and chroming, can cause a number of human diseases including inflammation and cancer. Cr(VI) exposure leads to severe damage to the liver, but the mechanisms involved in Cr(VI)-mediated toxicity in the liver are unclear. The present study provides evidence that Cr(VI) enhances reactive oxygen species (ROS) accumulation by inhibiting the mitochondrial respiratory chain complex (MRCC) I. Cr(VI) did not affect the expression levels of antioxidative proteins such as superoxide dismutase (SOD), catalase and thioredoxin (Trx), indicating that the antioxidative system was not involved in Cr(VI)-induced ROS accumulation. We found that ROS mediated caspase-3 activation partially depends on the downregulation of the heat shock protein (HSP) 70 and 90. In order to confirm our hypothesis that ROS plays a key role in Cr(VI)-mediated cytotoxicity, we used N-acetylcysteine (NAC) to inhibit the accumulation of ROS. NAC successfully blocked the inhibition of HSP70 and HSP90 as well as the activation of caspase-3, suggesting that ROS is essential in Cr(VI)-induced caspase-3 activation. By applying different MRCC substrates as electron donors, we also confirmed that Cr(VI) could accept the electrons leaked from MRCC I and the reduction occurs at MRCC I. In conclusion, the present study demonstrates that Cr(VI) induces ROS-dependent caspase-3 activation by inhibiting MRCC I activity, and MRCC I has been identified as a new target and a new mechanism for the apoptosis-inducing activity displayed by Cr(VI).

Crystal Structure and Energy Transfer in Double-Complex Salts Composed of Tris(2,2'-bipyridine)ruthenium(II) or Tris(2,2'-bipyridine)osmium(II) and Hexacyanochromate(III).

PubMed

Otsuka, Takuhiro; Takahashi, Naoto; Fujigasaki, Naoki; Sekine, Akiko; Ohashi, Yuji; Kaizu, Youkoh

1999-03-22

In crystals of double-complex salts [M(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (M(2+) = Ru(2+), Os(2+); bpy = 2,2'-bipyridine), luminescence from (3)CT state of [M(bpy)(3)](2+) is partially quenched by [Cr(CN)(6)](3)(-) at 77 K and room temperature (RT). This quenching is attributed to intermolecular excitation energy transfer from the (3)CT state of [M(bpy)(3)](2+) to the (2)E(g) state of [Cr(CN)(6)](3)(-). Crystal structure and crystal parameters of [Os(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O: monoclinic, C2, a = 22.384(4) Å, b = 13.827(4) Å, c = 22.186(3) Å, beta = 90.70(2) degrees, V = 6866(2) Å(3), Z = 4, R = 0.0789, R(w) = 0.1932: are almost the same as those of [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O: monoclinic, C2, a = 22.414(2) Å, b = 13.7686(15) Å, c = 22.207(2) Å, beta = 90.713(8) degrees, V = 6852.9(12) Å(3), Z = 4, R = 0.0554, R(w) = 0.1679. Moreover, these double complex salts have the same distance and relative orientation between donor and acceptor. The rate of intermolecular energy transfer from [M(bpy)(3)](2+) to [Cr(CN)(6)](3)(-) was evaluated by the decay time of luminescence from (3)CT state of [M(bpy)(3)](2+) in single- and double-complex salts. The rate of energy transfer in [Os(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (4.9 x 10(7) s(-)(1)) is about eight times larger than that in [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (6.0 x 10(6) s(-)(1)) at 77 K. The difference of energy transfer rate is brought about by only the spectral overlap between the normalized luminescence spectrum from the (3)CT state of donor ([M(bpy)(3)](2+)) and the normalized excitation spectrum of the (2)E(g) state of acceptor ([Cr(CN)(6)](3)(-)) in the salts. Decay rates of the (3)CT state in [M(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O were measured as a function of temperature. A large enhancement of a decay rate from the (3)CT state was obtained for [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O as the temperature was increased. This result implies that an additional path from the (3)CT state of [Ru(bpy)(3)](2+) to the (2)T(2g) state of [Cr(CN)(6)](3)(-) would be opened for energy transfer with a rise in temperature in [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O.

Kinetics and Mechanism of the Hydrogenation of CpCr(CO)3•/[CpCr(CO)3]2 Equilibrium to CpCr(CO)3H

DOE Office of Scientific and Technical Information (OSTI.GOV)

Norton, Jack R.; Spataru, Tudor; Camaioni, Donald M.

2014-05-26

The kinetics of the hydrogenation of 2 CpCr(CO)3•/[CpCr(CO)3]2 to CpCr(CO)3H has been investigated. The reaction is second-order in Cr and first-order in H2, with a rate constant of 45 M 2s 1 at 25 °C in benzene. DFT calculations rule out an H2 complex as an intermediate, and suggest (a) end-on approach of H2 to one Cr of [CpCr(CO)3]2 as the Cr-Cr bond undergoes heterolytic cleavage, (b) heterolytic cleavage of the coordinated H2 between O and Cr, and (c) isomerization of the resulting O-protonated CpCr(CO)2(COH) to CpCr(CO)3H. The work at Pacific Northwest National Laboratory (PNNL) was supported by the U.S.more » Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences; Battelle operates PNNL for DOE.« less

Structural and Functional Characterization of an Archaeal Clustered Regularly Interspaced Short Palindromic Repeat (CRISPR)-associated Complex for Antiviral Defense (CASCADE)*

PubMed Central

Lintner, Nathanael G.; Kerou, Melina; Brumfield, Susan K.; Graham, Shirley; Liu, Huanting; Naismith, James H.; Sdano, Matthew; Peng, Nan; She, Qunxin; Copié, Valérie; Young, Mark J.; White, Malcolm F.; Lawrence, C. Martin

2011-01-01

In response to viral infection, many prokaryotes incorporate fragments of virus-derived DNA into loci called clustered regularly interspaced short palindromic repeats (CRISPRs). The loci are then transcribed, and the processed CRISPR transcripts are used to target invading viral DNA and RNA. The Escherichia coli “CRISPR-associated complex for antiviral defense” (CASCADE) is central in targeting invading DNA. Here we report the structural and functional characterization of an archaeal CASCADE (aCASCADE) from Sulfolobus solfataricus. Tagged Csa2 (Cas7) expressed in S. solfataricus co-purifies with Cas5a-, Cas6-, Csa5-, and Cas6-processed CRISPR-RNA (crRNA). Csa2, the dominant protein in aCASCADE, forms a stable complex with Cas5a. Transmission electron microscopy reveals a helical complex of variable length, perhaps due to substoichiometric amounts of other CASCADE components. A recombinant Csa2-Cas5a complex is sufficient to bind crRNA and complementary ssDNA. The structure of Csa2 reveals a crescent-shaped structure unexpectedly composed of a modified RNA-recognition motif and two additional domains present as insertions in the RNA-recognition motif. Conserved residues indicate potential crRNA- and target DNA-binding sites, and the H160A variant shows significantly reduced affinity for crRNA. We propose a general subunit architecture for CASCADE in other bacteria and Archaea. PMID:21507944

Structural and functional characterization of an archaeal clustered regularly interspaced short palindromic repeat (CRISPR)-associated complex for antiviral defense (CASCADE).

PubMed

Lintner, Nathanael G; Kerou, Melina; Brumfield, Susan K; Graham, Shirley; Liu, Huanting; Naismith, James H; Sdano, Matthew; Peng, Nan; She, Qunxin; Copié, Valérie; Young, Mark J; White, Malcolm F; Lawrence, C Martin

2011-06-17

In response to viral infection, many prokaryotes incorporate fragments of virus-derived DNA into loci called clustered regularly interspaced short palindromic repeats (CRISPRs). The loci are then transcribed, and the processed CRISPR transcripts are used to target invading viral DNA and RNA. The Escherichia coli "CRISPR-associated complex for antiviral defense" (CASCADE) is central in targeting invading DNA. Here we report the structural and functional characterization of an archaeal CASCADE (aCASCADE) from Sulfolobus solfataricus. Tagged Csa2 (Cas7) expressed in S. solfataricus co-purifies with Cas5a-, Cas6-, Csa5-, and Cas6-processed CRISPR-RNA (crRNA). Csa2, the dominant protein in aCASCADE, forms a stable complex with Cas5a. Transmission electron microscopy reveals a helical complex of variable length, perhaps due to substoichiometric amounts of other CASCADE components. A recombinant Csa2-Cas5a complex is sufficient to bind crRNA and complementary ssDNA. The structure of Csa2 reveals a crescent-shaped structure unexpectedly composed of a modified RNA-recognition motif and two additional domains present as insertions in the RNA-recognition motif. Conserved residues indicate potential crRNA- and target DNA-binding sites, and the H160A variant shows significantly reduced affinity for crRNA. We propose a general subunit architecture for CASCADE in other bacteria and Archaea.

The influence of episodic flooding on a pelagic ecosystem in the East China Sea

NASA Astrophysics Data System (ADS)

Chen, Chung-Chi; Gong, Gwo-Ching; Chou, Wen-Chen; Chung, Chih-Ching; Hsieh, Chih-Hao; Shiah, Fuh-Kwo; Chiang, Kuo-Ping

2017-05-01

This study was designed to determine the effects of flooding on a pelagic ecosystem in the East China Sea (ECS) with a focus on plankton activity and plankton community respiration (CR). In July 2010, a flood occurred in the Changjiang River. As a comparison, a variety of abiotic and biotic parameters were monitored during this flooding event and during a non-flooding period (July 2009). During the flood, the Changjiang diluted water (CDW) zone covered almost two-thirds of the ECS, which was approximately 6 times the area covered during the non-flooding period. The mean nitrate concentration was 3-fold higher during the 2010 flood (6.2 vs. 2.0 µM in 2009). CR was also higher in the 2010 flood: 105.6 mg C m-3 d-1 vs. only 73.2 mg C m-3 d-1 in 2009. The higher CR in 2010 could be attributed to phytoplankton respiration, especially at stations in the CDW zone that were not previously characterized by low sea surface salinity in 2009. In addition, zooplankton (> 330 µm) were another important component contributing to the high CR rate observed during the 2010 flood; this was a period also associated with a significant degree of fCO2 drawdown. These results collectively suggest that the 2010 flood had a significant effect on the carbon balance in the ECS. This effect might become more pronounced in the future, as extreme rainfall and flooding events are predicted to increase in both frequency and magnitude due to climate change.

Improvement of chemical composition, structure and mechanical properties of heat-resistant chromium-nickel alloy

NASA Astrophysics Data System (ADS)

Varlamova, S.; Trushnikova, A.; Rumyantsev, B.; Butrim, V.; Simonov, V.

2018-04-01

A thermodynamic analysis of a multicomponent system of the Cr-Ni alloy (Cr-32Ni-1,5W-0,25V-0,5Ti) with small additions of refractory metals was carried out. The microstructure and phase composition of the base alloy (I) and alloy with additional alloying (II) were studied. The effect of additives on the mechanical properties of the Cr-Ni alloy at 20, 900 and 1080 °C was shown. The microstructure of alloys I and II was studied in the fracture zone of samples after tensile tests at different temperatures. We studied the effect of small additives on the microstructure of alloys and changes in the morphology of the structural components (phases) as a function of temperature and degree of deformation.

A New Insight of Graphene oxide-Fe(III) Complex Photochemical Behaviors under Visible Light Irradiation

NASA Astrophysics Data System (ADS)

Liu, Renlan; Zhu, Xiaoying; Chen, Baoliang

2017-01-01

Graphene oxide (GO) contains not only aromatic carbon lattice but also carboxyl groups which enhanced the aqueous solubility of GO. To study the transformation of GO nanosheets in natural environments, GO aqueous dispersion was mixed with Fe3+ ions to form photoactive complex. Under visible light irradiation, Fe(III) of the complex would be reduced to Fe(II) which could subsequently reduce highly toxic Cr(VI) to Cr3+. The electron of the reduction was contributed by the decarboxylation of carboxyl groups on GO and iron was acting as a catalyst during the photoreduction. On the other hand, the consumption of carboxyl groups may convert GO to rGO which are tend to aggregate since the decreased electrostatic repulsion and the increased π-π attraction. The formed Cr3+ may be electrostatically adsorbed by the rGO sheets and simultaneously precipitated with the aggregated rGO sheets, resulting the effective removal of chromium and GO nanosheets from the aqueous environment. This study may shed a light on understanding the environmental transformation of GO and guide the treatment of Cr(VI).

Assessment of heavy metal contamination in sediment at Sukinda ultramafic complex using HAADF-STEM analysis.

PubMed

Equeenuddin, Sk Md; Pattnaik, Binaya Kumar

2017-10-01

The Sukinda ultramafic complex in Odisha has the largest chromite reserve in India. Sediment derived from ultramafic rocks has been enriched with various metals. Further, mining activities enhance the influx of metals into sediment by dumping mine overburden and tailings in the open area. Metal concentration in sediment is found in order of Cr Total (Cr) > Mn > Ni > Co > Zn > Cu with average concentration 26,778 mg/kg, 3098 mg/kg, 1813 mg/kg, 184 mg/kg, 116 mg/kg and 44 mg/kg respectively. Concentration of Cr(VI) varies from 5.25 to 26.47 mg/L with an average of 12.27 mg/L. Based on various pollution indices, it is confirmed that the area is severely contaminated. Nano-scale goethite, kaolinite, clinochlore and chromite have been identified and have high concentration of Cr, Co and Ni. Goethite has shown maximum metal retention potential as deciphered by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The HAADF-STEM mapping and principal component analysis indicate that Cr and Co mostly derived from chromite whereas Ni and Zn are derived from serpentine. Later, these metals co-precipitate and/or adsorbed onto the goethite and clay minerals. Fractionation study of metals confirms that Cu is the most mobile element followed by Zn. However, at low pH condition Ni is mobilized and likely to be bioavailable. Though Cr mostly occurs in residual fraction but as its concentration is very high, a small proportion of exchangeable fraction contributes significantly in terms of its bioavailability. Thus bioavailable Cr can pose severe threat to the environment in the Sukinda ultramafic complex. Copyright © 2017 Elsevier Ltd. All rights reserved.

Inhibition of plasma membrane Ca(2+)-ATPase by CrATP. LaATP but not CrATP stabilizes the Ca(2+)-occluded state.

PubMed

Moreira, Otacilio C; Rios, Priscila F; Barrabin, Hector

2005-07-15

The bidentate complex of ATP with Cr(3+), CrATP, is a nucleotide analog that is known to inhibit the sarcoplasmic reticulum Ca(2+)-ATPase and the Na(+),K(+)-ATPase, so that these enzymes accumulate in a conformation with the transported ion (Ca(2+) and Na(+), respectively) occluded from the medium. Here, it is shown that CrATP is also an effective and irreversible inhibitor of the plasma membrane Ca(2+)-ATPase. The complex inhibited with similar efficiency the Ca(2+)-dependent ATPase and the phosphatase activities as well as the enzyme phosphorylation by ATP. The inhibition proceeded slowly (T(1/2)=30 min at 37 degrees C) with a K(i)=28+/-9 microM. The inclusion of ATP, ADP or AMPPNP in the inhibition medium effectively protected the enzyme against the inhibition, whereas ITP, which is not a PMCA substrate, did not. The rate of inhibition was strongly dependent on the presence of Mg(2+) but unaltered when Ca(2+) was replaced by EGTA. In spite of the similarities with the inhibition of other P-ATPases, no apparent Ca(2+) occlusion was detected concurrent with the inhibition by CrATP. In contrast, inhibition by the complex of La(3+) with ATP, LaATP, induced the accumulation of phosphoenzyme with a simultaneous occlusion of Ca(2+) at a ratio close to 1.5 mol/mol of phosphoenzyme. The results suggest that the transport of Ca(2+) promoted by the plasma membrane Ca(2+)-ATPase goes through an enzymatic phospho-intermediate that maintains Ca(2+) ions occluded from the media. This intermediate is stabilized by LaATP but not by CrATP.

Physicochemical Characterization of Aerosol Generated in the Gas Tungsten Arc Welding of Stainless Steel.

PubMed

Miettinen, Mirella; Torvela, Tiina; Leskinen, Jari T T

2016-10-01

Exposure to stainless steel (SS) welding aerosol that contain toxic heavy metals, chromium (Cr), manganese (Mn), and nickel (Ni), has been associated with numerous adverse health effects. The gas tungsten arc welding (GTAW) is commonly applied to SS and produces high number concentration of substantially smaller particles compared with the other welding techniques, although the mass emission rate is low. Here, a field study in a workshop with the GTAW as principal welding technique was conducted to determine the physicochemical properties of the airborne particles and to improve the understanding of the hazard the SS welding aerosols pose to welders. Particle number concentration and number size distribution were measured near the breathing zone (50cm from the arc) and in the middle of the workshop with condensation particle counters and electrical mobility particle sizers, respectively. Particle morphology and chemical composition were studied using scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy. In the middle of the workshop, the number size distribution was unimodal with the geometric mean diameter (GMD) of 46nm. Near the breathing zone the number size distribution was multimodal, and the GMDs of the modes were in the range of 10-30nm. Two different agglomerate types existed near the breathing zone. The first type consisted of iron oxide primary particles with size up to 40nm and variable amounts of Cr, Mn, and Ni replacing iron in the structure. The second type consisted of very small primary particles and contained increased proportion of Ni compared to the proportion of (Cr + Mn) than the first agglomerate type. The alterations in the distribution of Ni between different welding aerosol particles have not been reported previously. © The Author 2016. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Packing of Russian doll clusters to form a nanometer-scale CsCl-type compound in a Cr–Zn–Sn complex metallic alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Weiwei; Cava, Robert J.; Miller, Gordon J.

A new cubic complex metallic alloy phase, Cr 22Zn 72Sn 24, with a lattice parameter near 2.5 nm was discovered in crystals grown using a Zn/Sn flux. The structure consists of Russian doll clusters or a 3-d network of Cr-centered icosahedra (shown) with bcc-metal fragments in void spaces.

Packing of Russian doll clusters to form a nanometer-scale CsCl-type compound in a Cr–Zn–Sn complex metallic alloy

DOE PAGES

Xie, Weiwei; Cava, Robert J.; Miller, Gordon J.

2017-07-03

A new cubic complex metallic alloy phase, Cr 22Zn 72Sn 24, with a lattice parameter near 2.5 nm was discovered in crystals grown using a Zn/Sn flux. The structure consists of Russian doll clusters or a 3-d network of Cr-centered icosahedra (shown) with bcc-metal fragments in void spaces.

Distribution of major and trace elements in surface sediments of the western Gulf of Thailand: Implications to modern sedimentation

NASA Astrophysics Data System (ADS)

Liu, Shengfa; Shi, Xuefa; Yang, Gang; Khokiattiwong, Somkiat; Kornkanitnan, Narumol

2016-04-01

In this study, we analyze major and trace elements (SiO2, Al2O3, Fe2O3, CaO, K2O, MgO, Na2O, TiO2, P2O5, MnO, Cu, Pb, Ba, Sr, V, Zn, Co, Ni, Cr, and Zr) and grain size of 157 surface sediment samples from the western Gulf of Thailand (GoT). On the basis of the space distribution characteristics, the study area can be classified into three geochemical provinces. Province I covers the northern and northwestern coastal zones of the GoT, including the whole upper GoT and thus the sediments from the rivers in the area. It contains high contents of SiO2. Province II is located in the middle of the GoT and has similar geochemistry composition as the South China Sea (SCS). It contains sediments that are characterized by higher contents of Na2O, TiO2, Ba, Cr, V, Zn, Zr, and Ni. Province Ш is located in the lower GoT, close to Malaysia. Major and trace elements in this area showed complex distribution patterns, which may be due to terrestrial materials from Malay rivers combining with some sediments from the SCS in this province. The results also indicate that grain size is the controlling factor in elemental contents, and that the hydrodynamic environment and mineral composition of the sediments play an important role in the distribution of these elements. The anthropogenic impact of heavy metal introduction (especially Cr, Zn, Cu, and Pb) can be seen in surface sediments from the nearshore region of Chantaburi province and north of Samui Island.

Modular-extramodular organization in developing multisensory shell regions of the mouse inferior colliculus.

PubMed

Dillingham, Christopher H; Gay, Sean M; Behrooz, Roxana; Gabriele, Mark L

2017-12-01

The complex neuroanatomical connections of the inferior colliculus (IC) and its major subdivisions offer a juxtaposition of segregated processing streams with distinct organizational features. While the tonotopically layered central nucleus is well-documented, less is known about functional compartments in the neighboring lateral cortex (LCIC). In addition to a laminar framework, LCIC afferent-efferent patterns suggest a multimodal mosaic, consisting of a patchy modular network with surrounding extramodular domains. This study utilizes several neurochemical markers that reveal an emerging LCIC modular-extramodular microarchitecture. In newborn and post-hearing C57BL/6J and CBA/CaJ mice, histochemical and immunocytochemical stains were performed for acetylcholinesterase (AChE), nicotinamide adenine dinucleotide phosphate-diaphorase (NADPH-d), glutamic acid decarboxylase (GAD), cytochrome oxidase (CO), and calretinin (CR). Discontinuous layer 2 modules are positive for AChE, NADPH-d, GAD, and CO throughout the rostrocaudal LCIC. While not readily apparent at birth, discrete cell clusters emerge over the first postnatal week, yielding an identifiable modular network prior to hearing onset. Modular boundaries continue to become increasingly distinct with age, as surrounding extramodular fields remain largely negative for each marker. Alignment of modular markers in serial sections suggests each highlight the same periodic patchy network throughout the nascent LCIC. In contrast, CR patterns appear complementary, preferentially staining extramodular LCIC zones. Double-labeling experiments confirm that NADPH-d, the most consistent developmental modular marker, and CR label separate, nonoverlapping LCIC compartments. Determining how this emerging modularity may align with similar LCIC patch-matrix-like Eph/ephrin guidance patterns, and how each interface with, and potentially influence developing multimodal LCIC projection configurations is discussed. © 2017 Wiley Periodicals, Inc.

Adaptation Options for Land Drainage Systems Towards Sustainable Agriculture and Environment: A Czech Perspective

NASA Astrophysics Data System (ADS)

Kulhavý, Zbyněk; Fučík, Petr

2015-04-01

In this paper, issues of agricultural drainage systems are introduced and discussed from the views of their former, current and future roles and functioning in the Czech Republic (CR). A methodologically disparate survey was done on thirty-nine model localities in CR with different intensity and state of land drainage systems, aimed at description of commonly occurred problems and possible adaptations of agricultural drainage as perceived by farmers, land owners, landscape managers or by protective water management. The survey was focused on technical state of drainage, fragmentation of land ownership within drained areas as well as on possible conflicts between agricultural and environmental interests in a landscape. Achieved results confirmed that there is obviously an increasing need to reassess some functions of prevailingly single-purpose agricultural drainage systems. Drainage intensity and detected unfavourable technical state of drainage systems as well as the risks connected with the anticipated climate change from the view of possible water scarcity claims for a complex solution. An array of adaptation options for agricultural drainage systems is presented, aiming at enhancement of water retention time and improvement of water quality. It encompasses additional flow-controlling measures on tiles or ditches, or facilities for making selected parts of a drainage system inoperable in order to retain or slow down the drainage runoff, to establish water accumulation zones and to enhance water self-cleaning processes. However, it was revealed that the question of landowner parcels fragmentation on drained land in CR would dramatically complicate design and realization of these measures. Presented solutions and findings are propounded with a respect to contemporary and future state policies and international strategies for sustainable agriculture, water management and environment.

Quenching the Quantum Tunneling of Magnetization in Heterometallic Octanuclear {TMIII4 DyIII4 } (TM=Co and Cr) Single-Molecule Magnets by Modification of the Bridging Ligands and Enhancing the Magnetic Exchange Coupling.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Murray, Keith S; Rajaraman, Gopalan

2017-01-31

We report the synthesis, structural characterisation, magnetic properties and provide an ab initio analysis of the magnetic behaviour of two new heterometallic octanuclear coordination complexes containing Co III and Dy III ions. Single-crystal X-ray diffraction studies revealed molecular formulae of [Co III 4 Dy III 4 (μ-OH) 4 (μ 3 -OMe) 4 {O 2 CC(CH 3 ) 3 } 4 (tea) 4 (H 2 O) 4 ]⋅4 H 2 O (1) and [Co III 4 Dy III 4 (μ-F) 4 (μ 3 -OH) 4 (o-tol) 8 (mdea) 4 ]⋅ 3 H 2 O⋅EtOH⋅MeOH (2; tea 3- =triply deprotonated triethanolamine; mdea 2- =doubly deprotonated N-methyldiethanolamine; o-tol=o-toluate), and both complexes display an identical metallic core topology. Furthermore, the theoretical, magnetic and SMM properties of the isostructural complex, [Cr III 4 Dy III 4 (μ-F 4 )(μ 3 -OMe) 1.25 (μ 3 -OH) 2.75 (O 2 CPh) 8 (mdea) 4 ] (3), are discussed and compared with a structurally similar complex, [Cr III 4 Dy III 4 (μ 3 -OH) 4 (μ-N 3 ) 4 (mdea) 4 (O 2 CC(CH 3 ) 3 ) 4 ] (4). DC and AC magnetic susceptibility data revealed single-molecule magnet (SMM) behaviour for 1-4. Each complex displays dynamic behaviour, highlighting the effect of ligand and transition metal ion replacement on SMM properties. Complexes 2, 3 and 4 exhibited slow magnetic relaxation with barrier heights (U eff ) of 39.0, 55.0 and 10.4 cm -1 respectively. Complex 1, conversely, did not exhibit slow relaxation of magnetisation above 2 K. To probe the variance in the observed U eff  values, calculations by using CASSCF, RASSI-SO and POLY_ANISO routine were performed on these complexes to estimate the nature of the magnetic coupling and elucidate the mechanism of magnetic relaxation. Calculations gave values of J Dy-Dy as -1.6, 1.6 and 2.8 cm -1 for complexes 1, 2 and 3, respectively, whereas the J Dy-Cr interaction was estimated to be -1.8 cm -1 for complex 3. The developed mechanism for magnetic relaxation revealed that replacement of the hydroxide ion by fluoride quenched the quantum tunnelling of magnetisation (QTM) significantly, and led to improved SMM properties for complex 2 compared with 1. However, the tunnelling of magnetisation at low-lying excited states was still operational for 2, which led to low-temperature QTM relaxation. Replacement of the diamagnetic Co III ions with paramagnetic Cr III led to Cr III ⋅⋅⋅Dy III coupling, which resulted in quenching of QTM at low temperatures for complexes 3 and 4. The best example was found if both Cr III and fluoride were present, as seen for complex 3, for which both factors additively quenched QTM and led to the observation of highly coercive magnetic hysteresis loops above 2 K. Herein, we propose a synthetic strategy to quench the QTM effects in lanthanide-based SMMs. Our strategy differs from existing methods, in which parameters such as magnetic coupling are difficult to control, and it is likely to have implications beyond the Dy III SMMs studied herein. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiscale Characterization of Microstructure in Near-Surface Regions of a 16MnCr5 Gear Wheel After Cyclic Loading

NASA Astrophysics Data System (ADS)

Medghalchi, Setareh; Jamebozorgi, Vahid; Bala Krishnan, Arjun; Vincent, Smobin; Salomon, Steffen; Basir Parsa, Alireza; Pfetzing, Janine; Kostka, Aleksander; Li, Yujiao; Eggeler, Gunther; Li, Tong

2018-05-01

The dependence of the microstructure on the degree of deformation in near-surface regions of a 16MnCr5 gear wheel after 2.1 × 106 loading cycles has been investigated by x-ray diffraction analysis, transmission electron microscopy, and atom probe tomography. Retained austenite and large martensite plates, along with elongated lamella-like cementite, were present in a less deformed region. Comparatively, the heavily deformed region consisted of a nanocrystalline structure with carbon segregation up to 2 at.% at grain boundaries. Spheroid-shaped cementite, formed at the grain boundaries and triple junctions of the nanosized grains, was enriched with Cr and Mn but depleted with Si. Such partitioning of Cr, Mn, and Si was not observed in the elongated cementite formed in the less deformed zone. This implies that rolling contact loading induced severe plastic deformation as well as a pronounced annealing effect in the active contact region of the toothed gear during cyclic loading.

Creep Strength of Dissimilar Welded Joints Using High B-9Cr Steel for Advanced USC Boiler

NASA Astrophysics Data System (ADS)

Tabuchi, Masaaki; Hongo, Hiromichi; Abe, Fujio

2014-10-01

The commercialization of a 973 K (700 °C) class pulverized coal power system, advanced ultra-supercritical (A-USC) pressure power generation, is the target of an ongoing research project initiated in Japan in 2008. In the A-USC boiler, Ni or Ni-Fe base alloys are used for high-temperature parts at 923 K to 973 K (650 °C to 700 °C), and advanced high-Cr ferritic steels are planned to be used at temperatures lower than 923 K (650 °C). In the dissimilar welds between Ni base alloys and high-Cr ferritic steels, Type IV failure in the heat-affected zone (HAZ) is a concern. Thus, the high B-9Cr steel developed at the National Institute for Materials Science, which has improved creep strength in weldments, is a candidate material for the Japanese A-USC boiler. In the present study, creep tests were conducted on the dissimilar welded joints between Ni base alloys and high B-9Cr steels. Microstructures and creep damage in the dissimilar welded joints were investigated. In the HAZ of the high B-9Cr steels, fine-grained microstructures were not formed and the grain size of the base metal was retained. Consequently, the creep rupture life of the dissimilar welded joints using high B-9Cr steel was 5 to 10 times longer than that of the conventional 9Cr steel welded joints at 923 K (650 °C).

First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: Synthesis, heterobimetallic complexation and self-assembly on Au(111)

PubMed Central

Applegate, Jason C.; Okeowo, Monisola K.; Erickson, Nathan R.; Neal, Brad M.

2015-01-01

Mercapto (-SH) and isocyano (-N≡C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic π-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N≡C end of this 2,6-azulenic motif was anchrored to the [Cr(CO)5] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC)5Cr(η1-2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] (7) with Ph3PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr0/AuI ensemble [(OC)5Cr(μ-η1:η1-2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh3] (8). Analysis of the 13C NMR chemical shifts for the [(NC)Cr(CO)5] core in a series of the related complexes [(OC)5Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = -N≡C, Br,H, SH, SCH2CH2CO2CH2CH3, SAuPPh3) unveiled remarkably consistent inverse-linear correlations δ(13COtrans) vs. δ(13CN) and δ(13COcis) vs. δ(13CN) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC)5Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF3, CFClCF2Cl, C2F3, and C6F5. In addition to functioning as asensitive 13C NMR handle, the essentially C4v-symmetric [(-NC)Cr(CO)5] moiety proved to be an informative, remote, νN≡C/νC≡O infrared reporter in probing chemisorption of 7 on the Au(111) surface. PMID:26877864

[Application of local Moran's I and GIS to identify hotspots of Ni, Cr of vegetable soils in high-incidence area of liver cancer from the Pearl River Delta, South China].

PubMed

Li, Yong; Zhou, Yong-Zhang; Zhang, Cheng-Bo; Dou, Lei; Du, Hai-Yan; Lin, Xiao-Ming; Fan, Rui; Du, Min; He, Xiang

2010-06-01

The index of local Moran's I is a useful tool for identifying hotspots of soil Ni and Cr, and for classifying them into spatial clusters and spatial outliers. To identify hotspots of vegetable soils Ni and Cr in high-incidence area of liver cancer, Shunde area of Foshan City, Pearl River Delta Economic Zone, 208 topsoil samples were collected from vegetable fields to measure the contents of nickel (Ni) and chromium (Cr). The results showed that the mean concentrations of two heavy metals Ni, Cr were 33.21 mg/kg, 80.84 mg/kg, respectively, Which were 130%, 60% higher than their soil background values of Guangdong Province, respectively. Generally, Ni is partly accumulated in soil but the accumulation of Cr is not obvious at all. The local Moran's I of Ni and Cr was calculated using 3 000, 6 000, 9 000 m as distance bands, respectively. The hotspots of Ni and Cr elements in soils were identified by local Moran's I which computed based on 6 000 m; "individual hotspots" are in the north which were affected by anthropogenic factors; "regional hotspots" are in the south which were controlled by parent materials. Moreover, the distributions of "regional hotspots" of Ni, Cr are the same as that of the highest mortality rate of liver cancer, this consistence could come up with a research direction that could reveal environmental etiologic factors of liver cancer.

Inhibition of Thymic Adipogenesis by Caloric Restriction Is Coupled with Reduction in Age-Related Thymic Involution1

PubMed Central

Yang, Hyunwon; Youm, Yun-Hee; Dixit, Vishwa Deep

2009-01-01

Aging of thymus is characterized by reduction in naive T cell output together with progressive replacement of lymphostromal thymic zones with adipocytes. Determining how calorie restriction (CR), a prolongevity metabolic intervention, regulates thymic aging may allow identification of relevant mechanisms to prevent immunosenescence. Using a mouse model of chronic CR, we found that a reduction in age-related thymic adipogenic mechanism is coupled with maintenance of thymic function. The CR increased cellular density in the thymic cortex and medulla and preserved the epithelial signatures. Interestingly, CR prevented the age-related increase in epithelial-mesenchymal transition (EMT) regulators, FoxC2, and fibroblast-specific protein-1 (FSP-1), together with reduction in lipid-laden thymic fibroblasts. Additionally, CR specifically blocked the age-related elevation of thymic proadipogenic master regulator, peroxisome proliferator activated receptor γ (PPARγ), and its upstream activator xanthine-oxidoreductase (XOR). Furthermore, we found that specific inhibition of PPARγ in thymic stromal cells prevented their adipogenic transformation in an XOR-dependent mechanism. Activation of PPARγ-driven adipogenesis in OP9-DL1 stromal cells compromised their ability to support T cell development. Conversely, CR-induced reduction in EMT and thymic adipogenesis were coupled with elevated thymic output. Compared with 26-mo-old ad libitum fed mice, the T cells derived from age-matched CR animals displayed greater proliferation and higher IL-2 expression. Furthermore, CR prevented the deterioration of the peripheral TCR repertoire diversity in older animals. Collectively, our findings demonstrate that reducing proadipogenic signaling in thymus via CR may promote thymopoiesis during aging. PMID:19648267

Relationship between Microstructure and Corrosion Behavior of Martensitic High Nitrogen Stainless Steel 30Cr15Mo1N at Different Austenitizing Temperatures.

PubMed

Jiang, Zhouhua; Feng, Hao; Li, Huabing; Zhu, Hongchun; Zhang, Shucai; Zhang, Binbin; Han, Yu; Zhang, Tao; Xu, Dake

2017-07-27

The relationship between microstructure and corrosion behavior of martensitic high nitrogen stainless steel 30Cr15Mo1N at different austenitizing temperatures was investigated by microscopy observation, electrochemical measurement, X-ray photoelectron spectroscopy analysis and immersion testing. The results indicated that finer Cr-rich M₂N dispersed more homogeneously than coarse M 23 C₆, and the fractions of M 23 C₆ and M₂N both decreased with increasing austenitizing temperature. The Cr-depleted zone around M 23 C₆ was wider and its minimum Cr concentration was lower than M₂N. The metastable pits initiated preferentially around coarse M 23 C₆ which induced severer Cr-depletion, and the pit growth followed the power law. The increasing of austenitizing temperature induced fewer metastable pit initiation sites, more uniform element distribution and higher contents of Cr, Mo and N in the matrix. In addition, the passive film thickened and Cr₂O₃, Cr 3+ and CrN enriched with increasing austenitizing temperature, which enhanced the stability of the passive film and repassivation ability of pits. Therefore, as austenitizing temperature increased, the metastable and stable pitting potentials increased and pit growth rate decreased, revealing less susceptible metastable pit initiation, larger repassivation tendency and higher corrosion resistance. The determining factor of pitting potentials could be divided into three stages: dissolution of M 23 C₆ (below 1000 °C), dissolution of M₂N (from 1000 to 1050 °C) and existence of a few undissolved precipitates and non-metallic inclusions (above 1050 °C).

Laser stereolithography by multilayer sintering of metal powders

NASA Astrophysics Data System (ADS)

Jendrzejewski, Rafal; Serbinski, W.; Sliwinski, Gerard

1997-10-01

Process parameters of the lser stereolithography by means of metal powder sintering are experimentally investigated for the bronze B10, Fe-Cr and Al-Ni alloys, pure Sn, and Cu. The multilaye structures ae prepared trace-on-trace by remelting of the previously deposited mela powder under the cw CO2 laser irradiation in an Ar flow environment. Severl trces of a hiehght of 0.1 - 0.9 mm connected via fusion zones are produced for each samle which results inan efficient formautlion f avolumetric structures of dimensins usfficient for microanalysis ndconsiderationof th emultlayer goemtry. For th beam intensities of about 105 W/cm2 and smaple feeding rates of 0.8 - 1.8 m/min th fusin zone thickness donot 4xceed several percent of th layer height. Rsutls indicate, that th epowderized Fe-Cr anAl-Ni alloys and also bronze B10 are well suited for a fast prorotyping due to th low porosity, homogeneous structure and good mechaniclpropetis acheivable.

Design of Boiler Welding for Improvement of Lifetime and Cost Control.

PubMed

Thong-On, Atcharawadi; Boonruang, Chatdanai

2016-11-03

Fe-2.25Cr-1Mo a widely used material for headers and steam tubes of boilers. Welding of steam tube to header is required for production of boiler. Heat affected zone of the weld can have poor mechanical properties and poor corrosion behavior leading to weld failure. The cost of material used for steam tube and header of boiler should be controlled. This study propose a new materials design for boiler welding to improve the lifetime and cost control, using tungsten inert gas (TIG) welding of Fe-2.25Cr-1Mo tube to carbon steel pipe with chromium-containing filler. The cost of production could be reduced by the use of low cost material such as carbon steel pipe for boiler header. The effect of chromium content on corrosion behavior of the weld was greater than that of the microstructure. The lifetime of the welded boiler can be increased by improvement of mechanical properties and corrosion behavior of the heat affected zone.

Design of Boiler Welding for Improvement of Lifetime and Cost Control

PubMed Central

Thong-On, Atcharawadi; Boonruang, Chatdanai

2016-01-01

Fe-2.25Cr-1Mo a widely used material for headers and steam tubes of boilers. Welding of steam tube to header is required for production of boiler. Heat affected zone of the weld can have poor mechanical properties and poor corrosion behavior leading to weld failure. The cost of material used for steam tube and header of boiler should be controlled. This study propose a new materials design for boiler welding to improve the lifetime and cost control, using tungsten inert gas (TIG) welding of Fe-2.25Cr-1Mo tube to carbon steel pipe with chromium-containing filler. The cost of production could be reduced by the use of low cost material such as carbon steel pipe for boiler header. The effect of chromium content on corrosion behavior of the weld was greater than that of the microstructure. The lifetime of the welded boiler can be increased by improvement of mechanical properties and corrosion behavior of the heat affected zone. PMID:28774014

The effect of particle size on the heat affected zone during laser cladding of Ni-Cr-Si-B alloy on C45 carbon steel

NASA Astrophysics Data System (ADS)

Tanigawa, Daichi; Abe, Nobuyuki; Tsukamoto, Masahiro; Hayashi, Yoshihiko; Yamazaki, Hiroyuki; Tatsumi, Yoshihiro; Yoneyama, Mikio

2018-02-01

Laser cladding is one of the most useful surface coating methods for improving the wear and corrosion resistance of material surfaces. Although the heat input associated with laser cladding is small, a heat affected zone (HAZ) is still generated within the substrate because this is a thermal process. In order to reduce the area of the HAZ, the heat input must therefore be reduced. In the present study, we examined the effects of the powdered raw material particle size on the heat input and the extent of the HAZ during powder bed laser cladding. Ni-Cr-Si-B alloy layers were produced on C45 carbon steel substrates in conjunction with alloy powders having average particle sizes of 30, 40 and 55 μm, while measuring the HAZ area by optical microscopy. The heat input required for layer formation was found to decrease as smaller particles were used, such that the HAZ area was also reduced.

Portrait of a giant deep-seated magmatic conduit system: The Seiland Igneous Province

NASA Astrophysics Data System (ADS)

Larsen, Rune B.; Grant, Thomas; Sørensen, Bjørn E.; Tegner, Christian; McEnroe, Suzanne; Pastore, Zeudia; Fichler, Christine; Nikolaisen, Even; Grannes, Kim R.; Church, Nathan; ter Maat, Geertje W.; Michels, Alexander

2018-01-01

The Seiland Igneous Province (SIP), Northern Norway, contains > 5000 km2 of mafic and ultramafic intrusions with minor alkaline, carbonatite and felsic rocks that were intruded into the lower continental crust at a depth of 25 to as much as 35 km. The SIP can be geochemically and temporally correlated to numerous dyke swarms throughout Scandinavia at 560-610 Ma, and is linked to magmatic provinces in W-Greenland and NE-America that are collectively known as the Central Iapetus Magmatic Province (CIMP). Revised mapping show that the SIP exposes 85-90% layered tholeiitic- alkaline- and syeno-gabbros, 8-10% peridotitic complexes, 2-5% carbonatite, syenite and diorite that formed within a narrow (< 10 Ma) time frame in the Ediacaran (560-570 Ma). Large peridotite complexes were emplaced into the still hot and unconsolidated gabbro (no dating available) and are regarded as the main-conduit systems. Gravimetric data implies an average thickness of igneous rocks of 4-5 km and also features six deep lithospheric roots of ultramafic rocks extending min 9 km into the crust. Together, the root structures represent the main volcanic conduits conveying thousands of km3 of mafic-ultramafic melts from the asthenosphere to the lithosphere. The ultramafic complexes were predominantly emplaced into the layered gabbros at four major igneous centres, respectively, Nordre Brumandsfjord, Melkvann, Kvalfjord and Reinfjord. All complexes are situated in a right-way-up position and are steep sided forming large plugs. A marginal hybrid zone forms at the contact with country-rock and transitions gradually from olivine-mela-gabbro over pyroxenites that grades in to an olivine-clinopyroxenite zone, which is followed by a wehrlite zone and, finally, the centre of the complexes comprises pure dunite. From pyroxenite to dunite, olivine changes from Fo72 to Fo85 and clinopyroxene from Di80 to Di92 i.e. the complexes observe a reverse fractional crystallisation sequence with time. Parental melt compositions modelled from early dykes indicate komatiitic to picritic melts with 16-22 wt% MgO, Cr of 1594 ppm and Ni of 611 ppm, which were emplaced at 1450-1500 °C. Melt compositions calculated from clinopyroxene compositions from Reinfjord are OIB-like with LREE enriched over HREE. The high abundance of carbonatites and lamproites demonstrates the volatile-rich nature of the mantle source region and is further corroborated by the unusually high abundance of magmatic sulphides (0.5-1%) and carbonated and hydrous assemblages (c. 1%) throughout the region. In Reinfjord, they are also closely associated with PGE-Cu-Ni reef deposits. Essentially, the ultramafic complexes in the SIP comprises deep-seated transient magma chambers that facilitated mixing and homogenisation of a rich diversity of fertile asthenospheric melts en route to the upper parts of the continental crust.

Influence of land-based Kaliningrad (Primorsky) amber mining on coastal zone.

PubMed

Krek, Alexander; Ulyanova, Marina; Koschavets, Svetlana

2018-06-01

In this paper, we report on the pollution in the coastal zone of the South-Eastern Baltic Sea (Russian coast). It was studied through a range of methods, including analyses potential water quality indicators (WQIs) and potentially harmful elements (PHEs). A contamination factor and modified degree of contamination were used for describing the contamination of the sediments by toxic substances. Special attention was paid to activity of the Kaliningrad Amber Combine (KAC), the biggest world amber mining company, located onshore close to the coastal zone (Kaliningrad Region). The amber extraction contribution to the ecological state of the coastal zone was estimated. Contamination of the quarry by metals (Cr, Co, Ni, Cu, Pb, Zn) was comparable with contamination of abrasion bench. The pollution of the western coastal zone of the Sambia Peninsula is caused both by land-based anthropogenic developments (including KAC) and natural processes (coastal abrasion). Copyright © 2018 Elsevier Ltd. All rights reserved.

Detection of Extremes with AIRS and CrIS

NASA Technical Reports Server (NTRS)

Aumann, Hartmut H.; Manning, Evan M.; Behrangi, Ali

2013-01-01

Climate change is expected to be detected first as changes in extreme values rather than in mean values. The availability of data of from two instruments in the same orbit, AIRS data for the past eleven years and AIRS and CrIS data from the past year, provides an opportunity to evaluate this using examples of climate relevance: Desertification, seen as changes in hot extremes, severe storm, seen as a change in extremely cold clouds and the warming of the polar zone. We use AIRS to establish trends for the 1%tile, the mean and 99%tile brightness temperatures measured with the 900 cm(exp -1) channel from AIRS for the past 11 years. This channel is in the clearest part of the 11 micron atmospheric window. Substantial trends are seen for land and ocean, which in the case of the 1%tile (cold) extremes are related to the current shift of deep convection from ocean to land. Changes are also seen in the 99%tile for day tropical land, but their interpretation is at present unclear. We also see dramatic changes for the mean and 99%tile of the North Polar area. The trends are an order of magnitude larger than the instrument trend of about 3 mK/year. We use the statistical distribution from the past year derived from AIRS to evaluate the accuracy of continuing the trends established with AIRS with CrIS data. We minimize the concern about differences in the spectral response functions by limiting the analysis to the channel at 900 cm(exp -1).While the two instruments agree within 100 mK for the global day/night land/ocean mean values, there are significant differences when evaluating the1% and 99%tiles. We see a consistent warm bias in the CrIS data relative to AIRS for the 1%tile (extremely cold, cloudy) data in the tropical zone, particularly for tropical land, but the bias is not day/night land/ocean consistent. At this point the difference appears to be due to differences in the radiometric response of AIRS and CrIS to differences in the day/night land/ocean cloud types. Unless the effect can be mitigated by a future reprocessing the CrIS data, it will significantly complicate the concatenation of the AIRS and CrIS data records for the continuation of trends in extreme values.

[Effect of different heat treatment on mechanical properties and microstructure of laser welding CoCr-NiCr dissimilar alloys].

PubMed

Liang, Rui-ying; Li, Chang-yi; Han, Ya-jing; Hu, Xin; Zhang, Lian-yun

2008-11-01

To evaluate the effect of heat treatment and porcelain-fused-to-metal (PFM) processing on mechanical properties and microstructure of laser welding CoCr-NiCr dissimilar alloys. Samples of CoCr-NiCr dissimilar alloys with 0.5 mm thickness were laser-welded single-side under the setting parameters of 280 V, 10 ms pulse duration. After being welded, samples were randomly assigned to three groups, 10 each. Group1 and 2 received heat treatment and PFM processing, respectively. Group 3 was control group without any treatment. Tensile strength, microstructure and element distribution of samples in the three groups were tested and observed using tensile test, metallographic examinations, scanning electron microscope (SEM), and energy dispersive spectroscopy (EDS) analysis. After heat treatment and PFM processing, tensile strength of the samples were (537.15 +/- 43.91) MPa and (534.58 +/- 48.47) MPa respectively, and elongation rates in Group 1 and 2 were (7.65 +/- 0.73)% and (7.40 +/- 0.45)%. Ductile structure can be found on tensile fracture surface of samples and it was more obvious in heat treatment group than in PFM group. The results of EDS analysis indicated that certain CoCr alloy diffused towards fusion zone and NiCr side after heat treatment and PFM processing. Compared with PFM processing group, the diffusion in the heat treatment group was more obvious. Heat treatment and PFM processing can improve the mechanical properties and microstructure of welded CoCr-NiCr dissimilar alloy to a certain degree. The improvements are more obvious with heat treatment than with porcelain treatment.

Relationship between Microstructure and Corrosion Behavior of Martensitic High Nitrogen Stainless Steel 30Cr15Mo1N at Different Austenitizing Temperatures

PubMed Central

Jiang, Zhouhua; Feng, Hao; Zhu, Hongchun; Zhang, Shucai; Zhang, Binbin; Han, Yu; Zhang, Tao; Xu, Dake

2017-01-01

The relationship between microstructure and corrosion behavior of martensitic high nitrogen stainless steel 30Cr15Mo1N at different austenitizing temperatures was investigated by microscopy observation, electrochemical measurement, X-ray photoelectron spectroscopy analysis and immersion testing. The results indicated that finer Cr-rich M2N dispersed more homogeneously than coarse M23C6, and the fractions of M23C6 and M2N both decreased with increasing austenitizing temperature. The Cr-depleted zone around M23C6 was wider and its minimum Cr concentration was lower than M2N. The metastable pits initiated preferentially around coarse M23C6 which induced severer Cr-depletion, and the pit growth followed the power law. The increasing of austenitizing temperature induced fewer metastable pit initiation sites, more uniform element distribution and higher contents of Cr, Mo and N in the matrix. In addition, the passive film thickened and Cr2O3, Cr3+ and CrN enriched with increasing austenitizing temperature, which enhanced the stability of the passive film and repassivation ability of pits. Therefore, as austenitizing temperature increased, the metastable and stable pitting potentials increased and pit growth rate decreased, revealing less susceptible metastable pit initiation, larger repassivation tendency and higher corrosion resistance. The determining factor of pitting potentials could be divided into three stages: dissolution of M23C6 (below 1000 °C), dissolution of M2N (from 1000 to 1050 °C) and existence of a few undissolved precipitates and non-metallic inclusions (above 1050 °C). PMID:28773221

Unexpected resonant response in [Fe(001)/Cr(001)]10/MgO(001) multilayers in a magnetic field.

PubMed

Aliev, F G; Pryadun, V V; Snoeck, E

2009-01-23

We observed unexpected resonant response in [Fe/Cr]10 multilayers epitaxially grown on MgO(100) substrates which exists only when both ac current and dc magnetic field are simultaneously applied. The magnitude of the resonances is determined by the multilayer magnetization proving their intrinsic character. The reduction of interface epitaxy leads to nonlinear dependence of the magnitude of resonances on the alternating current density. We speculate that the existence of the interface transition zone could facilitate the subatomic vibrations in thin metallic films and multilayers grown on bulk insulating substrates.

Heterogeneous dislocation loop formation near grain boundaries in a neutron-irradiated commercial FeCrAl alloy

DOE PAGES

Field, Kevin G.; Briggs, Samuel A.; Hu, Xunxiang; ...

2016-11-01

FeCrAl alloys are an attractive materials class for nuclear power applications due to their increased environmental compatibility over more traditional nuclear materials. Preliminary studies into the radiation tolerance of FeCrAl alloys under accelerated neutron testing between 300-400 °C have shown post-irradiation microstructures containing dislocation loops and Cr-rich ' phase. Although these initial works established the post-irradiation microstructures, little to no focus was applied towards the influence of pre-irradiation microstructures on this response. Here, a well annealed commercial FeCrAl alloy, Alkrothal 720, was neutron irradiated to 1.8 dpa at 382 °C and then the role of random high angle grain boundariesmore » on the spatial distribution and size of dislocation loops, dislocation loops, and black dot damage was analyzed using on-zone scanning transmission electron microscopy. Results showed a clear heterogeneous dislocation loop formation with dislocation loops showing an increased number density and size, black dot damage showing a significant number density decrease, and an increased size of dislocation loops in the vicinity directly adjacent to the grain boundary. Lastly, these results suggest the importance of the pre-irradiation microstructure on the radiation tolerance of FeCrAl alloys.« less

Understanding the role of clay minerals in the chromium(VI) bioremoval by Pseudomonas aeruginosa CCTCC AB93066 under growth condition: microscopic, spectroscopic and kinetic analysis.

PubMed

Kang, Chunxi; Wu, Pingxiao; Li, Yuewu; Ruan, Bo; Li, Liping; Tran, Lytuong; Zhu, Nengwu; Dang, Zhi

2015-11-01

Laboratory batch experiments were conducted to investigate the role of clay minerals, e.g., kaolinite and vermiculite, in microbial Cr(VI) reduction by Pseudomonas aeruginosa under growth condition in glucose-amended mediums as a method for treating Cr(VI)-contaminated subsurface environment such as soil. Our results indicated that glucose could acted as an essential electron donor, and clay minerals significantly enhanced microbial Cr(VI) reduction rates by improving the consumption rate of glucose and stimulating the growth and propagation of P. aeruginosa. Cr(VI) bioreduction by both free cells and clay minerals-amended cells followed the pseudo-first-order kinetic model, with the latter one fitting better. The mass balance analyses and X-ray photoelectron spectroscopy analysis found that Cr(VI) was reduced to Cr(III) and the adsorption of total chromium on clay minerals-bacteria complex was small, implying that Cr(VI) bioremoval was not mainly due to the adsorption of Cr(VI) onto cells or clay minerals or clay minerals-cells complex but mainly due to the Cr(VI) reduction capacity of P. aeruginosa under the experimental conditions studied (e.g., pH 7). Atomic force microscopy revealed that the addition of clay minerals (e.g. vermiculite) decreased the surface roughness of Cr(VI)-laden cells and changed the cell morphology and dimension. Fourier transform infrared spectroscopy revealed that organic matters such as aliphatic species and/or proteins played an important role in the combination of cells and clay minerals. Scanning electron microscopy confirmed the attachment of cells on the surface of clay minerals, indicating that clay minerals could provide a microenvironment to protect cells from Cr(VI) toxicity and serve as growth-supporting materials. These findings manifested the underlying influence of clay minerals on microbial reduction of Cr(VI) and gave an understanding of the interaction between pollutants, the environment and the biota.

[Assessment of occupational exposure of welders based on determination of fumes and their components produced during stainless steel welding].

PubMed

Stanisławska, Magdalena; Janasik, Beata; Trzcinka-Ochocka, Małgorzata

2011-01-01

Occupational exposure to welding fumes is a known health hazard. The aim of this study was to determine concentrations of welding fumes components such as: iron, manganese, nickel and chromium (including chromium speciation) to assess exposure of stainless steel welders. The survey covered 14 workers of two metallurgic plants engaged in welding stainless steel (18% Cr and 8% Ni) by different techniques: manual metal arc (MMA), metal inert gas (MIG) and tungsten inert gas (TIG). Personal air samples were collected in the welders' breathing zone over a period of about 6-7 h (dust was collected on a membrane and glass filter) to determine time weighted average (TWA) concentration of welding fumes and its components. The concentrations of welding fumes (total particulate) were determined with use of the gravimetric method. Concentrations and welding fume components, such as: iron, manganese, nickel and chromium were determined by ICP-MS technique. The total hexavalent chromium was analyzed by applying the spectrophotometry method according to NIOSH. The water-soluble chromium species were analyzed by HPLC-ICP-MS. Time weighted average concentrations of the welding fumes and its components at the worker's breathing zone were (mg/m3): dust, 0.14-10.7; iron, 0.004-2.9; manganese, 0.001-1.12; nickel, < 0.001-0.2; and chromium <0.002-0.85 (mainly Cr(III) and insoluble Cr(VI)). The maximum admissible limits for workplace pollutants (TLV-TWA) were exceeded for manganese and for insoluble chromium Cr (VI). For Cr (III) the limit was exceeded in individual cases. The assessment of the workers' occupational exposure, based on the determined time weighted average (TWA) of fumes and their components, shows that the stainless steel welders worked in conditions harmful to their health owing to the significantly exceeded maximum admissible limits for manganese and the exceeded TLV value for insoluble chromium (VI).

Heavy metal fluxes at the sediment-water interface of three coastal ecosystems from south-west of the Iberian Peninsula

PubMed

Blasco; Saenz; Gomez-Parra

2000-03-20

Concentrations of the heavy metals Cr, Cu, Fe and Mn were measured in sediments and porewater samples collected in three coastal ecosystems southwest of the Iberian Peninsula: the Odiel and Barbate River Salt Marshes and the Bay of Cadiz. Both the sediment and the porewater metal concentrations in the Odiel River Salt Marshes are higher than the values found in the Bay of Cadiz and Barbate River Salt Marsh, particularly for copper, a metal associated with mining activity. In porewater, the profiles were not the same as those in the solid phase and reflect the different behaviours of the elements in relation to the redox conditions. The heavy metals Cr and Cu show a typical enrichment in the porewater of the oxic zone. The heavy metals Mn and Fe show an increase in the porewater at the depths where the maximum nitrate and phosphate concentrations occur, respectively. Significant differences between background levels for each heavy metal in the various studied zones exist. Iron and Cu showed larger background levels in the Odiel River Salt Marshes than those in the Cadiz Bay and the Barbate River Salt Marshes. In the Bay of Cadiz the background levels are also high, particularly for Cr. At the Odiel River Salt Marshes the diffusive flux of Cu is high (1.3-230.1 microg cm(-2) year(-1)), which suggests that the Odiel River Salt Marshes are subject to strong contamination by Cu, which is presumably introduced to the sediment in particulate form. In the Bay of Cadiz, Cr is the only metal with positive diffusive flux (2.15 microg cm(-2) year(-1)). It is higher than those obtained in other coastal ecosystems including the Odiel River Salt Marshes. The positive diffusive flux of Cr has been associated with the input of this metal by the naval industry and the manufacturing of car and aircraft components.

A new supramolecular chromium(III) complex: Synthesis, structural determination, optical study, magnetic and antibacterial activity

NASA Astrophysics Data System (ADS)

Dridi, Rihab; Dhieb, Cyrine; Cherni, Saoussen Namouchi; Boudjada, Nassira Chniba; Sadfi Zouaoui, Najla; Zid, Mohamed Faouzi

2018-01-01

A new chromium (III) complex 1,5-Naphthyridine Trans-diaquadioxalatochromate (III) dihydrate, had been synthesized by self-assembly of chromium (III) nitrate with oxalic acid and 1,5-Naphthyridine. The complex was characterized by X-ray diffraction, Fourier Transform Infrared spectroscopy, thermogravimetric analysis and UV-Visible spectroscopy. The crystal morphology was carried out using Bravais-Friedel-Donnay-Harker (BFDH) model. Single crystal X-Ray structure determination revealed that the complex posses two crystallographically independent Cr(III) centers. Each Cr(III) has a distorted octahedron geometry involving two axial O atoms from two water molecules and four equatorial O atoms from two oxalate dianions forming trans-[Cr(C2O4)2(H2O)2]- complex anions. The charge compensation is accomplished by the incorporation of 1,5-Naphthyridine cations. Connection between these entities is ensured by means of strong hydrogen bonds giving rise to 3D supramolecular architecture. Hirshfeld surface analysis and the related 2D fingerprint plots were used for decoding plausible intermolecular interactions in the crystal packing. The magnetic properties of the complex had been investigated and discussed in the context of its structure. The antimicrobial activity was evaluated by disc diffusion method highlighting an antagonistic effect of the synthesized complex against Gram-positive and Gram-negative species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Funke, L.A.; Espenson, J.H.

Reactions of chromium(II) perchlorate with acidified solutions of hydrogen peroxide in water containing modest concentrations of an organic nitrile (RCN) give rise to the cationic organochromium complexes CrCH/sub 2/CN/sup 2 +/ (RCN = acetonitrile), CrCH/sub 2/CH/sub 2/CN/sup 2 +/ (propionitrile), and CrCH/sub 2/CH(CH/sub 3/)CN/sup 2 +/ (isobutyronitrile). These cyanoalkyl complexes are quite resistant to decomposition in aqueous perchloric acid and can be separated by ion-exchange chromatography. Their composition was established by identification of the organic bromide formed by reaction with aqueous bromine. The complexes react with Hg/sup 2 +/ first to form the corresponding HgR/sup +/ and then (if excessmore » organochromium is present) HgR/sub 2/. Kinetic studies for the first stage of this reaction were carried out. The data are consistent with a bimolecular electrophilic substitution process (S/sub E/2 mechanism).« less

Synthesis, structure and antidiabetic activity of chromium(III) complexes of metformin Schiff-bases

NASA Astrophysics Data System (ADS)

Mahmoud, M. A.; Zaitone, S. A.; Ammar, A. M.; Sallam, S. A.

2016-03-01

A series of Cr3+ complexes with Schiff-bases of metformin with each of salicylaldehyde (HL1); 2,3-dihydroxybenzaldehyde (H2L2); 2,4-dihydroxybenzaldehyde (H2L3); 2,5-dihydroxybenzaldehyde (H2L4); 3,4-dihydroxybenzaldehyde (H2L5) and 2-hydroxynaphthaldehyde (HL6) were synthesized by template reaction. The new compounds were characterized through elemental analysis, conductivity and magnetic moment measurements, IR, UV-Vis., NMR and mass spectroscopy. The complexes have octahedral structure with μ value of hexacoordinated chromium ion. TGA, DTG and DTA analysis confirm the proposed stereochemistry and a mechanism for thermal decomposition was proposed. Thermodynamic parameters are calculated for the second and third decomposition steps. [CrL4Cl(H2O)2].3H2O and [CrL5Cl(H2O)2].2½H2O were able to produce significant decreases in the blood glucose level.

Effects of Heat Treatments and Compositional Modification on Carbide Network and Matrix Microstructure in Ultrahigh Carbon Steels

NASA Astrophysics Data System (ADS)

Hecht, Matthew David

This dissertation investigates microstructure/property relations in ultrahigh carbon steel (UHCS) with the aim of improving toughness while retaining high hardness. Due to high C contents (ranging from 1 to 2 wt%), UHCS exhibit high strength, hardness, and wear resistance. Despite this, applications for UHCS are currently limited because they typically contain a continuous network of proeutectoid cementite that greatly reduces ductility and toughness. In previous research, thermomechanic processing had seen considerable success in breaking up the network. However, the processing is difficult and has thus far seen very limited industrial application. Chemical modification of the steel composition has also seen some success in network break-up, but is still not well understood. There have been relatively few fundamental studies of microstructure evolution in UHCS; studies in the literature typically focused on lower C steels (up to 1 wt% C) or on cast irons (>2.1 wt% C). Thus, this work was undertaken to gain a better understanding of microstructural changes that occur during heat treatment and/or chemical modification of UHCS with a focus on the distribution of proeutectoid cementite within the microstructure. This dissertation is composed of eight chapters. The first chapter presents an introduction to phases found in UHCS, descriptions of research materials used in each chapter, and the hypotheses and objectives guiding the work. The second chapter describes a study of the microstructure found in a 2C-4Cr UHCS before and after an industrial-scale austenitizating heat treatment that increased hardness and toughness and also produced discrete carbide particles in the matrix. The third chapter establishes and demonstrates a metric for measuring connectivity in carbide networks. The fourth chapter describes a series of heat treatments designed to investigate kinetics of spheroidization and coarsening of carbide particles and denuded zones near cementite network branches in 2C-4Cr UHCS. The fifth chapter describes an additional series of heat treatments comparing coarsening kinetics in 2C-1Cr and 2C-4Cr UHCS. Lowering the Cr content caused clustering of cementite particles near grain boundaries, in contrast to the denuded zones observed in the higher Cr UHCS. The fifth chapter details four in situ confocal laser scanning microscopy heat treatments of 2C-4Cr UHCS. The seventh chapter investigates the effects of a 2wt% Nb addition on 2C-4Cr UHCS. The eighth and final chapter summarizes the findings of all the experiments of the previous chapters and revisits the objectives and conclusions.

Sensitized spectrophotometric determination of Cr(III) ion for speciation of chromium ion in surfactant media using alpha-benzoin oxime.

PubMed

Ghaedi, Mehrorang; Asadpour, Enayat; Vafaie, Azam

2006-01-01

A simple and accurate micellanized spectrophotometric method for determination of trace amounts of Cr(III) ion in tab and top water and a synthetic mixture has been described. The micellar method is based on effect of organized molecular assemblies such as micelles in spectrophotometric measurement due to their effect on the systems of interest. The ability of micellar system in solubilizing of sparingly soluble ligand or complexes has been used for increasing figures of merit of an analytical method. Due to solubility increasing in aqueous media requirement for a primary extraction can be eliminated. Using the alpha-benzoin oxime (alpha-BO) spectrophotometric determination of Cr(III) ion has been performed and results are compared. The spectrophotometric determination of Cr(III) ion using alpha-BO in the presence of non-ionic surfactant Triton X-100 has been performed. The influence of type and amount of surfactant, pH, complexation time and amount of ligand were examined. Finally, the repeatability, accuracy and the effect of interfering ions on the determination of Cr(III) ion was evaluated. The proposed methods successfully with recovery yield of almost 100% have been applied to the rapid and simple determination of Cr(III) ion in the real samples. There is a good agreement between methods and atomic absorption spectrometry. The Beers law is obeyed over the concentration range of 0.1-13.7 microg mL(-1) for micellar media. The detection limit is 0.8 ng mL(-1). The molar absorptivity of complex is 5350 L mol(-1) cm(-1).

Sensitized spectrophotometric determination of Cr(III) ion for speciation of chromium ion in surfactant media using α-benzoin oxime

NASA Astrophysics Data System (ADS)

Ghaedi, Mehrorang; Asadpour, Enayat; Vafaie, Azam

2006-01-01

A simple and accurate micellanized spectrophotometric method for determination of trace amounts of Cr(III) ion in tab and top water and a synthetic mixture has been described. The micellar method is based on effect of organized molecular assemblies such as micelles in spectrophotometric measurement due to their effect on the systems of interest. The ability of micellar system in solubilizing of sparingly soluble ligand or complexes has been used for increasing figures of merit of an analytical method. Due to solubility increasing in aqueous media requirement for a primary extraction can be eliminated. Using the α-benzoin oxime (α-BO) spectrophotometric determination of Cr(III) ion has been performed and results are compared. The spectrophotometric determination of Cr(III) ion using α-BO in the presence of non-ionic surfactant Triton X-100 has been performed. The influence of type and amount of surfactant, pH, complexation time and amount of ligand were examined. Finally, the repeatability, accuracy and the effect of interfering ions on the determination of Cr(III) ion was evaluated. The proposed methods successfully with recovery yield of almost 100% have been applied to the rapid and simple determination of Cr(III) ion in the real samples. There is a good agreement between methods and atomic absorption spectrometry. The Beers law is obeyed over the concentration range of 0.1-13.7 μg mL-1 for micellar media. The detection limit is 0.8 ng mL-1. The molar absorptivity of complex is 5350 L mol-1 cm-1.

Mineralogy and geochemistry of the Neo-Tethyan Orhaneli ultramafic suite, NW Turkey: Evidence for the initiation and evolution of magmatic processes in a developing crust-mantle boundary

NASA Astrophysics Data System (ADS)

Uysal, Ibrahim; Dokuz, Abdurrahman; Kapsiotis, Argyris; Kaliwoda, Melanie; Karsli, Orhan; Müller, Dirk; Aydin, Faruk

2017-04-01

The eastern Orhaneli ophiolitic massif, located in NW Anatolia, Turkey, forms part of the northwestern branch of the so-called Neotethys Ocean across the Izmir-Ankara-Erzincan Suture Zone. It is comprised mainly of a well preserved ultramafic suite, dominated by voluminous dunite exposures, accompanied by subsidiary harzburgite occurrences. The entire suite is commonly cross cut by a complex network of relatively undeformed clinopyroxenite veins. Clinopyroxene and spinel compositions in harzburgites are moderately depleted, whereas their whole-rock heavy rare earth element (HREE) abundances are consistent with harzburgite formation after approximately 19% dry melting of a spinel-bearing fertile mantle protolith at an extentional geotectonic regime. Nevertheless, textural data indicate that protracted dissolution of pyroxene coupled with precipitation of olivine happened during the transformation of harzburgites to replacive dunites, containing olivine with high Fo [Fo = 100×Mg/(Mg + Fe2+)] content (91.3-94.2) and spinel with elevated Cr# [100×Cr/(Cr + Al)] values (78-82). Such highly depleted mineralogical signatures imply that dunite for harzburgite substitution occurred under hydrous melting conditions in the mantle region above a subducted oceanic slab. Enrichments in incompatible elements (e.g., Cs, Rb and Sr) and the characteristic U-shaped chondrite-normalized rare earth elements (REE) profiles exhibited by replacive dunites along with the elevated TiO2 (0.20-0.36 wt.%) contents in their accessory spinels indicate that the reactive melt had an intermediate affinity between boninite and island arc tholeiite (IAT) regimes. The metasomatic reaction triggered an additional 8% melting of the harzburgite residue. The resultant melt fractionated (,almost in situ,) to crystallize cumulate dunites composed of olivine with relatively high Fo content (88.8-92.3), spinel with moderate Cr# values (62-74), as well as clinopyroxene with a depleted composition (low TiO2 and Al2O3 contents and high Mg#) identical of clinopyroxene in arc-derived peridotites. These magmatically formed dunites are rich in light rare earth elements (LREE) and commonly carry elevated Pt+Pd concentrations (up to 17.92 ppb), especially compared to replacive dunites that are almost deprived of Pt and Pd (up to 3.92 ppb). Further upward movement and differentiation of this melt caused the formation of clinopyroxenites, containing spinel similar in composition to that of cumulate dunites, with elevated Pt+Pd abundances (up to 499.75 ppb) and LREE-depleted multi-element patterns typical of crystallization from a melt with comparable composition between boninite and IAT. Overall data indicate that the studied ultramafic suite represents part of a sub-oceanic Moho transition zone, which preserves mixed mantle and cumulate characteristics.

Absorption, excretion and retention of 51Cr from labelled Cr-(III)-picolinate in rats.

PubMed

Kottwitz, Karin; Laschinsky, Niels; Fischer, Roland; Nielsen, Peter

2009-04-01

The bioavailability of chromium from Cr-picolinate (CrPic(3)) and Cr-chloride (CrCl(3)) was studied in rats using (51)Cr-labelled compounds and whole-body-counting. The intestinal absorption of Cr was twice as high from CrPic(3) (1.16% vs 0.55%) than from CrCl(3), however most of the absorbed (51)Cr from CrPic(3) was excreted into the urine within 24 h. After i.v. or i.p. injection, the whole-body retention curves fitted well to a multiexponential function, demonstrating that plasma chromium is in equilibrium with three pools. For CrPic(3), a large pool exists with a very rapid exchange (T (1/2) = <0.5 days), suggesting that CrPic(3) is absorbed as intact molecule, from which the main part is directly excreted by the kidney before degradation of the chromium complex in the liver can occur. CrCl(3) is less well absorbed but the rapid exchange pool is much smaller, resulting in even higher Cr concentrations in tissue such as muscle and fat. However, 1-3 days after application, the relative distribution of (51)Cr from both compounds was similar in all tissues studied, indicating that both compounds contribute to the same storage pool. In summary, the bioavailability of CrPic(3) in rats is not superior compared to CrCl(3).

Application of a surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for micro-volume based spectrophotometric determination of low level of Cr(VI) ions in aquatic samples.

PubMed

Sobhi, Hamid Reza; Azadikhah, Efat; Behbahani, Mohammad; Esrafili, Ali; Ghambarian, Mahnaz

2018-05-09

A fast, simple, low cost surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for the determination of low level of Cr(VI) ions in several aquatic samples has been developed. Initially, Cr(VI) ions present in the aqueous sample were readily reacted with 1,5‑diphenylcarbazide (DPC) in acidic medium through complexation. Sodium dodecyl sulfate (SDS), as an anionic surfactant, was then employed as an ion-pair agent to convert the cationic complex into the neutral one. Following on, the whole aqueous phase underwent a dispersive liquid-liquid microextraction (DLLME) leading to the transfer of the neutral complex into the fine droplet of organic extraction phase. A micro-volume spectrophotometer was used to determine Cr(VI) concentrations. Under the optimized conditions predicted by the statistical design, the limit of quantification (LOQ) obtained was reported to be 5.0 μg/L, and the calibration curve was linear over the concentration range of 5-100 μg/L. Finally, the method was successfully implemented for the determination of low levels of Cr(VI) ions in various real aquatic samples and the accuracies fell within the range of 83-102%, while the precision varied in the span of 1.7-5.2%. Copyright © 2018. Published by Elsevier B.V.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hailin; Li, Ping; Wang, Zheming

Boehmite (γ-AlOOH) was synthesized to selectively adsorb V(V) from K 2CrO 4-KVO 3-H 2O solutions with highly concentrated Cr(VI) and low concentration V(V). The synthesized γ-AlOOH has a BET surface area of 433.2 m 2/g and an average pore size of 3.5 nm. It possesses a maximum adsorption capacity of V(V) of 1.53 mmol/g from K 2CrO 4-KVO 3-H 2O solutions. The adsorption of V(V) onto γ-AlOOH follows the Langmuir isotherm model and pseudo-second-order kinetics equation by forming innersphere complexes while the Cr(VI) adsorption forms both inner-sphere and outer-sphere chromate complexes depending on solution pH. The γ-AlOOH was further synthesizedmore » in situ by adding HNO 3 into the K 2CrO 4-KAlO 2- KVO 3-H 2O solutions and then used for synchronous adsorption of V(V) and Cr(VI), resulting in increased adsorption capacity of V(V) of 2.88 mmol/g and decreased adsorption capacity of Cr(VI) to 0.073 mmol/g, respectively. In the latter process, adsorption pH values were adjustable, and adsorption reached equilibrium instantaneously, supporting a novel in situ synthesis and adsorption integration strategy with adjustable surface charge of adsorbent and disappearance of diffusion effect.« less

The development of an energy-independent personnel neutron dosimeter using CR-39

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doremus, S.W.

The addition of specialized (n,{alpha}) radiators to a standard polyethylene/CR-39 (PE/CR-39) neutron dosimetry system was evaluated for improved response to low energy neutrons. Specialized radiators consisting of poly(vinyl alcohol) complexed with boron (natural and enriched boron-10) and poly(acrylic acid) complexed with lithium (enriched lithium-6) were evaluated. The complexion of boron with poly(vinyl alcohol) was accomplished by incorporation or surface coating. The complexion of lithium with poly(acrylic acid) was exclusively performed by incorporation. The dosimeter was designed such that the specialized radiator was in contact with the CR-39 detector (i.e., the specialized radiator was sandwiched between the CR-39 detector and polyethylenemore » radiator). The neutron response of this dosimetry system was investigated using {sup 252}Cf (moderated and bare) spontaneous fission neutrons. Detectors were chemically etched and then read with a Nikon OPTIPHOT microscope. The mean response (tracks {center dot} field{sup {minus}1}) of detectors treated with specialized (n,{alpha}) radiators were evaluated against PE/CR-39 controls. The results of this investigation demonstrate that PE/CR-39 dosimeters equipped with specialized (n,{alpha}) radiators have a noticeable response to low energy neutrons that in many instances is significantly greater than that of the controls. The addition of specialized radiators to this dosimetry system did not effect (diminish) its response to fast neutrons.« less

Mobility of Source Zone Heavy Metals and Radionuclides: The Mixed Roles of Fermentative Activity on Fate and Transport of U and Cr. Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerlach, Robin; Peyton, Brent M.; Apel, William A.

2014-01-29

Various U. S. Department of Energy (DOE) low and medium-level radioactive waste sites contain mixtures of heavy metals, radionuclides and assorted organic materials. In addition, there are numerous sites around the world that are contaminated with a mixture of organic and inorganic contaminants. In most sites, over time, water infiltrates the wastes, and releases metals, radionuclides and other contaminants causing transport into the surrounding environment. We investigated the role of fermentative microorganisms in such sites that may control metal, radionuclide and organics migration from source zones. The project was initiated based on the following overarching hypothesis: Metals, radionuclides and othermore » contaminants can be mobilized by infiltration of water into waste storage sites. Microbial communities of lignocellulose degrading and fermenting microorganisms present in the subsurface of contaminated DOE sites can significantly impact migration by directly reducing and immobilizing metals and radionuclides while degrading complex organic matter to low molecular weight organic compounds. These low molecular weight organic acids and alcohols can increase metal and radionuclide mobility by chelation (i.e., certain organic acids) or decrease mobility by stimulating respiratory metal reducing microorganisms. We demonstrated that fermentative organisms capable of affecting the fate of Cr6+, U6+ and trinitrotoluene can be isolated from organic-rich low level waste sites as well as from less organic rich subsurface environments. The mechanisms, pathways and extent of contaminant transformation depend on a variety of factors related to the type of organisms present, the aqueous chemistry as well as the geochemistry and mineralogy. This work provides observations and quantitative data across multiple scales that identify and predict the coupled effects of fermentative carbon and electron flow on the transport of radionuclides, heavy metals and organic contaminants in the subsurface; a primary concern of the DOE Environmental Remediation Science Division (ERSD) and Subsurface Geochemical Research (SBR) Program.« less

Determining the Specificity of Cascade Binding, Interference, and Primed Adaptation In Vivo in the Escherichia coli Type I-E CRISPR-Cas System.

PubMed

Cooper, Lauren A; Stringer, Anne M; Wade, Joseph T

2018-04-17

In clustered regularly interspaced short palindromic repeat (CRISPR)-Cas (CRISPR-associated) immunity systems, short CRISPR RNAs (crRNAs) are bound by Cas proteins, and these complexes target invading nucleic acid molecules for degradation in a process known as interference. In type I CRISPR-Cas systems, the Cas protein complex that binds DNA is known as Cascade. Association of Cascade with target DNA can also lead to acquisition of new immunity elements in a process known as primed adaptation. Here, we assess the specificity determinants for Cascade-DNA interaction, interference, and primed adaptation in vivo , for the type I-E system of Escherichia coli Remarkably, as few as 5 bp of crRNA-DNA are sufficient for association of Cascade with a DNA target. Consequently, a single crRNA promotes Cascade association with numerous off-target sites, and the endogenous E. coli crRNAs direct Cascade binding to >100 chromosomal sites. In contrast to the low specificity of Cascade-DNA interactions, >18 bp are required for both interference and primed adaptation. Hence, Cascade binding to suboptimal, off-target sites is inert. Our data support a model in which the initial Cascade association with DNA targets requires only limited sequence complementarity at the crRNA 5' end whereas recruitment and/or activation of the Cas3 nuclease, a prerequisite for interference and primed adaptation, requires extensive base pairing. IMPORTANCE Many bacterial and archaeal species encode CRISPR-Cas immunity systems that protect against invasion by foreign DNA. In the Escherichia coli CRISPR-Cas system, a protein complex, Cascade, binds 61-nucleotide (nt) CRISPR RNAs (crRNAs). The Cascade complex is directed to invading DNA molecules through base pairing between the crRNA and target DNA. This leads to recruitment of the Cas3 nuclease, which destroys the invading DNA molecule and promotes acquisition of new immunity elements. We made the first in vivo measurements of Cascade binding to DNA targets. Thus, we show that Cascade binding to DNA is highly promiscuous; endogenous E. coli crRNAs can direct Cascade binding to >100 chromosomal locations. In contrast, we show that targeted degradation and acquisition of new immunity elements require highly specific association of Cascade with DNA, limiting CRISPR-Cas function to the appropriate targets. Copyright © 2018 Cooper et al.

Structural and magnetic diversity in cyano-bridged bi- and trimetallic complexes assembled from cyanometalates and [M(rac-CTH)]n+ building blocks (CTH = d,l-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane).

PubMed

Rodríguez-Diéguez, Antonio; Kivekäs, Raikko; Sillanpää, Reijo; Cano, Joan; Lloret, Francesc; McKee, Vickie; Stoeckli-Evans, Helen; Colacio, Enrique

2006-12-25

Seven new cyano-bridged heterometallic systems have been prepared by assembling [M'(rac-CTH)]n+ complexes (M' = CrIII, NiII, CuII), which have two cis available coordination positions, and [M(CN)6]3- (M = FeIII, CrIII) and [Fe(CN)2(bpy)2]+ cyanometalate building blocks. The assembled systems, which have been characterized by X-ray crystallography and magnetic investigations, are the molecular squares (meso-CTH-H2)[{Ni(rac-CTH)}2{Fe(CN)6)}2].5H2O (2) and [{Ni(rac-CTH)}2{Fe(CN)2(bpy)2}2](ClO4)4.H2O (5), the bimetallic chain [{Ni(rac-CTH)}2{Cr(CN)6)}2Ni(meso-CTH)].4H2O (3), the trimetallic chain [{Ni(rac-CTH)}2{Fe(CN)6)}2Cu(cyclam)]6H2O (4), the pentanuclear complexes [{Cu(rac-CTH}3{Fe(CN)6}2].2H2O (6) and [{Cu(rac-CTH)}3{Cr(CN)6)}2].2H2O (7), and the dinuclear complex [Cr(rac-CTH)(H2O)Fe(CN)6].2H2O (8). With the exception of 5, all compounds exhibit ferromagnetic interaction between the metal ions (JFeNi = 12.8(2) cm-1 for 2; J1FeCu= 13.8(2) cm-1 and J2FeCu= 3.9(4) cm-1 for 6; J1CrCu= 6.95(3) cm-1 and J2CrCu= 1.9(2)cm-1 for 7; JCrFe = 28.87(3) cm-1 for 8). Compound 5 exhibits the end of a transition from the high-spin to the low-spin state of the octahedral FeII ions. The bimetallic chain 3 behaves as a metamagnet with a critical field Hc = 300 G, which is associated with the occurrence of week antiferromagnetic interactions between the chains. Although the trimetallic chain 4 shows some degree of spin correlation along the chain, magnetic ordering does not occur. The sign and magnitude of the magnetic exchange interaction between CrIII and FeIII in compound 8 have been justified by DFT type calculations.

Effect of Isothermal Hold on the Microstructural Evolution of the Stainless Steel 304L/Zircaloy-4 Interface

NASA Astrophysics Data System (ADS)

Lebaili, A.; Taouinet, M.; Nibou, D.; Lebaili, S.; Hodaj, F.

2017-07-01

The transition from solid-state bonding of the stainless steel 304L/Zircaloy-4 diffusion couple to a partial liquid-phase bonding is important for the bonding process at temperatures ranging from 950 to 1050 °C. In this study, the temperature at which a melting process occurs at the interface after 45 min of isothermal holdings is determined experimentally. This melting process leads to a drastic change in the thickness of the reaction products zone (RPZ) as well as on its microstructure. Diffusion couples were characterized by SEM-EDS, and quantitative chemical analyses of different phases are performed by EPMA. The RPZ consists of three layers: the (α-Fe-Cr) phase layer and two layers consisting of Zr(Fe,Cr)2 (ɛ), Zr2(Fe,Ni) and (α-Zr) phases. The thickness of these layers strongly depends on the holding temperature. The analysis allowed the description of the physicochemical phenomena occurring during isothermal holding as well as during cooling. The solidification paths are determined at 1000, 1020 and 1050 °C. Hardness tests are performed on the bonded samples in order to qualify the mechanical properties of different phases of the RPZ. This study leads to a better understanding of the complex phenomena intervening in the joining process which is very useful for applications in industrial scale.

Photodynamic therapy and fluorescent diagnostics of skin cancer with radochlorine and photosense: comparing efficacy and toxicity

NASA Astrophysics Data System (ADS)

Vakulovskaya, Elena G.; Kemov, Yuriy V.; Zalevsky, Igor D.; Reshetnikov, Andrew V.; Umnova, Loubov V.; Vorozhcsov, Georgiu N.

2004-06-01

Photodynamic therapy (PDT) and fluorescent diagnostics (FD) with Radaclorine (RadaPharma, Russia) (RC) have been provided in 32 patients with T1-4 stage basal cell carcinoma (BCC) and in 81 patients with Photsense. Pharmacocynetic studies with detecting the borders of tumor growth and intensity of accumulation of photosensizers in tumor, normal tissues and visualization have been done by Spectral-fluorescent Complex and spectranalyser LESA-01 (He-Ne-laser, λ=633nm). We've got fluorescence of all tumors and additional fluorescence zones were found, cytological verification of BCC was got in most of cases. The fluorescent signs of RC in normal skin were found till 5 days after injection. As a source of light for PDT we used simeconductive lasers: Milon - λ = 660+2nm, light dose was 200-300 J/cm2 and Biospec (λ+672+2nm), multiple laser surface and interstitial irradiation was performed 24 hours after PS injection with total light dose till 400-600 J/cm2. 2 months after PDT with RC complete response (CR) in 65.6% of cases, partial response-in 34.4% of cases. The efficacy of PDT with PS was higher (CR-84.0%, PR-14.8%). Our experience show pronounced efficacy of PDT with RC for BCC without side effects and very short skin toxicity.

Diffusion in thoriated and nonthoriated nickel and nickel-chromium alloys at 1260 C

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1972-01-01

Various solid-solid diffusion couples were assembled from thoriated and nonthoriated nickel-base alloys, welded, and diffusion annealed at 1260 C. Concentration profiles indicated that a thoria dispersion does not affect diffusion in Cr(alloy):Ni and Ni-4.8Al:Ni types of couples unless a fine grain structure is retained by the thoria particles. Metallography revealed the presence of thoria-free bands in the thoriated-Ni side of the diffusion zone. The bands contained grain boundaries and, in some cases, non-Kirkendall porosity. A mechanism based on the operation of vacancy sources is proposed to explain the thoria-free bands. In addition, a particular DS-NiCr:Ni couple had negligible Kirkendall porosity. This behavior was related to the grain structure of the particular lot of DS-NiCr.

Heat-affected zone microstructure and mechanical properties evolution for laser remanufacturing 35CrMoA axle steel

NASA Astrophysics Data System (ADS)

Feng, Xiangyi; Dong, Shiyun; Yan, Shixing; Liu, Xiaoting; Xu, Binshi; Pan, Fusheng

2018-03-01

In this article, by using orthogonal test the technological test was conducted and the optimum processing of the remanufacturing35CrMoA axle were obtained. The evolution of microstructure and mechanical property of HAZ were investigated. The microstructure of HAZ was characterized by means of OM and SEM. Meanwhile hardness distribution in HAZ and tensile property of cladding-HAZ-substrate samples were measured. The microstructure of cladding and HAZ were observed. The microsturcture evoltion and the mechanism of harden in the HAZ was discussed and revealed. The results indicated that the remanufacturing part has excellent strength due to grain refining and dispersive distribution of nanoscale cementite. The remanufacturing part will have uniform microstructure and hardness matching with that of 35CrMoA axle by using stress-relieving annealing at 580°.

Hexavalent chromium exposure and control in welding tasks.

PubMed

Meeker, John D; Susi, Pam; Flynn, Michael R

2010-11-01

Studies of exposure to the lung carcinogen hexavalent chromium (CrVI) from welding tasks are limited, especially within the construction industry where overexposure may be common. In addition, despite the OSHA requirement that the use of engineering controls such as local exhaust ventilation (LEV) first be considered before relying on other strategies to reduce worker exposure to CrVI, data on the effectiveness of LEV to reduce CrVI exposures from welding are lacking. The goal of the present study was to characterize breathing zone air concentrations of CrVI during welding tasks and primary contributing factors in four datasets: (1) OSHA compliance data; (2) a publicly available database from The Welding Institute (TWI); (3) field survey data of construction welders collected by the Center for Construction Research and Training (CPWR); and (4) controlled welding trials conducted by CPWR to assess the effectiveness of a portable LEV unit to reduce CrVI exposure. In the OSHA (n = 181) and TWI (n = 124) datasets, which included very few samples from the construction industry, the OSHA permissible exposure level (PEL) for CrVI (5 μg/m(3)) was exceeded in 9% and 13% of samples, respectively. CrVI concentrations measured in the CPWR field surveys (n = 43) were considerably higher, and 25% of samples exceeded the PEL. In the TWI and CPWR datasets, base metal, welding process, and LEV use were important predictors of CrVI concentrations. Only weak-to-moderate correlations were found between total particulate matter and CrVI, suggesting that total particulate matter concentrations are not a good surrogate for CrVI exposure in retrospective studies. Finally, in the controlled welding trials, LEV reduced median CrVI concentrations by 68% (p = 0.02). In conclusion, overexposure to CrVI in stainless steel welding is likely widespread, especially in certain operations such as shielded metal arc welding, which is commonly used in construction. However, exposure could be substantially reduced with proper use of LEV.

Influence of minor combined addition of Cr and Pr on microstructure, mechanical properties and corrosion behaviors of an ultrahigh strength Al-Zn-Mg-Cu-Zr alloy.

PubMed

Wang, Ming; Huang, Lanping; Chen, Kanghua; Liu, Wensheng

2018-01-01

This work focuses on controlling grain boundary structure in an ultra-high strength Al-8.6Zn-2.5Mg-2.2Cu-0.16Zr (wt.%) alloy by the combined addition of trace Cr (0.1wt.%) and Pr (0.14wt.%), and evaluating mechanical properties and localized corrosion behaviors of the alloy in the peak aged condition. The introduction of trace Cr and Pr leads to the formation of nanoscale Cr, Pr-containing Al 3 Zr and Zr-containing PrCr 2 Al 20 dispersoids which can obviously inhibit the recrystallization and sub-grain growth of the super-high strength Al-Zn-Mg-Cu alloys, and retain the deformation-recovery microstructure dominated by low-angle grain boundaries. The nearly ellipsoidal dispersoids with a size of 10-35nm are discretely distributed and precipitate free zones are hardly formed in low-angle grain boundaries. This new alloy composition exhibits better combined properties, higher resistance to stress corrosion, exfoliation corrosion and inter-granular corrosion with the undamaged strength, ductility and fracture toughness. Copyright © 2017 Elsevier Ltd. All rights reserved.

Radiation Tolerance of Controlled Fusion Welds in High Temperature Oxidation Resistant FeCrAl Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gussev, Maxim N.; Field, Kevin G.

High temperature oxidation resistant iron-chromium-aluminum (FeCrAl) alloys are candidate alloys for nuclear applications due to their exceptional performance during off-normal conditions such as a loss-of-coolant accident (LOCA) compared to currently deployed zirconium-based claddings [1]. A series of studies have been completed to determine the weldability of the FeCrAl alloy class and investigate the weldment performance in the as-received (non-irradiated) state [2,3]. These initial studies have shown the general effects of composition and microstructure on the weldability of FeCrAl alloys. Given this, limited details on the radiation tolerance of FeCrAl alloys and their weldments exist. Here, the highest priority candidate FeCrAlmore » alloys and their weldments have been investigated after irradiation to enable a better understanding of FeCrAl alloy weldment performance within a high-intensity neutron field. The alloys examined include C35M (Fe-13%Cr-5% Al) and variants with aluminum (+2%) or titanium carbide (+1%) additions. Two different sub-sized tensile geometries, SS-J type and SS-2E (or SS-mini), were neutron irradiated in the High Flux Isotope Reactor to 1.8-1.9 displacements per atom (dpa) in the temperature range of 195°C to 559°C. Post irradiation examination of the candidate alloys was completed and included uniaxial tensile tests coupled with digital image correlation (DIC), scanning electron microscopy-electron back scattered diffraction analysis (SEM-EBSD), and SEM-based fractography. In addition to weldment testing, non-welded parent material was examined as a direct comparison between welded and non-welded specimen performance. Both welded and non-welded specimens showed a high degree of radiation-induced hardening near irradiation temperatures of 200°C, moderate radiation-induced hardening near temperatures of 360°C, and almost no radiation-induced hardening at elevated temperatures near 550°C. Additionally, low-temperature irradiations showed the non-welded specimens to exhibit strain-induced softening (decrease in the true stress level) with increasing plastic strain during tensile testing. Fracture for the weldments was found to occur exclusively within the fusion zone. The mechanical performance of the weldment was speculated to be directly linked to variances in the radiation-induced microstructure including the formation of dislocation loops and precipitation of the Cr-rich α' phase. The localized microstructural variation within the weldments, including grain size, was determined to play a significant role in the radiation-induced microstructure. The results summarized within highlight the need for additional data on the radiation tolerance of weldments as the mechanical performance of the fusion zone was shown to be the limiting factor in the overall performance of the weldments.« less

Extending lifetimes of lanthanide-based near-infrared emitters (Nd, Yb) in the millisecond range through Cr(III) sensitization in discrete bimetallic edifices.

PubMed

Imbert, Daniel; Cantuel, Martine; Bünzli, Jean-Claude G; Bernardinelli, Gérald; Piguet, Claude

2003-12-24

A [Cr(alpha,alpha'-diimine)3]3+ chromophore is used as a donor for sensitizing NdIII and YbIII near-infrared (NIR) emitters in the heterobimetallic helicates [LnCrIIIL3]6+. The intramolecular CrIII --> LnIII energy transfer process controls the population of the lanthanide-centered emitting levels, thus leading to unprecedented extension of the NIR luminescence decay times in the millisecond range for Nd and Yb ions incorporated in coordination complexes.

The Preparation of an Ultrastable Mesoporous Cr(III)-MOF via Reductive Labilization

DTIC Science & Technology

2015-09-02

of metal clusters from a template MOF with a known structure. Fe(III)-MOFs can serve as practical structural templates because iron resembles chromium ...clusters in PCN-333 are able to accommodate both di- and trivalent metal ions by varying the charges of the terminal ligands, the bridging oxygen atoms, and...molecules in trivalent aqua complexes27 Inert complexes Labile complexes M(OH2) Cr(OH2)6 3+ Ir(OH2)6 3+ V(OH2)6 3+ Fe(OH2)6 3+ Ti(OH2)6 3+ k (s1) 2.4 10

The first defective extended chromium atom chain complex with amine ligand containing naphthyridine and pyrazine

NASA Astrophysics Data System (ADS)

Wang, Wen-Zhen; Geng, Shu-Bo; Liu, Shuang; Zhao, Dan; Jia, Xin-Gang; Wei, Hai-Long; Ismayilov, Rayyat H.; Yeh, Chen-Yu; Lee, Gene-Hsiang; Peng, Shie-Ming

2017-06-01

Through a pyrazine and naphthyridine-containing diamino ligand, N2,N7-di(pyrazin-2-yl)-1,8-naphthyridine-2,7-diamine (H2dpznda), defective extended metal atom chain complexes with one chromium(II) metal absent in centre, [Cr5(μ5-dpznda)4Cl2] (1) and [Cr5(μ5-dpznda)4(NCS)2] (2) were obtained. An electrochemistry research showed that the pentachromium(II) complexes were quite resistant to reduction although accessible to oxidation, with two reversible redox couples at E1/2 = +0.59 and +0.30 V.

Coarsening of Inter- and Intra-granular Proeutectoid Cementite in an Initially Pearlitic 2C-4Cr Ultrahigh Carbon Steel

NASA Astrophysics Data System (ADS)

Hecht, Matthew D.; Picard, Yoosuf N.; Webler, Bryan A.

2017-05-01

We have examined spheroidization and coarsening of cementite in an initially pearlitic 2C-4Cr ultrahigh carbon steel containing a cementite network. Coarsening kinetics of spheroidized cementite and growth of denuded zones adjacent to the cementite network were investigated by analyzing particle sizes from digital micrographs of water-quenched steel etched with Nital. Denuded zones grew at a rate proportional to t 1/4- t 1/5. Spheroidization of pearlite was completed within 90 minutes at 1073 K and 1173 K (800 °C and 900 °C), and within 5 minutes at 1243 K (970 °C). Bimodal particle size distributions were identified in most of the samples and were more pronounced at higher temperatures and hold times. Peaks in the distributions were attributed to the coarsening of intragranular and grain boundary particles at different rates. A third, non-coarsening peak of particles was present at 1073 K (800 °C) only and was attributed to particles existing prior to the heat treatment. Particle sizes were plotted vs time to investigate possible coarsening mechanisms. The coarsening exponent for the growth of grain boundary carbides was closest to 4, indicating grain boundary diffusion control. The coarsening exponent was closest to 5 for intragranular carbides, indicating suppression of volumetric diffusion (possibly due to reduced effective diffusivity because of Cr alloying) and control by dislocation diffusion.

Effect of parameters on picosecond laser ablation of Cr12MoV cold work mold steel

NASA Astrophysics Data System (ADS)

Wu, Baoye; Liu, Peng; Zhang, Fei; Duan, Jun; Wang, Xizhao; Zeng, Xiaoyan

2018-01-01

Cr12MoV cold work mold steel, which is a difficult-to-machining material, is widely used in the mold and dye industry. A picosecond pulse Nd:YVO4 laser at 1064 nm was used to conduct the study. Effects of operation parameters (i.e., laser fluence, scanning speed, hatched space and number of scans) were studied on ablation depth and quality of Cr12MoV at the repetition rate of 20 MHz. The experimental results reveal that all the four parameters affect the ablation depth significantly. While the surface roughness depends mainly on laser fluence or scanning speed and secondarily on hatched space or number of scans. For laser fluence and scanning speed, three distinct surface morphologies were observed experiencing transition from flat (Ra < 1.40 μm) to bumpy (Ra = 1.40 - 2.40 μm) eventually to rough (Ra > 2.40 μm). However, for hatched space and number of scan, there is a small bumpy and rough zone or even no rough zone. Mechanisms including heat accumulation, plasma shielding and combustion reaction effects are proposed based on the ablation depth and processing morphology. By appropriate management of the laser fluence and scanning speed, high ablation depth with low surface roughness can be obtained at small hatched space and high number of scans.

Very large cooperative effects in heterobimetallic titanium-chromium catalysts for ethylene polymerization/copolymerization.

PubMed

Liu, Shaofeng; Motta, Alessandro; Mouat, Aidan R; Delferro, Massimiliano; Marks, Tobin J

2014-07-23

The heterobimetallic complexes, (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-CnH2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-Cr(SNS); n = 2, Ti-C2-Cr(SNS); n = 6, Ti-C6-Cr(SNS)), (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-C2H4-[N,N-bis((o-OMe-C6H4)2P)amine]CrCl3 (Ti-C2-Cr(PNP)), and (η(5)-indenyl)[1-Me2Si((t)BuN)TiCl2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine]CrCl3 (Ti-C2-Cr(NNN)), are synthesized, fully characterized, and employed as olefin polymerization catalysts. With ethylene as the feed and MAO as cocatalyst/activator, SNS-based complexes Ti-C0-Cr(SNS), Ti-C2-Cr(SNS), and Ti-C6-Cr(SNS) afford linear low-density polyethylenes (LLDPEs) with exclusive n-butyl branches (6.8-25.8 branches/1000 C), while under identical polymerization conditions Ti-C2-Cr(PNP) and Ti-C2-Cr(NNN) produce polyethylenes with heterogeneous branching (C2, C4, and C≥6) or negligible branching, respectively. Under identical ethylene polymerization conditions, Ti-C0-Cr(SNS) produces polyethylenes with higher activity (4.5× and 6.1×, respectively), Mn (1.3× and 1.8×, respectively), and branch density (1.4× and 3.8×, respectively), than Ti-C2-Cr(SNS) and Ti-C6-Cr(SNS). Versus a CGC(Et)Ti + SNSCr tandem catalyst, Ti-C0-Cr(SNS) yields polyethylene with somewhat lower activity, but with 22.6× higher Mn and 4.0× greater branching density under identical conditions. In ethylene +1-pentene competition experiments, Ti-C0-Cr(SNS) yields 5.5% n-propyl branches and 94.5% n-butyl branches at [1-pentene] = 0.1 M, and the estimated effective local concentration of 1-hexene is ∼8.6 M. In contrast, the tandem CGC(Et)Ti + SNSCr system yields 91.0% n-propyl branches under identical reaction conditions. The homopolymerization and 1-pentene competition results argue that close Ti···Cr spatial proximity together with weak C-H···Ti and C-H···S interactions significantly influence relative 1-hexene enchainment and chain transfer rates, supported by DFT computation, and that such effects are conversion insensitive but cocatalyst and solvent sensitive.

Effects of activating fluxes on the weld penetration and corrosion resistant property of laser welded joint of ferritic stainless steel

NASA Astrophysics Data System (ADS)

Wang, Yonghui; Hu, Shengsun; Shen, Junqi

2015-10-01

This study was based on the ferritic stainless steel SUS430. Under the parallel welding conditions, the critical penetration power values (CPPV) of 3mm steel plates with different surface-coating activating fluxes were tested. Results showed that, after coating with activating fluxes, such as ZrO2, CaCO3, CaF2 and CaO, the CPPV could reduce 100~250 W, which indicating the increases of the weld penetrations (WP). Nevertheless, the variation range of WP with or without activating fluxes was less than 16.7%. Compared with single-component ones, a multi-component activating flux composed of 50% ZrO2, 12.09% CaCO3, 10.43% CaO, and 27.49% MgO was testified to be much more efficient, the WP of which was about 2.3-fold of that without any activating fluxes. Furthermore, a FeCl3 spot corrosion experiment was carried out with samples cut from weld zone to test the effects of different activating fluxes on the corrosion resistant (CR) property of the laser welded joints. It was found that all kinds of activating fluxes could improve the CR of the welded joints. And, it was interesting to find that the effect of the mixed activating fluxes was inferior to those single-component ones. Among all the activating fluxes, the single-component of CaCO3 seemed to be the best in resisting corrosion. By means of Energy Dispersive Spectrometer (EDS) testing, it was found that the use of activating fluxes could effectively restrain the loss of Cr element of weld zone in the process of laser welding, thus greatly improving the CR of welded joints.

Paleomagnetic results from IODP Expedition 344 Site U1381 and implications for the initial subduction of the Cocos Ridge

NASA Astrophysics Data System (ADS)

Li, Yong-Xiang; Zhao, Xixi; Jovane, Luigi; Petronotis, Katerina; Gong, Zheng; Xie, Siyi

2016-04-01

Understanding the processes that govern the strength, nature, and distribution of slip along subduction zones is a fundamental and societally relevant goal of modern earth science. The Costa Rica Seismogenesis Project (CRISP) is specially designed to understand the processes that control nucleation and seismic rupture of large earthquakes at erosional subduction zones. Drilling directly on the Cocos Ridge (CR) during International Ocean Drilling Program (IODP) Expedition 344 discovered a sedimentary hiatus in Site U1381 cores. In this study, we conducted a magnetostratigraphic and rock magnetic study on the Cenozoic sedimentary sequences of site U1381. Anisotropy of magnetic susceptibility data from sediments above and below the hiatus show oblate fabrcis, but the Kmin axes of the AMS data from sediments below the hiatus are more dispersed than those from sediments above the hiatus, implying that formation of hiatus may have affected AMS. Paleomagnetic results of the U1381 core, together with available Ar-Ar dates of ash layers from sediments below the hiatus, allow us to establish a geomagnetic polarity timescale that brackets the hiatus between ca. 9.61 and 1.52 Ma. Analyses of sedimentary records from ODP/IODP cores in the vicinity reveal that the hiatus appears to be regional, spanning the northeastern end of the CR. Also, the hiatus appears to occur only at certain locations. Its regional occurrence at unique locations implies a link to the initial shallow subduction of the Cocos Ridge. The hiatus was probably produced by either bottom current erosion or the CR buckling upon its initial collision with the Middle American trench (MAT). Thus, the initial subduction of the CR must have taken place on or before 1.52 Ma.

[Distribution of Urban Soil Heavy Metal and Pollution Evaluation in Different Functional Zones of Yinchuan City].

PubMed

Wang, You-qi; Bai, Yi-ru; Wang, Jian-yu

2016-02-15

Surface soil samples (0-20 cm) from eight different functional areas in Yinchuan city were collected. There were 10 samples respectively in each functional area. The urban soil heavy metals (Zn, Cd, Pb, Mn, Cu and Cr) pollution characteristics and sources in eight different functional areas were evaluated by mathematical statistics and geostatistical analysis method. Meanwhile, the spatial distributions of heavy metals based on the geography information system (GIS) were plotted. The average values of total Zn, Cd, Pb, Mn, Cu and Cr were 74.87, 0.15, 29.02, 553.55, 40.37 and 80.79 mg x kg(-1), respectively. The results showed that the average value of soil heavy metals was higher than the soil background value of Ningxia, which indicated accumulation of the heavy metals in urban soil. The single factor pollution index of soil heavy metals was in the sequence of Cu > Pb > Zn > Cr > Cd > Mn. The average values of total Zn, Cd, Pb and Cr were higher in north east, south west and central city, while the average values of Mn and Cu were higher in north east and central city. There was moderate pollution in road and industrial area of Yinchuan, while the other functional areas showed slight pollution according to Nemoro synthesis index. The pollution degree of different functional areas was as follows: road > industrial area > business district > medical treatment area > residential area > public park > development zone > science and education area. The results indicated that the soil heavy metal pollution condition in Yinchuan City has been affected by human activities with the development of economy.

The Tribological Difference between Biomedical Steels and CoCrMo-Alloys

PubMed Central

Fischer, Alfons; Weiß, Sabine; Wimmer, Markus A.

2012-01-01

In orthopedic surgery different self-mating metal couples are used for sliding wear applications. Despite the fact that in mechanical engineering self-mating austenitic alloys often lead to adhesion and seizure in biomedical engineering the different grades of Co-base alloys show good clinical results e.g. as hip joints. The reason stems from the fact that they generate a so-called tribomaterial during articulation, which consists of a mixture of nanometer small metallic grains and organic substances from the interfacial medium, which act as boundary lubricant. Even though stainless steels also generate such a tribomaterial they were ruled out from the beginning already in the 1950 as “inappropriate”. On the basis of materials with a clinical track record this contribution shows that the cyclic creep characteristics within the shear zone underneath the tribomaterial are another important criterion for a sufficient wear behavior. By means of sliding wear and torsional fatigue tests followed by electron microscopy it is shown, that austenitic materials generate wear particles of either nano- or of microsize. The latter are produced by crack initiation and propagation within the shear fatigue zone which is related to the formation of subsurface dislocation cells and, therefore, by the fact that a Ni-containing CrNiMo solid solution allows for wavy-slip. In contrast to this a Ni-free CrMnMo solid solution with further additions of C and N only shows planar slip. This leads to the formation of nanosize wear particles and distinctly improves the wear behavior. Still the latter does not fully achieve that of CoCrMo, which also shows solely planar-slip behavior. This explains why for metallurgical reasons the Ni-containing 316L-type of steels had to fail in such boundary lubricated sliding wear tribosystems. PMID:22498283

Zic deficiency in the cortical marginal zone and meninges results in cortical lamination defects resembling those in type II lissencephaly.

PubMed

Inoue, Takashi; Ogawa, Masaharu; Mikoshiba, Katsuhiko; Aruga, Jun

2008-04-30

The formation of the highly organized cortical structure depends on the production and correct placement of the appropriate number and types of neurons. The Zic family of zinc-finger transcription factors plays essential roles in regulating the proliferation and differentiation of neuronal progenitors in the medial forebrain and the cerebellum. Examination of the expression of Zic genes demonstrated that Zic1, Zic2, and Zic3 were expressed by the progenitor cells in the septum and cortical hem, the sites of generation of the Cajal-Retzius (CR) cells. Immunohistochemical studies have revealed that Zic proteins were abundantly expressed in the meningeal cells and that the majority of the CR cells distributed in the medial and dorsal cortex also expressed Zic proteins in the mid-late embryonic and postnatal cortical marginal zones. During embryonic cortical development, Zic1/Zic3 double-mutant and hypomorphic Zic2 mutant mice showed a reduction in the number of CR cells in the rostral cortex, whereas the cell number remained unaffected in the caudal cortex. These mutants also showed mislocalization of the CR cells and cortical lamination defects, resembling the changes noted in type II (cobblestone) lissencephaly, throughout the brain. In the Zic1/3 mutant, reduced proliferation of the meningeal cells was observed before the thinner and disrupted organization of the pial basement membrane (BM) with reduced expression of the BM components and the meningeal cell-derived secretory factor. These defects correlated with the changes in the end feet morphology of the radial glial cells. These findings indicate that the Zic genes play critical roles in cortical development through regulating the proliferation of meningeal cells and the pial BM assembly.

Irradiation-induced damage evolution in concentrated Ni-based alloys

DOE PAGES

Velisa, Gihan; Ullah, Mohammad Wali; Xue, Haizhou; ...

2017-06-06

Understanding the effects of chemical complexity from the number, type and concentration of alloying elements in single-phase concentred solid-solution alloys (SP-CSAs) on defect dynamics and microstructure evolution is pivotal for developing next-generation radiation-tolerant structural alloys. A specially chosen set of SP-CSAs with different chemical complexity (Ni 80Fe 20, Ni 80Cr 20 and Ni 40Fe 40Cr 20) are investigated using 1.5 MeV Mn ions over a wide fluence range, from 2 × 10 13 to 1 × 10 16 ions cm –2 at room temperature. Based on an integrated study of Rutherford backscattering spectroscopy in channeling geometry and molecular dynamics simulations,more » the results demonstrate that Ni 40Fe 40Cr 20 is more radiation tolerant than Ni 80Fe 20, Ni 80Cr 20 and elemental Ni in the low fluence regime. While chemical complexity of this set of SP-CSAs is clearly demonstrated to affect defect evolution through suppressed defect production and enhanced recombination at early stages, the effect of the mixed ferro- and anti-ferromagnetic interactions is not the only controlling factor responsible for the improved radiation performance. As a result, the observed strong alloying effect on defect evolution is attributed to the altered defect migration mobilities of defect clusters in these alloys, an intrinsic characteristic of the complex energy landscapes in CSAs.« less

Irradiation-induced damage evolution in concentrated Ni-based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Velisa, Gihan; Ullah, Mohammad Wali; Xue, Haizhou

Understanding the effects of chemical complexity from the number, type and concentration of alloying elements in single-phase concentred solid-solution alloys (SP-CSAs) on defect dynamics and microstructure evolution is pivotal for developing next-generation radiation-tolerant structural alloys. A specially chosen set of SP-CSAs with different chemical complexity (Ni 80Fe 20, Ni 80Cr 20 and Ni 40Fe 40Cr 20) are investigated using 1.5 MeV Mn ions over a wide fluence range, from 2 × 10 13 to 1 × 10 16 ions cm –2 at room temperature. Based on an integrated study of Rutherford backscattering spectroscopy in channeling geometry and molecular dynamics simulations,more » the results demonstrate that Ni 40Fe 40Cr 20 is more radiation tolerant than Ni 80Fe 20, Ni 80Cr 20 and elemental Ni in the low fluence regime. While chemical complexity of this set of SP-CSAs is clearly demonstrated to affect defect evolution through suppressed defect production and enhanced recombination at early stages, the effect of the mixed ferro- and anti-ferromagnetic interactions is not the only controlling factor responsible for the improved radiation performance. As a result, the observed strong alloying effect on defect evolution is attributed to the altered defect migration mobilities of defect clusters in these alloys, an intrinsic characteristic of the complex energy landscapes in CSAs.« less

Assembly of Francisella novicida Cpf1 endonuclease in complex with guide RNA and target DNA

PubMed Central

Montoya, Guillermo; Stella, Stefano

2017-01-01

Bacteria and archaea use the CRISPR–Cas system as an adaptive response against infection by foreign nucleic acids. Owing to its remarkable flexibility, this mechanism has been harnessed and adopted as a powerful tool for genome editing. The CRISPR–Cas system includes two classes that are subdivided into six types and 19 subtypes according to conservation of the cas gene and loci organization. Recently, a new protein with endonuclease activity belonging to class 2 type V has been identified. This endonuclease, termed Cpf1, in complex with a single CRISPR RNA (crRNA) is able to recognize and cleave a target DNA preceded by a 5′-TTN-3′ protospacer-adjacent motif (PAM) complementary to the RNA guide. To obtain structural insight into the inner workings of Cpf1, the crystallization of an active complex containing the full extent of the crRNA and a 31-nucleotide dsDNA target was attempted. The gene encoding Cpf1 from Francisella novicida was cloned, overexpressed and purified. The crRNA was transcribed and purified in vitro. Finally, the ternary FnCpf1–crRNA–DNA complex was assembled and purified by preparative electrophoresis before crystallization. Crystals belonging to space group C2221, with unit-cell parameters a = 85.2, b = 137.6, c = 320.5 Å, were obtained and subjected to preliminary diffraction experiments. PMID:28695850

New generation ion-imprinted nanocarrier for removal of Cr(VI) from wastewater

NASA Astrophysics Data System (ADS)

Uygun, Murat; Feyzioğlu, Esra; Özçalışkan, Emir; Caka, Müşerref; Ergen, Aygen; Akgöl, Sinan; Denizli, Adil

2013-08-01

The purpose of this study was to prepare a novel ion-imprinted nanoparticle to remove Cr(VI) ions from waste water. For this, Cr(VI) ions were complexed with 2-methacryloylamido histidine (MAH) and then Cr(VI)-imprinted poly(HEMAH) nanoparticles were synthesized by surfactant-free emulsion polymerization technique. The templates, Cr(VI) ions, were removed from the nanoparticles using 0.1 M of HNO3 solution. The specific surface area of the Cr(VI)-imprinted poly(HEMAH) nanoparticles was found to be 1,397.85 m2/g, and the particle size was calculated as 155.3 nm. These Cr(VI)-imprinted nanoparticles were used for the adsorption/desorption of Cr(VI) ions from its aqueous solutions. The effects of initial Cr(VI) concentration and medium pH on the Cr(VI) adsorption capacity were also studied. The maximum adsorbed amount of Cr(VI) on the imprinted nanoparticles was found to be 3,830.58 mg/g nanoparticle in pH 4.0. In order to investigate the selectivity of the imprinted nanoparticle, adsorption studies were repeated using Cr(III) ions. The selectivity results demonstrated that Cr(VI)-imprinted poly(HEMAH) nanoparticles showed high affinity for the Cr(VI) ions than Cr(III). The Cr(VI)-imprinted nanoparticles were used several times without decreasing their Cr(VI) adsorption capacities.

Variations of trace element concentration of magnetite and ilmenite from the Taihe layered intrusion, Emeishan large igneous province, SW China: Implications for magmatic fractionation and origin of Fe-Ti-V oxide ore deposits

NASA Astrophysics Data System (ADS)

She, Yu-Wei; Song, Xie-Yan; Yu, Song-Yue; He, Hai-Long

2015-12-01

In situ LA-ICP-MS trace elemental analysis has been applied to magnetite and ilmenite of the Taihe layered intrusion, Emeishan large igneous province, SW China, in order to understand better fractionation processes of magma and origin of Fe-Ti-V oxide ore deposits. The periodic reversals in Mg, Ti, Mn in magnetite and Mg, Sc in ilmenite are found in the Middle Zone of the intrusion and agree with fractionation trends as recorded by olivine (Fo), plagioclase (An) and clinopyroxene (Mg#) compositions. These suggest the Taihe intrusion formed from open magma chamber processes in a magma conduit with multiple replenishments of more primitive magmas. The V and Cr of magnetite are well correlated with V and Cr of clinopyroxene indicating that they became liquidus phases almost simultaneously at an early stage of magma evolution. Ilmenite from the Middle and Upper Zones shows variable Cr, Ni, V, Mg, Nb, Ta and Sc contents indicating that ilmenite at some stratigraphic levels crystallized slightly earlier than magnetite and clinopyroxene. The early crystallization of magnetite and ilmenite is the result of the high FeOt and TiO2 contents in the parental magma. The ilmenite crystallization before magnetite in the Middle and Upper Zones can be attributed to higher TiO2 content of the magma due to the remelting of pre-existing ilmenite in a middle-level magma chamber. Compared to the coeval high-Ti basalts, the relatively low Zr, Hf, Nb and Ta contents in both magnetite and ilmenite throughout the Taihe intrusion indicate that they crystallized from Fe-Ti-(P)-rich silicate magmas. Positive correlations of Ti with Mg, Mn, Sc and Zr of magnetite, and Zr with Sc, Hf and Nb of ilmenite also suggest that magnetite and ilmenite crystallized continuously from the homogeneous silicate magma rather than an immiscible Fe-rich melt. Therefore, frequent replenishments of Fe-Ti-(P)-rich silicate magma and gravitational sorting and settling are crucial for the formation the massive and apatite-rich disseminated ores in the Lower and Middle Zones of the Taihe intrusion.

50 CFR 680.6 - Crab economic data report (EDR).

Code of Federal Regulations, 2010 CFR

2010-10-01

... 50 Wildlife and Fisheries 9 2010-10-01 2010-10-01 false Crab economic data report (EDR). 680.6... ADMINISTRATION, DEPARTMENT OF COMMERCE (CONTINUED) SHELLFISH FISHERIES OF THE EXCLUSIVE ECONOMIC ZONE OFF ALASKA General § 680.6 Crab economic data report (EDR). Persons participating in the CR crab fisheries are...

50 CFR 680.6 - Crab economic data report (EDR).

Code of Federal Regulations, 2011 CFR

2011-10-01

... 50 Wildlife and Fisheries 11 2011-10-01 2011-10-01 false Crab economic data report (EDR). 680.6... ADMINISTRATION, DEPARTMENT OF COMMERCE (CONTINUED) SHELLFISH FISHERIES OF THE EXCLUSIVE ECONOMIC ZONE OFF ALASKA General § 680.6 Crab economic data report (EDR). Persons participating in the CR crab fisheries are...

50 CFR 680.6 - Crab economic data report (EDR).

Code of Federal Regulations, 2012 CFR

2012-10-01

... 50 Wildlife and Fisheries 13 2012-10-01 2012-10-01 false Crab economic data report (EDR). 680.6... ADMINISTRATION, DEPARTMENT OF COMMERCE (CONTINUED) SHELLFISH FISHERIES OF THE EXCLUSIVE ECONOMIC ZONE OFF ALASKA General § 680.6 Crab economic data report (EDR). Persons participating in the CR crab fisheries are...

IN-SITU REDUCTION OF CHROMIUM-CONTAMINATED GROUNDWATER, SOILS, AND SEDIMENTS BY SODIUM DITHIONITE

EPA Science Inventory

Laboratory studies were conducted to characterize the extent of chromium contamination in the groundwater and underlying soils and sediments of a chrome-plating shop at the USCG Support Center near Elizabeth City, NC. Most of the mobile Cr(VI) is present in the capillary zone ...

Efficient Multiple Genome Modifications Induced by the crRNAs, tracrRNA and Cas9 Protein Complex in Zebrafish

PubMed Central

Ohga, Rie; Ota, Satoshi; Kawahara, Atsuo

2015-01-01

The type II clustered regularly interspaced short palindromic repeats (CRISPR) associated with Cas9 endonuclease (CRISPR/Cas9) has become a powerful genetic tool for understanding the function of a gene of interest. In zebrafish, the injection of Cas9 mRNA and guide-RNA (gRNA), which are prepared using an in vitro transcription system, efficiently induce DNA double-strand breaks (DSBs) at the targeted genomic locus. Because gRNA was originally constructed by fusing two short RNAs CRISPR RNA (crRNA) and trans-activating crRNA (tracrRNA), we examined the effect of synthetic crRNAs and tracrRNA with Cas9 mRNA or Cas9 protein on the genome editing activity. We previously reported that the disruption of tyrosinase (tyr) by tyr-gRNA/Cas9 mRNA causes a retinal pigment defect, whereas the disruption of spns2 by spns2-gRNA1/Cas9 mRNA leads to a cardiac progenitor migration defect in zebrafish. Here, we found that the injection of spns2-crRNA1, tyr-crRNA and tracrRNA with Cas9 mRNA or Cas9 protein simultaneously caused a migration defect in cardiac progenitors and a pigment defect in retinal epithelial cells. A time course analysis demonstrated that the injection of crRNAs and tracrRNA with Cas9 protein rapidly induced genome modifications compared with the injection of crRNAs and tracrRNA with Cas9 mRNA. We further show that the crRNA-tracrRNA-Cas9 protein complex is functional for the visualization of endogenous gene expression; therefore, this is a very powerful, ready-to-use system in zebrafish. PMID:26010089

Role of Microbial Exopolymeric Substances (EPS) on Chromium Sorption and Transport in Heterogeneous Subsurface Soils: I. Cr(III) Complexation with EPS in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

C Kantar; H Demiray; N Dogan

2011-12-31

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Role of microbial exopolymeric substances (EPS) on chromium sorption and transport in heterogeneous subsurface soils: I. Cr(III) complexation with EPS in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kantar, C.; Dodge, C.; Demiray, H.

2011-01-26

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Use of Major- and Minor-Element Mapping to Measure Chemical Variability in Diogenite Pyroxenes

NASA Astrophysics Data System (ADS)

Spilde, M. N.; Papike, J. J.

1993-07-01

Diogenite orthopyroxene grains have been shown to exhibit chemical variability within individual meteorite samples, e.g., the population groups reported by Hewins [1]. Our previous work [2] has shown a great deal of inter- and intragrain variability in OPX. The Garland diogenite, for example, appears to have two distinct populations of OPX, based on Cr/Al ratios. However, within individual crystals, excursions of Cr/Al ratios are present that may span a wide range within each population group. We are presently conducting SIMS analysis of OPX in diogenites and, therefore, the chemical variability of analyzed pyroxenes must be completely determined in order to find that portion of the crystal that most accurately records the igneous, rather than the metamorphic history. Optical analysis alone is not sufficient to categorize the pyroxene crystals. For example, numerous grains in EET 83246 appear to be zoned, with changes in interference colors toward the rims. However, EDS mapping indicates that the rims are chemically similar to the cores; the interference colors are interpreted to be due to some sort of grain abrasion process that occurred during brecciation. Backscattered image mapping at low magnification can identify intergrain variations and gross intragrain chemical variations, but this must be followed up with more detailed elemental mapping. Our microprobe employs a Link (Oxford) eXL II analyzer with full-stage automation, so that we can combine EDS maps of major elements with WDS maps of minor elements (Al, Ti, Mn, Cr). Large area maps (>1 mm) are produced using stage rastering to avoid defocusing of the WDS spectrometers. In a final step, quantitative elemental maps of target grains are produced, whereby the characteristic X-ray intensity collected at each map pixel is background suppressed and fitted against a standard intensity to yield an apparent concentration. Appropriate standards, close to the composition of the mapped grain, are used such that the apparent concentration is close to the real (ZAF-corrected) concentration. A number of grains have been mapped in Roda, Garland, EET 83246 and LEW 88008. Except for Garland, OPX grains are relatively homogeneous. Some large Roda grains show very fine (100) augite lamellae along with small augite blebs and scattered spinel along relict grain boundaries. Orthopyroxenes in Garland exhibit rare zoning and thin augite lamellae. Both symmetrical and asymmetrical zoning are evident in elemental maps; an example of nearly symmetrical zoning is shown in the Fe and Mg quantitative maps in Fig. 1, which appears in the hard copy (note a companion abstract [3] that illustrates a microprobe traverse across this grain). In addition, some grains show evidence of partial relict rims, indicating that the grains are brecciated fragments of larger, zoned grains. These brecciated pieces may explain some, but not all, of the intragrain variability seen in Garland. Because Cr decreases toward the rim while Al remains relatively constant, those fragments from the grain core will have higher Cr/Al ratios than fragments from the rim. Acknowledgment: This research was supported by NASA Grant NAGW-3347 and the Institute of Meteoritics. References: [1] Hewins R. (1980) LPSC XI, 441-443. [2] Papike J. J. et al. (1993) LPSC XXIV, 1109-110. [3] Papike J. J. and Spilde M. N. (1993), this volume.

Segregation Coefficients of Impurities in Selenium by Zone Refining

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Sha, Yi-Gao

1998-01-01

The purification of Se by zone refining process was studied. The impurity solute levels along the length of a zone-refined Se sample were measured by spark source mass spectrographic analysis. By comparing the experimental concentration levels with theoretical curves the segregation coefficient, defined as the ratio of equilibrium concentration of a given solute in the solid to that in the liquid, k = x(sub s)/x(sub l) for most of the impurities in Se are found to be close to unity, i.e., between 0.85 and 1.15, with the k value for Si, Zn, Fe, Na and Al greater than 1 and that for S, Cl, Ca, P, As, Mn and Cr less than 1. This implies that a large number of passes is needed for the successful implementation of zone refining in the purification of Se.

Evaluation of the effects of chromium supplementation on growth and nitrogen balance of camel calves under summer conditions.

PubMed

Abdoun, Khalid Ahmed; Alsofi, Mohamed Abdulwahed; Samara, Emad Mohamed; Alhidary, Ibrahim Abdullah; Okab, Aly Bassuny; Al-Haidary, Ahmed Abraheem

2015-03-01

One of the most important problems in the production of camels in arid and semi-arid zones is the reduced feed intake and consequent low growth rate during summer. Under these stressful environmental conditions, chromium (Cr) supplementation to the diet of growing camel calves may be beneficial. Therefore, the objective of this study was to evaluate the effects of feeding a diet supplemented with different levels of Cr on growth performance of camel calves reared in a hot arid environment. A total of 15 male camel calves (4-5-month-old, 123 ± 7 kg body weight) were used in this study. The animals were divided into three equal groups (A, B, C), 5 animals each, and housed individually under shelter. Camel calves were fed ad libitum on either total mixed ration (TMR) without Cr supplementation (group A), TMR supplemented with 0.5 mg Cr/kg DM (group B), or TMR supplemented with 1.0 mg Cr/kg DM (group C). Supplementation of 0.5 mg Cr/kg DM to the diet of camel calves did not alter feed intake, however, increased not significantly (P = 0.086) average daily gain (ADG) and N retention. Plasma cortisol level was reduced by 10%, and feed utilization efficiency was improved by 12% in 0.5 mg Cr/kg DM-supplemented group compared to the control. Thus, 0.5 mg Cr/kg DM dietary supplementation to camel calves reared under hot summer condition increased weight gain by 17% and reduced feeding cost of producing a unit of weight by 11%.

Microstructure and mechanical properties of FeCrAl alloys under heavy ion irradiations

NASA Astrophysics Data System (ADS)

Aydogan, E.; Weaver, J. S.; Maloy, S. A.; El-Atwani, O.; Wang, Y. Q.; Mara, N. A.

2018-05-01

FeCrAl ferritic alloys are excellent cladding candidates for accident tolerant fuel systems due to their high resistance to oxidation as a result of formation of a protective Al2O3 scale at high temperatures in steam. In this study, we report the irradiation response of the 10Cr and 13Cr FeCrAl cladding tubes under Fe2+ ion irradiation up to ∼16 dpa at 300 °C. Dislocation loop size, density and characteristics were determined using both two-beam bright field transmission electron microscopy and on-zone scanning transmission electron microscopy techniques. 10Cr (C06M2) tube has a lower dislocation density, larger grain size and a slightly weaker texture compared to the 13Cr (C36M3) tube before irradiation. After irradiation to 0.7 dpa and 16 dpa, the fraction of <100> type sessile dislocations decreases with increasing Cr amount in the alloys. It has been found that there is neither void formation nor α‧ precipitation as a result of ion irradiations in either alloy. Therefore, dislocation loops were determined to be the only irradiation induced defects contributing to the hardening. Nanoindentation testing before the irradiation revealed that the average nanohardness of the C36M3 tube is higher than that of the C06M2 tube. The average nanohardness of irradiated tube samples saturated at 1.6-2.0 GPa hardening for both tubes between ∼3.4 dpa and ∼16 dpa. The hardening calculated based on transmission electron microscopy was found to be consistent with nanohardness measurements.

Microstructure and mechanical properties of FeCrAl alloys under heavy ion irradiations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aydogan, E.; Weaver, J. S.; Maloy, S. A.

FeCrAl ferritic alloys are excellent cladding candidates for accident tolerant fuel systems due to their high resistance to oxidation as a result of formation of a protective Al 2O 3 scale at high temperatures in steam. In this study, we report the irradiation response of the 10Cr and 13Cr FeCrAl cladding tubes under Fe 2+ ion irradiation up to ~16 dpa at 300 °C. Dislocation loop size, density and characteristics were determined using both two beam bright field transmission electron microscopy and on-zone scanning transmission electron microscopy techniques. 10Cr (C06M2) tube has a lower dislocation density, larger grain size andmore » a slightly weaker texture compared to the 13Cr (C36M3) tube before irradiation. After irradiation to 0.7 dpa and 16 dpa, the fraction of <100> type sessile dislocations decreases with increasing Cr amount in the alloys. It has been found that there is neither void formation nor α' precipitation as a result of ion irradiations in either alloy. Therefore, dislocation loops were determined to be the only irradiation induced defects contributing to the hardening. Nanoindentation testing before the irradiation revealed that the average nanohardness of the C36M3 tube is higher than that of the C06M2 tube. The average nanohardness of irradiated tube samples saturated at 1.6-2.0 GPa hardening for both tubes between ~3.4 dpa and ~16 dpa. The hardening calculated based on transmission electron microscopy was found to be consistent with nanohardness measurements.« less

Microstructure and mechanical properties of FeCrAl alloys under heavy ion irradiations

DOE PAGES

Aydogan, E.; Weaver, J. S.; Maloy, S. A.; ...

2018-03-02

FeCrAl ferritic alloys are excellent cladding candidates for accident tolerant fuel systems due to their high resistance to oxidation as a result of formation of a protective Al 2O 3 scale at high temperatures in steam. In this study, we report the irradiation response of the 10Cr and 13Cr FeCrAl cladding tubes under Fe 2+ ion irradiation up to ~16 dpa at 300 °C. Dislocation loop size, density and characteristics were determined using both two beam bright field transmission electron microscopy and on-zone scanning transmission electron microscopy techniques. 10Cr (C06M2) tube has a lower dislocation density, larger grain size andmore » a slightly weaker texture compared to the 13Cr (C36M3) tube before irradiation. After irradiation to 0.7 dpa and 16 dpa, the fraction of <100> type sessile dislocations decreases with increasing Cr amount in the alloys. It has been found that there is neither void formation nor α' precipitation as a result of ion irradiations in either alloy. Therefore, dislocation loops were determined to be the only irradiation induced defects contributing to the hardening. Nanoindentation testing before the irradiation revealed that the average nanohardness of the C36M3 tube is higher than that of the C06M2 tube. The average nanohardness of irradiated tube samples saturated at 1.6-2.0 GPa hardening for both tubes between ~3.4 dpa and ~16 dpa. The hardening calculated based on transmission electron microscopy was found to be consistent with nanohardness measurements.« less

Successive reactive liquid flow episodes in a layered intrusion (Unit 9, Rum Eastern Layered Intrusion, Scotland)

NASA Astrophysics Data System (ADS)

Leuthold, Julien; Blundy, Jon; Holness, Marian

2014-05-01

We will present a detailed microstructural and geochemical study of reactive liquid flow in Unit 9 of the Rum Eastern Layered Intrusion. In the study region, Unit 9 comprises an underlying lens-like body of peridotite overlain by a sequence of troctolite and gabbro (termed allivalite), with some local and minor anorthosite. The troctolite is separated from the overlying gabbro by a distinct, sub-horizontal, undulose horizon (the major wavy horizon). Higher in the stratigraphy is another, similar, horizon (the minor wavy horizon) that separates relatively clinopyroxene-poor gabbro from an overlying gabbro. To the north of the peridotite lens, both troctolite and gabbro grade into poikilitic gabbro. Clinopyroxene habit in the allivalite varies from thin rims around olivine in troctolite, to equigranular crystals in gabbro, to oikocrysts in the poikilitic gabbro. The poikilitic gabbros contain multiple generations of clinopyroxene, with Cr-rich (~1.1 wt.% Cr2O3), anhedral cores with moderate REE concentrations (core1) overgrown by an anhedral REE-depleted second generation with moderate Cr (~0.7 wt.% Cr2O3) (core2). These composite cores are rimmed by Cr-poor (~0.2 wt.% Cr2O3) and REE-poor to moderate clinopyroxene. We interpret these microstructures as a consequence of two separate episodes of partial melting triggered by the intrusion of hot olivine-phyric picrite to form the discontinuous lenses that comprise the Unit 9 peridotite. Loss of clinopyroxene-saturated partial melt from the lower part of the allivalite immediately following the early stages of sill intrusion resulted in the formation of clinopyroxene-poor gabbro. The spatial extent of clinopyroxene loss is marked by the minor wavy horizon. A further partial melting event stripped out almost all clinopyroxene from the lowest allivalite, to form a troctolite, with the major wavy horizon marking the extent of melting during this second episode. The poikilitic gabbro formed from clinopyroxene-saturated melt moving upwards and laterally through the cumulate pile. The Rum layered intrusion is an open intrusive complex, composed of individual partially molten zones, evolving independently. The Rum layered intrusion offers a direct overview of processes taking place in shallow intra-plate and ridge magma chambers. Intrusion of hot magma into a pre-existing cumulate pile results in the modification both the incoming liquid and the host-rock cumulates. Our study highlights the necessity of considering this type of process when modelling the geochemistry of lavas erupted from magma chambers subject to repeated replenishment.

Nano iron oxide impregnated in chitosan bead as a highly efficient sorbent for Cr(VI) removal from water.

PubMed

Lu, Jianbo; Xu, Kai; Yang, Jinmei; Hao, Yarong; Cheng, Fang

2017-10-01

Using Fe(III) salts and chitosan, nano iron oxide impregnated in chitosan bead (NIOC) was successfully synthesized for aqueous Cr(VI) detoxification via sol-gel technique without any additional crosslinking agent. NIOC characterization demonstrated that the iron in NIOC mainly existed as nano akaganeite (β-FeOOH) and complex with chitosan. Intraparticle diffusion was the major rate-limiting step. The maximal adsorption capacity was 69.8mg/g (pH 5.0, 20°C). Normal concentration of coexisting anions (SO 4 2- , CO 3 2- , SiO 3 2 -) showed insignificant competition, whereas PO 4 3- suppressed the Cr(VI) sorption. Cr(VI)-loaded NIOC could be effectively regenerated by alkaline solutions. Column adsorption runs using granular NIOC could effectively treat about 1600 bed volumes of Cr(VI) solution (from 3.7mg Cr/L in influent to <0.5mg Cr/L in effluent). The Cr(VI) removal mechanisms involved the direct sorption of Cr(VI) (electrostatic attraction and ligand exchange), reduction of Cr(VI) into Cr(III) and re-sorption of Cr(III) via chelation on NIOC surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dynamics of a Cr spin in a semiconductor quantum dot: Hole-Cr flip-flops and spin-phonon coupling

NASA Astrophysics Data System (ADS)

Lafuente-Sampietro, A.; Utsumi, H.; Sunaga, M.; Makita, K.; Boukari, H.; Kuroda, S.; Besombes, L.

2018-04-01

A detailed analysis of the photoluminescence (PL) intensity distribution in singly Cr-doped CdTe/ZnTe quantum dots (QDs) is performed. First of all, we demonstrate that hole-Cr flip-flops induced by an interplay of the hole-Cr exchange interaction and the coupling with acoustic phonons are the main source of spin relaxation within the exciton-Cr complex. This spin flip mechanism appears in the excitation power dependence of the PL of the exciton as well as in the intensity distribution of the resonant PL. The resonant optical pumping of the Cr spin which was recently demonstrated can also be explained by these hole-Cr flip-flops. Despite the fast exciton-Cr spin dynamics, an analysis of the PL intensity under magnetic field shows that the hole-Cr exchange interaction in CdTe/ZnTe QDs is antiferromagnetic. In addition to the Cr spin dynamics induced by the interaction with carriers' spin, we finally demonstrate using time resolved optical pumping measurements that a Cr spin interacts with nonequilibrium acoustic phonons generated during the optical excitation inside or near the QD.

Understanding the effects of Cr doping in rutile TiO2 by DFT calculations and X-ray spectroscopy.

PubMed

Vásquez, G Cristian; Maestre, David; Cremades, Ana; Ramírez-Castellanos, Julio; Magnano, Elena; Nappini, Silvia; Karazhanov, Smagul Zh

2018-06-07

The effects of Cr on local environment and electronic structure of rutile TiO 2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr Ti 0 and Cr Ti 1- as well as Cr-oxygen vacancy complex 2Cr Ti  + V O are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO 2 at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t 2g states of the Cr ions in order to reach the stable oxidation state of Cr 3+ . Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO 2 cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO 2 are very sensitive to the concentration of Cr.

Biosorption of Cr(VI) by coconut coir: spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material.

PubMed

Shen, Ying-Shuian; Wang, Shan-Li; Huang, Shiuh-Tsuen; Tzou, Yu-Min; Huang, Jang-Hung

2010-07-15

In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment. 2010 Elsevier B.V. All rights reserved.

Influence of compositional complexity on interdiffusion in Ni-containing concentrated solid-solution alloys

DOE PAGES

Jin, Ke; Zhang, Chuan; Zhang, Fan; ...

2018-03-07

To investigate the compositional effects on thermal-diffusion kinetics in concentrated solid-solution alloys, interdiffusion in seven diffusion couples with alloys from binary to quinary is systematically studied. The alloys with higher compositional complexity exhibit in general lower diffusion coefficients against homologous temperature, however, an exception is found that diffusion in NiCoFeCrPd is faster than in NiCoFeCr and NiCoCr. While the derived diffusion parameters suggest that diffusion in medium and high entropy alloys is overall more retarded than in pure metals and binary alloys, they strongly depend on specific constituents. The comparative features are captured by computational thermodynamics approaches using a self-consistentmore » database.« less

Time-resolved nonlinear optics in strongly correlated insulators

NASA Astrophysics Data System (ADS)

Dodge, J. Steven

2000-03-01

Transition metal oxides form the basis for much of our understanding of Mott insulators, and have enjoyed a renaissance of interest since the discovery of high temperature superconductivity in the cuprates. They are characterized by complex interactions among spin, lattice, orbital and charge degrees of freedom, which lead to dynamical behavior on time scales ranging from femtoseconds to microseconds. We have applied time resolved nonlinear optical spectroscopy to probe these dynamics. In one well-studied antiferromagnetic insulator, Cr_2O_3, we observed spin-wave dynamics on a picosecond time scale by performing pump-probe spectroscopy of the exciton-magnon transition(J. S. Dodge, et al.), Phys. Rev. Lett. 83, 4650 (1999).. At excitation densities ~ 10-3/Cr, a lineshape associated with the exciton-magnon absorption appears in the pump-probe spectrum. We assign this nonlinearity to a time-dependent renormalization of the magnon band structure, which in turn modifies the lineshape of the exciton-magnon transition. At long time delays, this assignment agrees semiquantitatively with calculations based on spin-wave theory. However, the initial population at the zone-boundary induces surprisingly little renormalization effect, indicating that spin-wave theory is insufficient to describe our observations in this regime. The renormalization lineshape grows on a time scale of ~ 50 ps, which we associate with the decay of the photoexcited, nonequilibrium population of zone-boundary spin-waves into a thermalized population of zone-center spin-waves. We have also performed a study of the linear and nonlinear optical properties of Sr_2CuO_2Cl_2, an insulating, two-dimensional cuprate. In the nonlinear optical experiments, we have performed pump-probe spectroscopy over a 1 eV spectral range, varying both the pump and the probe energy. We observe a pump-probe lineshape which varies considerably as a function of pump energy and temperature, and which differs sharply from those typically observed in band insulators. At low-temperatures, in particular, we observe an overall increase of spectral weight in our probe range, indicating that states are shifting over an energy scale larger than 1 eV. We attribute this behavior to the strongly correlated nature of the electronic structure in this material. Studies of the elementary excitations in other magnetic oxides, currently in progress, will be discussed.

Lithium Zoning in Kīlauea Olivine: Growth vs. Diffusion?

NASA Astrophysics Data System (ADS)

Shea, T.; Lynn, K. J.; Garcia, M. O.; Costa Rodriguez, F.

2016-12-01

Lithium is a fast-diffusing element with the potential to characterize magmatic processes that occur on timescales of hours to days [1]. However, Li diffusion in olivine is complex. Experimental studies show that it can diffuse via two paths: a `fast' interstitial mechanism and a `slow' vacancy mechanism [1]. Charge balancing relationships with other incompatible trace elements may also play a role in Li diffusion [2]. A detailed study of lithium zoning in natural olivine was undertaken to better understand how Li is correlated with other trace elements and determine if Li diffusion profiles can be used to extract meaningful timescales of magmatic processes. Olivine crystals from the Keanakāko`i explosive period at Kīlauea Volcano (HI) were used in this study because (a) the lavas and tephra generally contain phenocrysts of only olivine in a rapidly quenched glass, which avoid complications of multi-phase systems and post-eruptive diffusion; (b) we previously constrained the magmatic histories of these crystals using major and minor elements; and (c) at concentrations (e.g. 1-10 ppm) and temperatures (e.g. 1150-1250 °C) typical of Kīlauea basalts, Li diffusion is probably dominated by the vacancy mechanism [1]. Euhedral crystals were carefully oriented and mounted on either the a- or b- crystallographic axes (c-axis is always within the plane of section) and polished to the crystal core. High precision LA-ICP-MS analyses of Li (2σ = 0.08 ppm), Na, Al, P, and Cr complement EPMA profiles of Si, Mg, Fe, Ni, and Ca (200 nA current). Core-to-rim transects were collected along two axes (c and a or b) to identify potential diffusion anisotropy effects for Li and other elements. Li zoning is correlated with Na, indicative of a growth signature (also observed for Al, P, and Cr), or is decoupled from incompatible trace elements and have profiles that indicate diffusive re-equilibration. Modeling of Li diffusion profiles yields timescales of hours to days, which probably represent the final stages of magma transport from crustal magma reservoirs and allow ascent rates to be estimated. [1] Dohmen et al. (2010), Geochimica et Cosmochimica Acta, 74, 274-292. [2] Spandler and O'Neill (2010), Contributions to Mineralogy and Petrology, 159, 791-818.

CX3CR1 Deficiency Alters Hippocampal-Dependent Plasticity Phenomena Blunting the Effects of Enriched Environment

PubMed Central

Maggi, Laura; Scianni, Maria; Branchi, Igor; D’Andrea, Ivana; Lauro, Clotilde; Limatola, Cristina

2011-01-01

In recent years several evidence demonstrated that some features of hippocampal biology, like neurogenesis, synaptic transmission, learning, and memory performances are deeply modulated by social, motor, and sensorial experiences. Fractalkine/CX3CL1 is a transmembrane chemokine abundantly expressed in the brain by neurons, where it modulates glutamatergic transmission and long-term plasticity processes regulating the intercellular communication between glia and neurons, being its specific receptor CX3CR1 expressed by microglia. In this paper we investigated the role of CX3CL1/CX3CR1 signaling on experience-dependent hippocampal plasticity processes. At this aim wt and CX3CR1GFP/GFP mice were exposed to long-lasting-enriched environment (EE) and the effects on hippocampal functions were studied by electrophysiological recordings of long-term potentiation of synaptic activity, behavioral tests of learning and memory in the Morris water maze paradigm and analysis of neurogenesis in the subgranular zone of the dentate gyrus (DG). We found that CX3CR1 deficiency increases hippocampal plasticity and spatial memory, blunting the potentiating effects of EE. In contrast, exposure to EE increased the number and migration of neural progenitors in the DG of both wt and CX3CR1GFP/GFP mice. These data indicate that CX3CL1/CX3CR1-mediated signaling is crucial for a normal experience-dependent modulation of hippocampal functions. PMID:22025910

Are starburst galaxies proton calorimeters?

NASA Astrophysics Data System (ADS)

Wang, Xilu; Fields, Brian D.

2018-03-01

Several starburst galaxies have been observed in the GeV and TeV bands. In these dense environments, gamma-ray emission should be dominated by cosmic ray (CR) interactions with the interstellar medium (pcrpism → π0 → γγ). Indeed, starbursts may act as proton `calorimeters' where a substantial fraction of CR energy input is emitted in gamma-rays. Here, we build a one-zone, `thick-target' model implementing calorimetry and placing a firm upper bound on gamma-ray emission from CR interactions. The model assumes that CRs are accelerated by supernovae (SNe), and all suffer nuclear interactions rather than escape. Our model has only two free parameters: the CR proton acceleration energy per SN ɛcr, and the proton injection spectral index s. We calculate the pionic gamma-ray emission from 10 MeV to 10 TeV, and derive thick-target parameters for six galaxies with Fermi, H.E.S.S., and/or VERITAS data. Our model provides good fits for the M82 and NGC 253, and yields ɛcr and s values suggesting that SN CR acceleration is similar in starbursts and in our Galaxy. We find that these starbursts are indeed nearly if not fully proton calorimeters. For NGC 4945 and NGC 1068, the models are consistent with calorimetry but are less well-constrained due to the lack of TeV data. However, the Circinus galaxy and the ultra-luminous infrared galaxy Arp 220 exceed our pionic upper-limit; possible explanations are discussed.

Alloy Design of Martensitic 9Cr-Boron Steel for A-USC Boiler at 650 °C — Beyond Grades 91, 92 and 122

NASA Astrophysics Data System (ADS)

Abe, Fujio; Tabuchi, M.; Tsukamoto, S.

Boundary hardening is shown to be the most important strengthening mechanism in creep of tempered martensitic 9% Cr steel base metal and welded joints at 650 °C. The enrichment of soluble boron near prior austenite grain boundaries (PAGBs) by the GB segregation is essential for the reduction of coarsening rate of M23C6 carbides near PAGBs, enhancing the boundary and sub-boundary hardening near PAGBs, and also for the change in α/γ transformation behavior in heat-affected-zone (HAZ) of welded joints during heating of welding, producing the same microstructure in HAZ as in the base metal. Excess addition of nitrogen to the 9Cr-boron steel promotes the formation of boron nitrides during normalizing heat treatment, which consumes most of soluble boron and degrades the creep strength. A NIMS 9Cr steel (MARBN; Martensitic 9Cr steel strengthened by boron and MX nitrides) with 120-150 ppm boron and 60-90 ppm nitrogen, where no boron nitride forms during normalizing heat treatment, exhibits not only much higher creep strength of base metal than Grades 91, 92 and 122 but also substantially no degradation in creep strength due to Type IV fracture in HAZ of welded joints at 650°C. The protective Cr2O3-rich scale forms on the surface of 9Cr steel by pre-oxidation treatment in Ar gas, which significantly improves the oxidation resistance in steam at 650°C.

Ligational behavior of clioquinol antifungal drug towards Ag(I), Hg(II), Cr(III) and Fe(III) metal ions: Synthesis, spectroscopic, thermal, morphological and antimicrobial studies

NASA Astrophysics Data System (ADS)

El-Megharbel, Samy M.; Refat, Moamen S.

2015-04-01

This article presents a synthesis, characterization, theoretical and biological (anti-bacterial, and anti-fugal) evaluation studies of Ag(I), Hg(II), Cr(III) and Fe(III) complexes of clioquinol (CQ) drug ligand. Structures of the titled complexes cited herein were discussed using elemental analyses and spectral measurements e.g., IR, 1H NMR, and electronic studies. The results confirmed the formation of the clioquinol complexes by three molar ratios (1:1) for Ag(I), (1:2) for Hg(II) and (1:3) for both Cr(III) and Fe(III) metal ions. The clioquinol reacts as a bidentate chelate bound to all respected metal ions through the oxygen and nitrogen of quinoline-8-ol. The metal(II) ions coordinated to clioquinol ligand through deprotonation of sbnd OH terminal group. Infrared and 1H NMR spectral data confirm that coordination is via the oxygen of phenolic group and nitrogen atom of quinoline moiety. The molar conductance measurements of the CQ complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ag(CQ)(H2O)2] H2O, [Hg(CQ)2]ṡ2H2O, [Cr(CQ)3] and [Fe(CQ)3]H2O. The Coats-Redfern method, the kinetic thermodynamic parameters like activation energies (E∗), entropies (ΔS∗), enthalpies (ΔH∗), and Gibbs free energies (ΔG∗) of the thermal decomposition reactions have been deduced from thermogravimetric curves (TG) with helpful of differential thermo gravimetric (DTG) curves. The narrow size distribution in nano-scale range for the clioquinol complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM), and X-ray energy dispersive spectrometer (EDX) analyzer.

Synthesis and spectroscopic studies of biologically active compounds derived from oxalyldihydrazide and benzil, and their Cr(III), Fe(III) and Mn(III) complexes.

PubMed

Singh, D P; Kumar, Ramesh; Singh, Jitender

2009-04-01

A new series of complexes have been synthesized by template condensation of oxalyldihydrazide and benzil in methanolic medium in the presence of trivalent chromium, manganese and iron salts forming complexes of the type [M(C(32)H(24)N(8)O(4))X]X(2) where M = Cr(III), Mn(III), Fe(III) and X = Cl(-1), NO(3)(-1), CH(3)COO(-1). The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility measurements, electronic, NMR, infrared and far infrared spectral studies. On the basis of these studies, a five coordinate square pyramidal geometry has been proposed for all these complexes. The biological activities of the metal complexes have been tested in vitro against a number of pathogenic bacteria to assess their inhibiting potential. Some of these complexes have been found to exhibit remarkable antibacterial activities.

Design and synthesis of single-source molecular precursors to homogeneous multi-component oxide materials

NASA Astrophysics Data System (ADS)

Fujdala, Kyle Lee

This dissertation describes the syntheses of single-source molecular precursors to multi-component oxide materials. These molecules possess a core metal or element with various combinations of -OSi(O tBu)3, -O2P(OtBu) 2, and -OB[OSi(OtBu)3] 2 ligands. Such molecules decompose under mild thermolytic conditions (<200°C) to provide homogeneous carbon-free materials via the elimination of isobutylene and water. A gel is formed when thermolyses are performed in non-polar solvents, and subsequent drying of the gel in a conventional manner yields high surface area xerogels. This thermolytic molecular precursor (TMP) approach has been utilized to provide a variety of oxide materials with tailored properties. In addition, the oxygen rich environment of the molecular precursors coupled with the presence of M-O-E heterolinkages permits use of them as models for oxide-supported metal species and multi-component oxides. Significantly, the first complexes to contain three or more heteroelements suitable for use in the TMP method have been synthesized. Compounds for use as single-source molecular precursors have been synthesized containing Al, B, Cr, Hf, Mo, V, W, and Zr, and their thermal transformations have been examined. Heterogeneous catalytic reactions have been examined for selected materials. Also, cothermolyses of molecular precursors and additional molecules (i.e., metal alkoxides) have been utilized to provide materials with several components for potential use as catalysts or catalyst supports. Reactions of one and two equivs of HOSi(OtBu) 3 with Cr(OtBu)4 afforded the first Cr(IV) alkoxysiloxy complexes (tBuO) 3CrOSi(OtBu)3 and ( tBuO)2Cr[OSi(OtBu) 3]2, respectively. The high-yielding, convenient synthesis of (tBuO)3CrOSi(O tBu)3 make this complex a useful single-source molecular precursor, via the TMP method, to Cr/Si/O materials. The thermal transformations of (tBuO)3CrOSi(O tBu)3 and (tBuO) 2Cr[OSi(OtBu)3]2 to chromia-silica materials occurr at low temperatures (≤180°C), to give isobutene as the major carbon-containing product. The material generated from the solid-state conversion of (tBuO) 3CrOSi(OtBu)3 (CrOS ss) has an unexpectedly high surface area of 315 m2 g-1 that is slightly reduced to 275 m2 g-1 after calcination at 500°C in O2. The xerogel obtained by the thermolysis of an n-octane solution of (tBuO)3CrOSi(O tBu)3 (CrOSixg) has a surface area of 315 m2 g-1 that is reduced to 205 m2 g-1 upon calcination at 500°C. Powder X-ray diffraction (PXRD) analysis revealed that Cr2O 3 is the only crystalline species present in CrOSiss and CrOSixg after calcination at temperatures up to 1200°C in O2. (Abstract shortened by UMI.)

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

USGS Publications Warehouse

Tuttle, M.L.; Dean, W.E.; Parduhn, N.L.

1983-01-01

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

Distribution of metals in various particle-size fractions in topsoils of a small dry valley system (European Russia, forest zone)

NASA Astrophysics Data System (ADS)

Samonova, Olga; Aseyeva, Elena

2017-04-01

A detailed study of heavy metals distribution in various soil grain-size fractions helps to increase the knowledge about the complex nature of metals' occurrence and their distribution pathways in the environment. On the basis of particle size fractionation of topsoil horizons we examined the specific behavior of heavy metals in a small erosional landform located in the humid temperate zone of the Russian Plain. The object of the study is a 400 m small U-shaped dry valley (balka in Russian) with a catchment area of 32.8 ha located in the central part of the Protva river basin, 100 km southwest of Moscow. The uppermost parts of the landform are incised in Late Pleistocene loessial loams, which cover significant portions of interfluve area in the region, while the middle and the lower parts cut through Middle Pleistocene glacial sediments. A total of 50 samples were collected from topsoil horizons of different landform geomorphic units along three cross-sections as well as along the bottom of the landform and its detrital fan. Samples were analyzed for Mn, Cu, Ni, Co, Cr, Zn, Pb, Ti, Zr, and Fe content. Eleven samples were chosen for physical fractionation into 5 grain-size fractions (1-0.25 mm, 0.25-0.05 mm, 0.05-0.01 mm, 0.01-0.001 mm and <0.001 mm) and further analysis for fractionized metal contents. Across the grain-size fractions the maximum Zr content was observed in the coarse silt fraction and Ti - in the medium and fine silt fraction, while other metals, such as Fe, Mn, Co, Ni, Cr, Pb, and Zn revealed their highest concentrations in the clay fraction. For Fe, Mn, Co and Ni a second concentration peak was observed in the coarse and medium sand fraction. Due to probably eolian genesis and (or) transformation during weathering, the coarse silt fraction in comparison to other fractions showed a depletion of the majority of metals while the minimum concentrations of Ti, Zr and Cr were limited to the coarse and medium sand. Statistical analysis showed that the variation of metal contents depends on particle sizes: the Cv coefficients calculated for Cu, Ni, Co, Fe, Mn, Ti and Zr reach their maximum in the 1-0.25 mm fraction (for Cu and Ni exceeding 75%, for Ti, Zr being around 40%). For Zn, Cr and Pb the maximum variation (50-60%) was found in the 0.25-0.05 mm fraction. In contrast, the two studied silt fractions and also the clay showed very low variations of all metal contents (except for Mn) characteristically in the range between 6% (Cr) and 23.5% (Zn). Unlike the finer fractions, which displayed very poor geochemical differentiation across the landform's geomorphic units, the coarser (sand) fractions showed distinct spatial patterns in the elements' distribution, possibly related to migration processes, the depletion of metals in the landforms' slopes and their prevalent enrichment in the bottom unit is observed.

Strike-slip linked core complexes: A new kinematic model of basement rock exhumation in a crustal-scale fault system

NASA Astrophysics Data System (ADS)

Meyer, Sven Erik; Passchier, Cees; Abu-Alam, Tamer; Stüwe, Kurt

2014-05-01

Metamorphic core complexes usually develop as extensional features during continental crustal thinning, such as the Basin and Range and the Aegean Terrane. The Najd fault system in Saudi Arabia is a 2000 km-long and 400 km-wide complex network of crustal-scale strike-slip shear zones in a Neoproterozoic collision zone. Locally, the anastomosing shear zones lead to exhumation of lower crustal segments and represent a new kinematic model for the development of core complexes. We report on two such structures: the Qazaz complex in Saudi Arabia and the Hafafit complex in Egypt. The 15 km-wide Qazaz complex is a triangular dome of gently dipping mylonitic foliations within the 140 km-long sinistral strike-slip Qazaz mylonite zone. The gneissic dome consists of high-grade rocks, surrounded by low-grade metasediments and metavolcanics. The main SE-trending strike-slip Qazaz shear zone splits southwards into two branches around the gneiss dome: the western branch is continuous with the shallow dipping mylonites of the dome core, without overprinting, and changes by more than 90 degrees from a NS-trending strike-slip zone to an EW-trending 40 degree south-dipping detachment that bounds the gneiss dome to the south. The eastern SE-trending sinistral strike-slip shear zone branch is slightly younger and transects the central dome fabrics. The gneiss dome appears to have formed along a jog in the strike-slip shear zone during 40 km of horizontal strike-slip motion, which caused local exhumation of lower crustal rocks by 25 km along the detachment. The eastern shear zone branch formed later during exhumation, transacted the gneiss dome and offset the two parts by another 70 km. The Hafafit core complex in Egypt is of similar shape and size to the Qazaz structure, but forms the northern termination of a sinistral strike-slip zone that is at least 100 km in length. This zone may continue into Saudi Arabia as the Ajjaj shear zone for another 100 km. The NW trending strike slip mylonite zone grades into a gently N-dipping detachment to the west which accommodated strike slip by exhumation of high-grade lower crustal rocks. The Qazaz and the Hafafit Domes are similar, mirror-image structures with small differences in the accommodating shear zones. It is likely that these types of strike-slip related oblique core complexes are common in the Arabian Nubian shield, and possibly elsewhere.

Influence of coronal mass ejections on parameters of high-speed solar wind: a case study

NASA Astrophysics Data System (ADS)

Shugay, Yulia; Slemzin, Vladimir; Rodkin, Denis; Yermolaev, Yuri; Veselovsky, Igor

2018-05-01

We investigate the case of disagreement between predicted and observed in-situ parameters of the recurrent high-speed solar wind streams (HSSs) existing for Carrington rotation (CR) 2118 (December 2011) in comparison with CRs 2117 and 2119. The HSSs originated at the Sun from a recurrent polar coronal hole (CH) expanding to mid-latitudes, and its area in the central part of the solar disk increased with the rotation number. This part of the CH was responsible for the equatorial flank of the HSS directed to the Earth. The time and speed of arrival for this part of the HSS to the Earth were predicted by the hierarchical empirical model based on EUV-imaging and the Wang-Sheeley-Arge ENLIL semi-empirical replace model and compared with the parameters measured in-situ by model. The predicted parameters were compared with those measured in-situ. It was found, that for CR 2117 and CR 2119, the predicted HSS speed values agreed with the measured ones within the typical accuracy of ±100 km s-1. During CR 2118, the measured speed was on 217 km s-1 less than the value predicted in accordance with the increased area of the CH. We suppose that at CR 2118, the HSS overtook and interacted with complex ejecta formed from three merged coronal mass ejections (CMEs) with a mean speed about 400 km s-1. According to simulations of the Drag-based model, this complex ejecta might be created by several CMEs starting from the Sun in the period between 25 and 27 December 2011 and arriving to the Earth simultaneously with the HSS. Due to its higher density and magnetic field strength, the complex ejecta became an obstacle for the equatorial flank of the HSS and slowed it down. During CR 2117 and CR 2119, the CMEs appeared before the arrival of the HSSs, so the CMEs did not influence on the HSSs kinematics.

Development and application of a method for Cr(III) determination in dairy products by HPLC-ICP-MS.

PubMed

Hernandez, Fanny; Jitaru, Petru; Cormant, Florence; Noël, Laurent; Guérin, Thierry

2018-02-01

This study describes the development of an analytical approach for the determination of Cr(III) in dairy products by microwave assisted extraction, complexation in situ by ethylenediaminetetraacetate (EDTA) and high performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The extraction step was optimised by using an experimental design. A limit of quantification of 38µgkg -1 dry weight (d.w.) was obtained whereas the bias (%) measured ranged from 10 to 18%. The repeatability and intermediate precision varied between 1.2-5.0% and 7.5-13.5%, respectively. The method was applied to the analysis of several dairy samples beforehand characterized in terms of Cr(VI) and total chromium (Cr total ). Cr(III) concentrations ranged from <13 to 255µgkg -1 d.w. The results showed a good agreement between Cr(III) and Cr total concentration levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

Internal strains after recovery of hardness in tempered martensitic steels for fusion reactors

NASA Astrophysics Data System (ADS)

Brunelli, L.; Gondi, P.; Montanari, R.; Coppola, R.

1991-03-01

After tempering, with recovery of hardness, MANET steels present internal strains; these residual strains increase with quenching rate prior to tempering, and they remain after prolonged tempering times. On account of their persistence, after thermal treatments which lead to low dislocation and sub-boundary densities, the possibility has been considered that the high swelling resistance of MANET is connected with these centres of strain, probably connected with the formation, in ferrite, of Cr-enriched and contiguous Cr-depleted zones which may act as sinks for interstitials. Comparative observations on the internal strain behaviour of cold worked 316L stainless steel appear consistent with this possibility.

Opaque minerals as aids in distinguishing between source and sorting effects on beach sand mineralogy in southwestern Oregon.

USGS Publications Warehouse

Luepke, G.

1980-01-01

Source area and wave sorting effects can be separated on 4 Oregon beaches bounded by prominent headlands by studying the magnetic fraction of the sand. On 3 beaches the percentage of magnetite in the sand from the upper swash zone consistently increases toward the N end of each beach, apparently owing to selective sorting during littoral transport. However, the percentages of Cr and Ti in the magnetite are generally independent of sorting effects. Each beach appears to be characterized by a fairly distinct range of Ti/Cr in the magnetic fraction and the range differs from beach to beach. -from Author

Microstructure of a safe-end dissimilar metal weld joint (SA508-52-316L) prepared by narrow-gap GTAW

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ming, Hongliang

The microstructure, residual strain and interfacial chemical composition distribution of a safe-end dissimilar metal weld joint (DMWJ, SA508-52-316L) prepared by narrow-gap gas-tungsten arc welding (NG-GTAW) were studied by optical microscope (OM) and scanning electron microscope equipped with an energy dispersive X-ray microanalysis (SEM/EDX) and an electron back scattering diffraction (EBSD) system. Complex microstructure and chemical composition distribution are found, especially at the SA508-52 interface and the 52-316L interface. In brief, a complicated microstructure transition exists within the SA508 heat affected zone (HAZ); the residual strain, the fraction of high angle random grain boundaries and low angle boundaries decrease with increasingmore » the distance from the fusion boundary in 316L HAZ; neither typical type II boundary nor obvious carbon-depleted zone is found near the SA508-52 interface; dramatic and complicated changes of the contents of the main elements, Fe, Cr and Ni, are observed at the distinct interfaces, especially at the SA508-52 interface. No carbon concentration is found at the SA508-52 interface. - Highlights: •Residual strain and GBCD change as a function of the distance from FB in 316L HAZ. •Neither type II boundary nor obvious carbon-depleted zone is found in SA508 HAZ. •No carbon concentration is found at the SA508-52 interface. •The middle part of the DMWJ has the highest residual strain.« less

Aerobic oxidations catalyzed by chromium corroles.

PubMed

Mahammed, Atif; Gray, Harry B; Meier-Callahan, Alexandre E; Gross, Zeev

2003-02-05

Oxochromium(V) complexes of 5,10,15-tris(pentafluorophenyl)corrole and brominated derivatives oxygenate substrates (triphenylphosphine and norbornene) with concomitant production of chromium(III). Regeneration of CrVO by reaction of dioxygen with CrIII completes an aerobic catalytic cycle, with very large solvent effects; in acetonitrile, rapid initial turnovers observed initially are shut down by formation of CrIVO, while in toluene, THF, and methanol, relatively slow reactions are further inhibited by product formation.

Spectrophotometric and electrochemical study for metal ion binding of azocalix[4]arene bearing p-ethylester group

NASA Astrophysics Data System (ADS)

Kim, Tae Hyun

2017-05-01

The complexation behavior of diazophenylcalix[4]arene bearing para-ethylester group (p-EAC) for alkali, alkaline earth, various heavy and transition metal ions (Li+, Na+, K+, Rb+, Cs+, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Cr3 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 +, Pb2 +) was investigated by spectrophotometric and electrochemical methods in CH3CN. p-EAC exhibits decreased absorbance at 353 nm in the presence of Cr3 +, Fe2 +, Pb2 +, and Cu2 +. The spectra of p-EAC showed bathochromic shift in absorption maximum on the addition of Cr3 +, Fe2 +, or Pb2 + with decreasing order of absorbance (Cr3 + > Fe2 + > Pb2 +), and on the other hand, hypsochromic shift on the addition of Cu2 +. This leads to the selective coloration from light green to orange and colorless for Cr3 + and Cu2 + that can be detected by the naked eye, respectively. In electrochemistry experiments, p-EAC also showed two different types of voltammetric changes toward Cr3 +, Fe2 +, or Pb2 +, and toward Cu2 +, whereas no significant changes occurred in the presence of the other metal ions. Nonlinear fitting curve procedure was used to determine a logarithmic value of 5.20, 4.92, 3.54 and 4.80 for the stability constants of the complex of p-EAC with Cr3 +, Fe2 +, Pb2 +, and Cu2 +, respectively.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

PubMed

Rusanova, Julia A; Semenaka, Valentina V; Dyakonenko, Viktoriya V; Shishkin, Oleg V

2015-09-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands. The Cu(II) ion adopts a distorted square-pyramidal coordination while the Cr(III) ion has a distorted octa-hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O-H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two -CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1).

Effects of 200 keV Ar-ions irradiation on the structural and optical properties of reactively sputtered CrN films

NASA Astrophysics Data System (ADS)

Novaković, M.; Popović, M.; Zhang, K.; Rakočević, Z.; Bibić, N.

2016-12-01

Modification in structural and optical properties of chromium-nitride (CrN) films induced by argon ion irradiation and thermal annealings were investigated using various experimental techniques. CrN films deposited by d. c. reactive sputtering on Si substrate were implanted with 200 keV argon ions, at fluences of 5-20 × 1015 ions/cm2. As-implanted samples were then annealed in vacuum, for 2 h at 700 °C. Rutherford backscattering spectrometry, X-ray diffraction, cross-sectional (high-resolution) transmission electron microscopy and spectroscopic ellipsometry (SE) measurements were carried out in order to study structural and optical properties of the layers. After irradiation with 200 keV Ar ions a damaged surface layer of nanocrystalline structure was generated, which extended beyond the implantation profile, but left an undamaged bottom zone. Partial loss of columnar structure observed in implanted samples was recovered after annealing at 700 °C and CrN started to decompose to Cr2N. This layer geometry determined from transmission electron microscopy was inferred in the analysis of SE data using the combined Drude and Tauc-Lorentz model, and the variation of the optical bandgap was deduced. The results are discussed on the basis of the changes induced in the microstructure. It was found that the optical properties of the layers are strongly dependent on the defects' concentration of CrN.

Heterogeneous dislocation loop formation near grain boundaries in a neutron-irradiated commercial FeCrAl alloy

NASA Astrophysics Data System (ADS)

Field, Kevin G.; Briggs, Samuel A.; Hu, Xunxiang; Yamamoto, Yukinori; Howard, Richard H.; Sridharan, Kumar

2017-01-01

FeCrAl alloys are an attractive class of materials for nuclear power applications because of their increased environmental compatibility compared with more traditional nuclear materials. Preliminary studies into the radiation tolerance of FeCrAl alloys under accelerated neutron testing between 300 and 400 °C have shown post-irradiation microstructures containing dislocation loops and a Cr-rich α‧ phase. Although these initial studies established the post-irradiation microstructures, there was little to no focus on understanding the influence of pre-irradiation microstructures on this response. In this study, a well-annealed commercial FeCrAl alloy, Alkrothal 720, was neutron irradiated to 1.8 displacements per atom (dpa) at 382 °C and then the effect of random high-angle grain boundaries on the spatial distribution and size of a〈100〉 dislocation loops, a/2〈111〉 dislocation loops, and black dot damage was analyzed using on-zone scanning transmission electron microscopy. Results showed a clear heterogeneous dislocation loop formation with a/2〈111〉 dislocation loops showing an increased number density and size, black dot damage showing a significant number density decrease, and a〈100〉 dislocation loops exhibiting an increased size in the vicinity of the grain boundary. These results suggest the importance of the pre-irradiation microstructure and, specifically, defect sink density spacing to the radiation tolerance of FeCrAl alloys.

Microstructural characterization and electron backscatter diffraction analysis across the welded interface of duplex stainless steel

NASA Astrophysics Data System (ADS)

Zhang, Zhiqiang; Jing, Hongyang; Xu, Lianyong; Han, Yongdian; Gao, Zhanqi; Zhao, Lei; Zhang, Jianli

2017-08-01

The microstructural evolution, orientation relationships, boundary characteristics, grain type, local deformation, and microhardness across the welded interface of duplex stainless steel (DSS) were investigated. The DSS welded joint consisted of four typical zones: base metal (BM), low-temperature heat-affected zone (LTHAZ), high-temperature heat-affected zone (HTHAZ), and weld metal (WM). The apparent microstructural changes in the HTHAZ and LTHAZ were secondary austenite and Cr2N precipitation. A modified cooperative precipitation mechanism of secondary austenite and Cr2N at the interface was proposed. Furthermore, the ferrite in both the HTHAZ and LTHAZ maintained the same distribution as the ferrite texture in the BM, while this ferrite texture disappeared completely in the WM. Different austenite grains in the different zones exhibited different orientation relationships with the ferrite matrix. Special grain boundaries were mainly distributed between the austenite grains, while the ferrite grains primarily contained random grain boundaries. Austenite twins constituted the largest proportion of the special boundaries. The special austenite grain boundaries in the BM and LTHAZ were higher in relative frequency than those in the HTHAZ and WM. The ferrite grains in the HTHAZ and WM mainly consisted of substructured grains. In the BM, the recrystallization degree of ferrite was significantly lower than that of austenite grains. The local deformations were mainly generated in the grain boundaries and within the deformed grains. The HTHAZ exhibited the highest hardness, while the BM had the lowest hardness. The LTHAZ had a lower hardness than the HTHAZ and higher hardness than the BM.

Effect of friction on anodic polarization properties of metallic biomaterials.

PubMed

Okazaki, Yoshimitsu

2002-05-01

The effect of friction on the anodic polarization properties of metallic biomaterials in a physiological saline solution was investigated. The current density during friction becomes higher than during the static condition. The fluctuation range of the current density caused by the destruction and formation of passive film was observed. For SUS316L stainless steel and Co-Cr-Mo casting alloy, the fluctuation range was observed in the passivity zone. Otherwise, for Ti alloys, the fluctuation range was observed in both the activity and passivity zones. The decrease of the corrosion potential for Ti alloys due to friction was much larger than that of SUS316L stainless steel and Co-Cr-Mo casting alloy. From this result, it was considered that in a the frictional environment, the stressing zone turned anodic and its periphery cathodic, and corrosion tended to progress more than in the static environment. The effect of wear on the anodic polarization curves also changed depending on the frictional load, potential zone and the pH of the solution. A rapid increase in current density due to corrosion starting from the frictional area was found in the Ti-6Al-4V and Ti-15Mo-5Zr-3Al alloys containing Al. However, for the new Ti-15Zr-4Nb-4Ta alloy, this rapid increase was not seen in the high-potential region. The effect of the lateral reciprocal speed was also negligible for the new Ti alloy. It was found that the new Ti-15Zr-4Nb-4Ta alloy exhibited excellent corrosion resistance under friction.

Natural and anthropogenic controls on sediment composition of an arid coastal environment: Sharm Obhur, Red Sea, Saudi Arabia.

PubMed

Ghandour, I M; Basaham, A S; Basaham, S; Al-Washmi, H A; Al-Washmi, A; Masuda, H

2014-03-01

The present study investigated the natural and anthropogenic processes that control the composition of the bottom sediments of Sharm Obhur, Red Sea. Mineralogical analysis using XRD indicated that the sediments consist of carbonate and non-carbonate minerals. Elemental interrelationships allowed differentiating two groups of elements of different sources and origin. Elements that are in the same group are positively correlated, while they correlate negatively with elements of the other group. The first group includes silicon, Al, Fe, Mn, Mg, vanadium (V), chromium (Cr), Co, Ni, Cu, and Zn, whereas the other group includes Ca, Sr, and CaCO3. The highest concentration levels of the first group and the highest content of non-carbonate minerals were obtained from the sediments near the head of the sharm (zone A), whereas the sediments near the mouth of the sharm (zone B) yielded high concentrations of second group and carbonate minerals. Metal enrichment and contamination factors and pollution load index were calculated. The values of these indices differentiate two groups of metals: lithogenic and non-lithogenic. Except for lead (Pb) at one sampling site, metals in zone A sediments are of lithogenic source, supplied to the sharm either naturally by aeolian transportation and through Wadi Al-Kuraa'a during rare but major floods or by human activities such as dumping and shore protection. Non-lithogenic Cr, Pb, V, and Mn were documented from some sampling sites in zone B, and their occurrences are related to waste disposal and fossil fuel combustion.

Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

DOE PAGES

Liu, Xiaolei; Dong, Hailiang; Yang, Xuewei; ...

2017-09-23

Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe 2+ and pyrite. In this study, the effects of citrate on Cr(VI) reduction by structural Fe(II) in nontronite (NAu-2) were investigated at pH 6. Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction. The decreased rate was likely due to competitive sorption of citrate and anionic dichromate (Cr 2O 7–) to NAu-2 surface sites, because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction was likely becausemore » citrate served as an additional electron donor to reduce Cr(VI) through ligand-metal electron transfer in the presence of soluble Fe 3+, which was possibly derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was a possible form of reduced Cr(VI) when citrate was present. Without citrate, nanometer-sized Cr 2O 3 particles were the product of Cr(VI) reduction. In conclusion, our study highlights the importance of citrate on Cr(VI) reduction and immobilization when iron-rich smectite is applied to treat Cr(VI) contaminant in organic carbon rich environments.« less

Kinetic stable Cr isotopic fractionation between aqueous Cr(III)-Cl-H2O complexes at 25 °C: Implications for Cr(III) mobility and isotopic variations in modern and ancient natural systems

NASA Astrophysics Data System (ADS)

Babechuk, Michael G.; Kleinhanns, Ilka C.; Reitter, Elmar; Schoenberg, Ronny

2018-02-01

The stable Cr isotope fractionation preserved in natural substances has been attributed predominantly to Cr(III)-Cr(VI) redox transformations. However, non-redox reaction pathways (e.g., ligand-promoted dissolution, ligand exchange, adsorption of Cr(III)) are liable to contribute to isotopic fractionation in natural systems given that soluble Cr(III)-ligands have been directly documented or modeled in several marine, continental, and hydrothermal environments. This study isolates the stable Cr isotope fractionation accompanying Cl-H2O ligand exchange during the transformation of three aqueous species in the Cr(III)-Cl-H2O system, [CrCl2(H2O)4]+aq (abr. CrCl2+ or S1), [CrCl(H2O)5]2+aq (abr. CrCl2+ or S2), and [Cr(H2O)6]3+aq (abr. Cr3+ or S3), at low pH (≤2). In dilute HCl (0.01 to 1 M), Cr3+ is the kinetically favoured species and transformation of CrCl2+ to CrCl2+ to Cr3+ via 2 steps of dechlorination/hydrolyzation begins immediately upon dissolution of a Cr(III)-Cl solid. Individual species are separated with cation exchange chromatography at different stages of transformation and inter- and intra-species (across an elution peak of one species) isotopic fractionation of up to 1 and 2‰ (δ53/52Cr), respectively, is documented. Comparison of peak elution characteristics with Cr-Cl-H-O isotopologue mass abundances suggests mass-dependent sorting of isotopologues alone cannot explain intra-species fractionation, supporting a previously published proposal that preferential adsorption of light Cr isotopes on the resin is driven by vibrational energy effects. The transformation of CrCl2+ to CrCl2+ is faster than CrCl2+ to Cr3+ and the rates of both transformations increase with solution pH. Preferential reaction of light Cr(III) isotopes into product species occurs during each transformation, consistent with closed-system, kinetic fractionation during Cl-H2O ligand exchange. Inter-species fractionation is assessed using time-series experiments beginning from the dissolution of two Cr(III)-Cl solids (dried NIST SRM979 standard and commercial CrCl3·6H2O salt) in 0.01 M HCl (pH ≈ 2). The ε53/52Cr(CrCl2+/CrCl2+) for the CrCl2+ to CrCl2+ reaction is -0.19‰ (SRM979) and -0.38‰ (salt) and the ε53/52Cr(Cr3+/CrCl2+) for the CrCl2+ to Cr3+ reaction is consistent for both experiments at -0.49‰ (SRM979) and -0.51‰ (salt). Experiments where SRM979 is dissolved in 0.1 and 1 M HCl for a longer aging period provide preliminary evidence that the Cr3+/CrCl2+ Cr(III) isotopic fractionation scales with HCl concentration (transformation rate). Chromium(III) dissolved in 6 M HCl and aged 5 months still yields an inter-species Cr isotope distribution that is apparently inherited from kinetic effects (light Cr isotopes in Cr3+), attesting to the slow development of inter-species isotopic equilibrium, which instead predicts progressively heavier Cr isotopes from CrCl2+ to CrCl2+ to Cr3+. The kinetic Cr(III) isotopic fractionation documented herein is proposed to be relevant to understanding systems where aqueous Cr(III)-Cl species may be temporarily stable (e.g., metamorphic and hydrothermal systems or lateritic weathering). Further, the complexation of Cr(III) with other ligands (e.g., CO32-, organics), combined with additional kinetic effects of Cr(III) potentially occurring in soils or sediment, must be explored prior to establishing the significance of empirical stable Cr isotope signatures in marine and continental environments. Further understanding of non-redox effects may lead to stable Cr isotopes developing as a proxy for system pH or ligand chemistry.

Evaluation of alloy 690 process pot at the contact with borosilicate melt pool during vitrification of high-level nuclear waste

NASA Astrophysics Data System (ADS)

Sengupta, Pranesh; Kaushik, C. P.; Kale, G. B.; Das, D.; Raj, K.; Sharma, B. P.

2009-08-01

Understanding the material behaviour under service conditions is essential to enhance the life span of alloy 690 process pot used in vitrification of high-level nuclear waste. During vitrification process, interaction of alloy 690 with borosilicate melt takes place for substantial time period. Present experimental studies show that such interactions may result in Cr carbide precipitation along grain boundaries, Cr depletion in austenitic matrix and intergranular attack close to alloy 690/borosilicate melt pool interfaces. Widths of Cr depleted zone within alloy 690 is found to follow kinetics of the type x = 10.9 × 10 -6 + 1 × 10 -8t1/2 m. Based on the experimental results it is recommended that compositional modification of alloy 690 process pot adjacent to borosilicate melt pool need to be considered seriously for any efforts towards reduction and/or prevention of process pot failures.

Characteristics of Ni-Cr-Fe laser clad layers on EA4T steel

NASA Astrophysics Data System (ADS)

Chen, Wenjing; Chen, Hui; Wang, Yongjing; Li, Congchen; Wang, Xiaoli

2017-07-01

The Ni-Cr-Fe metal powder was deposited on EA4T steel by laser cladding technology. The microstructure and chemical composition of the cladding layer were analyzed by optical microscopy (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The bonding ability between the cladding layer and the matrix was measured. The results showed that the bonding between the cladding layer and the EA4T steel was metallurgical bonding. The microstructure of cladding layer was composed of planar crystals, columnar crystals and dendrite, which consisted of Cr2Ni3, γ phase, M23C6 and Ni3B phases. When the powder feeding speed reached 4 g/min, the upper bainite occurred in the heat affected zone (HAZ). Moreover, the tensile strength of the joint increased, while the yield strength and the ductility decreased.

Thermonuclear 46Cr(p ,γ )47Mn rate in type-I x-ray bursts

NASA Astrophysics Data System (ADS)

He, J. J.; Parikh, A.; Xu, Y.; Zhang, Y. H.; Zhou, X. H.; Xu, H. S.

2017-10-01

The thermonuclear rate of the 46Cr(p ,γ )47Mn reaction has been determined using a newly evaluated proton separation energy of Sp(47Mn) =380 ±30 keV and nuclear structure information from the mirror nucleus 47Ti. The astrophysical impact of this new rate and previously available rates has been investigated through one-zone postprocessing type-I x-ray burst calculations. The present 46Cr(p ,γ )47Mn rate leads to a mass fraction at A =46 that is 60 times larger than that obtained using a statistical model rate. The new results constrain the calculated maximum and minimum mass fractions at A =46 and A =48 to be within factors of 12 and 4, respectively. Experimental studies of the level structure of 47Mn near the proton threshold are required to improve these model predictions.

First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: Synthesis, heterobimetallic complexation and self-assembly on Au(111).

PubMed

Applegate, Jason C; Okeowo, Monisola K; Erickson, Nathan R; Neal, Brad M; Berrie, Cindy L; Gerasimchukand, Nikolay N; Barybin, Mikhail V

2016-02-01

Mercapto (-SH) and isocyano (-N≡C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic π-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N≡C end of this 2,6-azulenic motif was anchrored to the [Cr(CO) 5 ] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC) 5 Cr(η 1 -2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] ( 7 ) with Ph 3 PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr 0 /Au I ensemble [(OC) 5 Cr(μ-η 1 :η 1 -2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh 3 ] ( 8 ). Analysis of the 13 C NMR chemical shifts for the [(NC)Cr(CO) 5 ] core in a series of the related complexes [(OC) 5 Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = -N≡C, Br,H, SH, SCH 2 CH 2 CO 2 CH 2 CH 3 , SAuPPh 3 ) unveiled remarkably consistent inverse-linear correlations δ( 13 C O trans ) vs. δ( 13 C N) and δ( 13 C O cis ) vs. δ( 13 C N) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC) 5 Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF 3 , CFClCF 2 Cl, C 2 F 3 , and C 6 F 5 . In addition to functioning as asensitive 13 C NMR handle, the essentially C 4v -symmetric [(-NC)Cr(CO) 5 ] moiety proved to be an informative, remote, ν N≡C /ν C≡O infrared reporter in probing chemisorption of 7 on the Au(111) surface.

Carcinogenicity of chromium and chemoprevention: a brief update

PubMed Central

Gu, Yuanliang; Song, Xin; Zhao, Jinshun

2017-01-01

Chromium has two main valence states: hexavalent chromium (Cr[VI]) and trivalent chromium (Cr[III]). Cr(VI), a well-established human carcinogen, can enter cells by way of a sulfate/phosphate anion-transport system, and then be reduced to lower-valence intermediates consisting of pentavalent chromium (Cr[V]), tetravalent chromium (Cr[IV]) or Cr(III) via cellular reductants. These intermediates may directly or indirectly result in DNA damage or DNA–protein cross-links. Although Cr(III) complexes cannot pass easily through cell membranes, they have the ability to accumulate around cells to induce cell-surface morphological alteration and result in cell-membrane lipid injuries via disruption of cellular functions and integrity, and finally to cause DNA damage. In recent years, more research, including in vitro, in vivo, and epidemiological studies, has been conducted to evaluate the genotoxicity/carcinogenicity induced by Cr(VI) and/or Cr(III) compounds. At the same time, various therapeutic agents, especially antioxidants, have been explored through in vitro and in vivo studies for preventing chromium-induced genotoxicity/carcinogenesis. This review aims to provide a brief update on the carcinogenicity of Cr(VI) and Cr(III) and chemoprevention with different antioxidants. PMID:28860815

Crystal structure of hexa­kis­(urea-κO)chromium(III) dichromate bromide monohydrate from synchrotron X-ray data

PubMed Central

Moon, Dohyun; Tanaka, Shinnosuke; Akitsu, Takashiro; Choi, Jong-Ha

2015-01-01

The title bromide salt, [Cr{CO(NH2)2}6](Cr2O7)Br·H2O, is isotypic to the corresponding chloride salt. Within the complex cation, the CrIII atom is coordinated by six O atoms of six urea ligands, displaying a slightly distorted octa­hedral coordination environment. The Cr—O bond lengths involving the urea ligands are in the range 1.9534 (13)–1.9776 (12) Å. The Cr2O7 2− anion has a nearly staggered conformation, with a bridging angle of 130.26 (10)°. The individual components are arranged in rows extending parallel to [100]. The Br− anion links the complex cation, as well as the solvent water mol­ecule, through N—H⋯Br and O—H⋯Br hydrogen-bonding inter­actions. The supra­molecular architecture also includes N—H⋯O and O—H⋯O hydrogen bonding between urea N—H and water O—H donor groups and the O atoms of the Cr2O7 2− anion as acceptor atoms, leading to a three-dimensional network structure. PMID:26594505

Ameliorative effect of chromium-d-phenylalanine complex on indomethacin-induced inflammatory bowel disease in rats.

PubMed

Nagarjun, S; Dhadde, Shivsharan B; Veerapur, Veeresh P; Thippeswamy, B S; Chandakavathe, Baburao N

2017-05-01

Present study was designed to evaluate the effect of chromium-d-phenylalanine complex (Cr (d-phe) 3 ) on indomethacin-induced inflammatory bowel disease (IBD) in rats. Adult Wistar rats were pretreated with vehicle/Cr (d-phe) 3 (30, 60 and 90μg/kg, p.o.) for 11days. On day 8 and 9, after one h of the above mentioned treatment, indomethacin (7.5mg/kg/day,s.c.) was administered to induce IBD. On day 12, blood samples were collected from animals for lactate dehydrogenase (LDH) estimation and ileum was isolated for macroscopic scoring, biochemical estimation (lipid peroxidation, reduced glutathione and myeloperoxidase activity) and histopathological study. Administration of indomethacin significantly altered the serum LDH, macroscopic and microscopic appearance and biochemical parameters in ileum tissue. Cr (d-phe) 3 , at all the tested doses, caused a significant reversal of changes induced by indomethacin. Present study demonstrates the protective effect of Cr (d-phe) 3 against indomethacin-induced IBD in rats. The observed protective effect might be attributed to the antioxidant and anti-inflammatory properties of Cr (d-phe) 3 . Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

2018-01-01

Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

Colour due to Cr3+ ions in oxides: a study of the model system MgO:Cr3+

NASA Astrophysics Data System (ADS)

Aramburu, J. A.; García-Fernández, P.; García-Lastra, J. M.; Barriuso, M. T.; Moreno, M.

2013-05-01

Seeking to understand why the cubic centre in MgO:Cr3+ has the same 10Dq value as emerald, ab initio cluster and periodic supercell calculations have been performed. It is found that the equilibrium Cr3+-O2- distance, R, in MgO:Cr3+ is equal to 2.03 Å and thus 0.06 Å higher than that measured for the emerald. Calculations carried out on the isolated {{CrO}}_{6}^{9-} complex at R = 2.03 Å give 10Dq = 14 510 cm-1, which is 10% smaller than the experimental figure for MgO:Cr3+. Nevertheless, when the internal electric field, ER(r), due to the rest of the lattice ions is also taken into account, the calculated 10Dq = 16 210 cm-1 coincides with the experimental value. Accordingly, the colour shift for different oxides doped with Cr3+ can be well understood on the basis of this extrinsic contribution to 10Dq usually ignored in a ligand field description. The calculated electrostatic potential, VR(r), related to ER(r), is found to be attractive when the electronic density is lying along <110> directions and |r| > 1 Å driven by the first shell of twelve Mg2+ ions. The action of VR(r) upon the {{CrO}}_{6}^{9-} complex slightly decreases the energy of t2g(xy,xz,yz) orbitals with respect to that for eg(3z2 - r2,x2 - y2) orbitals, thus enhancing the 10Dq value by 0.2 eV. However, the addition of VR(r) induces very small changes in the electronic density, a relevant fact that is related to the {}^{2}{E}({{t}}_{2{g}}^{3})\\hspace{0.167em} {\\rightarrow \\hspace{0.167em} }^{4}{{A}}_{2}({{t}}_{2{g}}^{3}) emission energy being nearly independent of the host lattice along the series of Cr3+-doped oxides.

Cultural Reciprocity in Sociocultural Perspective: Adapting the Normalization Principle for Family Collaboration.

ERIC Educational Resources Information Center

Harry, Beth; Rueda, Robert; Kalyanpur, Maya

1999-01-01

Findings from a collaborative action research project involving seven culturally diverse families with children with disabilities are used to illustrate how professionals can provide assistance in a family's zone of proximal development, rather than targeting goals that are normative for the mainstream, but not for the family. (Author/CR)

76 FR 49423 - Fisheries of the Exclusive Economic Zone Off Alaska; Bering Sea and Aleutian Islands Crab...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-10

... market information used to conduct arbitration proceedings. This action is intended to promote the goals and objectives of the Magnuson-Stevens Fishery Conservation and Management Act, the FMP, and other... Conservation and Management Act. Amendments 18 and 19 to the FMP implemented the CR Program. Regulations...

Cr localization and speciation in roots of chromate fed Helianthus annuus L. seedlings using synchrotron techniques.

PubMed

de la Rosa, Guadalupe; Castillo-Michel, Hiram; Cruz-Jiménez, Gustavo; Bernal-Alvarado, Jesús; Córdova-Fraga, Teodoro; López-Moreno, Laura; Cotte, Marine

2014-01-01

In order to gain knowledge on the potential use of Helianthus annuus L. for the remediation of Cr(VI) polluted waters, hydroponics experiments were set up to determine Cr uptake and tolerance in different Cr(VI)-sulfate conditions, and Cr biotransformations. Results indicated that Cr(VI) promoted seed germination, and plant tolerance was higher at younger plant stages. Cr uptake was dependent on sulfate concentrations. The highest Cr levels in roots and shoots (13,700 and 2,500 mg kg(-1) dry weight (DW), respectively) were obtained in 1 mM sulfate. The lowest Cr uptake in roots (10,600 mg kg(-1) DW) was observed in seedlings treated with no sulfate. In shoots, Cr concentration was of 1,500 mg kg(-1)DW for the 1 mM sulfate treatment, indicating a different level of interaction between chromate and sulfate in both tissues. For the first time, using micro X-ray florescence (muXRF), we demonstrated Cr reaches the root stele and is located in the walls of xylem vessels. Bulk and micro X-ray Absorption Near-Edge Structure (muXANES) results showed that Cr in the roots is mostly in the form of Cr(III) phosphate (80%), with the remainder complexed to organic acids. Our results suggest this plant species may serve for Cr(VI) rhizofiltration purposes.

Differential determination of chromium(VI) and total chromium in natural waters using flow injection on-line separation and preconcentration electrothermal atomic absorption spectrometry.

PubMed

Sperling, M; Yin, X; Welz, B

1992-03-01

A rapid, sensitive and selective method for the differential determination of CrIII and CrVI in natural waters is described. Chromium(vi) can be determined directly by flow injection on-line sorbent extraction preconcentration coupled with electrothermal atomic absorption spectrometry using sodium diethyldithiocarbamate as the complexing agent and C18 bonded silica reversed-phase sorbent as the column material. Total Cr can be determined after oxidation of CrIII to CrVI by potassium peroxydisulfate. Chromium(III) can be calculated by difference. The optimum conditions for sorbent extraction of CrVI and oxidation of CrIII to CrVI are evaluated. A 12-fold enhancement in sensitivity compared with direct introduction of 40 microliters samples was achieved after preconcentration for 60 s, giving detection limits of 16 ng l-1 for CrVI and 18 ng l-1 for total Cr (based on 3 sigma). Results obtained for sea-water and river water reference materials were all within the certified range for total Cr with a precision of better than 10% relative standard deviation in the range 100-200 ng l-1. The selectivity of the determination of CrVI was evaluated by analysing spiked reference materials in the presence of CrIII, resulting in quantitative recovery of CrVI.

Friction Stir Welding (FSW) of Aged CuCrZr Alloy Plates

NASA Astrophysics Data System (ADS)

Jha, Kaushal; Kumar, Santosh; Nachiket, K.; Bhanumurthy, K.; Dey, G. K.

2018-01-01

Friction Stir Welding (FSW) of Cu-0.80Cr-0.10Zr (in wt pct) alloy under aged condition was performed to study the effects of process parameters on microstructure and properties of the joint. FSW was performed over a wide range of process parameters, like tool-rotation speed (from 800 to 1200 rpm) and tool-travel speed (from 40 to 100 mm/min), and the resulting thermal cycles were recorded on both sides (advancing and retreating) of the joint. The joints were characterized for their microstructure and tensile properties. The welding process resulted in a sound and defect-free weld joint, over the entire range of the process parameters used in this study. Microstructure of the stir zone showed fine and equiaxed grains, the scale of which varied with FSW process parameters. Grain size in the stir zone showed direct correlation with tool rotation and inverse correlation with tool-travel speed. Tensile strength of the weld joints was ranging from 225 to 260 MPa, which is substantially lower than that of the parent metal under aged condition ( 400 MPa), but superior to that of the parent material under annealed condition ( 220 MPa). Lower strength of the FSW joint than that of the parent material under aged condition can be attributed to dissolution of the precipitates in the stir zone and TMAZ. These results are presented and discussed in this paper.

Mechanisms for the Reduction of Actinides and Tc(VII) in Geobacter sulfurreducens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lloyd, Jonathan R.

2004-06-01

The mechanism of the reduction of U(VI) and Cr(VI) has now been studied in detail. Cr(VI) is reduced by one-electron transfer reactions to Cr(III), via a cell-bound Cr(V) intermediate identified by EPR spectroscopy. Studies with a cytochrome c7 mutant demonstrate that the electron transfer chain includes this protein which may be the terminal reductase for Cr(VI). Potential mechanisms of inhibition of Cr(III) precipitation, involving complex formation with organic acids commonly used as electron donors for metal reduction in the subsurface have also been identified. We have also initiated a collaboration with computational chemists led by Prof Ian Hillier in Manchester,more » to model metal binding to cytochrome c7, and subsequent electron transfer from the enzyme to the metal quantum mechanically.« less

A DFT based ligand field model for magnetic exchange coupling in transition metal dimer complexes:. (ii) application to magnetic systems with more than one unpaired electron per site

NASA Astrophysics Data System (ADS)

Atanasov, M.; Daul, C. A.

2003-11-01

The DFT based ligand field model for magnetic exchange coupling proposed recently, has been extended to systems containing more than one unpaired electron per site. The guidelines for this extension are described using a model example - the complex (NH 3) 3Cr III(OH) 3Cr III (NH 3) 33+. The exchange Hamiltonian, H ex=-J 12S1S2 has been simplified using symmetry principles, i.e. utilizing the D 3h(C 3v) Cr III - dimer(site) symmetry. Both antiferro- and ferromagnetic exchange coupling constants are found to yield important contributions to the value of the (negative, antiferromagnetic) exchange coupling constant in good agreement with experiment.

EPR and magnetization studies on single crystals of a heterometallic (Cu II and Cr III) complex: Zero-field splitting determination

NASA Astrophysics Data System (ADS)

Novosel, Nikolina; Žilić, Dijana; Pajić, Damir; Jurić, Marijana; Perić, Berislav; Zadro, Krešo; Rakvin, Boris; Planinić, Pavica

2008-10-01

Magnetic properties of single crystals of the heterometallic complex [Cu(bpy) 3] 2[Cr(C 2O 4) 3]NO 3·9H 2O (bpy = 2,2'-bipyridine) have been investigated. From the recorded EPR spectra, the spin-Hamiltonian parameters have been determined. The magnetization measurements have shown magnetic anisotropy at low temperatures, which has been analysed as a result of the zero-field splitting of the Cr III ion. By fitting the exactly derived magnetization expression to the measured magnetization data, the axial zero-field splitting parameter, D, has been calculated. Comparing to the EPR measurements, it has been confirmed that D can be determined from the measurements of the macroscopic magnetization on the single crystals.

Correlation between bulk- and surface chemistry of Cr-tanned leather and the release of Cr(III) and Cr(VI).

PubMed

Hedberg, Yolanda S; Lidén, Carola; Odnevall Wallinder, Inger

2014-09-15

About 1-3% of the adult general population in Europe is allergic to chromium (Cr). The assessment of the potential release of Cr(III) and Cr(VI) from leather is hence important from a human health and environmental risk perspective. The Cr(VI) content in leather was recently restricted in the European Union. The aim of this study was to assess possible correlations between the bulk and surface chemistry of leather, released Cr(III) and Cr(VI), and capacities of co-released leather specific species to reduce and complex released Cr. Four differently tanned leathers were characterized by scanning electron microscopy with energy dispersive spectroscopy, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and the diphenylcarbazide colorimetric method. Their characteristics were compared with results on Cr(III) and Cr(VI) release into artificial sweat (ASW, pH<6.5) and phosphate buffer (PB, pH 7.5-8.0), measured by means of spectrophotometry and atomic absorption spectroscopy. Co-released leather-specific species were shown to reduce Cr(VI), both in ASW and in PB. Their reduction capacities correlated with findings of the surface content of Cr and of released Cr. Leather samples without this capacity, and with less aromatic surface groups visible by ATR-FTIR, revealed Cr(VI) both at the surface and in solution (PB). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Femtosecond-picosecond laser photolysis studies on the dynamics of excited charge-transfer complexes: Aromatic hydrocarbon-acid anhydride, -tetracyanoethylene, and -tetracyanoquinodimethane systems in acetonitrile solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asahi, Tsuyoshi; Mataga, Noboru

1991-03-07

Formation processes of contact ion pairs (CIP) from the excited Franck-Condon (FC) state of charge-transfer (CT) complexes of aromatic hydrocarbons with acid anhydride as well as cyano compound acceptors in acetonitrile solution and charge recombination (CR) rates (k{sub CR}{sup CIP}) of produced CIP states have been investigated by femtosecond and picosecond laser phototlysis and time-resolved absorption spectral measurements covering a wide range of free energy gap-{Delta}G{degree}{sub ip} between the ion pair and the ground state. It has been confirmed that the CIP formation becomes faster and k{sub CR}{sup CIP} of the produced CIP increases with increase of the strengths ofmore » the electron donor (D) and acceptor (A) in the complex, i.e., with decrease of the {minus}{Delta}G{degree}{sub ip} value. This peculiar energy gap dependence of k{sub CR}{sup CIP}, quite different from the bell-shaped one observed in the case of the solvent-separated ion pairs (SSIP) or loose ion pairs (LIP) formed by encounter between fluorescer and quencher in the fluoresence quenching reaction, has been interpreted by assuming the change of electronic and geometrical structures of CIP depending on the strengths of D and A.« less

Evidence for the dissolution of molybdenum during tribocorrosion of CoCrMo hip implants in the presence of serum protein.

PubMed

Simoes, Thiago A; Bryant, Michael G; Brown, Andy P; Milne, Steven J; Ryan, Mary; Neville, Anne; Brydson, Rik

2016-11-01

We have characterized CoCrMo, Metal-on-Metal (MoM) implant, wear debris particles and their dissolution following cycling in a hip simulator, and have related the results to the tribocorrosion of synthetic wear debris produced by milling CoCrMo powders in solutions representative of environments in the human body. Importantly, we have employed a modified ICP-MS sample preparation procedure to measure the release of ions from CoCrMo alloys during wear simulation in different media; this involved use of nano-porous ultrafilters which allowed complete separation of particles from free ions and complexes in solution. As a result, we present a new perspective on the release of metal ions and formation of metal complexes from CoCrMo implants. The new methodology enables the mass balance of ions relative to complexes and particles during tribocorrosion in hip simulators to be determined. A much higher release of molybdenum ions relative to cobalt and chromium has been measured. The molybdenum dissolution was enhanced by the presence of bovine serum albumin (BSA), possibly due to the formation of metal-protein complexes. Overall, we believe that the results could have significant implications for the analysis and interpretation of metal ion levels in fluids extracted from hip arthroplasty patients; we suggest that metal levels, including molybdenum, be analysed in these fluids using the protocol described here. We have developed an important new protocol for the analysis of metal ion levels in fluids extracted from hip implant patients and also hip simulators. Using this procedure, we present a new perspective on the release of metal ions from CoCrMo alloy implants, revealing significantly lower levels of metal ion release during tribocorrosion in hip simulators than previously thought, combined with the release of much higher percentages of molybdenum ions relative to cobalt and chromium. This work is of relevance, both from the perspective of the fundamental science and study of metal-protein interactions, enabling understanding of the ongoing problem associated with the biotribocorrosion and the link to inflammation associated with Metal-on-Metal (MoM) hip implants made from CoCrMo alloys. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Speciation of hexavalent chromium in welding fumes interference by air oxidation of chromium.

PubMed

Zatka, V J

1985-06-01

The determination of various chromium species in welding fume normally involves digestion in a hot alkaline solution. This work confirms that Cr(III) can be oxidized to Cr(VI) during this digestion. However, only dissolved forms of Cr(III), such as the hydroxochromate(III) ion, [Cr(OH)4], are susceptible to oxidation under these conditions. The air oxidation of Cr(III) can be prevented by hydrolytic destabilization of the hydroxochromate(III) complex by the presence of magnesium hydroxide precipitate. The procedure has been used successfully in the determination of insoluble chromium(VI) in welding fumes. Excellent reproducibility is documented for soluble and insoluble chromium(VI) fractions in the analysis of a bulk sample of welding fume.

Evaluation of the relationship between hepatocellular carcinoma location and transarterial chemoembolization efficacy.

PubMed

Miki, Izumi; Murata, Satoru; Uchiyama, Fumio; Yasui, Daisuke; Ueda, Tatsuo; Sugihara, Fumie; Saito, Hidemasa; Yamaguchi, Hidenori; Murakami, Ryusuke; Kawamoto, Chiaki; Uchida, Eiji; Kumita, Shin-Ichiro

2017-09-21

To evaluate the relationship between the location of hepatocellular carcinoma (HCC) and the efficacy of transarterial chemoembolization (TACE). We evaluated 115 patients (127 nodules), excluding recurrent nodules, treated with TACE between January 2011 and June 2014. TACE efficacy was evaluated according to mRECIST. The HCC location coefficient was calculated as the distance from the central portal portion to the HCC center (mm)/liver diameter (mm) on multiplanar reconstruction images rendered (MPR) to visualize bifurcation of the right and left branches of the portal vein and HCC center. The HCC location coefficient was compared between complete response (CR) and non-CR groups in Child-Pugh grade A and B patients. The median location coefficient of HCC among all nodules, the right lobe, and the medial segment was significantly higher in the CR group than in the non-CR group in the Child-Pugh grade A patients (0.82 vs 0.62, P < 0.001; 0.71 vs 0.59, P < 0.01; 0.81 vs 0.49, P < 0.05, respectively). However, there was no significant difference in the median location coefficient of the HCC in the lateral segment between in the CR and in the non-CR groups (0.67 vs 0.65, P > 0.05). On the other hand, in the Child-Pugh grade B patients, the HCC median location coefficient in each lobe and segment was not significantly different between in the CR and in the non-CR groups. Improved TACE efficacy may be obtained for HCC in the peripheral zone of the right lobe and the medial segment in Child-Pugh grade A patients.

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective.

PubMed

Hedberg, Yolanda; Gustafsson, Johanna; Karlsson, Hanna L; Möller, Lennart; Odnevall Wallinder, Inger

2010-09-03

Production of ferrochromium alloys (FeCr), master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr), ferrosiliconchromium (FeSiCr), stainless steel (316L), iron (Fe), chromium (Cr), and chromium(III)oxide (Cr2O3), in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549). The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF) of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III)-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III) from all particles investigated and was strongly complexed by organic species of ALF. Cr2O3 particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death after 24 h exposure. It is evident that particle and alloy characteristics such as particle size and surface composition are important aspects to consider when assessing particle toxicity and metal release from alloy particles compared to pure metal particles. Generated results clearly elucidate that neither the low released concentrations of metals primarily as a result of protective and poorly soluble surface oxides, nor non-bioavailable chromium complexes, nor the particles themselves of occupational relevance induced significant acute toxic response, with exception of DNA damage from stainless steel.

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective

PubMed Central

2010-01-01

Background Production of ferrochromium alloys (FeCr), master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr), ferrosiliconchromium (FeSiCr), stainless steel (316L), iron (Fe), chromium (Cr), and chromium(III)oxide (Cr2O3), in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549). Results The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF) of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III)-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III) from all particles investigated and was strongly complexed by organic species of ALF. Cr2O3 particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death after 24 h exposure. Conclusion It is evident that particle and alloy characteristics such as particle size and surface composition are important aspects to consider when assessing particle toxicity and metal release from alloy particles compared to pure metal particles. Generated results clearly elucidate that neither the low released concentrations of metals primarily as a result of protective and poorly soluble surface oxides, nor non-bioavailable chromium complexes, nor the particles themselves of occupational relevance induced significant acute toxic response, with exception of DNA damage from stainless steel. PMID:20815895

Incidence and distribution of heavy metals in soils of a Mediterranean coastal wetland (L'Albufera de Valencia, Spain)

NASA Astrophysics Data System (ADS)

Andreu, V.; Gimeno, E.; Fernandez-Despiau, E.; Pascual, J. A.

2012-04-01

One of the most important issues in environmental conservation nowadays is the preservation of wetlands, mainly the coastal ones. This becomes more imperative in the Mediterranean. These particular ecosystems have suffered during the last decades an increasing human pressure. This has been reflected through the intensification of agriculture and construction of infrastructures in their surroundings or even draining part of them. As a result, the density of population and its residues affect them in a first place. This work has been developed in the Natural Park of La Albufera (Valencia, Spain), which includes a coastal lagoon, marshlands, dunes and pinewoods, surrounded by rice fields in its not urbanized part. In spite of this great ecological value, it suffers impacts derived from the high human and industrial occupation, and of the hydrological contributions from the connected irrigation systems. In addition, this park is one of the most important wetland in Europe, included in the RAMSAR agreement, being a key point for migratory birds and contains in its area one of the most important zones on rice production in Europe. In the park area, 28 sampling zones were selected to determine the degree of heavy metals incidence in soils. Total concentrations of Cd, Co, Cr, Cu, Ni, Pb, and Zn were evaluated. Their distribution in the surficial and sub-surficial horizons was determined together with their spatial distribution, and the possible sources of contamination. Zn, Cr and Cu show the highest concentrations in all land uses and zones. Cr is the metal that present maximum concentration in the studied area (254.93 ppm), being almost the only metal studied that exceeds the limits established by the Spanish an EU legislation. Co and Ni shows a tendency to accumulate below the 30 cm depth, the other metal studied continue with the cumulative trend in surface horizons. All the studied metals, except Co have highly significant correlations with the available phosphorous, which indicates a possible influence of fertilizers and organophosphorous pesticides as main input ways, mainly in the case of rice farming soils. This study shows that inside the Natural Park, the northern zone is the most contaminated one in all cases and soil uses. In this zone, the sampling points closer to the coast are those that present higher concentrations of metals, mainly the sampling zones 11 and 15 Acknowledgements This work has been supported by by the Spanish Ministry of Science and Innovation through the project HUCOMED (CGL2008-01693/BTE), as well as by this Ministry and the European Regional Development Funds (ERDF) (projects CGL2011-29703-C02-00, CGL2011-29703-C02-01).

The Campanian-Maastrichtian foraminiferal biostratigraphy of the basement sediments from the southern Pannonian Basin (Vojvodina, northern Serbia): implications for the continuation of the Eastern Vardar and Sava zones

NASA Astrophysics Data System (ADS)

Dunčić, Milena; Dulić, Ivan; Popov, Olivera; Bogićević, Goran; Vranjković, Alan

2017-04-01

Micropalaeontological and biostratigraphical studies included Campanian-Maastrichtian complexes from five oil exploration wells drilled in northern Serbia (Vojvodina): the first is a carbonate-clastic complex and second is a complex containing ophiolites intercalated with hemipelagic and pelagic sediments. Within the studied complexes, rich associations of planktonic and benthic foraminifera, calcareous nannoplankton, palynomorphs, as well as shallow and deep-water fossil detritus were determined. The presence of relatively rich associations of planktonic foraminifera allowed recognition of two biozones: the Globotruncana ventricosa Zone, observed in the sediments of the carbonate-clastic complex and the Gansserina gansseri Zone, observed in both complexes. Except biozones, based on documented index species, for some units in both complexes, larger benthic foraminifera species had special biostratigraphical value, and in some of them, the calcareous nannoplankton zones were recognized. The studied complexes represent deep-water formations, generated in oceanic island arc and trough zones. The presence of limestones, which originate from destroyed rudist reefs, is explained by transfer by means of gravitational transport mechanisms of shallow-water sediments to deep-water depositional environments. In this paper, the results of more detailed biostratigraphical and palaeo-ecological studies of foraminifera associations in Campanian-Maastrichtian complexes in Vojvodina are presented. Combined with lithological studies, seven units were determined within the complexes. The obtained results are important as a part of multidisciplinary, regional exploration of both complexes, generated in specific geological conditions, that today constitute a part of the pre-Neogene basement complex in the southeastern part of the Pannonian Basin. The Campanian- Maastrichtian carbonate-clastic complex represents sedimentary cover of the Eastern Vardar Ophiolitic Unit, while the ophiolites intercalated with hemipelagic and pelagic limestones belongs to the Sava Zone.

A newly validated and characterized spectrophotometric method for determination of a three water pollutants metal ions

NASA Astrophysics Data System (ADS)

Mohamed, Marwa E.; Frag, Eman Y. Z.; Mohamed, Mona A.

2018-01-01

A simple, fast and accurate spectrophotometric method had been developed to determine lead (II), chromium (III) and barium (II) ions in pure forms and in spiked water samples using thoron (THO) as a reagent forming colored complexes. It was found that the formed complexes absorbed maximally at 539, 540 and 538 nm for Pb(II)-THO, Cr(III)-THO and Ba(II)-THO complexes, respectively. The optimum experimental conditions for these complexes had been studied carefully. Beer's law was obeyed in the range 1-35, 1-70, and 1-45 μg mL- 1 for Pb (II), Cr(III) and Ba(II) ions with THO reagent, respectively. Different parameters such as linearity, selectivity, recovery, limits of quantification and detection, precision and accuracy were also evaluated in order to validate the proposed method. The results showed that, THO was effective in simultaneous determination of Pb(II), Cr(III) and Ba(III) ions in pure forms and in spiked water samples. Also, the results of the proposed method were compared with that obtained from atomic absorption spectrometry. The isolated solid complexes had been characterized using elemental analysis, X-ray powder diffraction (XRD), IR, mass spectrometry and TD-DFT calculations. Their biological activities were investigated against different types of bacteria and fungi organisms.

Anneal-Hardening Behavior of Cr-Fe-C Alloy Deposits Prepared in a Cr3+-Based Bath with Fe2+ Ions

PubMed Central

Huang, Ching An; Chen, Jhih You; Wang, Hai

2017-01-01

Cr-Fe-C alloy deposits were successfully prepared on high-carbon tool steel in a Cr3+-based electroplating bath containing Fe2+ ions and suitable complex agents. A Cr-based alloy deposit was obtained with an electroplating current density higher than 25 Adm−2, and a Fe-based alloy deposit was obtained using a current density of 20 Adm−2. Following electroplating, these alloy deposited specimens were annealed via rapid thermal annealing (RTA) at 500 °C for different periods up to 30 s. The experimental results show that Cr- and Fe-based alloy deposits could be significantly hardened after RTA at 500 °C for a few seconds. The maximum hardness was that of the Cr-Fe-C alloy deposit annealed at 500 °C for 10 s. The maximum hardness of 1205 Hv was detected from the annealed Cr-based alloy deposit prepared with 30 ASD. The hardening mechanism of annealed Cr- and Fe-based alloy deposits is attributed to the precipitation of C-related membranes. The hardness values of the annealed Cr- and Fe-based alloy deposits increase with the increasing degree of crystallization of the C-related membranes. PMID:29206206

Effect and removal mechanisms of 6 different washing agents for building wastes containing chromium.

PubMed

Xing-run, Wang; Yan-xia, Zhang; Qi, Wang; Jian-min, Shu

2012-01-01

With the building wastes contaminated by chromium in Haibei Chemical Plan in China as objects, we studied the contents of total Cr and Cr (VI) of different sizes, analyzed the effect of 6 different washing agents, discussed the removal mechanisms of 6 different washing agents for Cr in various forms, and finally selected applicable washing agent. As per the results, particle size had little impact on the contents of total Cr and Cr (VI); after one washing with water, the removal rate of total Cr and Cr (VI) was 75% and 78%, respectively, and after the second washing with 6 agents, the removal rate of citric acid was the highest, above 90% for total Cr and above 99% for hexavalent chromium; the pH of building wastes were reduced by citric acid, and under acid condition, hexavalent chromium was reduced to trivalent chromium spontaneously by organic acid, which led to better removal rate of acid soluble Cr and reducible Cr; due to the complexing action, citric acid had best removal rate for oxidizable trivalent chromium. In conclusion, citric acid is the most applicable second washing agent for building wastes.

Effects of nitrogen in shielding gas on microstructure evolution and localized corrosion behavior of duplex stainless steel welding joint

NASA Astrophysics Data System (ADS)

Zhang, Zhiqiang; Jing, Hongyang; Xu, Lianyong; Han, Yongdian; Zhao, Lei; Zhou, Chao

2017-05-01

The effects of nitrogen addition in shielding gas on microstructure evolution and localized corrosion behavior of duplex stainless steel (DSS) welds were studied. N2-supplemented shielding gas facilitated the primary austenite formation, suppressed the Cr2N precipitation in weld root, and increased the microhardnesses of weld metal. Furthermore, N2-supplemented shielding gas increased pitting resistance equivalent number (PREN) of austenite, but which decreased slightly PREN of ferrite. The modified double loop electrochemical potentiokinetic reactivation in 2 M H2SO4 + 1 M HCl was an effective method to study the localized corrosion of the different zones in the DSS welds. The adding 2% N2 to pure Ar shielding gas improved the localized corrosion resistance in the DSS welds, which was due to compensation for nitrogen loss and promoting nitrogen further solution in the austenite phases, suppression of the Cr2N precipitation in the weld root, and increase of primary austenite content with higher PREN than the ferrite and secondary austenite. Secondary austenite are prone to selective corrosion because of lower PREN compared with ferrite and primary austenite. Cr2N precipitation in the pure Ar shielding weld root and heat affected zone caused the pitting corrosion within the ferrite and the intergranular corrosion at the ferrite boundary. In addition, sigma and M23C6 precipitation resulted in the intergranular corrosion at the ferrite boundary.

Bipartite recognition of target RNAs activates DNA cleavage by the Type III-B CRISPR–Cas system

PubMed Central

Elmore, Joshua R.; Sheppard, Nolan F.; Ramia, Nancy; Deighan, Trace; Li, Hong; Terns, Rebecca M.; Terns, Michael P.

2016-01-01

CRISPR–Cas systems eliminate nucleic acid invaders in bacteria and archaea. The effector complex of the Type III-B Cmr system cleaves invader RNAs recognized by the CRISPR RNA (crRNA ) of the complex. Here we show that invader RNAs also activate the Cmr complex to cleave DNA. As has been observed for other Type III systems, Cmr eliminates plasmid invaders in Pyrococcus furiosus by a mechanism that depends on transcription of the crRNA target sequence within the plasmid. Notably, we found that the target RNA per se induces DNA cleavage by the Cmr complex in vitro. DNA cleavage activity does not depend on cleavage of the target RNA but notably does require the presence of a short sequence adjacent to the target sequence within the activating target RNA (rPAM [RNA protospacer-adjacent motif]). The activated complex does not require a target sequence (or a PAM) in the DNA substrate. Plasmid elimination by the P. furiosus Cmr system also does not require the Csx1 (CRISPR-associated Rossman fold [CARF] superfamily) protein. Plasmid silencing depends on the HD nuclease and Palm domains of the Cmr2 (Cas10 superfamily) protein. The results establish the Cmr complex as a novel DNA nuclease activated by invader RNAs containing a crRNA target sequence and a rPAM. PMID:26848045

Multispecies reactive tracer test in an aquifer with spatially variable chemical conditions

USGS Publications Warehouse

Davis, J.A.; Kent, D.B.; Coston, J.A.; Hess, K.M.; Joye, J.L.

2000-01-01

A field investigation of multispecies reactive transport was conducted in a well‐characterized, sand and gravel aquifer on Cape Cod, Massachusetts. The aquifer is characterized by regions of differing chemical conditions caused by the disposal of secondary sewage effluent. Ten thousand liters of groundwater with added tracers (Br, Cr(VI), and EDTA complexed with Pb, Zn, Cu, and Ni) were injected into the aquifer and distributions of the tracers were monitored for 15 months. Most of the tracers were transported more than 200 m; transport was quantified using spatial moments computed from the results of a series of synoptic samplings. Cr(VI) transport was retarded relative to Br; the retardation factor varied from 1.1 to 2.4 and was dependent on chemical conditions. At 314 days after the injection, dissolved Cr(VI) mass in the tracer cloud had decreased 85%, with the likely cause being reduction to Cr(III) in a suboxic region of the aquifer. Transport of the metal‐EDTA complexes was affected by aqueous complexation, adsorption, and dissolution‐precipitation reactions of Fe oxyhydroxide minerals in the aquifer sediments. Dissolved Pb‐EDTA complexes disappeared from the tracer cloud within 85 days, probably due to metal exchange reactions with Fe and adsorbed Zn (present prior to the injection from contamination by the sewage effluent). About 30% of the Cu‐EDTA complexes remained within the tracer cloud 314 days after injection, even though the thermodynamic stability of the Pb‐EDTA complex is greater than Cu‐EDTA. It is hypothesized that stronger adsorption of Pb2+ to the aquifer sediments causes the Pb‐EDTA complex to disassociate to a greater degree than the Cu‐EDTA complex. The mass of dissolved Zn‐EDTA increased during the first 175 days of the tracer test to 140% of the mass injected, with the increase due to desorption of sewage‐derived Zn. Dissolved Ni‐EDTA mass remained nearly constant throughout the tracer test, apparently only participating in reversible adsorption reactions. The results of the field experiment provide a chemically complex data set that can be used in the testing of reactive transport models of flow coupled with chemical reactions.

Developing precipitation hardenable high entropy alloys

NASA Astrophysics Data System (ADS)

Gwalani, Bharat

High entropy alloys (HEAs) is a concept wherein alloys are constructed with five or more elements mixed in equal proportions; these are also known as multi-principle elements (MPEs) or complex concentrated alloys (CCAs). This PhD thesis dissertation presents research conducted to develop precipitation-hardenable high entropy alloys using a much-studied fcc-based equi-atomic quaternary alloy (CoCrFeNi). Minor additions of aluminium make the alloy amenable for precipitating ordered intermetallic phases in an fcc matrix. Aluminum also affects grain growth kinetics and Hall-Petch hardenability. The use of a combinatorial approach for assessing composition-microstructure-property relationships in high entropy alloys, or more broadly in complex concentrated alloys; using laser deposited compositionally graded AlxCrCuFeNi 2 (0 < x < 1.5) complex concentrated alloys as a candidate system. The composition gradient has been achieved from CrCuFeNi2 to Al 1.5CrCuFeNi2 over a length of ˜25 mm, deposited using the laser engineered net shaping process from a blend of elemental powders. With increasing Al content, there was a gradual change from an fcc-based microstructure (including the ordered L12 phase) to a bcc-based microstructure (including the ordered B2 phase), accompanied with a progressive increase in microhardness. Based on this combinatorial assessment, two promising fcc-based precipitation strengthened systems have been identified; Al0.3CuCrFeNi2 and Al0.3CoCrFeNi, and both compositions were subsequently thermo-mechanically processed via conventional techniques. The phase stability and mechanical properties of these alloys have been investigated and will be presented. Additionally, the activation energy for grain growth as a function of Al content in these complex alloys has also been investigated. Change in fcc grain growth kinetic was studied as a function of aluminum; the apparent activation energy for grain growth increases by about three times going from Al0.1CoCrFeNi (3% Al (at%)) to Al0.3CoCrFeNi. (7% Al (at%)). Furthermore, Al addition leads to the precipitation of highly refined ordered L12 (gamma') and B2 precipitates in Al0.3CoCrFeNi. A detailed investigation of precipitation of the ordered phases in Al0.3CoCrFeNi and their thermal stability is done using atom probe tomography (APT), transmission electron microscopy (TEM) and Synchrotron X-ray in situ and ex situ analyses. The alloy strengthened via grain boundary strengthening following the Hall-Petch relationship offers a large increment of strength with small variation in grain size. Tensile strength of the Al0.3CoFeNi is increased by 50% on precipitation fine-scale gamma' precipitates. Furthermore, precipitation of bcc based ordered phase B2 in Al0.3CoCrFeNi can further strengthen the alloy. Fine-tuning the microstructure by thermo-mechanical treatments achieved a wide range of mechanical properties in the same alloy. The Al0.3CoCrFeNi HEA exhibited ultimate tensile strength (UTS) of ˜250 MPa and ductility of ˜65%; a UTS of ˜1100 MPa and ductility of ˜30%; and a UTS of 1850 MPa and a ductility of 5% after various thermo-mechanical treatments. Grain sizes, precipitates type and size scales manipulated in the alloy result in different strength ductility combinations. Henceforth, the alloy presents a fertile ground for development by grain boundary strengthening and precipitation strengthening, and offers very high activation energy of grain growth aptly suitable for high-temperature applications.

Chromium isotope inventory of Cr(VI)-polluted groundwaters at four industrial sites in Central Europe

NASA Astrophysics Data System (ADS)

Novak, Martin; Martinkova, Eva; Chrastny, Vladislav; Stepanova, Marketa; Curik, Jan; Szurmanova, Zdenka; Cron, Marcel; Tylcer, Jiri; Sebek, Ondrej

2016-04-01

Chromium is one of the most toxic elements, especially in its dissolved Cr(VI) form. In the Czech Republic (Central Europe), massive contamination of groundwater has been reported at more than 200 industrial operations. Under suitable conditions, i.e., low Eh, and high availability of reductive agents, Cr(VI) in groundwater may be spontaneously reduced to solid, largely non-toxic Cr(III). This process is associated with a Cr isotope fractionation, with the residual liquid Cr(VI) becoming enriched in the heavier isotope 53Cr. At industrial operations that have been closed and/or where no further leakage of Cr(VI) occurs, the contaminated groundwater plume may be viewed as a closed system. At such sites, an increasing degree of Cr(VI) reduction should result in an increasing del53/52Cr value of the residual liquid. Here we present del53/52Cr systematics at four contaminated Czech sites, focusing on groundwaters. At two of the four sites (Zlate Hory, Loucna) we were also able to analyze the source of contamination. Chromium in the electroplating solutes was isotopically relatively light, with del53/52Cr values <1 per mil. At the remaining two sites (Letnany and Velesin), the Cr isotope signature of the source of contamination was not known. At all four sites, most del53/52Cr values were positive, with means higer than 1 per mil: At Zlate Hory, del53/52Cr ranged between -2.2 and +3.0 per mil (mean of +1.5 per mil); at Loucna, del53/52Cr ranged between 0 and +4.0 per mil (mean of +1.7 per mil); at Letnany, del53/52Cr ranged between +2.0 and +4.5 per mil (mean of +3.2 per mil); and at Velesin, del53/52Cr ranged between +0.5 and +4.5 per mil (mean of +2.7 per mil). Cr(VI) reduction may proceed at Zlate Hory and Loucna, where del53/52Cr(VI) values in groundwater were on average higher than those of the contamination source. At these two sites, our Cr isotope data are not consistent with the existing estimates of the amount of dissolved and precipitated Cr: The pool size of solid Cr(III) in the soil was estimated at 6600 and 500 kg at Zlate Hory and Loucna, respectively. At the same time, the pool size of dissolved Cr(VI) was estimated at 50 and 1.2 kg at Zlate Hory and Loucna, respectively. It follows that, at both sites, less than 1 % of the entire Cr that had leaked into the aquifer an a liquid form remained in the liquid form. If, indeed, most solid Cr now present in the saturated zone had undergone anaerobic reduction, we would expect much higher del53/52Cr values of the residual liquid Cr(VI) than those actually observed. Our understanding of the system is incomplete. Currently, del53/52Cr values of the contaminated soils are being determined in an attempt to close a Cr isotope mass balance.

Hexavalent chromium availability and phytoremediation potential of Cichorium spinosum as affect by manure, zeolite and soil ageing.

PubMed

Antoniadis, Vasileios; Polyzois, Theologos; Golia, Evaggelia E; Petropoulos, Spyridon A

2017-03-01

Cichorium spinosum (spiny chicory) is a wild edible vegetable, and a possible suitable species for Cr(VI)-phytoremediation. There are three approaches for altering Cr(VI) dynamics: reduction to Cr(III) by organic matter addition, soil ageing, and Cr(VI) retention by high binding capacity materials added to soil, e.g., zeolite. Our aim was to assess spiny chicory as a phytoremediation species in relation to these three methods of altering Cr(VI) soil dynamics. There were 5 treatments: control (C); soil with 100 mg kg -1 Cr(VI) (S); soil with zeolite plus 100 mg kg -1 Cr(VI) (Z); soil with manure plus 100 mg kg -1 Cr(VI) (M); and soil added with 100 mg kg -1 Cr(VI) one year before this experiment (AS, "aged soil"). In soil, Cr(VI) was higher at S, while Z, M and AS were lower. In plant, Cr(VI) at Z, S, and AS were similar and significantly higher than M. This indicates that added manure decrease Cr(VI) availability to chicory due to the formation of organometallic complexes. However, chicory uptake amounted to 0.26-0.40 kg Cr(VI) ha -1 for Z, S, and AS, while uptake at M was lower. In conclusion, manure addition was more successful in decreasing Cr(VI) bioavailability, but it also slowed Cr(VI)-phytoremediation process. Copyright © 2016. Published by Elsevier Ltd.

Microstructure characterization and room temperature deformation of a rapidly solidified NiAl-based eutectic alloy containing trace Dy

NASA Astrophysics Data System (ADS)

Li, Hutian; Guo, Jianting; Huai, Kaiwen; Ye, Hengqiang

2006-04-01

The microstructure and room temperature compressive deformation behavior of a rapidly solidified NiAl-Cr(Mo)-Dy eutectic alloy fabricated by water-cooled copper mold method were studied by a combination of SEM, EDS and compressive tests. The morphology stability after hot isostatic pressing (HIP) treatment was evaluated. Rapid solidification resulted in a shift in the coupled zone for the eutectic growth towards the Cr(Mo) phase, indicating a hypoeutectic composition, hence increasing the volume fraction of primary dendritic NiAl. Meanwhile, significantly refined microstructure and lamellar/rod-like Cr(Mo) transition were observed due to trace rare earth (RE) element Dy addition and rapid solidification effects. Compared with the results in literature [H.E. Cline, J.L. Walter, Metall. Trans. 1(1970)2907-2917; P. Ferrandini, W.W. Batista, R. Caram, J. Alloys Comp. 381(2004)91-98], an interesting phenomenon, viz., NiAl halos around the primary Cr(Mo) dendrites in solidified NiAl-Cr(Mo) hypereutectic alloy, was not observed in this study. This difference was interpreted in terms of their different reciprocal nucleation ability. In addition, it was proposed that the localized destabilization of morphology after HIP treatment is closely related to the presence of primary NiAl dendrites. The improved mechanical properties can be attributed to the synergistic effects of rapid solidification and Dy addition, which included refined microstructure, suppression of the crack development along eutectic grain boundaries, enhancement of density of geometrically necessary dislocations located at NiAl/Cr(Mo) interfaces and the Cr solubility extension in NiAl.

Mantle melting and melt extraction processes in the upper part of the ophiolitic mantle section of the Caledonian Feragen-Raudhammeren ophiolite complex, Central Norway.

NASA Astrophysics Data System (ADS)

Pryadunenko, A.; Nilsson, L. P.; Larsen, R. B.

2016-12-01

The border area between Norway and Sweden is known for exposures of dismembered ophiolitic fragments that presumably were formed during Cambrian and emplaced during the Caledonian orogenesis on a passive margin of Baltica. Mid-ocean ridge tectonic settings were inferred for these ophiolites in contrast to Caledonian subduction related ophiolites outcropping along the coast of Norway. At the Feragen - Raudhammeren area to the east-southeast of the historic mining town of Røros mantle tectonites consist of peridotite (cpx-bearing harzburgite to cpx-poor lherzolite) with an equal amount of dunite. Within the northwestern quarter of the 16 km2 Feragen body, resembling the mantle - crust boundary, the amount of dunite exceeds that of mantle peridotite. Dunites occur as layers as well as bodies discordant to banding in the harzburgite. Dunites have contacts to harzburgites from sharp in dyke-like bodies, to transitional with oPx fading out on a scale of 1 cm to several meters. Layers of Cr-spinel are common. Peridotites, dunites and dunite-peridotite transition zones were sampled at Feragen-Raudhammeren area. Gradual increase in MgO content of the rocks is observed from 39,5 wt % in peridotites to > 41 wt % within the transition zones. Dunites show > 43 wt % of MgO. Similar trends occur for nickel, with peridotites and transition zones always showing Ni < 2000 ppm and dunites containing > 2000 ppm of Ni. SiO2 contents shows inverse correlation with MgO content of the rocks being as low as 34,5 wt % in dunites and increasing gradually through the transition zones up to > 38 wt % in peridotites. Pt is the only element of the PGE group showing relative enrichment up to 36 ppb. Other PGE group elements are depleted in the rock with contents often being below detection limits. Patches of harzburgite are observed within the dunite pods. These patches preserve the same banding as the host harzburgite suggesting that these relicts have not been rotated from their original position and that the formation of dunites took place as a volume replacement of the harzburgite. Dunite bodies within the mantle section of ophiolite complexes are considered to represent sites of melt extraction and migration and essentially controls the composition, physical properties and ore-forming potential of melts emplaced up section in the ophiolite stratigraphy.

Chromium immobilization by extra- and intraradical fungal structures of arbuscular mycorrhizal symbioses.

PubMed

Wu, Songlin; Zhang, Xin; Sun, Yuqing; Wu, Zhaoxiang; Li, Tao; Hu, Yajun; Lv, Jitao; Li, Gang; Zhang, Zhensong; Zhang, Jing; Zheng, Lirong; Zhen, Xiangjun; Chen, Baodong

2016-10-05

Arbuscular mycorrhizal (AM) fungi can enhance plant Cr tolerance through immobilizing Cr in mycorrhizal roots. However, the detailed processes and mechanisms are unclear. The present study focused on cellular distribution and speciation of Cr in both extraradical mycelium (ERM) and mycorrhizal roots exposed to Cr(VI) by using field emission scanning electron microscopy equipped with energy dispersive X-ray spectrometer (FE-SEM-EDS), scanning transmission soft X-ray microscopy (STXM) and X-ray absorption fine structure (XAFS) spectroscopy techniques. We found that amounts of particles (possibly extracellular polymeric substances, EPS) were produced on the AM fungal surface upon Cr(VI) stress, which contributed greatly to Cr(VI) reduction and immobilization. With EDS of the surface of AM fungi exposed to various Cr(VI) levels, a positive correlation between Cr and P was revealed, suggesting that phosphate groups might act as counter ions of Cr(III), which was also confirmed by the XAFS analysis. Besides, STXM and XAFS analyses showed that Cr(VI) was reduced to Cr(III) in AM fungal structures (arbuscules, intraradical mycelium, etc.) and cell walls in mycorrhizal roots, and complexed possibly with carboxyl groups or histidine analogues. The present work provided evidence of Cr immobilization on fungal surface and in fungal structures in mycorrhizal roots at a cellular level, and thus unraveled the underlying mechanisms by which AM symbiosis immobilize Cr. Copyright © 2016 Elsevier B.V. All rights reserved.

Phenol oxidation through its adduct formation with chromium complex of 1,4,8,11-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane: A theoretical study

NASA Astrophysics Data System (ADS)

Narayanan, Jayanthi; Guadalupe, Hernández J.; Thangarasu, Pandiyan

2017-04-01

Structural and electronic properties of [cis-[Cr(tmpcH)X2]n+ (n = 2 or 4; X = OH-, Cl-, Br- and H2O; tmpcH = 1,4,8,11-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane were analyzed by DFT and TD-DFT methods. The local reactivity active site of the ligand was determined by the condensed-to atom Fukui indexes (CAFI) f(r). In the study, the axial bond distance with metal ion undergoes a considerable change from shorter to longer as OH < Cl- < Br- < H2O, agreeing with the molecular orbital analysis where the dz2 energy is lowered for OH- compared to H2O at the axial position. After analyzing the geometrical data collected from literature for the complexes of Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn (II) with tmpcH, it was found that the bond distance decreases with increasing number of d-electrons in the 3d orbital, suggesting that the over-lapping of oribital (π) from Npy with the metal d-orbital is more effective than those from Ncyclam with metal d-orbital. Therefore, the change of different oxidation states for [cis-[Cr(tmpcH)X2]n+ influences significantly the geometrical and electronic parameters. For cis-[Cr(tmpcH)Cl2]2+ the calculated bands are red shifted except for the lower energy band (595 nm) which agrees qualitatively with the experimental one; in addition, the effect of solvent on the electronic transition was analyzed. Furthermore, we collected the electronic data for several chromium complexes from the literature, and compared with our results by plotting the data against number of chromium compounds. Finally, the phenol oxidation properties of the chromium complexes were studied, and phenol forms an adduct with [Cr(tmpcH)Cl]3+ to yield [Cr(tmpcH)Cl-OPh]2+ which could produce the phenol radical, which is enhanced by the presence of -OCH3 group at para- position in the phenolic ring.

Low temperature synthesis and enhanced electrical properties by substitution of Al3+ and Cr3+ in Co-Ni nanoferrites

NASA Astrophysics Data System (ADS)

Pervaiz, Erum; Gul, I. H.

2013-10-01

Aluminum and chromium substituted Co-Ni spinel nanoferrites were prepared by sol-gel auto combustion method. Structural parameters along with electrical and magnetic properties have been investigated in the present work. Crystallite sizes of nano ferrite estimated from the peak (311) lies in the range of 13-21 nm ±2 nm and compared with crystallite sizes calculated from Williamsons-Hall plots. DC electrical resistivity variations due to the concentration of aluminum and chromium in the host ferrite have been measured from 368 K to 573 K. Increase in the room temperature DC electrical resistivity was observed up to a concentration x=0.2 and then decreases for x >0.2. Dielectric parameters (real and imaginary part of complex permittivity, dielectric loss tangent) were studied as a function of frequency (20 Hz-5 MHz) and a decrease in the dielectric parameters was observed due to substitution of nickel, aluminum and chromium ions in cobalt nanoferrites. AC conductivity, complex impedance and complex electrical modulus were studied as a function of frequency for the conduction and relaxation mechanisms in the present ferrite system. Saturation magnetization, coercivity, canting angles and magneto crystalline anisotropy variations with composition were observed and presented for the present ferrites under an applied magnetic field of 10 kOe at room temperature. It was found that both magnetization and coercivity decreases with increase in the concentration of aluminum and chromium along with a decrease in the anisotropy parameters. High DC resistivity with low dielectric parameters of the present nanoferrites make them suitable for high frequency and electromagnetic wave absorbing devices. High purity mixed Co-Ni-Al-Cr nanoferrites have been prepared by sol-gel auto combustion method. DC electrical resistivity increases due to substitution of Al3+ and Cr3+. Complex permittivity decrease for Co-Ni-Al-Cr nanoferrites. Detailed AC response analysis has been presented for mixed Co-Ni-Al-Cr nanoferrites. Magnetization and coercively reduces for Al3+ and Cr3+ doped Co-Ni ferrite nanoparticles showing that material is becoming soft magnetic.

Compositional variations and tectonic settings of podiform chromitites and associated ultramafic rocks of the Neoproterozoic ophiolite at Wadi Al Hwanet, northwestern Saudi Arabia

NASA Astrophysics Data System (ADS)

Ahmed, Ahmed Hassan; Harbi, Hesham M.; Habtoor, Abdelmonem M.

2012-08-01

Wadi Al Hwanet area in NW of Saudi Arabia is part of the Jebel Ess ophiolite constituting the northeastern part of the ˜700 Ma Yanbu-Sol Hamed-Onib-Allaqi-Heiani suture of the northern Arabian-Nubian Shield. The mantle section of Wadi Al Hwanet ophiolite consists mainly of voluminous harzburgites overlain by thick, massive transition-zone dunites, and small-scale chromitite pods. The harzburgites and massive dunites are exceptionally fresh; primary magmatic textures and silicate minerals are still preserved. Two modes of podiform chromitites exist; small lensoidal pods (group I), and relatively large dike-like pods (group II). Geochemically, the former chromitite type contains chromian spinels with high Cr# (0.79-0.81) and displays a PGE-poor character, with steep negatively-sloped PGE distribution patterns, whereas the latter chromitite type contains chromian spinels with relatively lower Cr# (0.61-0.71) and is PGE-rich (up to 1000 ppb), with positively-sloped PGE distribution patterns. The group II chromitites have much higher sulfide content than the group I suite. Parental melt compositions, in equilibrium with podiform chromitites, vary in Al2O3, FeO*/MgO and TiO2 contents from group I to group II chromitites, although both of them are in the range of the boninitic melts. The differences in the chromitites chemistry are most probably due to variable degrees of partial melting of the involved melts. Two stages of a magmatic activity were inferred for the chromitites genesis. The group I chromitites, of high Cr# of chromian spinels and PGE-poor negatively-sloped patterns, were precipitated in the first stage from a boninitic melt produced by a high degree of partial melting at a supra-subduction zone setting. The second chromitite-forming stage involves a relatively low degree of partial melting under high activities of sulfur and oxygen to produce the group II chromitites with enrichment in sulfides and PGE contents, possibly in a supra-subduction zone setting. In contrast to the chromitites, the harzburgites have low PGE contents, with characteristic unfractionated patterns, and low Cr# (0.46-0.57) of the chromian spinels suggesting mantle residues after low degrees of mantle melting beneath a mid-ocean ridge setting. Together with the entire plotting within the olivine-spinel mantle array, the similarity of olivine and spinel chemistry of dunites with those of harzburgites suggests a replacement origin for the dunites by the consumption of pyroxenes. It is likely that Wadi Al Hwanet mantle section was initially derived from a mid-ocean ridge environment and modified later, under a supra-subduction zone regime, to form podiform chromitites.

Uptake of Cr3+ from aqueous solution by lignite-based humic acids.

PubMed

Arslan, G; Pehlivan, E

2008-11-01

Humic acid (HA) produced from brown coal, a relatively abundant and inexpensive material is currently being investigated as an adsorbent to remove toxic metals from aqueous solution. The influence of five parameters (contact time, solution pH, initial metal concentration, temperature and amount of adsorbent) on the removal at 20+/-1 degrees C was studied. HAs were prepared from lignites by using alkaline extraction, sedimentation and acidic precipitation. Adsorption equilibrium was achieved in about 60 min for Cr3+ ion. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 0.17 mmol for Ilgin (HA1), 0.29 mmol for Beysehir (HA2) and 0.18 mmol Ermenek (HA3) and 0.17 mmol of Cr3+/g for activated carbon (AC) was achieved, respectively at pH of 4.1. More than 84% of Cr3+ was removed by HA2, 54% by HA3 and 51% by HA1 and 50% by AC from aqueous solution. The adsorption was strongly dependent on pH but independent of ionic strength and metal ions. The adsorption of Cr3+ was higher between pH 4.1 and 5.1 for all HAs and maximum sorption was observed at pH 4.1. The rise in temperature caused a slight decrease in the value of the equilibrium constant (Kc) for the sorption of Cr3+ ion. Complex mechanisms including ion exchange, complexation and adsorption and size exclusion are possible for sorption of Cr3+ ion on HAs.

New oxalate-bridged CrIII-MnII polymeric network incorporating a spin-crossover [Co(terpy)2]2+ cation.

PubMed

Kou, Hui-Zhong; Sato, Osamu

2007-11-12

The reaction of Mn2+ with [Cr(ox)3]3- in the presence of the spin-crossover [Co(terpy)2]2+ cation gives rise to a 1D [Co(terpy)2][Mn(H2O)ClCr(ox)3].H2O.0.5MeOH (1) or a 2D [Co(terpy)2][Mn(H2O)Cr(ox)3]2.5H2O.0.5MeOH (2). The trimetallic complexes display dominant ferromagnetic behavior, and spin-crossover of [Co(terpy)2]2+ is suppressed by the chemical pressure of the polymeric oxalate-bridged network.