Reactions of aqueous iron-DFOB (desferrioxamine B) complexes with flavin mononucleotide in the absence of strong iron(II) chelators

The mechanisms controlling microbial uptake of Fe^III-siderophore complexes and subsequent release of the metal for cellular use have been extensively studied in recent years. Reduction of the Fe^III center is believed to be necessary to labilize the coordinated Fe and facilitate exchange with cellular ligands. Previous studies report reduction of Fe^III-DFOB by various reducing agents in solutions containing Fe^II-chelating colorimetric agents for monitoring reaction progress, but the importance of these findings is unclear because the colorimetric agents themselves stabilize and enhance the reactions being monitored. This study examines the reduction of Fe^III complexes with DFOB (desferrioxamine B), a trihydroxamate siderophore, by the fully reduced hydroquinone form of flavin mononucleotide (FMN_HQ) in the absence of strong Fe^II-chelating agents, and Fe redox cycling in solutions containing DFOB and oxidized and reduced FMN species. Experimental results demonstrate that the rate and extent of Fe^III-DFOB reduction is strongly dependent on pH and FMN_HQ concentration. At pH ? 5, incomplete Fe^III reduction is observed due to two processes that re-oxidize Fe^II, namely, the autodecomposition of Fe^II-DFOB complexes (Fe^II oxidation is coupled with reduction of a protonated hydroxamate moiety) and reaction of Fe^II-DFOB complexes with the fully oxidized flavin mononucleotide product (FMN_OX). Chemical speciation-dependent kinetic models for the forward reduction process and both reverse Fe^II oxidation processes are developed, and coupling kinetic models for all three Fe redox processes leads to successful predictions of steady-state Fe^II concentrations observed over a range of pH conditions in the presence of excess FMN_HQ and FMN_OX. The observed redox reactions are also in agreement with thermodynamic constraints imposed by the combination of Fe^III/Fe^II and FMN_OX/FMN_HQ redox couples. Quantitative comparison between kinetic trends and changing Fe speciation reveals that FMN species react predominantly with diprotonated Fe^III-DFOB and Fe^II-DFOB complexes, where protonation of one hydroxamate group opens up two Fe coordination positions. This finding suggests that ternary complex formation (FMN-Fe-DFOB) facilitates inner-sphere electron transfer reactions between the flavin and Fe center.     

Planning issues in the territorial integration of the Korean peninsula

The historic summit between the leaders of the two Koreas in June 2000 provided a new opportunity for inter-Korean dialogue. Despite many uncertainties regarding the form and substance of inter-Korean economic cooperation, Korean people believe that inter-Korean economic cooperation will expand and eventually lead to economic and territorial integration of the two Koreas. This essay discusses the progress and issues of inter-Korean economic cooperation including infrastructure development. In particular, the essay examines long-term planning issues surrounding the territorial integration of the Korean peninsula and their implications for balanced development. With the German case of economic integration as a point of reference, the essay points out a few strategic problems involved in inter-Korean economic cooperation and suggests an alternative strategy to achieve balanced development.     

Hydration, 18O enrichment and oxidation during ocean floor hydrothermal metamorphism of ophiolitic metabasic rocks from E. Liguria,Italy

During ocean-floor hydrothermal metamorphism of a 225 m thick allochthonous Jurassic sequence of ophiolitic pillow lavas and underlying material in E. Liguria, Italy, the rocks were hydrated, enriched in ¹⁸O and oxidised. H₂O⁺ contents increased from ~0.3 to 3.8 wt.%, δ¹⁸O values increased from ~ +6‰ to values as high as +13.2‰, and ($\text{Fe}{}_2\text{O}{}_3\text{FeO}$1) increased from 0.18 to ratios as high as 1.0. Both δ¹⁸O values and oxidation ratios decrease in the original direction of increasing depth. Pillow margins are consistently more enriched in ¹⁸O and are more oxidised than cores.These observations are qualitatively interpreted in terms of a non-isothermal, heterogeneous reaction model of interaction of basalt with oxygen-bearing sea water during flow through the packed bed of pillows. Fluid flow approximated undirectional downward motion, and occurred in the recharge part of a cycle of single pass convection. Mass transfer through the pile was by flow (infiltration metasomatism), whereas intra-pillow mass transfer was diffusional. Oxygen isotope exchange and oxidation did not occur under conditions of perfect incremental equilibrium. An integrated bulk volumetric water/rock ratio of ~2 × 10³:1 is estimated from the oxidation profile.     

Enhanced bioremoval of refractory compounds from dyeing wastewater using optimized sequential anaerobic/aerobic process

The upflow anaerobic sludge blanket process followed by the biological aerated filter process was employed to improve the removal of color and recalcitrant compounds from real dyeing wastewater. The highest removal efficiency for color was observed in the anaerobic process, at 8-h hydraulic retention time, seeded with the sludge granule. In the subsequent aerobic process packed with the microbe-immobilized polyethylene glycol media, the removal efficiency for chemical oxygen demand increased significantly to 75 %, regardless of the empty bed contact time. The average influent non-biodegradable soluble chemical oxygen demand was 517 mg/L, and the average concentration in effluent from the anaerobic reactor was 363 mg/L, suggesting the removal of some recalcitrant matters together with the degradable ones. The average non-biodegradable soluble chemical oxygen demand in effluent from the aerobic reactor was 87, 93, and 118 mg/L, with the removal efficiency of 76, 74, and 67 %, at 24-, 12-, and 8-h empty bed contact time, respectively. The combined anaerobic sludge blanket and aerobic cell-entrapped process was effective to remove the refractory compounds from real dyeing wastewater as well as in reducing organic loading to meet the effluent discharge limits. This integrated process is considered an effective and economical treatment technology for dyeing wastewater.     

Influence of relative density,particle shape,and stress path on the plane strain compression behavior of granular materials

Two types of stress path-controlled plane strain compression tests were performed on both loose and dense specimens of angular and sub-angular sands and two rounded glass beads with different particle sizes. Digital image correlation method was used to analyze local deformation developments, especially shear band patterns. The material behavior in response to shearing has been found to be dependent on the relative density, particle shape, and stress path. The results of analysis on local deformation developments showed that the onset of shear bands occurred prior to their peak strengths in both dense and loose specimens. The growth rates of local maximum shear strain along a shear band were approximately consistent with an increasing global axial strain after the onset of shear band. The shear band width was influenced by both the mean particle size and the particle shape. The measured shear band inclination angles were in between those estimated by Coulomb’s and Roscoe’s formulas.     

Constraints on the application of the MBT/CBT palaeothermometer at high latitude environments (Svalbard,Norway)

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are membrane lipids of unknown bacteria that are ubiquitous in soil and peat. Two indices based on the distribution of these lipids in soils, the Cyclization of Branched Tetraethers (CBT) and the Methylation of Branched Tetraethers (MBT) indices have been shown to correlate with soil pH, and mean annual air temperature (MAT) and soil pH, respectively, and can be used to reconstruct MAT in palaeoenvironments. To verify the extent to which branched GDGTs in marine sediments reflect the distribution pattern on land and whether these proxies are applicable for palaeoclimate reconstruction in high latitude environments with a MAT of <0 °C, we compared the branched GDGT distribution in Svalbard soils and nearby fjord sediments. Although branched GDGT concentrations in the soil are relatively low (0.02–0.95 μg/g dry weight (dw)) because of the cold climate and the short growing season, reconstructed MATs based on the MBT/CBT proxy are ca. ?4 °C, close to the measured MAT (ca. ?6 °C). Concentrations of branched GDGTs (0.01–0.20 μg/g dw) in fjord sediments increased towards the open ocean and the distribution was strikingly different from that in soil, i.e. dominated by GDGTs with one cyclopentane moiety. This resulted in MBT/CBT-reconstructed MAT values of 11–19 °C, well above measured MAT. The results suggest that at least part of the branched GDGTs in marine sediments in settings with a low soil organic matter (OM) input may be produced in situ. In these cases, the application of the MBT/CBT palaeothermometer will generate unrealistic MAT reconstructions. The MBT/CBT proxy should therefore only be used at sites with a substantial input of soil OM relative to the amount of marine OM, i.e. at sites close to the mouth of rivers with a catchment area where sufficient soil formation takes place and the soil thus contains substantial amounts of branched GDGTs.     

Application of an optimum design technique for determining the coefficient of consolidation by using piezocone test data

For normally consolidated clay, several researchers have developed a number of theoretical time factors to determine the coefficient of consolidation from piezocone test results. However, depending on assumptions and analytical techniques, it could vary considerably, even for a specific degree of consolidation. In this paper a method is proposed to determine a consistent coefficient of consolidation by applying the concept of an optimum design technique over all ranges of the degree of consolidation. Initial excess pore pressure distribution is assumed to be capable of being obtained by the successive spherical cavity expansion theory. The dissipation of pore pressure is simulated by means of a two-dimensional linear-uncoupled axi-symmetric consolidation analysis. The minimization of differences between measured and predicted excess pore pressure was carried out by the BFGS unconstrained optimum design algorithm with a one-dimensional golden section search technique. By analyzing numerical examples and in-situ test results, it was found that the adopted optimum design technique gives consistent and convergent results.