Photochemical formation of polybrominated dibenzo-p-dioxins from environmentally abundant hydroxylated polybrominated diphenyl ethers

High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols.     

Tectonic Articulation: Making Engineering Logics Speak

As much of the responsibility of a building's physical design and fabrication has increasingly shifted to engineers, spatial communication has remained the sole and significant preserve of architects. Patrik Schumacher , Partner at Zaha Hadid Architects (ZHA), explains how tectonic articulation through architectural design – the selection and employment of technically engineered forms and details – enables the legible enunciation of a building's forms in a manner that has the potential to give it social meaning and expression.     

Photoelectrochemical and photocatalytic activity of tungsten doped TiO2 nanotube layers in the near visible region

In the present work we study the effect of WO₃ doping on the photo-electrochemical behavior of self-organized TiO₂ nanotube layers. Mixed oxide nanotubes were grown by anodization of Ti–W alloys containing 0.2 and 9% W, with a thicknesses of the oxide nanotube layers adjusted to about 1.1–1.2 μm. We show that by WO₃ doping, the near visible photoresponse and photocatalytic performance can drastically be enhanced. While a content of 9 at% WO₃ in photoresponse experiments is most beneficial, in long term experiments a higher efficiency is observed for the 0.2 at% W content. This is due to a gradual leaching of WO₃ (dissolution into the electrolyte) for the higher WO₃ content. This demonstrates that under optimized WO₃ doping conditions a lasting visible light activation of TiO₂ nanotubes can be achieved.     

Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions

The corrosion mechanisms of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys have been investigated by potentiodynamic and potentiostatic polarization. Very good passivation of the Al–Cr–Fe surface is exhibited from 1 M H₂SO₄ to 1 M NaOH solutions, which was confirmed by ICP-OES analysis over a period of 273 days. Potentiostatically formed passive films analysed by XPS revealed chromium enrichment in the outermost layer of the aluminium oxy-hydroxide film. Although Al–Cu–Fe–Cr showed passivation during potentiodynamic polarization, heavy active corrosion at OCP was revealed by ICP-OES. For the Al–Cu–Fe–Cr alloy, the 10% content of Cr is insufficient to maintain a protective “chemically stable” Cr oxide/hydroxide.     

Electrochemical growth of self-organized TiO2�CWO3 composite nanotube layers: effects of applied voltage and time

The present work demonstrates that morphology of TiO₂?CWO₃ composite nanotubes formed by alloy anodization can be tuned by controlling applied voltages and time. Distinctive tube morphology can be formed by applying a voltage of more than 80?V. Nanotube diameter and length have a linear relationship with the anodization voltage with a current efficiency of almost 100?%. Furthermore, compared to pure TiO₂, the composite nanotubes show a very uniform tube diameter along the tube axis even at the extended anodization time.     

Calculated phase diagrams,iron tolerance limits,and corrosion of Mg-Al alloys

The factors determining corrosion are reviewed in this paper, with an emphasis on iron tolerance limit and the production of high-purity castings. To understand the iron impurity tolerance limit, magnesium phase diagrams were calculated using the Pandat software package. Calculated phase diagrams can explain the iron tolerance limit and the production of high-purity castings by means of control of melt conditions; this is significant for the production of quality castings from recycled magnesium. Based on the new insight, the influence of the microstructure on corrosion of magnesium alloys is reviewed.     

An exploratory study of the corrosion of Mg alloys during interrupted salt spray testing

A first systematic investigation was carried out to understand the corrosion of common Mg alloys (Pure Mg, AZ31, AZ91, AM30, AM60, ZE41) exposed to interrupted salt spray. The corrosion rates were also evaluated for these alloys immersed in 3 wt.% NaCl by measuring hydrogen evolution and an attempt was made to estimate the corrosion rate using Tafel extrapolation of the cathodic branch of the polarisation curve. The corrosion of these alloys immersed in the 3 wt.% NaCl solution was controlled by the following factors: (i) the composition of the alpha-Mg matrix, (ii) the volume fraction of second phase and (iii) the electrochemical properties of the second phase. The Mg(OH)₂ surface film on Mg alloys is probably formed by a precipitation reaction when the Mg²⁺ ion concentration at the corroding surface exceeds the solubility limit. Improvements are suggested to the interrupted salt spray testing; the ideal test cycle would be a salt spray of duration X min followed by a drying period of (120-X) min. Appropriate apparatus changes are suggested to achieve 20% RH rapidly within several minutes after the end of the salt spray and to maintain the RH at this level during the non-spray part of the cycle. The electrochemical measurements of the corrosion rate, based on the “corrosion current” at the free corrosion potential, did not agree with direct measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.     

Calculated phase diagrams and the corrosion of die-cast Mg-Al alloys

The corrosion of commercial die-cast Mg-Al alloys was elucidated by a study, of the corrosion in 3% NaCl, of (i) high-pressure die-cast (HPDC) model Mg-Al alloys, (ii) low-purity Mg, (iii) high-purity (HP) Mg and (iv) HP Mg heat treated at 550 °C. HPDC is the most important route for the production of Mg components. The corrosion of the model alloys was dominated by the Fe impurity element. The present research identified the appearance of the Fe-rich particles in the microstructure. In high magnification (∼1000× to 5000×) secondary electron images, they appear as small white features, typically less than 1 μm in diameter. In order to understand the impurity tolerance limits, (i) the appropriate corrosion literature was summarised and reviewed and (ii) Mg phase diagrams were calculated using the Pandat software package. Calculated phase diagrams can explain (i) the tolerance levels for Fe and Cu and (ii) the production of high-purity castings by means of control of melt conditions; this has high significance for the production of quality castings from recycled Mg. A full analysis requires that the Mg database be extended to include Ni, Co and some RE. The Fe tolerance limit is ∼5-10 ppm for cast HP Mg heat treated at 550 °C. Analysis of the Mg corrosion literature indicates that several studies have been dominated by the Fe impurity content and have not dealt with the stated aims; it means that the full chemical composition should be reported in all studies of the corrosion of Mg alloys.     

Multivariate analysis of a biologically activated carbon (BAC) system and its efficiency for removing PAHs and aliphatic hydrocarbons from wastewater polluted with petroleum products

The efficiency of a biologically activated carbon system for treating wastewater polluted with petroleum products was examined and the effects of process parameters on its efficacy were evaluated. In each experiment 17 alkylated and 19 non-alkylated polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPHs, C₁₀–C₄₀) were extracted using semipermeable membrane devices from wastewater before and after treatment. The acquired data during experiments were analyzed using principal component analysis (PCA). The treatment system robustly removed dissolved PAHs across the studied ranges of the process parameters, providing overall removal efficiencies of 96.9–99.7% for the sum of 36 PAHs. However, the major contributor to their removal was sorption rather than biodegradation, and despite the general efficiency of the process there was up to a 9-fold range in the sums of quantified PAHs in the effluents between experiments. Combinations of long process contact time (24 h) with high temperature (24 °C) and moderate oxygen concentration (6–7 mg O₂ L⁻¹) resulted in good removal of bioavailable PAHs. The removal of TPHs was more dependent on biological activities during the wastewater treatment, and consequently more dependent on the process parameters. In addition, small but significant proportions of PAHs were volatilized and released during the wastewater treatment.     

A column generation method for spatial TDMA scheduling in ad hoc networks

An ad hoc network can be set up by a number of units without the need of any permanent infrastructure. Two units establish a communication link if the channel quality is sufficiently high. As not all pairs of units can establish direct links, traffic between two units may have to be relayed through other units. This is known as the multi-hop functionality. In military command and control systems, ad hoc networks are also referred to as multi-hop radio networks.

Spatial TDMA (STDMA) is a scheme for access control in ad hoc networks. STDMA improves TDMA by allowing simultaneous transmission of multiple units. In this paper, we study the optimization problem of STDMA scheduling, where the objective is to find minimum-length schedules. Previous work for this problem has focused on heuristics, whose performance is difficult to analyze when optimal solutions are not known. We develop novel mathematical programming formulations for this problem, and present a column generation solution method. Our numerical experiments show that the method generates a very tight bound to the optimal schedule length, and thereby enables optimal or near-optimal solutions. The column generation method can be used to provide benchmarks when evaluating STDMA scheduling algorithms. In particular, we use the bound obtained in the column generation method to evaluate a simple greedy algorithm that is suitable for distributed implementations.