Controlled RAFT polymerization and zinc binding performance of catechol-inspired homopolymers

Incorporation of catechols into polymers has long been of interest due to their ability to chelate heavy metals and their use in the design of adhesives, metal-polymer nanocomposites, antifouling coatings, and so on. This paper reports, for the first time, the reversible addition-fragmentation chain transfer (RAFT) polymerization of a protected catechol-inspired monomer, 3,4-dimethoxystyrene (DMS), using commercially available trithiocarbonate, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT), as a chain transfer agent. Our identified RAFT system produces well-defined polymers across a range of molecular weights (5-50 kg/mol) with low molar mass dispersities (Mw/Mn < 1.3). Subsequent facile demethylation of poly(3,4-dimethoxystyrene) (PDMS) yields poly(3,4-dihydroxystyrene) (PDHS), a catechol-bearing polymer, in quantitative yields. Semiquantitative zinc binding capacity analysis of both polymers using SEM/EDXA has demonstrated that both PDMS and PDHS have considerable surface binding (65% and 87%, respectively), although the films deposited from PDMS are of a better quality and processability due to solubility and lower processing temperatures. © 2014 American Chemical Society.

Synthesis, characterization and study of physical properties of novel M(n+1)AX(n) compounds

Mn+1AXn compounds, the ternary layered nanolaminates have gathered momentum in the last decade since its advent because of their unusual but exciting properties. These technologically important compounds combine some of the best properties of metals and ceramics. Like ceramics they are refractory, oxidation resistant, elastically stiff and relatively light. They also exhibit metallic properties like excellent machinability, thermal and electrical conductivity. This dissertation concentrates on the synthesis of germanium-based 211 Mn+1AXn compounds. The main objective of the research was to synthesize predominantly single phase samples of Cr2GeC, V2GeC and Ti2GeC. Another goal was to study the effect of solid substitutions on the M-site of Mn+1AXn compounds with Ge as an A-element. This study is in itself the first to demonstrate the synthesis of (Cr0.5V0.5)2GeC a novel Mn+1AXn compound. Scanning electron microscopy coupled with energy dispersive spectroscopy, x-ray diffraction and electron probe microanalysis were employed to confirm the presence of predominantly single phase samples of M2GeC compounds where M = Ti, V, Cr and (Cr 0.5V0.5). A large part of the dissertation also focuses on the effect of the compressibility on the Ge-based 211 Mn+1AXn compounds with the aid of diamond anvil cell and high energy synchrotron radiation. This study also concentrates on the stability of these compounds at high temperature and thereby determines its suitability as high temperature structural materials. In order to better understand the effect of substitutions on A-site of 211 Mn+1 AXn compounds under high pressure and high temperature, a comparison is made with previously reported 211 Mn+1AXn compounds with Al, Ga and S as A-site elements.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Annotated record and illustrations of Mn nodules retrieved during cruise KH-73-4 of the R/V Hakuho Maru and cruises GH76-1 and GH77-1 of the R/V Hakurei Maru

Deep sea manganese nodules from the Central Pacific Basin are mainly composed of 10Å manganite and d-MnO2 Two zones equivalent to the minerals are evidently distinguishable according to their optical properties. Microscopic and microprobe analyses revealed quite different chemical compositions and textnral characteristics of the two zones. These different feature of the two zones of nodules suggest the different conditions under which they were formed. Concentrations of 11 metal elements in the zones and inter-element relationships show that the 10Å manganite zone is a monomineralic oxide phase containing a large amount of manganese and minor amounts of useful metals, and that the d-MnO2 zone which is apparently homogeneous under the microscope is a mixture of three or more different minerals. The chemical characteristics of the two zones can explain the variation of bulk composition of deep sea manganese nodules and inter-element relationships previously reported, suggesting that the bulk compositions are attributable to the mixing of the 10Å manganite and d-MnO2 zones in various ratios. Characteristic morphology and surface structure of some types of nodules and their relationships to chemistry are also attribut able to the textural and chemical features of the above mentioned two phases. Synthesis of hydrated manganese oxides was carried out in terms of the formation of manganese minerals in the ocean. The primary product which is an equivalent to d-MnO2 was precipitated from Mn 2+ -bearing alkaline solution under oxigenated condition by air bubbling at one atmospheric pressure and room temperature. The primary product was converted to a l0Å manganite equivalent by contact with Ni 2+, Cu 2++ or CO2+ chloride solutions. This reaction caused the decrease of Ni2+, Cu2+ or CO2+ concentrations and the increase of Na+ concentration in the solution. The reaction also proceeded even in diluted solutions of nickel chloride and resulted in a complete removal of Ni2+ from the solution. Reaction products were exclusively 10Å manganite equivalents and their chemical compositions were very similar to those of 10Å manganite in manganese nodules. The maximum value of(Cu+Ni+Co)/Mn ratio of 10Å manganite zones in manganese nodules is 0.16, and the Ni/Mn ratio of synthetic 10Å manganite ranges from 0.15 to 0.18 with the average of 0.167.

(Table 1) Downcore age and bulk geochemistry of sediment core GS7202-35

The distribution of redox-sensitive metals in sediments is potentially a proxy for past ocean ventilation and productivity, but deconvolving these two major controls has proved difficult to date. Here we present a 740 kyr long record of trace element concentrations from an archived sediment core collected at ~15°S on the western flank of the East Pacific Rise (EPR) on 1.1 Myr old crust and underlying the largest known hydrothermal plume in the world ocean. The downcore trace element distribution is controlled by a variable diagenetic overprint of the inferred primary hydrothermal plume input. Two main diagenetic processes are operating at this site: redox cycling of transition metals and ferrihydrite to goethite transition during aging. The depth of oxidation in these sediments is controlled by fluctuations in the relative balance of bottom water oxygen and electron donor input (organic matter and hydrothermal sulfides). These fluctuations induce apparent variations in the accumulation of redox-sensitive species with time. Subsurface U and P peaks in glacial age sediments, in this and other published data sets along the southern EPR, indicate that basin-wide changes in deep ocean ventilation, in particular at glacial-interglacial terminations II, III, IV, and V, alter the depth of the oxidation front in the sediments. These basin-wide changes in the deep Pacific have significant implications for carbon partitioning in the ocean-atmosphere system, and the distribution of redox-sensitive metals in ridge crest sediment can be used to reconstruct past ocean conditions at abyssal depths in the absence of alternative proxy records.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Atomic resolution studies of oxide superlattices and ultrathin films

The ability to grow ultrathin films layer-by-layer with well-defined epitaxial relationships has allowed research groups worldwide to grow a range of artificial films and superlattices, first for semiconductors, and now with oxides. In the oxides thin film research community, there have been concerted efforts recently to develop a number of epitaxial oxide systems grown on single crystal oxide substrates that display a wide variety of novel interfacial functionality, such as enhanced ferromagnetic ordering, increased charge carrier density, increased optical absorption, etc, at interfaces. The magnitude of these novel properties is dependent upon the structure of thin films, especially interface sharpness, intermixing, defects, and strain, layering sequence in the case of superlattices and the density of interfaces relative to the film thicknesses. To understand the relationship between the interfacial thin film oxide atomic structure and its properties, atomic scale characterization is required. Transmission electron microscopy (TEM) offers the ability to study interfaces of films at high resolution. Scanning transmission electron microscopy (STEM) allows for real space imaging of materials with directly interpretable atomic number contrast. Electron energy loss spectroscopy (EELS), together with STEM, can probe the local chemical composition as well as local electronic states of transition metals and oxygen. Both techniques have been significantly improved by aberration correctors, which reduce the probe size to 1 Å, or less. Aberration correctors have thus made it possible to resolve individual atomic columns, and possibly probe the electronic structure at atomic scales. Separately, using electron probe forming lenses, structural information such as the crystal structure, strain, lattice mismatches, and superlattice ordering can be measured by nanoarea electron diffraction (NED). The combination of STEM, EELS, and NED techniques allows us to gain a fundamental understanding of the properties of oxide superlattices and ultrathin films and their relationship with the corresponding atomic and electronic structure. In this dissertation, I use the aforementioned electron microscopy techniques to investigate several oxide superlattice and ultrathin film systems. The major findings are summarized below. These results were obtained with stringent specimen preparation methods that I developed for high resolution studies, which are described in Chapter 2. The essential materials background and description of electron microscopy techniques are given in Chapter 1 and 2. In a LaMnO3-SrMnO3 superlattice, we demonstrate the interface of LaMnO3-SrMnO3 is sharper than the SrMnO3-LaMnO3 interface. Extra spectral weights in EELS are confined to the sharp interface, whereas at the rougher interface, the extra states are either not present or are not confined to the interface. Both the structural and electronic asymmetries correspond to asymmetric magnetic ordering at low temperature. In a short period LaMnO3-SrTiO3 superlattice for optical applications, we discovered a modified band structure in SrTiO3 ultrathin films relative to thick films and a SrTiO3 substrate, due to charge leakage from LaMnO3 in SrTiO3. This was measured by chemical shifts of the Ti L and O K edges using atomic scale EELS. The interfacial sharpness of LaAlO3 films grown on SrTiO3 was investigated by the STEM/EELS technique together with electron diffraction. This interface, when prepared under specific conditions, is conductive with high carrier mobility. Several suggestions for the conductive interface have been proposed, including a polar catastrophe model, where a large built-in electric field in LaAlO3 films results in electron charge transfer into the SrTiO3 substrate. Other suggested possibilities include oxygen vacancies at the interface and/or oxygen vacancies in the substrate. The abruptness of the interface as well as extent of intermixing has not been thoroughly investigated at high resolution, even though this can strongly influence the electrical transport properties. We found clear evidence for cation intermixing through the LaAlO3-SrTiO3 interface with high spatial resolution EELS and STEM, which contributes to the conduction at the interface. We also found structural defects, such as misfit dislocations, which leads to increased intermixing over coherent interfaces.

Effects of various salt purity levels on lipid oxidation and sensory characteristics of ground turkey and pork

Salt use in meat products is changing. Consumers desire sea salt which may also contain trace metals and the government is demanding a reduction in sodium. Therefore a need exists to understand how varying impurity levels in salt affect meat quality. This study evaluated the effects of various salt preparations on lipid oxidation, sensory characteristics, protein extractability, and bind strength of ground turkey and pork. This study was a completely randomized design with 5 treatment groups and 6 replications in 2 species. Ground, turkey and pork meat was formulated into one hundred and fifty gram patties with sodium chloride (1%) containing varying amounts of metal impurities (copper, iron, and manganese). Samples were randomly assigned to frozen storage periods of 0, 3, 6, and 9 weeks. After storage, samples were packaged in PVC overwrap and stored under retail display for 5 days. Samples were evaluated for proximate analysis to ensure the fat content was similar for all of the starting material.Thiobarbituric acid reactive substances (TBARS) were determined on raw and cooked samples to evaluate lipid oxidation. A trained six member sensory panel evaluated the samples at each storage period for saltiness, off flavor, and oxidized odor. Break strength was conducted using a Texture Analyzer and compared with salt soluble proteins (increasing salt concentrations) to evaluate protein extractability characteristics. Statistical analyses were conducted using the MIXED procedure of SAS within repeated measures over time where appropriate. No significant differences were observed among the salt treatments for raw and cooked TBARS when the control group was removed (P>0.05). Sensory panelists detected increased levels of off flavor and oxidized odor over the entire storage duration. Less force was required to break the patties from the control group when compared with the salt treatments (P<0.05). As salt concentration increased salt-soluble protein extraction increased, but there was no effect of salt type. Overall, no meaningful statistical differences among the various salt treatments were observed for all of the parameters evaluated for turkey and pork. Salt at a 1% inclusion rate containing varying levels of copper, iron, and manganese impurities in ground turkey thigh meat and ground pork served as a prooxidant. However, if a meat processor uses a 1% inclusion rate of salt in turkey and pork regardless of impurities included, it is unlikely that differences in shelf life or protein functionality would be observed.

Seasonal variation of acetylcholinesterase, catalase, glutathione s transferase in different size of Pinctada radiata and metal pollution (Pb, Cd, Ni) in Persian Gulf

There are various tools for monitoring the concentration of pollutants on aquatic ecosystems. Today these studies are based on biological monitoring and biomarkers. The aim of this study was to measure the concentration of the acetylcholinesterase (AChE), glutathione S-transferase and catalase as biomarkers of heavy metal contamination in pearl oyster Pinctada radiata and their mechanism in aquatic ecosystems. Heavy metals lead, cadmium and nickel were measured in soft tissue and studied stations in four seasons. Samples were collected seasonally in Lavan stations, Hendurabi and Nakhilo (in the northern Persian Gulf) from spring 2013 to winter of that year by scuba diving. Pearl oysters are divided according to their shells size; shells separated from soft tissues and were transferred to the laboratory for analysis of heavy metals and enzymes. Moopam standard method for were used for measuring the concentration of heavy metals and for analyzing tissue concentrations of glutathione S-transferase in Clam the method recommended by Habig et al in 1974 were used. For measuring acetylcholinesterase Ellman method were used. Catalase contamination in pearl oyster in the supernatant obtained from the study based on the method homogeate soft tissue of mussels (Abei, 1974) was evaluated. The results showed that the concentration of lead has significant difference in sediments station, the concentration of lead in Lavan is significantly higher than the other two stations, This could be due to the movement of tanker, boats and floating refueling and with a considerable amount of wastewater containing oil and Petroleum into the water, and also due to precipitation and industrial discharges the lead in the region is increasing, land-disposed sewage sludge, has large concentrations of lead. Compare the results of this study with standards related and other similar studies at the regional and international level showed that pollutant concentration of heavy metals in all cases significantly less than all the standards and guide values associated. And also compared to other world research results have been far less than others, Being Less of the conclusion given in this research according that nickel is one of the indicators of oil pollution in the study area and emissions have been relatively low of oil. The concentration of acetylcholinesterase at several stations, in large and small sizes and in the seasons had no significant difference. Variations of catalase, and glutathione S-transferase were almost similar to each other and parameters, station and seasons were significantly different in the concentrations of these enzymes. The effects and interaction between various parameters indicate that following parameters has impact on the concentration of catalase and glutathione S-transferase. Stations; Seasonal changes in antioxidant enzymes related to (assuming a constant in salinity and oxygen) to age, reproductive cycle, availability of food and water temperature. With increasing temperature at warm season, antioxidant enzymes were increase, with increasing temperature and abundance of food in the environment the amount of antioxidant enzymes may increase. The presence of the enzyme concentration may indicate that the higher levels of the enzyme to eliminate ROS activities to be any healthier situation. At the time of gonads maturation and spawning season catalase activity increases. This study also indicates that catalase was significantly higher in the warm season. Due to low pollutants of heavy metals in the study area, a lower level of contaminants were observed in shellfish tissue incidents of international standards and strong correlation between the amount of heavy metal contamination in pearl oyster tissue and enzymes was not observed. Therefore, we can say that the pearl oyster remains in a healthy condition and the amount of enzyme is normal.

Toxicity and Contamination in Bear Creek Sediment: Spatial Analysis and Implications for Risk Assessment

The sediments of Bear Creek near Baltimore, Maryland demonstrate substantial toxicity to benthic organisms, and contain a complex mixture of organic and inorganic contaminants. The present study maps the spatial extent and depth profile of toxicity and contamination in Bear Creek, and explores correlations between heavy metals, organic contaminants, and toxic responses. Two novel analytical techniques – handheld XRF and an antibody-based PAH biosensor – were applied to samples from the site to quantify total metals and total PAHs in sediments. By comprehensively assessing toxicity in Bear Creek, the present study provides data to inform future risk assessments and management decisions relating for the site, while demonstrating the benefits of applying joint biological assays and chemical assessment methods to sediments with complex contaminant mixtures.

Evaluation and measurement of chromium in sea water in order to remove it with mineral absorbent kaolin for desalination

Today, the use of heavy metals and chemical products industry expanded. The presence of significant amounts of, pollutants in industrial waste water can lead to serious risks to the environment and human health have heavy metals like chromium is one example of the future of salmon knock pond environment. Chromium is an essential element in the diet, but high doses of this element is very dangerous. Hence the use of chemical methods as a tool for the removal of metals from waste water pond be used. The aim of this study was to investigate the mineral kaolin adsorbents for the removal of chromium is water. Thus, the effect of different concentrations of absorbent micro amounts of chromium absorption and variable temperature, pH and electrolytes were studied. During the investigation of spectroscopic instrument (Varian) UV-VIS are used. Comparison of the absorption mechanism of chromium adsorption by the adsorbent with nano-absorbent kaolin kaolin was investigated. According to the studies done in the same conditions of temperature, pH and shaking rate of chromium absorption by nano kaolin kaolin is much more attractive. Therefore, its use as an adsorbent abundant, cheap, accessible, efficient and effective is proposed.

Development of site-specific sediment quality guidelines for North and South Atlantic littoral zones: Comparison against national and international sediment quality benchmarks

We aimed to develop site-specific sediment quality guidelines (SQGs) for two estuarine and port zones in Southeastern Brazil (Santos Estuarine System and Paranagua Estuarine System) and three in Southern Spain (Ria of Huelva, Bay of Cadiz, and Bay of Algeciras), and compare these values against national and traditionally used international benchmark values. Site-specific SQGs were derived based on sediment physical-chemical, toxicological, and benthic community data integrated through multivariate analysis. This technique allowed the identification of chemicals of concern and the establishment of effects range correlatively to individual concentrations of contaminants for each site of study. The results revealed that sediments from Santos channel, as well as inner portions of the SES, are considered highly polluted (exceeding SQGs-high) by metals, PAHs and PCBs. High pollution by PAHs and some metals was found in Sao Vicente channel. In PES, sediments from inner portions (proximities of the Ponta do Mix port's terminal and the Port of Paranagua) are highly polluted by metals and PAHs, including one zone inside the limits of an environmental protection area. In Gulf of Cadiz, SQGs exceedences were found in Ria of Huelva (all analysed metals and PAHs), in the surroundings of the Port of CAdiz (Bay of CAdiz) (metals), and in Bay of Algeciras (Ni and PAHs). The site-specific SQGs derived in this study are more restricted than national SQGs applied in Brazil and Spain, as well as international guidelines. This finding confirms the importance of the development of site-specific SQGs to support the characterisation of sediments and dredged material. The use of the same methodology to derive SQGs in Brazilian and Spanish port zones confirmed the applicability of this technique with an international scope and provided a harmonised methodology for site-specific SQGs derivation. (C) 2009 Elsevier B.V. All rights reserved.

Growth and symbiosis of plants with arbuscular mycorrhizal fungi in soil submitted to biochar application.

Arbuscular mycorrhizal fungi (AMF), which is intrinsically present or may be introduced in soils by inoculation, is an example of natural and renewable resource to increase plant nutrient uptake. This kind of fungi produces structures (hyphae, arbuscles and sometimes vesicles) inside the plant root cortex. This mutualistic relationship promotes plant gains in terms of water and nutrient absorption (mainly phosphorus). Biochar can benefit plant interaction with AMF, however, it can contain potentially toxic compounds such as heavy metals and organic compounds (e.g. dioxins, furans and polycyclic aromatic hydrocarbons), depending on the feedstock and pyrolysis conditions, which may damage organisms. For these reasons, the present work will approach the impacts of biochar application on soil attributes, AMF-plant symbiosis and its responses in plant growth and phosphorus uptake. Eucalyptus biochar produced at high temperatures increases sorghum growth; symbiosis with AMF; and enhances spore germination. Enhanced plant growth in the presence of high temperature biochar and AMF is a response of root branching stimulated by an additive effect between biochar characteristics and root colonization. Biochar obtained at low temperature reduces AMF spore germination; however it does not affect plant growth and symbiosis in soil.

Atomistic exploration of deformation properties of copper nanowires with pre-existing defects

Based on the embedded atom method (EAM) and molecular dynamics (MD) method, in this paper, the tensile deformation properties of Cu nanowires (NWs) with different pre-existing defects, including single surface defects, surface bi-defects and single internal defects, are systematically studied. In-depth deformation mechanisms of NWs with pre-existing defects are also explored. It is found that Young's modulus is insensitive to different pre-existing defects, but yield strength shows an obvious decrease. Defects are observed influencing greatly on NWs' tensile deformation mechanisms, and playing a role of dislocation sources. Besides of the traditional deformation process dominated by the nucleation and propagation of partial dislocations, the generations of twins, grain boundaries, fivefold deformation twins, hexagonal close-packed (HCP) structure and phase transformation from face-centred cubic (FCC) structure to HCP structure have been triggered by pre-existing defects. It is found that surface defect intends to induce larger influence to yield strength than internal defect. Most importantly, the defect that lies on slip planes exerts larger influence than other defects. As expected, it is also found that the more or longer of the defect, the bigger influence will be induced.