Response of a First-Order Stream in Maine to Short-Term In-Stream Acidification

An experimental short-term acidification with HCl at a first-order stream in central Maine, USA was used to study processes controlling the changes in stream chemistry and to assess the ability of stream substrate to buffer pH. The streambed exerted a strong buffering capacity against pH change by ion exchange during the 6-hour acidification. Streambed substrates had substantial cation and anion exchange capacity in the pH range of 4.1 to 6.5. The ion exchange for cations and SO42- were rapid and reversible. The speed of release of cations from stream substrates was Na1+ > Ca2+ > Mg2+ > Aln+ > Be2+, perhaps relating to charge density of these cations. Ca2+ desorption dominated neutralisation of excess H+ for the first 2 hr. As the reservoir of exchangeable Ca diminished, desorption land possibly dissolution) of Al3+ became the dominant neutralising mechanism. The exchangeable land possibly soluble) reservoir of Al was not depleted during the 6-hour acidification. Sulphate adsorption during the acidification reduced the concentration of SO42- in stream water by as much as 20 mu eq L-1 (from 70 mu eq L-1). Desorption of SO42- and adsorption of base cat ions after the artificial acidification resulted in a prolongation of the pH depression. The streambed had the capacity to buffer stream water chemistry significantly during an acidifying event affecting the entire upstream catchment.

QL-CONST1: an expert system for quality level prediction in concrete structures

Current trends in the fields of artifical intelligence and expert systems are moving towards the exciting possibility of reproducing and simulating human expertise and expert behaviour into a knowledge base, coupled with an appropriate, partially ‘intelligent’, computer code. This paper deals with the quality level prediction in concrete structures using the helpful assistance of an expert system, QL-CONST1, which is able to reason about this specific field of structural engineering. Evidence, hypotheses and factors related to this human knowledge field have been codified into a knowledge base. This knowledge base has been prepared in terms of probabilities of the presence of either hypotheses or evidence and the conditional presence of both. Human experts in the fields of structural engineering and the safety of structures gave their invaluable knowledge and assistance to the construction of the knowledge base. Some illustrative examples for, the validation of the expert system behaviour are included.

Critical comparative evaluation of design methodologies for the ultimate limit state of fatigue in concrete structures

La aparición de la fatiga ha sido ampliamente investigada en el acero y en otros materiales metálicos, sin embargo no se conoce en tanta profundidad en el hormigón estructural. Esto crea falta de uniformidad y enfoque en el proceso de verificación de estructuras de hormigón para el estado límite último de la fatiga. A medida que se llevan a cabo más investigaciones, la información sobre los parámetros que afectan a la fatiga en el hormigón comienzan a ser difundidos e incluso los que les afectan de forma indirecta. Esto conlleva a que se estén incorporando en las guías de diseño de todo el mundo, a pesar de que la comprobación del estado límite último no se trata por igual entre los distintos órganos de diseño. Este trabajo presentará un conocimiento básico del fenómeno de la fatiga, qué lo causa y qué condiciones de carga o propiedades materiales amplían o reducen la probabilidad de fallo por fatiga. Cuatro distintos códigos de diseño serán expuestos y su proceso de verificación ha sido examinado, comparados y valorados cualitativa y cuantitativamente. Una torre eólica, como ejemplo, fue analizada usando los procedimientos de verificación como se indica en sus respectivos códigos de referencia. The occurrence of fatigue has been extensively researched in steel and other metallic materials it is however, not as broadly understood in concrete. This produces a lack of uniformity in the approach and process in the verification of concrete structures for the ultimate limit state of fatigue. As more research is conducted and more information is known about the parameters which cause, propagate, and indirectly affect fatigue in concrete, they are incorporated in design guides around the world. Nevertheless, this ultimate limit state verification is not addressed equally by various design governing bodies. This report presents a baseline understanding of what the phenomenon of fatigue is, what causes it, and what loading or material conditions amplify or reduce the likelihood of fatigue failure. Four different design codes are exposed and their verification process has been examined, compared and evaluated both qualitatively and quantitatively. Using a wind turbine tower structure as case study, this report presents calculated results following the verification processes as instructed in the respective reference codes.

Uncertainties in the modal estimation from output-only data in civil structures

Cualquier estructura vibra según unas frecuencias propias definidas por sus parámetros modales (frecuencias naturales, amortiguamientos y formas modales). A través de las mediciones de la vibración en puntos clave de la estructura, los parámetros modales pueden ser estimados. En estructuras civiles, es difícil excitar una estructura de manera controlada, por lo tanto, las técnicas que implican la estimación de los parámetros modales sólo registrando su respuesta son de vital importancia para este tipo de estructuras. Esta técnica se conoce como Análisis Modal Operacional (OMA). La técnica del OMA no necesita excitar artificialmente la estructura, atendiendo únicamente a su comportamiento en servicio. La motivación para llevar a cabo pruebas de OMA surge en el campo de la Ingeniería Civil, debido a que excitar artificialmente con éxito grandes estructuras no sólo resulta difícil y costoso, sino que puede incluso dañarse la estructura. Su importancia reside en que el comportamiento global de una estructura está directamente relacionado con sus parámetros modales, y cualquier variación de rigidez, masa o condiciones de apoyo, aunque sean locales, quedan reflejadas en los parámetros modales. Por lo tanto, esta identificación puede integrarse en un sistema de vigilancia de la integridad estructural. La principal dificultad para el uso de los parámetros modales estimados mediante OMA son las incertidumbres asociadas a este proceso de estimación. Existen incertidumbres en el valor de los parámetros modales asociadas al proceso de cálculo (internos) y también asociadas a la influencia de los factores ambientales (externas), como es la temperatura. Este Trabajo Fin de Máster analiza estas dos fuentes de incertidumbre. Es decir, en primer lugar, para una estructura de laboratorio, se estudian y cuantifican las incertidumbres asociadas al programa de OMA utilizado. En segundo lugar, para una estructura en servicio (una pasarela de banda tesa), se estudian tanto el efecto del programa OMA como la influencia del factor ambiental en la estimación de los parámetros modales. Más concretamente, se ha propuesto un método para hacer un seguimiento de las frecuencias naturales de un mismo modo. Este método incluye un modelo de regresión lineal múltiple que permite eliminar la influencia de estos agentes externos. A structure vibrates according to some of its vibration modes, defined by their modal parameters (natural frequencies, damping ratios and modal shapes). Through the measurements of the vibration at key points of the structure, the modal parameters can be estimated. In civil engineering structures, it is difficult to excite structures in a controlled manner, thus, techniques involving output-only modal estimation are of vital importance for these structure. This techniques are known as Operational Modal Analysis (OMA). The OMA technique does not need to excite artificially the structure, this considers its behavior in service only. The motivation for carrying out OMA tests arises in the area of Civil Engineering, because successfully artificially excite large structures is difficult and expensive. It also may even damage the structure. The main goal is that the global behavior of a structure is directly related to their modal parameters, and any variation of stiffness, mass or support conditions, although it is local, is also reflected in the modal parameters. Therefore, this identification may be within a Structural Health Monitoring system. The main difficulty for using the modal parameters estimated by an OMA is the uncertainties associated to this estimation process. Thus, there are uncertainties in the value of the modal parameters associated to the computing process (internal) and the influence of environmental factors (external), such as the temperature. This Master’s Thesis analyzes these two sources of uncertainties. That is, firstly, for a lab structure, the uncertainties associated to the OMA program used are studied and quantified. Secondly, for an in-service structure (a stress-ribbon footbridge), both the effect of the OMA program and the influence of environmental factor on the modal parameters estimation are studied. More concretely, a method to track natural frequencies of the same mode has been proposed. This method includes a multiple linear regression model that allows to remove the influence of these external agents.

Application of the dynamic models to the detection of imperfections in plate Structures

This paper is part of a set of publications related with the development of mathematical models aimed to simulate the dynamic input and output of experimental nondestructive tests in order to detect structural imperfections. The structures to be considered are composed by steel plates of thin thickness. The imperfections in these cases are cracks and they can penetrate either a significant part of the plate thickness or be micro cracks or superficial imperfections. The first class of cracks is related with structural safety and the second one is more connected to the structural protection to the environment, particularly if protective paintings can be deteriorated. Two mathematical groups of models have been developed. The first group tries to locate the position and extension of the imperfection of the first class of imperfections, i.e. cracks and it is the object of the present paper. Bending Kirchoff thin plate models belong to this first group and they are used to this respect. The another group of models is dealt with membrane structures under the superficial Rayleigh waves excitation. With this group of models the micro cracks detection is intended. In the application of the first group of models to the detection of cracks, it has been observed that the differences between the natural frequencies of the non cracked and the cracked structures are very small. However, geometry and crack position can be identified quite accurately if this comparison is carried out between first derivatives (mode rotations) of the natural modes are used instead. Finally, in relation with the analysis of the superficial crack existence the use of Rayleigh waves is very promising. The geometry and the penetration of the micro crack can be detected very accurately. The mathematical and numerical treatment of the generation of these Rayleigh waves present and a numerical application has been shown.

Measures of residue density in protein structures

A hierarchy of residue density assessments and packing properties in protein structures are contrasted, including a regular density, a variety of charge densities, a hydrophobic density, a polar density, and an aromatic density. These densities are investigated by alternative distance measures and also at the interface of multiunit structures. Amino acids are divided into nine structural categories according to three secondary structure states and three solvent accessibility levels. To take account of amino acid abundance differences across protein structures, we normalize the observed density by the expected density defining a density index. Solvent accessibility levels exert the predominant influence in determinations of the regular residue density. Explicitly, the regular density values vary approximately linearly with respect to solvent accessibility levels, the linearity parameters depending on the amino acid. The charge index reveals pronounced inequalities between lysine and arginine in their interactions with acidic residues. The aromatic density calculations in all structural categories parallel the regular density calculations, indicating that the aromatic residues are distributed as a random sample of all residues. Moreover, aromatic residues are found to be over-represented in the neighborhood of all amino acids. This result might be attributed to nucleation sites and protein stability being substantially associated with aromatic residues.

Atom density in protein structures

The residue environment in protein structures is studied with respect to the density of carbon (C), oxygen (O), and nitrogen (N) atoms within a certain distance (say 5 Å) of each residue. Two types of environments are evaluated: one based on side-chain atom contacts (abbreviated S-S) and the other based on all atom (side-chain + backbone) contacts (abbreviated A-A). Different atom counts are observed about nine-residue structural categories defined by three solvent accessibility levels and three secondary structure states. Among the structural categories, the S-S atom count ratios generally vary more than the A-A atom count ratios because of the fact that the backbone (O) and (N) atoms contribute equal counts. Secondary structure affects the (C) density for the A-A contacts whereas secondary structure has little influence on the (C) density for the S-S contacts. For S-S contacts, a greater density of (O) over (N) atom neighbors stands out in the environment of most amino acid types. By contrast, for A-A contacts, independent of the solvent accessibility levels, the ratio (O)/(N) is ≈1 in helical states, consistent with the geometry of α-helical residues whose side-chains tilt oppositely to the amino to carboxy α-helical axis. The highest ratio of neighbor (O)/(N) is achieved under solvent exposed conditions. This (O) vs. (N) prevalence is advantageous at the protein surface that generally exhibits an acid excess that helps to enhance protein solubility in the cell and to avoid nonspecific interactions with phosphate groups of DNA, RNA, and other plasma constituents.

The extended environment of mononuclear metal centers in protein structures

The objectives of this and the following paper are to identify commonalities and disparities of the extended environment of mononuclear metal sites centering on Cu, Fe, Mn, and Zn. The extended environment of a metal site within a protein embodies at least three layers: the metal core, the ligand group, and the second shell, which is defined here to consist of all residues distant less than 3.5 Å from some ligand of the metal core. The ligands and second-shell residues can be characterized in terms of polarity, hydrophobicity, secondary structures, solvent accessibility, hydrogen-bonding interactions, and membership in statistically significant residue clusters of different kinds. Findings include the following: (i) Both histidine ligands of type I copper ions exclusively attach the Nδ1 nitrogen of the histidine imidazole ring to the metal, whereas histidine ligands for all mononuclear iron ions and nearly all type II copper ions are ligated via the Nɛ2 nitrogen. By contrast, multinuclear copper centers are coordinated predominantly by histidine Nɛ2, whereas diiron histidine contacts are predominantly Nδ1. Explanations in terms of steric differences between Nδ1 and Nɛ2 are considered. (ii) Except for blue copper (type I), the second-shell composition favors polar residues. (iii) For blue copper, the second shell generally contains multiple methionine residues, which are elements of a statistically significant histidine–cysteine–methionine cluster. Almost half of the second shell of blue copper consists of solvent-accessible residues, putatively facilitating electron transfer. (iv) Mononuclear copper atoms are never found with acidic carboxylate ligands, whereas single Mn2+ ion ligands are predominantly acidic and the second shell tends to be mostly buried. (v) The extended environment of mononuclear Fe sites often is associated with histidine–tyrosine or histidine–acidic clusters.

Classification of mononuclear zinc metal sites in protein structures

Our study of the extended metal environment, particularly of the second shell, focuses in this paper on zinc sites. Key findings include: (i) The second shell of mononuclear zinc centers is generally more polar than hydrophobic and prominently features charged residues engaged in an abundance of hydrogen bonding with histidine ligands. Histidine–acidic or histidine–tyrosine clusters commonly overlap the environment of zinc ions. (ii) Histidine tautomeric metal bonding patterns in ligating zinc ions are mixed. For example, carboxypeptidase A, thermolysin, and sonic hedgehog possess the same ligand group (two histidines, one unibidentate acidic ligand, and a bound water), but their histidine tautomeric geometries markedly differ such that the carboxypeptidase A makes only Nδ1 contacts, thermolysin makes only Nɛ2 contacts, and sonic hedgehog uses one of each. Thus the presence of a similar ligand cohort does not necessarily imply the same topology or function at the active site. (iii) Two close histidine ligands HXmH, m ≤ 5, rarely both coordinate a single metal ion in the Nδ1 tautomeric conformation, presumably to avoid steric conflicts. Mononuclear zinc sites can be classified into six types depending on the ligand composition and geometry. Implications of the results are discussed in terms of divergent and convergent evolution.

Structural code for DNA recognition revealed in crystal structures of papillomavirus E2-DNA targets

Transcriptional regulation in papillomaviruses depends on sequence-specific binding of the regulatory protein E2 to several sites in the viral genome. Crystal structures of bovine papillomavirus E2 DNA targets reveal a conformational variant of B-DNA characterized by a roll-induced writhe and helical repeat of 10.5 bp per turn. A comparison between the free and the protein-bound DNA demonstrates that the intrinsic structure of the DNA regions contacted directly by the protein and the deformability of the DNA region that is not contacted by the protein are critical for sequence-specific protein/DNA recognition and hence for gene-regulatory signals in the viral system. We show that the selection of dinucleotide or longer segments with appropriate conformational characteristics, when positioned at correct intervals along the DNA helix, can constitute a structural code for DNA recognition by regulatory proteins. This structural code facilitates the formation of a complementary protein–DNA interface that can be further specified by hydrogen bonds and nonpolar interactions between the protein amino acids and the DNA bases.

From local to global in quasiconformal structures.

We exhibit a large class of metric spaces whose infinitesimal quasiconformal structure is strong enough to capture the global quasiconformal structure. A sufficient condition for this to happen is described in terms of a Poincaré-type inequality.

Trapping of branched DNA in microfabricated structures.

We have observed electrostatic trapping of tribranched DNA molecules undergoing electrophoresis in a microfabricated pseudo-two-dimensional array of posts. Trapping occurs in a unique transport regimen in which the electrophoretic mobility is extremely sensitive to polymer topology. The arrest of branched polymers is explained by considering their center-of-mass motion; in certain conformations, owing to the constraints imposed by the obstacles a molecule cannot advance without the center of mass first moving a short distance backwards. The depth of the resulting local potential well can be much greater than the thermal energy so that escape of an immobilized molecule can be extremely slow. We summarize the expected behavior of the mobility as a function of field strength and topology and point out that the microfabricated arrays are highly suitable for detecting an extremely small number of branched molecules in a very large population of linear molecules.