Detecting the oxidative reactivity of nanoparticles: a new protocol for reducing artifacts

Understanding the oxidative reactivity of nanoparticles (NPs; <100 nm) could substantially contribute to explaining their toxicity. We attempted to refine the use of 2′7-dichlorodihydrofluorescein (DCFH) to characterize NP generation of reactive oxygen species (ROS). Several fluorescent probes have been applied to testing oxidative reactivity, but despite DCFH being one of the most popular for the detection of ROS, when it has been applied to NPs there have been an unexplainably wide variability in results. Without a uniform methodology, validating even robust results is impossible. This study, therefore, identified sources of conflicting results and investigated ways of reducing occurrence of artificial results. Existing techniques were tested and combined (using their most desirable features) to form a more reliable method for the measurement of NP reactivity in aqueous dispersions. We also investigated suitable sample ranges necessary to determine generation of ROS. Specifically, ultrafiltration and time-resolved scan absorbance spectra were used to study possible optical interference when using high sample concentrations. Robust results were achieved at a 5 µM DCFH working solution with 0.5 unit/mL horseradish peroxidase (HRP) dissolved in ethanol. Sonication in DCFH-HRP working solution provided more stable data with a relatively clean background. Optimal particle concentration depends on the type of NP and in general was in the µg/mL range. Major reasons for previously reported conflicting results due to interference were different experimental approaches and NP sample concentrations. The protocol presented here could form the basis of a standardized method for applying DCFH to detect generation of ROS by NPs.

Building the niche through time: using 13,000 years of data to predict the effects of climate change on three tree species in Europe

Aim Species distribution models (SDMs) based on current species ranges underestimate the potential distribution when projected in time and/or space. A multi-temporal model calibration approach has been suggested as an alternative, and we evaluate this using 13,000 years of data. Location Europe. Methods We used fossil-based records of presence for Picea abies, Abies alba and Fagus sylvatica and six climatic variables for the period 13,000 to 1000yr bp. To measure the contribution of each 1000-year time step to the total niche of each species (the niche measured by pooling all the data), we employed a principal components analysis (PCA) calibrated with data over the entire range of possible climates. Then we projected both the total niche and the partial niches from single time frames into the PCA space, and tested if the partial niches were more similar to the total niche than random. Using an ensemble forecasting approach, we calibrated SDMs for each time frame and for the pooled database. We projected each model to current climate and evaluated the results against current pollen data. We also projected all models into the future. Results Niche similarity between the partial and the total-SDMs was almost always statistically significant and increased through time. SDMs calibrated from single time frames gave different results when projected to current climate, providing evidence of a change in the species realized niches through time. Moreover, they predicted limited climate suitability when compared with the total-SDMs. The same results were obtained when projected to future climates. Main conclusions The realized climatic niche of species differed for current and future climates when SDMs were calibrated considering different past climates. Building the niche as an ensemble through time represents a way forward to a better understanding of a species' range and its ecology in a changing climate.

Global habitat suitability models of terrestrial mammals.

Detailed large-scale information on mammal distribution has often been lacking, hindering conservation efforts. We used the information from the 2009 IUCN Red List of Threatened Species as a baseline for developing habitat suitability models for 5027 out of 5330 known terrestrial mammal species, based on their habitat relationships. We focused on the following environmental variables: land cover, elevation and hydrological features. Models were developed at 300 m resolution and limited to within species' known geographical ranges. A subset of the models was validated using points of known species occurrence. We conducted a global, fine-scale analysis of patterns of species richness. The richness of mammal species estimated by the overlap of their suitable habitat is on average one-third less than that estimated by the overlap of their geographical ranges. The highest absolute difference is found in tropical and subtropical regions in South America, Africa and Southeast Asia that are not covered by dense forest. The proportion of suitable habitat within mammal geographical ranges correlates with the IUCN Red List category to which they have been assigned, decreasing monotonically from Least Concern to Endangered. These results demonstrate the importance of fine-resolution distribution data for the development of global conservation strategies for mammals.

Are niche-based species distribution models transferable in space?

Aim To assess the geographical transferability of niche-based species distribution models fitted with two modelling techniques. Location Two distinct geographical study areas in Switzerland and Austria, in the subalpine and alpine belts. Methods Generalized linear and generalized additive models (GLM and GAM) with a binomial probability distribution and a logit link were fitted for 54 plant species, based on topoclimatic predictor variables. These models were then evaluated quantitatively and used for spatially explicit predictions within (internal evaluation and prediction) and between (external evaluation and prediction) the two regions. Comparisons of evaluations and spatial predictions between regions and models were conducted in order to test if species and methods meet the criteria of full transferability. By full transferability, we mean that: (1) the internal evaluation of models fitted in region A and B must be similar; (2) a model fitted in region A must at least retain a comparable external evaluation when projected into region B, and vice-versa; and (3) internal and external spatial predictions have to match within both regions. Results The measures of model fit are, on average, 24% higher for GAMs than for GLMs in both regions. However, the differences between internal and external evaluations (AUC coefficient) are also higher for GAMs than for GLMs (a difference of 30% for models fitted in Switzerland and 54% for models fitted in Austria). Transferability, as measured with the AUC evaluation, fails for 68% of the species in Switzerland and 55% in Austria for GLMs (respectively for 67% and 53% of the species for GAMs). For both GAMs and GLMs, the agreement between internal and external predictions is rather weak on average (Kulczynski's coefficient in the range 0.3-0.4), but varies widely among individual species. The dominant pattern is an asymmetrical transferability between the two study regions (a mean decrease of 20% for the AUC coefficient when the models are transferred from Switzerland and 13% when they are transferred from Austria). Main conclusions The large inter-specific variability observed among the 54 study species underlines the need to consider more than a few species to test properly the transferability of species distribution models. The pronounced asymmetry in transferability between the two study regions may be due to peculiarities of these regions, such as differences in the ranges of environmental predictors or the varied impact of land-use history, or to species-specific reasons like differential phenotypic plasticity, existence of ecotypes or varied dependence on biotic interactions that are not properly incorporated into niche-based models. The lower variation between internal and external evaluation of GLMs compared to GAMs further suggests that overfitting may reduce transferability. Overall, a limited geographical transferability calls for caution when projecting niche-based models for assessing the fate of species in future environments.

Naturschutzforschung am Auerhuhn in der Schweiz: eine Übersicht

The Western Capercaille Tetrao urogallus is a large forest grouse with narrow habitat preferences and large home ranges. As Capercaille populations are declining in most of their central European range and the species has been shown to be an umbrella for high species richness, a profound knowledge of the species' ecology is essential for the conservation of the charismatic bird.

Low latitude Paleocene to early Eocene radiolarian systematics, biochronology and paleoenvironmental analysis

Highly diverse radiolarian faunas of latest Maastrichtian to early Eocene age have been recovered from the low latitude realm in order to contribute to the clarification of radiolarian taxonomy, construct a zonation based on a discrete sequence of co-existence intervals of species ranging from the late Paleocene to early Eocene and to describe a rich low latitude latest Cretaceous to late Paleocene fauna. 225 samples of late Paleocene to early Eocene age have been collected from ODP Leg 171 B-Hole 1051 A (Blake Nose), DSDP Leg 43-Site 384 (Northwest Atlantic) and DSDP Leg 10-Sites 86, 94, 95, 96. Sequences consist of mainly pelagic oozes and chalks, with some clay and ash layers. A new imaging technique is devised to perform (in particular on topotypic material) both transmitted light microscopy and SEM imaging on individual radiolarian specimens. SEM precedes transmitted light imaging. Radiolarians are adhered to a cover slip (using nail varnish) which is secured to a stub using conductive levers. Specimens are then photographed in low vacuum (40-50Pa; 0.5mbar), which enables charge neutralization by ionized molecules of the chamber atmosphere. Thus gold coating is avoided and subsequently this allows transmitted light imaging to follow. The conductive levers are unscrewed and the cover slip is simply overturned and mounted with Canada balsam. In an attempt towards a post-Haeckelian classification, the initial spicule (Entactinaria), micro- or macrosphere (Spumellaria) and initial spicule and cephalis (Nassellaria) have been studied by slicing Entactinaria and Spumellaria, and by tilting Nassellaria in the SEM chamber. A new genus of the family Coccodiscidae is erected and Spongatractus HAECKEL is re-located to the subfamily Axopruinae. The biochronology has been carried out using the Unitary Association Method (Guex 1977, 1991). A database recording the occurrences of 112 species has been used to establish a succession of 22 Unitary Associations. Each association is correlated to chronostratigraphy via calcareous microfossils that were previously studied by other authors. The 22 UAs have been united into seven Unitary Associations Zones (UAZones) (JP10- JE4). The established zones permit to distinguish supplementary subdivisions within the existing zonation. The low-latitude Paleocene radiolarian zonation established by Sanfilippo and Nigrini (1998a) is incomplete due to the lack of radiolarian-bearing early Paleocene sediments. In order to contribute to the study of sparsely known low latitude early Paleocene faunas, 80 samples were taken from the highly siliceous Guayaquil Formation (Ecuador). The sequence consists of black cherts, shales, siliceous limestones and volcanic ash layers. The carbonate content increases up section. Age control is supplied by sporadic occurrences of silicified planktonic foraminifera casts. One Cretaceous zone and seven Paleocene zones have been identified. The existing zonation for the South Pacific can be applied to the early-early late Paleocene sequence, although certain marker species have significantly shorter ranges (notably Buryella foremanae and B. granulata). Despite missing marker species in the late Paleocene, faunal distribution correlates reasonably to the Low-Latitude zonation. An assemblage highly abundant in Lithomelissa, Lophophaena and Cycladophora in the upper RP6 zone (correlated by the presence of Pterocodon poculum, Circodiscus circularis, Pterocodon? sp. aff. P. tenellus and Stylotrochus nitidus) shows a close affinity to contemporaneous faunas reported from Site 1121, Campbell Plateau. Coupled with a high diatom abundance (notably Aulacodiscus spp. and Arachnoidiscus spp.), these faunas are interpreted as reflecting a period of enhanced biosiliceous productivity during the late Paleocene. The youngest sample is void of radiolarians, diatoms and sponge spicules yet contains many pyritized infaunal benthic foraminifera which are akin to the midway-type fauna. The presence of this fauna suggests deposition in a neritic environment. This is in contrast to the inferred bathyal slope depositional environment of the older Paleocene sediments and suggests a shoaling of the depositional environment which may be related to a coeval major accretionary event. RESUME DE LA THESE Des faunes de radiolaires de basses latitudes très diversifiées d'âge Maastrichtien terminal à Eocène inférieur, ont été étudiées afin de contribuer à la clarification de leur taxonomie, de construire une biozonation basée sur une séquence discrète d'intervalles de coexistence des espèces d'age Paléocène supérieur à Eocène inférieur et de décrire une riche faune de basse latitude allant du Crétacé terminal au Paléocène supérieur. L'étude de cette faune contribue particulièrement à la connaissance des insaisissables radiolaires de basses latitudes du Paléocène inférieur. 225 échantillons d'âge Paléocène supérieur à Eocène inférieur provenant des ODP Leg 171B-Site 1051A (Blake Nose), Leg DSDP 43-Site 384 (Atlantique Nord -Ouest) et des DSDP Leg 10 -Sites 86, 94, 95, 96, ont été étudiés. Ces séquences sont constituées principalement de « ooze » et de « chalks »pélagiques ainsi que de quelques niveaux de cendres et d'argiles. Une nouvelle technique d'imagerie a été conçue afin de pouvoir prendre conjointement des images en lumière transmise et au Microscope Electronique à Balayage (MEB) de spécimens individuels. Ceci à été particulièrement appliqué à l'étude des topotypes. L'imagerie MEB précède l'imagerie en lumière transmise. Les radiolaires sont collés sur une lame pour micropaléontologie (au moyen de vernis à ongles) qui est ensuite fixée à un porte-objet à l'aide de bras métalliques conducteurs. Les spécimens sont ensuite photographiés en vide partiel (40-50Pa; 0.5mbar), ce qui permet la neutralisation des charges électrostatiques dues à la présence de molécules ionisées dans l'atmosphère de la chambre d'observation. Ainsi la métallisation de l'échantillon avec de l'or n'est plus nécessaire et ceci permet l'observation ultérieure en lumière transmise. Les bras conducteurs sont ensuite dévissés et la lame est simplement retournée et immergée dans du baume du Canada. Dans une approche de classification post Haeckelienne, le spicule initial (Entactinaires), la micro- ou macro -sphère (Spumellaires) et le spicule initial et cephalis (Nassellaires) ont été étudiés. Ceci a nécessité le sectionnement d'Entactinaires et de Spumellaires, et de pivoter les Nassellaires dans la chambre d'observation du MEB. Un nouveau genre de la Famille des Coccodiscidae a été érigé et Spongatractus HAECKEL à été réassigné à la sous-famille des Axopruninae. L'analyse biostratigraphique à été effectuée à l'aide de la méthode des Associations Unitaires {Guex 1977, 1991). Une base de données enregistrant les présences de 112 espèces à été utilisée poux établir une succession de 22 Associations Unitaires. Chaque association est corrélée à la chronostratigraphie au moyen de microfossiles calcaires précédemment étudiés par d'autres auteurs. Les 22 UAs ont été combinées en sept Zones d'Associations Unitaires (UAZones) (JP10- JE4). Ces Zones permettent d'insérer des subdivisions supplémentaires dans la zonation actuelle. La zonation de basses latitudes du Paléocène établie par Sanfilippo et Nigrini (1998a) est incomplète due au manque de sédiments du Paléocène inférieur contenant des radiolaires. Afin de contribuer à l'étude des faunes peu connues des basses latitudes du Paléocène inférieur, 80 échantillons ont été prélevés d'une section siliceuse de la Formation de Guayaquil (Equateur). La séquence est composée de cherts noirs, de shales, de calcaires siliceux et de couches de cendres volcaniques. La fraction carbonatée augmente vers le haut de la section. Des contraintes chronologiques sont fournies par la présence sporadique de moules de foraminifères planctoniques. Une zone d'intervalles du Crétacé et sept du Paléocène ont été mises en évidence. Bien que certaines espèces marqueur ont des distributions remarquablement plus courtes (notamment Buryella foremanae et B. granulata), la zonation existante pour le Pacifique Sud est applicable à la séquence d'age Paléocène inférieure à Paléocène supérieur basal étudiée. Malgré l'absence d'espèces marqueur du Paléocène supérieur, la succession faunistique se corrèle raisonnablement avec la zonation pour les basses latitudes. Un assemblage contenant d'abondants représentant du genre Lithomelissa, Lophophaena et Cycladophora dans la zone RP6 (correlée par la présence de Pterocodon poculum, Circodiscus circularis, Pterocodon? sp. aff. P. tenellus et Stylotrochus nitidus) montre une grande similitude avec certaines faunes issues des hauts latitudes et d'age semblable décrites par Hollis (2002, Site 1121, Campbell Plateau). Ceci, en plus d'une abondance importante en diatomés (notamment Aulacodiscus spp. et Arachnoidiscus spp.) nous mènent à interpréter cette faune comme témoin d'un épisode de productivité biosiliceuse accrue dans le Paléocène supérieur. L'échantillon le plus jeune, dépourvu de radiolaires, de diatomés et de spicules d'éponge contient de nombreux foraminifères benthiques infaunaux pyritisés. Les espèces identifiées sont caractéristiques d'une faune de type midway. La présence de ces foraminifères suggère un environnement de type néritique. Ceci est en contraste avec l'environnement de pente bathyale caractérisent les sédiments sous-jacent. Cette séquence de diminution de la tranche d'eau peut être associée à un événement d'accrétion majeure. RESUME DE LA THESE (POUR LE GRAND PUBLIC) Les radiolaires constituent le groupe de plancton marin le plus divers et le plus largement répandu de l'enregistrement fossile. Un taux d'évolution rapide et une variation géographique considérable des populations font des radiolaires un outil de recherche sans égal pour la biostratigraphie et la paléocéanographie. Néanmoins, avant de pouvoir les utiliser comme outils de travail, il est essentiel d'établir une solide base taxonomique. L'étude des Radiolaires peut impliquer plusieurs techniques d'extraction, d'observation et d'imagerie qui sont dépendantes du degré d'altération diagénétique des spécimens. Le squelette initial, qu'il s'agisse d'un spicule initial (Entactinaria), d'une micro- ou macro -sphère (Spumellaria) ou d'un spicule initial et d'un cephalis (Nassellaria), est l'élément le plus constant au cours de l'évolution et devrait représenter le fondement de la systématique. Des échantillons provenant de carottes de basses latitudes du Deep Sea Drilling Project et de l' Ocean Drilling ont été étudiés. De nouvelles techniques d'imagerie et de sectionnement ont été développées sur des topotypes de radiolaires préservés en opale, dans le but d'étudier les caractéristiques de leur squelette initial qui n'étaient pas visibles dans leur illustration originale. Ceci aide entre autre à comparer des spécimens recristallisés en quartz, provenant de terrains accrétés, avec les holotypes en opale de la littérature. La distribution des espèces étudiés a fourni des données biostratigraphiques qui ont été compilées à l'aide de la méthode des Associations Unitaires (Guez 1977, 1991). Il s'agit d'un modèle mathématique déterministe conçu pour exploiter la totalité de l'assemblage plutôt que de se confiner à l'utilisation de taxons marqueurs individuels. Une séquence de 22 Associations Unitaires a été établie pour la période allant du Paléocène supérieur à l'Éocène inférieur. Chaque Association Unitaire a été corrélée à l'échelle de temps absolue à l'aide de microfossiles calcaires. Les 22 UAs ont été combinées en sept Zones d'Associations Unitaires (JP10- JE4). Ces Zones permettent d'insérer des subdivisions supplémentaires dans la zonation actuelle. Les radiolaires du Paléocène inférieur à moyen des basses latitudes sont rares. Les meilleures sections connues se trouvent dans les hautes latitudes (Nouvelle Zélande). Quelques assemblages épars ont été mentionnés par le passé en Californie, en Équateur et en Russie. Une séquence siliceuse de 190 mètres dans la Formation de Guayaquil (Équateur), s'étendant du Maastrichtien supérieur au Paléocène supérieur, a fourni des faunes relativement bien préservées. L'étude de ces faunes a permis de mettre en évidence la première séquence complète de radiolaires de basses latitudes dans le Paléocène inférieure. Huit zones allant du Crétacé terminal au Paléocène supérieur ont pu être appliqués et la présence de foraminifères planctoniques a fournie plusieurs points d'attache chronologiques. Dans le Paléocène supérieur, un riche assemblage contenant d'abondants diatomés et radiolaires ayant des similitudes faunistiques marquantes avec des assemblages de hautes latitudes de Nouvelle Zélande, témoigne d'un épisode de productivité biosiliceuse accrue pendant cette période. Étant donné que la pointe du continent sud-américain et l'Antarctique étaient plus proches au cours du Paléocène, ce phénomène peut être expliqué par le transport, le long de la côte ouest de l'Amérique du Sud, d'eaux riches en nutriments en provenance de l'Océan Antarctique. Suite à cet épisode, l'enregistrement en radiolaires est interrompu. Ceci peut être associé à des événements tectoniques régionaux qui ont eu pour effet de diminuer la tranche d'eau relative, rendant l'environnement plus favorable aux foraminifères benthiques qui sont abondamment présents dans l'échantillon le plus jeune de la séquence.

Aortic root rupture: implications of catheter-guided aortic valve replacement.

PURPOSE OF REVIEW: The safety and efficiency of trans catheter aortic valve implantation (TAVI) has been clearly demonstrated. In high-risk patients, the number of procedures is constantly increasing and in western European countries this procedure is employed in more than 30% of isolated aortic valve replacements. The literature, however, focusing on perioperative aortic root (AoR) rupture is rather limited to just a few reports. The aim of this review is to analyze the pathophysiology of AoR rupture during TAVI, stressing the implications of the morphology of the AoR for this devastating complication. RECENT FINDINGS: Currently, perioperative AoR rupture ranges between 0.5 and 1.5% during TAVI, with almost 100% mortality. Recently, valve oversizing and balloon dilatation in a calcified and small AoR were considered as the most important predictive factors for this complication. SUMMARY: The most fragile unit of the AoR is its anchoring substrate to the ostium of the left ventricle. This membranous structure is not involved in the degenerative process leading to aortic valve stenosis. Due to the TAVI and/or balloon dilatation of the calcium stationed on the three leaflets and their attachment, a lesion may result on this structure. And, as a consequence, there is rupture of the AoR.

Coherency and sharpness measures by using ICA algorithms. An investigation for Alzheimer’s disease discrimination

In this paper, we present a comprehensive study of different Independent Component Analysis (ICA) algorithms for the calculation of coherency and sharpness of electroencephalogram (EEG) signals, in order to investigate the possibility of early detection of Alzheimer’s disease (AD). We found that ICA algorithms can help in the artifact rejection and noise reduction, improving the discriminative property of features in high frequency bands (specially in high alpha and beta ranges). In addition to different ICA algorithms, the optimum number of selected components is investigated, in order to help decision processes for future works.

Subject-based steroid profiling and the determination of novel biomarkers for DHT and DHEA misuse in sports.

Doping with natural steroids can be detected by evaluating the urinary concentrations and ratios of several endogenous steroids. Since these biomarkers of steroid doping are known to present large inter-individual variations, monitoring of individual steroid profiles over time allows switching from population-based towards subject-based reference ranges for improved detection. In an Athlete Biological Passport (ABP), biomarkers data are collated throughout the athlete's sporting career and individual thresholds defined adaptively. For now, this approach has been validated on a limited number of markers of steroid doping, such as the testosterone (T) over epitestosterone (E) ratio to detect T misuse in athletes. Additional markers are required for other endogenous steroids like dihydrotestosterone (DHT) and dehydroepiandrosterone (DHEA). By combining comprehensive steroid profiles composed of 24 steroid concentrations with Bayesian inference techniques for longitudinal profiling, a selection was made for the detection of DHT and DHEA misuse. The biomarkers found were rated according to relative response, parameter stability, discriminative power, and maximal detection time. This analysis revealed DHT/E, DHT/5β-androstane-3α,17β-diol and 5α-androstane-3α,17β-diol/5β-androstane-3α,17β-diol as best biomarkers for DHT administration and DHEA/E, 16α-hydroxydehydroepiandrosterone/E, 7β-hydroxydehydroepiandrosterone/E and 5β-androstane-3α,17β-diol/5α-androstane-3α,17β-diol for DHEA. The selected biomarkers were found suitable for individual referencing. A drastic overall increase in sensitivity was obtained.The use of multiple markers as formalized in an Athlete Steroidal Passport (ASP) can provide firm evidence of doping with endogenous steroids. Copyright © 2010 John Wiley & Sons, Ltd.

Techniques for Estimating Flood-Frequency Discharges for Streams in Iowa, HR-395A, 2001

A statewide study was conducted to develop regression equations for estimating flood-frequency discharges for ungaged stream sites in Iowa. Thirty-eight selected basin characteristics were quantified and flood-frequency analyses were computed for 291 streamflow-gaging stations in Iowa and adjacent States. A generalized-skew-coefficient analysis was conducted to determine whether generalized skew coefficients could be improved for Iowa. Station skew coefficients were computed for 239 gaging stations in Iowa and adjacent States, and an isoline map of generalized-skew-coefficient values was developed for Iowa using variogram modeling and kriging methods. The skew map provided the lowest mean square error for the generalized-skew- coefficient analysis and was used to revise generalized skew coefficients for flood-frequency analyses for gaging stations in Iowa. Regional regression analysis, using generalized least-squares regression and data from 241 gaging stations, was used to develop equations for three hydrologic regions defined for the State. The regression equations can be used to estimate flood discharges that have recurrence intervals of 2, 5, 10, 25, 50, 100, 200, and 500 years for ungaged stream sites in Iowa. One-variable equations were developed for each of the three regions and multi-variable equations were developed for two of the regions. Two sets of equations are presented for two of the regions because one-variable equations are considered easy for users to apply and the predictive accuracies of multi-variable equations are greater. Standard error of prediction for the one-variable equations ranges from about 34 to 45 percent and for the multi-variable equations range from about 31 to 42 percent. A region-of-influence regression method was also investigated for estimating flood-frequency discharges for ungaged stream sites in Iowa. A comparison of regional and region-of-influence regression methods, based on ease of application and root mean square errors, determined the regional regression method to be the better estimation method for Iowa. Techniques for estimating flood-frequency discharges for streams in Iowa are presented for determining ( 1) regional regression estimates for ungaged sites on ungaged streams; (2) weighted estimates for gaged sites; and (3) weighted estimates for ungaged sites on gaged streams. The technique for determining regional regression estimates for ungaged sites on ungaged streams requires determining which of four possible examples applies to the location of the stream site and its basin. Illustrations for determining which example applies to an ungaged stream site and for applying both the one-variable and multi-variable regression equations are provided for the estimation techniques.

Deterioration of Iowa Highway Concrete Pavements: A Petrographic Study, HR-1065, 1999

Major highway concrete pavements in Iowa have exhibited premature deterioration attributed to effects of ettringite formation, alkali-silica expansive reactions, and to frost attack, or some combination of them. These pavements were constructed in the mid- 1980s as non-reinforced, dual-lane, roads ranging in thickness between 200 mm and 300 mm, with skewed joints reinforced with dowels. Deterioration was initially recognized with a darkening of joint regions, which occurred for some pavements as soon as four years after construction. Pavement condition ranges from severe damage to none, and there appeared to be no unequivocal materials or processing variables correlated with failure. Based upon visual examinations, petrographic evaluation, and application of materials models, the deterioration of concrete highway pavements in Iowa appear related to a freeze-thaw failure of the coarse aggregate and the mortar. Crack patterns sub-parallel to the concrete surface transecting the mortar fraction and the coarse aggregate are indicative of freeze-thaw damage of both the mortar and aggregate. The entrained air void system was marginal to substandard, and filling of some of the finer-sized voids by ettringite appears to have further degraded the air void system. The formation of secondary ettringite within the entrained air voids probably reflects a relatively high degree of concrete saturation causing the smaller voids to be filled with pore solution when the concrete freezes. Alkali-silica reaction (ASR) affects some quartz and shale in the fine aggregate, but is not considered to be a significant cause of the deterioration. Delayed ettringite formation was not deemed likely as no evidence of a uniform paste expansion was observed. The lack of field-observed expansion is also evidence against the ASR and DEF modes of deterioration. The utilization of fly ash does not appear to have affected the deterioration as all pavements with or without fly ash exhibiting substantial damage also exhibit significant filling of the entrained air void system, and specimens containing fly ash from sound pavements do not have significant filling. The influence of the mixture design, mixing, and placing must be evaluated with respect to development of an adequate entrained air void system, concrete homogeneity, longterm drying shrinkage, and microcracking. A high-sand mix may have contributed to the difficult mixture characteristics noted upon placement and exacerbate concrete heterogeneity problems, difficulty in developing an adequate entrained air void system, poor consolidation potential, and increased drying shrinkage and cracking. Finally, the availability of moisture must also be considered, as the secondary precipitation of ettringite in entrained air voids indicates they were at least partially filled with pore solution at times. Water availability at the base of the slabs, in joints, and cracks may have provided a means for absorbing water to a point of critical saturation.

Modelling ecological niches with support vector machines

1. The ecological niche is a fundamental biological concept. Modelling species' niches is central to numerous ecological applications, including predicting species invasions, identifying reservoirs for disease, nature reserve design and forecasting the effects of anthropogenic and natural climate change on species' ranges. 2. A computational analogue of Hutchinson's ecological niche concept (the multidimensional hyperspace of species' environmental requirements) is the support of the distribution of environments in which the species persist. Recently developed machine-learning algorithms can estimate the support of such high-dimensional distributions. We show how support vector machines can be used to map ecological niches using only observations of species presence to train distribution models for 106 species of woody plants and trees in a montane environment using up to nine environmental covariates. 3. We compared the accuracy of three methods that differ in their approaches to reducing model complexity. We tested models with independent observations of both species presence and species absence. We found that the simplest procedure, which uses all available variables and no pre-processing to reduce correlation, was best overall. Ecological niche models based on support vector machines are theoretically superior to models that rely on simulating pseudo-absence data and are comparable in empirical tests. 4. Synthesis and applications. Accurate species distribution models are crucial for effective environmental planning, management and conservation, and for unravelling the role of the environment in human health and welfare. Models based on distribution estimation rather than classification overcome theoretical and practical obstacles that pervade species distribution modelling. In particular, ecological niche models based on machine-learning algorithms for estimating the support of a statistical distribution provide a promising new approach to identifying species' potential distributions and to project changes in these distributions as a result of climate change, land use and landscape alteration.

Strength Development of Concrete Based on Maturity and Pulse Velocity, MLR-95-03, 1995

The effect of curing temperature, in the range of 4.4 to 22.8 degrees C (40 to 73 degrees F), on strength development was studied based on the maturity and pulse velocity measurements in this report. The strength-maturity relationships for various mixes using a Type I cement and using a Type IP cement, respectively, were experimentally developed. The similar curves for early age strength development of both the patching concrete, using a Type I cement with the addition of calcium chloride, and the fast track concrete, using a Type III cement and fly ash, have also been proposed. For the temperature ranges studied, the strength development of concrete can be determined using a pulse velocity measurement, but only for early ages up to 24 hours. These obtained relationships can be used to determine when a pavement can be opened to traffic. The amount of fly ash substitution, up to 30%, did not have a significant influence on the strength-maturity relationship.

Guidelines for Removal of Traffic Control Devices in Rural Areas, TR-527, 2005

It is commonly regarded that the overuse of traffic control devices desensitizes drivers and leads to disrespect, especially for low-volume secondary roads with limited enforcement. The maintenance of traffic signs is also a tort liability concern, exacerbated by unnecessary signs. The Federal Highway Administration’s (FHWA) Manual on Uniform Traffic Control Devices (MUTCD) and the Institute of Transportation Engineer’s (ITE) Traffic Control Devices Handbook provide guidance for the implementation of STOP signs based on expected compliance with right-of-way rules, provision of through traffic flow, context (proximity to other controlled intersections), speed, sight distance, and crash history. The approach(es) to stop is left to engineering judgment and is usually dependent on traffic volume or functional class/continuity of system. Although presently being considered by the National Committee on Traffic Control Devices, traffic volume itself is not given as a criterion for implementation in the MUTCD. STOP signs have been installed at many locations for various reasons which no longer (or perhaps never) met engineering needs. If in fact the presence of STOP signs does not increase safety, removal should be considered. To date, however, no guidance exists for the removal of STOP signs at two-way stop-controlled intersections. The scope of this research is ultra-low-volume (< 150 daily entering vehicles) unpaved intersections in rural agricultural areas of Iowa, where each of the 99 counties may have as many as 300 or more STOP sign pairs. Overall safety performance is examined as a function of a county excessive use factor, developed specifically for this study and based on various volume ranges and terrain as a proxy for sight distance. Four conclusions are supported: (1) there is no statistical difference in the safety performance of ultra-low-volume stop-controlled and uncontrolled intersections for all drivers or for younger and older drivers (although interestingly, older drivers are underrepresented at both types of intersections); (2) compliance with stop control (as indicated by crash performance) does not appear to be affected by the use or excessive use of STOP signs, even when adjusted for volume and a sight distance proxy; (3) crash performance does not appear to be improved by the liberal use of stop control; (4) safety performance of uncontrolled intersections appears to decline relative to stop-controlled intersections above about 150 daily entering vehicles. Subject to adequate sight distance, traffic professionals may wish to consider removal of control below this threshold. The report concludes with a section on methods and legal considerations for safe removal of stop control.

Predicting the physicochemical profile of diastereoisomeric histidine-containing dipeptides by property space analysis.

OBJECTIVES: This study aimed at measuring the lipophilicity and ionization constants of diastereoisomeric dipeptides, interpreting them in terms of conformational behavior, and developing statistical models to predict them. METHODS: A series of 20 dipeptides of general structure NH(2) -L-X-(L or D)-His-OMe was designed and synthetized. Their experimental ionization constants (pK(1) , pK(2) and pK(3) ) and lipophilicity parameters (log P(N) and log D(7.4) ) were measured by potentiometry. Molecular modeling in three media (vacuum, water, and chloroform) was used to explore and sample their conformational space, and for each stored conformer to calculate their radius of gyration, virtual log P (preferably written as log P(MLP) , meaning obtained by the molecular lipophilicity potential (MLP) method) and polar surface area (PSA). Means and ranges were calculated for these properties, as was their sensitivity (i.e., the ratio between property range and number of rotatable bonds). RESULTS: Marked differences between diastereoisomers were seen in their experimental ionization constants and lipophilicity parameters. These differences are explained by molecular flexibility, configuration-dependent differences in intramolecular interactions, and accessibility of functional groups. Multiple linear equations correlated experimental lipophilicity parameters and ionization constants with PSA range and other calculated parameters. CONCLUSION: This study documents the differences in lipophilicity and ionization constants between diastereoisomeric dipeptides. Such configuration-dependent differences are shown to depend markedly on differences in conformational behavior and to be amenable to multiple linear regression. Chirality 24:566-576, 2012. © 2012 Wiley Periodicals, Inc.