Minimal analytical characterization of engineered nanomaterials needed for hazard assessment in biological matrices.

Abstract This paper presents the outcomes from a workshop of the European Network on the Health and Environmental Impact of Nanomaterials (NanoImpactNet). During the workshop, 45 experts in the field of safety assessment of engineered nanomaterials addressed the need to systematically study sets of engineered nanomaterials with specific metrics to generate a data set which would allow the establishment of dose-response relations. The group concluded that international cooperation and worldwide standardization of terminology, reference materials and protocols are needed to make progress in establishing lists of essential metrics. High quality data necessitates the development of harmonized study approaches and adequate reporting of data. Priority metrics can only be based on well-characterized dose-response relations derived from the systematic study of the bio-kinetics and bio-interactions of nanomaterials at both organism and (sub)-cellular levels. In addition, increased effort is needed to develop and validate analytical methods to determine these metrics in a complex matrix.

Sublimation of new matrix candidates for high spatial resolution imaging mass spectrometry of lipids: enhanced information in both positive and negative polarities after 1,5-diaminonapthalene deposition.

Matrix sublimation has demonstrated to be a powerful approach for high-resolution matrix-assisted laser desorption ionization (MALDI) imaging of lipids, providing very homogeneous solvent-free deposition. This work presents a comprehensive study aiming to evaluate current and novel matrix candidates for high spatial resolution MALDI imaging mass spectrometry of lipids from tissue section after deposition by sublimation. For this purpose, 12 matrices including 2,5-dihydroxybenzoic acid (DHB), sinapinic acid (SA), α-cyano-4-hydroxycinnamic acid (CHCA), 2,6-dihydroxyacetphenone (DHA), 2',4',6'-trihydroxyacetophenone (THAP), 3-hydroxypicolinic acid (3-HPA), 1,8-bis(dimethylamino)naphthalene (DMAN), 1,8,9-anthracentriol (DIT), 1,5-diaminonapthalene (DAN), p-nitroaniline (NIT), 9-aminoacridine (9-AA), and 2-mercaptobenzothiazole (MBT) were investigated for lipid detection efficiency in both positive and negative ionization modes, matrix interferences, and stability under vacuum. For the most relevant matrices, ion maps of the different lipid species were obtained from tissue sections at high spatial resolution and the detected peaks were characterized by matrix-assisted laser desorption ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) mass spectrometry. First proposed for imaging mass spectrometry (IMS) after sublimation, DAN has demonstrated to be of high efficiency providing rich lipid signatures in both positive and negative polarities with high vacuum stability and sub-20 μm resolution capacity. Ion images from adult mouse brain were generated with a 10 μm scanning resolution. Furthermore, ion images from adult mouse brain and whole-body fish tissue sections were also acquired in both polarity modes from the same tissue section at 100 μm spatial resolution. Sublimation of DAN represents an interesting approach to improve information with respect to currently employed matrices providing a deeper analysis of the lipidome by IMS.

Fate of the herbicide glyphosate and its metabolite AMPA in soils and their transfer to surface waters: A multi-scale approach in the Lavaux vineyards, western Switzerland

The use of herbicides in agriculture may lead to environmental problems, such as surface water pollution, with a potential risk for aquatic organisms. The herbicide glyphosate is the most used active ingredient in the world and in Switzerland. In the Lavaux vineyards it is nearly the only molecule applied. This work aimed at studying its fate in soils and its transfer to surface waters, using a multi-scale approach: from molecular (10-9 m) and microscopic scales (10-6 m), to macroscopic (m) and landscape ones (103 m). First of all, an analytical method was developed for the trace level quantification of this widely used herbicide and its main by-product, aminomethylphosphonic acid (AMPA). Due to their polar nature, their derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was done prior to their concentration and purification by solid phase extraction. They were then analyzed by ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The method was tested in different aqueous matrices with spiking tests and validated for the matrix effect correction in relevant environmental samples. Calibration curves established between 10 and 1000ng/l showed r2 values above 0.989, mean recoveries varied between 86 and 133% and limits of detection and quantification of the method were as low as 5 and 10ng/l respectively. At the parcel scale, two parcels of the Lavaux vineyard area, located near the Lutrive River at 6km to the east of Lausanne, were monitored to assess to which extent glyphosate and AMPA were retained in the soil or exported to surface waters. They were equipped at their bottom with porous ceramic cups and runoff collectors, which allowed retrieving water samples for the growing seasons 2010 and 2011. Results revealed that the mobility of glyphosate and AMPA in the unsaturated zone was likely driven by the precipitation regime and the soil characteristics, such as slope, porosity structure and layer permeability discrepancy. Elevated glyphosate and AMPA concentrations were measured at 60 and 80 cm depth at parcel bottoms, suggesting their infiltration in the upper parts of the parcels and the presence of preferential flow in the studied parcels. Indeed, the succession of rainy days induced the gradual saturation of the soil porosity, leading to rapid infiltration through macropores, as well as surface runoff formation. Furthermore, the presence of more impervious weathered marls at 100 cm depth induced throughflows, the importance of which for the lateral transport of the herbicide molecules was determined by the slope steepness. Important rainfall events (>10 mm/day) were clearly exporting molecules from the soil top layer, as indicated by important concentrations in runoff samples. A mass balance showed that total loss (10-20%) mainly occurred through surface runoff (96%) and, to a minor extent, by throughflows in soils (4%), with subsequent exfiltration to surface waters. Observations made in the Lutrive River revealed interesting details of glyphosate and AMPA dynamics in urbanized landscapes, such as the Lavaux vineyards. Indeed, besides their physical and chemical properties, herbicide dynamics at the catchment level strongly depend on application rates, precipitation regime, land use and also on the presence of drains or constructed channels. Elevated concentrations, up to 4970 ng/l, observed just after the application, confirmed the diffuse export of these compounds from the vineyard area by surface runoff during main rain events. From April to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Small vineyard surfaces could generate high concentrations of herbicides and contribute considerably to the total load calculated at the outlet, due to their steep slopes (~10%). The extrapolated total amount transferred yearly from the Lavaux vineyards to the Lake of Geneva was of 190kg. At the molecular scale, the possible involvement of dissolved organic matter (DOM) in glyphosate and copper transport was studied using UV/Vis fluorescence spectroscopy. Combined with parallel factor (PARAFAC) analysis, this technique allowed characterizing DOM of soil and surface water samples from the studied vineyard area. Glyphosate concentrations were linked to the fulvic-like spectroscopic signature of DOM in soil water samples, as well as to copper, suggesting the formation of ternary complexes. In surface water samples, its concentrations were also correlated to copper ones, but not in a significant way to the fulvic-like signature. Quenching experiments with standards confirmed field tendencies in the laboratory, with a stronger decrease in fluorescence intensity for fulvic-like fluorophore than for more aromatic ones. Lastly, based on maximum concentrations measured in the river, an environmental risk for these compounds was assessed, using laboratory tests and ecotoxicity data from the literature. In our case and with the methodology applied, the risk towards aquatic species was found negligible (RF<1).

Textual autocorrelation : formalism and illustrations

Abstract Textual autocorrelation is a broad and pervasive concept, referring to the similarity between nearby textual units: lexical repetitions along consecutive sentences, semantic association between neighbouring lexemes, persistence of discourse types (narrative, descriptive, dialogal...) and so on. Textual autocorrelation can also be negative, as illustrated by alternating phonological or morpho-syntactic categories, or the succession of word lengths. This contribution proposes a general Markov formalism for textual navigation, and inspired by spatial statistics. The formalism can express well-known constructs in textual data analysis, such as term-document matrices, references and hyperlinks navigation, (web) information retrieval, and in particular textual autocorrelation, as measured by Moran's I relatively to the exchange matrix associated to neighbourhoods of various possible types. Four case studies (word lengths alternation, lexical repulsion, parts of speech autocorrelation, and semantic autocorrelation) illustrate the theory. In particular, one observes a short-range repulsion between nouns together with a short-range attraction between verbs, both at the lexical and semantic levels. Résumé: Le concept d'autocorrélation textuelle, fort vaste, réfère à la similarité entre unités textuelles voisines: répétitions lexicales entre phrases successives, association sémantique entre lexèmes voisins, persistance du type de discours (narratif, descriptif, dialogal...) et ainsi de suite. L'autocorrélation textuelle peut être également négative, comme l'illustrent l'alternance entre les catégories phonologiques ou morpho-syntaxiques, ou la succession des longueurs de mots. Cette contribution propose un formalisme markovien général pour la navigation textuelle, inspiré par la statistique spatiale. Le formalisme est capable d'exprimer des constructions bien connues en analyse des données textuelles, telles que les matrices termes-documents, les références et la navigation par hyperliens, la recherche documentaire sur internet, et, en particulier, l'autocorélation textuelle, telle que mesurée par le I de Moran relatif à une matrice d'échange associée à des voisinages de différents types possibles. Quatre cas d'étude illustrent la théorie: alternance des longueurs de mots, répulsion lexicale, autocorrélation des catégories morpho-syntaxiques et autocorrélation sémantique. On observe en particulier une répulsion à courte portée entre les noms, ainsi qu'une attraction à courte portée entre les verbes, tant au niveau lexical que sémantique.

Maintenance and Design of Steel Abutment Piles in Iowa Bridges, TR-622, 2014

Soil consolidation and erosion caused by roadway runoff have exposed the upper portions of steel piles at the abutments of numerous bridges, leaving them susceptible to accelerated corrosion rates due to the abundance of moisture, oxygen, and chlorides at these locations. This problem is compounded by the relative inaccessibility of abutment piles for close-up inspection and repair. The objective of this study was to provide bridge owners with recommendations for effective methods of addressing corrosion of steel abutment piles in existing and future bridges A review of available literature on the performance and protection of steel piles exposed to a variety of environments was performed. Eight potential coating systems for use in protecting existing and/or new piles were selected and subjected to accelerated corrosion conditions in the laboratory. Two surface preparation methods were evaluated in the field and three coating systems were installed on three piles at an existing bridge where abutment piles had been exposed by erosion. In addition, a passive cathodic protection (CP) system using sacrificial zinc anodes was tested in the laboratory. Several trial flowable mortar mixes were evaluated for use in conjunction with the CP system. For existing abutment piles, application of a protective coating system is a promising method of mitigating corrosion. Based on its excellent performance in accelerated corrosion conditions in the laboratory on steel test specimens with SSPC-SP3, -SP6, and -SP10 surface preparations, glass flake polyester is recommended for use on existing piles. An alternative is epoxy over organic zinc rich primer. Surface preparation of existing piles should include abrasive blast cleaning to SSPC-SP6. Although additional field testing is needed, based on the results of the laboratory testing, a passive CP system could provide an effective means of protecting piles in existing bridges when combined with a pumped mortar used to fill voids between the abutment footing and soil. The addition of a corrosion inhibitor to the mortar appears to be beneficial. For new construction, shop application of thermally sprayed aluminum or glass flake polyester to the upper portion of the piles is recommended.

Agronomical and molecular characterization of banana germplasm

The objective of the present work was to characterize banana accessions from the Germplasm Bank at Embrapa Mandioca e Fruticultura Tropical (Brazil), using agronomical, physical and physicochemical characteristics of fruit and simple sequence repeats (SSR) markers. Twenty-six accessions were analyzed, in which high genetic variability was found, especially for the agronomical characters number of fruit and weight of bunch. Accessions with high contents of carotenoids (diploid 'Jaran'), polyphenols (triploid 'Caipira' and tetraploid 'Teparod') and vitamin C (diploid 'Tuugia' and an unknown triploid AAA) in the fruit were identified. Thirteen microsatellite primers revealed an average of 7.23 alleles, which showed high variability. A dendrogram was prepared using the Gower algorithm for the distance matrices obtained from the agronomical, physical and physicolchemical analysis of fruit and SSR markers. Adopting the average genetic divergence as the cut-off point, three clusters were found: G1, formed by the diploids 'Jaran', 028003-01 and M-48; G2, by the diploids 'Malbut' and 'Ido 110'; and G3, by 21 tri-and tetraploid accessions, including one diploid, 'Tuugia'. The triploids with the B genome 'Thap Maeo', 'Walha', 'Pacha Nadan' and 'Champa Madras' were grouped in G2. Results from this work can be used for breeding hybrids with good agronomical traits and fruit quality.

JPEG standard uniform quantization error modeling with applications to sequential and progressive operation modes

In this paper we propose a method for computing JPEG quantization matrices for a given mean square error or PSNR. Then, we employ our method to compute JPEG standard progressive operation mode definition scripts using a quantization approach. Therefore, it is no longer necessary to use a trial and error procedure to obtain a desired PSNR and/or definition script, reducing cost. Firstly, we establish a relationship between a Laplacian source and its uniform quantization error. We apply this model to the coefficients obtained in the discrete cosine transform stage of the JPEG standard. Then, an image may be compressed using the JPEG standard under a global MSE (or PSNR) constraint and a set of local constraints determined by the JPEG standard and visual criteria. Secondly, we study the JPEG standard progressive operation mode from a quantization based approach. A relationship between the measured image quality at a given stage of the coding process and a quantization matrix is found. Thus, the definition script construction problem can be reduced to a quantization problem. Simulations show that our method generates better quantization matrices than the classical method based on scaling the JPEG default quantization matrix. The estimation of PSNR has usually an error smaller than 1 dB. This figure decreases for high PSNR values. Definition scripts may be generated avoiding an excessive number of stages and removing small stages that do not contribute during the decoding process with a noticeable image quality improvement.

Genetic diversity of irrigated barley based on molecular and quantitative data and on malting quality

The objective of this work was to quantify the genetic diversity of elite genotypes of irrigated barley in the Brazilian savanna. Thirty elite barley genotypes from Embrapa Cerrados' collection were evaluated using 160 RAPD markers, 12 agronomic traits related to yield components, and 10 malting quality parameters. The genetic dissimilarity matrices based on molecular markers, quantitative traits, and malting quality characters were calculated and a cluster analysis was performed using the unweighted pair-group method with arithmetic mean (UPGMA) as grouping criterion. High genetic diversity among accessions were observed. The estimated genetic dissimilarities were weakly correlated, showing the complementarity of the different character groups. Selection indices and graphical dispersion analysis allowed the selection of promising genotypes and the indication of suitable crosses for maximizing the heterotic effects in breeding programs for irrigated barley in the Brazilian savanna.

Maternal exposure to polychlorinated biphenyls and the secondary sex ratio: an occupational cohort study.

Background: Though commercial production of polychlorinated biphenyls was banned in the United States in 1977, exposure continues due to their environmental persistence. Several studies have examined the associationbetween environmental polychlorinated biphenyl exposure and modulations of the secondary sex ratio, with conflicting results.Objective: Our objective was to evaluate the association between maternal preconceptional occupational polychlorinated biphenyl exposure and the secondary sex ratio.Methods: We examined primipara singleton births of 2595 women, who worked in three capacitor plants at least one year during the period polychlorinated biphenyls were used. Cumulative estimated maternal occupationalpolychlorinated biphenyl exposure at the time of the infant's conception was calculated from plant-specific job exposure matrices. A logistic regression analysis was used to evaluate the association between maternalpolychlorinated biphenyl exposure and male sex at birth (yes/no).Results: Maternal body mass index at age 20, smoking status, and race did not vary between those occupationally exposed and those unexposed before the child's conception. Polychlorinated biphenyl-exposed mothers were, however, more likely to have used oral contraceptives and to have been older at the birth of their first child than non-occupationally exposed women. Among 1506 infants liveborn to polychlorinated biphenyl-exposedprimiparous women, 49.8% were male; compared to 49.9% among those not exposed (n = 1089). Multivariate analyses controlling for mother's age and year of birth found no significant association between the odds of amale birth and mother's cumulative estimated polychlorinated biphenyl exposure to time of conception.Conclusions: Based on these data, we find no evidence of altered sex ratio among children born to primiparous polychlorinated biphenyl-exposed female workers.

Aplicaciones de la Teoría de Matrices en Matemática Discreta

Se describen algunas aplicaciones de la teoría de matrices a diversos temas pertenecientes alámbito de la matem\'atica discreta.

Average performance analysis of circular and hyperbolic geolocation

A comparative performance analysis of four geolocation methods in terms of their theoretical root mean square positioning errors is provided. Comparison is established in two different ways: strict and average. In the strict type, methods are examined for a particular geometric configuration of base stations(BSs) with respect to mobile position, which determines a givennoise profile affecting the respective time-of-arrival (TOA) or timedifference-of-arrival (TDOA) estimates. In the average type, methodsare evaluated in terms of the expected covariance matrix ofthe position error over an ensemble of random geometries, so thatcomparison is geometry independent. Exact semianalytical equationsand associated lower bounds (depending solely on the noiseprofile) are obtained for the average covariance matrix of the positionerror in terms of the so-called information matrix specific toeach geolocation method. Statistical channel models inferred fromfield trials are used to define realistic prior probabilities for therandom geometries. A final evaluation provides extensive resultsrelating the expected position error to channel model parametersand the number of base stations.

Genetic variability of hull-less barley accessions based on molecular and quantitative data

The objective of this work was to characterize and quantify the genetic, molecular, and agronomic variability of hull-less barley genotypes, for the selection of parents and identification of genotypes adapted to the irrigated production system in the Brazilian Cerrado. Eighteen hull-less barley accessions were evaluated, and three covered barley accessions served as reference. The characterization was based on 157 RAPD molecular markers and ten agronomic traits. Genetic distance matrices were obtained based on molecular markers and quantitative traits. Graphic grouping and dispersion analyses were performed. Genetic, molecular, and agronomic variability was high among genotypes. Ethiopian accessions were genetically more similar, and the Brazilian ones were genetically more distant. For agronomic traits, two more consistent groupings were obtained, one with the most two-rowed materials, and the other with six-rowed materials. The more diverging materials were the two-rowed CI 13453, CN Cerrado 5, CN Cerrado 1, and CN Cerrado 2. The PI 356466, CN Cerrado 1, PI 370799, and CI 13453 genotypes show agronomic traits of interest and, as genetically different genotypes, they are indicated for crossing, in breeding programs.

The use of external mesh reinforcement to reduce intimal hyperplasia and preserve the structure of human saphenous veins.

The saphenous vein is the conduit of choice in bypass graft procedures. Haemodynamic factors play a major role in the development of intimal hyperplasia (IH), and subsequent bypass failure. To evaluate the potential protective effect of external reinforcement on such a failure, we developed an ex vivo model for the perfusion of segments of human saphenous veins under arterial shear stress. In veins submitted to pulsatile high pressure (mean pressure at 100 mmHg) for 3 or 7 days, the use of an external macroporous polyester mesh 1) prevented the dilatation of the vessel, 2) decreased the development of IH, 3) reduced the apoptosis of smooth muscle cells, and the subsequent fibrosis of the media layer, 4) prevented the remodelling of extracellular matrix through the up-regulation of matrix metalloproteinases (MMP-2, MMP-9) and plasminogen activator type I. The data show that, in an experimental ex vivo setting, an external scaffold decreases IH and maintains the integrity of veins exposed to arterial pressure, via increase in shear stress and decrease wall tension, that likely contribute to trigger selective molecular and cellular changes.

Unsaturated Polyester Resins from Recycled Polyethyleneterephthalate

Tämän diplomityön tarkoituksena oli tutkia miten kuluttajien kierrättämästä polyeteenitereftalaatista ( PET ) voi valmistaa tyydyttymättömiä polyesterihartseja. Työssä valmistettiin yleiskäyttöön soveltuva laminointihartsi sekä 'gel coat' -hartsi jota käytetään esim. veneiden pintamaalina. Yleishartsin depolymerointiin käytettiin propyleeniglykolia ja 'gel coat' -hartsin valmistamiseen neopentyyliglykolia. Polykondensaatiovaiheessa reaktioon lisättiin maleiinihappoa ja lopuksi hartsit liuotettiin styreeniin. Kirjallisuusosassa esitetään eri menetelmiä PET:n depolymeroimiseksi. Lisäksi esitetään eri vaihtoehtoja glykolien, happojen, katalyyttien ja vinyylimonomeerien valitsemiseksi tyydyttymättömien polyesterihartsien valmistuksessa. Analyysimenetelmiä nestemäisten ja kovetettujen hartsien tutkimiseen ja vertailuun käydään läpi kuten myös erilaisia sovelluksia polyesterihartsien käyttämiseksi. Kokeellinen osa todisti että PET-pullojäte voidaan prosessoida hartsiksiilman uusia investointeja prosessilaitteistoon. PET:n glykolyysi kesti viidestäseitsemään tuntia ja polykondensaatiovaihe kahdesta ja puolesta viiteen tuntiin. Hartsien molekyylipainot ja mekaanisten testien tulokset olivat vertailukelpoisia kaupallisten hartsien antamien tulosten kanssa. Glykolyysivaiheen momomeeri- ja oligomeeripitoisuudet mitattiin geelipermeaatiokromatografialla, jotta nähtiin miten pitkälle depolymerisaatio oli edennyt. Tätä tietoa voidaan hyödyntää uusien hartsireseptin suunnittelussa. Polymeeriketjussa jäljellä olevien C=C kaksoissidosten määrä ja niiden isomeraatioaste maleaattimuodosta fumaraattimuotoon mitattiin 1H-NMR -menetelmällä. Tislevesien koostumus määritettiin kaasukromatografialla, ja tulokset kertoivat katalyytin sisältämän kloorin reagoineen glykolien kanssa, johtaen suureen glykolikulutukseen ja muihin ei-toivottuihin sivureaktioihin. Hartsien sietokykyä auringon valolle mitattiin niiden UV-absorption avulla. Kummastakin hartsista valmistettiin 'gel coat' -maalit jotkalaitettiin sääkoneeseen, joka simuloi auringonpaistetta ja vesisadetta vuorotellen. Näistä 'gel coateista' mitattiin niiden kellastumista. Kummastakin hartsista tehdyt valut asetettiin myös sääkoneeseen ja IR-spektreistä ennen jajälkeen koetta nähtiin että C=O ja C-O esterisidoksia oli hajonnut.

Self-Organising Maps and Correlation Analysis as a Tool to Explore Patterns in Excitation-Emission Matrix Data Sets and to Discriminate Dissolved Organic Matter Fluorescence Components

Dissolved organic matter (DOM) is a complex mixture of organic compounds, ubiquitous in marine and freshwater systems. Fluorescence spectroscopy, by means of Excitation-Emission Matrices (EEM), has become an indispensable tool to study DOM sources, transport and fate in aquatic ecosystems. However the statistical treatment of large and heterogeneous EEM data sets still represents an important challenge for biogeochemists. Recently, Self-Organising Maps (SOM) has been proposed as a tool to explore patterns in large EEM data sets. SOM is a pattern recognition method which clusterizes and reduces the dimensionality of input EEMs without relying on any assumption about the data structure. In this paper, we show how SOM, coupled with a correlation analysis of the component planes, can be used both to explore patterns among samples, as well as to identify individual fluorescence components. We analysed a large and heterogeneous EEM data set, including samples from a river catchment collected under a range of hydrological conditions, along a 60-km downstream gradient, and under the influence of different degrees of anthropogenic impact. According to our results, chemical industry effluents appeared to have unique and distinctive spectral characteristics. On the other hand, river samples collected under flash flood conditions showed homogeneous EEM shapes. The correlation analysis of the component planes suggested the presence of four fluorescence components, consistent with DOM components previously described in the literature. A remarkable strength of this methodology was that outlier samples appeared naturally integrated in the analysis. We conclude that SOM coupled with a correlation analysis procedure is a promising tool for studying large and heterogeneous EEM data sets.