Structural and chemical embrittlement of grain boundaries by impurities: A general theory and first-principles calculations for copper

First-principles calculations of the Sigma 5(310)[001] symmetric tilt grain boundary in Cu with Bi, Na, and Ag substitutional impurities provide evidence that in the phenomenon of Bi embrittlement of Cu grain boundaries electronic effects do not play a major role; on the contrary, the embrittlement is mostly a structural or "size" effect. Na is predicted to be nearly as good an embrittler as Bi, whereas Ag does not embrittle the boundary in agreement with experiment. While we reject the prevailing view that "electronic" effects (i.e., charge transfer) are responsible for embrittlement, we do not exclude the role of chemistry. However, numerical results show a striking equivalence between the alkali metal Na and the semimetal Bi, small differences being accounted for by their contrasting "size" and "softness" (defined here). In order to separate structural and chemical effects unambiguously if not uniquely, we model the embrittlement process by taking the system of grain boundary and free surfaces through a sequence of precisely defined gedanken processes; each of these representing a putative mechanism. We thereby identify three mechanisms of embrittlement by substitutional impurities, two of which survive in the case of embrittlement or cohesion enhancement by interstitials. Two of the three are purely structural and the third contains both structural and chemical elements that by their very nature cannot be further unraveled. We are able to take the systems we study through each of these stages by explicit computer simulations and assess the contribution of each to the net reduction in intergranular cohesion. The conclusion we reach is that embrittlement by both Bi and Na is almost exclusively structural in origin; that is, the embrittlement is a size effect.

Galactic Edge Clouds I. Molecular Line Observations and Chemical Modelling of Edge Cloud 2

Edge Cloud 2 (EC2) is a molecular cloud, about 35 pc in size, with one of the largest galactocentric distances known to exist in the Milky Way. We present observations of a peak CO emission region in the cloud and use these to determine its physical characteristics. We calculate a gas temperature of 20 K and a density of n(H2)~10^4 cm-3. Based on our CO maps, we estimate the mass of EC2 at around 10^4 Msolar and continuum observations suggest a dust-to-gas mass ratio as low as 0.001. Chemical models have been developed to reproduce the abundances in EC2, and they indicate that heavy element abundances may be reduced by a factor of 5 relative to the solar neighborhood (similar to dwarf irregular galaxies and damped Lya systems), very low extinction (A_V <4 mag) due to a very low dust-to-gas mass ratio, an enhanced cosmic-ray ionization rate, and a higher UV field compared to local interstellar values. The reduced abundances may be attributed to the low level of star formation in this region and are probably also related to the continuing infall of primordial (or low-metallicity) halo gas since the Milky Way formed. Finally, we note that shocks from the old supernova remnant GSH 138-01-94 may have determined the morphology and dynamics of EC2.

Early pain experience, child and family factors, as precursors of somatization:a prospective study of extremely premature and fullterm children

In a prospective study of 36 children who were extremely low birthweight (ELBW: <1000 g) preterm infants and 36 matched full-term controls, differences were found in somatization at age 4 1/2 years. Only children who had been extremely premature, and thereby experienced prolonged hospitalization and repeated medical intervention in infancy, had clinically high somatization scores on the Personality Inventory for Children. The combination of family relations at age 4 1/2 years, neonatal intensive care experience, poor maternal sensitivity to child cues in mother-child interaction observed at age 3 years, and child avoidance of touch or holding at age 3, predicted somatization scores, prior to school entry. Due to the known higher incidence of actual medical problems among children with a history of extreme prematurity, the high somatization ELBW children were compared with the normal somatization ELBW children. There were no differences in prevalence of actual medical problems between the 2 ELBW groups, and the importance of maternal factors in relation to somatization was confirmed. Child temperament at age 3, but not personality at 4 1/2, was related to somatization. The etiology of recurrent physical complaints of no known medical cause appears to be a multi-dimensional problem. Non-optimal parenting may contribute to the development of inappropriate strategies for coping with common pains of childhood, or of chronic pain patterns, in some children who have experienced prolonged or repeated pain as neonates.

Prevalence and risk factors of depressive symptoms in a Canadian palliative home care population: a cross-sectional study

Background: Depression in palliative care patients is important because of its intrinsic burden and association with elevated physical symptoms, reduced immunity and increased mortality risk. Identifying risk factors associated with depression can enable clinicians to more readily diagnose it, which is important since depression is treatable. The purpose of this cross-sectional study was to determine the prevalence of depressive symptoms and risk factors associated with them in a large sample of palliative home care patients.

Methods: The data come from interRAI Palliative Care assessments completed between 2006 and 2012. The sample (n = 5144) consists of adults residing in Ontario (Canada), receiving home care services, classified as palliative, and not experiencing significant cognitive impairment. Logistic regression identified the risk factors associated with depressive symptoms. The dependent variable was the Depression Rating Scale (DRS) and the independent variables were functional indicators from the interRAI assessment and other variables identified in the literature. We examined the results of the complete case and multiple imputation analyses, and found them to be similar.

Results: The prevalence of depressive symptoms was 9.8%. The risk factors associated with depressive symptoms were (pooled estimates, multiple imputation): low life satisfaction (OR = 3.01 [CI = 2.37-3.82]), severe and moderate sleep disorders (2.56 [2.05-3.19] and 1.56 [1.18-2.06]), health instability (2.12 [1.42-3.18]), caregiver distress 2.01 [1.62-2.51]), daily pain (1.73 [1.35-2.22]), cognitive impairment (1.45 [1.13-1.87]), being female (1.37 [1.11-1.68]), and gastrointestinal symptoms (1.27 [1.03-1.55]). Life satisfaction mediated the effect of prognostic awareness on depressive symptoms.

Conclusions: The prevalence of depressive symptoms in our study was close to the median of 10-20% reported in the palliative care literature, suggesting they are present but by no means inevitable in palliative patients. Most of the factors associated with depressive symptoms in our study are amenable to clinical intervention and often targeted in palliative care programs. Designing interventions to address them can be challenging, however, requiring careful attention to patient preferences, the spectrum of comorbid conditions they face, and their social supports. Life satisfaction was one of the strongest factors associated with depressive symptoms in our study, and is likely to be among the most challenging to address.

Factors influencing the compressive strengths of fly ash based geopolymers

Several factors affecting the reactivity of pulverised fuel ash (pfa) as a precursor for geopolymer concrete have been investigated. These include physical and chemical properties of various pfa sources, inclusion of ground granulated blast furnace slag (ggbs), chemical activator dosages and curing temperature. Alkali-activated pfa was found to require elevated curing temperatures and high alkali concentrations. A mixture of sodium hydroxide and sodium silicate was used and this was shown to result in high strengths, as high as 70 MPa at 28-days. The presence of silicates in solution was found to be a key factor. Detailed physical and chemical characterisation was carried out on thirteen pfa sources from the UK. The most important factor affecting the reactivity was found to be the particle size of pfa. The loss on ignition (LOI) and the amorphous content are also important parameters that need to be considered for the selection of pfa for use in geopolymer concrete. The partial replacement of pfa by ground granulated blast furnace slag (ggbs) was found to be beneficial in not only avoiding the need for elevated curing temperatures but also in improving compressive strengths. Microstructural characterisation with scanning electron microscope (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) was performed on pfa/ggbs pastes. The reaction product of pfa and ggbs in these binary systems was calcium aluminium silicate hydrate gel (C-A-S-H) with inclusion of Na in the structure.

Gamma-ray Spectra and Enhancement Factors for Positron Annihilation with Core Electrons

Many-body theory is developed to calculate the γ spectra for positron annihilation in noble-gas atoms. Inclusion of electron-positron correlation effects and core annihilation gives spectra in excellent agreement with experiment [K. Iwata et al., Phys. Rev. Lett. 79, 39 (1997)]. The calculated correlation enhancement factors γnl for individual electron orbitals nl are found to scale with the ionization energy I_nl (in eV), as γnl=1+ √A/Inl+(B/I_nl)β, where A≈40  eV, B≈24  eV, and β≈2.3.

Single and joint effects of natural and chemical stressors to the terrestrial isopod Porcellionides pruinosus

Environmental contamination and climate changes constitute two of the most serious problems affecting soil ecosystems in agricultural fields. Agriculture is nowadays a highly optimized process that strongly relies on the application of multiple pesticides to reduce losses and increase yield production. Although constituting, per se, a serious problem to soil biota, pesticide mixtures can assume an even higher relevance in a context of unfavourable environmental conditions. Surprisingly, frameworks currently established for environmental risk assessments keep not considering environmental stressors, such as temperature, soil moisture or UV radiation, as factors liable to influence the susceptibility of organisms to pesticides, or pesticide mixtures, which is raising increasing apprehension regarding their adequacy to actually estimate the risks posed by these compounds to the environment. Albeit the higher attention received on the last few years, the influence of environmental stressors on the behaviour and toxicity of chemical mixtures remains still poorly understood. Aiming to contribute for this discussion, the main goal of the present thesis was to evaluate the single and joint effects of natural stressors and pesticides to the terrestrial isopod Porcellionides pruinosus. The first approach consisted on evaluating the effects of several abiotic factors (temperature, soil moisture and UV radiation) on the performance of P. pruinosus using several endpoints: survival, feeding parameters, locomotor activity and avoidance behaviour. Results showed that these stressors might indeed affect P. pruinosus at relevant environmental conditions, thus suggesting the relevance of their consideration in ecotoxicological assays. At next, a multiple biomarker approach was used to have a closer insight into the pathways of damage of UV radiation and a broad spectrum of processes showed to be involved (i.e. oxidative stress, neurotoxicity, energy). Furthermore, UV effects showed to vary with the environment medium and growth-stage. A similar biomarker approach was employed to assess the single and joint effects of the pesticides chlorpyrifos and mancozeb to P. pruinosus. Energy-related biomarkers showed to be the most differentiating parameters since age-classes seemed to respond differently to contamination stress and to have different metabolic costs associated. Finally, the influence of temperature and soil moisture on the toxicity of pesticide mixtures was evaluated using survival and feeding parameters as endpoints. Pesticide-induced mortality was found to be oppositely affected by temperature, either in single or mixture treatments. Whereas chlorpyrifos acute toxicity was raised under higher temperatures the toxicity of mancozeb was more prominent at lower temperatures. By the opposite, soil moisture showed no effects on the pesticide-induced mortality of isopods. Contrary to survival, both temperature and soil moisture showed to interact with pesticides to influence isopods’ feeding parameters. Nonetheless, was however the most common pattern. In brief, findings reported on this thesis demonstrated why the negligence of natural stressors, or multiple stressors in general, is not a good solution for risk assessment frameworks.

Vitamin D levels and associated factors: a population-based study in Switzerland.

QUESTIONS UNDER STUDY: To update the prevalence of vitamin D insufficiency and to identify factors associated with vitamin D status in the Swiss adult population. METHODS: Data from the 2010-2011 Swiss Study on Salt intake, a population-based study in the Swiss population, was used. Vitamin D concentration in serum was measured by liquid chromatography- tandem mass spectrometry. Major factors that influence vitamin D levels were taken into account. Survey statistical procedures were used to estimate means and prevalences of vitamin D levels and status. Monthly-specific tertiles of vitamin D and ordinal logistic regression were used to determine the associations of covariates of interest with vitamin D status. RESULTS: The prevalences of vitamin D insufficiency (serum 25-hydroxyvitamin D: 20-29.9 ng/ml) and deficiency (<20 ng/ml) were the highest in the January-March period; 26.4% (95%CI: 21.6-31.7) and 61.6% (95%CI: 56.0-67.0), respectively. In the same period, more than 9 of ten men were vitamin D insufficient or deficient. Each unit increase of Body Mass Index was associated with an 8% decreased likelihood of being in a higher vitamin D tertiles. Oral contraceptive, altitude, urinary excretion of calcium, use of vitamin D supplement or treatment, high wine consumption, physical activity were associated with vitamin D tertiles. Compared to the French-speaking region, the Italian-speaking region was independently associated with a higher likelihood of being in higher vitamin D tertiles (OR: 1.66, 95%CI: 1.14-2.43). CONCLUSIONS: Low levels of vitamin D are common among Swiss adults, in particular during winter months and outside the Italian-speaking region.

Personality and neuropsychological factors involved in females' relational aggression

The personality and neuropsychological factors associated with relational aggression were examined in a group of30 grade 6,7, and 8 girls identified through cluster analysis as being highly, yet almost exclusively, relationally aggressive and a group of 30 nonaggressive matched controls. Parents of the students in both groups completed the Coolidge Personality and Neuropsychological Inventory (1998), a 200- item DSM-IV -TR aligned, parent-as-respondent, standardized measure of c.hildren' s psychological functioning. It was found that high levels of relational aggression, in the absence of physical and verbal aggression, were associated with symptoms of DSM-IV - TR Axis I oppositional defiant disorder and conduct disorder and a wide variety of personality traits associated with DSM-IV -TR Axis II paranoid, borderline, narcissistic, histrionic, schizotypal, and passive aggressive personality disorders. Implications of these findings for theory, practice, and further research are discussed.

Clustering algorithms and shape factor methods to discriminate among small GTPase phenotypes using DIC image analysis.

Naïvement perçu, le processus d’évolution est une succession d’événements de duplication et de mutations graduelles dans le génome qui mènent à des changements dans les fonctions et les interactions du protéome. La famille des hydrolases de guanosine triphosphate (GTPases) similaire à Ras constitue un bon modèle de travail afin de comprendre ce phénomène fondamental, car cette famille de protéines contient un nombre limité d’éléments qui diffèrent en fonctionnalité et en interactions. Globalement, nous désirons comprendre comment les mutations singulières au niveau des GTPases affectent la morphologie des cellules ainsi que leur degré d’impact sur les populations asynchrones. Mon travail de maîtrise vise à classifier de manière significative différents phénotypes de la levure Saccaromyces cerevisiae via l’analyse de plusieurs critères morphologiques de souches exprimant des GTPases mutées et natives. Notre approche à base de microscopie et d’analyses bioinformatique des images DIC (microscopie d’interférence différentielle de contraste) permet de distinguer les phénotypes propres aux cellules natives et aux mutants. L’emploi de cette méthode a permis une détection automatisée et une caractérisation des phénotypes mutants associés à la sur-expression de GTPases constitutivement actives. Les mutants de GTPases constitutivement actifs Cdc42 Q61L, Rho5 Q91H, Ras1 Q68L et Rsr1 G12V ont été analysés avec succès. En effet, l’implémentation de différents algorithmes de partitionnement, permet d’analyser des données qui combinent les mesures morphologiques de population native et mutantes. Nos résultats démontrent que l’algorithme Fuzzy C-Means performe un partitionnement efficace des cellules natives ou mutantes, où les différents types de cellules sont classifiés en fonction de plusieurs facteurs de formes cellulaires obtenus à partir des images DIC. Cette analyse démontre que les mutations Cdc42 Q61L, Rho5 Q91H, Ras1 Q68L et Rsr1 G12V induisent respectivement des phénotypes amorphe, allongé, rond et large qui sont représentés par des vecteurs de facteurs de forme distincts. Ces distinctions sont observées avec différentes proportions (morphologie mutante / morphologie native) dans les populations de mutants. Le développement de nouvelles méthodes automatisées d’analyse morphologique des cellules natives et mutantes s’avère extrêmement utile pour l’étude de la famille des GTPases ainsi que des résidus spécifiques qui dictent leurs fonctions et réseau d’interaction. Nous pouvons maintenant envisager de produire des mutants de GTPases qui inversent leur fonction en ciblant des résidus divergents. La substitution fonctionnelle est ensuite détectée au niveau morphologique grâce à notre nouvelle stratégie quantitative. Ce type d’analyse peut également être transposé à d’autres familles de protéines et contribuer de manière significative au domaine de la biologie évolutive.

Parental separation and child adjustment : longitudinal perspective and risk factors

Malgré de nombreuses études qui soutiennent l'idée que les enfants ayant vécu la rupture de leurs parents rencontrent un plus haut niveau de difficultés affectives et comportementales que les enfants de familles intactes, certaines questions restent à éclaircir. Notamment, les données empiriques existantes ne conduisent pas à des conclusions précises quant au moment exact de l’apparition de ces difficultés. De plus, ce n'est pas clair si ces difficultés sont associées à la séparation en soi, ou à bien d'autres facteurs liés à la séparation. Cette thèse est constituée de deux articles empiriques. Le premier examine l’adaptation de l’enfant avant et après la séparation en fonction du sexe et de l'âge au moment de la séparation. Le second article présente une étude qui a pour objectif de départager l’importance des facteurs parentaux et contextuels et celle de la séparation parentale pour expliquer l’adaptation de l’enfant. Les participants proviennent de l'Étude Longitudinale du Développement des Enfants du Québec (ÉLDEQ, 1998-2006). À chaque enquête de l'ÉLDEQ, une entrevue structurée réalisée auprès de la mère a permis d'évaluer les niveaux d’hyperactivité/impulsivité, d’anxiété et d’agressivité physique de l’enfant. Pendant cette entrevue, les mères ont également répondu à des questions sur la qualité de leurs pratiques parentales et sur le revenu du ménage. Finalement, un questionnaire auto-administré à la mère a permis d'évaluer ses propres symptômes de dépression et d'anxiété. La première étude inclus 143 enfants de familles séparées et 1705 enfants de familles intactes. Deux sous-groupes ont été créés selon que l’enfant ait vécu la séparation entre 2 et 4 ans, ou entre 4 et 6 ans. L’adaptation de l'enfant a été évaluée à un temps de mesure avant la séparation et à deux temps de mesure après la séparation. Les résultats de cette première étude démontrent qu’avant la séparation, les enfants de familles intactes et séparées ne se distinguent pas significativement quant à leurs niveaux d’hyperactivité/impulsivité et d’anxiété. Par contre, ces difficultés deviennent significativement plus élevées chez les enfants de familles séparées après la rupture des parents. D’autres parts, le niveau d’agressivité physique est plus élevé chez les enfants de la séparation indépendamment du temps de mesure. Finalement, les différences entre les deux groupes d’enfants ne dépendent pas du sexe ou de l’âge au moment de la séparation. La deuxième étude inclus 358 enfants de 8 ans qui ont vécu la séparation de leurs parents, et 1065 enfants du même âge provenant de familles intactes. Après avoir contrôlé pour le sexe de l’enfant, les résultats ont démontré que lorsqu’on tient compte de la contribution des symptômes maternels de dépression et d'anxiété, de la qualité des pratiques parentales et du revenu du ménage dans l’adaptation de l’enfant, la séparation parentale ne demeurent plus liée aux niveaux d’anxiété et d'agressivité physique de l’enfant. Par contre, la relation entre la séparation parentale et l’hyperactivité/impulsivité de l’enfant demeure significative. Les résultats présentés dans les articles sont discutés ainsi que leurs implications.

Space and time characterization of laser-induced plasmas for applications in chemical analysis and thin film deposition

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz.

Cellular and humoral factors involved in defense mechanisms of Fenneropenaeus indicus (H. Milne Edwards, 1837)

The present investigation revealed three types of circulating haemocytes in the haemolymph of F. indicus: hyalinocytes, small-granule haemocytes, and large-granule haemocytes. Intermediate stages indicate the maturing process of a single cell. The presence of enzymes such as peroxidase, phenoloxidase and acid phosphatase in the haemocytes, and the substantial production of oxygen radicals during phagocytosis show that the haemocytes are capable of mounting a fme cellular defense mechanism. The enzyme activities of the serum and the presence of agglutinins in the serum, which may act as opsonins, agglutinate foreign particles and augment phagocytosis, confirm the presence of a superior humoral immune system in F. indicus.Bacterial infection caused considerable variations in the cellular and humoral factors, such as the number of circulating cells and haemagglutinating activity, especially in the initial hours of infection. The total haemocyte count, haemagglutination titer and phenoloxidase enzyme showed significant reductions on bacterial presence and could be used as indicators of bacterial infection.The number of circulating cells showed drastic fluctuation on exposure to pollutants. Nuvan at low concentrations was able to produce changes in the haemolymph factors and in the tissue organization, which implies that the animal is under stress and is easily prone to infections. Exposure to nuvan resulted in significant variation in all of the cellular and humoral factors, especially, the total haemocyte count, percentage of small granule haemocytes, phagocytic activity and the haemagglutinating activity, which might be good indicators of pesticide pollution. Heavy metal exposure caused significant increase in total haemocyte count and reduction in phenoloxidase enzyme activity Even changes in the physio-chemical parameters, such as salinity caused fluctuations in the defense factors, indicating stress in this euryhaline species. The dietary incorporation of a commercial immunostimulant containing P-l,3 glucan resulted in stimulation of some of the humoral defense factors of F indicus, but was time dependent. The modulations, on exposure to various external factors, in the cellular and humoral factors, especially, total haemocyte count, phagocytic activity, haemagglutinating activity and the phenoloxidase and acid phosphatase enzymes suggest that these parameters could be used as indicators of the health status of F indicus, which assist in better monitoring and effective health management of this important cultured species.

Culture and growth kinetics of selected nanoplankters

The present study on naoplankton is based on the isolation and development of unialgai culturas from the inshore waters at Cochin. characterization of their growth assimilation products. ecophysioiogy and evaluation of nutritional quality. The work was carried out during the period 1980-1983. The nanoplankters were isolated and grown in the labratory as batch cultures to study the increase in cell population, the photosynthetic pigment: ana physioiogical activity. The chemical composition of these organisms and their rate of excretion were also determined. The environmental factors physical and chemical that influence the growth of these Cultures were defined by conducting independentexperiments. These cultures of the isolated nanoplankters have raised indoor and fed to the larvae of edible oyster to test their suitability as live-food.

Distribution and mobility of trace elements in soils and vegetation around the mining and smelting areas of Tharsis, Riotinto and Huelva, Iberian Pyrite Belt, SW Spain

Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling their distribution and transfer within the soil and vegetation systems are not always well defined. Total concentrations of up to 15,195 mg center dot kg (-1) As, 6,690 mg center dot kg(-1) Cu, 24,820 mg center dot kg(-1) Pb and 9,810 mg center dot kg(-1) Zn in soils, and 62 mg center dot kg(-1) As, 1,765 mg center dot kg(-1) Cu, 280 mg center dot kg(-1) Pb and 3,460 mg center dot kg (-1) Zn in vegetation were measured. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters (maximum 2-3 km). Parent material, prevailing wind direction, and soil physical and chemical characteristics were found to correlate poorly with the restricted trace element distributions in soils. Hypotheses are given for this unusual distribution: (1) the contaminated soils were removed by erosion or (2) mines and smelters released large heavy particles that could not have been transported long distances. Analyses of the accumulation of trace elements in vegetation (median ratios: As 0.06, Cu 0.19, Pb 0.54 and Zn 1.07) and the percentage of total trace elements being DTPA extractable in soils (median percentages: As 0.06%, Cu 15%, Pb 7% and Zn 4%) indicated higher relative trace element mobility in soils with low total concentrations than in soils with elevated concentrations.