Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

Manganese nodule geochemistry from the Challenger Expedition

C. W. Gümbel received nodules from J. Murray which were collected at a depth of 2740 fathoms, between Japan and the Sandwich Islands, by the "Challenger" Expedition. They were either round or long in shape, with a dull, dirty-brown coloured surface, and enclosed fragments of pumice-stone, and more rarely teeth of sharks or fragments of mussels. They were analysed by A. Schwager.

Analysis of manganese nodules in lakes of Scotland

During the "Challenger" Deep-Sea Exploring Expedition a great many peculiar-looking manganese nodules or concretions were dredged from the floor of the ocean at great depths, chiefly in the Red Clay areas of the Pacific. In the present paper we propose to point out the distribution of the oxides of manganese in the geological series of rocks, in fresh and sea water, and in marine deposits, with special reference to our explorations in the lochs of the west of Scotland; to give an account of investigations undertaken to ascertain the source of the manganese present in marine deposits in the form of the higher oxides, and thereafter to discuss the various views that have been advanced to explain the formation and distribution of manganese concretions in marine deposits in general.

(Table 2, page 1177) Composition of manganese deposit samples from Cuba

Todorokite is a very abundant manganese oxide mineral in many deposits in Cuba and has been noted from other localities. Six new analyses are givenl they lead to the approximate formula (Na, Ca, K, Mn+2)(Mn+4, Mn+2, Mg)6O12.3H2O. Electron diffraction data show the mineral to be orthorhombic, or monoclinic with beta near 90°. The x-ray powder pattern is indexed on a cell with a=0.75A, b=2.849A, c=9.59A, beta=90°. A differential thermal analysis curve is given.

(Table 3, page 264), Composition of a manganese micronodule found in a fossil red clay bed from Western Timor

Chemical analyses are presented for two Cretaceous clays from Noil Tobee, Timor. Mineralogical examination has shown that they consist principally of quartz, feldspar, illite and chlorite, together with minor amounts of montmorillonite. Both chemically and mineralogically the clays are very similar to the recent argillaceous deep-sea sediments of the Pacific and Indian Oceans, which confirms Molengraaff's theory (1921) that they are of deep-sea origin. Further confirmation of this theory is provided by comparison of the composition of micromanganese nodules, separated from one of these clays, with that of manganese nodules from the Pacific Ocean.

(Table 1, page 1169) Chemical composition of land (fossil) manganese deposits rich in todorokite

Chemical, x-ray and other data are given for todorokite, (Mn, Mg, Ca, Ba, Na, K)2.Mn5O12.3H2O, from Charco Redondo, Cuba, Farragudo, Portugal, and Hüttenberg, Austria. Additional localities at Romanèche, France, Saipan Island, Bahia, Brazil and Sterling Hill, New Jersey, are noted. Delatorreite of Simon and Straczek (1958) is identical with todorokite.

Quantification of air quality in space and time and its effects on health

The long-term adverse effects on health associated with air pollution exposure can be estimated using either cohort or spatio-temporal ecological designs. In a cohort study, the health status of a cohort of people are assessed periodically over a number of years, and then related to estimated ambient pollution concentrations in the cities in which they live. However, such cohort studies are expensive and time consuming to implement, due to the long-term follow up required for the cohort. Therefore, spatio-temporal ecological studies are also being used to estimate the long-term health effects of air pollution as they are easy to implement due to the routine availability of the required data. Spatio-temporal ecological studies estimate the health impact of air pollution by utilising geographical and temporal contrasts in air pollution and disease risk across $n$ contiguous small-areas, such as census tracts or electoral wards, for multiple time periods. The disease data are counts of the numbers of disease cases occurring in each areal unit and time period, and thus Poisson log-linear models are typically used for the analysis. The linear predictor includes pollutant concentrations and known confounders such as socio-economic deprivation. However, as the disease data typically contain residual spatial or spatio-temporal autocorrelation after the covariate effects have been accounted for, these known covariates are augmented by a set of random effects. One key problem in these studies is estimating spatially representative pollution concentrations in each areal which are typically estimated by applying Kriging to data from a sparse monitoring network, or by computing averages over modelled concentrations (grid level) from an atmospheric dispersion model. The aim of this thesis is to investigate the health effects of long-term exposure to Nitrogen Dioxide (NO2) and Particular matter (PM10) in mainland Scotland, UK. In order to have an initial impression about the air pollution health effects in mainland Scotland, chapter 3 presents a standard epidemiological study using a benchmark method. The remaining main chapters (4, 5, 6) cover the main methodological focus in this thesis which has been threefold: (i) how to better estimate pollution by developing a multivariate spatio-temporal fusion model that relates monitored and modelled pollution data over space, time and pollutant; (ii) how to simultaneously estimate the joint effects of multiple pollutants; and (iii) how to allow for the uncertainty in the estimated pollution concentrations when estimating their health effects. Specifically, chapters 4 and 5 are developed to achieve (i), while chapter 6 focuses on (ii) and (iii). In chapter 4, I propose an integrated model for estimating the long-term health effects of NO2, that fuses modelled and measured pollution data to provide improved predictions of areal level pollution concentrations and hence health effects. The air pollution fusion model proposed is a Bayesian space-time linear regression model for relating the measured concentrations to the modelled concentrations for a single pollutant, whilst allowing for additional covariate information such as site type (e.g. roadside, rural, etc) and temperature. However, it is known that some pollutants might be correlated because they may be generated by common processes or be driven by similar factors such as meteorology. The correlation between pollutants can help to predict one pollutant by borrowing strength from the others. Therefore, in chapter 5, I propose a multi-pollutant model which is a multivariate spatio-temporal fusion model that extends the single pollutant model in chapter 4, which relates monitored and modelled pollution data over space, time and pollutant to predict pollution across mainland Scotland. Considering that we are exposed to multiple pollutants simultaneously because the air we breathe contains a complex mixture of particle and gas phase pollutants, the health effects of exposure to multiple pollutants have been investigated in chapter 6. Therefore, this is a natural extension to the single pollutant health effects in chapter 4. Given NO2 and PM10 are highly correlated (multicollinearity issue) in my data, I first propose a temporally-varying linear model to regress one pollutant (e.g. NO2) against another (e.g. PM10) and then use the residuals in the disease model as well as PM10, thus investigating the health effects of exposure to both pollutants simultaneously. Another issue considered in chapter 6 is to allow for the uncertainty in the estimated pollution concentrations when estimating their health effects. There are in total four approaches being developed to adjust the exposure uncertainty. Finally, chapter 7 summarises the work contained within this thesis and discusses the implications for future research.

O Cuidado de Enfermagem na Prevenção das Flebites.

A flebite é uma complicação com elevada taxa de incidência hospitalar (Mangerote et al., 2011; Urbanetto et al., 2011; Intravenous Nurses Society, 2011). As suas consequências são graves para a saúde da pessoa, implicando ainda custos económicos acrescidos. Apesar do conhecimento disponível sobre os vários fatores de risco e sobre as boas práticas recomendadas na preveção da infeção associada ao cateter venoso, reconhece-se que os resultados tardam em melhorar e se constituem como um desafio para os enfermeiros, Como principais objetivos definiram-se: identificar a percentagem de flebites na venopunção periférica nos doentes internados num serviço de área médica de um hospital central e analisar alguns fatores de risco de flebite. Desenvolveu-se um estudo observacional, descritivo-correlacional. Os dados recolhidos durante 76 dias, através de uma grelha de observação incluíram, entre outras variáveis, as relacionadas com o doente (género e idade), com a medicação (antibioterapia, terapêutica de manutenção e polimedicação) e com os cuidados de enfermagem na inserção e otimização do CVP (calibre, local, higienização das mãos do enfermeiro, desinfetante da pele, fixação, tempo de permanência). Incluíram-se 175 CVP (em 75 doentes), cujos critérios principais foi terem sido introduzidos apenas no serviço de internamento, em doentes adultos. Verificou-se uma taxa de flebite de 37,4% (Grau I - 6,7%; Grau II - 17,9%; Grau III - 9,7%; Grau IV - 3,1%). A análise das variáveis em estudo permitiu identificar a coexistência de vários fatores de risco, no entanto apenas o tipo de desinfetante do local a puncionar revelou correlação estatisticamente significativa com o desenvolvimento de flebite (menor taxa com Álcool 70% do que com Clorohexidina 2%). Os resultados deste estudo, fornecem bases para a reflexão sobre os fatores de risco modificaveis, contribuindo para a promoção de estratégias e medidas de melhoria da taxa de flebite.

Tratamento de sementes para manejo do percevejo-barriga-verde na cultura de soja e milho em sucessão.

RESUMO: O objetivo deste trabalho foi avaliar o efeito do tratamento de sementes com inseticidas sobre o manejo de Dichelops melacanthus e a produtividade da soja e do milho, cultivados em sucessão. O estudo foi realizado em campo, nas safras 2012/2013 (I) e 2013/2014 (II). Avaliaram-se os inseticidas imidacloprido, tiametoxam, tiodicarbe, fipronil e abamectina. Determinaram-se: a densidade populacional do percevejo, a produtividade de soja e milho, e a intensidade da injúria em milho. A densidade do percevejo permaneceu abaixo de um inseto por metro quadrado, na maior parte do ciclo da soja. Os picos populacionais foram observados nas primeiras semanas, após a emergência do milho, e atingiram 2,2 (safra I) e 6,7 (safra II) percevejos por metro quadrado. Na cultura da soja, os inseticidas não reduziram a densidade populacional do percevejo. Na cultura do milho, o imidacloprido reduziu a densidade do percevejo em 23,2% (safra I) e 38,8% (safra II), e a injúria em 61,8% (safra I) e 26,4% (safra II). O tiametoxam reduziu a densidade dos insetos em 27,8% (safra II) e a injúria em 42,7% (safra I). O tratamento de sementes com inseticidas não proporciona aumento de produtividade à soja e ao milho, portanto, não se justifica sua utilização nas condições deste estudo. ABSTRACT: The objective of this work was to evaluate the effect of seed treatment with insecticides on the management of Dichelops melacanthus on the yield of soybean and corn, grown in succession. The study was carried out in a field, in the 2012/2013 (I) and 2013/2014 (II) crop seasons. The evaluated insecticides were: imidacloprid, thiamethoxam, thiodicarb, fipronil, and abamectin. The following were determined: stink bug population density, soybean and corn yield, and corn injury. Population density remained below one stink bug per square meter, in most of the soybean cycle. Population peaks were observed in the first weeks, after corn emergence, and they reached 2.2 (crop season I) and 6.7 (crop season II) stink bugs per square meter. In the soybean crop, the insecticides did not reduce the stink bug population density. In the corn crop, imidacloprid reduced the stink bug density in 23.2% (crop season I) and 38.8% (crop season II), and injury in 61.8% (crop season I) and 26.4% (crop season II). Thiamethoxam reduced the insect population density in 27.8% (crop season II) and injury in 42.7% (crop season I). Seed treatment with insecticides does not provide increase for soybean and corn yields, therefore, their use is not justified in this study's conditions.

Design of luminescent metal complexes for polymer science

The program of my PhD studies has been dealing with the investigation of the research outcomes that may result from the use of luminescent Iridium(III) cyclometalated complexes in the field of polymer science. In particular, my activity has been focused on exploring two main applicative contexts, i.e. Ir(III) complexes for preparing polymers and in combination with polymers. In the first part, a new set of luminescent Ir(III) complexes was exploited as photocatalysts for light-assisted atom transfer radical polymerization of methyl methacrylate. The decoration of both cyclometalated and ancillary ligands with sp3 hybridized nitrogen substituents together with the use of specific counterions, imparted suitable photophysical and redox properties for an efficient photocatalyzed process. The second part has been focused on the employment of Ir(III) tetrazole complexes as phosphorescent dyes in polymeric materials. Colourless luminescent solar concentrators were prepared blending two Ir(III) cyclometalates with acrylate polymers. Their performances were investigated, leading to promising outcomes comparable, or superior, to those obtained from colourless LSCs based on organic fluorophores. As a complementary approach, Ir(III) complexes were covalently linked to polymers in the side chain, to obtain a new class of metallopolymers. To this extent, a bifunctional tetrazolate molecule, equipped with a coordination site and a polymerizable unit, was designed. The photophysical properties of the resultant luminescent polymeric films were discussed. In the end, an additional project involving both polymers and metal compounds was carried out during my experience as a visiting PhD student at Humboldt – University of Berlin. Polystyrene and polyethylene glycol -based ion-exchange resins were functionalized with peptides through a ligation pathway, for the selective chelation of Copper(II) in aqueous solutions. The coordinating capability of the materials towards Cu2+ ions was tested by ICP-MS analysis. The resins strategically modified with ion-selective peptides, may be exploited in the preparation of water-processing devices.

Organic photosensitizers and nanostructured semiconductors for photoredox catalysis and artificial photosynthesis

Over the course of evolution, Nature has elegantly learned to use light to drive chemical reactions. On the other hand, humans have only recently started learning how to play with this powerful tool to carry out chemical transformations. In particular, a step forward was possible thanks to molecules and materials that can absorb light and trigger a series of processes that can drive chemical reactions. However, scarce elements are extensively employed in the design of most of these compounds and considerations on their scarcity and toxicity have sparked interest on alternatives based on earth-abundant elements. In this framework, the focus of this thesis has been the development and employment of heavy-metal free chromophores and of earth-abundant oxides. The first chapter regards the functionalization of boron-dipyrromethenes (BODIPYs) so as to allow access to their triplet excited state and tune their redox potentials, which was achieved thanks to the design of orthogonal donor-acceptor dyads. The BODIPY dyads were used to promote a photoredox reaction, and the mechanism of the reaction was clarified. In the second chapter, organic chromophores that display thermally-activated delayed fluorescence (TADF) were studied. These were used to perform enantioselective photoredox reactions, and a mechanistic investigation allowed to elucidate the fate of these photosensitizers in the reaction. Thanks to their stronger reducing power, it was possible to demonstrate the employability of TADF dyes in artificial photosynthesis, as well. Last, the oxidation of biomass-derived compounds was studied in a photoelectrochemical cell. For this purpose, hematite photoanodes were synthesized in collaboration with Prof. Caramori’s group at the University of Ferrara (Italy) and they were tested in the presence of a redox mediator. In addition to this, the possibility of repurposing a copper(II) water oxidation catalyst for the oxidation of biomass was investigated in collaboration with Prof. Llobet’s group at ICIQ (Tarragona, Spain).

Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008

The preparation and characterization of seven-coordinate tin(IV) complexes of the 2,6-diacetylpyridine Schiff bases of S-alkyl/aryl-dithiocarbazates and the X-ray crystal structure of the [Sn(dapsme)I-2] complex (dapsme=doubly deprotonated form of the 2,6

New tin(IV) complexes of empirical formula, Sn(SNNNS)I-2 (SNNNS = anionic form of the 2,6-diacetylpyridine Schiff bases of S-methyl- or S-benzyldithiocarbazate) have been prepared and characterized by a variety of physico-chemical techniques. The structure of Sn(dapsme)I-2 has been determined by single crystal X-ray crystallographic structural analysis. The complex has a seven-coordinate distorted pentagonal-bipyramidal geometry with the Schiff base coordinated to the tin(IV) ion as a dinegatively charged pentadentate chelating agent via the pyridine nitrogen atom, the two azomethine nitrogen atoms and the two thiolate sulfur atoms. The ligand occupies the equatorial plane and the iodo ligands are coordinated to the tin(IV) ion at axial positions. The distortion from an ideal pentagonal bipyramidal geometry is attributed to the restricted bite size of the pentadentate ligands. (C) 2004 Elsevier Ltd. All rights reserved.