Geochemistry at DSDP Hole 69-504B

Cores from Deep Sea Drilling Project Holes 501, 504B and 505B have an unusual near-vein zonation in basalts. Megascopically, zonation occurs as differently colored strips and zones whose typical thickness does not exceed 6 to 7 cm. Microscopically, the color of zones depends on variably colored clay minerals which are the products of low-temperature hydrothermal alteration in basalt. These differently colored zones form the so called "oxidative" type of alteration of basalts. Another "background," or, less precisely termed, "non-oxidative," type of alteration in basalts is characterized by large-scale, homogeneous replacement of olivine, and filling of vesicles and cracks by an olive-brown or olive-green clay mineral. The compositions of clay minerals of the "background" type of alteration, as well as the composition of co-existing titanomagnetites, were determined with an electron microprobe. There are sharp maxima in potassium and iron content, and minima in alumina, silica, and magnesia in clay minerals in the colored zones near veins. Coloring of clay and rock-forming minerals by iron hydroxides and a decrease of the amount of titanomagnetite, which apparently was the source of redeposited iron, occur frequently in colored zones. We assume that the large-scale "background" alteration in the basalts occurred under the effect of pore waters slowly penetrating through bottom sediments. Faulting can facilitate access of fresh sea water to basalts; thus above the general homogeneous background arise zones of "oxidative" alteration along fractures in basalts. The main factors controlling these processes are time (age of basalt), grain size, temperature, thickness of sedimentary cover, and heat flow.

Paleomagnetic of ODP Holes 122-762B and 122-763A

The magnetostratigraphy of Neogene sediments from Holes 762B and 763A are presented in this paper. Hole 762B contains 17 reversals. All reversals above the base of the Gilbert are correlated with the magnetic polarity time scale (Haq et al., 1988). Hole 763A yields a record of about 20 reversals that can be correlated to the magnetic polarity time scale, documenting all reversals to the base of Chron 4A. Based on the correlation, the sediment accumulation vs. time for Holes 762B and 763A are determined. The age-depth curves obtained show a similar pattern of sedimentation rate since 6.8 Ma. The study also indicates a correlation between the fluctuations in the magnetic parameters (natural remanent magnetization intensity and susceptibility), the lithologic changes, and changes in iron content at both holes. This correlation suggests that the natural remanent magnetization intensity and susceptibility changes observed in Holes 762B and 763A are controlled by changes in depositional processes probably associated with climatic variations.

Abundance and sizes of European oak species (Quercus petraea (Matt.) Liebl., Quercus robur L.) in dependence of neighborhood and environmental factors

Quercus robur L. (pedunculate oak) and Quercus petraea (Matt.) Liebl. (sessile oak) are two European oak species of great economic and ecological importance. Even though both oaks have wide ecological amplitudes of suitable growing conditions, forests dominated by oaks often fail to regenerate naturally. The regeneration performance of both oak species is assumed to be subject to a variety of variables that interact with one another in complex ways. The novel approach of this research was to study the effect of many ecological variables on the regeneration performance of both oak species together and identify key variables and interactions for different development stages of the oak regeneration on a large scale in the field. For this purpose, overstory and regeneration inventories were conducted in oak dominated forests throughout southern Germany and paired with data on browsing, soil, and light availability. The study was able to verify the assumption that the occurrence of oak regeneration depends on a set of variables and their interactions. Specifically, combinations of site and stand specific variables such as light availability, soil pH and iron content on the one hand, and basal area and species composition of the overstory on the other hand. Also browsing pressure was related to oak abundance. The results also show that the importance of variables and their combinations differs among the development stages of the regeneration. Light availability becomes more important during later development stages, whereas the number of oaks in the overstory is important during early development stages. We conclude that successful natural oak regeneration is more likely to be achieved on sites with lower fertility and requires constantly controlling overstory density. Initially sufficient mature oaks in the overstory should be ensured. In later stages, overstory density should be reduced continuously to meet the increasing light demand of oak seedlings and saplings.

Realidad estratégica de la sostenibilidad de los recursos naturales: La explotación del hierro

Es en el campo de los recursos naturales y su aplicación a la industria, el entorno donde se desarrolla esta Tesis. El objetivo de la misma es demostrar cómo la minería del hierro puede resultar una actividad sostenible, logrando continuar de esta manera la estrecha relación de siempre entre las necesidades del hombre y la pervivencia de los recursos naturales. Es en la minería del hierro donde hace mayor énfasis este trabajo, dando lugar a un nuevo Indicador Sostenible que intenta evaluar las explotaciones de mineral de hierro desde una visión sostenible, empleando el consumo energético y las emisiones de CO2 como principales herramientas. Como se observa en el día a día, el tema de la sostenibilidad es de plena actualidad, lográndose en este trabajo implicar, tanto a la eficiencia energética, como al control de emisiones de gases efecto invernadero; ambas herramientas cobran más importancia cada día que pasa. La Tesis se desarrolla en 5 capítulos, aparte de su bibliografía correspondiente. En el primer capítulo se introduce el sentido de la sostenibilidad, desde sus inicios conceptuales, hasta sus actuales clasificaciones y definiciones empleadas; todo ello desde el punto de vista de los recursos naturales, y más habitualmente desde la minería. Resulta llamativo el contraste de opiniones, en lo que se ha dado a llamar la paradoja de la minería sostenible, quedando tras su lectura, la posición de la minería en una situación, si no ventajosa, si de equilibrio en importancia entre las necesidades a cubrir y el agotamiento de recursos. El segundo capítulo nos muestra el entorno donde se va a conducir la Tesis. El marco que engloba este trabajo se extiende desde la extracción del mineral de hierro (minería), su tratamiento y concentración (mineralurgia), su venta a los hornos altos (mercados) hasta su posterior fabricación en acero terminado (siderurgia). En este capítulo se presentan los principales actores que entrarán en el sector de la minería del hierro (productores y fabricantes) incluyendo una serie de datos estadísticos de gran interés para el desarrollo de la Tesis. El tercer capítulo se refiere al proceso completo que precisa la actividad sobre la que se va a evaluar la sostenibilidad. Es donde se definen, paso a paso, y obteniendo todos los datos de consumos energéticos y emisiones de CO2, las diferentes etapas por las que pasa el mineral de hierro, hasta encontrarse laminado en la acería. Es aquí donde se analizan los diversos tipos de yacimientos de hierro dispersos por el mundo y el mineral extraído, de manera que las propiedades aprendidas se puedan emplear más adelante en un indicador, y que así diferencie la sostenibilidad en función de los orígenes motivo de las necesidades energéticas para su transformación. El capítulo 4 consta de dos bloques: el uso de las herramientas de medida de la sostenibilidad, a día de hoy en el mundo industrial, y de una manera pormenorizada, el consumo energético y sus emisiones medioambientales como herramienta de gestión ambiental para la minería del hierro. Esta herramienta resultará básica para el cálculo del indicador buscado para la medida de la sostenibilidad. El capítulo 5 constituye el núcleo de la tesis, y supone el desarrollo del indicador, la metodología de uso y las conclusiones obtenidas. A través de varios ejemplos se logra entender la aplicación del indicador, dando lugar a una clasificación sostenible sencilla y práctica, situando en orden las diferentes explotaciones en función de un nivel de sostenibilidad determinado. Este último capítulo da origen al Indicador Sostenible Energético buscado, mostrándose en todo su esplendor y descubriendo cómo la relación ponderada entre el consumo energético y sus emisiones de CO2 permite, a través de una valoración, mostrar todos los parámetros de relevancia para el mineral de hierro y su posterior transformación en acero. Esa cifra obtenida por el indicador, clasificará la explotación teniendo en cuenta, el tipo de yacimiento, características del mineral (especie mineralógica, tipo de mineral, ley del mineral en hierro, tipo de ganga, características físicas como dureza o tamaño de grano, susceptibilidad magnética, etc.), situación geográfica, infraestructuras, etc. Sin profundizar en la siderurgia, por lo menos sí incluir los principales parámetros (relacionados siempre desde el mineral) que pudieran tener influencia en la disminución de energía requerida (y sus emisiones de CO2 relacionadas): la reducibilidad, el contenido en hierro, y mencionar la influencia del SiO2. Se completa la Tesis con las referencias bibliográficas y documentales, así como con una bibliografía general. ABSTRACT This Thesis is set in a context of natural resources and applied science. The aim of this document is to prove that iron mining is a sustainable activity, so the ancient relationship between men and natural resources will continue. Iron mining is the main subject of this work, so a new sustainable indicator is created in order to evaluate the iron mining from a sustainable point of view. The main tools applied are energy consumption and CO2 emissions. In this research document two relevant issues are involved: energy efficiency and GHGs control; both tools gain significance by the day. This thesis develops along 5 chapters and its bibliography. The first chapter refers to the concept of sustainability, from the beginning to the current definitions and classifications; all this information is focused from the natural resources point of view, especially mining. The contrast of opinion is remarkable, which has been called the “paradox of sustainable mining”; however this chapter concludes that taking into account the less bright side of the mining its activity maintains an important balance between necessities to cover, available resources and environment. The second chapter sets out where this Thesis has been conducted. The frame of this work lies between iron mining, ore processing, the market and the latter steel fabrication (steelmaking). This chapter shows the iron mining key stakeholders, supported with statistical data. The third chapter refers to the whole process definition. From the iron mineral to the rolled steel, all data related with energy consumption and CO2 emissions are considered step by step. Different iron deposits widespread all over the world are analyzed now, as well as the exploited iron mineral in order to apply the lessons learned to create a new sustainability tool. Then, our sustainability studies will consider the influence of this in the energy necessities when iron is transformed. Chapter four is divided in the currently applied sustainability measurement tools, and focusing on energy consumption and CO2 emissions linked to the iron mining process. This tool is essential to calculate the required indicator that reflects the sustainability. Chapter five is the Thesis’ core: it is where the new sustainable indicator is developed, the methodology stated and the final conclusions obtained. Through several examples the indicator application is explained, and a practical and simple sustainable classification will show the ranking of every exploitation. This last chapter develops the sustainable tool and discovers how the weighted relation between energy consumption and CO2 emissions allows understanding all the relevant parameters in the iron mineral transformation. The number calculated will be used to classify the mineral exploitation, taking into account the deposit typology, mineral characteristics (mineralogy, type of mineral, iron percentage, physical properties as hardness or grain size, magnetic susceptibility, etc.), geographic situation, infrastructures, etc. Although steelmaking is not studied in depth, main parameters (from the mineral side) which can operate in the energy decrease (and CO2 emissions in parallel) are referred to: reducibility, iron content and SiO2 influence. The bibliography used is included at the end of this paper.

Puesta a punto de métodos de análisis de combustibles basados en la espectrometría atómica

El presente proyecto tiene como objeto la puesta a punto de métodos de análisis de combustibles basados en la espectrometría atómica, centrándose en un equipo de absorción atómica que, como su nombre indica, funciona bajo el principio de la absorción atómica y un equipo ICP que trabaja por plasma acoplado inductivamente y que se rige bajo el principio espectrométrico de la emisión atómica. La finalidad de la puesta a punto de ambos métodos es llevar un control de calidad periódico sobre los combustibles. Se pondrán a punto dos métodos normalizados de ensayos, uno bajo la norma UNE EN 16135 para la determinación del contenido de manganeso en gasolinas; otro bajo la norma EN 16576 para determinar el contenido de manganeso y de hierro en gasóleos de automoción. La puesta a punto de ambos métodos tiene un procedimiento asociado que se puede resumir en cuatro pasos: lectura de la norma, creación del método en el software informático con el que trabaja el equipo, calibración del mismo y realización del estudio de exactitud del método. Abstract The aim of this project is to tune up analytical methods based on the principle of the atomic spectrometry, focusing on testing equipment which works under the principle of atomic absorption and Inductively Coupled Plasma (ICP) equipment governed under the principle of atomic emission. The purpose of tuning up both methods is to perform a quality control on fuels. Two different standard methods will be developed: One under the standard UNE EN 16135 for measuring the content of manganese in gasolines; the other one under the standard EN 16576 for the determination of manganese and iron content in middle distillate fuels. Tune up of both methods procedure can be summarized in four steps: Reading the standard, creation of the method on the computer software associated to the equipment, calibration of the equipment and completion of accuracy study.

Estresse oxidativo em porfiria hepática experimental disparada por succinilacetona - um inibidor da ácido 5-aminolevulínico desidratase

Para otimizar um modelo experimental para o estudo do desbalanço redox em porfirias relacionadas ao acúmulo de ácido 5-aminolevulínico-(ALA), via inibição da ALA desidratase-(ALA-D), ratos foram tratados com o éster metílico de succinilacetona-(SAME), um catabólito da tirosina que inibe fortemente a ALA-O, mimetízando o estado metabólico observado nos portadores de portirias e tirosinemias. Estabeleceram-se modelos de tratamento agudo por 36 e 18 h. No primeiro, os animais receberam 3 injeções de SAME (10, 40 ou 80 mg/kg, grupos Ali-IV). No segundo, os animais receberam 3 injeções de 40 mg/kg de SAME, ALA ou éster metílico de ALA (grupos BII-IV), ALA:SAME (30: 10 mg/kg, grupo BV), ou 10 mg/kg SAME (grupo BVI). Paralelamente, avaliou-se se os sintomas neurológicos característicos das portirias decorriam de danos oxidativos mitocondriais. Para isso, aplicou-se uma tecnologia óptica para medidas da difusão da depressão cortical que determinou a oxigenação e o estado redox do cit c em mitocôndrias do córtex cerebral de ratos submetidos ao tratamento crônico com ALA (40 mg/kg), SAME (10 e 40 mg/kg) e ALA:SAME (30: 1O mg/kg), a cada 48 h, durante 30 dias. Tratamento agudo/36 h: Os níveis de ALA no plasma, fígado, cérebro e urina e o clearance renal do ALA aumentaram nos grupos tratados. A atividade de ALA-D e a coproporfirina urinária reduziram. A marcação para proteínas carboniladas, ferro e ferritina aumentou no fígado e cérebro dos grupos tratados, especialmente no All. Os níveis de malondialdeído hepático aumentaram no grupo AIV. A razão GSH/GSH+GSSG e a atividade de GPx cerebrais aumentaram nos grupos AIV e AIII, respectivamente. Consistentemente com estes dados indicando um desbalanço oxidativo induzido pelo SAME, alterações mitocondriais e citosólicas ultraestruturais foram reveladas, especialmente no fígado. Tratamento agudo/18 h: Os níveis de ALA plasmáticos aumentaram nos grupos tratados, exceto em BIV. O grupo BII mostrou aumento dos níveis hepáticos de ALA. Interessantemente, a inibição da atividade de ALA-D não foi evidenciada. O conteúdo de ferro plasmático aumentou no grupo BII. Para os grupos tratados com 10 e 40 mg SAME/kg, a atividade de SOD hepática reduziu ~50% com a extensão do tratamento de 18 para 36 h, sugerindo que este último é mais efetivo em promover danos oxidativos induzidos pelo ALA. Tratamento crônico/30 dias: Embora nenhuma alteração tenha sido evidenciada no estado redox dos animais tratados, o tratamento com ALA reduziu o fluxo sanguíneo cerebral (CBF) e o consumo de oxigênio-(CMRO2), sugerindo uma vasoconstrição mediada pelo ALA, efeito este confirmado por ensaios de reatividade vascular conduzidos em anéis de aorta de ratos incubados com ALA. O tratamento com ALA:SAME restaurou os níveis de CBF e CMRO2. Interessantemente, a disponibilidade do radical superóxido-(O2•-) estava reduzida nos anéis de aorta incubados com ALA. Juntos, estes dados: a)validam o modelo de tratamento agudo/36 h para o estudo bioquímico e dos possíveis efeitos fisiológicos induzidos pelo ALA, e b)sugerem que as alterações mediadas pelo ALA exógeno levam à vasoconstrição.

Morphological features of interfacial intermetallics and interfacial reaction rate in Al-11Si-2.5Cu-(0.15/0.60)Fe cast alloy/die steel couples

Soldering reactions are commonly observed during high pressure die casting of aluminium alloys, and involve the formation and growth of interfacial intermetallics between the die and the cast alloy. It is generally believed that close to 1% Fe is necessary in the aluminium alloy to reduce soldering. However, the role of iron in the interfacial reaction has not been studied in detail. In this investigation, reaction couples were formed between H13 tool steel substrates and an Al-11Si-2.5Cu melt containing either 0.15 or 0.60% Fe. Examination revealed distinctly different intermetallic layer morphology. The overall growth and chemistry of the reaction layer and the reaction rate measured by the consumption of the substrate were compared for the two alloy melts. It was demonstrated that a higher iron content reduces the rate of interfacial reaction, consistent with an observed thicker compact ( solid) intermetallic layer. Hence, the difference in reaction rate can be explained by a significant reduction in the diffusion flux due to a thicker compact layer. Finally, the mechanism of the growth of a thicker compact layer in the higher iron melt is proposed, based on the phase relations and diffusion both within and near the interfacial reaction zone. (C) 2004 Kluwer Academic Publishers.

Anomalous magnetic susceptibility values and traces of subsurface microbial activity in carbonate banks on San Salvador Island, Bahamas

Pure limestones beneath the paleosols on San Salvador Island, Bahamas, contain strong positive magnetic susceptibility anomalies, although the iron content is generally very low. These magnetic phenomena differ from those associated with disconformities, which are marked by accumulation of paramagnetic airborne dust deposits with relatively high iron content. The strength and characters of the magnetic response in these subsurface zones correspond to the presence of magnetite, particularly small single-domain magnetite crystals of microbial origin. These crystals are not present elsewhere in the intergranular rock pores or microvugs. They are preferentially concentrated in capillary microborings, which developed concurrently with formation of calcite cements that have soil-related C and O isotope compositions. These magnetic zones occur several meters below the overlying soil horizons. Very thin and long linear microborings may be attributable to cyanobacterial microborers. The single-domain magnetites in these micrometer-size tunnels plugged by calcite appear to result from later occupation of these tiny holes by magnetotactic bacteria. Inorganic origin of the magnetite seems unlikely. Numerous traces that suggest subsurface microbial activity provide evidence that may be used to develop possible scenarios for subsequent biological studies of the precise bacteria involved.

(Table 2, Page 252) Average chemical composition of 11 manganese nodules and crust from the Pacific Ocean

The ability of the hydrated oxides of manganese and iron to adsorb ions from solution (scavenging) is considered in relation to some problems in marine geology, chemistry, and biology. In the ferruginous sediments of the Pacific Ocean, iron oxides are accompanied by titanium, cobalt, and zirconium in amounts proportional to the iron content. Similarly, copper and nickel are linearly related to the manganese content. These observations are explained on the basis of scavenging. An electrochemical theory for the formation of manganese nodules is presented. Marine sediments are classified on the basis of the geosphere in which the solid phases originate. The distribution of certain ionic species in sea water between the solid and aqueous phases is considered on the basis of scavenging and co-ordination compound theory. The concentration of minor elements by members of the marine biosphere is explained either by the direct uptake of the element or by the uptake of iron or manganese oxides with the accompanying scavenged element.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

Decadal-to-centennial scale variations during the Holocene reconstructed from sediment core D13902

Sea surface temperature (SST), marine productivity, and fluvial input have been reconstructed for the last 11.5 calendar (cal) ka B.P. using a high-resolution study of C37 alkenones, coccolithophores, iron content, and higher plant n-alkanes and n-alkan-1-ols in sedimentary sequences from the inner shelf off the Tagus River Estuary in the Portuguese Margin. The SST record is marked by a continuous decrease from 19C, at 10.5 and 7 ka, to 15C at present. This trend is interrupted by a fall from 18C during the Roman and Medieval Warm Periods to 16C in the Little Ice Age. River input was very low in the early Holocene but increased in the last 3 cal ka B.P. in association with an intensification of agriculture and deforestation and possibly the onset of the North Atlantic Oscillation/Atlantic Multidecadal Oscillation modes of variability. River influence must have reinforced the marine cooling trend relative to the lower amplitude in similar latitude sites of the eastern Atlantic. The total concentration of alkenones reflects river-induced productivity, being low in the early Holocene but increasing as river input became more important. Rapid cooling, of 1-2C occurring in 250 years, is observed at 11.1, 10.6, 8.2, 6.9, and 5.4 cal ka B.P. The estimated age of these events matches the ages of equivalent episodes common in the NE Atlantic- Mediterranean region. This synchronicity reveals a common widespread climate feature, which considering the twentieth century analog between colder SSTs and negative North Atlantic Oscillation (NAO), is likely to reflect periods of strong negative NAO.

Sediment and pore water chemistry and physical oceanography of samples obtained during Baltic Sea research cruises

Sediment samples from approximately 40 stations in the Western, middle and eastern Baltic Sea were investigated for manganese and iron content. In a series of interstitial water samples and numerous deep and surface water samples, the manganese content was likewise determined. A strong enrichment of these elements in the basin sediments was shown. In many instances, several percent manganese were present. As a maximum value, 13% was found in a 1 mm thick layer. Furthermore, a distinct decrease in manganese content with increasing sediment depth was shown in the upper 10 to 20 cm of the Sediment at almost all stations. Both phenomena may be explained by the release of manganese from the Sediment through diffusion. In the flat parts of the Baltic and those parts having good bottom water circulation, this diffusion progresses especially vigorously as a result of a steep gradient of the Mn++ concentration in the interstitial water-deep water interface. The manganese which hereby passes into the water overlying the bottom (manganese contents between 10 and 100 y Mn/l were determined in numerous deep water samples) is partly reprecipitated on the Sediment surface, and partly carried by currents into the deeper basins where it is finallv deposited. It is bound there as a manganese-rich mixed carbonate, the composition of which can be proved chemically and by x-ray methods. Iron is likewise of higher content in the basinal sediments, however, the extent of its enrichment is far less since it is less soluble than manganese under the reducing conditions in the sediments. The fine bands of manganese- and iron-rich layers in the basin sediments may likewise be explained as a result of diffusion.

Characterization of hepcidin response to holotransferrin in novel recombinant TfR1 HepG2 cells

Hepcidin is the key regulator of systemic iron homeostasis. The iron-sensing mechanisms and the role of intracellular iron in modulating hepatic hepcidin secretion are unclear. Therefore, we created a novel cell line, recombinant-TfR1 HepG2,expressing iron-response-element-independent TFRC mRNA to promote cellular iron overload and examined the effect of excess holotransferrin (5 g/L) on cell-surface TfR1, iron content, hepcidin secretion and mRNA expressions of TFRC, HAMP, SLC40A1,HFE and TFR2. Results showed that the recombinant cells exceeded levels of cell surface TfR1 in wild-type cells under basal (2.8-fold; p<0.03) and holotransferrin supplemented conditions for 24 h and 48 h (4.4- and 7.5-fold, respectively; p<0.01). Also, these cells showed higher intracellular iron content than wild-type cells under basal (3-fold; p<0.03) and holotransferrin-supplemented conditions (6.6-fold at 4 h; p<0.01). However, hepcidin secretion was not higher than wild-type cells. Moreover, holotransferrin treatment to recombinant cells did not elevate HAMP responses compared to untreated or wild-type cells. In conclusion, increased intracellular iron content in recombinant cells did not increase hepcidin responses compared to wild-type cells, resembling hemochromatosis. Furthermore, TFR2 expression altered within 4 h of treatment, while HFE expression altered later at 24 h and 48 h, suggesting that TFR2 may function prior to HFE in HAMP regulation.

Degradation of Biofumigant Isothiocyanates and Allyl Glucosinolate in Soil and Their Effects on the Microbial Community Composition

Brassicales species rich in glucosinolates are used for biofumigation, a process based on releasing enzymatically toxic isothiocyanates into the soil. These hydrolysis products are volatile and often reactive compounds. Moreover, glucosinolates can be degraded also without the presence of the hydrolytic enzyme myrosinase which might contribute to bioactive effects. Thus, in the present study the stability of Brassicaceae plant-derived and pure glucosinolates hydrolysis products was studied using three different soils ( model biofumigation). In addition, the degradation of pure 2-propenyl glucosinolate was investigated with special regard to the formation of volatile breakdown products. Finally, the influence of pure glucosinolate degradation on the bacterial community composition was evaluated using denaturing gradient gel electrophoresis of 16S rRNA gene amplified from total community DNA. The model biofumigation study revealed that the structure of the hydrolysis products had a significant impact on their stability in the soil but not the soil type. Following the degradation of pure 2-propenyl glucosinolate in the soils, the nitrile as well as the isothiocyanate can be the main degradation products, depending on the soil type. Furthermore, the degradation was shown to be both chemically as well as biologically mediated as autoclaving reduced degradation. The nitrile was the major product of the chemical degradation and its formation increased with iron content of the soil. Additionally, the bacterial community composition was significantly affected by adding pure 2-propenyl glucosinolate, the effect being more pronounced than in treatments with myrosinase added to the glucosinolate. Therefore, glucosinolates can have a greater effect on soil bacterial community composition than their hydrolysis products.

Applications of synchrotron x-ray powder diffraction in hydrated cements: high-resolution and high-pressure studies

The main aim of this study is to apply synchrotron radiation techniques for the study of hydrated cement pastes. In particular, the tetracalcium aluminoferrite phase, C4AF in cement nomenclature, is the major iron-containing phase in Ordinary Portland Cement (OPC) and in iron rich belite calcium sulfoaluminate cements. In a first study, the hydration mechanism of pure tetracalcium aluminoferrite phase with water-to-solid ratio of 1.0 has been investigated by HR-SXRPD (high resolution synchrotron X-ray powder diffraction). C4AF in the presence of water hydrates to form mainly an iron-containing hydrogarnet-type (katoite) phase, C3A0.84F0.16H6, as single crystalline phase. Its crystal structure and stoichiometry were determined by the Rietveld method and the final disagreement factors were RWP=8.1% and RF=4.8% [1]. As the iron content in the product is lower than that in C4AF, it is assumed that part of the iron also goes to an amorphous iron rich gel, like the hydrated alumina-type gel, as hydration proceeds. Further results from the high-resolution study will be discussed. In a second study, the behavior of pure and iron-containing katoites (C3AH6 and C3A0.84F0.16H6) under pressure have been analyzed by SXRPD using a diamond anvil cell (DAC) and then their bulk moduli were determined. The role of the pressure transmitting medium (PTM) has also been studied. In this case, silicone oil as well as methanol/ethanol mixtures have been used as PTM. Some “new peaks” were detected in the pattern for C3A0.84F0.16H6 as pressure increases, when using ethanol/methanol as PTM. These new peaks were still present at ambient pressure after releasing the applied pressure. They may correspond to crystalline nordstrandite or doyleite from the crystallization of amorphous aluminium hydroxide. The results from the high-pressure study will also be discussed.