Speciation analysis of inorganic arsenic in river water by Amberlite IRA 910 resin immobilized in a polyacrylamide gel as a selective binding agent for As(v) in diffusive gradient thin film technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Magnetic Properties of γ - Fe2O3 Nanoparticles at the Verge of Nucleation Process.

A low-energy new method based in a one-step synthesis at room temperature produces very small maghemite nanopar ticles. The fast neutralization reaction (co-precipitation) of a ferric solution (FeCl3 aqueous) in a basic medium (NH4OH concentrated) produces an intermediate phase, presumably two-line ferrihydrite, that in oxidizing conditions is transformed to maghemite nanopar ticles. That “primordial soup” is characterized by small atom arrangements that are the base for maghemite tiny crystals. The final product of the reaction was characterized by X-ray diffraction, high-resolution transmission electron microscopy, X-ray absorption fine structure, Mössbauer spectroscopy, and magnetometry.

Ortsaufgelöste Speziation von Schwermetallen in geogenen Proben mit Röntgenabsorptionsspektrometrie (my-XAS)

Die Vergesellschaftung und Bindungsform von Arsen in Düngekalk wurde durch chemische und mineralogische Analysen sowie XANES/EXAFS-Messungen untersucht. Die durch-schnittliche As-Konzentration im Düngekalk (70 mg/kg) überschreitet den Grenzwert der DüMV (40 mg/kg). Arsen ist in Mn- (Romanechit) und Fe-Dendriten (Goethit, Ferrihydrit) angereichert. Seine Oxidationsstufe ist jeweils 5+. µ-EXAFS-Untersuchungen ergaben Hin-weise auf zweizähnige und einzähnige mononukleare Durchdringungskomplexe mit Eisen-oxid. Das Mobilisierungsverhalten von Arsen wurde durch sequentielle Extraktion des Dün-gekalks und Mobilisierungsversuche mit wassergesättigtem Boden untersucht. Die Lösung erfolgte vorwiegend im dritten Extraktionsschritt gemeinsam mit kristallinen Eisenoxiden. Unter moderat anoxischen Bedingungen war im Boden keine zusätzliche Mobilisierung von Arsen aus dem Düngekalk nachweisbar. Erhöhte As-Konzentrationen und As3+-Anteile im Porenwasser traten bei niedrigem Eh unabhängig von Kalkzugabe auf. Eine Kopplung des Arsen-Grenzwerts an den Eisenoxidgehalt erscheint sinnvoll. Ein Messaufbau für Mikro-XAS Imaging wurde in Betrieb genommen. Er ermöglicht die si-multane Erfassung einer Probenfläche von 26,6×6,6 mm² wahlweise im Transmissions- oder Fluoreszenzmodus mit der räumlichen Auflösung 52×52 µm² durch eine CCD-Kamera. Zur Datenverarbeitung wurden IDL-Programme sowie die Fernerkundungssoftware ENVI ver-wendet. Die Messergebnisse zeigen weniger Störungen und Rauschen als die Ergebnisse frü-herer Messungen mit einem Prototyp. Die Ergebnisse und Erfahrungen der Messungen liefern Hinweise für die weitere erfolgreiche Nutzung des Messaufbaus.

Sources and pathways of methane formed in oxidative environments

Methane is the most abundant reduced organic compound in the atmosphere. As the strongest known long-lived greenhouse gas after water vapour and carbon dioxide methane perturbs the radiation balance of Earth’s atmosphere. The abiotic formation of methane requires ultraviolet irradiation of organic matter or takes place in locations with high temperature and/or pressure, e.g. during biomass burning or serpentinisation of olivine, under hydrothermal conditions in the oceans deep or below tectonic plates. The biotic methane formation was traditionally thought to be formed only by methanogens under strictly anaerobic conditions, such as in wetland soils, rice paddies and agricultural waste. rnIn this dissertation several chemical pathways are described which lead to the formation of methane under aerobic and ambient conditions. Organic precursor compounds such as ascorbic acid and methionine were shown to release methane in a chemical system including ferrihydrite and hydrogen peroxide in aquatic solution. Moreover, it was shown by using stable carbon isotope labelling experiments that the thio-methyl group of methionine was the carbon precursor for the methane produced. Methionine, a compound that plays an important role in transmethylation processes in plants was also applied to living plants. Stable carbon isotope labelling experiments clearly verified that methionine acts as a precursor compound for the methane from plants. Further experiments in which the electron transport chain was inhibited suggest that the methane generation is located in the mitochondria of the plants. The abiotic formation of methane was shown for several soil samples. Important environmental parameter such as temperature, UV irradiation and moisture were identified to control methane formation. The organic content of the sample as well as water and hydrogen peroxide might also play a major role in the formation of methane from soils. Based on these results a novel scheme was developed that includes both biotic and chemical sources of methane in the pedosphere.rn

Comparison of iron isotope variations in modern and Ordovician siliceous Fe oxyhydroxide deposits

Formation pathways of ancient siliceous iron formations and related Fe isotopic fractionation are still not completely understood. Investigating these processes, however, is difficult as good modern analogues to ancient iron formations are scarce. Modern siliceous Fe oxyhydroxide deposits are found at marine hydrothermal vent sites, where they precipitate from diffuse, low temperature fluids along faults and fissures on the seafloor. These deposits exhibit textural and chemical features that are similar to some Phanerozoic iron formations, raising the question as to whether the latter could have precipitated from diffuse hydrothermal fluids rather than from hydrothermal plumes. In this study, we present the first data on modern Fe oxyhydroxide deposits from the Jan Mayen hydrothermal vent fields, Norwegian-Greenland Sea. The samples we investigated exhibited very low δ56Fe values between -2.09‰ and -0.66‰. Due to various degrees of partial oxidation, the Fe oxyhydroxides are with one exception either indistinguishable from low-temperature hydrothermal fluids from which they precipitated (-1.84‰ and -1.53‰ in δ56Fe) or are enriched in the heavy Fe isotopes. In addition, we investigated Fe isotope variations in Ordovician jasper beds from the Løkken ophiolite complex, Norway, which have been interpreted to represent diagenetic products of siliceous ferrihydrite precursors that precipitated in a hydrothermal plume, in order to compare different formation pathways of Fe oxyhydroxide deposits. Iron isotopes in the jasper samples have higher δ56Fe values (-0.38‰ to +0.89‰) relative to modern, high-temperature hydrothermal vent fluids (ca. -0.40‰ on average), supporting the fallout model. However, formation of the Ordovician jaspers by diffuse venting cannot be excluded, due to lithological differences of the subsurface of the two investigated vent systems. Our study shows that reliable interpretation of Fe isotope variations in modern and ancient marine Fe oxyhydroxide deposits depends on comprehensive knowledge of the geological context. Furthermore, we demonstrate that very negative δ56Fe values in such samples might not be the result of microbial dissimilatory iron reduction, but could be caused instead by inorganic reactions.

Description and chemical and mineral composition of iron oxide samples from two Finnish lakes

Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

Sesquióxidos de hierro en bosques templado húmedos del estado de Hidalgo, México

Se estudian las formas de hierro extraídas con oxalato ácido de amonio, pirofosfato de sodio, ditionito-citrato-bicarbonato, así como el hierro total en disolución en suelos Alisoles en el municipio de Acaxochitlán, Hidalgo, México. Los suelos estudiados soportan distintos tipos de vegetación forestal: Pinus patula Schlecht and Cham (Pp), Pinus teocote, (Pt) y Quercus spp, (Q). El objetivo del trabajo fue determinar si la vegetación influye significativamente sobre las diferentes fracciones de hierro (Fe) en el suelo. Los contenidos de Fe total son significativamente mayores en suelos bajo vegetación de Pp (14,5% de Fe2O3), el mayor porcentaje de ferrihidrita (38,0% del Fe total en suelo) y de complejos organominerales de Fe y óxidos amorfos de Fe (20,9% y 16,3% respectivamente del Fe total en suelo, se dio en el bosque de Pt. En los suelos bajo bosques de Pp predominaron formas de Fe lábil (56,7% del Fe total en suelo) y formas cristalinas de Fe (goetita/hematita). La vegetación de Q mostró mayor alteración de los suelos y en el caso de Pt y Pp se presentó una mayor evolución en el proceso de organización estructural de los oxihidróxidos de Fe. El tipo de vegetación forestal influye en el grado de evolución del suelo, y en la distribución, contenido y formas de óxidos de Fe. En un orden de mayor a menor el contenido de Fe total en el suelo fue Pinus patula > Quercus spp > Pinus teocote.

Pore water and sediment geochemistry of the Bothian Sea

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

(Table 2) Concentrations of particulate chemical elements in waters of the Pechora Sea

Mineralogy of suspended matter from surface and bottom waters has been studied at two sites in the Barents Sea. Along with terrigenous minerals, particulate matter samples contain authigenic mineral phases of iron and manganese oxyhydroxides. Mn-feroxyhite, Fe-vernadite, goethite, and proto-ferrihydrite have been identified in samples from the surface waters, whereas birnessite and non-ferruginous vernadite have been found in samples from the bottom waters. Formation of suspended manganese minerals in the bottom waters is explained by an additional Mn supply from underlying reduced sediments during their early diagenesis and oxygen depletion in the near-bottom nepheloid layer. Bacteria are supposed to take part in the authigenic mineral formation.

Paleomagnetic of ODP Leg 133 holes

Paleomagnetic and rock-magnetic analyses from discrete samples of carbonate sites on the Queensland Plateau were used to determine magnetic polarity reversal stratigraphy and the nature of magnetization in these sediments. Magnetic polarity zones were correlated with the geomagnetic polarity time scale in the upper portions of cores at Sites 812 through 814, usually back to a late Pliocene age. Loss of reliable directional data was coincidental with a major decrease in magnetic intensity, below which, no stable polarity zones could be identified. The intensity reduction is either an in-situ alteration of magnetic grains, or an input signal representing progressive increase in the magnetic component of Queensland Plateau sediments. Although not conclusive at this point, the geochemical conditions and differing age of intensity reduction support the former hypothesis. Rock-magnetic analysis of carbonate sediments suggests that ultrafine-grained magnetite or maghemite crystals is an important carrier of remanence and may be biogenic in origin. Application of a recently calibrated anhysteretic remanent magnetization test to assess configuration of single-domain crystal within a natural matrix indicates that cementation (ooze-chalk-limestone) may be important in post-depositional changes affecting magnetostatic grain interaction.

Fe-Mn crusts from the Atlantic Ocean

Mineral and chemical compositions of a set of crust samples collected from the North, Central and South Atlantic were examined by means of analytical electron microscopy and ICP-MS, chemical, and microchemical elemental analysis. Vernadite, asbolane, and goethite are dominant mineral phases of the crusts, ferrihydrite is minor, hematite and feroxyhyte are rare. The samples show wide variability in major and trace element contents; however, their characteristic geochemical signatures indicate hydrogenous origin. A comparison between compositions of oceanic hydrogenous and hydrothermal crusts and metalliferous hydrothermal sediments from different ocean areas suggests that the geochemical approach may be insufficient in some cases and fail to identify hydrothermal input in ferromanganese crusts of mixed composition.

Pore water and solid-phase data from site Scharendijke (Lake Grevelingen, NL)

Will be submitted by the author

Characterication of metals in hemolymph and tissues of the Antarctic bivalve Laternula elliptica

A high input of lithogenic sediment from glaciers was assumed to be responsible for high Fe and Mn contents in the Antarctic soft shell clam Laternula elliptica at King George Island. Indeed, withdrawal experiments indicated a strong influence of environmental Fe concentrations on Fe contents in bivalve hemolymph, but no significant differences in hemolymph and tissue concentrations were found among two sites of high and lower input of lithogenic debris. Comparing Fe and Mn concentrations of porewater, bottom water, and hemolymph from sampling sites, Mn appears to be assimilated as dissolved species, whereas Fe apparently precipitates as ferrihydrite within the oxic sediment or bottom water layer prior to assimilation by the bivalve. Hence, we attribute the high variability of Fe and Mn accumulation in tissues of L. elliptica around Antarctica to differences in the geochemical environment of the sediment and the resulting Fe and Mn flux across the benthic boundary.

Geochemistry of sediment core HE337/001-1, North Sea

Reactive iron (oxyhydr)oxide minerals preferentially undergo early diagenetic redox cycling which can result in the production of dissolved Fe(II), adsorption of Fe(II) onto particle surfaces, and the formation of authigenic Fe minerals. The partitioning of iron in sediments has traditionally been studied by applying sequential extractions that target operationally-defined iron phases. Here, we complement an existing sequential leaching method by developing a sample processing protocol for d56Fe analysis, which we subsequently use to study Fe phase-specific fractionation related to dissimilatory iron reduction in a modern marine sediment. Carbonate-Fe was extracted by acetate, easily reducible oxides (e.g. ferrihydrite and lepidocrocite) by hydroxylamine-HCl, reducible oxides (e.g. goethite and hematite) by dithionite-citrate, and magnetite by ammonium oxalate. Subsequently, the samples were repeatedly oxidized, heated and purified via Fe precipitation and column chromatography. The method was applied to surface sediments collected from the North Sea, south of the Island of Helgoland. The acetate-soluble fraction (targeting siderite and ankerite) showed a pronounced downcore d56Fe trend. This iron pool was most depleted in 56Fe close to the sediment-water interface, similar to trends observed for pore-water Fe(II). We interpret this pool as surface-reduced Fe(II), rather than siderite or ankerite, that was open to electron and atom exchange with the oxide surface. Common extractions using 0.5 M HCl or Na-dithionite alone may not resolve such trends, as they dissolve iron from isotopically distinct pools leading to a mixed signal. Na-dithionite leaching alone, for example, targets the sum of reducible Fe oxides that potentially differ in their isotopic fingerprint. Hence, the development of a sequential extraction Fe isotope protocol provides a new opportunity for detailed study of the behavior of iron in a wide-range of environmental settings.