Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

Geologia, petrografia e geoquímica das associações TTGs e Leucogranodioritos do extremo norte do Domínio Rio Maria, Província Carajás

O mapeamento geológico realizado à sudeste de Água Azul do Norte/PA, porção norte do Domínio Rio Maria, aliado aos dados petrográficos e geoquímicos permitiram a individualização de associações TTGs e leucogranodioritos. Nesta região, os trabalhos de mapeamento foram realizados apenas em escala regional o que possibilitou a extrapolação da área de ocorrência de rochas similares ao Tonalito Caracol e rondhjemito Mogno. Os TTGs estudados foram individualizados em duas unidades com base no conteúdo de minerais máficos, concentrações de epidoto magmático e no grau de saussuritização (descalcificação) do plagioclásio em: (1) Epidoto-Biotita Tonalito e; (2) Biotita Trondhjemito. Em geral, são rochas que apresentam foliação definida pelo bandamento composicional, localmente pode ser perturbada por dobras e bandas de cisalhamento. Suas características geoquímicas são compatíveis com os TTGs arqueanos do grupo de alto Al2O3, sendo ainda relativamente pobres em elementos ferromagnesianos, com padrões ETRP moderado a fortemente fracionados e anomalias de Eu discretas. As diferenças nas razões La/Yb e anomalia de Eu, possibilitou a discriminação de três grupos distintos de rochas: Os TTGs pertencentes ao grupo de alto La/Yb e Sr/Y são similares às rochas do Trondhjemito Mogno, descritos no Domínio Rio Maria. Estas rochas incluem a maioria das amostras da unidade Biotita Trondhjemito. No caso dos TTGs com médio a baixo La/Yb e Sr/Y quando comparadas com as rochas do Domínio Rio Maria possuem forte correlação com o Tonalito Caracol. Estes grupos são compostos principalmente pela unidade Epidoto-Biotita Tonalito, incluindo também amostras isoladas do Biotita Trondhjemito. Com base nos critérios utilizados acima, os leucogranodioritos da área foram divididos em dois grupos: Biotita Granodiorito e Leucogranodiorito. As rochas do Biotita Granodiorito possuem ampla ocorrência espacial na porção oeste da área, relações de campo mostram que são intrusivas nos granitoides TTGs. Os dados geoquímicos apontam que o Biotita Granodiorito possui padrões de ETR fortemente fracionados, com alta razão La/Yb (33 – 186) e anomalia de Eu positiva (1,11 < Eu/Eu* < 3,26), enquanto os leucogranodioritos mostram padrões levemente fracionados, com moderadas razões La/Yb (24,7 – 34,7) e anomalia de Eu ausente (Eu/Eu*= 1,03). Os diagramas de Harker para elementos maiores e traços não favorecem uma ligação genética por processo de cristalização fracionada entre o Biotita Granodiorito e as associações TTGs, uma vez que apresentam trends de evolução distintos, indicando portanto que as condições de sua gênese e diferenciação foram bem diferentes, tampouco por fusão parcial de uma fonte TTG, pelo fato de não apresentar significante anomalia negativa de Eu, bem como por exibir padrões similares de fracionamento de ETR em relação aos TTGs, atestando que essas rochas provavelmente não foram oriundas de magmas precursores desses TTGs.

Petrography, magnetic susceptibility and geochemistry of the Rio Branco Granite, Carajás Province, southeast of Pará, Brazil

Petrografia, suscetibilidade magnética e geoquímica do Granito Rio Branco, Província Carajás, sudeste do Pará, Brazil. O Granito Rio Branco é um stock paleoproterozoico intrusivo no biotita-monzogranito arqueano Cruzadão. Ocorre a oeste da cidade de Canaã dos Carajás, nas proximidades da mina de cobre do Sossego na Província Carajás. É constituído por sienogranitos não deformados e isotrópicos, hololeucocráticos, em geral de granulação média. A mineralogia é formada por feldspato alcalino pertítico, quartzo e plagioclásio. A biotita, intensamente cloritizada, é a principal fase máfica, acompanhada por flluorita, allanita, zircão, pirita e calcopirita como minerais acessórios. Albitização e, com menor intensidade greisenização, afetaram o granito, sendo a mineralogia secundária albita, fluorita, topázio, clorita, muscovita, siderofilita e óxidos e/ou hidróxidos de ferro. O Granito Rio Branco apresenta valores sistematicamente baixos de suscetibilidade magnética (SM) variando de 1,3 x 10^-5 a 6,96 x 10^-4 (SI). Geoquimicamente, é metaluminoso a peraluminoso, possui altas razões FeOt/(FeOt + MgO) e mostra afinidades com granitos ferrosos, tipo-A do subtipo A2. Os padrões dos ETR revelam um ligeiro enriquecimento de ETR leves em relação ao ETR pesados e anomalia negativa acentuada de Eu (Eu/Eu* = 0,08 - 0,13), resultando feição em "gaivota", característica de granitos evoluídos. O conjunto de dados obtidos demonstra o caráter evoluído do Granito Rio Branco e sua derivação a partir de líquidos reduzidos e enriquecidos em voláteis, causadores das transformações hidrotermais tardias. O estudo comparativo deste corpo com aqueles das suítes anorogênicas da Província Carajás sugere que o Granito Rio Branco possui maior afinidade com os granitos das suítes Velho Guilherme e, em menor grau, Serra dos Carajás. Por outro lado, é claramente distinto da Suíte Jamon. Embora apresente características similares às dos granitos especializados em estanho, não há mineralizações desta natureza associadas ao corpo.

The behaviour of incompatible elements during hydrous melting of metasomatized peridotite at 4–6 GPa and 1000 °C–1200 °C

Trace element behavior during hydrous melting of a metasomatized garnet–peridotite was examined at pressures of 4–6 GPa and temperatures of 1000 °C–1200 °C, conditions appropriate for fluid penetrating the mantle wedge atop the subducting slab. Experiments were performed in a rocking multi-anvil apparatus using a diamond-trap setup. The compositions of the fluid and melt phases were measured using the cryogenic LA-ICP-MS technique. The water-saturated solidus of the K-lherzolite composition is located between 900 °C and 1000 °C at 4 GPa and between 1000 °C and 1100 °C at 5 and 6 GPa. The partition coefficients between fluid or melt and clinopyroxene reveal an asymmetric MREE trough with a minimum at Dy. The clinopyroxene in equilibrium with aqueous fluids is characterized by DUfluid–cpx > DThfluid–cpx while DUmelt–cpx tends to be similar to DThmelt–cpx. The partition coefficients between fluid or melt and garnet reveal very strong light to heavy REE fractionation, DLa/DLu from 95 (hydrous melt) to 1600 (aqueous fluid). The LILE are highly incompatible with partition coefficients > 50. The behavior of HFSE are decoupled, with DZr,Hf close to 1 while DNb,Ta > 10. Garnet is characterized by DUmelt/fluid–garnet < DThmelt/fluid–garnet. A comparison of our experimental partitioning results for trivalent cations as well as the results from the literature and the calculations carried out using the lattice strain model adapted to the presence of water in the bulk system indicates that H2O in the fluid or melt phase has a prominent effect on trace element partitioning. Garnet in mantle rocks in equilibrium with an aqueous fluid is characterized by significantly higher Do(3 +) for REE in the X site of the garnet compared with the partitioning values of the optimal cation in garnet in equilibrium with hydrous melts. Our data show for the first time that the change in the nature of the mobile phase (fluid vs. melt) does affect the affinities of trace elements into the garnet crystal at conditions below the second critical endpoint of the system. The same also applies for clinopyroxene, although this is less clear. Consequently, our new data allow for refinements in predictive modeling of element transfer from the slab to the mantle wedge and of possible compositions of metasomatized mantle that sources OIB magmatism.

Element stratigraphy across the Cretaceous-Tertiary boundary in ODP Hole 119-738C

Neutron activation analyses of iridium and other chemical elements were performed across a 1-m-thick, partly nonbioturbated, clay-rich interval at the Cretaceous/Tertiary boundary in ODP Hole 738C. The results show that the boundary interval holds one of the highest Ir enrichments (320 ng Ir/cm2) of all known Cretaceous/Tertiary boundary layers. Iridium concentrations are highest (18 ppb Ir, whole-rock samples) a few centimeters above the base of the clayrich interval and gradually tail off upsection. Compared with background levels the most Ir-rich interval also shows strongly enhanced concentrations of Cr (215 ppm) and slightly elevated Co concentrations (13 ppm). The Ir-rich interval shows low As (< 15 ppm) and Sb (<0.8 ppm) concentrations, a fact that is congruent with absence of abundant authigenic sulfides in the sediment. Irregularly distributed Fe enrichments and a greenish gray color of the Fe-rich intervals may indicate the presence of glauconitic clay minerals and suboxic, slightly reducing conditions during deposition. Rare earth element (REE) abundance patterns change considerably across the Cretaceous/Tertiary boundary interval, reflecting either a change in Cretaceous/Tertiary boundary seawater REE composition or the occurrence of different REE fractionation processes due to changing depositional environment. Element-vs.-element ratios of Hf, Ta, Th, U, Cs, and Sc are similar between the most Ir-rich layers of the boundary section and other levels with lower Ir concentrations. This may imply that the clay fraction of the Ir-rich layers of the Cretaceous/Tertiary boundary interval is made up predominantly of locally derived material. Calculated calcite-free abundances of Hf, Ta, Th, U, Cs, and Sc, on the other hand, are reconcilable with an extraneous origin of the bulk of the clay in the most Ir-rich layers. The Ir in the Cretaceous/Tertiary boundary clay-rich zone in Hole 738C is most likely derived from an earth-impacting asteroid; however, the origin of the clay-rich zone remains enigmatic.

Volcanic rocks from the submarine Vityaz Ridge: their age, chemical and isotopic compositions

Results of geological studies at the submarine Vityaz Ridge carried out during cruises 37 and 41 of R/V Akademik Lavrent'ev in 2005 and 2006 are reported. The studied area is located at an near-island trench of the slope in the central part of the Kuril Island arc. Morphologically it consists of two parts: an inner volcanic arc represented by the Great Kuril Range and an outer arc corresponding to the submarine Vityaz Ridge. Diverse rocks composing the basement and the sedimentary cover of the ridge were recovered by dredging. Based on K-Ar dating and geochemistry, volcanics were divided into Paleocene, Eocene, late Oligocene, and Pliocene-Pleistocene complexes. Each of the complexes reflects a tectonomagmatic stage in the ridge evolution. Geochemical and isotope data on the volcanics indicate contribution of ancient crustal material in the magma source and, correspondingly, formation of this structure on the continental basement. Two-stage model ages (TDM2) vary in a wide range from zero values in mafic rocks to 0.77 Ga in felsic varieties, pointing to presence of Precambrian protolith in the source of the felsic rocks of the Vityaz Ridge. The Pliocene-Pleistocene volcanics are classed with tholeiitic, calc-alkaline, and subalkaline series, which differ in alkali contents and REE fractionation. Values of (La/Sm)_n and (La/Yb)_n ratios vary from 0.74 and 0.84 in the tholeiitic varieties to 1.19 and 1.44 in the calc-alkaline and 2.32 and 3.73 in the subalkaline rocks. All three varieties occur within the same volcanic edifices and formed during differentiation of magmatic melts that were channeled along fault zones from the mantle source slightly enriched in crustal component.

Rare earth elements and neodymium isotopes in world river sediments revisited

Over the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world’s major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with ΔεNd (clay-silt) < |1.| A subtle decoupling of Nd isotopes between clays and silts was identified however in a few major river systems (e.g. Nile, Mississippi, Fraser), with clays being systematically shifted towards more radiogenic values. This observation suggests that preferential weathering of volcanic and/or sedimentary rocks relative to more resistant lithologies may occur in river basins, possibly leading locally to Nd isotopic decoupling between different size fractions. Except for volcanogenic sediments, silt fractions generally displayed homogeneous REE concentrations, exhibiting relatively flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance studies. Finally, we propose a set of values for a World River Average Clay (WRAC) and Average Silt (WRAS), which provide new estimates for the average composition of the weathered and eroded upper continental crust, respectively, and could be used for future comparison purposes.

Speciation and fractionation of Ca and the REE in fresh and marine waters

This study is concerned with speciation and fractionation of the rare earth elements (REE) and calcium (Ca) in aqueous solutions. The aim is to investigate the chemical states and physical sizes in which these elements can be present. The REE (including neodymium) and Ca have contrasting geochemical behavior in aqueous solutions. Ca is a major dissolved element, while the REE are trace components and highly reactive with aquatic particles. The major interests of the five papers included in this thesis are the following: · Papers I and V deal with the behavior of neodymium (Nd) and its isotopes in the Kalix River and some marine waters. · The diffusive gradients in thin-films (DGT) method is developed for measuring Ca and Mg in Paper II. · Paper III presents a speciation and fractionation study of Ca in the Kalix and Amazonian rivers. · The rare earth elements and their carrier phases are investigated in the Kalix river in Paper IV. For most elements a detailed study of speciation and fractionation can not be performed using only one method. This is due to the overall heterogeneity of the material, considering both size and chemical composition, which is present in aquatic solutions. During this project the aquatic geochemistry of the REE and Ca has been studied using mainly three methods; cross-flow filtration (CFF), field-flow fractionation (FFF) and diffusive gradients in thin-films (DGT). Field work has to a large part been conducted in the Kalix River, in northern Sweden, which is one of the last pristine river systems in Europe. Some field work has also been conducted in the Baltic Sea and the Arctic Ocean. Results from Amazonian rivers are also presented. These are the main conclusions from this work: The DGT technique works equally well for measuring Ca and Mg in natural waters as previously reported for trace metal. A significant colloidal phase for Ca could be detected in the Kalix River and in different Amazonian rivers. This was concluded independently using both CFF and FFF. Variations in REE signatures in the Kalix River suggests two different pathways for the REE during weathering and release form soil profiles and transport in the river. No significant variation in Nd-isotopic composition could be detected in the Kalix River although concentrations varied by a factor of ~10. This suggests that there is one major source for Nd in the river although different pathways for the REE may exist. A study of Nd in the Kalix River, the Baltic Sea and the Arctic Ocean showed that the isotopic compositions in the diffusible fractions were similar to water samples. However, the relative amount of diffusible Nd increased with salinity, probably reflecting the lower concentration of colloidal and particulate material in marine waters.

Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Species Fractionation In Atomic Chains From Mechanically Stretched Alloys.

Bettini et al (2006 Nat. Nanotechnol. 1 182-5) reported the first experimental realization of linear atomic chains (LACs) composed of different atoms (Au and Ag). The different contents of Au and Ag were observed in the chains from what was found in the bulk alloys, which raises the question of what the wire composition is, if it is in equilibrium with a bulk alloy. In this work we address the thermodynamic driving force for species fractionation in LACs under tension, and we present the density-functional theory results for Ag-Au chain alloys. A pronounced stabilization of the wires with an alternating Ag-Au sequence is observed, which could be behind the experimentally observed Au enrichment in LACs from alloys with high Ag content.

Determination and fractionation of barium in Brazil nuts

Several sample preparation strategies were employed for determination and fractionation of barium in Brazil nuts using measurements by graphite furnace atomic absorption spectrometry (GF AAS) and inductively coupled plasma optical emission spectrometry with axial view (ICP OES). This food is widely consumed because of its nutritional value and good taste. The chemical analysis of Brazil nuts is not trivial due to their complex matrix. The fractionation of barium in Brazil nuts was studied owing to the toxicity of this element and the strong correlation between chemical form and absorption. Total concentrations of barium varied from 860 to 2084 mg kg-1. Sequential extractions were performed based on solubility in different media and also according to lipids, proteins and low molecular weight fractions (LMW). The greatest contents of barium were determined in the LMW and in the water insoluble fractions with concentrations in the range 778 to 1606 and 551 to 1520 mg kg-1, respectively. Based on these results it can be inferred that Ba is not absorbed when Brazil nuts are ingested. Considering both the contents of barium and sulfur in different fractions and stoichiometric calculations it was also possible to assume that barium occurs mainly in the BaSO4 form. The presence of this chemical form was also confirmed by thermogravimetric measurements.

Fractionation and interesterification of palm (Elaeis guineensis) oil from Peruvian Amazon

In the present work, the physical and chemical characteristics of the fruit of the oily palm coming from the river basin of the Manitf (Region Loreto - Peru) were studied. Also, the fractionation of the palm oil and the interesterification of mixtures of palm oil/estearin was carried out. Physico- chemical properties of the crude oil and of the products obtained and fatty acids were analysed by gas chromatography The level of saturated fatty acids increased from 51,17% in the palm oil to 54,31% in the stearin. The best products for the food industry were the interesterified samples as they had melting points close to 37 degrees C.

CHEMICAL AND PHYSICO-CHEMICAL CHARACTERIZATION OF LIGNINS OBTAINED FROM ETHANOL-WATER FRACTIONATION OF BAGASSE

Organosolv lignins can replace petroleum chemicals such as phenol either partially or totally in various applications. Eight lignins, seven of which corresponded to the ethanol-water fractionation of bagasse and the other to a reference lignin (Alcell (R)) were analyzed with the aim to evaluate their chemical and physicochemical characteristics. The purity of the lignin fractions was determined by high pressure liquid chromatography (HPLC) and by ash content. Fourier Transform-Infrared Spectroscopy (FTIR) techniques and differential UV spectroscopy were applied to identify the chemical groups in the lignin samples. The molecular weight distribution was determined by size exclusion chromatography (HPSEC). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to determine the mass loss due to the high temperature treatment. The lignins studied showed the presence of p-hydroxyphenyl (H unit) and a greater proportion of guaiacyl (G unit) moieties, lower purity, similar or greater amount of phenolic hydroxyl groups, and higher degradation temperatures, than the Alcell (R) lignin.

Soil Carbon Turnover Measurement by Physical Fractionation at a Forest-to-Pasture Chronosequence in the Brazilian Amazon

The effect of conversion from forest-to-pasture upon soil carbon stocks has been intensively discussed, but few studies focus on how this land-use change affects carbon (C) distribution across soil fractions in the Amazon basin. We investigated this in the 20 cm depth along a chronosequence of sites from native forest to three successively older pastures. We performed a physicochemical fractionation of bulk soil samples to better understand the mechanisms by which soil C is stabilized and evaluate the contribution of each C fraction to total soil C. Additionally, we used a two-pool model to estimate the mean residence time (MRT) for the slow and active pool C in each fraction. Soil C increased with conversion from forest-to-pasture in the particulate organic matter (> 250 mu m), microaggregate (53-250 mu m), and d-clay (< 2 mu m) fractions. The microaggregate comprised the highest soil C content after the conversion from forest-to-pasture. The C content of the d-silt fraction decreased with time since conversion to pasture. Forest-derived C remained in all fractions with the highest concentration in the finest fractions, with the largest proportion of forest-derived soil C associated with clay minerals. Results from this work indicate that microaggregate formation is sensitive to changes in management and might serve as an indicator for management-induced soil carbon changes, and the soil C changes in the fractions are dependent on soil texture.

Fractionation of Zn, Cd and Pb in a Tropical Soil After Nine-Year Sewage Sludge Applications

A long-term field experiment was carried out in the experiment farm of the Sao Paulo State University, Brazil, to evaluate the phytoavailability of Zn, Cd and Pb in a Typic Eutrorthox soil treated with sewage sludge for nine consecutive years, using the sequential extraction and organic matter fractionation methods. During 2005-2006, maize (Zea mays L.) was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. The treatments consisted of four sewage sludge rates (in a dry basis): 0.0 (control, with mineral fertilization), 45.0, 90.0 and 127.5 t ha(-1), annually for nine years. Before maize sowing, the sewage sludge was manually applied to the soil and incorporated at 10 cm depth. Soil samples (0-20 cm layer) for Zn, Cd and Pb analysis were collected 60 days after sowing. The successive applications of sewage sludge to the soil did not affect heavy metal (Cd and Pb) fractions in the soil, with exception of Zn fractions. The Zn, Cd and Pb distributions in the soil were strongly associated with humin and residual fractions, which are characterized by stable chemical bonds. Zinc, Cd and Pb in the soil showed low phytoavailability after nine-year successive applications of sewage sludge to the soil.