Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

A simplified, sequential, phosphorus fractionation method

Hedley er al. (1982) developed what has become the most widely used land modified), phosphorus (P) fractionation technique. It consists of sequential extraction of increasingly less phytoavailable P pools. Extracts are centrifuged at up to 25000 g (RCF) and filtered to 0.45 mu m to ensure that soil is not lost between extractions. In attempting to transfer this method to laboratories with limited facilities, it was considered that access to high-speed centrifuges, and the cost of frequent filtration may prevent adoption of this P fractionation technique. The modified method presented here was developed to simplify methodology, reduce cost, and therefore increase accessibility of P fractionation technology. It provides quantitative recovery of soil between extractions, using low speed centrifugation without filtration. This is achieved by increasing the ionic strength of dilute extracts, through the addition of NaCl, to flocculate clay particles. Addition of NaCl does not change the amount of P extracted. Flocculation with low speed centrifugation produced extracts comparable with those having undergone filtration (0.025 mu m). A malachite green colorimetric method was adopted for inorganic P determination, as this simple manual method provides high sensitivity with negligible interference from other anions. This approach can also be used for total P following digestion, alternatively non-discriminatory methods, such as inductively coupled plasma atomic emission spectroscopy, may be employed.

Effects of tillage intensity on soil C, N, and P pools with different stability

Es ist bekannt, dass die Umsatzdynamik der organischen Substanz von der Bodenbearbeitungsintensität abhängt. Bis jetzt sind nur wenige Daten zum Einfluss der Bearbeitungsintensität und des Zwischenfruchtanbaus auf C-, N-, und P-Dynamik im Ober- (0-5 cm Tiefe) und Unterboden (5-25 cm Tiefe) von Lössböden verfügbar. Hauptziele dieser Arbeit waren die (i) Quantifizierung des Einflusses von verschiedenen langzeitig durchgeführten Bearbeitungssystemen auf labile, intermediäre, und passive C- und N-Pools; (ii) Quantifizierung des Einflusses dieser Systeme auf P-Fraktionen mit unterschiedlicher Verfügbarkeit für die Pflanzenaufnahme; (iii) Quantifizierung des Einflusses des Zwischenfruchtanbaus in Verbindung mit einer unterschiedlichen Einarbeitungstiefe der der Zwischenfrüchte auf mineralisierbares C und N. Die Ergebnisse des 1. und 2. Teilexperiments basieren auf Untersuchungen von 4 Langzeitfeldexperimenten (LFE) in Ost- und Süddeutschland, die zwischen 1990 und 1997 durch das Institut für Zuckerrübenforschung angelegt wurden. Jedes LFE umfasst 3 Bearbeitungssysteme: konventionelle Bearbeitung (CT), reduzierte Bearbeitung (RT) und Direktsaat (NT). Die Ergebnisse des 3. Teilexperiments basieren auf einem Inkubationsexperiment. Entsprechend den Hauptfragestellungen wurden folgende Untersuchungsergebnisse beschrieben: (i) Im Oberboden von NT wurden höhere labile C-Vorräte gefunden (C: 1.76 t ha-1, N: 166 kg ha-1), verglichen mit CT (C: 0.44 t ha-1, N: 52 kg ha-1). Im Gegensatz dazu waren die labile- C-Vorräte höher im Unterboden von CT mit 2.68 t ha-1 verglichen zu NT mit 2 t ha-1 und RT mit 1.87 t ha-1. Die intermediären C-Vorräte betrugen 73-85% der gesamten organischen C-Vorräte, intermediäre N-Vorräte betrugen 70-95% des Gesamt-N im Ober- und Unterboden und waren vielfach größer als die labilen und passiven C- und N-Vorräte. Nur im Oberboden konnte ein Effekt der Bearbeitungsintensität auf die intermediären N-Pools mit höheren Vorräten unter NT als CT festgestellt werden. Die passiven C- und N-Pools waren eng mit den mineralischen Bodeneigenschaften verbunden und unabhängig vom Bearbeitungssystem. Insgesamt hat sich gezeigt, dass 14 bis 22 Jahre durchgängige Direktsaatverfahren nur im Oberboden zu höheren labilen C- und N-Vorräten führen, verglichen zu konventionellen Systemen. Dies lässt eine tiefenabhängige Stärke der Dynamik der organischen Bodensubstanz vermuten. (ii) Die Konzentration des Gesamt-P (Pt) im Oberboden war höher in NT (792 mg kg-1) und ~15% höher als die Pt-Konzentration in CT (691 mg kg 1). Die Abnahme der Pt-Konzentration mit zunehmender Bodentiefe war höher in NT als in CT. Dies gilt auch für die einzelnen P-Fraktionen, ausgenommen der stabilsten P-Fraktion (residual-P). Generell hatte das Bearbeitungssystem nur einen kleinen Einfluss auf die P-Konzentration mit höheren Pt-Konzentrationen in Böden unter NT als CT. Dies resultiert vermutlich aus der flacheren Einarbeitung der Pflanzenreste als in CT. (iii) Im Zwischenfruchtexperiment war der Biomassezuwachs von Senf am höchsten und nimmt in der Reihenfolge ab (oberirdischer Ertrag in t / ha): Senf (7.0 t ha-1) > Phacelia (5.7 t ha-1) > Ölrettich (4.4 t ha-1). Damit war potentiell mineralisierbares C und N am höchsten in Böden mit Senfbewuchs. Kumulative CO2- und N2O-Emissionen während der Inkubation unterschieden sich nicht signifikant zwischen den Zwischenfruchtvarianten und waren unabhängig von der Verteilung der Pflanzenreste im Boden. Die kumulativen ausgewaschenen mineralisierten N (Nmin)-Vorräte waren in den brachliegenden Böden am höchsten. Die Nmin-Vorräte waren 51-72% niedriger in den Varianten mit Zwischenfrucht und Einarbeitung verglichen zur Brache. In den Varianten ohne Einarbeitung waren die Nmin-Vorräte 36-55% niedriger verglichen zur Brache. Dies weißt auf einen deutlichen Beitrag von Zwischenfrüchten zur Reduzierung von Nitrat-Auswaschung zwischen Winter und Frühjahr hin. Insgesamt führte reduzierte Bearbeitung zu einer Sequestrierung von C und N im Boden und der Zwischenfruchtanbau führte zu reduzierten N-Verlusten. Die P-Verfügbarkeit war höher unter Direktsaat verglichen zur konventionellen Bearbeitung. Diese Ergebnisse resultieren aus den höheren Konzentrationen der OS in den reduzierten, als in den konventionellen Systemen. Die Ergebnisse zeigen deutlich das Potential von reduzierter Bearbeitung zur Sequestrierung von intermediärem C und N zur Reduzierung von klimarelevanten Treibhausgasen. Gleichzeitig steigen die Konzentrationen an pflanzenverfügaren P-Gehalten. Zwischenfrüchte führen auch zu einem Anstieg der C- und N-Vorräte im Boden, offensichtlich unabhängig von der Zwischenfruchtart.

Nitrogen speciation and phosphorus fractionation dynamics in a lowland chalk catchment

A detailed analysis of temporal and spatial trends in nitrogen (N) speciation and phosphorus (P) fractionation in the Wylye, a lowland Chalk sub-catchment of the Hampshire Avon, UK is presented, identifying the sources contributing to nutrient enrichment, and temporal variability in the fractionation of nutrients in transit from headwaters to lower reaches of the river. Samples were collected weekly from ten monitoring stations with daily sampling at three further sites over one year, and monthly inorganic N and total reactive P (TRP) concentrations at three of the ten weekly monitoring stations over a ten year period are also presented. The data indicate significant daily and seasonal variation in nutrient fractionation in the water column, resulting from plant uptake of dissolved organic and inorganic nutrient fractions in the summer months, increased delivery of both N and P from diffuse sources in the autumn to winter period and during high flow events, and lack of dilution of point source discharges to the Wylye from septic tank, small package Sewage Treatment Works (STW) and urban Waste Water Treatment Works (WwTW) during the summer low flow period. Weekly data show that contributing source areas vary along the river with headwater N and P strongly influenced by diffuse inorganic N and particulate P fluxes, and SRP and organic-rich point source contributions from STW and WwTW having a greater influence in the lower reaches. Long-term data show a decrease in TRP concentrations at all three monitoring stations, with the most pronounced decrease occurring downstream from Warminster WwTW, following the introduction of P stripping at the works in 2001. Inorganic N demonstrates no statistically significant change over the ten year period of record in the rural headwaters, but an increase in the lower reaches downstream from the WwTW which may be due to urban expansion in the lower catchment.

Phosphorous forms in cultivated indian black earth (anthrosols) of varying texture in the brazilian Amazon

Despite the agricultural importance of Indian Black Earth (IBE) in the Amazon region, there are few studies that report on the relation between soil texture and chemical fertility of IBE. These soils of pre-Colombian origin, with high contents of P, Ca and other nutrients are found across the Amazon valley. IBE profiles were studied to evaluate the total contents of P, its primary chemical forms and the P transformation phases in areas with IBE soils of variable texture and in adjacent reference soils. The soil texture strongly influenced soil fertility, changing in terms of transformation of the primary P forms and, consequently, predominant P forms in IBE. Soils with texture varying between clay and heavy clay had higher total P contents and primary Ca-P forms. Highest P-Al and lowest total P amounts were observed at the site Rio Preto da Eva, where texture varies from sandy loam to sandy clay loam. In the IBE with clay texture the amounts of soluble P, extracted with NH4Cl were highest, although different from Mehlich 1-extractable amounts.

Ruzigrass affecting soil-phosphorus availability

The objective of this work was to evaluate the effectiveness of ruzigrass (Urochloaruziziensis) in enhancing soil-P availability in areas fertilized with soluble or reactive rock phosphates. The area had been cropped for five years under no-till, in a system involving soybean, triticale/black-oat, and pearl millet. Previously to the five-year cultivation period, corrective phosphorus fertilization was applied once on soil surface, at 0.0 and 80 kg ha-1 P2O5, as triple superphosphate or Arad rock phosphate. After this five-year period, plots received the same corrective P fertilization as before and ruzigrass was introduced to the cropping system in the stead of the other cover crops. Soil samples were taken (0-10 cm) after ruzigrass cultivation and subjected to soil-P fractionation. Soybean was grown thereafter without P application to seed furrow. Phosphorus availability in plots with ruzigrass was compared to the ones with spontaneous vegetation for two years. Ruzigrass cultivation increased inorganic (resin-extracted) and organic (NaHCO3) soil P, as well as P concentration in soybean leaves, regardless of the P source. However, soybean yield did not increase significantly due to ruzigrass introduction to the cropping system. Soil-P availability did not differ between soluble and reactive P sources. Ruzigrass increases soil-P availability, especially where corrective P fertilization is performed.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 1 - the water column

This paper investigates phosphorus (P) transport and transformation dynamics in two contrasting sub-catchments of the River Kennel, England. Samples were collected daily under baseflow and hourly under stormflow conditions using autosamplers for 2 years and analysed for a range of determinands (full P fractionation, suspended sediment (SS), cations, pH, alkalinity, temperature and oxygen). Concentrations of SRP, SUP, PP and SS were higher in the flashy River Enborne (means of 0.186, 0.071, 0.101 and 34 mg l(-1), respectively) than the groundwater-fed River Lambourn (0.079, 0.057, 0.028 and 9 mg l(-1), respectively). A seasonal trend in the daily P dataset was evident, with lower concentrations during intermediate flows and the spring (caused by a dilution effect and macrophyte uptake) than during baseflow conditions. However, in the hourly P dataset, highest concentrations were observed during storm events in the autumn and winter (reflecting higher scour with increased capacity to entrain particles). Storm events were more significant in contributing to the total P load in the River Enborne than the River Lambourn, especially during August to October, when dry antecedent conditions were observed in the catchment. Re-suspension of P-rich sediment that accumulated within the channel during summer low flows might account for these observations. It is suggested that a P-calcite co-precipitation mechanism was operating during summer in the River Lambourn, while adsorption by metal oxyhydroxide groups was an important mechanism controlling P fractionation in the River Enborne. The influence of flow conditions and channel storage/release mechanisms on P dynamics in these two lowland rivers is assessed. (C) 2004 Elsevier B.V. All rights reserved.

Ruzigrass affecting soil-phosphorus availability

The objective of this work was to evaluate the effectiveness of ruzigrass (Urochloaruziziensis) in enhancing soil-P availability in areas fertilized with soluble or reactive rock phosphates. The area had been cropped for five years under no-till, in a system involving soybean, triticale/black-oat, and pearl millet. Previously to the five-year cultivation period, corrective phosphorus fertilization was applied once on soil surface, at 0.0 and 80 kg ha-1 P2O5, as triple superphosphate or Arad rock phosphate. After this five-year period, plots received the same corrective P fertilization as before and ruzigrass was introduced to the cropping system in the stead of the other cover crops. Soil samples were taken (0-10 cm) after ruzigrass cultivation and subjected to soil-P fractionation. Soybean was grown thereafter without P application to seed furrow. Phosphorus availability in plots with ruzigrass was compared to the ones with spontaneous vegetation for two years. Ruzigrass cultivation increased inorganic (resin-extracted) and organic (NaHCO3) soil P, as well as P concentration in soybean leaves, regardless of the P source. However, soybean yield did not increase significantly due to ruzigrass introduction to the cropping system. Soil-P availability did not differ between soluble and reactive P sources. Ruzigrass increases soil-P availability, especially where corrective P fertilization is performed.

Disponibilidade de fósforo em solo cultivado com braquiária em rotação com soja

Pós-graduação em Agronomia (Agricultura) - FCA

Collection of data on particulate and dissolved soil phosphorus in the Jena Experiment (Main Experiment, time series since 2002)

This data set contains two time series of measurements of dissolved phosphorus (organic, inorganic and total with a biweekly resolution) and dissolved inorganic phosphorus with a seasonal resolution. In addition, data on phosphorus from soil samples measured in 2007 and fractionated by different acid-extrations (Hedley fractions) are provided. All data measured at the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. 1. Dissolved phosphorus in soil solution: Suction plates installed on the field site in 10, 20, 30 and 60 cm depth were used to sample soil pore water. Cumulatively extracted soil solution was collected every two weeks from October 2002 to May 2006. The biweekly samples from 2002, 2003 and 2004 were analyzed for dissolved organic phosphorus (DOP), dissolved inorganic phosphorus (PO4P) and dissolved total phosphorus (TDP) by Continuous Flow Analyzer (CFA SAN ++, SKALAR [Breda, The Netherlands]). 2. Seasonal values of dissolved inorganic phosphorus in soil solution were calculated as volume-weighted mean values of the biweekly measurements (spring = March to May, summer = June to August, fall = September to November, winter = December to February). 3. Phosphorus fractions in soil: Five independent soil samples per plot were taken in a depth of 0-15 cm using a soil corer with an inner diameter of 1 cm. The five samples per plot were combined to one composite sample per plot. A four-step sequential P fractionation (Hedley fractions) was applied and concentrations of P fractions in soil were measured photometrically (molybdenum blue-reactive P) with a Continuous Flow Analyzer (Bran&Luebbe, Germany).

Phosphorus fractions in soil of the Jena Experiment (Main Experiment, year 2007)

This data set contains measurements of phosphorus fractions (Hedley fractions) in soil collected 2007 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five independent soil samples per plot were taken in a depth of 0-15 cm using a soil corer with an inner diameter of 1 cm. The five samples per plot were combined to one composite sample per plot. A four-step sequential P fractionation (Hedley fractions) was applied. Sequentially, 20 ml NaHCO3 (adjusted to pH 8.5), 30 ml NaOH, and 35 ml HCl were used as extraction solutions for 0.5 g soil. The last step comprised the combustion (550 °C) of the remaining soil to destroy all organic material followed by shaking with 20 ml H2SO4. Organic P concentrations of the respective fractions were calculated as the difference between total dissolved P and inorganic P. Duplicate phosphate concentrations of P fractions in soil were measured photometrically (molybdenum blue-reactive P) with a Continuous Flow Analyzer (Bran&Luebbe, Germany).

Residuos orgánicos como fuentes de fósforo

En este trabajo, se han llevado a cabo distintos experimentos en laboratorio, con el objetivo de estudiar el efecto de la aplicación de residuos orgánicos como fuentes de P en las pérdidas de este elemento, que se producen en suelo, tanto por escorrentía superficial como por lixiviación. El interés por evaluar las pérdidas de P se debe a la necesidad de conocer mejor los factores que influyen en los procesos de pérdidas de este elemento y así, poder reducir los problemas de eutrofización de aguas, tanto superficiales como subterráneas, provocadas por un exceso de este nutriente, junto con otros como el nitrógeno. Los trabajos experimentales que se han llevado a cabo se detallan a continuación: Se ha realizado el estudio de las formas de P contenidas en una serie de 14 residuos orgánicos, de distinto origen y tratamiento (compost, lodos, purines y digestato), comparando la información aportada por tres protocolos de fraccionamientos de P diferentes, seleccionados entre los principales métodos utilizados: protocolo de fraccionamiento de Ruttemberg (1992), protocolo de Normas, medidas y ensayos (Ruban et al., 2001a) y protocolo de Huang et al. (2008). Todos los métodos de fraccionamiento empleados aportaron información útil para conocer las formas de P de los residuos, a pesar de que alguno de ellos fue descrito para sedimentos o suelos. Sin embargo, resulta difícil comparar los resultados entre unos y otros, ya que cada uno emplea extractantes y tiempos de ensayos diferentes. Las cantidades de P total determinadas por cada método mantienen una relación lineal, aunque el método SMT, por ser más directo, obtiene las cantidades más elevadas para todos los residuos. Los métodos secuenciales (métodos de Huang y Ruttemberg), a pesar de ser más largos y tediosos, aportan información más detallada de la disponibilidad de las formas de P, y con ello, permiten obtener una mejor estimación de las pérdidas potenciales de este elemento tras su aplicación en suelo. Se han encontrado relaciones positivas entre las fracciones determinadas por estos dos métodos. Así mismo, se encuentra una correlación entre las formas solubles de P y la concentración de los iones [Ca + Fe + Al] de los residuos, útiles como indicadores de la disponibilidad de este elemento. Sin embargo, el protocolo SMT, no obtiene información de la solubilidad o disponibilidad de las formas de P contenidas, ni las formas determinadas mantienen relaciones directas con las de los otros métodos, con excepción del P total. Para el estudio del comportamiento de los residuos aplicados en suelos, se pusieron a punto sistemas de lluvia simulada, con el objetivo de caracterizar las pérdidas de P en la escorrentía superficial generada. Por otra parte, se emplearon columnas de suelos enmendados con residuos orgánicos, para el estudio de las pérdidas de P por lixiviación. Los ensayos de simulación de lluvia se llevaron a cabo de acuerdo al “National Phosphorus Research proyect“ (2001), que consigue simular eventos sucesivos de lluvia en unas condiciones semejantes a la realidad, empleando cajas llenas de suelo del horizonte superficial, con residuos aplicados tanto superficialmente como mediante mezcla con el propio suelo. Los ensayos se realizaron con seis residuos de diferente naturaleza y sometidos a distintos tratamientos. Se encontraron diferencias significativas en las pérdidas de las formas de P analizadas, tanto disueltas como particuladas, en las aguas de escorrentía generadas. En general, las pérdidas en el primer evento de lluvia tras la aplicación de los residuos fueron mayores a las generadas en el segundo evento, predominando las formas de P particuladas respecto a las disueltas en ambos. Se encontró una relación positiva entre las pérdidas de P en las aguas de escorrentía generadas en cada ensayo, con los contenidos de P soluble en agua y fácilmente disponible de los residuos empleados, determinados por los protocolos de fraccionamientos secuenciales. Además, se emplearon los modelos matemáticos desarrollados por Vadas et al. (2005, 2007), de evaluación de las pérdidas de P por escorrentía para fertilizantes y estiércoles. La predicción de estos modelos no se cumple en el caso de todos los residuos. Las distintas propiedades físicas de los residuos pueden afectar a las diferencias entre las pérdidas experimentales y las esperadas. Los ensayos de simulación del proceso de lixiviación se llevaron a cabo en columnas de percolación, con suelos enmendados con residuos orgánicos, de acuerdo a la norma “CEN/TS 14405–2004: Caracterización de los residuos – Test de comportamiento de lixiviación – Test de flujo ascendente”. Las pérdidas de P por procesos de lixiviación de agua, han sido despreciadas durante mucho tiempo respecto a las pérdidas por escorrentía. Sin embargo, se ha demostrado que deben tenerse en consideración, principalmente en algunos tipos de suelos o zonas cercanas a acuíferos. Se utilizaron tres suelos de distinta procedencia para los ensayos, de manera que se pudo estudiar la influencia del tipo de suelo en las pérdidas de P para cada tipo de residuo (purín, compost, digestato y lodo de EDAR). Los índices de adsorción de P determinados para cada suelo permiten evaluar aquellos que presentarán más riesgo de producir pérdidas de este elemento al aplicarse fuentes externas de P, encontrando una relación positiva entre ambos. Las pérdidas de P en los lixiviados varían en función tanto del residuo como del suelo empleado. Para el compost, el purín y el lodo, se encontró una relación entre las pérdidas generadas en el agua lixiviada de las columnas y las formas de P soluble contenidas en los residuos. Sin embargo, en el caso del digestato, no existía esta correlación. Las pérdidas para este residuo fueron en todos los casos menores a las estimadas, considerando las formas de P contenido. El estudio de la mojabilidad, propiedad física del residuo que evalúa la capacidad de interacción residuo-agua, permitió explicar el comportamiento anómalo de este residuo, con una mayor resistencia a que el agua entrara en su estructura y por tanto, una mayor dificultad de solubilizar el P contenido en el propio residuo, que en el caso de otros residuos. En general, podemos considerar que el estudio de las formas de P más disponibles o solubles en agua, aporta información útil de las pérdidas potenciales de P. Sin embargo, es necesario estudiar las propiedades físicas de los residuos orgánicos aplicados y la capacidad de adsorción de P de los suelos, para estimar las pérdidas de P y con ello, colaborar a controlar los procesos de eutrofización en aguas. ABSTRACT This dissertation explores the effect of organic wastes application as sources of P in losses of this element that occur by both surface runoff and leaching in soil. To do so, diverse laboratory experiments are conducted and presented here. Evaluating P losses is necessary to better understand the factors that influence the processes behind the loss of this element. Reducing P losses reduces eutrophication problems of both surface water and groundwater caused by an excess of this nutrient, along with other as nitrogen. Details of the experiments are presented below: The first experiment studies the forms of P contained in a series of 14 organic wastes of different origin and treatment (compost, sludge, slurry and digestate), comparing the information provided by three methods of P fractionation. The methods selected were: Ruttemberg protocol (1992); Standards, Measurements and Testing protocol (Ruban et al., 2001a); and Huang protocol (Huang et al., 2008). All fractionation methods employed successfully contribute to our knowledge of P forms in wastes, even though one of them was originally described for sediments or soils information. However, it is difficult to compare results among each other, as each protocol employs different extractants and time in the trials. Total amounts of P obtained by each method show a linear relationship, although the SMT method, which is more direct, obtains the highest amounts for all residues. Sequential methods (Huang and Ruttemberg’s protocols), despite being longer and more tedious, provide more detailed information on the availability of the forms of P. Therefore, allow the estimation of the potential losses of P after application in soil. Furthermore, positive relationships have been found among fractions obtained by these methods. Positive relationship has been found also among soluble forms of P and the concentration of ions Fe + Ca + Al, which is useful as an indicator of the availability of this element. However, the SMT protocol does not collect information about solubility or availability of forms of P contained; neither do certain forms maintain direct relations with the forms from other methods, with the exception of total P methods. To study the behavior of wastes applied to soils two experiments were conducted. Simulated rain systems were prepared to characterize P losses in the surface runoff generated. In addition, columns of soils amended with organic waste were developed for the study of P leaching losses. Simulated rain systems were carried out according to the ’National Phosphorus Research Project’ (2001), which manages to simulate successive rainfall events in conditions resembling reality. The experiment uses boxes filled with soil from the surface horizon amended with residues, both superficially and by mixing with the soil. Tests were conducted with six residues of different type and subjected to diverse treatments. Findings show significant differences in losses of the P forms analyzed in the generated runoff water, in both solution and particulate forms. In general, losses in the first rainfall event after application of waste were higher than the losses generated in the second event, predominating particulate forms of P over dissolved forms in both events. In all trials, a positive relationship was found between various P forms determined by sequential fractionation protocols (water soluble P and readily available P forms) and P losses in runoff. Furthermore, results from Vadas´s mathematical models (Vadas et al., 2005; 2007) to assess P losses by runoff fertilizers and manures indicate that the prediction of this model is not fulfilled in the case of all residues. The diverse physical properties of wastes may affect the differences between experimental and expected losses. Finally, leaching simulation processes were carried out in percolation columns, filled with soils amended with organic wastes, following the ‘CEN/TS 14405-2004 standard: Characterization of waste - Leaching behavior test - Test Flow ascending ’. P losses by leaching have been neglected for a long time with respect to runoff losses. However, findings corroborate previous studies showing that these P losses have to be taken into account, especially in certain types of soils and in zones near aquifers. To study the influence of soil type on P losses, experiments were carried out with three different soils and for each type of waste (manure, compost, digestate and sludge WWTP). Each soil’s P adsorption rates allow assessing which soils imply a higher risk of P losses when external sources of P are applied. P losses in leachate vary according to the type of soil employed and according to the specific residue. In the case of compost, manure and sludge, there is a relationship between leaching losses and residues’ soluble forms of P. The exception being the digestate, where there was no such correlation. Digestate P losses by leaching were lower than expected in all cases considering the forms of P contained. Moreover, examining digestate wettability -- that is, the physical property of the residue that assesses the capacity of waste-water interaction -- allowed explaining the anomalous behavior of this residue. Digestate has a high resistance to water entering its structure and thus higher difficulty to solubilize the P contained. Overall, studying the more available or soluble P forms provides useful information about the potential loss of P. However, this dissertation shows that it is necessary to examine the physical properties of organic residues applied as well as the P adsorption capacity of soils to estimate P losses, and thus to control eutrophication in water.

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.