Estudo da influência de parâmetros ambientais (Fe e N) na produtividade lipídica da microalga Chlamydomonas sp.

Mestrado em Engenharia Química - Ramo Tecnologias de Protecção Ambiental

Iron oxides in plinthic soils on sedimentary deposits in northeastern Brazil

This study was conducted to examine the distribution and nature of Fe oxides in plinthic soils on the sediments of Barreiras Group (in the state of Piauí) and Itapecuru Formation (in the state of Maranhão) in Northeastern Brazil. Four pedons were selected: a "plinthic, dystrophic, epieutrophic Gray Podzolic with low activity clay" and a "dystrophic Plinthosol with low activity clay" (both Plinthic Kandiustalfs) on the Barreiras sediments, as well as an "eutrophic Plinthosol with low activity clay" and an "allic Plinthosol with low activity clay" (both Plinthustalfs) on the Itapecuru sediments. Soil samples were fractionated into > 2 mm (pisoliths), water-stable aggregates (plinthite) and matrices; the aggregates and matrices were further fractionated into sand, silt and clay sizes. Dithionite extractable iron (Fe d) and aluminum (Al d), as well as oxalate extractable iron (Fe o), were determined for all fractions, and X-ray diffraction analyses were performed on the pisoliths. It was observed that the Plinthustalfs contain more iron oxides, exhibit more extensive plinthite development and have a greater potential for further plinthite development than the Kandiustalfs. The distribution of values for the Fe d indicates that plinthite formation and induration in all soils were accompanied by an enrichment of Fe oxides in all particle size fractions. This Fe segregation was accompanied by aggregation of particles leading to a greater degree of crystallinity, as indicated by analysis of the ratios of Al d:Fe d. Larger ratios of goethite to hematite, and relatively smaller amounts of silicates in the more mature pisoliths were revealed by X-ray diffraction analysis. Ratios of Al d:Fe d were larger in the Kandiustalfs than in the Plinthustalfs, and also larger than expected for Al-substituted Fe oxides. According to ratios of Al d:Fe d, Fe mobilization in all soils has likely occurred under reducing conditions, facilitated by organic matter on the soil surface.

Field trials to assess the uptake of arsenic by vegetables from contaminated soils and soil remediation with iron oxides

The uptake of arsenic (As) by plants from contaminated soils presents a health hazard that may affect the use of agricultural and former industrial land. Methods for limiting the hazard are desirable. A proposed remediation treatment comprises the precipitation of iron (Fe) oxides in the contaminated soil by adding ferrous sulfate and lime. The effects on As bioavailability were assessed using a range of vegetable crops grown in the field. Four UK locations were used, where soil was contaminated by As from different sources. At the most contaminated site, a clay loam containing a mean of 748 mg As kg(-1) soil, beetroot, calabrese, cauliflower, lettuce, potato, radish and spinach were grown. For all crops except spinach, ferrous sulfate treatment caused a significant reduction in the bioavailability of As in some part of the crop. Application of ferrous sulfate in solution, providing 0.2% Fe oxides in the soil (0-10 cm), reduced As uptake by a mean of 22%. Solid ferrous sulfate was applied to give concentrations of 0.5% and 1% Fe oxides: the 0.5% concentration reduced As uptake by a mean of 32% and the 1% concentration gave no significant additional benefit. On a sandy loam containing 65 mg As kg(-1) soil, there was tentative evidence that ferrous sulfate treatment up to 2% Fe oxides caused a significant reduction in lettuce As, but calabrese did not respond. At the other two sites, the effects of ferrous sulfate treatment were not significant, but the uptake of soil As was low in treated and untreated soils. Differences between sites in the bioavailable fraction of soil As may be related to the soil texture or the source of As. The highest bioavailability was found on the soil which had been contaminated by aerial deposition and had a high sand content. (C) 2003 Elsevier Science B.V. All rights reserved.

Field trials to assess the uptake of arsenic by vegetables from contaminated soils and soil remediation with iron oxides

The uptake of arsenic (As) by plants from contaminated soils presents a health hazard that may affect the use of agricultural and former industrial land. Methods for limiting the hazard are desirable. A proposed remediation treatment comprises the precipitation of iron (Fe) oxides in the contaminated soil by adding ferrous sulfate and lime. The effects on As bioavailability were assessed using a range of vegetable crops grown in the field. Four UK locations were used, where soil was contaminated by As from different sources. At the most contaminated site, a clay loam containing a mean of 748 mg As kg(-1) soil, beetroot, calabrese, cauliflower, lettuce, potato, radish and spinach were grown. For all crops except spinach, ferrous sulfate treatment caused a significant reduction in the bioavailability of As in some part of the crop. Application of ferrous sulfate in solution, providing 0.2% Fe oxides in the soil (0-10 cm), reduced As uptake by a mean of 22%. Solid ferrous sulfate was applied to give concentrations of 0.5% and 1% Fe oxides: the 0.5% concentration reduced As uptake by a mean of 32% and the 1% concentration gave no significant additional benefit. On a sandy loam containing 65 mg As kg(-1) soil, there was tentative evidence that ferrous sulfate treatment up to 2% Fe oxides caused a significant reduction in lettuce As, but calabrese did not respond. At the other two sites, the effects of ferrous sulfate treatment were not significant, but the uptake of soil As was low in treated and untreated soils. Differences between sites in the bioavailable fraction of soil As may be related to the soil texture or the source of As. The highest bioavailability was found on the soil which had been contaminated by aerial deposition and had a high sand content. (C) 2003 Elsevier Science B.V. All rights reserved.

Efeitos da suplementação de fitase sobre a disponibilidade aparente de Mg, Ca, Zn, Cu, Mn e Fe em alimentos vegetais para a tilápia-do-nilo

Cem juvenis de tilápia-do-nilo (Oreochromis niloticus; PV = 100.0 ± 5.0 g) foram distribuídos em 10 tanques-rede com o objetivo de avaliar o efeito da suplementação da enzima fitase (0, 1.000 e 2.000 UFA/kg) sobre a disponibilidade de minerais em alguns alimentos energéticos (milho, milho extrusado, farelo de trigo, farelo de arroz e farelo de sorgo) e protéicos (farelo de soja extrusado, farelo de soja, farelo de girassol, farelo de algodão e glúten de milho) utilizados na alimentação de tilápia-do-nilo (Oreochromis niloticus). Para determinação dos coeficientes de disponibilidade aparente (CDA) do cálcio (Ca), magnésio (Mg), zinco (Zn), cobre (Cu), ferro (Fe) e manganês (Mn), foram confeccionadas 31 rações, marcadas com 0,10% de óxido de crômio III uma referência (ração purificada) e 30 contendo os dez alimentos e os diferentes níveis de suplementação da enzima fitase. O CDA dos nutrientes foi calculado com base no teor de crômio da ração e das fezes. A fitase aumenta, nos vegetais, a disponibilidade do Mg, Cu, Zn e Mn, os quais apresentam tendência diferenciada, em razão do seu valor biológico e do nível de suplementação de enzima.

Iron(II) djenkolate: synthesis and properties

Djenkolate complex of iron, [Fe(C(7)H(12)N(2)O(4)S(2))]. H(2)O, has been synthesized by the reaction of potassium djenkolate with Fe(SO(4)). 7H(2)O under nitrogen atmosphere. X-Ray diffraction pattern has been indexed in orthorhombic system with lattice parameters: a=11.24 Angstrom, b=7.50 Angstrom and c=6.96 Angstrom. According to IR spectroscopy, coordination is performed through COO(-) and NH(2) groups. An octahedral geometry for Fe ion is suggested by UV-Vis and Mossbauer spectroscopies. Thermal decomposition leads to the formation of Fe(2)O(3) (hematite). The compound shows poor solubility in water and in common organic solvents. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Effect of iron on bovine enamel and on the composition of the dental biofilm formed in situ

Objectives: This study investigated in situ the effect of iron (Fe) on the reduction of demineralization of bovine enamel, as well as on the composition of dental biofilm.Design and methods: Twelve volunteers were included in this blind crossover study, which was conducted in two stages of 14 days each. For each stage, the volunteers received palatal appliances containing four blocks of bovine enamel (4 mm x 4 mm x 2.5 mm). Six volunteers dripped a solution of 15 mmol L-1 ferrous sulphate onto the fragments and the remaining six dripped deionized water (eight times per day). After five minutes, a fresh 20% (w/v) sucrose solution was dripped onto all enamel blocks. During the experimental period the volunteers brushed their teeth with non-fluoridated dentifrice. After each stage, the percentage of surface microhardness change (%SMHC) and area of mineral toss (Delta Z) were determined on enamel and the dental biofilm formed on the blocks was collected and analysed for F, P, Ca, Fe and alkali-soluble carbohydrates. The concentrations of F, Ca and Fe in enamel were also analysed after acid biopsies.Results: There was a statistically significant increase in the P and Fe concentrations in the biofilms treated with ferrous sulphate (p < 0.05), which was not observed for F, Ca and alkali-soluble carbohydrates. The group treated with ferrous sulphate had significantly lower %SMHC and Delta Z when compared to control (p < 0.05).Conclusions: These results showed that ferrous sulphate reduced the demineralization of enamel blocks and altered the ionic composition of the dental biofilm formed in situ. (c) 2005 Elsevier Ltd. All rights reserved.

Improvement of grapevine iron nutrition by a bovine blood-derived compound

Iron (Fe) is essential for chlorophyll formation and plant growth. Irondeficiency chlorosis is a major nutritional disorder in several fruit trees cultivated in calcareous and alkaline soils, reducing fruit yield and quality and causing heavy economic losses. Since chelated Fe, the most widespread fertilizers used for preventing or curing Fe deficiency, pose risks of environmental pollution, the development of sustainable agronomic alternatives represents a priority for the fruit industry. In this work, we investigated the effectiveness of a bovine blood-derived product (BB; 0,125% Fe) for preventing Fe-deficiency in grapevine plants. During the vegetative season 2011 potted plants of five graft combinations: Sangiovese/S4O, Cabernet Sauvignon/S4O and Cabernet Sauvignon/140 Ruggeri, 140 Ruggeri/Cabernet Sauvignon, Vitis riparia/Cabernet Sauvignon were grown on calcareous soil. Soil treatments included: 1) Control; 2) Fe-EDDHA (Fe 6%); 3) Bovine-Blood (5 g/L); 4) Bovine-Blood (20 g/L). With the exception of Cabernet Sauvignon/S4O plants, Fe-EDDHA increased SPAD units (leaf chlorophyll content). Bovine-blood at low concentrations had similar or higher SPAD units than Fe-EDDHA. Increasing concentration resulted in further increases in SPAD units only in some graft combinations. Data highlight the efficiency of Fe blood-compound in the prevention of grapevine Fe-deficiency over one growing season.

Relative bioavailability of iron from organic sources for weanling piglets

Some authors consider minerals from organic sources more bioavailable for pig nutrition in comparison with inorganic sources. To evaluate the relative iron bioavailability from the organic source iron carbo-amino-phospho-chelate (ICAPC) to weanling piglets, it was conducted an experiment with 126 commercial piglets, using iron sulfate monohydrate (S) as standard. The experiment had a randomized block design with seven treatments (diet without adding specific source of iron, diet with 50, 100 and 150 ppm iron from S and diet with 50, 100 and 150 ppm iron from ICAPC), six replications and three animals per experimental unit. Performance parameters (average daily gain - ADG, feed: gain ratio - F:G) and blood variables (hemoglobin - Hb, hematocrit - Ht, transferrin - TR, latent iron-binding capacity - LIBC, total iron-binding capacity - TIBC, serum iron - Fe and transferrin saturation index - TSI) were evaluated. At the end of the experiment a piglet from each experimental unit was slaughtered and its liver and spleen removed for assessment of iron concentration by flame atomic absorption spectrometry (FAAS). The evaluated sources of iron yielded similar results for the variables of interest, but the increase in iron intake was followed by a linear increase in ADG, Hb, Ht, Fe and TSI as well as a linear decrease in the values of F:G, TR, LIBC and TIBC. Iron bioavailabilities from both ICAPC and S sources are similar for weanling piglets.

Continuous Flow Analysis of labile iron in ice-cores

The important active and passive role of mineral dust aerosol in the climate and the global carbon cycle over the last glacial/interglacial cycles has been recognized. However, little data on the most important aeolian dust-derived biological micronutrient, iron (Fe), has so far been available from ice-cores from Greenland or Antarctica. Furthermore, Fe deposition reconstructions derived from the palaeoproxies particulate dust and calcium differ significantly from the Fe flux data available. The ability to measure high temporal resolution Fe data in polar ice-cores is crucial for the study of the timing and magnitude of relationships between geochemical events and biological responses in the open ocean. This work adapts an existing flow injection analysis (FIA) methodology for low-level trace Fe determinations with an existing glaciochemical analysis system, continuous flow analysis (CFA) of ice-cores. Fe-induced oxidation of N,N′-dimethyl-p-pheylenediamine (DPD) is used to quantify the biologically more important and easily leachable Fe fraction released in a controlled digestion step at pH ∼1.0. The developed method was successfully applied to the determination of labile Fe in ice-core samples collected from the Antarctic Byrd ice-core and the Greenland Ice-Core Project (GRIP) ice-core.

Iron fluxes to Talos Dome, Antarctica, over the past 200 kyr

Atmospheric fluxes of iron (Fe) over the past 200 kyr are reported for the coastal Antarctic Talos Dome ice core, based on acid leachable Fe concentrations. Fluxes of Fe to Talos Dome were consistently greater than those at Dome C, with the greatest difference observed during interglacial climates. We observe different Fe flux trends at Dome C and Talos Dome during the deglaciation and early Holocene, attributed to a combination of deglacial activation of dust sources local to Talos Dome and the reorganisation of atmospheric transport pathways with the retreat of the Ross Sea ice shelf. This supports similar findings based on dust particle sizes and fluxes and Rare Earth Element fluxes. We show that Ca and Fe should not be used as quantitative proxies for mineral dust, as they all demonstrate different deglacial trends at Talos Dome and Dome C. Considering that a 20 ppmv decrease in atmospheric CO2 at the coldest part of the last glacial maximum occurs contemporaneously with the period of greatest Fe and dust flux to Antarctica, we confirm that the maximum contribution of aeolian dust deposition to Southern Ocean sequestration of atmospheric CO2 is approximately 20 ppmv.�

Revised composite depth scale, Fe content and orbital tuning of Middle Eocene Climate Optimum samples from ODP Site 207-1260

A high-resolution stratigraphy is essential toward deciphering climate variability in detail and understanding causality arguments of events in earth history. Because the highly dynamic middle to late Eocene provides a suitable testing ground for carbon cycle models for a waning warm world, an accurate time scale is needed to decode climate-driving mechanisms. Here we present new results from ODP Site 1260 (Leg 207) which covers a unique expanded middle Eocene section (magnetochrons C18r to C20r, late Lutetian to early Bartonian) of the tropical western Atlantic including the chron C19r transient hyperthermal event and the Middle Eocene Climate Optimum (MECO). To establish a detailed cyclostratigraphy we acquired a distinctive iron intensity records by XRF scanning Site 1260 cores. We revise the shipboard composite section, establish a cyclostratigraphy and use the exceptional eccentricity modulated precession cycles for orbital tuning. The new astrochronology revises the age of magnetic polarity chrons C19n to C20n, validates the position of very long eccentricity minima at 40.2 and 43.0 Ma in the orbital solutions, and extends the Astronomically Tuned Geological Time Scale back to 44 Ma. For the first time the new data provide clear evidence for an orbital pacing of the chron C19r event and a likely involvement of the very long eccentricity cycle contributing to the evolution of the MECO.

Water chemistry and iron speciation in samples taken during SWEDARP 97/98 campaign with S.A. Agulhas to the Southern Ocean

The distribution and speciation of iron was determined along a transect in the eastern Atlantic sector (6°E) of the Southern Ocean during a collaborative Scandinavian/South African Antarctic cruise conducted in late austral summer (December 1997/January 1998). Elevated concentrations of dissolved iron (>0.4 nM) were found at 60°S in the vicinity of the Spring Ice Edge (SIE) in tandem with a phytoplankton bloom, chiefly dominated by Phaeocystis sp. This bloom had developed rapidly after the loss of the seasonal sea ice cover. The iron that fuelled this bloom was mostly likely derived from sea ice melt. In the Winter Ice Edge (WIE), around 55°S, dissolved iron concentrations were low (<0.2 nM) and corresponded to lower biological productivity, biomass. In the Antarctic Polar Front, at approximately 50°S, a vertical profile of dissolved iron showed low concentrations (<0.2 nM); however, a surface survey showed higher concentrations (1-3 nM), and considerable patchiness in this dynamic frontal region. The chemical speciation of iron was dominated by organic complexation throughout the study region. Organic iron-complexing ligands ([L]) ranged from 0.9 to 3.0 nM Fe equivalents, with complex stability log K'(FeL) = 21.4-23.5. Estimated concentrations of inorganic iron (Fe') ranged from 0.03 to 0.79 pM, with the highest values found in the Phaeocystis bloom in the SIE. A vertical profile of iron-complexing ligands in the WIE showed a maximum consistent with a biological source for ligand production and near surface minimum possibly consistent with loss via photodecomposition. This work further confirms the role iron that has in the Southern Ocean in limiting primary productivity.

Effects of high CO2 levels on the ecophysiology of the diatom Thalassiosira weissflogii differ depending on the iron nutritional status

Iron availability in seawater, namely the concentration of dissolved inorganic iron ([Fe']), is affected by changes in pH. Such changes in the availability of iron should be taken into account when investigating the effects of ocean acidification on phytoplankton ecophysiology because iron plays a key role in phytoplankton metabolism. However, changes in iron availability in response to changes in ocean acidity are difficult to quantify specifically using natural seawater because these factors change simultaneously. In the present study, the availability of iron and carbonate chemistry were manipulated individually and simultaneously in the laboratory to examine the effect of each factor on phytoplankton ecophysiology. The effects of various pCO2 conditions (390, 600, and 800 µatm) on the growth, cell size, and elemental stoichiometry (carbon [C], nitrogen [N], phosphorus [P], and silicon [Si]) of the diatom Thalassiosira weissflogii under high iron ([Fe'] = 240 pmol/l) and low iron ([Fe'] = 24 pmol/l) conditions were investigated. Cell volume decreased with increasing pCO2, whereas intracellular C, N, and P concentrations increased with increasing pCO2 only under high iron conditions. Si:C, Si:N, and Si:P ratios decreased with increasing pCO2. It reflects higher production of net C, N, and P with no corresponding change in net Si production under high pCO2 and high iron conditions. In contrast, significant linear relationships between measured parameters and pCO2 were rarely detected under low iron conditions. We conclude that the increasing CO2 levels could affect on the biogeochemical cycling of bioelements selectively under the iron-replete conditions in the coastal ecosystems.

Effects of pCO2 and iron on the elemental composition and cell geometry of the marine diatom Pseudo-nitzschia pseudodelicatissima//(Bacillariophyceae)

Partial pressure of CO2 (pCO2) and iron availability in seawater show corresponding changes due to biological and anthropogenic activities. The simultaneous change in these factors precludes an understanding of their independent effects on the ecophysiology of phytoplankton. In addition, there is a lack of data regarding the interactive effects of these factors on phytoplankton cellular stoichiometry, which is a key driving factor for the biogeochemical cycling of oceanic nutrients. Here, we investigated the effects of pCO2 and iron availability on the elemental composition (C, N, P, and Si) of the diatom Pseudo-nitzschia pseudodelicatissima (Hasle) Hasle by dilute batch cultures under 4 pCO2 (~200, ~380, ~600, and ~800 µatm) and five dissolved inorganic iron (Fe'; ~5, ~10, ~20, ~50, and ~100 pmol /L) conditions. Our experimental procedure successfully overcame the problems associated with simultaneous changes in pCO2 and Fe' by independently manipulating carbonate chemistry and iron speciation, which allowed us to evaluate the individual effects of pCO2 and iron availability. We found that the C:N ratio decreased significantly only with an increase in Fe', whereas the C:P ratio increased significantly only with an increase in pCO2. Both Si:C and Si:N ratios decreased with increasing pCO2 and Fe'. Our results indicate that changes in pCO2 and iron availability could influence the biogeochemical cycling of nutrients in future oceans with high- CO2 levels, and, similarly, during the time course of phytoplankton blooms. Moreover, pCO2 and iron availability may also have affected oceanic nutrient biogeochemistry in the past, as these conditions have changed markedly over the Earth's history.