Biogenic calcium phosphate transformation in soils over millennial time scales

Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, beta-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

Sequential extraction of phosphorus in an Oxisol amended with biosolids in a long-term field experiment in Brazil

The continued growth of large cities is producing increasing volumes of urban sewage sludge. Disposing of this waste without damaging the environment requires careful management. The application of large quantities of biosolids (treated sewage sludge) to agricultural lands for many years may result in the excessive accumulation of nutrients like phosphorus (P) and thereby raise risks of eutrophication in nearby water bodies. We evaluated the fractionation of P in samples of an Oxisol collected as part of a field experiment in which biosolids were added at three rates to a maize (Zea mays L) plantation over four consecutive years. The biosolids treatments were equivalent to one, two and four times the recommended N rate for maize crops. In a fourth treatment, mineral fertilizer was applied at the rate recommended for maize. Inorganic P forms were extracted with ammonium chloride to remove soluble and loosely bound P; P bound to aluminum oxide (P-Al) was extracted with ammonium fluoride; P bound to iron oxide (P-Fe) was extracted with sodium hydroxide; and P bound to calcium (P-Ca) was extracted with sulfuric acid. Organic P was calculated as the difference between total P and inorganic P. The predominant fraction of P was P-Fe, followed by P-Al and P-Ca. P fractions were positively correlated to the amounts of P applied, except for P-Ca. The low values of P-Ca were due to the advanced weathering processes to which the Oxisol have been subjected, under which forms of P-Ca are converted to P-Fe and P-Al. The fertilization with P via biosolids increased P availability for maize plants even when a large portion of P was converted to more stable forms. Phosphorus content in maize leaves and grains was positively correlated with P fractions in soils. From these results it can be concluded that the application of biosolids in highly weathered tropical clayey soils for many years, even above the recommended rate based on N requirements for maize, tend to be less potentially hazardous to the environment than in less weathered sandy soils because the non-readily P fractions are predominant after the addition of biosolids. (C) 2012 Elsevier B.V. All rights reserved.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Organic light emitting diodes with europium (III) emissive layers based on beta-diketonate complexes: The influence of the central ligand

This work shows a comparative study of organic light emitting diodes based on four different europium complexes with the general formula, Eu(CLs)(3)bipyridine, where the central ligands are DBM [tris(dibenzoylmethane)], TTA [tris(1-(2-thieneyl)-4,4,4-trifluoro-1,3-butanedione)], NTA [tris(1-(2-naphthoyl)-3,3,3-trifluoroacetone)] and BTA [tris(1-(2-benzoyl)-3,3,3-trifluoroacetone)]. All devices have a driving voltage of 14-16 V, a very low electrical current at normal operation (less than 1 mA) and a good Wall Plug Efficiency (up to near 10(-3)%). The most suitable central ligand was found to be DBM, with an optical power up to 200 nW (at 612 nm). The BTA exhibits the lowest stability under high applied voltages. The other central ligands have similar results among them. The electroluminescence spectra clearly show the europium ion transitions (with a strong (5)D(0) -> (7)F(2) line) with a CIE color coordinate around (0.56, 0.34). (C) 2008 Elsevier B.V. All rights reserved.

Photo and electroluminescence behavior of Tb(ACAC)(3)phen complex used as emissive layer on organic light emitting diodes

This work shows the luminescence properties of a rare-earth organic complex, the Tb(ACAC)(3)phen. The results show the (5)D(4)->(7)F(3,4,5,6) transitions with no influence of the ligand. The photoluminescence excitation spectrum is tentatively interpreted by the ligands absorption. An organic light emitting diode (CLED) was made by thermal evaporation using TPD (N,N`-bis(3-methylphenyl)N,N`-diphenylbenzidine) and Alq3 (aluminum-tris(8-hydroxyquinoline)) as hole and electron transport layers, respectively. The emission reproduces the photoluminescence spectrum of the terbium complex at room temperature, with Commission Internationale de l`Eclairage - CIE (x,y) color coordinates of (0.28,0.55). No presence of any bands from the ligands was observed. The potential use of this compound in efficient devices is discussed. (C) 2008 Elsevier B.V. All rights reserved.

Benthic responses to organic matter variation in a subtropical coastal area off SE Brazil

Organic matter quality, expressed as the proportion of chlorophyll a (Chl a) to degraded organic material (i.e. phaeopigments), is known to influence the structure of benthic associations and plays an important role in the functioning of the ecosystem. This study investigates the vertical distribution of microbial biomass, meiofauna and macrofauna with respect to organic matter variation in Ubatuba, Brazil, a southeastern, subtropical coastal area. On three occasions, samples were collected in exposed and sheltered stations, at high and low hydrodynamic conditions. We hypothesize that benthic assemblages will have high meio- and macrofaunal densities and high microbial biomass at the sediment surface at the sheltered site, and lower and vertically homogeneous microbial biomass and densities of meio- and macrofauna are expected at the exposed site. The accumulation of fresh organic matter at the sediment surface was observed at both stations over the three sampling dates, which contributed to the higher densities of meiofauna in the first layers of the sediment column. Macrofauna followed the same trend only at the exposed station, but changes in the number of species, biodiversity and feeding groups were registered for both stations. Microbial biomass increased at the sheltered station over the three sampling dates, whereas at the exposed station, microbial biomass was nearly constant. Physical exposure did not influence organic matter loading at the sites and therefore did not affect overall structure of benthic assemblages, which negates our original hypothesis. Most of the benthic system components reacted to organic matter quality and quantity, but relationships between different-sized organisms (i.e. competition and/or predation) may explain the unchanged microbial profiles at the exposed site and homogeneous vertical distribution of macrofauna at the sheltered site. In conclusion, the high quality of organic matter was a crucial factor in sustaining and regulating the benthic system, but coupled results showed that interactions between micro-, meio- and macrofauna can be highly complex.

Influence of allochthonous organic matter on bacterioplankton biomass and activity in a eutrophic, sub-tropical estuary

Heterotrophic bacterial and phytoplankton biomass, production, specific growth rates, and growth efficiencies were studied in the Northern region of the Cananeia-Iguape estuarine system, which has recently experienced an intense eutrophication due to anthropogenic causes. Two surveys were carried out during spring and neap tide periods of the dry season of 2005 and the rainy season of 2006. This region receives large freshwater inputs with organic seston and phosphate concentrations that reach as high as 1.0 mg l(-1) and 20.0 mu M, respectively. Strong decreasing gradients of seston and dissolved inorganic nutrients were observed from the river/estuary boundary to the estuary/coastal interface. Gradients were also observed in phytoplankton and bacterial production rates. The production rates of phytoplankton were 5.6-fold higher (mean 8.5 mu g Cl(-1) h(-1)) during the dry season. Primary production rates (PP) positively correlated with salinity and euphoric depth, indicating that phytoplankton productivity was light-limited. On the other hand, bacterial biomass (BB) and production rates (BP) were 1.9- and 3.7-fold higher, respectively, during the rainy season, with mean values of up to 40.4 mu g Cl(-1) and 7.9 mu g Cl(-1) h-1, respectively. Despite such a high BP, bacterial abundance remained <2 x 106 cells ml(-1), indicating that bacterial production and removal were coupled. Mean specific growth rates ranged between 0.9 and 5.5 d(-1). BP was inversely correlated with salinity and positively correlated with temperature, organic matter, exopolymer particles, and particulate-attached bacteria; this last accounted for as much as 89.6% of the total abundance. During the rainy season, BP was generally much higher than PP, and values of BP/PP > 20 were registered during high freshwater input, suggesting that under these conditions, bacterial activity was predominantly supported by allochthonous inputs of organic carbon. In addition, BB probably represented the main pathway for the synthesis of high-quality (low C:N) biomass that may have been available to the heterotrophic components of the plankton food web, particularly nanoheterotrophs. (C) 2008 Elsevier Ltd. All rights reserved.

Accumulation of semivolatile organic compounds in Antarctic vegetation: A case study of polybrominated diphenyl ethers

Antarctic plant communities are dominated by lichens and mosses which accumulate semivolatile organic compounds (SOCs) such as polybrominated diphenyl ethers (PBDEs) directly from the atmosphere. Differences in the levels of PBDEs observed in lichens and mosses collected at King George Island in the austral summers 2004-05 and 2005-06 are probably explained by environmental and/or plant parameters. Contamination of lichens showed a positive correlation with local precipitation, suggesting that wet deposition processes are a major mechanism controlling the uptake of most PBDE congeners. These findings are in agreement with physical-chemical data supporting that tetra- through hepta-BDEs in the Antarctic atmosphere are basically bound to aerosols. Conversely, accumulation of PBDEs in mosses appears to be controlled by other environmental factors and/or plant-specific characteristics. Model simulations demonstrated that an ocean-atmosphere coupling may have played a role in the long-range transport of less volatile SOCs such as PBDEs to Antarctica. According to simulations, the atmosphere is the most important transport medium for PBDEs while the surface ocean serves as a temporary storage compartment, boosting the deposition/volatilization ""hopping"" effect similarly to vegetation on continents. (C) 2011 Elsevier B.V. All rights reserved.

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of Sao Paulo, Brazil

The State of Sao Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of Sao Paulo between 1997 and 2003. DDTs (15.9 mu g g(-1) lipid: mean for all pooled individuals) and PCBs (8.08 mu g g(-1)) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 mu g g(-1)), HCB (0.051 mu g g(-1)), CHLs (0.008 mu g g(-1)) and HCHs (0.007 mu g g(-1)) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p`-DDT is more recalcitrant than p,p`-DDT in the body of the animals and/or the environment. In contrast to p,p`-DDT, residues of o,p`-DDT seem to be preferentially converted into o,p`-DDD rather than op-DDE. (C) 2010 Elsevier Ltd. All rights reserved.

Holocenic proxies of sedimentary organic matter and the evolution of Lake Arari-Amazon Region

Four sediment cores were sampled from Lake Arari, located on Marajo Island at the mouth of the Amazon River. The island's vegetation cover is composed mainly of Amazon coastal forest, herbaceous and varzea vegetation. The integration of data on sedimentary structures, pollen, carbon and nitrogen isotope records, C/N ratios and radiocarbon ages allowed the identification of changes in vegetation and the sources of organic matter accumulated in the lake during the Holocene. The data indicate a relatively high flow energy, marine water influence and the presence of mangroves during the lagoon phase between 8990 and 8690 cal yr B.P. and 2310-2230 cal yr B.P. Between 2310 and 2230 cal yr B.P. and similar to 1000 cal yr B.P., the flow energy decreased and the mangroves were replaced by herbaceous vegetation following the decline in marine influence, likely due to the increase in freshwater river discharge. During the last 1000 years, Lake Arari was established in association with the expansion of herbaceous vegetation and the dominance of freshwater algae. (C) 2011 Elsevier BM. All rights reserved.

Compatibility of Beauveria bassiana commercial isolate with botanical insecticides utilized in organic crops in southern Brazil

Products based on botanical insecticides and entomopathogenic fungi have been widely used in organic farming, especially in southern Brazil. Thus, this study investigated, in vitro, the effect of aqueous extracts and commercial formulations of plants with insecticidal activity on Beauveria bassiana. The treatments comprised the botanical insecticides Neempro (azadiractin +3-tigloylazadirachtol), at the concentrations of 0.25, 0.5, 0.75, and 1.0% (v/v), and DalNeem (neem oil emulsifiable), at 0.5, 1.0, 1.5, and 2.0% (v/v) (both commercial formulations of Azadirachta indica (neem)), and the aqueous extracts, at the concentrations of 2.5, 5.0, 7.5, and 10.0% (w/v), of neem seeds, tobacco powder (Nicotiana tabacum), and catigua leaves (Trichilia clausenii). In potato, dextrose, and agar culture medium, the effects of each product on the mycelial growth and the production and viability of conidia of B. bassiana were estimated. According to the adopted compatibility index, the aqueous extracts of neem seeds and leaves catigua, depending on the concentration used, and the botanical insecticide Neempro, were classified as compatible with the entomopathogen, becoming important alternatives to integrate programmes of integrated pest management, especially in organic farming systems.

Long-Term Occupational Exposure to Organic Solvents Affects Color Vision, Contrast Sensitivity and Visual Fields

The purpose of this study was to evaluate the visual outcome of chronic occupational exposure to a mixture of organic solvents by measuring color discrimination, achromatic contrast sensitivity and visual fields in a group of gas station workers. We tested 25 workers (20 males) and 25 controls with no history of chronic exposure to solvents (10 males). All participants had normal ophthalmologic exams. Subjects had worked in gas stations on an average of 9.6 +/- 6.2 years. Color vision was evaluated with the Lanthony D15d and Cambridge Colour Test (CCT). Visual field assessment consisted of white-on-white 24-2 automatic perimetry (Humphrey II-750i). Contrast sensitivity was measured for sinusoidal gratings of 0.2, 0.5, 1.0, 2.0, 5.0, 10.0 and 20.0 cycles per degree (cpd). Results from both groups were compared using the Mann-Whitney U test. The number of errors in the D15d was higher for workers relative to controls (p<0.01). Their CCT color discrimination thresholds were elevated compared to the control group along the protan, deutan and tritan confusion axes (p<0.01), and their ellipse area and ellipticity were higher (p<0.01). Genetic analysis of subjects with very elevated color discrimination thresholds excluded congenital causes for the visual losses. Automated perimetry thresholds showed elevation in the 9 degrees, 15 degrees and 21 degrees of eccentricity (p<0.01) and in MD and PSD indexes (p<0.01). Contrast sensitivity losses were found for all spatial frequencies measured (p<0.01) except for 0.5 cpd. Significant correlation was found between previous working years and deutan axis thresholds (rho = 0.59; p<0.05), indexes of the Lanthony D15d (rho = 0.52; p<0.05), perimetry results in the fovea (rho = -0.51; p<0.05) and at 3, 9 and 15 degrees of eccentricity (rho = -0.46; p<0.05). Extensive and diffuse visual changes were found, suggesting that specific occupational limits should be created.

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Effect of quarantine treatments on the carbohydrate and organic acid content of mangoes (cv. Tommy Atkins)

Brazil is one of the largest mango producers and the third largest mango exporter worldwide. Irradiation treatment and its commercial feasibility have been studied in our country to make it possible to develop new markets and, consequently, to compete with the major exporters of mangoes, Mexico and India. This work was designed to compare irradiation treatment with the hot water dip treatment in mangoes cv. Tommy Atkins for export and to verify that the main attributes for acceptance, color and texture, as well as carbohydrate and organic acid contents, were maintained. In this study, the fruit was divided into groups: control, hot water dip-treated (46 degrees C for 90 min), and irradiation-treated at doses of 0.4 kGy and 1.0 kGy. The fruit was stored at low temperature (11 degrees C +/- 2) for 14 days and then at room temperature (23 degrees C +/- 2) until the end of the study. The results indicated that the fruit given a dose of 1.0 kGy remained in a less advanced stage of ripening (stage 3) throughout the storage period, but experienced a greater loss of texture in the beginning of the experiment. It was noted that only the control group had higher levels of citric acid and succinic acid on the last day of the experiment. There were no significant differences in the total sugar content between any treatment groups. Gamma radiation can be used as a quarantine treatment and does not interfere negatively with the quality attributes of mangoes. (C) 2012 Elsevier Ltd. All rights reserved.

Antioxidant capacity and environmentally friendly synthesis of dihydropyrimidin-(2H)-ones promoted by naturally occurring organic acids

The Biginelli reaction is a multicomponent reaction involving the condensation between an aldehyde, a beta-ketoester, and urea or thiourea, in the presence of an acid catalyst, producing dihydropyrimidinones (DHPMs). Owing to their important pharmacological properties, the DHPMs have been studied by many authors. However, most of the methodologies used for the synthesis of these compounds require drastic reaction conditions. In the current study, we report an efficient and clean procedure for preparing DHPMs by the use of citric acid or tartaric acid as a promoter of the Biginelli synthesis in ethanol as solvent. In addition, we have evaluated the antioxidant capacity of the compounds synthesized by the 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay and the thiobarbituric acid-reactive species test. Two compounds presented antioxidant activity and also reduced lipid peroxidation at concentrations of 200 and 300 mu M. In summary, we report an environmentally friendly procedure for the preparation of DHPMs and demonstrate the antioxidant capacity of some of the compounds. (C) 2012 Wiley Periodicals, Inc. J Biochem Mol Toxicol 26:155161, 2012; View this article online at . DOI 10.1002/jbt.20424