Upland rice growth and mineral nutrition as affected by cultivars and sulfur availability

A better understanding of the differential growth of upland rice (Oryza sativa L.) cultivars with increasing soil S availability could help improve rice yield under upland conditions. The objective of this study was to evaluate root and shoot growth and nutrition of upland traditional and modern rice cultivars as affected by S availability. The experimental design was completely randomized in a 3 (rates of S) × 3 (cultivars) factorial with four replications. Low availability of S in the soil reduces root and shoot development and the efficiency of N, P, and S uptake, as well as the concentration and content of these nutrients in rice cultivars. At 0 mg dm-3 of S, rice cultivars prioritize root growth over shoots, and the traditional cultivar does so with greater intensity. Our results suggested that more development of traditional cultivars under low S availability facilitates its adaptation in soils under this condition. On the other hand, the intermediate and modern cultivars are more responsive to S fertilization. Moreover, S fertilization allows significant increases in upland rice growth and must be considered in cropping systems aiming for high yields. © Soil Science Society of America.

Evaluation of lines of boron, phosphorus and sulfur by high-resolution continuum source flame atomic absorption spectrometry for plant analysis

The wavelength-integrated absorbance (WIA) and summation of absorbance (∑ lines) of different lines were evaluated to enhance sensitivity and determine B, P and S in medicinal plants by HR-CS FAAS. The lowest LOD for B (0.5mgL-1) and P (13.7mgL-1) was obtained by integration of lines 249.773nm (3pixels) and 247.620nm (5pixels), respectively. The ∑ lines for CS at 257.595nm and 257.958nm furnished LOD=30.5mgL-1, ca. 10% lower than the LOD obtained for the WIA using 257.595nm and 5pixels. Data showed the advantage of WIA over ∑ lines to improve sensitivity for all analytes. Under optimized conditions, calibration curves in the 1.0-100mgL-1 B and 50.0-2000mgL-1 P, S ranges were consistently obtained. Results obtained with the HR-CS FAAS method were in agreement at 98% and 95% confidence level with certified values for B and P, respectively. And results for S were in accordance to non-certified values. Concentrations of B, P, and S in 12 medicinal plants analyzed by the proposed method varied within the 19.4-34.5mgkg-1 B, 719-3910mgkg-1 P and 1469-7653mgkg-1 S ranges. © 2012 Elsevier B.V.

Selenium and sulfur: mitigation in plant stresses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Selenium and sulfur: mitigation in plant stresses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Soil sulfur fractions dynamics and distribution in a tropical grass pasture amended with nitrogen and sulfur fertilizers

Soil sulfur (S) partitioning among the various pools and changes in tropical pasture ecosystems remain poorly understood. Our study aimed to investigate the dynamics and distribution of soil S fractions in an 8-year-old signal grass (Brachiaria decumbens Stapf.) pasture fertilized with nitrogen (N) and S. A factorial combination of two N rates (0 and 600?kg N ha1 y1, as NH4NO3) and two S rates (0 and 60?kg S ha1 y1, as gypsum) were applied to signal grass pastures during 2 y. Cattle grazing was controlled during the experimental period. Organic S was the major S pool found in the tropical pasture soil, and represented 97% to 99% of total S content. Among the organic S fractions, residual S was the most abundant (42% to 67% of total S), followed by ester-bonded S (19% to 42%), and C-bonded S (11% to 19%). Plant-available inorganic SO4-S concentrations were very low, even for the treatments receiving S fertilizers. Low inorganic SO4-S stocks suggest that S losses may play a major role in S dynamics of sandy tropical soils. Nitrogen and S additions affected forage yield, S plant uptake, and organic S fractions in the soil. Among the various soil fractions, residual S showed the greatest changes in response to N and S fertilization. Soil organic S increased in plots fertilized with S following the residual S fraction increment (16.6% to 34.8%). Soils cultivated without N and S fertilization showed a decrease in all soil organic S fractions.

Sulfur Radicals as Tethers for the Adsorption of Aromatic Molecules on Silicon Surface

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of benzenethiol and diphenyl disulfide with the silicon (001) surface. A direct comparison of different adsorption structures with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) allow us to identify that benzenethiol and diphenyl disulfide dissociatively adsorb on the silicon surface. In addition, theoretically obtained data suggests that the C6H5SH:Si(001) presents a higher Schottky barrier height contact when compared to other similar aromatic molecules.

Sulfur in agriculture

Sulfur (S) deficiency in soils is becoming increasingly common in many areas of the world as a result of agronomic practices, high biomass exportation and reduced S emissions to the atmosphere. In this review, the incidence and commercial exploitation of S pools in nature are discussed, as well as the importance of S for plants and the organic and inorganic S forms in soil and their transformations, especially the process of microbiological oxidation of elemental sulfur (S0) as an alternative to the replenishment of S levels in the soil. The diversity of S0-oxidizing microorganisms in soils, in particular the genus Thiobacillus, and the biochemical mechanisms of S0 oxidation in bacteria were also addressed. Finally, the main methods to measure the S0 oxidation rate in soils and the variables that influence this process were revised.

Isotope determination of sulfur by mass spectrometry in soil samples

Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

A dynamic model of oceanic sulfur (DMOS) applied to the Sargasso Sea: Simulating the dimethylsulfide (DMS) summer paradox

[EN]A new one-dimensional model of DMSP/DMS dynamics (DMOS) is developed and applied to the Sargasso Sea in order to explain what drives the observed dimethylsulfide (DMS) summer paradox: a summer DMS concentration maximum concurrent with a minimum in the biomass of phytoplankton, the producers of the DMS precursor dimethylsulfoniopropionate (DMSP). Several mechanisms have been postulated to explain this mismatch: a succession in phytoplankton species composition towards higher relative abundances of DMSP producers in summer; inhibition of bacterial DMS consumption by ultraviolet radiation (UVR); and direct DMS production by phytoplankton due to UVR-induced oxidative stress. None of these hypothetical mechanisms, except for the first one, has been tested with a dynamic model. We have coupled a new sulfur cycle model that incorporates the latest knowledge on DMSP/DMS dynamics to a preexisting nitrogen/carbon-based ecological model that explicitly simulates the microbial-loop. This allows the role of bacteria in DMS production and consumption to be represented and quantified. The main improvements of DMOS with respect to previous DMSP/DMS models are the explicit inclusion of: solar-radiation inhibition of bacterial sulfur uptakes; DMS exudation by phytoplankton caused by solar-radiation-induced stress; and uptake of dissolved DMSP by phytoplankton. We have conducted a series of modeling experiments where some of the DMOS sulfur paths are turned “off” or “on,” and the results on chlorophyll-a, bacteria, DMS, and DMSP (particulate and dissolved) concentrations have been compared with climatological data of these same variables. The simulated rate of sulfur cycling processes are also compared with the scarce data available from previous works. All processes seem to play a role in driving DMS seasonality. Among them, however, solar-radiation-induced DMS exudation by phytoplankton stands out as the process without which the model is unable to produce realistic DMS simulations and reproduce the DMS summer paradox.

Sulfur isotope analysis of aerosol particles by NanoSIMS

A new method to measure the sulfur isotopic composition of individual aerosol particles by NanoSIMS has been developed and tested on several standards such as barite (BaSO4), anhydrite (CaSO4), gypsum (CaSO4·2H2O), mascagnite ((NH4)2SO4), epsomite (MgSO4·7H2O), magnesium sulfate (MgSO4·xH2O), thenardite (Na2SO4), boetite (K2SO4) and cysteine (an amino acid). This ion microprobe technique employs a Cs+ primary ion beam and measures negative secondary ions permitting the analysis of sulfur isotope ratios in individual aerosol particles down to 500 nm in size (0.001-0.5 ng of sample material). The grain-to-grain reproducibility of measurements is typically 5‰ (1σ) for micron-sized grains, <5‰ for submicron-sized grains, and <2‰ for polished thin sections and ultra microtome sections which were studied for comparison. The role of chemical omposition (matrix effect) and sample preparation techniques on the instrumental mass fractionation (IMF) of the 34S/32S ratio in the NanoSIMS has been investigated. The IMF varies by ~15‰ between the standards studied here. A good correlation between IMF and ionic radius of the cations in sulfates was observed. This permits to infer IMF corrections even for sulfates for which no isotope standards are available. The new technique allows to identify different types of primary and secondary sulfates based on their chemical composition and to measure their isotopic signature separately. It was applied to marine aerosol samples collected in Mace Head and urban aerosol samples collected in Mainz. It was shown that primary sulfate particles such as sulfate in NaCl or gypsum particles precipitated from ocean water retain the original isotopic signature of their source. The isotopic composition of secondary sulfate depends on the isotopic composition of precursor SO2 and the oxidation pathway. The 34S/32S fractionation with respect to the precursor SO2 is -9‰ for homogeneous oxidation and +16.5‰ for heterogeneous oxidation. This large difference between the isotopic fractionation of both pathways allows identifying the oxidation pathway from which the SO42- in a secondary sulfate particle is derived, by means of its sulfur isotope ratio, provided that the isotopic signature of the precursor SO2 is known. The isotopic composition of the precursor SO2 of secondary sulfates was calculated based on the isotopic composition of particles with known oxidation pathway such as fine mode ammonium sulfate.

Using sulfur isotope fractionation to understand the atmospheric oxidation of SO 2

Sulfate aerosol plays an important but uncertain role in cloud formation and radiative forcing of the climate, and is also important for acid deposition and human health. The oxidation of SO2 to sulfate is a key reaction in determining the impact of sulfate in the environment through its effect on aerosol size distribution and composition. This thesis presents a laboratory investigation of sulfur isotope fractionation during SO2 oxidation by the most important gas-phase and heterogeneous pathways occurring in the atmosphere. The fractionation factors are then used to examine the role of sulfate formation in cloud processing of aerosol particles during the HCCT campaign in Thuringia, central Germany. The fractionation factor for the oxidation of SO2 by ·OH radicals was measured by reacting SO2 gas, with a known initial isotopic composition, with ·OH radicals generated from the photolysis of water at -25, 0, 19 and 40°C (Chapter 2). The product sulfate and the residual SO2 were collected as BaSO4 and the sulfur isotopic compositions measured with the Cameca NanoSIMS 50. The measured fractionation factor for 34S/32S during gas phase oxidation is αOH = (1.0089 ± 0.0007) − ((4 ± 5) × 10−5 )T (°C). Fractionation during oxidation by major aqueous pathways was measured by bubbling the SO2 gas through a solution of H2 O2

Sulfur-containing polymers for surface attachment

Different concepts for the synthesis of sulfur-containing polymers as well as their adsorption onto gold surfaces were studied. The present work is divided into three parts. The main part focuses on the synthesis of poly(1,2-alkylene sulfides) (“polysulfides”) with complex architectures on the basis of polyether-based macroinitiators by the anionic ring-opening polymerization of ethylene sulfide and propylene sulfide. This synthetic tool kit allowed the synthesis of star-shaped, brush-like, comb-like and pom-pom-like polysulfides, the latter two with an additional poly(ethylene glycol) chain. Additionally, the number of polysulfide arms as well as the monomer composition could be varied over a wide range to obtain copolymers with multiple thioether functionalities.rnThe second section deals with the synthesis of a novel lipoic acid-based initiator for ring-opening polymerizations for lactones and epoxides. A straightforward approach was selected to accomplish the ability to obtain tailored polymers with a common used disulfide-anchoring group, without the drawbacks of post-polymerization functionalization. rnIn the third part, a new class of block-copolymers consisting of polysulfides and polyesters were investigated. For the first time this approach enabled the use of hydroxyl-terminated poly(propylene sulfide) as macroinitiator for the synthesis of a second block.rnThe adsorption efficiency of those different polymer classes onto gold nanoparticles as well as gold rnsupports was studied via different methods.rn

Homeopathic Preparations of Quartz, Sulfur and Copper Sulfate Assessed by UV-Spectroscopy

Homeopathic preparations are used in homeopathy and anthroposophic medicine. Although there is evidence of effectiveness in several clinical studies, including double-blinded randomized controlled trials, their nature and mode of action could not be explained with current scientific approaches yet. Several physical methods have already been applied to investigate homeopathic preparations but it is yet unclear which methods are best suited to identify characteristic physicochemical properties of homeopathic preparations. The aim of this study was to investigate homeopathic preparations with UV-spectroscopy. In a blinded, randomized, controlled experiment homeopathic preparations of copper sulfate (CuSO(4); 11c-30c), quartz (SiO(2); 10c-30c, i.e., centesimal dilution steps) and sulfur (S; 11×-30×, i.e., decimal dilution steps) and controls (one-time succussed diluent) were investigated using UV-spectroscopy and tested for contamination by inductively coupled plasma mass spectrometry (ICP-MS). The UV transmission for homeopathic preparations of CuSO(4) preparations was significantly lower than in controls. The transmission seemed to be also lower for both SiO(2) and S, but not significant. The mean effect size (95% confidence interval) was similar for the homeopathic preparations: CuSO(4) (pooled data) 0.0544% (0.0260-0.0827%), SiO(2) 0.0323% (-0.0064% to 0.0710%) and S 0.0281% (-0.0520% to 0.1082%). UV transmission values of homeopathic preparations had a significantly higher variability compared to controls. In none of the samples the concentration of any element analyzed by ICP-MS exceeded 100 ppb. Lower transmission of UV light may indicate that homeopathic preparations are less structured or more dynamic than their succussed pure solvent.