Surface properties and catalytic activity of phosphate modified zirconia

Preparation and physico-chemical characterization or phosphate modified zirconia systems and their application to Friedel-Crafts benzylation and benzoylation of toluene have been reported. The influence of transition metals on the surface properties and catalytic activity has also been discussed.

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Electrical conductivity, dielectric constant and phase transitions in pure and doped diammonium hydrogen phosphate

DC and AC electrical conductivity measurements in single crystals of diammonium hydrogen phosphate along the c axis show anomalous variations at 174, 246 and 416 K. The low-frequency dielectric constant also exhibits peaks exactly at these temperatures with a thermal hysteresis of 13 degrees C for the peak at 416 K. These specific features of the electrical properties are in agreement with earlier NMR second-moment data and can be identified with three distinct phase transitions that occur in the crystal. The electrical conductivity values have been found to increase linearly with impurity concentration in specimens doped with a specific amount of SO42- ions. The mechanisms of the phase transition and of the electrical conduction process are discussed in detail.

High‐temperature phase transitions in pure and deuterated ammonium dihydrogen phosphate: Conductivity and dielectric measurements

Results of axiswise measurements of the electrical conductivity (dc and ac) and dielectric constant of NH4H2PO4 confirm the occurrence of the recently suggested high‐temperature phase transition in this crystal (at 133 °C). The corresponding transition in ND4D2PO4 observed here for the first time takes place at 141.5 °C. The mechanism involved in these transitions and those associated with the electrical conduction and dielectric anomalies are explained on the basis of the motional effects of the ammonium ions in these crystals. Conductivity values for deuterated crystals give direct evidence for the predominance of protonic conduction throughout the entire range of temperatures studied (30–260 °C).

Contribution of size fractions of planktonic algae to primary organic productivity in the coastal waters of Cochin- south west coast of lndia

This thesis entitled “Contribution of size fractions of planktonic algae to primary organic productivity in the coastal waters of cochin,south west coast of india”. Marine ecosystems planktonic algae are the most important primary producers on wliich considerable attention is being given on account of their supreme status in the marine food chain.The study of primary production in the Indian Ocean started With DANA (I928-30),, John Murray t I933-34). Discovery ( I934) and Albatross (I947-48) expeditions which tried to evaluate productivity from nutrients and standing crop of phytoplankton .The bioproductivity of the marine environment is dependent on various primary producers. ranging in size from picoplankton to larger macro phytoplankton. The quantity and quality of various size fractions of planktonic algae at any locality depend mainly on the hydrographic conditions of the area .In the coastal waters of Cochin- south west coast of lndia. Planktonic algal community is composed mainly of the diatoms, the dinoflagellates, the blue-green algae and the silicoflagellates, the former two contributing the major flora and found distributed in the all size fractions. The maximum number of species of diatoms at station 1 and station 2 was found in the pre-monsoon season.. The size groups of planktonic algae greater than 53 um are dominated by filamentous- chain forming and colonial diatoms. The coastal waters of Cochin. planktonic algae less than 53 um in size contribute significantly to primary productivity and the biodiversity of the microflora, indicating the presence of rich fishery resources in the south west coast of india.The study of different size fractions of planktonic algae and their relative contribution to the primary organic production is a useful tool for the estimation of the quantity and quality of fisheries.A deeper investigation on the occurrence of these microalgae and proper identification of their species would be of immense help for the assessment of the specificity and magnitude of fishery resources.

Fractionation and bioavailability of phosphorus in a tropical estuary, Southwest India

Phosphorus fractionation was employed to find the bioavailability of phosphorus and its seasonal variations in the Panangad region of Cochin estuary, the largest estuarine system in the southwest coast of India. Sequential extraction of the surficial sediments using chelating agents was taken as a tool for this. Phosphate in the water column showed seasonal variations, with high values during the monsoon months, suggesting external runoff. Sediment texture was found to be the main factor influencing the spatial distribution of the geochemical parameters in the study region. Similarly, total phosphorus also showed granulometric dependence and it ranged between 319.54 and 2,938.83 μg/g. Calcium-bound fraction was the main phosphorus pool in the estuary. Significant spatial variations were observed for all bioavailable fractions; iron-bound inorganic phosphorus (5.04–474.24 μg/g), calcium-bound inorganic phosphorus (11.16–826.09 μg/g), and acidsoluble organic phosphorus (22.22–365.86 μg/g). Among the non-bioavailable phosphorus, alkalisoluble organic fraction was the major one (51.92– 1,002.45 μg/g). Residual organic phosphorus was K. R. Renjith (B) · N. Chandramohanakumar · M. M. Joseph Department of Chemical Oceanography, School of Marine Sciences, Cochin University of Science and Technology, Kochi 682016, Kerala, India e-mail: renjithaqua@gmail.com comparatively smaller fraction (3.25–14.64% of total). The sandy and muddy stations showed distinct fractional composition and the speciation study could endorse the overall geochemical character. There could be buffering of phosphorus, suggested by the increase in the percentage of bioavailable fractions during the lean premonsoon period, counteracting the decreases in the external loads. Principal component analysis was employed to find the possible processes influencing the speciation of phosphorus in the study region

Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Effects of Different Feeding Regimes on the Digestibility and Faecal Excretion of Nitrogen, Soluble Carbohydrates and Fibre Fractions in Water Buffaloes kept under Subtropical Conditions

In the course of the ‘Livestock Revolution’, extension and intensification of, among others, ruminant livestock production systems are current phenomena, with all their positive and negative side effects. Manure, one of the inevitable secondary products of livestock rearing, is a valuable source of plant nutrients and its skillful recycling to the soil-plant interface is essential for soil fertility, nutrient - and especially phosphorus - uses efficiency and the preservation or re-establishment of environmentally sustainable farming systems, for which organic farming systems are exemplarily. Against this background, the PhD research project presented here, which was embedded in the DFG-funded Research Training Group 1397 ‘Regulation of soil organic matter and nutrient turnover in organic agriculture ’ investigated possibilities to manipulate the diets of water buffalo (Bubalus bubalis L.) so as to produce manure of desired quality for organic vegetable production, without affecting the productivity of the animals used. Consisting of two major parts, the first study (chapter 2) tested the effects of diets differing in their ratios of carbon (C) to nitrogen (N) and of structural to non-structural carbohydrates on the quality of buffalo manure under subtropical conditions in Sohar, Sultanate of Oman. To this end, two trials were conducted with twelve water buffalo heifers each, using a full Latin Square design. One control and four tests diets were examined during three subsequent 7 day experimental periods preceded each by 21 days adaptation. Diets consisted of varying proportions of Rhodes grass hay, soybean meal, wheat bran, maize, dates, and a commercial concentrate to achieve a (1) high C/N and high NDF (neutral detergent fibre)/SC (soluble carbohydrate) ratio (HH), (2) low C/N and low NDF/SC ratio (LL); (3) high C/N and low NDF/SC ratio (HL) and (4) low C/N and high NDF/SC (LH) ratio. Effects of these diets, which were offered at 1.45 times maintenance requirements of metabolizable energy, and of individual diet characteristics, respectively, on the amount and quality of faeces excreted were determined and statistically analysed. The faeces produced from diets HH and LL were further tested in a companion PhD study (Mr. K. Siegfried) concerning their nutrient release in field experiments with radish and cabbage. The second study (chapter 3) focused on the effects of the above-described experimental diets on the rate of passage of feed particles through the gastrointestinal tract of four randomly chosen animals per treatment. To this end, an oral pulse dose of 683 mg fibre particles per kg live weight marked with Ytterbium (Yb; 14.5 mg Yb g-1 organic matter) was dosed at the start of the 7 day experimental period which followed 21 days of adaptation. During the first two days a sample for Yb determination was kept from each faecal excretion, during days 3 – 7 faecal samples were kept from the first morning and the first evening defecation only. Particle passage was modelled using a one-compartment age-dependent Gamma-2 model. In both studies individual feed intake and faecal excretion were quantified throughout the experimental periods and representative samples of feeds and faeces were subjected to proximate analysis following standard protocols. In the first study the organic matter (OM) intake and excretion of LL and LH buffaloes were significantly lower than of HH and HL animals, respectively. Digestibility of N was highest in LH (88%) and lowest in HH (74%). While NDF digestibility was also highest in LH (85%) it was lowest in LL (78%). Faecal N concentration was positively correlated (P≤0.001) with N intake, and was significantly higher in faeces excreted by LL than by HH animals. Concentrations of fibre and starch in faecal OM were positively affected by the respective dietary concentrations, with NDF being highest in HH (77%) and lowest in LL (63%). The faecal C/N ratio was positively related (P≤0.001) to NDF intake; C/N ratios were 12 and 7 for HH and LL (P≤0.001), while values for HL and LH were 11.5 and 10.6 (P>0.05). The results from the second study showed that dietary N concentration was positively affecting faecal N concentration (P≤0.001), while there was a negative correlation with the faecal concentration of NDF (P≤0.05) and the faecal ratios of NDF/N and C/N (P≤0.001). Particle passage through the mixing compartment was lower (P≤0.05) for HL (0.033 h-1) than for LL (0.043 h-1) animals, while values of 0.034 h-1 and 0.038 h-1 were obtained for groups LH and HH. At 55.4 h, total tract mean retention time was significantly (P≤0.05) lower in group LL that in all other groups where these values varied between 71 h (HH) and 79 h (HL); this was probably due to the high dietary N concentration of diet LL which was negatively correlated with time of first marker appearance in faeces (r= 0.84, P≤0.001), while the dietary C concentration was negatively correlated with particle passage through the mixing compartment (r= 0.57, P≤0.05). The results suggest that manure quality of river buffalo heifers can be considerably influenced by diet composition. Despite the reportedly high fibre digestion capacity of buffalo, digestive processes did not suppress the expression of diet characteristics in the faeces. This is important when aiming at producing a specific manure quality for fertilization purposes in (organic) crop cultivation. Although there was a strong correlation between the ingestion and the faecal excretion of nitrogen, the correlation between diet and faecal C/N ratio was weak. To impact on manure mineralization, the dietary NDF and N concentrations seem to be the key control points, but modulating effects are achieved by the inclusion of starch into the diet. Within the boundaries defined by the animals’ metabolic and (re)productive requirements for energy and nutrients, diet formulation may thus take into account the abiotically and biotically determined manure turnover processes in the soil and the nutrient requirements of the crops to which the manure is applied, so as to increase nutrient use efficiency along the continuum of the feed, the animal, the soil and the crop in (organic) farming systems.

Effects of Tithonia diversifolia, farmyard manure and urea, and phosphate fertiliser application methods on maize yields in western Kenya

Maize production in western Kenya is often limited by deficiencies of nitrogen and phosphorus. We assessed the effectiveness of Tithonia diversifolia green manure (tithonia), farmyard manure (FYM) and urea as sources of nitrogen (N) for maize when inorganic phosphorus (P) fertiliser was either broadcast (BR) or spot-placed in the planting hole (SP) for two consecutive seasons; October to December of 1998 and April to August of 1999 at two sites; Nyabeda and Khwisero in western Kenya. A randomised complete block design with four replications was used. Maize yields were higher at Nyabeda and responded to P application better than at Khwisero. At the same N rate, tithonia and FYM were as effective as urea in increasing maize yields at both sites. There were no significant differences in maize yields when phosphate fertiliser was either BR or SP regardless of the N source used in the first season. However, in the second season, the residual yields for the BR treatments were consistently higher than those of the SP. Our results suggest that tithonia and FYM can substitute for urea as N sources and that fertiliser P should be broadcast and incorporated together with the organic materials at the time of planting to save on labour costs.

Continued Fractions

Lecture notes

Accumulated metal speciation in earthworm populations with multi-generational exposure to metalliferous soils: cell fractionation and high energy synchrotron analyses

Predicting metal bioaccumulation and toxicity in soil organisms is complicated by site-specific biotic and abiotic parameters. In this study we exploited tissue fractionation and digestion techniques, combined with X-ray absorption spectroscopy (XAS), to investigate the whole-body and subcellular distributions, ligand affinities, and coordination chemistry of accumulated Pb and Zn in field populations of the epigeic earthworm Lumbricus rubellus inhabiting three contrasting metalliferous and two unpolluted soils. Our main findings were (i) earthworms were resident in soils with concentrations of Pb and Zn ranging from 1200 to 27 000 mg kg(-1) and 200 to 34 000 mg kg(-1), respectively; (ii) Pb and Zn primarily accumulated in the posterior alimentary canal in nonsoluble subcellular fractions of earthworms; (iii) site-specific differences in the tissue and subcellular partitioning profiles of populations were observed, with earthworms from a calcareous site partitioning proportionally more Pb to their anterior body segments and Zn to the chloragosome-rich subcellular fraction than their acidic-soil inhabiting counterparts; (iv) XAS indicated that the interpopulation differences in metal partitioning between organs were not accompanied by qualitative differences in ligand-binding speciation, because crystalline phosphate-containing pyromorphite was a predominant chemical species in the whole-worm tissues of all mine soil residents. Differences in metal (Pb, Zn) partitioning at both organ and cellular levels displayed by field populations with protracted histories of metal exposures may reflect their innate ecophysiological responses to essential edaphic variables, such as Ca2+ status. These observations are highly significant in the challenging exercise of interpreting holistic biomarker data delivered by "omic" technologies.

Assessment of the effect of time and temperature on the availability of residual phosphate in a glasshouse study of four soils using the Olsen method

The Olsen method is an indicator of plant-available phosphorus (P). The effect of time and temperature on residual phosphate in soils was measured using the Olsen method in a pot experiment. Four soils were investigated: two from Pakistan and one each from England (calcareous) and Colombia (acidic). Two levels of residual phosphate were developed in each soil after addition of phosphate by incubation at either 10degreesC or 45degreesC. The amount of phosphate added was based on the P maximum of each soil, calculated using the Langmuir equation. Rvegrass was used as the test crop. The pooled data for the four soils incubated at 10degreesC showed good correlation between Olsen P and dry matter yield or P uptake (r(2) = 0.85 and 0.77, respectively), whereas at 45 degreesC, each soil had its own relationship and pooled data did not show correlation of Olsen P with dry matter yield or P uptake. When the data at both temperatures were pooled, Olsen P was a good indicator of yield and uptake for the English soil. For the Pakistani soils, Olsen P after 45 degreesC treatment was an underestimate relative to the 10 degreesC data and for the Colombian soil it was an overestimate. The reasons for these differences need to be explored further before high temperature incubation can be used to simulate long-term changes in the field.

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.