Synthesis, structure and magnetic characterisation of a new layered ammonium manganese(II) diphosphate hydrate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)]

A new layered ammonium manganese(II) diphosphate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)], has been synthesised under solvothermal conditions at 433 K in ethylene glycol and the structure determined at 293 K using single-crystal X-ray diffraction data (M-r = 584.82, monoclinic, space group P2(1)/a, a = 9.4610( 8), b = 8.3565( 7), c = 9.477(1) Angstrom, beta = 99.908(9) degrees, V = 738.07 Angstrom(3), Z = 2, R = 0.0351 and R-w = 0.0411 for 1262 observed data (I > 3(sigma(I))). The structure consists of chains of cis- and trans-edge sharing MnO6 octahedra linked via P2O7 units to form layers of formula [Mn3P4O14(H2O)(2)](2-) in the ab plane. Ammonium ions lie between the manganese-diphosphate layers. A network of interlayer and ammonium-layer based hydrogen bonding holds the structure together. Magnetic measurements indicate Curie - Weiss behaviour above 30 K with mu(eff) = 5.74(1) mu(B) and theta = -23(1) K, consistent with the presence of high-spin Mn2+ ions and antiferromagnetic interactions. However, the magnetic data reveal a spontaneous magnetisation at 5 K, indicating a canting of Mn2+ moments in the antiferromagnetic ground state. On heating (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)] in water at 433 K under hydrothermal conditions, Mn-5(HPO4)(2)(PO4)(2).4H(2)O, synthetic hureaulite, is formed.

Polymorphism and optical properties in [NH4][InSe2]

The solvothermal synthesis and characterization of two indium selenides with stoichiometry [NH4][InSe2] is described. Yellow [NH4][InSe2] (1), which exhibits a layered structure, was initially prepared in an aqueous solution of trans-1,4-diaminocyclohexane, and subsequently using a concentrated ammonia solution. A red polymorph of one-dimensional character, [NH4][InSe2] (2), was obtained using 3,5-dimethylpyridine as solvent. [NH4][InSe2] (1) crystallizes in the non-centrosymmetric space group Cc (a=11.5147(6), b=11.3242(6), c=15.9969(9) Å and β=100.354(3)°). The structural motif of the layers is the In4Se10 adamantane unit, composed of four corner-linked InSe4 tetrahedra. These units are linked by their corners, forming [InSe2]− layers which are stacked back to back along the c-direction, and interspaced by [NH4]+cations. The one-dimensional polymorph, (2), crystallizes in the tetragonal space group, I4/mcm (a=8.2519(16), c=6.9059 (14) Å). This structure contains infinite chains of edge-sharing InSe4 tetrahedra separated by [NH4]+ cations.

Carbon (C-13) and nitrogen (N-15) translocation in a maize-Striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Enhanced phytoextraction: In search of EDTA alternatives

Enhanced phytoextraction proposes the use of soil amendments to increase the heavy-metal content of above-ground harvestable plant tissues. This study compares the effect of synthetic aminopolycarboxylic acids [ethylenediamine tetraacetatic acid (EDTA), nitriloacetic acid (NTA), and diethylenetriamine pentaacetic acid (DTPA)] with a number of biodegradable, low-molecular weight, organic acids (citric acid, ascorbic acid, oxalic acid, salicylic acid, and NH4 acetate) as potential soil amendments for enhancing phytoextraction of heavy metals (Cu, Zn, Cd, Pb, and Ni) by Zea mays. The treatments in this study were applied at a dose of 2 mmol/kg(-1) 1 d before sowing. To compare possible effects between presow and postgermination treatments, a second smaller experiment was conducted in which EDTA, citric acid, and NH4 acetate were added 10 d after germination as opposed to 1 d before sowing. The soil used in this screening was a moderately contaminated topsoil derived from a dredged sediment disposal site. This site has been in an oxidized state for more than 8 years before being used in this research. The high carbonate, high organic matter, and high clay content characteristic to this type of sediment are thought to suppress heavy-metal phytoavailability. Both EDTA and DTPA resulted in increased levels of heavy metals in the above-ground biomass. However, the observed increases in uptake were not as large as reported in the literature. Neither the NTA nor organic acid treatments had any significant effect on uptake when applied prior to sowing. This was attributed to the rapid mineralization of these substances and the relatively low doses applied. The generally low extraction observed in this experiment restricts the use of phytoextraction as an effective remediation alternative under the current conditions, with regard to amendments used, applied dose (2 mmol/kg(-1) soil), application time (presow), plant species (Zea mays), and sediment (calcareous clayey soil) under study.

Effect of mycorrhizae and pH change at the root-soil interface on phosphorus uptake by Sorghum using a rhizocylinder technique

Sorghum (Sorghum bicolor) was grown for 40 days in. rhizocylinder (a growth container which permitted access to rh zosphere and nonrhizosphere soil), in two soils of low P status. Soils were fertilized with different rates of ammonium and nitrate and supplemented with 40 mg phosphorus (P) kg(-1) and inoculated with either Glomus mosseae (Nicol. and Gerd.) or nonmycorrhizal root inoculum.. N-serve (2 mg kg(-1)) was added to prevent nitrification. At harvest, soil from around the roots was collected at distances of 0-5, 5-10, and 10-20 mm from the root core which was 35 mm diameter. Sorghum plants, with and without mycorrhiza, grew larger with NH4+ than with NO3- application. After measuring soil pH, 4 3 suspensions of the same sample were titrated against 0.01 M HCl or 0.01 M NaOH until soil pH reached the nonplanted pH level. The acid or base requirement for each sample was calculated as mmol H+ or OFF kg(-1) soil. The magnitude of liberated acid or base depended on the form and rate of nitrogen and soil type. When the plant root was either uninfected or infected with mycorrhiza., soil pH changes extended up to 5 mm from the root core surface. In both soils, ammonium as an N source resulted in lower soil pH than nitrate. Mycorrhizal (VAM) inoculation did not enhance this difference. In mycorrhizal inoculated soil, P depletion extended tip to 20 mm from the root surface. In non-VAM inoculated soil P depletion extended up to 10 mm from the root surface and remained unchanged at greater distances. In the mycorrhizal inoculated soils, the contribution of the 0-5 mm soil zone to P uptake was greater than the core soil, which reflects the hyphal contribution to P supply. Nitrogen (N) applications that caused acidification increased P uptake because of increased demand; there is no direct evidence that the increased uptake was due to acidity increasing the solubility of P although this may have been a minor effect.

Integrated Nitrogen CAtchment model (INCA) applied to a tropical catchment in the Atlantic Forest, Sao Paulo, Brazil

Stream-water flows and in-stream nitrate and ammonium concentrations in a small (36.7 ha) Atlantic Forest catchment were simulated using the Integrated Nitrogen in CAtchments (INCA) model version 1.9.4. The catchment, at Cunha, is in the Serra do Mar State Park, SE Brazil and is nearly pristine because the nearest major conurbations, Sao Paulo and Rio, are some 450 km distant. However, intensive farming may increase nitrogen (N) deposition and there are growing pressures for urbanisation. The mean-monthly discharges and NO3-N concentration dynamics were simulated adequately for the calibration and validation periods with (simulated) loss rates of 6.55 kg.ha(-1) yr(-1) for NO3-N and 3.85 kg.ha(-1) yr(-1) for NH4-N. To investigate the effects of elevated levels of N deposition in the future, various scenarios for atmospheric deposition were simulated; the highest value corresponded to that in a highly polluted area of Atlantic Forest in Sao Paulo City. It was found that doubling the atmospheric deposition generated a 25% increase in the N leaching rate, while at levels approaching the highly polluted Sao Paulo deposition rate, five times higher than the current rate, leaching increased by 240%, which would create highly eutrophic conditions, detrimental to downstream water quality. The results indicate that the INCA model can be useful for estimating N concentration and fluxes for different atmospheric deposition rates and hydrological conditions.

Influence of aluminum hydroxide on potassium release from two Colombian soils

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non-exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2 : 1 clay minerals and High Terrace with predominantly 1 : 1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl-Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K2O, respectively. They were used either untreated or prepared by adding AlCl3 and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10mM NH4OAc at pH 7.0 and 10 mM CaCl2 at pH 5.8 for 120 h at 6 mL h(-1) to examine the release of Kex and Knex. In the untreated soils, NH4+ and Ca-2(+) released the same amounts of Kex from Caribia, whereas NH4+ released about twice as much Kex as Ca2+ from High Terrace. This study proposes that the small ionic size of NH4+ (0.54nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca2+ (0.96 nm) cannot have access. As expected for a soil dominated by 2 : 1 clay minerals, Ca2+ caused Knex to be released from Caribia with no release by NH4+. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca2+ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl3 which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH4 salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.

Acid-base reactions between an acidic soil and plant residues

The elemental composition of residues of maize (Zea mays), sorghum (S. bicolor), groundnuts (Arachis hypogea), soya beans (Glycine max), leucaena (L. leucocephala), gliricidia (G. sepium), and sesbania (S. sesban) was determined as a basis for examining their alkalinity when incorporated into an acidic Zambian Ferralsol. Potential (ash) alkalinity, available alkalinity by titration to pH 4 and soluble alkalinity (16 It water extract titrated to pH 4) were measured. Potential alkalinity ranged from 3 73 (maize) to 1336 (groundnuts) mmol kg(-1) and was equivalent to the excess of their cation charge over inorganic anion charge. Available alkalinity was about half the potential alkalinity. Cations associated with organic anions are the source of alkalinity. About two thirds of the available alkalinity is soluble. Residue buffer curves were determined by titration with H2SO4 to pH 4. Soil buffer capacity measured by addition of NaOH was 12.9 mmol kg(-1) pH(-1). Soil and residue (10 g:0.25 g) were shaken in solution for 24 h and suspension pH values measured. Soil pH increased from 4.3 to between 4.6 (maize) and 5.2 (soyabean) and the amounts of acidity neutralized (calculated from the rise in pH and the soil buffer capacity) were between 3.9 and 11.5 mmol kg(-1), respectively. The apparent base contributions by the residues (calculated from the buffer curves and the fall in pH) ranged between 105 and 350 mmol kg(-1) of residue, equivalent to 2.6 and 8.8 mmol kg(-1) of soil, respectively. Therefore, in contact with soil acidity, more alkalinity becomes available than when in contact with H2SO4 solution. Available alkalinity (to pH 4) would be more than adequate to supply that which reacts with soil but soluble alkalinity would not. It was concluded that soil Al is able to displace cations associated with organic anions in the residues which are not displaced by H+, or that residue decomposition may have begun in the soil suspension releasing some of the non-available alkalinity. Soil and four of the residues were incubated for 100 days and changes in pH, NH4+ and NO3- concentrations measured. An acidity budget equated neutralized soil acidity with residue alkalinity and base or acid produced by N transformations. Most of the potential alkalinity of soyabean and leucaena had reacted after 14 days, but this only occurred after 100 days for gliricidia, and for maize only the available alkalinity reacted. For gliricidia and leucaena, residue alkalinity was primarily used to react with acidity produced by nitrification. Thus, the ability of residues to ameliorate acidity depends not only on their available and potential alkalinity but also on their potential to release mineral N. (C) 2004 Elsevier B.V. All rights reserved.

Presubmergence and green manure affect the transformations of nitrogen-15-labeled urea under lowland soil conditions

The effect of presubmergence and green manuring on various processes involved in [N-15]-urea transformations were studied in a growth chamber after [N-15]-urea application to floodwater. Presubmergence for 14 days increased urea hydrolysis rates and floodwater pH, resulting in higher NH3 volatilization as compared to without presubmergence. Presubmergence also increased nitrification and subsequent denitrification but lower N assimilation by floodwater algae caused higher gaseous losses. Addition of green manure maintained higher NH4+-N concentration in floodwater mainly because of lower nitrification rates but resulted in highest NH3 volatilization losses. Although green manure did not affect the KCl extractable NH4+-N from applied fertilizer, it maintained higher NH4+-N content due to its decomposition and increased mineralization of organic N. After 32 days about 36.9% (T-1), 23.9% (T-2), and 36.4% (T-3) of the applied urea N was incorporated in the pool of soil organic N in treatments. It was evident that the presubmergence has effected the recovery of applied urea N.

Short-term effects of manipulated increase in acid deposition on soil, soil solution chemistry and fine roots in Scots pine (Pinus sylvestris) stand on a podzol

A manipulated increase in acid deposition (15 kg S ha(-1)), carried out for three months in a mature Scots pine (Pinus sylvestris) stand on a podzol, acidified the soil and raised dissolved Al at concentrations above the critical level of 5 mg l(-1) previously determined in a controlled experiment with Scots pine seedlings. The induced soil acidification reduced tree fine root density and biomass significantly in the top 15 cm of soil in the field. The results suggested that the reduction in fine root growth was a response not simply to high Al in solution but to the depletion of exchangeable Ca and Mg in the organic layer, K deficiency, the increase in NH4:NO3 ratio in solution and the high proton input to the soil by the acid manipulation. The results from this study could not justify the hypothesis of Al-induced root damage under field conditions, at least not in the short term. However, the study suggests that a short exposure to soil acidity may affect the fine root growth of mature Scots pine.

Carbon (C-13) and nitrogen (N-15) translocation in a maize-Striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Agronomic techniques to control Lobesia botrana

The grapevine moth Lobesia botrana (Denis & Schiffermuller) (Lepidoptera: Tortricidae) is a key pest of grapevines in Greece. As part of a broader study on integrated pest management, the effects were investigated of different cultural methods on the establishment and survival of L. botrana, specifically: application of different nitrogen levels (30 and 100 units of ammonium sulfate or 70 units of Agrobiosol); summer leaf and shoot pruning; application of growth regulators (Regalis, probexadione-calcium; or Falgro, gibberellic acid). There were significant differences among the three levels of N application. The lowest L. botrana infestation rates were found in plots treated with 30 units of (NH4)(2)SO4 and plots that received some summer pruning. Following the application of plant growth regulators, the lowest L. botrana infestation levels occurred in the plots treated with Regalis or Falgro at the manufacturers' recommended concentrations. On vines where growth regulators had been applied, the clusters had fewer berries than those not treated with growth regulators.

Carbon (13C) and nitrogen (15 N) translocation in a maize-striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Isolation and characterisation of phytase from dormant Corylus avellana seeds

Phytase (myo-inositol-1,2,3,4,5,6-hexakisphosphate phosphohydrolase, EC 3.1.3.26), which catalyses the step-wise hydrolysis of phytic acid, was purified from cotyledons of dormant Corylus avellana L. seeds. The enzyme was separated from the major soluble acid phosphatase by successive (NH4)2SO4 precipitation, gel filtration and cation exchange chromatography resulting in a 300-fold purification and yield of 7.5%. The native enzyme positively interacted with Concanavalin A suggesting that it is putatively glycosylated. After size exclusion chromatography and SDS–PAGE it was found to be a monomeric protein with molecular mass 72±2.5 kDa. The hazel enzyme exhibited optimum activity for phytic acid hydrolysis at pH 5 and, like other phytases, had broad substrate specificity. It exhibited the lowest Km (162 μM) and highest specificity constant (Vmax/Km) for phytic acid, indicating that this is the preferred in vivo substrate. It required no metal ion as a co-factor, while inorganic phosphate and fluoride competitively inhibited enzymic activity (Ki=407 μM and Ki=205 μM, respectively).

Effluent quality and ammonia emissions from out-wintering pads in England, Wales and Ireland

Out-wintering pads offer a reduced cost system for wintering cattle, minimising damage to pasture, providing animal welfare and production benefits, and generate, potentially, a more manageable effluent and lower ammonia emissions. The objectives of the present study were (i) to contribute to improved understanding of the factors impacting on effluent quality, ammonia emissions and animal welfare via observations on four farm-based out-wintering pads (ComOWPs) in England, Wales and Ireland and more detailed studies undertaken on four experimental OWPs (ExpOWPs) constructed at Rothamsted Research North Wyke, Devon, England and (ii) to corroborate the effluent quality data from both the ComOWPs and the ExpOWPs, with findings in the literature. Woodchip size, feeding management and area allowance were the treatment factors applied on the ExpOWPs. These three factors were randomised across the four ExpOWPs, over four 6–7 week periods. Effluent quality from the ExpOWPs was sampled frequently in a flow proportional way and analysed for total N (TN); total P (TP); total solids (TS); ammonium-N (NH4+-N); nitrate-N (NO3−-N). Beef cattle were periodically weighed for determination of live weight gain (LWG). An approximate nitrogen balance was calculated as a means of understanding its partitioning and fate during and after the ExpOWPs use. Effluent quality from the ComOWPs was sampled frequently, also in a flow-proportional way, and analysed for TN, TP, TS, NH4+-N, NO3−-N, total K and COD. Effluent quality data from the ExpOWPs showed no significant differences (P > 0.05) between treatments, with average concentrations of 1095 mg l−1, and 806 mg l−1, for TN and NH4+-N, respectively. Average effluent concentrations from the ComOWPs were 356 mg l−1 TN and 124 mg l−1 NH4+-N. Ammonia emissions from the ExpOWPs showed no significant differences (P > 0.05) between the treatments, with average mean emission rates of 2.5 g m−2 d−1 NH3-N, respectively. A positive correlation was established between NH3-N emission rate and wind speed. Emission rates from the ComOWPs ranged from 0.7 to 1.6 g m−2 d−1 NH3-N. Average daily LWG on the ExpOWPs was 1.33 kg steer−1 d−1. The effluent from both the ComOWPs and ExpOWPs were more similar with dirty water and of consistently lower strength than beef cattle slurry, as supported by findings in the literature, and therefore, it is suggested to be subject to the regulatory requirements of dirty water rather than slurry.