Identification of the causes of subsoil ammonium accumulations in southeastern Queensland

Unusually high concentrations of exchangeable-NH4+ (up to 270 kg-N/ha) were observed in a Vertisol below 1 m in southeast Queensland. This study aimed to identify the source of this NH4+. Preliminary sampling of native vegetation and cropping areas had found that elevated NH4+was only present under cropped soil, indicating that clearing was linked to the NH4+formation. Mechanisms of NH4+formation that may have occurred in the subsoil after clearing were hypothesised to be a) mineralisation of organic-N; b) NO3- reduction to NH4+; and/or c) the release of fixed-NH4+. In addition it was proposed that nitrification was inhibited in the subsoil, and that this allowed any NH4+formed to accumulate over time. Incubation experiments to examine nitrification rates revealed that nitrification was undetectable, and appeared to be limited by a combination of subsoil acidity and low numbers of nitrifying organisms. Mineralisation studies also revealed that the mineralisation of organic-N was undetectable, and that mineralising organisms were limited by acidity. A small amount of nitrate ammonification could be observed with the aid of a 15N tracer if the soil was waterlogged. However, this NH4+was insufficient to account for the overall NH4+accumulation, and these waterlogged conditions were not observed in the field. Concentrations of fixed- NH4+ measured were also too low to have been responsible for the accumulation of exchangeable-NH4+. It was concluded that none of the proposed hypotheses of NH4+formation could account for the NH4+accumulation observed.

Nitrate ammonification and its relationship to the accumulation of ammonium in a Vertisol subsoil

High concentrations of ammonium ( up to 270 kg N/ha) have been observed in a Vertisol soil below 1 m depth near Warra in south-east Queensland. This study examined the possibility that increased water movement into the subsoil after the removal of native vegetation, and a subsequent increase in periods of waterlogging, could have triggered nitrate ammonification and be responsible for the production of ammonium. Two incubation experiments were conducted to test this hypothesis. The first involved the incubation of repacked cores that had been amended with 30 mg N/kg of 5 atom% N-15 nitrate under low oxygen conditions for a period of 360 days. Over this time period the N-15 enrichment of the exchangeable ammonium fraction was monitored in order to detect any reduction of nitrate to ammonium. The second experiment involved the incubation of soil amended with 30 mg N/ kg of 5 atom% N-15 nitrate under waterlogged and low oxygen conditions for 75 days. During this period the redox potential of the soil was monitored using a field test to determine if reducing conditions would develop in this soil over a period of waterlogging, combined with the monitoring of any nitrate reduction to ammonium. The results of these experiments indicated that a small amount of nitrate ammonification (< 0.1 mg N/ kg) could be observed in the Warra subsoil, but that unless the rate of reduction were to significantly increase with time, this could not account for the accumulation of ammonium observed in the field. The environmental conditions that would make either dissimilatory or abiotic nitrate ammonification favourable were not observed to develop. Consequently, it has been concluded that the observed nitrate ammonification occurred via an assimilatory pathway. Due to the low rate of microbial activity in this subsoil it is considered unlikely that this process was responsible for the subsoil ammonium accumulation at Warra.

Using quantity/intensity relationships to assess the potential for ammonium leaching in a Vertosol

High concentrations of ammonium (up to 0.1 cmol/kg) have been observed below 1 m depth in a Vertosol soil near Warra in south-eastern Queensland. This study examined whether ammonium leaching could be responsible for the ammonium accumulation observed in the Warra soil. This was done by using quantity/intensity (Q/I) relationships to compare the ammonium retention capacity of the Warra soil with other similar soils throughout the region that did not contain elevated subsoil ammonium concentrations. Analysis of Q/I curves revealed that in the concentration range studied, the amount of ammonium retained on high affinity adsorption sites in all 3 soils was low, and the Warra soil was not significantly different from the other 2 soils. The ability of the soils to retain ammonium in the soil solution against leaching [i.e. their potential buffer capacity (PBC)] did differ between soils and was greatest at Warra. This indicates that at any one time the Warra soil holds more ammonium on the exchange complex and less in solution than the other soils examined. It was concluded that ammonium is no more likely to leach through the surface horizons of the Warra soil than the other soils examined. Indeed, the data indicated that the Warra soil probably has greater capacity to retain ammonium against leaching due to its greater PBC. Consequently, it is considered unlikely that leaching of ammonium has been a major contributor to the subsoil ammonium concentrations at Warra.

Nitrification in a Vertisol subsoil and its relationship to the accumulation of ammonium-nitrogen at depth

Unusually high concentrations of ammonium have been observed in a Vertisol below 1 m depth in southeast Queensland. This study investigated the possibility that an absence of nitrification is allowing this ammonium to accumulate and persist over time, and examined the soil environmental characteristics that may be responsible for limiting nitrifying organisms. The possibility that anaerobiosis, soil acidity, soil salinity, low organic carbon concentrations, and/or an absence of active nitrifying microorganisms were responsible for limiting nitrification was examined in laboratory and field studies. The presence/absence of anaerobic conditions was determined qualitatively using a field test to give an indication of electron lability. In addition, an incubation study was conducted and soil environmental conditions were improved for nitrifying organisms by adjusting the pH from 4.4 to 7, adjusting the electrical conductivity from 1.6 to 0.5 dS/m, amending with a soluble carbon substrate at a rate of 500 mg/kg, and using microorganisms from the surface horizon to inoculate to the subsoil. Over a 180-day period no nitrification was detected in the control samples from the incubation study, indicating that an extremely low rate of nitrification is likely to be responsible for allowing ammonium to accumulate in this soil. Analysis of the effect of soil environmental conditions on nitrification revealed that anaerobic conditions did not exist at depth and that pH, EC, organic carbon, and inoculation treatments added in isolation had no effect on nitrification. However, when inoculum was added to the soil in combination with pH, a significant increase in nitrification was observed, and the greatest amount of nitrification was observed when inoculum, pH, and EC treatments were added in combination. It was concluded that the reason for the low rate of nitrification in this soil is primarily the absence of a significant population of active nitrifying microorganisms, which may have been unable to colonise the subsoil environment due to its acidic, and to a lesser extent, its saline environment.

Ammonium piperidine-1-carbodithioate

The title compound, NH(4) +center dot C(6)H(10)NS(2) -, is composed of an ammonium cation and a piperidine-1-carbodithioate anion which exhibits positional disorder. The atoms of the ring have a structural disorder and they are divided into two sites, with occupancy factors of 0.584 and 0.426.. In the crystal, the cation and anion are linked by N-H...S hydrogen bonds to form an infinite two-dimensional network.

Removal of ammonium via simultaneous nitrification-denitrification nitrite-shortcut in a single packed-bed batch reactor

A polyurethane packed-bed-biofilm sequential batch reactor was fed with synthetic substrate simulating the composition of UASB reactor effluents. Two distinct ammonia nitrogen concentrations (125 and 250 mg l(-1)) were supplied during two sequential long-term experiments of 160 days each (320 total). Cycles of 24 h under intermittent aeration for periods of 1 h were applied, and ethanol was added as a carbon source at the beginning of each anoxic period. Nitrite was the main oxidized nitrogen compound which accumulated only during the aerated phases of the batch cycle. A consistent decrease of nitrite concentration started always immediately after the interruption of oxygen supply and addition of the electron donor. Removal to below detection limits of all nitrogen soluble forms was always observed at the end of the 24 h cycles for both initial concentrations. Polyurethane packed-bed matrices and ethanol amendments conferred high process stability. Microbial investigation by cloning suggested that nitrification was carried out by Nitrosomonas-like species whereas denitrification was mediated by unclassified species commonly observed in denitrifying environments. The packed-bed batch bioreactor favored the simultaneous colonization of distinct microbial groups within the immobilized microbial biomass. The biofilm was capable of actively oxidizing ammonium and denitrification at high ratios in intermittent intervals within 24 h cycles. (c) 2008 Elsevier Ltd. All rights reserved.

Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

Evaluation of the effect of ammonium carbamate on the stability of proteins

BACKGROUND: The use of the volatile salt ammonium carbamate in protein downstream processing has recently been proposed. The main advantage of using volatile salts is that they can be removed from precipitates and liquid effluents through pressure reduction or temperature increase. Although previous studies showed that ammonium carbamate is efficient as a precipitant agent, there was evidence of denaturation in some enzymes. In this work, the effect of ammonium carbamate on the stability of five enzymes was evaluated. RESULTS: Activity assays showed that alpha-amylase (1,4-alpha-D-glucan glucanohydrolase, EC 3.2.1.1), lysozyme (1,4-beta-N-acetylmuramoylhydrolase, EC 3.2.1.17) and lipase (triacyl glycerol acyl hydrolase, EC 3.1.1.3) did not undergo activity loss in ammonium carbamate solutions with concentrations from 1.0 to 5.0 mol kg(-1), whereas cellulase complex (1,4-(1,3 : 14)-beta-D-glucan 4-glucano-hydrolase, EC 3.2.1.4) and peroxidase (hydrogen peroxide oxidoreductase, EC 1.11.1.7) showed an average activity loss of 55% and 44%, respectively. Precipitation assays did not show enzyme denaturation or phase separation for alpha-amylase and lipase, while celullase and peroxidase precipitated with some activity reduction. Analysis of similar experiments with ammonium and sodium sulfate did not affect the activity of enzymes. CONCLUSION: Celullase and peroxidase were denatured by ammonium carbamate. While more systematic studies are not available, care must be taken in designing a protein precipitation with this salt. The results suggest that the generally accepted idea that salts that denature proteins tend to solubilize them does not hold for ammonium carbamate. (C) 2010 Society of Chemical Industry

Phase equilibria of lysozyme precipitation with the volatile salt ammonium carbamate

Lysozyme precipitation induced by the addition of the volatile salt ammonium carbamate was studied through cloud-point measurements and precipitation assays. Phase equilibrium experiments were carried out at 5.0, 15.0 and 25.0 degrees C and the compositions of the coexisting phases were determined. A complete separation of the coexisting liquid and solid phases could not be achieved. Nevertheless it was possible to determine the composition of the solid precipitate through the extensions of experimental tie lines. The same precipitate was found at all temperatures. Lysozyme enzymatic activities of the supernatant and precipitate phases were also determined. The activity balance suggests that ammonium carbamate preserves lysozyme activity after the salting-out precipitation. (C) 2010 Elsevier B.V. All rights reserved.

Influence of Urea and Ammonium Sulfate on Soil Acidity Indices in Lowland Rice Production

Urea and ammonium sulfate are principal nitrogen (N) sources for crop production. Two field experiments were conducted during three consecutive years to evaluate influence of urea and ammonium sulfate application on grain yield, soil pH, calcium (Ca) saturation, magnesium (Mg) saturation, base saturation, aluminum (Al) saturation, and acidity (H + Al) saturation in lowland rice production. Grain yield was significantly influenced by urea as well as ammonium sulfate fertilization. Soil pH linearly decreased with the application of N by ammonium sulfate and urea fertilizers. However, the magnitude of the pH decrease was greater by ammonium sulfate than by urea. The Ca and Mg saturations were decreased at the greater N rates compared to low rates of N by both the fertilizer sources. The Al and acidity saturation increased with increasing N rates by both the fertilizer sources. However, these acidity indices were increased more with the application of ammonium sulfate compared with urea. Rice grain yield had negative associations with pH, Ca saturation, Mg saturation, and base saturation and positive associations with Al and acidity saturation. This indicates that rice plant is tolerant to soil acidity.

Influence of ammonium sulphate feeding time on fed-batch Arthrospira (Spirulina) platensis cultivation and biomass composition with and without pH control

Previous work demonstrated that a mixture of NH(4)Cl and KNO(3) as nitrogen source was beneficial to fed-batch Arthrospira (Spirulina) platensis cultivation, in terms of either lower costs or higher cell concentration. On the basis of those results, this study focused on the use of a cheaper nitrogen source mixture, namely (NH(4))(2)SO(4) plus NaNO(3), varying the ammonium feeding time (T = 7-15 days), either controlling the pH by CO(2) addition or not. A. platensis was cultivated in mini-tanks at 30 degrees C, 156 mu mol photons m(-2) s(-1), and starting cell concentration of 400 mg L(-1), on a modified Schlosser medium. T = 13 days under pH control were selected as optimum conditions, ensuring the best results in terms of biomass production (maximum cell concentration of 2911 mg L(-1), cell productivity of 179 mg L(-1) d(-1) and specific growth rate of 0.77 d(-1)) and satisfactory protein and lipid contents (around 30% each). (C) 2011 Elsevier Ltd. All rights reserved.

Evaluation of the composition of continuously-cultivated Arthrospira (Spirulina) platensis using ammonium chloride as nitrogen source

This work is focused on the influence of dilution rate (0.08 <= D <= 0.32 d(1)) on the continuous cultivation and biomass composition of Arthrospira (Spirulina) platensis using three different concentrations of ammonium chloride (c(No) = 1.0, 5.0 and 10 mol m (3)) as nitrogen source. At c(No) = 1.0 and 5.0 mol m (3) the biomass protein content was an increasing function of D, whereas, when using c(No) = 10 mol m (3), the highest protein content (72.5%) was obtained at D = 0.12 d (1). An overall evaluation of the process showed that biomass protein content increased with the rate of nitrogen supply (D c(No)) up to 72.5% at D c(No) = 1.20 mol m (3) d (1). Biomass lipid content was an increasing function of D only when the nitrogen source was the limiting factor for the growth (D c(No) <= 0.32 mol m (-3) d (1)), which occurred solely with c(No), = 1.0 mol m (3). Under such conditions, A. platensis reduced its nitrogen reserve in the form of proteins, while maintaining almost unvaried its lipid content. The latter was affected only when the concentration of nitrogen was extremely low (c(No) = 1.0 mol m (3)). The most abundant fatty acids were the palmitic (45.8 +/- 5.20%) and the gamma-linolenic (20.1 +/- 2.00%) ones. No significant alteration in the profiles either of saturated or unsaturated fatty acids was observed with c(No) <= 5.0 mol m (3), prevailing those with 16 and 18 carbons. (C) 2010 Elsevier Ltd. All rights reserved.

A New Approach to Ammonium Sulphate Feeding for Fed-Batch Arthrospira (Spirulina) platensis Cultivation in Tubular Photobioreactor

Arthrospira platensis was cultivated in tubular photobioreactor using different photosynthetic photon flux densities (PPFD) and protocols of (NH(4))(2)SO(4) fed-hatch supply. Results were evaluated by variance analysis selecting maximum cell concentration (X(m)), cell productivity (P(x)), nitrogen-to-cell conversion factor (Y(X/N)) and biomass, protein and lipid contents as responses. At PPFD of 120 and 240 mu mol-photons/m(2) s, a parabolic profile of (NH(4))(2)SO(4) addition aiming at producing biomass with 7% nitrogen content ensured X(m) values (14.1 and 12.2 g/L, respectively) comparable to those obtained with NaNO(3). At PPFD of 240 mu mol-photons/m(2) s, P(x) (1.69 g/Ld) was 36% higher, although the photosynthetic efficiency (3.0%) was less than one-half that at PPFD of 120 mu mol-photons/m(2) s. Biomass was shown to be constituted by about 35% proteins and 10% lipids, without any dependence on PPFD or kind of nitrogen source. These results highlight the possible use of (NH(4))(2)SO(4) as alternative, cheap nitrogen source for A. platensis cultivation in tubular photobioreactors. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 26: 1271-1277, 2010

Fed-batch cultivation of Arthrospira (Spirulina) platensis: Potassium nitrate and ammonium chloride as simultaneous nitrogen sources

Arthrospira platensis was cultivated in minitanks at 13 klux, using a mixture of KNO(3) and NH(4)Cl as nitrogen source. Fed-batch daily supply of NH(4)Cl at exponentially-increasing feeding rate allowed preventing ammonia toxicity and nitrogen deficiency, providing high maximum cell concentration (X(m)) and high-quality biomass (21.85 mg chlorophyll g cells(-1); 20.5% lipids; 49.8% proteins). A central composite design combined to response surface methodology was utilized to determine the relationships between responses (X(m), cell productivity and nitrogen-to-cell conversion factor) and independent variables (KNO(3) and NH(4)Cl concentrations). Under optimum conditions (15.5 mM KNO3; 14.1 mM NH(4)Cl), X(m) was 4327 mg L(-1), a value almost coincident with that obtained with only 25.4 mM KNO(3), but more than twice that obtained with 21.5 mM NH(4)Cl. A 30%-reduction of culture medium cost can be estimated when compared to KNO(3)-batch runs, thus behaving as a cheap alternative for the commercial production of this cyanobacterium. (C) 2010 Elsevier Ltd. All rights reserved.