Hydrazine-hydrate intercalated halloysite under controlled-rate thermal analysis conditions

The thermal behaviour of halloysite fully expanded with hydrazine-hydrate has been investigated in nitrogen atmosphere under dynamic heating and at a constant, pre-set decomposition rate of 0.15 mg min-1. Under controlled-rate thermal analysis (CRTA) conditions it was possible to resolve the closely overlapping decomposition stages and to distinguish between adsorbed and bonded reagent. Three types of bonded reagent could be identified. The loosely bonded reagent amounting to 0.20 mol hydrazine-hydrate per mol inner surface hydroxyl is connected to the internal and external surfaces of the expanded mineral and is present as a space filler between the sheets of the delaminated mineral. The strongly bonded (intercalated) hydrazine-hydrate is connected to the kaolinite inner surface OH groups by the formation of hydrogen bonds. Based on the thermoanalytical results two different types of bonded reagent could be distinguished in the complex. Type 1 reagent (approx. 0.06 mol hydrazine-hydrate/mol inner surface OH) is liberated between 77 and 103°C. Type 2 reagent is lost between 103 and 227°C, corresponding to a quantity of 0.36 mol hydrazine/mol inner surface OH. When heating the complex to 77°C under CRTA conditions a new reflection appears in the XRD pattern with a d-value of 9.6 Å, in addition to the 10.2 Ĺ reflection. This new reflection disappears in contact with moist air and the complex re-expands to the original d-value of 10.2 Å in a few h. The appearance of the 9.6 Å reflection is interpreted as the expansion of kaolinite with hydrazine alone, while the 10.2 Å one is due to expansion with hydrazine-hydrate. FTIR (DRIFT) spectroscopic results showed that the treated mineral after intercalation/deintercalation and heat treatment to 300°C is slightly more ordered than the original (untreated) clay.

GIS-based mapping and statistical analysis of air pollution and mortality in Brisbane, Australia

In this thesis, the relationship between air pollution and human health has been investigated utilising Geographic Information System (GIS) as an analysis tool. The research focused on how vehicular air pollution affects human health. The main objective of this study was to analyse the spatial variability of pollutants, taking Brisbane City in Australia as a case study, by the identification of the areas of high concentration of air pollutants and their relationship with the numbers of death caused by air pollutants. A correlation test was performed to establish the relationship between air pollution, number of deaths from respiratory disease, and total distance travelled by road vehicles in Brisbane. GIS was utilized to investigate the spatial distribution of the air pollutants. The main finding of this research is the comparison between spatial and non-spatial analysis approaches, which indicated that correlation analysis and simple buffer analysis of GIS using the average levels of air pollutants from a single monitoring station or by group of few monitoring stations is a relatively simple method for assessing the health effects of air pollution. There was a significant positive correlation between variable under consideration, and the research shows a decreasing trend of concentration of nitrogen dioxide at the Eagle Farm and Springwood sites and an increasing trend at CBD site. Statistical analysis shows that there exists a positive relationship between the level of emission and number of deaths, though the impact is not uniform as certain sections of the population are more vulnerable to exposure. Further statistical tests found that the elderly people of over 75 years age and children between 0-15 years of age are the more vulnerable people exposed to air pollution. A non-spatial approach alone may be insufficient for an appropriate evaluation of the impact of air pollutant variables and their inter-relationships. It is important to evaluate the spatial features of air pollutants before modeling the air pollution-health relationships.

Measuring and decomposing changes in agricultural productivity, nitrogen use efficiency and cumulative exergy efficiency: Application to OECD agriculture

This paper uses an aggregate quantity space to decompose the temporal changes in nitrogen use efficiency and cumulative exergy use efficiency into changes of Moorsteen–Bjurek (MB) Total Factor Productivity (TFP) changes and changes in the aggregate nitrogen and cumulative exergy contents. Changes in productivity can be broken into technical change and changes in various efficiency measures such as technical efficiency, scale efficiency and residual mix efficiency. Changes in the aggregate nitrogen and cumulative exergy contents can be driven by changes in the quality of inputs and outputs and changes in the mixes of inputs and outputs. Also with cumulative exergy content analysis, changes in the efficiency in input production can increase or decrease the cumulative exergy transformity of agricultural production. The empirical study in 30 member countries of the Organisation for Economic Co-operation Development from 1990 to 2003 yielded some important findings. The production technology progressed but there were reductions in technical efficiency, scale efficiency and residual mix efficiency levels. This result suggests that the production frontier had shifted up but there existed lags in the responses of member countries to the technological change. Given TFP growth, improvements in nutrient use efficiency and cumulative exergy use efficiency were counteracted by reductions in the changes of the aggregate nitrogen contents ratio and aggregate cumulative exergy contents ratio. The empirical results also confirmed that different combinations of inputs and outputs as well as the quality of inputs and outputs could have more influence on the growth of nutrient and cumulative exergy use efficiency than factors that had driven productivity change. Keywords: Nutrient use efficiency; Cumulative exergy use efficiency; Thermodynamic efficiency change; Productivity growth; OECD agriculture; Sustainability

Particulate air pollution and cardiorespiratory hospital admissions in a temperate Australian city: A case-crossover analysis

Although ambient air pollution exposure has been linked with poor health in many parts of the world, no previous study has investigated the effect on morbidity in the city of Adelaide, South Australia. To explore the association between particulate matter (PM) and hospitalisations, including respiratory and cardiovascular admissions in Adelaide, South Australia. Methods: For the study period September 2001 to October 2007, daily counts of all-cause, cardiovascular and respiratory hospital admissions were collected, as well as daily air quality data including concentrations of particulates, ozone and nitrogen dioxide. Visibility codes for presentweather conditions identified dayswhen airborne dust or smoke was observed. The associations between PM and hospitalisations were estimated using timestratified case-crossover analyses controlling for covariates including temperature, relative humidity, other pollutants, day of the week and public holidays. Mean PM10 concentrations were higher in the warm season, whereas PM2.5 concentrations were higher in the cool season. Hospital admissions were associated with PM10 in the cool season and with PM2.5 in both seasons. No significant effect of PM on all-age respiratory admissions was detected, however cardiovascular admissions were associated with both PM2.5 and PM10 in the cool season with the highest effects for PM2.5 (4.48%, 95% CI: 0.74%, 8.36% increase per 10 μg/m3 increase in PM2.5). These findings suggest that despite the city's relatively low levels of air pollution, PMconcentrations are associated with increases in morbidity in Adelaide. Further studies are needed to investigate the sources of PM which may be contributing to the higher cool season effects.

Environmental and economic evaluation of N fertilizer rates in a maize crop in Italy : a spatial and temporal analysis using crop models

Crop simulation models have the potential to assess the risk associated with the selection of a specific N fertilizer rate, by integrating the effects of soil-crop interactions on crop growth under different pedo-climatic and management conditions. The objective of this study was to simulate the environmental and economic impact (nitrate leaching and N2O emissions) of a spatially variable N fertilizer application in an irrigated maize field in Italy. The validated SALUS model was run with 5 nitrogen rates scenarios, 50, 100, 150, 200, and 250 kg N ha−1, with the latter being the N fertilization adopted by the farmer. The long-term (25 years) simulations were performed on two previously identified spatially and temporally stable zones, a high yielding and low yielding zone. The simulation results showed that N fertilizer rate can be reduced without affecting yield and net return. The marginal net return was on average higher for the high yield zone, with values ranging from 1550 to 2650 € ha−1 for the 200 N and 1485 to 2875 € ha−1 for the 250 N. N leaching varied between 16.4 and 19.3 kg N ha−1 for the 200 N and the 250 N in the high yield zone. In the low yield zone, the 250 N had a significantly higher N leaching. N2O emissions varied between 0.28 kg N2O ha−1 for the 50 kg N ha−1 rate to a maximum of 1.41 kg N2O ha−1 for the 250 kg N ha−1 rate.

Genomic organisation, activity and distribution analysis of the microbial putrescine oxidase degradation pathway

The catalytic action of putrescine specific amine oxidases acting in tandem with 4-aminobutyraldehyde dehydrogenase is explored as a degradative pathway in Rhodococcus opacus. By limiting the nitrogen source, increased catalytic activity was induced leading to a coordinated response in the oxidative deamination of putrescine to 4-aminobutyraldehyde and subsequent dehydrogenation to 4-aminobutyrate. Isolating the dehydrogenase by ion exchange chromatography and gel filtration revealed that the enzyme acts principally on linear aliphatic aldehydes possessing an amino moiety. Michaelis-Menten kinetic analysis delivered a Michaelis constant (KM=0.014mM) and maximum rate (Vmax=11.2μmol/min/mg) for the conversion of 4-aminobutyraldehyde to 4-aminobutyrate. The dehydrogenase identified by MALDI-TOF mass spectrometric analysis (E value=0.031, 23% coverage) belongs to a functionally related genomic cluster that includes the amine oxidase, suggesting their association in a directed cell response. Key regulatory, stress and transport encoding genes have been identified, along with candidate dehydrogenases and transaminases for the further conversion of 4-aminobutyrate to succinate. Genomic analysis has revealed highly similar metabolic gene clustering among members of Actinobacteria, providing insight into putrescine degradation notably among Micrococcaceae, Rhodococci and Corynebacterium by a pathway that was previously uncharacterised in bacteria.

Analysis of photoluminescence background of Raman spectra of carbon nanotips grown by plasma-enhanced chemical vapor deposition

Carbon nanotips with different structures were synthesized by plasma-enhanced hot filament chemical vapor deposition and plasma-enhanced chemical vapor deposition using different deposition conditions, and they were investigated by scanning electron microscopy and Raman spectroscopy. The results indicate that the photoluminescence background of the Raman spectra is different for different carbon nanotips. Additionally, the Raman spectra of the carbon nanotips synthesized using nitrogen-containing gas precursors show a peak located at about 2120 cm-1 besides the common D and G peaks. The observed difference in the photoluminescence background is related to the growth mechanisms, structural properties, and surface morphology of a-C:H and a-C:H:N nanotips, in particular, the sizes of the emissive tips.

Dynamics of nitrogen and suspended solids removal in experimental stormwater biofilters under intermittent wetting and drying

This research study comprehensively analyses the dynamics of nitrogen and suspended solids removal in stormwater biofilters. The study focuses on pollutant removal during an event with time, rather than the conventional event-mean analysis. Antecedent dry days (number of days in between rainfall) during which biofilters remain dry and the inflow concentration of pollutants were two other important variables analysed in this study. The research outcome highlights the significance of dry-phase processes and the process of stabilization on filter performance and sets a paradigm shift from the current approach towards an innovative way of performance analysis of biofilters.

Removal characteristics of ammonium nitrogen from wastewater by modified Ca-bentonites

A modified inorganic bentonite (Na/Al) based on purified Ca-bentonite was prepared through exchanging Al and Na ions in the interlayer space of Ca-bentonite. The structural properties of purified and modified bentonites were characterized by XRD and SEM analysis. Batch experiments were performed for the adsorption of ammonium nitrogen and different experimental conditions were studied in order to investigate the optimum adsorption conditions. Comparative experiments were also carried out for natural Ca-bentonite (RB), unmodified purified bentonite (PB) and modified purified bentonite (MB). Through the thermodynamic analysis, the ammonium nitrogen adsorption process can be spontaneous, the standard heat was −41.46kJmol −1 , and the adsorption process based on ion exchange adsorption. The ammonium nitrogen adsorption capacity of MB (46.904mg/g) was improved compared to raw bentonite (RB) (26.631mg/g), which was among the highest values of ammonium nitrogen adsorption compared with other adsorbents according to the literatures. The described process provides a potential pathway for the removal of ammonium nitrogen at low concentrations encountered in most natural waters.

Anthropogenic nitrogen deposition predicts local grassland primary production worldwide

Humans dominate many important Earth system processes including the nitrogen (N) cycle. Atmospheric N deposition affects fundamental processes such as carbon cycling, climate regulation, and biodiversity, and could result in changes to fundamental Earth system processes such as primary production. Both modelling and experimentation have suggested a role for anthropogenically altered N deposition in increasing productivity, nevertheless, current understanding of the relative strength of N deposition with respect to other controls on production such as edaphic conditions and climate is limited. Here we use an international multiscale data set to show that atmospheric N deposition is positively correlated to aboveground net primary production (ANPP) observed at the 1-m2 level across a wide range of herbaceous ecosystems. N deposition was a better predictor than climatic drivers and local soil conditions, explaining 16% of observed variation in ANPP globally with an increase of 1 kg N·ha-1·yr-1 increasing ANPP by 3%. Soil pH explained 8% of observed variation in ANPP while climatic drivers showed no significant relationship. Our results illustrate that the incorporation of global N deposition patterns in Earth system models are likely to substantially improve estimates of primary production in herbaceous systems. In herbaceous systems across the world, humans appear to be partially driving local ANPP through impacts on the N cycle.

Geometry Of Proline And Hydroxyproline .1. An Analysis Of X-Ray Crystal-Structure Data

We have carried out an analysis of crystal structure data on prolyl and hydroxyprolyl moieties in small molecules. The flexibility of the pyrrolidine ring due to the pyramidal character of nitrogen has been defined in terms of two projection angles δ1 and δ2. The distribution of these parameters in the crystal structures is found to be consistent with results of the energy calculations carried out on prolyl moieties in our laboratory.

Remote sensing of nitrogen and water stress in wheat

Nitrogen (N) is the largest agricultural input in many Australian cropping systems and applying the right amount of N in the right place at the right physiological stage is a significant challenge for wheat growers. Optimizing N uptake could reduce input costs and minimize potential off-site movement. Since N uptake is dependent on soil and plant water status, ideally, N should be applied only to areas within paddocks with sufficient plant available water. To quantify N and water stress, spectral and thermal crop stress detection methods were explored using hyperspectral, multispectral and thermal remote sensing data collected at a research field site in Victoria, Australia. Wheat was grown over two seasons with two levels of water inputs (rainfall/irrigation) and either four levels (in 2004; 0, 17, 39 and 163 kg/ha) or two levels (in 2005; 0 and 39 kg/ha N) of nitrogen. The Canopy Chlorophyll Content Index (CCCI) and modified Spectral Ratio planar index (mSRpi), two indices designed to measure canopy-level N, were calculated from canopy-level hyperspectral data in 2005. They accounted for 76% and 74% of the variability of crop N status, respectively, just prior to stem elongation (Zadoks 24). The Normalised Difference Red Edge (NDRE) index and CCCI, calculated from airborne multispectral imagery, accounted for 41% and 37% of variability in crop N status, respectively. Greater scatter in the airborne data was attributable to the difference in scale of the ground and aerial measurements (i.e., small area plant samples against whole-plot means from imagery). Nevertheless, the analysis demonstrated that canopy-level theory can be transferred to airborne data, which could ultimately be of more use to growers. Thermal imagery showed that mean plot temperatures of rainfed treatments were 2.7 °C warmer than irrigated treatments (P < 0.001) at full cover. For partially vegetated fields, the two-Dimensional Crop Water Stress Index (2D CWSI) was calculated using the Vegetation Index-Temperature (VIT) trapezoid method to reduce the contribution of soil background to image temperature. Results showed rainfed plots were consistently more stressed than irrigated plots. Future work is needed to improve the ability of the CCCI and VIT methods to detect N and water stress and apply both indices simultaneously at the paddock scale to test whether N can be targeted based on water status. Use of these technologies has significant potential for maximising the spatial and temporal efficiency of N applications for wheat growers. ‘Ground–breaking Stuff’- Proceedings of the 13th Australian Society of Agronomy Conference, 10-14 September 2006, Perth, Western Australia.

Analysis of high yielding maize production - A study based on a commercial crop

This paper reports on the use of APSIM - Maize for retrospective analysis of performance of a high input, high yielding maize crop and analysis of predicted performance of maize grown with high inputs over the long-term (>100 years) for specified scenarios of environmental conditions (temperature and radiation) and agronomic inputs (sowing date, plant population, nitrogen fertiliser and irrigation) at Boort, Victoria, Australia. It uses a high yielding (17 400 kg/ha dry grain, 20 500 kg/ha at 15% water) commercial crop grown in 2004-05 as the basis of the study. Yield for the agronomic and environmental conditions of 2004-05 was predicted accurately, giving confidence that the model could be used for the detailed analyses undertaken. The analysis showed that the yield achieved was close to that possible with the conditions and agronomic inputs of 2004-05. Sowing dates during 21 September to 26 October had little effect on predicted yield, except when combined with reduced temperature. Single year and long-term analyses concluded that a higher plant population (11 plants/m2) is needed to optimise yield, but that slightly lower N and irrigation inputs are appropriate for the plant population used commercially (8.4 plants/m2). Also, compared with changes in agronomic inputs increases in temperature and/or radiation had relatively minor effects, except that reduced temperature reduces predicted yield substantially. This study provides an approach for the use of models for both retrospective analysis of crop performance and assessment of long-term variability of crop yield under a wide range of agronomic and environmental conditions.

Functional dynamics of the nitrogen balance of sorghum: I. N demand of vegetative plant parts.

Stay-green, an important trait for grain yield of sorghum grown under water limitation, has been associated with a high leaf nitrogen content at the start of grain filling. This study quantifies the N demand of leaves and stems and explores effects of N stress on the N balance of vegetative plant parts of three sorghum hybrids differing in potential crop height. The hybrids were grown under well-watered conditions at three levels of N supply. Vertical profiles of biomass and N% of leaves and stems, together with leaf size and number, and specific leaf nitrogen (SLN), were measured at regular intervals. The hybrids had similar minimum but different critical and maximum SLN, associated with differences in leaf size and N partitioning, the latter associated with differences in plant height. N demand of expanding new leaves was represented by critical SLN, and structural stem N demand by minimum stem N%. The fraction of N partitioned to leaf blades increased under N stress. A framework for N dynamics of leaves and stems is developed that captures effects of N stress and genotype on N partitioning and on critical and maximum SLN.