Complexes of lanthanide nitrates with 2-N-(6-picoIyl)-benzamide

New complexes of lanthanide nitrates with 2-N-(6-picolyl)-benzamide of the formulae Ln2[6-pic-BA], [NO3l6 (Ln = Y and La-Yb) have been prepared and characterised by chemical analysis, infrared, molar conductance and electronic spectral data. Molar conductance data along with IR data point to the presence of co-ordinated nitrate groups. IR spectra prove the bidentate co-ordination of the ligand to the metal ion, through the oxygen of the secondary amide and the nitrogen of the heterocyclic ring. Electronic spectral studies in the visible region suggest an eight co-ordinate geometry around the metal ions.

Metabolite mobilization in the stem galls of Parthenium hysterophorus induced by Epiblema strenuana inferred from the signatures of isotopic carbon and nitrogen and concentrations of total non-structural carbohydrates

Parthenium hysterophorus L. (Asteraceae) is a weed of national significance in Australia. Among the several arthropod agents introduced into Australia to control populations of P. hysterophorus biologically, Epiblema strenuana Walker (Lepidoptera: Tortricidae) is the most widespread and abundant agent. By intercepting the normal transport mechanisms of P. hysterophorus, the larvae of E. strenuana drain nutrients, other metabolic products, and energy, and place the host plant under intense metabolic stress. In this study, determinations of total non-structural carbohydrates (TNC) levels and carbon and nitrogen isotope ratios of fixed products in different parts of the plant tissue, including the gall, have been made to establish the function of gall as a sink for the nutrients. Values of δ13C and δ15N in galls were significantly different than those in proximal and distal stems, whereas the TNC levels were insignificant, when measured in the total population of P. hysterophorus, regardless of plant age. However, carbon, nitrogen, and TNC signatures presented significant results, when assayed in different developmental stages of P. hysterophorus. Carbon isotope ratios in galls were consistently more negative than those from the compared plant organs. Nitrogen isotope ratios in galls, on the contrary, were either similar to or less negative than the compared plant organs, especially within a single host-plant stage population (i.e., either rosette, preflowering, or flowering stage). TNC levels varied within compared plant populations. The stem distal to the gall functioned more efficiently as a nodal channel than the stem proximal to the gall, especially in the translocation of nitrogenous nutrients. Our findings indicate that the gall induced by E. strenuana functions as a sink for the assayed nutrients, although some variations have been observed in the patterns of nutrient mobilization. By creating a sink for the nutrients in the gall, E. strenuana is able to place the overall plant metabolism under stress, and this ability indicates E. strenuana has the necessary potential for use as a biological-control agent.

Functional dynamics of the nitrogen balance of sorghum. II. Grain filling period.

Maintenance of green leaf area during grain filling can increase grain yield of sorghum grown under terminal water limitation. This 'stay-green' trait has been related to the nitrogen (N) supply-demand balance during grain filling. This study quantifies the N demand of grain and N translocation rates from leaves and stem and explores effects of genotype and N stress on onset and rate of leaf senescence during the grain filling period. Three hybrids differing in potential height were grown at three levels of N supply under well-watered conditions. Vertical profiles of biomass, leaf area, and N% of leaves, stem and grain were measured at regular intervals. Weekly SPAD chlorophyll readings on main shoot leaves were correlated with observed specific leaf nitrogen (SLN) to derive seasonal patterns of leaf N content. For all hybrids, individual grain N demand was sink determined and was initially met through N translocation from the stem and rachis. Only if this was insufficient did leaf N translocation occur. Maximum N translocation rates from leaves and stem were dependent on their N status. However, the supply of N at canopy scale was also related to the amount of leaf area senescing at any one time. This supply-demand framework for N dynamics explained effects of N stress and genotype on the onset and rate of leaf senescence.

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.

Losses of nitrogen in surface runoff from a plantation horticulture farm in coastal Queensland, Australia.

Surface losses of nitrogen from horticulture farms in coastal Queensland, Australia, may have the potential to eutrophy sensitive coastal marine habitats nearby. A case-study of the potential extent of such losses was investigated in a coastal macadamia plantation. Nitrogen losses were quantified in 5 consecutive runoff events during the 13-month study. Irrigation did not contribute to surface flows. Runoff was generated by storms at combined intensities and durations that were 20–40 mm/h for >9 min. These intensities and durations were within expected short-term (1 year) and long-term (up to 20 years) frequencies of rainfall in the study area. Surface flow volumes were 5.3 ± 1.1% of the episodic rainfall generated by such storms. Therefore, the largest part of each rainfall event was attributed to infiltration and drainage in this farm soil (Kandosol). The estimated annual loss of total nitrogen in runoff was 0.26 kg N/ha.year, representing a minimal loading of nitrogen in surface runoff when compared to other studies. The weighted average concentrations of total sediment nitrogen (TSN) and total dissolved nitrogen (TDN) generated in the farm runoff were 2.81 ± 0.77% N and 1.11 ± 0.27 mg N/L, respectively. These concentrations were considerably greater than ambient levels in an adjoining catchment waterway. Concentrations of TSN and TDN in the waterway were 0.11 ± 0.02% N and 0.50 ± 0.09 mg N/L, respectively. The steep concentration gradient of TSN and TDN between the farm runoff and the waterway demonstrated the occurrence of nutrient loading from the farming landscapes to the waterway. The TDN levels in the stream exceeded the current specified threshold of 0.2–0.3 mg N/L for eutrophication of such a waterway. Therefore, while the estimate of annual loading of N from runoff losses was comparatively low, it was evident that the stream catchment and associated agricultural land uses were already characterised by significant nitrogen loadings that pose eutrophication risks. The reported levels of nitrogen and the proximity of such waterways (8 km) to the coastline may have also have implications for the nearshore (oligotrophic) marine environment during periods of turbulent flow.

Measuring and predicting canopy nitrogen nutrition in wheat using a spectral index—The canopy chlorophyll content index (CCCI).

Varying the spatial distribution of applied nitrogen (N) fertilizer to match demand in crops has been shown to increase profits in Australia. Better matching the timing of N inputs to plant requirements has been shown to improve nitrogen use efficiency and crop yields and could reduce nitrous oxide emissions from broad acre grains. Farmers in the wheat production area of south eastern Australia are increasingly splitting N application with the second timing applied at stem elongation (Zadoks 30). Spectral indices have shown the ability to detect crop canopy N status but a robust method using a consistent calibration that functions across seasons has been lacking. One spectral index, the canopy chlorophyll content index (CCCI) designed to detect canopy N using three wavebands along the "red edge" of the spectrum was combined with the canopy nitrogen index (CNI), which was developed to normalize for crop biomass and correct for the N dilution effect of crop canopies. The CCCI-CNI index approach was applied to a 3-year study to develop a single calibration derived from a wheat crop sown in research plots near Horsham, Victoria, Australia. The index was able to predict canopy N (g m-2) from Zadoks 14-37 with an r2 of 0.97 and RMSE of 0.65 g N m-2 when dry weight biomass by area was also considered. We suggest that measures of N estimated from remote methods use N per unit area as the metric and that reference directly to canopy %N is not an appropriate method for estimating plant concentration without first accounting for the N dilution effect. This approach provides a link to crop development rather than creating a purely numerical relationship. The sole biophysical input, biomass, is challenging to quantify robustly via spectral methods. Combining remote sensing with crop modelling could provide a robust method for estimating biomass and therefore a method to estimate canopy N remotely. Future research will explore this and the use of active and passive sensor technologies for use in precision farming for targeted N management.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

The performance of irrigated mixtures of tall fescue, ryegrass and white clover in subtropical Australia. 1. The effects of sowing mixture combinations, nitrogen and oversowing on establishment, productivity, botanical composition and persistence.

In the subtropics of Australia, the ryegrass component of irrigated perennial ryegrass (Lolium perenne) - white clover (Trifolium repens) pastures declines by approximately 40% in the summer following establishment, being replaced by summer-active C4 grasses. Tall fescue (Festuca arundinacea) is more persistent than perennial ryegrass and might resist this invasion, although tall fescue does not compete vigorously as a seedling. This series of experiments investigated the influence of ryegrass and tall fescue genotype, sowing time and sowing mixture as a means of improving tall fescue establishment and the productivity and persistence of tall fescue, ryegrass and white clover-based mixtures in a subtropical environment. Tall fescue frequency at the end of the establishment year decreased as the number of companion species sown in the mixture increased. Neither sowing mixture combinations nor sowing rates influenced overall pasture yield (of around 14 t/ha) in the establishment year but had a significant effect on botanical composition and component yields. Perennial ryegrass was less competitive than short-rotation ryegrass, increasing first-year yields of tall fescue by 40% in one experiment and by 10% in another but total yield was unaffected. The higher establishment-year yield (3.5 t/ha) allowed Dovey tall fescue to compete more successfully with the remaining pasture components than Vulcan (1.4 t/ha). Sowing 2 ryegrass cultivars in the mixture reduced tall fescue yields by 30% compared with a single ryegrass (1.6 t/ha), although tall fescue alone achieved higher yields (7.1 t/ha). Component sowing rate had little influence on composition or yield. Oversowing the ryegrass component into a 6-week-old sward of tall fescue and white clover improved tall fescue, white clover and overall yields in the establishment year by 83, 17 and 11%, respectively, but reduced ryegrass yields by 40%. The inclusion of red (T. pratense) and Persian (T. resupinatum) clovers and chicory (Cichorium intybus) increased first-year yields by 25% but suppressed perennial grass and clover components. Yields were generally maintained at around 12 t/ha/yr in the second and third years, with tall fescue becoming dominant in all 3 experiments. The lower tall fescue seeding rate used in the first experiment resulted in tall fescue dominance in the second year following establishment, whereas in Experiments 2 and 3 dominance occurred by the end of the first year. Invasion by the C4 grasses was relatively minor (<10%) even in the third year. As ryegrass plants died, tall fescue and, to a lesser extent, white clover increased as a proportion of the total sward. Treatment effects continued into the second, but rarely the third, year and mostly affected the yield of one of the components rather than total cumulative yield. Once tall fescue became dominant, it was difficult to re-introduce other pasture components, even following removal of foliage and moderate renovation. Severe renovation (reducing the tall fescue population by at least 30%) seems a possible option for redressing this situation.

Modelling the nitrogen-driven trade-off between nitrogen utilisation efficiency and water use efficiency of wheat in eastern Australia.

The nitrogen-driven trade-off between nitrogen utilisation efficiency (yield per unit nitrogen uptake) and water use efficiency (yield per unit evapotranspiration) is widespread and results from well established, multiple effects of nitrogen availability on the water, carbon and nitrogen economy of crops. Here we used a crop model (APSIM) to simulate the yield, evapotranspiration, soil evaporation and nitrogen uptake of wheat, and analysed yield responses to water, nitrogen and climate using a framework analogous to the rate-duration model of determinate growth. The relationship between modelled grain yield (Y) and evapotranspiration (ET) was fitted to a linear-plateau function to derive three parameters: maximum yield (Ymax), the ET break-point when yield reaches its maximum (ET#), and the rate of yield response in the linear phase ([Delta]Y/[Delta]ET). Against this framework, we tested the hypothesis that nitrogen deficit reduces maximum yield by reducing both the rate ([Delta]Y/[Delta]ET) and the range of yield response to evapotranspiration, i.e. ET# - Es, where Es is modelled median soil evaporation. Modelled data reproduced the nitrogen-driven trade-off between nitrogen utilisation efficiency and water use efficiency in a transect from Horsham (36°S) to Emerald (23°S) in eastern Australia. Increasing nitrogen supply from 50 to 250 kg N ha-1 reduced yield per unit nitrogen uptake from 29 to 12 kg grain kg-1 N and increased yield per unit evapotranspiration from 6 to 15 kg grain ha-1 mm-1 at Emerald. The same increment in nitrogen supply reduced yield per unit nitrogen uptake from 30 to 25 kg grain kg-1 N and increased yield per unit evapotranspiration from 6 to 25 kg grain ha-1 mm-1 at Horsham. Maximum yield ranged from 0.9 to 6.4 t ha-1. Consistent with our working hypothesis, reductions in maximum yield with nitrogen deficit were associated with both reduction in the rate of yield response to ET and compression of the range of yield response to ET. Against the notion of managing crops to maximise water use efficiency in low rainfall environments, we emphasise the trade-off between water use efficiency and nitrogen utilisation efficiency, particularly under conditions of high nitrogen-to-grain price ratio. The rate-range framework to characterise the relationship between yield and evapotranspiration is useful to capture this trade-off as the parameters were responsive to both nitrogen supply and climatic factors.

Gaseous Nitrogen Losses Following Soil Amendment with Biosolids under Controlled Conditions.

This paper quantifies gaseous N losses due to ammonia volatilisation and denitrification under controlled conditions at 30 degrees C and 75% to 150% of Field Capacity (FC). Biosolids were mixed with two contrasting soils from subtropical Australia at a rate designed to meet crop N requirements for irrigated cotton or maize (i.e., equivalent to 180 kg N ha(-1)). In the first experiment, aerobically (AE) and anaerobically (AN) digested biosolids were mixed into a heavy Vertosol soil and then incubated for 105 days. Ammonia volatilization over 72 days accounted for less than 4% of the applied NH4-N but 24% (AN) to 29% (AE) of the total applied biosolids' N was lost through denitrification in 105 days. In the second experiment AN biosolids with and without added polyacrimide polymer were mixed with either a heavy Vertosol or a lighter Red Ferrosol and then incubated for 98 days. The N loss was higher from the Vertosol with 16-29% of total N applied versus the Red Ferrosol with 7-10% of total N applied, while addition of polymer to the biosolids increased N loss from 7 to 10% and from 16 to 29% in the Red Ferrosol and Vertosol, respectively. A major product from the denitrification process was N-2 gas, accounting for >90% of the emitted N gases from both experiments. Our findings demonstrate that denitrification could be a major pathway of gaseous N losses under warm and moist conditions.

Nutritional constraints on displacement of Fusarium pseudograminearum from cereal straw by antagonists.

Displacement of the fungus Fusarium pseudograminearum from stubble by antagonists is a potential means of biocontrol of crown rot in cereals. The role of carbon and nitrogen nutrition in interactions between the pathogen and the antagonists Fusarium equiseti, Fusarium nygamai, Trichoderma harzianum and the non-antagonistic straw fungus Alternaria infectoria was investigated. Sole carbon source utilization patterns on Biolog plates were similar among the three Fusarium species, suggesting a possible role for competition. However, carbon niche overlap was unlikely to be important in antagonism by T. harzianum. Straw medium supplemented with sugars generally reduced the inhibitory effect of antagonists on growth of F. pseudograminearum in dual culture, indicating that availability of simple carbon sources does not limit antagonism. Adding nitrogen as urea, nitrate or ammonium to straw medium had little effect on antagonism by F. equiseti and F. nygamai, but ammonium addition removed the inhibitory effect of T. harzianum on growth of F. pseudograminearum. Displacement of F. pseudograminearum from straw by all fungi in a Petri dish assay was greater when urea or nitrate was used as a nitrogen source than with ammonium. All forms of nitrogen significantly increased displacement of F. pseudograminearum from straw under simulated field conditions when straws were either inoculated with T. harzianum or exposed to resident soil microbes. However, in 2 out of 3 experiments urea and nitrate were more effective than ammonium. The results suggest that availability of nitrogen, but not carbon, is limiting the activities of antagonists of F. pseudograminearum in straw, and the way nitrogen is applied can influence the rate of displacement and mortality of the pathogen in host residues.

DFT study of electronic and optical properties of anatase titanium dioxide tuned by nitrogen and lithium co-doping

The electronic and optical properties of anatase titanium dioxide (TiO2), co-doped by nitrogen (N) and lithium (Li), have been investigated by density functional theory plus Hubbard correction term U, namely DFT+U. It is found that Li-dopants can effectively balance the net charges brought by N-dopants and shift the local state to the top of valence band. Depending on the distribution of dopants, the adsorption edges of TiO2 may be red- or blue-shifted, being consistent with recent experimental observations.

Thermoanalysis of ammonium perchlorate and sodium nitrate mixture

A binary mixture of ammonium perchlorate-sodium nitrate in molar proportion undergoes partial fusion at 223°C and the transformation of the mixture to sodium perchlorate-ammonium nitrate occurs in the broad endothermic region. The mixture was heated and quenched at various temperatures in a differential thermal analysis assembly. Thermogravimetric analysis, X-ray diffraction, and infrared spectroscopic techniques were used to determine the composition of the quenched sample in order to explain the overall thermal phenomenon. Visual observations of the morphological changes that occur during the course of heating were made using a hot-stage microscope, 30–350°C.

Rice husk biochar and crop residue amendment in subtropical cropping soils: Effect on biomass production, nitrogen use efficiency and greenhouse gas emissions

We investigated the effect of maize residues and rice husk biochar on biomass production, fertiliser nitrogen recovery (FNR) and nitrous oxide (N2O) emissions for three different subtropical cropping soils. Maize residues at two rates (0 and 10 t ha−1) combined with three rates (0, 15 and 30 t ha-1) of rice husk biochar were added to three soil types in a pot trial with maize plants. Soil N2O emissions were monitored with static chambers for 91 days. Isotopic 15N-labelled urea was applied to the treatments without added crop residues to measure the FNR. Crop residue incorporation significantly reduced N uptake in all treatments but did not affect overall FNR. Rice husk biochar amendment had no effect on plant growth and N uptake but significantly reduced N2O and carbon dioxide (CO2) emissions in two of the three soils. The incorporation of crop residues had a contrasting effect on soil N2O emissions depending on the mineral N status of the soil. The study shows that effects of crop residues depend on soil properties at the time of application. Adding crop residues with a high C/N ratio to soil can immobilise N in the soil profile and hence reduce N uptake and/or total biomass production. Crop residue incorporation can either stimulate or reduce N2O emissions depending on the mineral N content of the soil. Crop residues pyrolysed to biochar can potentially stabilise native soil C (negative priming) and reduce N2O emissions from cropping soils thus providing climate change mitigation potential beyond the biochar C storage in soils. Incorporation of crop residues as an approach to recycle organic materials and reduce synthetic N fertiliser use in agricultural production requires a thorough evaluation, both in terms of biomass production and greenhouse gas emissions.

Tertiary Treatment of Ayr Municipal Wastewater using Bioremediation: A Pilot-Scale Study. A Report Prepared for the Burdekin Shire Council and the Burdekin Rangeland Reef Initiative

This joint DPI/Burdekin Shire Council project assessed the efficacy of a pilot-scale biological remediation system to recover Nitrogen (N) and Phosphorous (P) nutrients from secondary treated municipal wastewater at the Ayr Sewage Treatment Plant. Additionally, this study considered potential commercial uses for by-products from the treatment system. Knowledge gained from this study can provide directions for implementing a larger-scale final effluent treatment protocol on site at the Ayr plant. Trials were conducted over 10 months and assessed nutrient removal from duckweed-based treatments and an algae/fish treatment – both as sequential and as stand-alone treatment systems. A 42.3% reduction in Total N was found through the sequential treatment system (duckweed followed by algae/fish treatment) after 6.6 days Effluent Retention Time (E.R.T.). However, duckweed treatment was responsible for the majority of this nutrient recovery (7.8 times more effective than algae/fish treatment). Likewise, Total P reduction (15.75% reduction after 6.6 days E.R.T.) was twice as great in the duckweed treatment. A phytoplankton bloom, which developed in the algae/fish tanks, reduced nutrient recovery in this treatment. A second trial tested whether the addition of fish enhanced duckweed treatment by evaluating systems with and without fish. After four weeks operation, low DO under the duckweed blanket caused fish mortalities. Decomposition of these fish led to an additional organic load and this was reflected in a breakdown of nitrogen species that showed an increase in organic nitrogen. However, the Dissolved Inorganic Nitrogen (DIN: ammonia, nitrite and nitrate) removal was similar between treatments with and without fish (57% and 59% DIN removal from incoming, respectively). Overall, three effluent residence times were evaluated using duckweed-based treatments; i.e. 3.5 days, 5.5 days and 10.4 days. Total N removal was 37.5%, 55.7% and 70.3%, respectively. The 10.4-day E.R.T. trial, however, was evaluated by sequential nutrient removal through the duckweed-minus-fish treatment followed by the duckweed-plus-fish treatment. Therefore, the 70.3% Total N removal was lower than could have been achieved at this retention time due to the abovementioned fish mortalities. Phosphorous removal from duckweed treatments was greatest after 10.4-days E.R.T. (13.6%). Plant uptake was considered the most important mechanism for this P removal since there was no clay substrate in the plastic tanks that could have contributed to P absorption as part of the natural phosphorous cycle. Duckweed inhibited phytoplankton production (therefore reducing T.S.S) and maintained pH close to neutral. DO beneath the duckweed blanket fell to below 1ppm; however, this did not limit plant production. If fish are to be used as part of the duckweed treatment, air-uplifts can be installed that maintain DO levels without disturbing surface waters. Duckweed grown in the treatments doubled its biomass on average every 5.7 days. On a per-surface area basis, 1.23kg/m2 was harvested weekly. Moisture content of duckweed was 92%, equating to a total dry weight harvest of 0.098kg/m2/week. Nutrient analysis of dried duckweed gave an N content of 6.67% and a P content of 1.27%. According to semi-quantitative analyses, harvested duckweed contained no residual elements from the effluent stream that were greater than ANZECC toxicant guidelines proposed for aquaculture. In addition, jade perch, a local aquaculture species, actively consumed and gained weight on harvested duckweed, suggesting potential for large-scale fish production using by-products from the effluent treatment process. This suggests that a duckweed-based system may be one viable option for tertiary treatment of Ayr municipal wastewater. The tertiary detention lagoon proposed by the Burdekin Shire Council, consisting of six bays approximately 290 x 35 metres (x 1.5 metres deep), would be suitable for duckweed culture with minor modification to facilitate the efficient distribution of duckweed plants across the entire available growing surface (such as floating containment grids). The effluent residence time resulting from this proposed configuration (~30 days) should be adequate to recover most effluent nutrients (certainly N) based on the current trial. Duckweed harvest techniques on this scale, however, need to be further investigated. Based on duckweed production in the current trial (1.23kg/m2/week), a weekly harvest of approximately 75 000kg (wet weight) could be expected from the proposed lagoon configuration under full duckweed production. A benefit of the proposed multi-bay lagoon is that full lagoon production of duckweed may not be needed to restore effluent to a desirable standard under the present nutrient load, and duckweed treatment may be restricted to certain bays. Restored effluent could be released without risk of contaminating the receiving waterway with duckweed by evacuating water through an internal standpipe located mid-way in the water column.