X-ray and IR characterisation of Nasicon solid solution, Na1+xZr2SixP3−xO12

X-ray and IR studies on Nasicon solid solutions, Na1+xZr2SixP3−xO12, are carried out as a function of composition x. X-ray diffraction studies show that the unit cell volume increases as x increases and exhibits a maximum at x ≈ 2. On further increase in x the unit cell volume decreases. The infrared absorption peak positions and the splitting of these absorption peaks suggest a distortion of the PO4 and SiO4 tetrahedra. But the distortion is not large enough to change the local symmetry around the phosphorus or silicon ion from Td to C3v.

Elastic properties of lead phosphomolybdate glassess

Elastic properties of lead phosphomolybdate [PbO-1bMoO3-1bP2O5] glasses have been investigated using ultrasonic velocity measurements at 10MHz. The composition dependence of elastic moduli, Poisson's ratio and the Debye temperature are found to be consistent with a structural model proposed earlier. According to this model lead acts both as a network former and as a network modifier in different composition regimes. It is suggested that the incorporation of lead into the network is accompanied by the conversion of three-connected [Image ] tetrahedra into four-connected Image tetrahedra in the network. lead; phosphorus; molybdenum

A novel approach to structure—flammability correlation in polyphosphate esters

The relationship between the structure and flammability of a number of polyphosphate esters has been examined. The conventional correlation of char residue with limiting oxygen index was found to be unproductive in these polymers, giving insight into the importance of gas-phase reactions in addition to condensed-phase reactions in determining their flammability. A novel approach was sought in understanding the structure-flammability relationships of these polymers relating thermal stability, phosphorus content and limiting oxygen index. An empirical relationship has been derived amongst these three parameters.

Characterisation of sweetpotato from Papua New Guinea and Australia: Physicochemical, pasting and gelatinisation properties.

The physicochemical and functional properties of flours from 25 Papua New Guinean and Australian sweetpotato cultivars were evaluated. The cultivars (white-, orange-, cream-, and purple-fleshed, and with dry matter, from 15 to 28 g/100 g), were obovate, oblong, elliptic, curved, irregular in shape, and essentially thin-cortexed (1-2 mm). Flour yield was less than 90 g/100 g solids, while starch, protein, amylose, water absorption and solubility indices, as well as total sugars, varied significantly (p < 0.05). Potassium, sodium, calcium, and phosphorus were the major minerals measured, and there were differences in the pasting properties, which showed four classes of shear-thinning and shear-thickening behaviours. Differential scanning calorimetry showed single-stage gelatinisation behaviour, with cultivar-dependent temperatures (61-84 degrees C) and enthalpies (12-27 J/g dry starch). Oval-, round- and angular-shaped granules were observed with a scanning electron microscope, while X-ray diffraction revealed an A-type diffraction pattern in the cultivars, with about 30% crystallinity. This study shows a wide range of sweetpotato properties, reported for the first time.

Commercial application of polychaete sand filters for wastewater remediation and broodstock feeds

Summary Prototype sand-worm filtration beds were constructed at two prawn farms and one fish farm to assess and demonstrate their polychaete (marine worm) production and wastewater remediation capacities at semi-commercial scale. Wastewater treatment properties were monitored and worms produced were assessed and either sold for bait or used by the farms’ hatcheries as broodstock (prawn or fish breeder) feed. More than 34 megalitres of prawn- and fish-pond water was beneficially treated in the 116-319-d trial. The design of the polychaete-assisted sand filters (PASFs) constructed at each farm affected their water handling rates, which on average ranged from 315 to 1000 L m-2 d-1 at the three farms. A low profile design incorporating shallow bunded ponds made from polyethylene liner and timber stakes provided the easiest method of construction. This simple design applied at broad scale facilitated the highest quantities of treated water and the greatest worm production. Designs with higher sides increased the head pressure above the sand bed surface, thus increasing the amount of water that could be treated each day. Most water qualities were affected in a similar way to that demonstrated in the previous tank trials: dissolved oxygen, pH, total suspended solids and chlorophyll a levels were all consistently significantly lowered as pond water percolated through the sand bed, and dissolved forms of nitrogen and phosphorus were marginally increased on several occasions. However, unlike the previous smaller-scale tank trials, total nitrogen (TN) and total phosphorus (TP) levels were both significantly lowered by these larger-scale PASFs. The reasons for this are still unclear and require further research. Maximum TN and TP removals detected in the trial were 48.8% and 67.5%, respectively, and average removals (in unfed beds) at the three farms ranged from 20.0 to 27.7% for TN and from 22.8 to 40.8% for TP. Collectively, these results demonstrate the best suspended solids, chlorophyll and macronutrient removal capacities so far reported for any mariculture wastewater treatment methodology to date. Supplemental feeding of PASFs with fish meal was also investigated at one farm as a potential means of increasing their polychaete biomass production. Whilst fed beds produced higher biomass (152 ± 35 g m-2) compared with unfed beds (89 ± 17 g m-2) after 3.7 months of operation, the low number of replicates (2) prevented statistically significant differences from being demonstrated for either growth or survival. At harvest several months later, worm biomass production was estimated to be similar to, or in slight excess of, previously reported production levels (300-400 g m-2). Several qualities of filtered water appear to have been affected by supplemental feeding: it appeared to marginally lower dissolved oxygen and pH levels, and increased the TN and TP levels though not so much to eliminate significant beneficial water treatment effects. Periodic sampling during an artificial-tide demonstrated the tendency for treated-water quality changes during the first hour of filtration. Total nitrogen and ammonia peaked early in the tidal flow and then fell to more stable levels for the remainder of the filtration period. Other dissolved nutrients also showed signs of this sand-bed-flushing pattern, and dissolved oxygen tended to climb during the first hour and become more stable thereafter. These patterns suggest that the routine sampling of treated water undertaken at mid-inflow during the majority of the wider study would likely have overestimated the levels of TN and dissolved nutrients discharged from the beds, and hence underestimated the PASFs treatment efficacies in this regard. Analyses of polychaete biomass collected from each bed in the study revealed that the worms were free from contamination with the main prawn viruses that would create concerns for their feeding to commercial prawn broodstock in Australia. Their documented proximal and nutritional contents also provide a guide for hatchery operators when using live or frozen stock. Their dry matter content ranged from 18.3 to 22.3%, ash ranged from 10.2 to 14.0%, gross energy from 20.2 to 21.5 MJ kg-1, and fat from 5.0 to 9.2%. Their cholesterol levels ranged from 0.86 to 1.03% of dry matter, whilst total phospholipids range from 0.41 to 0.72%. Thirty-one different fatty acids were present at detectable (≥0.005% of dry matter) levels in the sampled worm biomass. Palmitic acid was by far the most prevalent fatty acid detected (1.21 ± 0.18%), followed by eicosapentaenoic (EPA) (0.48 ± 0.03%), stearic (0.46 ± 0.04%), vaccenic (0.38 ± 0.05%), adrenic (0.35 ± 0.02%), docosadienoic (0.28 ± 0.02%), arachidonic (AA) (0.22 ± 0.01%), palmitoleic (0.20 ± 0.04%) and 23 other fatty acids with average contents of less than 0.2% of dry matter. Supplemental feeding with fish meal at one farm appeared to increase the docosahexaenoic acid (DHA) content of the worms considerably, and modify the average AA : EPA : DHA from 1.0 : 2.7 : 0.3 to 1.0 : 2.0 : 1.1. Consistent with previous results, the three most heavily represented amino acids in the dry matter of sampled worms were glutamic acid (8.5 ± 0.2%), aspartic acid (5.5 ± 0.1%) and glycine (4.9 ± 0.5%). These biomass content results suggest that worms produced in PASF systems are well suited to feeding to prawn and fish broodstock, and provide further strong evidence of the potential to modify their contents for specific nutritional uses. The falling wild-fishery production of marine bloodworms in Queensland is typical of diminishing polychaete resources world-wide and demonstrates the need to develop sustainable production methods here and overseas. PASF systems offer the dual benefits of wastewater treatment for environmental management and increased productivity through a valuable secondary crop grown exclusively on waste nutrients.

Polychaete-assisted sand filters – prawn farm wastewater remediation trial

Medium bedding sand which is commonly available in coastal sedimentary deposits, and a marine polychaete-worm species from Moreton Bay recently classified as Perinereis helleri (Nereididae), were deployed in a simple low-maintenance sand filter design that potentially has application at large scale. Previous work had shown that this physical and biological combination can provide a new option for saline wastewater treatment, since the worms help to prevent sand filter blocking with organic debris and offer a profitable by-product. To test the application of this new concept in a commercial environment, six 1.84 m2 Polychaete-assisted sand filters were experimentally tested for their ability to treat wastewater from a semi-intensive prawn culture pond. Polychaetes produced exclusively on the waste nutrients that collected in these gravity-driven sand filters were assessed for their production levels and nutritional contents. Water parameters studied included temperature, salinity, pH, dissolved oxygen (DO), oxidation/ reduction potential (redox), suspended solids, chlorophyll a, biological oxygen demand (BOD), and common forms of nitrogen and phosphorus. Pond water which had percolated through the sand bed had significantly lower pH, DO and redox levels compared with inflow water. Suspended solids and chlorophyll a levels were consistently more than halved by the process. Reductions in BOD appeared dependant on regular subsurface flows. Only marginal reductions in total nitrogen and phosphorus were documented, but their forms were altered in a potentially useful way: dissolved forms (ammonia and orthophosphate) were generated by the process, and this remineralisation also seemed to be accentuated by intermittent flow patterns. Flow rates of approximately 1,500 L m-2 d-1 were achieved suggesting that a 1 ha polychaete bed of this nature could similarly treat the discharge from a 10 ha semi-intensive prawn farm. Sixteen weeks after stocking sand beds with one-month-old P. helleri, over 3.6 kg of polychaete biomass (wet weight) was recovered from the trial. Production on a sand bed area basis was 328 g m-2. Similar (P>0.05) overall biomass production was found for the two stocking densities tested (2000 and 6000 m-2; n = 3), but survival was lower and more worms were graded as small (<0.6 g) when produced at the higher density (28.2 ± 1.5 % and approx. 88 %, respectively) compared with the lower density (46.8 ± 4.4 % and approx. 76 %, respectively). When considered on a weight for weight basis, about half of the worm biomass produced was generally suitable for use as bait. The nutritional contents of the worms harvested were analysed for different stocking densities and graded sizes. These factors did not significantly affect their percentages of dry matter (DM) (18.23 ± 0.57 %), ash (19.77 ± 0.80 % of DM) or gross energy 19.39 ± 0.29 MJ kg-1 DM) (n = 12). Although stocking density did not affect the worms’ nitrogen and phosphorus contents, small worms had a higher mean proportion of nitrogen and phosphorus (10.57 ± 0.17 % and 0.70 ± 0.01 % of DM, respectively) than large worms (9.99 ± 0.12 % and 0.65 ± 0.01 % of DM, respectively) (n = 6). More lipid was present in large worms grown at the medium density (11.20 ± 0.19 %) compared with the high density (9.50 ± 0.31 %) and less was generally found in small worms (7.1-7.6 % of DM). Mean cholesterol and total phospholipid levels were 5.24 ± 0.15 mg g-1 and 13.66 ± 2.15 mg g-1 DM, respectively (n = 12). Of the specific phospholipids tested, phosphatidyl-serine or sphingomyelin were below detection limits (<0.05 mg g-1), whilst mean levels of phosphatidyl-ethanolamine, phosphatidyl-inositol, phosphatidyl-choline and lysophosphatidyl-choline were 6.89 ± 1.09, 0.89 ± 0.26, 4.04 ± 1.17 and 1.84 ± 0.37 mg g-1, respectively (n = 12). Culture density generally had a more pronounced effect on phospholipid contents than did size of worms. By contrast, worm size had a more pronounced effect on total fatty acid contents, with large worms containing significantly higher (P<0.001) levels on a DM basis (46.88 ± 2.46 mg g-1) than smaller worms (27.76 ± 1.28 mg g-1). A very broad range of fatty acids were detected with palmitic acid being the most heavily represented class (up to 14.23 ± 0.49 mg g-1 DM or 27.28 ± 0.22 % of total fatty acids). Other heavily represented classes included stearic acid (7.4-8.8 %), vaccenic acid (6.8-7.8 %), arachidonic acid (3.5-4.4 %), eicosapentaenoic acid (9.9-13.8 %) and docosenoic acid (5.7-7.0 %). Stocking density did not affect (P>0.05) the levels of amino acids present in polychaete DM, but there was generally less of each amino acid tested on a weight per weight basis in large worms than in small worms. This difference was significant (P<0.05) for the most heavily represented classes being glutamic acid (73-77 mg g-1), aspartic acid (50-54 mg g-1), and glycine (46-53 mg g-1). These results demonstrate how this polychaete species can be planted and sorted at harvest according to various strategies aimed at providing biomass with specific physical and nutritional qualities for different uses.

Growing banana prawns in prawn farm settlement ponds to utilise and help remove waste nutrients.

To assess their utility for profitable wastewater bioremediation, banana prawns, Penaeus (Fenneropenaeus) merguiensis (de Man), were stocked at low densities (1 – 5 m-2) and grown without supplemental feeding in five commercial-prawn-farm settlement ponds (0.3 to 6.0 ha). The prawns free-ranged in the variously designed ponds for 160 to 212 days after stocking as PL15. Survival estimates ranged from 12% to 60% with production of 50 – 528 kg ha-1. Over 1150 kg of marketable product was produced in the study. Exceptional growth was monitored at one farm where prawns reached an average size of 17g in 80 days. Nutrients in water flowing into (8 - 40 ML d-1) and out of the settlement pond at that farm were assessed twice weekly along with routine water quality measurements. Only small differences in water qualities were detected between waters running into and out of this settlement pond. Total nitrogen levels gradually increased from 1 - 1.5 mg L-1 early in the season to over 3 mg L-1 towards the end of the season. Total phosphorus levels similarly rose from 0.1 - 0.2 mg L-1 to 0.3 - 0.4 mg L-1 in the middle of the season, but fell to 0.2 – 0.3 mg L-1 towards the end when approximately 12,000 prawns were harvested with a total weight of 175 kg. No significant differences (P > 0.05) were detected in the overall acceptability of prawns harvested from each of the 5 settlement ponds in small-scale consumer sensory analyses. The prawns from settlement ponds were rated similarly to banana prawns grown with commercial diets at two other establishments. Microbiological analyses of prawns from all farms showed bacterial levels to be well within food-grade standards and lower than prawns produced in a normal growout pond. These results demonstrate that high quality food grade banana prawns can be produced in these wastewater treatment systems.

Nutrient levels in experimental tanks supplied with prawn pond effluent: the effect of artificial substrate and different densities of the banana prawn Penaeus merguiensis (de Man)

To experimentally investigate the effect of vertical artificial substrate and different densities of the banana prawn Penaeus (Fenneropenaeus) merguiensis on nutrient levels in prawn pond effluent, a time series experiment was conducted in a replicated tank system supplied periodically with discharge from a prawn production pond. Few differences (P>0.05) were detected between tanks without prawns, and tanks with low densities (5 prawns in 1700 litres) of prawns (10-12 g), in terms of nitrogen and phosphorus in the water column over the 28-day experimental period. Higher densities of prawns (starting at 25 or 50 per tank) caused an elevation of these macronutrients in the water column. This was partly due to prawn biomass losses from mortalities and weight reductions in the tank system. The survival and condition of prawns was significantly (P<0.05) reduced in tanks at these higher densities. The presence of artificial substrate (2 m2 tank-1) did not affect (P>0.05) the levels of nutrients in tank water columns, but significantly (P<0.05) increased the amount of nitrogen in tank residues left at the end of the trial when no prawns were present. The prawns had obviously been grazing on surfaces inside the tanks, and their swimming actions appeared to keep light particulate matter in suspension. Higher prawn densities increased microalgal blooms, which presumably kept ammonia levels low, and it is suggested that this association may provide the means for improved remediation of prawn farm effluent in the future.

Testing the effectiveness of the SKIM foam fractionator to reduce nutrient levels in prawn farm effluent

To experimentally investigate the effect of the “SKIM” mechanical foam fractionator on suspended material and the nutrient levels in prawn farm effluent, a series of standardised short-term treatments were applied to various effluent types in a static 10,000-litre water body. Prawn pond effluents were characterised by watercolour and dominance of phytoplankton species. Three effluent types were tested, namely 1) particulate-rich effluent with little apparent phytoplankton, 2) green mircoalgal bloom predominately made up of single celled phytoplankton, and 3) brown microalgal bloom with higher prevalence of diatoms. The effluent types were similar (P>0.05) in non-volatile particulate material, and nitrate/nitrite but varied from each other in the following ways: 1) The particulate-rich effluents were lower (P<0.05) in volatile solids (compared to brown blooms), total Kjeldahl nitrogen, dissolved organic nitrogen, dissolved organic phosphorus and chlorophyll a (compared to both green and brown blooms). 2) The brown blooms were higher (P<0.05) in ammonia (compared to green blooms), total nitrogen and total phosphorus (compared to both green and particulate-rich effluent), but were lower (P<0.05) in inorganic phosphorus (compared to both green and particulate-rich effluent). 3) The green blooms were higher (P<0.05) in dissolved (both organic and inorganic) phosphorus (compared to both brown and particulate-rich effluents). Although the effluent types varied significantly in these aspects the effect of the Skim treatment was similar for all parameters measured except total phosphorus. Bloom type and Skim-treatment period significantly (P<0.05) affected total Kjeldahl phosphorus concentrations. For all effluent types there was a continuous significant reduction (P<0.05) in total Kjeldahl phosphorus during the initial 6-hour treatment period. Levels of total suspended solids and volatile suspended solids in all effluent types were significantly (P<0.05) reduced in the first 2 hours but not thereafter. Non-volatile suspended solids were also significantly (P<0.05) reduced in the first 2 hours (30 to 40 % reduction) and a further 40% reduction occurred in the particulate-rich effluent over the next 2 hours. Mean values for total ammonia, dissolved organic nitrogen, total Kjeldahl nitrogen, total nitrogen, chlorophyll a and dissolved organic or inorganic phosphorus levels were not significantly (P>0.05) affected by the Skim unit in any bloom type during the initial 6 hours of testing. Nevertheless, non-significant nitrogen reductions did occur. Foam production by the Skim unit varied with different blooms, resulting in different concentrate volumes and different end points for separate experiments. Concentrate volumes were generally high for the particulate-rich and green blooms (175 – 370 litres) and low for the brown blooms (25 – 80 litres). This was due to the low tendency of the brown bloom to produce foam. This generated higher nutrient concentrations in the associated condensed foam, but may have limited the treatment efficiency. The results suggest that in this application, the Skim unit did not remove micro-algae as effectively as was anticipated. However, it was effective at removing other suspended solids. Considering these attributes and the other uses of this machinery documented by the manufactures, the unit’s oxygenation mixing capacities coupled with inorganic solids removal may provide a suitable mechanism for construction of a continuously mixed bioreactor that utilises the filtration and profit making abilities of bivalves.

Phosphonate use for Phytophthora root rot management in Shepard

Phytophthora root rot of avocados and is the major limiting factor to avocado production in Australia. The disease has a significant impact on productivity. An integrated program is recommended for Phytophthora root rot management with phosphorus acid a key component of this strategy. Monthly root analyses will be conducted on 5 avocado orchards across a range of growing environments on the Atherton Tablelands. Detailed tree phenology data will be collected orchard at the same time the root sampling occurs. In conjunction with the phenological data, decay curves will allow the development of recommendations to optimize phosphorous acid applications for the management of Phytophthora root rot in Shepard avocados.

Defining critical soil nutrient concentrations in soils supporting grains and cotton in Northern NSW and Queensland

This project focussed on the phosphorus (P) and potassium (K) status of northern cropping soils. Stores of P and K have been depleted by crop removal and limited fertiliser application, with depletion most significant in the subsoil. Soil testing strategies are confounded by slowly available mineral reserves with uncertain availability. The utility of new soil tests was assessed to measure these reserves, their availability to plants quantified and a regional sampling strategy undertaken to identify areas of greatest P and K deficit. Fertiliser application strategies for P and K have been tested and the interactions between these and other nutrients have been determined in a large field program.

Reaction of Hexachlorocyclotriphosphazene with Sodium p-Cresoxide

The reaction of hexachlorocyclotriphosphazene (N3P3Cl6) with sodium p-cresoxide proceeds by a predominantly nongeminal pathway. The presence of geminal isomers at the bis- and tris-stages of substitution in tiny quantities (< 5%) has also been observed. All the chloro(p-cresoxy)cyclotriphosphazenes and their dimethylamino derivatives have been characterized by 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy. The reaction of N3P3Cl6 with sodium phenoxide has been reinvestigated. The relative yields of the products at various stages of substitution and their isomeric compositions are almost the same for both phenoxy and p-cresoxy systems. Possible mechanisms to explain the observed isomeric compositions are discussed. A through-space interaction involving oxygen-2p and phosphorus-3d orbitals is invoked to explain the greater yield of the cis isomer of N3P3Cl4(OAr)2 than that of its trans isomer.

Studies of phosphazenes. Part 10. Spirocyclic derivatives of cyclotriphosphazatrienes

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, and its geminal bis-t-butylamino- and diphenyl derivatives, with ethylenediamine and ethanolamine are reported. In each case, both chlorine atoms attached to the same phosphorus atoms are replaced, giving rise to spirocyclic derivatives. A small quantity of a bis spirocyclic derivative, N3P3(NHCH2CH2O)2Cl2, is also obtained; this compound occurs in both cis and trans forms. Attempts to prepare fully substituted tris spirocyclic derivatives have been unsuccessful and only resinous materials were obtained. The 1H and 31P n.m.r. spectra of the products are discussed.

Swan’s Lagoon Celebrating 50 years

Swan’s Lagoon, which is 125 km south-south-west of Townsville, was purchased by the Queensland Government as a beef cattle research station in 1961. It is situated within the seasonally-dry tropical spear grass region of North Queensland. The station was expanded from 80 km2 to 340 km2 by purchase of the adjoining Expedition block in 1978. The first advisory committee formed and initiated research in 1961. The median annual rainfall of 708 mm (28 inches) is highly variable, with over 80% usually falling in December–April. Annual evaporation is 2.03 metres. The 60% of useable area is mostly flat with low fertility duplex soils, of which more than 50% is phosphorus deficient. Natural spear grass-based pastures predominate over the station. Swan’s Lagoon research has contributed to understanding the biology of many aspects of beef production for northern Australia. Research outcomes have provided options to deal with the region’s primary challenges of weaning rates averaging less than 60%, annual growth rates averaging as little as 100 kg, high mortality rates and high management costs. All these relate to the region’s variable and highly seasonal rainfall—challenges that add to insect-borne viruses, ticks, buffalo fly and internal parasites. As well as the vast amount of practical beef production science produced at Swan’s Lagoon, generations of staff have been trained there to support beef producers throughout Queensland and northern Australia to increase their business efficiency. The Queensland Government has provided most of the funds for staffing and operations. Strong beef industry support is reflected in project funding from meat industry levies, managed by Meat and Livestock Australia (MLA) and its predecessors. MLA has consistently provided the majority of operational research funding since the first grant for ‘Studies of management practices, adaption of different breeds and strains to tropical environments, and studies on tick survival and resistance’ in 1962–63. A large number of other agencies and commercial companies have also supported research.

Kinetic studies of the reactions of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene with t-butylamine

The rates of the reactions of hexachlorocyclotriphosphazene (N3P3Cl6) and octachlorocyclotetraphosphazene (N4P4Cl8) with t-butylamine in methyl cyanide were determined at three temperatures in the range 273–308 K. The reaction of N3P3Cl6 was also studied in tetrahydrofuran. Rigorous purification of the chlorophosphazenes and the solvents was essential to obtain reproducible results. An SN2(P) mechanism involving the formation of a five-co-ordinate phosphorus intermediate is in accord with the kinetic data. The greater reactivity of N4P4Cl8 compared to that of N3P3Cl6 arises entirely from the lowering of the enthalpy of activation. The effects of ring size and the solvent on the rates are discussed in terms of the activation parameters.