Fate and recovery of nitrogen applied as slow release brown coal-urea in field microcosms: 15N tracer study.

The over-use of synthetic nitrogen (N) fertilisers for crop production can cause environmental pollution through leaching and gaseous losses, resulting in low N use efficiency (NUE). Previous work has shown that brown coal (BC) combined with urea can slow down the fertiliser-N release to better synchronise soil N supply with crop N demand. The study aimed to evaluate the impact of granulated BC-urea (BCU) applied to sweet corn on NUE, fate and recovery of fertiliser-N using an 15N tracer technique. In this in-field microcosm study, 10 atom percent enriched 15N-labelled urea (46% N) and BCU (20% N) were applied as N fertilisers at rates of 90 or 180 kg N ha-1. On average, BCU fertiliser reduced the urea-derived 15N losses as nitrous oxide (N2O) by 64%, ammonia (NH3) by 73% and downward movement of total N by 59% compared to urea. Reduced losses of applied BCU fertiliser-15N were associated with significantly increased microbial immobilisation, soil retention and availability of fertiliser-15N to plants for longer periods of time, compared with urea. As a result, BCU enhanced cob yield by an average of 23%, 15N uptake by 21% and fertiliser NUE by 21% over urea. The plant recovery of fertiliser-15N was significantly higher from BCU (59%) than the recovery from urea (38%). Moreover, mining of native soil-N was lower when the N-fertiliser source was BCU cf. urea, suggesting that BCU could be used as a more N-efficient alternative to urea in cropping systems.

Effects of liming on oxic and anoxic N2O and CO2 production in different horizons of boreal acid sulfate soil and non-acid soil under controlled conditions.

In acid sulfate (AS) soils, organic rich topsoil and subsoil horizons with highly variable acidity and moisture conditions and interconnected reactions of sulfur and nitrogen make them potential sources of greenhouse gases (GHGs). Subsoil liming can reduce the acidification of sulfidic subsoils in the field. However, the mitigation of GHG production in AS subsoils by liming, and the mechanisms involved, are still poorly known. We limed samples from different horizons of AS and non-AS soils to study the effects of liming on the N2O and CO2 production during a 56-day oxic and subsequent 72-h anoxic incubation. Liming to pH ≥ 7 decreased oxic N2O production by 97-98 % in the Ap1 horizon, 38-50 % in the Bg1 horizon, and 34-36 % in the BC horizon, but increased it by 136-208 % in the C horizon, respectively. Liming decreased anoxic N2O production by 86-94 % and 78-91 % in Ap1 and Bg1 horizons, but increased it by 100-500 % and 50-162 % in BC and C horizons, respectively. Liming decreased N2O/(N2O + N2) in anoxic denitrification in most horizons of both AS and non-AS soils. Liming significantly increased the cumulative oxic and anoxic CO2 production in AS soil, but less so in non-AS soil due to the initial high soil pH. Higher carbon and nitrogen contents in AS soil compared to non-AS soil agreed with the respectively higher cumulative oxic N2O production in all horizons, and the higher CO2 production in the subsoil horizons of all lime treatments. Overall, liming reduced the proportion of N2O in the GHGs produced in most soil horizons under oxic and anoxic conditions but reduced the total GHG production (as CO2 equivalents) only in the Ap1 horizon of both soils. The results suggest that liming of subsoils may not always effectively mitigate GHG emissions due to concurrently increased CO2 production and denitrification.

Modulating superabsorbent polymer properties by adjusting the amphiphilicity.

The role of amphiphilicity in polysaccharide-based superabsorbent polymers is paramount in determining material properties. While the performance of freeze-dried polymers is improved by maximizing hydrophilicity, this may not be the case for evaporative-dried polymers. In this study, four diglycidyl ether crosslinkers, with varying chain lengths and amphiphilicities, were used to synthesize a series of evaporative-dried carboxymethyl cellulose-based superabsorbent films. Through structural and physiochemical characterization, the effect of amphiphilicity on swelling and mechanical properties was established. Contrary to freeze-dried polymers, it was found that the addition of hydrophobic moieties by crosslinking with novel poly(propylene glycol) diglycidyl ether crosslinkers increased the swelling performance of evaporative-dried polymers. By adding hydrophobic functional groups, a reduction in inter-chain hydrogen bonding occurs during evaporative-drying, reducing the degree of hornification and decreasing the entropy requirement for water uptake. By optimizing the amphiphilic ratio, a poly(propylene glycol)-carboxymethyl cellulose polymer achieved a swelling capacity of 182 g/g which is competitive with freeze-dried cellulose-based hydrogels. The mechanical properties of these films improved with the addition of the crosslinkers, with glycerol-carboxymethyl cellulose polymers achieving a tensile strength of 39 MPa and a Young's Modulus of 4.0 GPa, indicating their potential application as low-cost, swellable films.

Transport and migration of plutonium in different soil types and rainfall regimes.

Leaching and transport of contaminants is a complex interacting system affected by a suite of environmental factors. This study demonstrates the potential significance of weather events and moisture movement when interpreting plutonium (Pu) migration and advective transport in the soil matrix. Using a column transport experiment, two soil types, a sandy soil and clay-rich soil, were spiked with 238Pu as a tracer to observe the effect of simulated tropical and arid rainfall events on Pu mobility. Partition coefficients (Kd) were determined over a period of weeks and under varying rainfall rates to establish the impact of changing weather events on Pu mobility. The variability of these temporal Kds covers six orders of magnitude over a relatively brief time period. This demonstrates the necessity for non-static Kds to accurately describe Pu transport in these systems. The Pu Kds determined by these column transport experiments fall within the bounds of anticipated values (approximately 80-300,000 mL g-1) from immobile (magnitude 106 mL g-1) to moderately mobile (magnitude 101 mL g-1). The overall transport rate, shown by a decrease in calculated Kd, increases in environments where rainfall is more episodic, such as in arid regions as opposed to the consistently abundant rainfall in tropical regions. In contrast to the 238Pu spike, 239+240Pu resulting from contamination from nuclear tests in the sandy soil (aged for >30 years) showed higher mobility; we hypothesise that the ageing of the contamination, in particular Pu-bearing particles, accounts for this significant increase in Pu mobility. Low intensity, high frequency events in tropical sandy soil systems containing Pu particle contamination have the potential to mobilise Pu (>105 decrease in calculated Kd) over shorter periods of weeks, and not years as previously assumed. This increased mobility, when applied to radioecological models using Kd as a site-specific parameter, shows that there is likely to be a continued impact (risk quotient >1) on non-human biota in tropical sandy soil ecosystems.

Effect of the counter-ion on nanocellulose hydrogels and their superabsorbent structure and properties.

HYPOTHESIS: Carboxylated nanocellulose gels and superabsorbents (SAPs) can be engineered by ion exchange of TEMPO treated cellulose fibers with different cations prior to shearing, thus creating a nanofibrous network ionically cross-linked. The structure and properties of these materials are highly influenced by the type counter-ion used as it controls both the degree of fibrillation and crosslinking. EXPERIMENTS: Functionalised nanocellulose SAPs were made using TEMPO-mediated oxidation followed by ion-exchange before fibrillation into a hydrogel and freeze-drying. Seven different cations were tested: 4 of valency 1 (H, Na, K, NH4), and 3 of valency 2 (Ca, Mg, and Zn). The effect of the counter-ion on the gelation mechanism and the superabsorbent performance was evaluated. The SAP absorption capacity in deionised water was related to the superabsorbent structure and morphology. FINDINGS: The gel stability of nanocellulose superabsorbents is governed by the counter-ion type and valency. The viscoelastic properties of all nanocellulose hydrogels are controlled by its elastic regime, that is storage modulus (G') > loss modulus (G″). The type of cation dictates the rheology of these gels by altering the fibrillation efficiency due to the extent of ionic cross-links occurring before and after fibrillation. The driving force for gelation in monovalent gels is due to the coupling of nanofibrils by physical interactions, creating an electrostatic stabilisation of the ionised COO- groups at high shear forces. Cation - carboxylate interactions dominate the gelation in divalent gels by supressing the repulsive charges generated by the COO- and also creating interfibril connections via ionic-crosslinks, as confirmed by the zeta potentials. The superabsorption performance is dominated by the counter-ion and is in the order of: NH4+ > K+ > Na+ > Mg2+ > Zn2+ > Ca2+. NH4+-SAPs present the slowest kinetics and the highest absorption capacity. Its high pore area, which extends the number of accessible carboxyl groups that participates in hydrogen bonding with water, is responsible for this behaviour. Nanocellulose SAPs are attractive renewable materials, suited for many applications, including as nutrient cation carriers in agriculture.

The nature of Pu-bearing particles from the Maralinga nuclear testing site, Australia.

The high-energy release of plutonium (Pu) and uranium (U) during the Maralinga nuclear trials (1955-1963) in Australia, designed to simulate high temperature, non-critical nuclear accidents, resulted in wide dispersion µm-sized, radioactive, Pu-U-bearing 'hot' particles that persist in soils. By combining non-destructive, multi-technique synchrotron-based micro-characterization with the first nano-scale imagining of the composition and textures of six Maralinga particles, we find that all particles display intricate physical and chemical make-ups consistent with formation via condensation and cooling of polymetallic melts (immiscible Fe-Al-Pu-U; and Pb ± Pu-U) within the detonation plumes. Plutonium and U are present predominantly in micro- to nano-particulate forms, and most hot particles contain low valence Pu-U-C compounds; these chemically reactive phases are protected by their inclusion in metallic alloys. Plutonium reworking was observed within an oxidised rim in a Pb-rich particle; however overall Pu remained immobile in the studied particles, while small-scale oxidation and mobility of U is widespread. It is notoriously difficult to predict the long-term environmental behaviour of hot particles. Nano-scale characterization of the hot particles suggests that long-term, slow release of Pu from the hot particles may take place via a range of chemical and physical processes, likely contributing to on-going Pu uptake by wildlife at Maralinga.

2000 Year-old Bogong moth (Agrotis infusa) Aboriginal food remains, Australia.

Insects form an important source of food for many people around the world, but little is known of the deep-time history of insect harvesting from the archaeological record. In Australia, early settler writings from the 1830s to mid-1800s reported congregations of Aboriginal groups from multiple clans and language groups taking advantage of the annual migration of Bogong moths (Agrotis infusa) in and near the Australian Alps, the continent's highest mountain range. The moths were targeted as a food item for their large numbers and high fat contents. Within 30 years of initial colonial contact, however, the Bogong moth festivals had ceased until their recent revival. No reliable archaeological evidence of Bogong moth exploitation or processing has ever been discovered, signalling a major gap in the archaeological history of Aboriginal groups. Here we report on microscopic remains of ground and cooked Bogong moths on a recently excavated grindstone from Cloggs Cave, in the southern foothills of the Australian Alps. These findings represent the first conclusive archaeological evidence of insect foods in Australia, and, as far as we know, of their remains on stone artefacts in the world. They provide insights into the antiquity of important Aboriginal dietary practices that have until now remained archaeologically invisible.

A slow release brown coal-urea fertiliser reduced gaseous N loss from soil and increased silver beet yield and N uptake.

Increasing crop yield and fertiliser nitrogen (N)-use efficiency is important for productive agricultural systems with a reduced environmental footprint. The aim of this study was to assess the effect of slow release brown coal-urea (BCU) fertiliser on the gaseous N losses, biomass yield and N uptake by silver beet (Beta vulgaris L.) compared to commercial urea. Two soils were amended with urea, BCU 1 (22% N) or BCU 2 (17% N) as N-fertiliser at the rate of 50 or 100 kg N ha-1. Five gas sampling periods were undertaken to measure the loss of N as N2O and NH3. After 10 weeks, biomass, N concentration, and N uptake of silver beet, and mineral and mineralisable N of post-harvest soil were measured. BCU substantially increased fertiliser N availability and uptake by silver beet, reduced N2O emission by 29% and NH3 emission by 36% compared to urea alone, irrespective of soil type. Compared to urea, BCU blends increased biomass yield by 27% and 23% in a Tenosol and Dermosol soil, respectively. In addition, application of BCU fertiliser substantially enhanced the potentially mineralisable N and organic carbon content of soil. These results provide evidence that granulation of urea with brown coal (BC) can increase silver beet N-use efficiency and yield in different soil types, and more work is now required to validate this technology for other crops.

Nitrogen Dynamics in Soil Fertilized with Slow Release Brown Coal-Urea Fertilizers.

Reducing the release rate of urea can increase its use efficiency and minimize negative effects on the environment. A novel fertilizer material that was formed by blending brown coal (BC) with urea, delayed fertilizer N release in controlled climatic conditions in a glasshouse, through strong retention facilitated by the extensive surface area, porous structure and chemical functional groups in the BC. However, the role of BC as a carrier of synthetic urea and the effect of their interaction with various soil types on the dynamics and mineralization of N remains largely unclear. Therefore, a soil column incubation study was conducted to assess the release, transformation and transportation of N from several different brown coal-urea (BCU) granules, compared to commercial urea. Blending and subsequent granulation of urea with BC substantially increased fertilizer N retention in soil by decreasing gaseous emissions and leaching of N compared to urea alone, irrespective of soil type. The BCU granule containing the highest proportion of BC had lower leaching and gaseous emissions and maintained considerably higher mineral and mineralizable N in topsoil. Possible modes of action of the BCU granules have been proposed, emphasizing the role of BC in enhancing N retention over a longer period of time. The results support the notion that BCU granules can be used as a slow release and enhanced efficiency fertilizer for increasing availability and use efficiency of N by crops.

Seawater-induced mobilization of trace metals from mackinawite-rich estuarine sediments.

Benthic sediments in coastal acid sulfate soil (CASS) drains can contain high concentrations (~1-5%) of acid volatile sulfide (AVS) as nano-particulate mackinawite. These sediments can sequester substantial quantities of trace metals. Because of their low elevation and the connectivity of drains to estuarine channels, these benthic sediments are vulnerable to rapid increases in ionic strength from seawater incursion by floodgate opening, floodgate failure, storm surge and seasonal migration of the estuarine salt wedge. This study examines the effect of increasing seawater concentration on trace metal mobilization from mackinawite-rich drain sediments (210-550 µmol g⁻¹ AVS) collected along an estuarine salinity gradient. Linear combination fitting of S K-edge XANES indicated mackinawite comprised 88-96% of sediment-bound S. Anoxic sediment suspensions were conducted with seawater concentrations ranging from 0% to 100%. We found that mobilization of some metals increased markedly with increasing ionic strength (Cu, Fe, Mn, Ni) whereas Al mobilization decreased. The largest proportion of metals mobilized from the labile metal pool, operationally defined as Σexchangeable + acid-extractable + organically-bound metals, occurred in sediments from relatively fresh upstream sites (up to 39% mobilized) compared to sediments sourced from brackish downstream sites (0-11% mobilized). The extent of relative trace metal desorption generally followed the sequence Mn > Ni ≈ Cu > Zn > Fe > Al. Trace metal mobilization from these mackinawite-rich sediments was attributed primarily to desorption of weakly-bound metals via competitive exchange with marine-derived cations and enhanced complexation with Cl⁻ and dissolved organic ligands. These results have important implications for trace metal mobilization from these sediments at near-neutral pH under current predicted sea-level rise and climate change scenarios.

Anthropogenic forcing of estuarine hypoxic events in sub-tropical catchments: landscape drivers and biogeochemical processes.

Episodic hypoxic events can occur following summer floods in sub-tropical estuaries of eastern Australia. These events can cause deoxygenation of waterways and extensive fish mortality. Here, we present a conceptual model that links key landscape drivers and biogeochemical processes which contribute to post-flood hypoxic events. The model provides a framework for examining the nature of anthropogenic forcing. Modification of estuarine floodplain surface hydrology through the construction of extensive drainage networks emerges as a major contributing factor to increasing the frequency, magnitude and duration of hypoxic events. Forcing occurs in two main ways. Firstly, artificial drainage of backswamp wetlands initiates drier conditions which cause a shift in vegetation assemblages from wetland-dominant species to dryland-dominant species. These species, which currently dominate the floodplain, are largely intolerant of inundation and provide abundant labile substrate for decomposition following flood events. Decomposition of this labile carbon pool consumes oxygen in the overlying floodwaters, and results in anoxic conditions and waters with excess deoxygenation potential (DOP). Carbon metabolism can be strongly coupled with microbially-mediated reduction of accumulated Fe and Mn oxides, phases which are common on these coastal floodplain landscapes. Secondly, artificial drainage enhances discharge rates during the flood recession phase. Drains transport deoxygenated high DOP floodwaters rapidly from backswamp wetlands to the main river channel to further consume oxygen. This process effectively displaces the natural carbon metabolism processes from floodplain wetlands to the main channel. Management options to reduce the impacts of post-flood hypoxia include i) remodifying drainage on the floodplain to promote wetter conditions, thereby shifting vegetation assemblages towards inundation-tolerant species, and ii) strategic retention of floodwaters in the backswamp wetlands to reduce the volume and rate during the critical post-flood recession phase.