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.

Relaxation Effects of Essential Oils Are Explained by Their Interactions with Human Brain Neurotransmitter Receptors and Electroencephalography Rhythms.

Inhaled essential oils (EOs) are bioavailable to the brain and are consistently reported to promote relaxation effects. Their mechanisms of action are however not well understood. The aim of this investigation was to assess the neuroactivity of EOs based on their (i) binding interactions to neurotransmitter receptors and (ii) bioelectrical activities in the brain as measured by electroencephalography (EEG). These EO properties were compared to those of reference pharmaceutical compounds with effects also measured by EEG. Relative receptor binding efficacies of 10 reference compounds, 180 EOs, and 9 EO extracts with 7 different neurotransmitter receptors were calculated using in silico molecular docking procedures. Changes in brain EEG rhythms, as standardized changes in absolute power, were determined for the reference compounds and selected EOs and compared to receptor binding efficacy results. The reference compounds had diverse receptor binding patterns, with EEG responses dominated by EEG-delta wave frequencies. In contrast, the receptor binding pattern of the EOs was remarkably consistent and replicated a subclinical affinity pattern corresponding to the inhibitory glycine-α-GLRA3 and dopamine-D2 receptors, producing responses dominated by EEG-alpha wave frequencies. The results support the hypothesis that EOs stimulate neuroactivity by modulating patterns of neurotransmission affecting alpha wave EEG responses.

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.

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.

Partial exchange of Fe(III) montmorillonite with hexadecyltrimethylammonium cation increases catalytic activity for hydrophobic substrates.

Fe(III) montmorillonite clay that was partially exchanged with hexadecyltrimethylammonium (HDTMA(+)) cations achieved increased catalytic activity for the oxidative coupling of hydrophobic organic substrates. A series of mixed-cation organoclays were produced, where the organic cation content ranged from 6 to 50% relative to the cation-exchange capacity (CEC) of the clay, and were tested for catalytic activity using different Fe(III)-mediated oxidative coupling reactions. Enhanced catalytic activity by Fe(3+)/HDTMA(+) montmorillonite for coupling hydrophobic substrates was observed, with maximum catalytic activity in the oxidative coupling of 2-naphthol observed at 6% HDTMA(+) coverage. However, maximum catalytic activity with a more hydrophobic substrate, anthrone, was achieved with 50% HDTMA(+) coverage, indicating that matching levels of organic modification to substrate hydrophobicity improves catalytic activity. The organization of the organic cations at the clay surfaces proved to be heterogeneous, as determined by scanning transmission X-ray microscopy (STXM) and powder X-ray diffraction. Results from molecular dynamics simulations supported the heterogeneous nature of the catalysts but also pointed toward large regions within the interlayers that may be filled with nonreactive hydrated Fe oxides resulting from the organic cation treatment. The exchangeable Fe content of the organic treated clays, as determined by AAS and ICP measurements, was observed to be higher than expected relative to that of Fe-saturated clay, substantiating this hypothesis. These findings have implications for the development of substrate-specific clay catalysts, where the composition and configuration of exchangeable cations can be matched to a particular substrate or reaction.

Extraction and crosslinking of bromelain aggregates for improved stability and reusability from pineapple processing waste.

The present study is first of its kind that focuses upon the extraction of bromelain from pineapple core waste and stabilising it as insoluble cross-linked aggregates. The influence of process variables such as the choice of precipitant, type of cross-linker, concentration of cross-linker and the reaction time for cross-linking step was investigated upon the activity recovery of bromelain cross-linked aggregates. The optimization of this biocatalyst preparation specifically recovered 87% of the enzymatic activity available in pineapple core waste by ammonium sulphate (60%, w/v) precipitation followed by cross-linking for 4 h with 80 mM glutaraldehyde. Cross-linked bromelain aggregates were thermally more stable and exhibited higher pH stability in comparison to free bromelain. The cross-linked bromelain aggregates exhibited higher operational stability in different organic solvents at 4 °C. The highest operational stability (% stability given in parenthesis) was observed in acetone (100%) followed by hexane (53.6%), ethyl acetate (39.6%), ethanol (32.5%) and chloroform (14.9%). The kinetic studies revealed higher Km value (5.45 mM) after the formation of cross-linked bromelain aggregates as compared to free bromelain (5.04 mM) with almost similar Vmax values. Cross-linked bromelain aggregates also showed significant reusability characteristics with an activity retention of >85% after 5-time cycles. Such recyclability of bromelain cross-linked aggregates could lead to potential industrial applications in both food and non-food sector. In addition, the present extraction method avoids costs related to purification and expensive immobilization carriers.

Chemical composition of composted grape marc.

Composted grape marc, produced at the vineyard using different procedures, is generally returned into the vineyard. Information on the chemical composition of these grape marc composts is lacking, particularly the variability that may result from different composting practices. In this study, grape marc composts, varying in age from 3 months to 3 years, were collected from four different vineyards and subjected to detailed chemical analysis. The chemical analysis revealed that all the grape marc composts contained levels of free potassium, in the range of 2-3% w/w. Plant macronutrients such as Ca, S, Mg were present at low levels (<1% w/w), while phosphorus (0.1-0.3% w/w) and nitrogen (1-2% w/w) levels were not very high and mainly present in "plant unavailable" form. The levels of soluble salts, though not excessive, were elevated in all the composts. These salt levels could cause a problem in some soils. Heavy metals were not present in any significant levels. All the grape marc composts analysed provided some benefit in returning nutrients into the vineyard and all were significant potassium sources.

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.

An integrated green biorefinery approach towards simultaneous recovery of pectin and polyphenols coupled with bioethanol production from waste pomegranate peels.

An integrated biorefinery, incorporating hydrothermal processing of waste pomegranate peels (WPP), was proposed for the acid and organic solvent-free simultaneous recovery of pectin and phenolics with bioethanol production. The hydrothermal treatment (HT) was optimized using Box-Behnken design and the maximum recovery of pectin (18.8-20.9%) and phenolics (10.6-11.8%) were obtained by hydrothermal treatment at 115 °C for 40 min with a liquid-solid ratio of 10. The WPP pectin was characterized by IR, 1H NMR, and TGA which showed close similarity to commercial pectin. Depending on WPP cultivar type the degree of esterification, galacturonic acid content and molecular weight of pectin were in the range of 68-74%, 71-72%, and 131,137-141,538 Da, respectively. The recovered phenolics contained 57-60% punicalagin. Enzyme digestibility of WPP improved using HT with 177 g glucose produced per kg dry mass which was fermented to obtain 80 g ethanol with 88% of theoretical yield.

CuSO4/H2O2-Catalyzed Lignin Depolymerization under the Irradiation of Microwaves.

The increasing demand for renewable materials in the world has resulted in sustained efforts to utilize biomass in a better way. Lignin, a natural and abundant polymer in plants, has provided an ongoing challenge for many researchers seeking ways to better utilize this abundant resource. Here, we report a very efficient lignin depolymerization strategy with the assistant of microwave radiation. Copper sulphate (CuSO4) and hydrogen peroxide (H2O2) were used to generate hydroxyl radicals to depolymerize lignin under the irradiation of microwaves. Three different types of lignin, organosolv lignin, kraft lignin, and alkali lignin, were all successfully depolymerized using microwave irradiation at a temperature of 110 °C for 7 min. The use of 1H/13C two-dimensional nuclear magnetic resonance spectroscopy enabled the confirmation of structural changes, comparing before and after depolymerization. Liquid chromatography-mass spectrometry was used to characterize the products. Both monomers and oligomers were detected after depolymerization.

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.

Hybrid brown coal-urea fertiliser reduces nitrogen loss compared to urea alone.

Synthetic nitrogen (N) fertilisers, such as urea, are susceptible to rapid dissipation from soil. More gradual release of mineral N from fertiliser may reduce the off-site movement of mineral N, thereby enhancing N supply to crops and minimising negative off-site impacts. We hypothesised that granulation of urea with humified brown coal (BC) delays mineral N release and maintains higher concentrations of N in soil than conventional urea granules. Four different brown coal-urea granules, with C:N ratios of 1-10, were prepared by pan granulation. Advanced spectroscopic and X-ray powder diffraction (XRD) techniques confirmed loading of urea-N into the BC structure. Nitrogen-release from BCU granules was slower than from urea, resulting in higher N retention over a longer period for increasing growth and N uptake by crop plants. This trend increased with higher loading of BC, emphasising the significant role of BC in N retention. These findings support the hypothesis that BC is suitable for developing slow release N fertilisers.

Bioactives from fruit processing wastes: Green approaches to valuable chemicals.

Fruit processing industries contribute more than 0.5billion tonnes of waste worldwide. The global availability of this feedstock and its untapped potential has encouraged researchers to perform detailed studies on value-addition potential of fruit processing waste (FPW). Compared to general food or other biomass derived waste, FPW are found to be selective and concentrated in nature. The peels, pomace and seed fractions of FPW could potentially be a good feedstock for recovery of bioactive compounds such as pectin, lipids, flavonoids, dietary fibres etc. A novel bio-refinery approach would aim to produce a wider range of valuable chemicals from FPW. The wastes from majority of the extraction processes may further be used as renewable sources for production of biofuels. The literature on value addition to fruit derived waste is diverse. This paper presents a review of fruit waste derived bioactives. The financial challenges encountered in existing methods are also discussed.

Photoelectrochemical water oxidation by screen printed ZnO nanoparticle films: effect of pH on catalytic activity and stability.

Nanostructured ZnO films are promising photoanode materials in photoelectrochemical water splitting. While such ZnO photoanodes have achieved high activity and good light conversion efficiency in the UV spectral region, their application in water splitting devices has been hampered by the susceptibility of ZnO towards photocorrosion in aqueous electrolytes. We report a systematic investigation aimed at optimising the electrolyte solution to improve the long-term stability of ZnO photoanodes. A stability diagram, based on the band edge positions of ZnO and the pH-dependent photodegradation potentials of ZnO (relative to the decomposition of water), indicates that the optimum pH operating conditions for ZnO photoanodes lie between pH 9-12.5. To verify this prediction experimentally, the activity and long-term stability of uniform screen-printed nano-ZnO films was tested in a wide range of buffered and non-buffered electrolytes (pH 6-13.5). The ZnO films were more active in buffered, than in non-buffered electrolytes, and the highest activities were observed close to the pKa of the phosphate and borate buffers used. Under zero applied potential, these screen-printed films achieved the highest reported photocurrents to date (0.42 mA cm(-2) at pH 6 and 0.67 mA cm(-2) at pH 10.5) for any pristine or modified ZnO-based water oxidation catalyst. The films were subjected to 12 h of controlled potential electrolysis, in selected electrolytes, under AM 1.5G simulated sunlight. The results are in good agreement with calculations based on thermodynamic data for ZnO. Films tested at pH 6 and 7 (representing typically used operating conditions) degraded rapidly, whereas they exhibited the highest stability when tested in a pH 10.5 borate buffer. In this case, 75% of the initial photoactivity was preserved after 12 hours, indicating that the lifetime of the electrode could be increased by over an order of magnitude compared to standard testing conditions.

Winery wastewater inhibits seed germination and vegetative growth of common crop species.

The ability to reuse winery wastewater would be of significant benefit to the wine industry, as it could potentially be a cost-effective method of wastewater management, whilst at the same time providing a valuable water resource. This study investigated the effects of different dilutions of a semi-synthetic winery wastewater on the growth and germination of four common crop species in a glasshouse study; barley (Hordeum vulgare), millet (Pennisetum glaucum), lucerne (Medicago sativa) and phalaris (Phalaris aquatica). The wastewater caused a significant delay in the germination of lucerne, millet and phalaris, although overall germination percentage of all species was not affected. Vegetative growth was significantly reduced in all species, with millet being the most severely affected. The germination index of barley correlated very highly (r(2)=0.99) with barley biomass, indicating that barley seed germination bioassays are highly relevant to plant growth, and therefore may be of use as a bioassay for winery wastewater toxicity.