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The persistence of conventional fossil fuel-derived plastics in marine ecosystems has raised significant environmental concerns. Biodegradable plastics are being explored as an alternative. This study investigates the biodegradation behaviour in two marine environments of melt-extruded sheets of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) bioplastic as well as blends of PHBV with a non-toxic plasticiser (triethyl citrate, TEC) and composites of PHBV with wood flour. Samples were submerged for up to 35 weeks in two subtropical marine conditions: on the sandy seabed in the sublittoral benthic zone and the sandy seabed of an open air mesocosm with pumped seawater. Rates of biodegradation, lag times and times to 95 % mass loss (T95) were determined through mass loss data and Gompertz modelling. Mechanisms of biodegradation were studied through changes in molecular weight, mechanical properties and surface features. Results reveal a rapid biodegradation rate for all PHBV samples, demonstrating a range of specific biodegradation rates relative to exposed surface area of 0.03 ± 0.01 to 0.09 ± 0.04 mg.d-1.cm-2. This rapid rate of biodegradation meant that the subtle variations in biodegradation mechanisms across different sample thicknesses and additive compositions had little effect on overall lifetimes, with the T95 for most samples being around 250-350 days, regardless of site, highlighting the robust biodegradability of PHBV in seawater. It was only the PHBV-wood flour composite that showed faster biodegradation, and that was only in the exposed ocean site. The mesocosm site was otherwise shown to be a good model for the open ocean, with very comparable biodegradation rates and changes in mechanical properties over time.
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Biodegradação Ambiental , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/análise , Poli-Hidroxialcanoatos/metabolismo , Água do Mar/química , Poliésteres/metabolismo , Plásticos Biodegradáveis/metabolismo , Poli-HidroxibutiratosRESUMO
Enhanced efficiency fertilizers (EEFs) can reduce nitrogen (N) losses in temperate agriculture but are less effective in the tropics. We aimed to design a new EEF and evaluate their performance in simple-to-complex tests with tropical soils and crops. We melt-extruded urea at different loadings into biodegradable polymer matrix composites using biodegradable polyhydroxyalkanoate (PHA) or polybutylene adipate-co-terephthalate (PBAT) polymers with urea distributed throughout the pellet. These contrast with commercially coated EEF that have a polymer-coated urea core. We hypothesized that matrix fertilizers would have an intermediate N release rate compared to fast release from urea or slow release from coated EEF. Nitrogen release rates in water and sand-soil columns confirmed that the matrix fertilizer formulations had a more progressive N release than a coated EEF. A more complex picture emerged from testing sorghum [Sorghum bicolor (L.) Moench] grown to maturity in large soil pots, as the different formulations resulted in minor differences in plant N accumulation and grain production. This confirms the need to consider soil interactions, microbial processes, crop physiology, and phenology for evaluating fertilizer performance. Promisingly, crop δ15N signatures emerged as an integrated measure of efficacy, tracking likely N conversions and losses. The three complementary evaluations combine the advantages of standardized high-throughput screening and more resource-intensive and realistic testing in a plant-soil system. We conclude that melt-blended biodegradable polymer matrix fertilizers show promise as EEF because they can be designed toward more abiotically or more microbially driven N release by selecting biopolymer type and N loading rate.
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Agricultura , Fertilizantes , Nitrogênio , Polímeros , Fertilizantes/análise , Nitrogênio/análise , Agricultura/métodos , Solo/química , Biodegradação Ambiental , SorghumRESUMO
Polyhydroxyalkanoates (PHAs) are a group of natural polyesters that are synthesised by microorganisms. In general, their thermoplasticity and (in some forms) their elasticity makes them attractive alternatives to petrochemical-derived polymers. However, the high crystallinity of some PHAs - such as poly(3-hydroxybutyrate) (P3HB) - results in brittleness and a narrow processing window for applications such as packaging. The production of copolymeric PHA materials is one approach to improving the mechanical and thermal properties of PHAs. Another solution is the manufacture of PHA-based block copolymers. The incorporation of different polymer and copolymer blocks coupled to PHA, and the resulting tailorable microstructure of these block copolymers, can result in a step-change improvement in PHA-based material properties. A range of production strategies for PHA-based block copolymers has been reported in the literature, including biological production and chemical synthesis. Biological production is typically less controllable, with products of a broad molecular weight and compositional distribution, unless finely controlled using genetically modified organisms. By contrast, chemical synthesis delivers relatively controllable block structures and narrowly defined compositions. This paper reviews current knowledge in the areas of the production and properties of PHA-based block copolymers, and highlights knowledge gaps and future potential areas of research.
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Poli-Hidroxialcanoatos , Poliésteres/química , Fenômenos FísicosRESUMO
This study presents a proof of concept for a technology train that integrates polyethylene terephthalate (PET) recovery from mixed plastic waste and plastic pyrolysis. PET is depolymerized into terephthalic acid (TPA) by hydrolysis using a low volatility oil as medium, which enables (i) low-pressure operation, and (ii) a selective separation and recovery of TPA from the product mix by a simple process of filtration, washing, and precipitation. Full PET conversion and high TPA recovery (>98 %) were achieved at 260 °C. This technology train is demonstrated to be effective for processing mixed waste streams, leading to higher yield and quality of liquid product from thermal pyrolysis when compared with feedstock that has not been pre-treated. Further, the technology could be readily integrated with a plastics pyrolysis process, whereby a by-product from the pyrolysis could be used as the low-volatility oil.
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Plásticos , Polietilenotereftalatos , Solventes , Pirólise , Reciclagem , HidrocarbonetosRESUMO
Bacterially derived polyhydroxyalkanoates (PHAs) are attractive alternatives to commodity petroleum-derived plastics. The most common forms of the short chain length (scl-) PHAs, including poly(3-hydroxybutyrate) (P3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), are currently limited in application because they are relatively stiff and brittle. The synthesis of PHA-b-PHA block copolymers could enhance the physical properties of PHAs. Therefore, this work explores the synthesis of PHBV-b-PHBV using relatively high molecular weight hydroxy-functionalised PHBV starting materials, coupled using facile diisocyanate chemistry, delivering industrially relevant high-molecular-weight block copolymeric products. A two-step synthesis approach was compared with a one-step approach, both of which resulted in successful block copolymer production. However, the two-step synthesis was shown to be less effective in building molecular weight. Both synthetic approaches were affected by additional isocyanate reactions resulting in the formation of by-products such as allophanate and likely biuret groups, which delivered partial cross-linking and higher molecular weights in the resulting multi-block products, identified for the first time as likely and significant by-products in such reactions, affecting the product performance.
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Plastic pollution is a critical problem that has the potential for long-lasting impact. While all plastics eventually break down to at least some degree, they can remain in different transition states, such as microplastics and nanoplastics, for extended periods of time before reaching complete mineralisation to non-hazardous end products. Each of the transition states represents different types of hazards, so it is critical to understand the factors driving the lifetimes of plastics within these states. To do this, we propose a framework for assessing plastic lifetimes in natural environments based on the flow of material through potentially hazardous states: macroplastic and mesoplastic, microplastic, nanoplastic and soluble products. State changes within this framework are underpinned by three key processes: fragmentation, depolymerisation, and bioassimilation, with the pathways for generation of the different plastic states, and the lifetimes within these states, varying widely for individual materials in different environments due to their dependence on polymer material type, form and properties, and environmental factors. The critical factors driving these processes can therefore appear complex, but molecular weight, crystallinity, oxygen and water diffusivity, and inherent polymer chain reactivity (including to enzymes) are key to our understanding. By analysing currently available data that take factors such as these into consideration, we have generated information on the most likely states in which a range of plastics with different environmental degradation behaviour may exist over time in natural environments. Polyethylene (PE), for example, should be expected to fragment and accumulate in the environment as microplastic and nanoplastic. Interestingly, the state-profile for the biodegradable plastic polylactic acid (PLA) is similar, albeit over shorter timeframes. PLA also likely fragments, but then the relatively slow process of abiotic depolymerisation results in accumulation of microplastic and nanoplastic. By contrast, the state-profile for the biodegradable plastic polyhydroxyalkanoate (PHA) would be expected to be very different. The bulk material is less susceptible to embrittlement and fragmentation as a primary path to biodegradation, since the rapid enzyme catalysed depolymerisation of exposed surfaces proceeds in conjunction with bioassimilation.
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Plásticos Biodegradáveis , Poluentes Químicos da Água , Plásticos/análise , Microplásticos , Poliésteres , Polímeros , Biodegradação Ambiental , Poluentes Químicos da Água/análiseRESUMO
While new biodegradable materials are being rapidly introduced to address plastic pollution, their end-of-life impacts remain unclear. Biodegradable plastics typically comprise a biopolymer matrix with functional additives and/or solid fillers, which may be toxic. Here, using an established method for continuous biodegradation monitoring, we investigated the impact of a commonly used plasticizer, dibutyl phthalate (DBP), on the biodegradation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) in soil. The presence of DBP delayed the initial stage of PHBV biodegradation but then accelerated subsequent rates of biodegradation. Furthermore, it led to significant increases in total bacterial and fungal biomass and altered the composition of microbial communities with significant increases in the relative abundances of Thauera (gammaproteobacterial) and Mucor circinelloides (fungal) populations. It is proposed, with evidence from biodegradation behavior and microbial analysis, that the presence of DBP likely stimulated a microbial community shift, introduced higher proportions of more readily degradable amorphous regions from the plasticizing effect, and facilitated access to the bulk polymer matrix for microorganisms or at least their associated enzymes. These effects in combination overcame the initial inhibition effect of the DBP and resulted in a net increase in the rate of biodegradation of PHBV.
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Ácidos Ftálicos , Poli-Hidroxialcanoatos , Plastificantes , Dibutilftalato/metabolismo , Biodegradação AmbientalRESUMO
Paunch is a fibrous solid residue consisting of partially digested feed from the stomachs of processed cattle. It is the largest untapped solid waste stream from animals at meat processing plants, and potentially a valuable source of fibres for the production of sustainable and potentially higher-value natural biocomposite materials. Paunch was obtained from the waste effluent of a red meat processing plant, and the fibre characteristics of the as-obtained material were studied and benchmarked against wood flour and ground buffel grass, with a view to evaluating the potential of paunch as a fibre for polymer composites. The ground paunch possessed a rough fibrous surface and fibre-like characteristics that were comparable to both wood flour and ground buffel grass, demonstrating their potential for use in composites. Without any pre-treatment or compatibilisation, composites of a representative biopolymer, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and ground paunch were successfully produced for the first time via extrusion, with up to 50 wt% paunch content. Mechanical property analysis showed that, at 30 wt% content, PHBV/ground paunch composites yielded mechanical properties that were comparable to those of composites with ground buffel grass.
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Significant efforts have recently been invested in assessing the physical and chemical properties of microbial nanowires for their promising role in developing alternative renewable sources of electricity, bioelectronic materials and implantable sensors. One of their outstanding properties, the ever-desirable conductivity has been the focus of numerous studies. However, the lack of a straightforward and reliable method for measuring it seems to be responsible for the broad variability of the reported data. Routinely employed methods tend to underestimate or overestimate conductivity by several orders of magnitude. In this work, synthetic peptide nanowires conductivity is interrogated employing a non-destructive measurement technique developed on a terahertz scanning near-field microscope to test if peptide aromaticity leads to higher electrical conductivity. Our novel peptide conductivity measurement technique, based on triple standards calibration method, shows that in the case of two biopolymer mimicking peptides, the sample incorporating aromatic residues (W6) is about six times more conductive than the negative control (L6). To the best of our knowledge, this is the first report of a quantitative nano-scale terahertz s-SNOM investigation of peptides. These results prove the suitability of the terahertz radiation-based non-destructive approach in tandem with the designer peptides choice as model test subjects. This approach requires only simple sample preparation, avoids many of the pitfalls of typical contact-based conductivity measurement techniques and could help understanding fundamental aspects of nature's design of electron transfer in biopolymers.
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Condutividade Elétrica , Nanofios/química , Peptídeos/química , Espectroscopia Terahertz , MicroscopiaRESUMO
In the present paper, we describe how a robust and fundamental methodology was developed for extraction and determination of a principal natural toxin compound, simplexin, from a series of bulk biocomposites. These complex matrices were fabricated by direct encapsulating either ground plant particles or an ethanolic crude extract of the Australian toxic pasture plant Pimelea trichostachya in the biodegradable polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Proton nuclear magnetic resonance spectroscopy was initially employed to examine the chemical compositions of these complicated systems. Then, a more sensitive strategy was developed and validated by combining solid-phase extraction and ultrahigh-performance liquid chromatography hyphenated with a quadrupole Orbitrap mass spectrometer for the quantification of simplexin embedded in different biocomposites. Satisfactory linearity (R2 > 0.99) and recovery ranges (86.8-116%) with precision (relative standard deviations) of between 0.2 and 13% (n = 3) were achieved from seven biocomposites. The established protocol was further shown to be accurate and reliable in confirming the homogeneous distribution of the simplexin in different biocomposite formulations. A limited mass transfer of simplexin (< 3.5%) from one of the biocomposites into a simulated but sterilized in vitro rumen environment after a 10-day incubation was also revealed by utilizing the method. This quantitative analysis of targeted natural product within plant material-integrated polymeric platforms has potential application when controlled release is required in the bovine rumen and other biological systems. Graphical abstract.
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Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas/métodos , Terpenos/química , Thymelaeaceae/química , Extratos Vegetais/química , Sensibilidade e EspecificidadeRESUMO
Ammonium sorption and recovery processes typically take place in conventional packed columns, with a configuration that enables maximum sorption by the sorbents. However, batch or semi-continuous operations in packed columns have associated issues such as scaling and frequent backwashing requirements, which are economically prohibitive. As an alternative, ammonium sorption could occur in well-mixed continuously stirred tanks, which would allow for the ammonium sorption process to be retrofitted in existing wastewater treatment plants, provided that efficient sorbent separation can be achieved. This study demonstrates, for the first time, the preparation of magnetic poly(acrylic acid)-based (PAA) ammonium sorbents through the incorporation of magnetic (Fe3O4) nanoparticles (MNP) produced via scalable and cost-effective electrochemical synthesis. The MNP and PAA hydrogels were synthesized independently and the MNPs subsequently integrated into the PAA hydrogel network by particle diffusion and physical entrapment. No adverse effects on swelling and ammonium sorption following immersion in either synthetic or real sewage were observed after MNPs were incorporated into the hydrogels. Importantly, PAA-MNP hydrogels demonstrated high ammonium sorption efficiencies (80-93%) in real sewage and achieved rapid ammonium recovery of 73 ± 1.1% within 15 min of mild acid washing (pH 4) 15 min at a maximum recovery.
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Pimelea poisoning of cattle, historically known as St. George Disease or Marree Disease, is a prevailing issue in arid grazing regions of inland Australia. Ingestion of the toxic native Pimelea species that contain the secondary metabolite simplexin, a diterpene orthoester with potent protein kinase C activity, induces diarrhoea, characteristic oedema and potentially fatal right-sided heart failure in cattle. Outbreaks of toxic Pimelea in the grazing field depend on seasonal prevalence. However, all stages of the plant carry the toxin, from seeds, juvenile plants to dead plant material. Livestock generally avoid consuming green Pimelea plants and only consume toxic Pimelea when pasture is minimal or where Pimelea growing through grass tussocks results in inadvertent ingestion. Our knowledge base of Pimelea poisoning has greatly improved with past research, yet the health hazards for livestock grazing in Pimelea affected pastures remains a significant issue whilst the ongoing search to develop effective strategies to mitigate poisoning continues. The goal of this review is to collate historical and recent research giving an overview of the current understandings of Pimelea poisoning, the toxin, its toxic effects and progress made towards remedies to alleviate the effects of Pimelea intoxication.
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Doenças dos Bovinos/epidemiologia , Intoxicação por Plantas/veterinária , Thymelaeaceae , Animais , Bovinos , Diterpenos , Gado , Intoxicação por Plantas/epidemiologia , Terpenos , Toxinas BiológicasRESUMO
Rapid and continuous ammonium adsorption from mainstream coupled with side-stream ammonium recovery and adsorbent regeneration could enable ammonium recovery from domestic wastewater. This study describes the use of tailored poly(acrylic acid)-based (NaPAA) hydrogels as effective sorbents for ammonium removal from domestic wastewater. Modified NaPAA hydrogels having 60% ionization and 4.8 mol % N',N'-methylenebisacrylamide as the cross-linker reduced the overall swelling by 92% from 407 to 31 g/g because of higher cross-linking density. At hydrogel loadings of 2.5-7.5 g/L, the NaPAA hydrogels achieved ammonium concentrations of 8.3 ± 0.6 to 10.1 ± 0.1 mg/L NH4-N, which corresponds to removal efficiencies of 53-77% after 10 min of contact time in real domestic wastewater. At the same hydrogel loadings, the ammonium removal efficiency of NaPAA hydrogels in synthetic wastewater was found to be comparable to that in real sewage (71% vs 69%, respectively), suggesting that the sorption performance is only marginally affected by organic constituents found in domestic wastewater. In addition, the NaPAA hydrogels removed 25-51% ammonium in 10 min from synthetic streams having 200-400% higher ionic strengths than those commonly observed in sewage. Furthermore, simulation studies showed that a discharge concentration of â¼1.9 mg/L NH4-N, well below the commonly applied discharge limits in most regions, can be achieved using mainstream ammonium removal by NaPAA hydrogels followed by biological assimilation from the growth of ordinary heterotrophic organisms.
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Compostos de Amônio , Águas Residuárias , Resinas Acrílicas , HidrogéisRESUMO
BACKGROUND: Various active chemical agents, such as soil microbial inhibitors, are commonly applied to agricultural landscapes to optimize plant yields or minimize unwanted chemical transformations. Dicyandiamide (DCD) is a common nitrification inhibitor. However, it rapidly decomposes under warm and wet conditions, losing effectiveness in the process. Blending DCD with an encapsulating polymer matrix could help overcome this challenge and slow its release. Here, we encapsulated DCD in a biodegradable matrix of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and investigated the effects of DCD crystal size and loading rates on release rates. RESULTS: Three DCD crystal size fractions (0-106, 106-250 and 250-420 µm) were blended with PHBV at 200, 400, 600 and 800 gkg-1 loadings through extrusion processing and release kinetics were studied in water over 8 weeks. For loadings ≥ 600 g kg-1 , more than 95% release was reached within the first 7 days. By contrast, at 200 g kg-1 loading only 10%, 36% and 57% of the DCD was mobilized after 8 weeks in water for 0 to 106 µm, 106 to 250 µm and 250 to 420 µm crystal size fractions, respectively. CONCLUSION: The lower percolation threshold for this combination of materials lies between 200 and 400 g kg-1 DCD loading. The grind size fraction of DCD significantly affects the quantity of burst release from the surface of the pellet, particularly below the lower percolation threshold. The results presented here are likely translatable to the encapsulation and release of other crystalline materials from hydrophobic polymer matrices used in controlled release formulations, such as fertilizers, herbicides and pesticides. © 2020 Society of Chemical Industry.
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Agroquímicos/química , Preparações de Ação Retardada/química , Composição de Medicamentos/métodos , Agricultura , Guanidinas/química , Cinética , Polímeros/químicaRESUMO
A rapid and cost-effective reactive extrusion (REx) method was employed in this study as an alternative technique for the graft-copolymerization of non-food grade native wheat starch with acrylamide, and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) monomers, with a total starch/monomer ratio of 3:1, using twin-screw extrusion technology. The influence of AMPS content ratio on the REx process was monitored using specific mechanical energy, die pressure and torque values recorded during the extrusion. The as-prepared starch-copolymers were characterized using ATR-FTIR, NMR, TG-DSC, and elemental analysis. An average grafting efficiency and monomer conversion of ~61 and ~86%, respectively, was achieved within 5 min of extrusion at a high starch concentration (0.75:1 w/w starch-water). The copolymer with starch/acrylamide/AMPS weight ratio of 75:20:4 showed the highest swelling capacity in water, while behaving similarly to polyelectrolyte networks in the presence of free ions in both NaCl and NH4Cl solutions. A steady NH4+ adsorption capacity was also recorded for these starch-copolymers within the pH range of ~5.5-8.5, which exceeded those of the natural sorbents. These findings indicate the suitability of the starch-copolymers as potential precursors of effective sorbents, thus confirming the feasibility of using REx to produce pH-responsive hybrid copolymers based on wheat starch at low-cost.
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Compostos de Amônio/isolamento & purificação , Polímeros/química , Amido/química , Água/química , Adsorção/efeitos dos fármacos , Compostos de Amônio/química , Concentração de Íons de Hidrogênio , Polimerização , Polímeros/síntese química , Polímeros/farmacologia , Solventes/química , Solventes/farmacologia , Amido/síntese química , Amido/farmacologia , Temperatura , Triticum/químicaRESUMO
To promote the large-scale production of starch-based biomaterials, we developed a method of synthesis based on reactive extrusion that combines the benefits of continuous manufacturing with the use of green chemistry principles. This paper describes the grafting of four different types of starches with acrylamide monomers via free radical copolymerization using twin-screw extrusion technology. The elemental analysis confirmed the success of this method, with an average monomer conversion of 80% and grafting efficiency of Ë74% across all samples. The 13C-NMR/1H-NMR and ATR-FTIR analysis revealed that the type of starch substrate used strongly influenced the mechanism of the grafting reaction. Thermal analysis (TG/DTG-DSC) indicated that the graft-copolymers thermal stability was influenced by the amylose-amylopectin content ratio. Swelling tests suggested that cationic modification of the substrate is a promising approach to produce stimuli-responsive graft-copolymers via reactive extrusion. The proposed method has proved to be a viable alternative for the production of starch-copolymers.
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Throughout the 20th century, the prevailing approach toward nitrogen management in municipal wastewater treatment was to remove ammonium by transforming it into dinitrogen (N2) using biological processes such as conventional activated sludge. While this has been a very successful strategy for safeguarding human health and protecting aquatic ecosystems, the conversion of ammonium into its elemental form is incompatible with the developing circular economy of the 21st century. Equally important, the activated sludge process and other emerging ammonium removal pathways have several environmental and technological limitations. Here, we assess that the theoretical energy embedded in ammonium in domestic wastewater represents roughly 38-48% of the embedded chemical energy available in the whole of the discharged bodily waste. The current routes for ammonium removal not only neglect the energy embedded in ammonium, but they can also produce N2O, a very strong greenhouse gas, with such emissions comprising the equivalent of 14-26% of the overall carbon footprint of wastewater treatment plants. N2O emissions often exceed the carbon emissions related to the electricity consumption for the process requirements of WWTPs. Considering these limitations, there is a need to develop alternative ammonium management approaches that center around recovery of ammonium from domestic wastewater rather than deal with its "destruction" into elemental dinitrogen. Current ammonium recovery techniques are applicable only at orders of magnitude above domestic wastewater strength, and so new techniques based on physicochemical adsorption are of particular interest. A new pathway is proposed that allows for mainstream ammonium recovery from wastewater based on physicochemical adsorption through development of polymer-based adsorbents. Provided adequate adsorbents corresponding to characteristics outlined in this paper are designed and brought to industrial production, this adsorption-based approach opens perspectives for mainstream continuous adsorption coupled with side-stream recovery of ammonium with minimal chemical requirements. This proposed pathway can bring forward an effective resource-oriented approach to upgrade the fate of ammonium in urban water management without generating hidden externalized environmental costs.
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Compostos de Amônio , Águas Residuárias , Ecossistema , Esgotos , Eliminação de Resíduos LíquidosRESUMO
Nanocellulose, as a biobased versatile nanomaterial that can be derived with tailorable surface functionalities, dimensions, and morphologies, has considerable implications for modifying the rheology, mechanical reinforcement, and influencing the carbonization efficiency in the production of polyacrylonitrile (PAN)-based carbon fibers. Herein, we report the influence of three different nanocellulose types, varying in the derivatization method, source, and aspect ratio, on the mechanical properties and thermal transformations of solution-spun PAN/nanocellulose nanocomposite fibers into carbon fibers. The incorporation of 0.1 wt % nanocellulose into solution-spun PAN fibers led to a 7-19% increase in tensile modulus and 0-27% increase in tensile strength in the solution-spun fibers, compared to a control PAN fiber. These improvements varied depending on the nanocellulose type. After low-temperature carbonization at 1200 °C, improvements in the mechanical properties of the nanocellulose-reinforced carbon fibers, compared with a PAN fiber, were also observed. In contrast to the precursor fibers, the improvement % in the carbonized fibers was found to be dependent on the nanocellulose morphology and was linearly correlated with increasing aspect ratio of nanocellulose. For example, in carbon fibers with a cotton-derived low-aspect-ratio cellulose nanocrystal and spinifex-derived high-aspect-ratio CNC and nanofiber, up to 4, 87, and 172% improvements in tensile moduli were observed, respectively. Due to the processing methods used, the nanocellulose aspect ratio and crystallinity are inversely related, and as such, the increase in the carbon fiber mechanical properties was also related to a decrease in crystallinity of the nanocellulose reinforcers. Raman spectra and electron microscopy analysis suggest that mechanical improvement after carbonization is due to internal reinforcement by highly ordered regions surrounding the carbonized nanocellulose, within the turbostratic carbon fibers.
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The production of polyhydroxyalkanoates (PHAs) from methane is limited to mesophiles and thus suffers from high energy requirements for cooling. To address this issue, the use of thermophilic processes is gaining interest, as this strategy may deliver improved economic feasibility for PHA production. This study reports the first thermophilic PHA-producing culture grown on methane at 55⯰C in fill-and-draw batch reactors. Harvested cells were incubated with various combinations of methane, propionic acid and valeric acid to assess their capacity for the synthesis of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Only PHB was produced when fed with methane alone. The addition of odd-carbon-number fatty acids resulted in higher PHA content with 3â¯HV fractions in the range of 15-99â¯mol%, depending on the types of fatty acids added. Acetic acid addition enhanced the synthesis of 3HB monomer, but not of 3â¯HV. On increasing the temperature to 58⯰C, PHA productivity was not significantly affected.