Добірка наукової літератури з теми "Biochar characterisation"

Biochar properties can be significantly influenced by feedstock source and pyrolysis conditions; this warrants detailed characterisation of biochars for their application to improve soil fertility and sequester carbon. We characterised 11 biochars, made from 5 feedstocks [Eucalyptus saligna wood (at 400°C and 550°C both with and without steam activation); E. saligna leaves (at 400°C and 550°C with activation); papermill sludge (at 550°C with activation); poultry litter and cow manure (each at 400°C without activation and at 550°C with activation)] using standard or modified soil chemical procedures. Biochar pH values varied from near neutral to highly alkaline. In general, wood biochars had higher total C, lower ash content, lower total N, P, K, S, Ca, Mg, Al, Na, and Cu contents, and lower potential cation exchange capacity (CEC) and exchangeable cations than the manure-based biochars, and the leaf biochars were generally in-between. Papermill sludge biochar had the highest total and exchangeable Ca, CaCO3 equivalence, total Cu, and potential CEC, and the lowest total and exchangeable K. Water-soluble salts were higher in the manure-based biochars, followed by leaf, papermill sludge, and wood biochars. Total As, Cd, Pb, and polycyclic aromatic hydrocarbons in the biochars were either very low or below detection limits. In general, increase in pyrolysis temperature increased the ash content, pH, and surface basicity and decreased surface acidity. The activation treatment had a little effect on most of the biochar properties. X-ray diffraction analysis showed the presence of whewellite in E. saligna biochars produced at 400°C, and the whewellite was converted to calcite in biochars formed at 550°C. Papermill sludge biochar contained the largest amount of calcite. Water-soluble salts and calcite interfered with surface charge measurements and should be removed before the surface charge measurements of biochar. The biochars used in the study ranged from C-rich to nutrient-rich to lime-rich soil amendment, and these properties could be optimised through feedstock formulation and pyrolysis temperature for tailored soil application.

Adopting the concept of the waste to wealth approach, agricultural waste from maize cob could be transformed into a renewable form of energy through thermo-chemical methods of treating the biomass. This method can be utilised for biochar production. The utilisation of biochar has several significant applications. These applications include the enhancement of the soil through amendment, stimulation of crop production by a variety nutrient inputs in the soil, etc. In this research work, a biochar was obtained through a slow pyrolysis process of maize cob waste. This experiment was carried out using a small-scale muffle furnace and subjecting the feedstock to heating at different temperatures (300, 400, 500 °C). The biochar was produced and characterised by a proximate analysis, scan electron microscope (SEM), Fourier transform infrared (FTIR) spectroscopy, while the surface area was determined by Saer's method. The effect of the temperature on the yield of the biochar was investigated. The results show that the biochar yield decreases with an increasing temperature for the maize cob biochar at 300, 400 and 500 °C. The results of the physiochemical properties showed that the temperature has a great impact on the physicochemical properties of the biochar. The biochar produced at 300 °C has the highest fixed carbon content of 60.5%. The largest surface area was (281.8 m2·g^–1) at 500 °C.

ABSTRACTPalm oil has been the world's main source of oil and fats since 2004, producing over 45 million tonnes in 2009. Malaysia alone has over 4·5 million hectares planted with oil palm and, based on common practice, ∼300 palm fronds are pruned per hectare per year. This agricultural waste is currently either being used as roughage feed or, more frequently, being left between rows of palm trees to prevent soil erosion, or for nutrient recycling purposes. This paper proposes an alternative use for palm frond as a source of biochar. A traditional method commonly use by gardeners in Malaysia to improve soil fertility was used to produce the biochar. A shallow earth pit was dug in the ground for the carbonisation process. The process is described and the impact of carbonisation on the earth wall is analysed and presented. The process was later re-assessed by using TGA-FTIR. Most of the hemicelluloses had fully disintegrated, but the depolymerisation of the cellulose was still incomplete at the carbonisation temperature. Most of the lignin aromatic structure was still present in the biochar. The carbonisation process was repeated in the laboratory and biochar was characterised by using BET, SEM and FTIR. An adsorption isotherm study was conducted and the experimental data were fitted to the Langmuir model. The model predicted Pb2+ adsorption rates of 83·3 mg/g, Cu2+ 41·4 mg/g, Ni2+ 13·0 mg/g and Zn2+ 19·7 mg/g.

AbstractMarabu (Dichrostachys cinerea) from Cuba and aspen (Populus tremula) from Britain are two rosid angiosperms that grow easily, as a weed and as a phytoremediator, respectively. As part of scientific efforts to valorise these species, their barks and woods were pyrolysed at 350, 450, 550 and 650 °C, and the resulting biochars were characterised to determine the potential of the products for particular applications. Percentage carbon composition of the biochars generally increased with pyrolysis temperature, giving biochars with highest carbon contents at 650 °C. Biochars produced from the core marabu and aspen wood sections had higher carbon contents (up to 85%) and BET surface areas (up to 381 m2 g−1) than those produced from the barks. The biochar porous structures were predominantly mesoporous, while micropores were developed in marabu biochars produced at 650 °C and aspen biochars produced above 550 °C. Chemical and thermal activation of marabu carbon greatly enhanced its adsorption capacity for metaldehyde, a molluscicide that has been detected frequently in UK natural waters above the recommended EU limit.

An investigation on the reduction of iron ore with carbonaceous material as a reductant was carried out at 1550°C. Iron ore was mixed with biochar from palm shell and coke as a reference at C/O molar ratio of 1.0. Characterisation of raw materials was performed using X-ray Fluorescence (XRF), Brunauer–Emmett–Teller (BET), Fourier Transmittance Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM-EDX). The samples after reduction were characterised to study the phase transformation and structural properties. The XRD results revealed the iron ore contained hematite as its main composition. After reduction at high temperature, the hematite has been successfully reduced to metallic iron using biochar as a reductant. It was found that the reaction proceeded in a stepwise reduction of iron oxide. The SEM micrographs proved the formation of metallic iron in the sample after reduction at 1550°C. Through characterisation, the biochar from palm shell has physical properties suitable to be an alternative carbon reductant to replace coke.

Ciprofloxacin is an antibiotic compound that is used for various health issues like headaches, nervousness, nausea, vomiting etc. Ciprofloxacin is the second generation of quinolones in the different categories of antibiotics. After using this antibiotic, some percentages of the compound are not metabolized in the body and is excreted along with the urine and excreta. This will reach the treatment plant and the conventional treatment method is not designed to treat these micropollutants, so it is released into the environment. The presence of ciprofloxacin is detected in surface water samples collected from different areas of the world. This study is conducted to find an effective adsorbent that can remove the ciprofloxacin from wastewater. Biochar produced from agricultural waste is highly rich in carbon and made from the process called pyrolysis. Pyrolysis of biomass is carried out under lower temperatures and low oxygen content. Biochar is used to remove antibiotic compounds, naphthalene, and heavy metals. Biochar is economical and does not have any adverse effects on the environment. Biochar can be prepared from different types of organic biodegradable waste. Since, the quantity of municipal solid waste reaching the landfill site is increasing day by day, converting the organic waste into biochar can reduce the amount of waste reaching the landfill site. In this study, biochar prepared from rice husk at 300°C is the best adsorbent to remove ciprofloxacin from aqueous solution. The adsorption of ciprofloxacin is studied for various conditions. The samples were analyzed in the UV-Vis spectrophotometer and it shows good removal efficiency.

Amazonian Dark Earths (Terra Preta) are anthropogenic soils with high organic carbon content and the ability to sustain higher fertility than adjacent, intensely weathered, acidic soils. Consequently, the microstructural development of biochar–mineral complexes, termed synthetic Terra Preta (STP), has been investigated. Here, biochar–mineral complexes are produced at elevated temperatures to mimic the structure of Terra Preta. These materials, if added to soils, may then also improve fertility. The raw materials used in STP were organic biowaste, such as sawdust, chicken manure, and blood and bone, and inorganic minerals such as kaolinite, bentonite, and cement kiln dust (which consists mainly of calcite). The STP samples were characterised using X-ray photoelectron spectroscopy, nuclear magnetic resonance, scanning electron microscopy (SEM), and transmission electron microscopy (TEM), and associated microchemical analytical methods, to gain an understanding of the interactions that occurred during processing between the organic and inorganic phases. The STP specimens exhibited microstructures that closely resemble Terra Preta. SEM and TEM revealed a complex aggregation of phases, together with evidence of the interfacial reactions, especially at higher processing temperatures. It is anticipated then that STP may be as effective in promoting plant growth and in sequestering carbon as Terra Preta

Carbon materials are becoming crucial in several industrial sectors. The drawbacks of these materials include their high cost and oil-based essence. In recent years, recycled materials have become possible alternative sources of carbon with several advantages. Firstly, the production of this alternative source of carbon may help to reduce biomass disposal, and secondly, it contributes to CO2 sequestration. The use of carbon derived from recycled materials by a pyrolysis treatment is called biochar. Here, we present composite materials based on different biochar filler contents dispersed in several thermoplastic polymer matrixes. Electrical conductivity and tensile break strength were investigated together with the material characterisation by DTA/TGA, XRD, and scanning electron microscopy (SEM) imaging. Materials with good flexibility and electrical conductivity were obtained. The local ordering in composites resembles both biochar and polymer ordering. The similarity between biochar and carbon nanotubes’ (CNTs) XRD patterns may be observed. As biochar is highly cost-effective, the proposed composites could become a valid substitute for CNT composites in various applications.

Thesis (MScEng)--Stellenbosch University, 2011.
ENGLISH ABSTRACT: According to recent studies, biochar has the potential to improve soil fertility, mitigate climate change, reduce off-site pollution and assist in managing wastes. The application of biochar to soil is not a new concept; Amazonian dark earths are carbon-rich soils with high soil fertility that were created before 1541. Vacuum pyrolysis is a thermo-chemical conversion technique in which biomass is transformed into bio-oil, biochar and non-condensable gas. The objective of this work was to investigate the chemical and physical properties of biochar produced from vacuum pyrolysis of black wattle, vineyard annual prunings and sugar cane bagasse for their potential as soil amendment and adsorbent. The vacuum pyrolysis of black wattle, vineyard prunings and sugar cane bagasse (pyrolysis temperature: 460°C, pressure: 8kPaabs, heating rate: 17°C/min) resulted in biochar yields of 23.5%, 31.0% and 19.7% on a weight basis, respectively. The nature of the biomass had a substantial effect on yields of the products. High ash content combined with high lignin composition led to higher biochar yields for vineyard prunings. The highest surface acidity was observed for sugar cane bagasse (2.3 mmol/g), whereas the lowest surface acidity was observed for vineyard biochar (1.67 mmol/g). Consequently, the pH of the biochars was in the order: vineyard (10.43)> black wattle (9.74)> sugar cane bagasse (6.56). The cation exchange capacities (CEC) of biochars were 122 cmol/kg, 101 cmol/kg and 65 cmol/kg for sugar cane bagasse, black wattle and vineyard, respectively. The electrical conductivities (EC) were highly correlated with feedstock nature. The Ca and K rich vineyard biochar resulted in the highest EC (0.83 dS/m), whilst EC values of black wattle and sugar cane bagasse were 0.67 dS/m and 0.17 dS/m, respectively. Biochars contained substantial amounts of plant-available nutrients, while being low in toxic inorganic content (Pb, As, Cd). The BET surface areas of sugar cane bagasse, black wattle and vineyard were 259 mª/g, 241 mª/g and 91 mª/g, respectively. The adsorption capacity was found to increase with increased contact time and initial solution concentration. The experimental equilibrium time were found to be 3505 min, 1350 min and 150 min for adsorption of 20 mg/L methylene blue solution for vineyard, black wattle and sugar cane bagasse, respectively. Equilibrium data were well fitted to Langmuir and Freundlich isotherms. The maximum adsorption capacities were found to be 15.15 mg/g, 14.49 mg/g and 19.23 mg/g for vineyard, black wattle and sugar cane bagasse when modelled with Langmuir isotherms. The adsorption kinetics was found to follow the pseudo-second order kinetic model. In summary, biochar from sugar cane bagasse is a promising adsorbent for the removal of basic dyes due to its high surface area and microporous structure. This biochar can be applied to slightly acidic soils for nutrient retention and the exchange of nutrients. On the other hand, possessing high amounts of nutrients, biochars from black wattle and vineyard are potential soil amendentment agents. Biochar from black wattle is more beneficial compared to biochar from vineyard due to its higher surface area, microporosity and cation exchange capacity.
AFRIKAANSE OPSOMMING: Volgens onlangse studies, het houtskool die potensiaal om grond vrugbaarheid te verbeter, klimaat verandering te versag, besoedeling te verlaag en ondersteuning te verleen in die bestuur van afval. Die toevoeging van houtskool in grond is nie ‘n nuwe konsep nie; Amazone donker gronde is koolstof ryk gronde met hoë vrugbaarheid wat voor 1541 geskep is. Vakuum pirolise is ‘n termo-chemiese omskakelings tegniek waarin biomassa afgebreek word na bio-olie, houtskool en nie-kondenseerbare gasse. Die doelwit van hierdie werk was om die chemiese en fisiese eienskappe van houtskool, wat geproduseer is deur die vakuum pirolise van swart wattel, jaarlikse wingerd snoeisels, en suikerriet bagasse, vir hulle potensiaal vir grond verbetering en adsorpsie toepassings te ondersoek. Die vakuum pirolise van swart wattel, jaarlikse wingerd snoeisels, en suikerriet bagasse (pirolise temperatuur: 460°C, druk: 8kPaabs, verhittingstempo: 17°C/min) het houtskool opbrengste van 23.5%, 31.0% en 19.7% op massa basis, respektiewelik tot gevolg. Die tipe biomassa het ‘n beduidende effek op die opbrengs van die produkte. Hoë as-inhoud, gekombineer met hoë lignien inhoud, lei tot hoër houtskool opbrengste vir wingerd snoeisels. Die hoogste oppervlak suurheid is gevind vir suikerriet bagasse (2.3 mmol/g), terwyl die laagste waarde gevind is vir die wingerd snoeisels (1.67 mmol/g). Gevolglik, is die pH van die houtskole in die volgorde van: wingerd (10.43) > swart wattle (9.74) > suikerriet bagasse (6.56). Die katioon uitruiling vermoë (CEC) van die houtskole was 122 cmol/kg, 101 cmol/kg and 65 cmol/kg vir suikerriet bagasse, swart wattel en wingerd snoeisels respektiewelik. Die elektriese konduktiwiteite (EC) is gekorreleer met die eienskappe van die biomassas. Die Ca en K ryke wingerd snoeisel houtskool het die hoogste EC waarde (0.83 dS/m) tot gevolg, terwyl die EC waardes vir swart wattel en suikerriet bagasse bepaal is as 0.67 dS/ 0.16 dS/m respektiewelik. Die houtskole het groot hoeveelhede plant-beskikbare voedingstowwe bevat, terwyl dit laag was in toksiese anorganiese stowwe (Pb, As, Cd). Die BET oppervlak areas van suikerriet bagasse, swart wattel en wingerd snoeisels was 259 mª/g, 241 mª/g en 91 mª/g respektiewelik. Daar is gevind dat die adsorpsie kapasiteit toeneem met toenemende kontak tyd met die aanvanklike oplossing. Die eksperimentele ewewigs tye is gevind as 350 min, 1350 min en 150 min vir die adsorpsie van ‘n 20 mg/L metileen blou oplossing vir wingerd snoeisels, swart wattel en suikerriet bagasse, respektiewelik. Die ewewigs data het die Langmuir en Freundlich isoterme goed gepas. Die maksimum adsorpsie kapasiteite is gevind as 15.15 mg/g, 14.9 mg/g en 19.23 mg/g vir wingerd snoeisels, swart wattel en suikerriet bagasse wanneer dit gemodeleer is met Langmuir isoterme. Daar is bevind dat die adsorpsie kinetika ‘n pseudo-tweede orde kintika model volg. In opsomming, houtskool van suikerriet bagasse is ‘n veelbelowende adsorpsie middel vir die verwydering van basiese kleurstowwe, as gevolg van die hoë oppervlak area en mikroporie-struktuur van hierdie houtskool. Dié houtskool kan gebruik word op effense suur gronde vir voedingstof behoud en uitruiling. Aan die ander kant, houtskole van swart wattel en wingerd snoeisels wat hoë hoeveelhede voedingsstowwe bevat, is potensiële grond verbeterings middels. Houtskool afkomstig van swart wattel is meer voordelig as die van wingerd snoeisels, as gevolg van die hoër oppervlak area, mikroporositeit en katioon uitruilings vermoë van die swart wattel houtskool.

The simultaneous use of willow as a vegetation filter and an energy crop can respond both to the increasing energy demand and to the problem of the soil and water contamination. Its characteristics guarantee that the resources are used economically. As a vegetation filter, willow uptakes organic and inorganic contaminants. As a fast growing energy crop it meets the requirements of rural areas without the exploitation of existing forestry. The aim of the research was to gather knowledge on the thermal behaviour of willow, uptaking contaminants and then used as an energy crop. For this reason pyrolysis experiments were performed in two different scales. In analytical scale metal-contaminated wood was investigated and bench scale pyrolysis experiments were performed with nitrogen-enriched willow, originated from a wastewater treatment plant. Results of the pyrolysis showed that 51-81 % of the wastewater derived nitrogen of willow was captured in the char product. Char had low surface area (1.4 to 5.4 m2/g), low bulk density (0.15–0.18 g/cm3), high pH values (7.8–9.4) and high water-holding capacity (1.8 to 4.3 cm3/g) while the bioavailability of char nutrients was low. Links were also established between the pyrolysis temperature and the product properties for maximising the biochar provided benefits for soil applications. Results also showed that the metal binding capacity of wood varied from one metal ion to another, char yield increased and levoglucosan yield decreased in their presence. While char yield was mainly affected by the concentration of the metal ions, levoglucosan yield was more dependent on the type of the ionic species. Combustion experiments were also carried out with metal-enriched char. The burnout temperatures, estimated ignition indices and the conversion indicate that the metal ions type and not the amount were the determining factors during the combustion. Results presented in the Thesis provide better understanding on the thermal behaviour of nitrogen-enriched and metal contaminated biomass which is crucial to design effective pyrolysis units and combustors. These findings are relevant for pyrolysis experiments, where the goal is to yield char for energetic or soil applications.

The rapid development of palm oil industry in Malaysia has generated significant amount of solid and liquid wastes, contributing to major environmental issues in the past five decades. Palm oil residues such as palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS) are difficult to be disposed of. Thus, the potential application of the oil palm wastes for synthesis of value added products such as adsorbents for heavy metals removal and solid biochars for fuel generation, are presented in this thesis. In the past three decades, industrialisation and urbanisation in Malaysia have led to an increase of heavy metals, such as copper, cadmium, lead, zinc, chromium and nickel, in the rivers and lakes. The presence of the heavy metals is causing harmful effects on the aquatic environment and human health, hence it is necessary to control the discharge of industrial effluent into the environment. Among various heavy metals abatement technologies, adsorption is by far the most promising technique due to its relatively easy operation and high efficiency. However, adsorption is associated with costly adsorbent, such as activated carbon which is usually made from non-renewable resource. This has motivated many researchers to investigate and develop cost effective adsorbents for the removal of heavy metals. In this research, biosorbent was prepared from palm oil sludge. The preparation steps were relatively simple and low cost, involving mechanical treatments such as drying, milling and sieving. The POS biosorbent was tested on removal of copper (Cu2+) and cadmium (Cd2+), followed by process optimisation using response surface methodology (RSM), based on central composite design (CCD). Comparing between one-factor-at-a-time (OFAT) and RSM-CCD methods, both studies produced results which were in good agreement. The investigation was carried out to evaluate the effects of adsorbent dosage (W), initial pH, initial concentration (C0) and contact time (t), on the heavy metals removal. From optimisation study using RSM-CCD, the optimum adsorption parameters for Cu2+ removal were as follows: W = 0.3 g; pH 4.56; C0 = 200 mg L-1; t = 60 min, with maximum adsorption capacity (q) of 15.84 mg g-1, and for Cd2+ removal were as follows: W = 0.3 g; pH 5.8; C0 = 200 mg L-1; t = 60 min, with maximum q of 18.49 mg g-1. The adsorption equilibrium of Cu2+ and Cd2+ were best described by Langmuir and Freundlich models, respectively, based on the lowest sum of normalised error (SNE). The adsorption kinetic of Cu2+ and Cd2+ were best fitted with pseudo-second-order kinetic model. Thermodynamically, the adsorption processes were spontaneous, exothermic and feasible. Regeneration of POS biosorbent was carried out using hydrochloric acid (HCl) as the eluent, and the results indicated the high desorption efficiency for Cu2+ (up to 0.98) and Cd2+ (0.95) from the biosorbent, respectively. The POS biomass was also converted to POS-char by slow pyrolysis which was subsequently used in lead (Pb2+) adsorption study. The synthesis of POS-char was optimised by RSM-CCD based on simultaneous maximisation of biochar yield and q of Pb2+. The interactive effects of nitrogen flowrate (FN2), heating rate (HR), pyrolysis temperature (Tpyro) and pyrolysis time (tpyro) on the responses were investigated. It was determined that the maximum biochar yield was 80.35 % and q was 4.11 mg g-1, formed at the following slow pyrolysis conditions: FN2 = 30 mL min-1; HR = 10 °C min-1; Tpyro = 500 °C; tpyro = 30 min. In Pb2+ adsorption study, the optimum parameters determined by RSM-CCD optimisation were as follows: W = 0.3 g, pH 3.2, C0 = 200 mg L-1 and t = 60 min, with a maximum q of 21.76 mg g-1. The adsorption equilibrium of Pb2+ was best represented by Freundlich model. This finding indicated that the sorption sites in POS-char were heterogeneous. The kinetic study revealed that at low concentrations, the kinetic of adsorption complied with pseudo-first-order model, while at high concentrations, it obeyed pseudo-second-order model. Regeneration of POS-char was successfully conducted using HCl and the adsorbent exhibited reusability up to 5 adsorption-desorption cycles, with the desorption efficiencies between 0.58 and 0.99. Beyond 3 cycles, the adsorbent showed noticeable structural damage. Overall, the adsorption of Pb2+ onto POS-char was spontaneous, exothermic and feasible. The slow pyrolysis of PKS and EFB to biochars was investigated by simultaneously varying factors such as FN2, HR, Tpyro and tpyro. The synthesis parameters were optimised by RSM-CCD with respect to multiple responses, including biochar yield, higher heating value (HHV) and energy yield. The interactive effects of FN2, HR, Tpyro and tpyro on the three responses were in good agreement with literature data. The determined optimum conditions for PKS-char and EFB-char production by slow pyrolysis were as follows: FN2 = 30 mL min-1, HR = 18.9 – 20.0 °C min-1, Tpyro = 500.0 – 504.3 °C and tpyro = 30 min. The combustion kinetic on the optimised PKS-char and EFB-char were found to possess favourable combustion characteristics such as low activation energy (Ea), high energy yield and HHV. Overall, the combustion of PKS-char and EFB-char occurred in multi-step kinetics behaviour until burnout. The cost analysis on synthesis of PKS-char, EFB-char, POS-char and POS biosorbent was performed based on independent case studies which considered the capital and operating costs. The results revealed that addition of the thermochemical conversion plant to existing oil palm mill was highly feasible. The unit cost for production of PKS-char, EFB-char, POS-char and POS were USD$ 3.94 kg-1, USD$ 1.21 kg-1, USD$ 2.17 kg-1 and USD$ 0.19 kg-1 ̧ respectively.

The thesis aimed at investigating the source, identity, and biological effects of organic compounds released from biochar into air and water. Biochar is the carbonaceous product of biomass pyrolysis for agro/environmental purposes. However, its application to soil could be hindered by the presence of contaminants. Apart from priority regulated compounds, a wide range of organic species can be adsorbed onto biochar porous structure during its production, and their mobility in the environment could generate beneficial or negative impacts. Techniques based on solid-phase microextraction (SPME) were developed to determine volatile (VOCs) and water-soluble organic compounds (WSOCs) released from several biochars from different feedstocks and pyrolysis conditions. Head space (HS) and direct immersion (DI)-SPME coupled with GC-MS suitably detected a variety of thermal degradation products of biomass biopolymers (lignin, hemi/cellulose, lipids and proteins). The patterns of VOCs/WSOCs were directly connected with the biochar carbonisation degree measured by H/C molar ratios. Biochars with H/C <0.7 presented distinctively different profiles and reduced intensities compared to less carbonised ones. SPME-GC-MS, ultra-high resolution mass spectrometry (Negative Electrospray Ionisation Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, ESI-FT-ICR-MS) and fluorescence spectroscopy-Parallel Factor Analysis (PARAFAC) were employed to compare the complex composition of WSOCs with that of the vapours condensed into bio-oil during pyrolysis. Biochar preferentially released aromatic species with acid functionalities resembling those of natural organic matter (fulvic acids), while lignin-like structures characterised the bio-oils. Germination tests revealed that high levels of VOCs/WSOCs can induce phytotoxicity, but when biochar contamination is low, organic species were associated to stimulating effects on seedlings growth. The green analytical methods based on SPME were suitable for screening the effect of pyrolysis process conditions on the presence of mobile compounds in the resulting biochar and its quality for soil applications.

Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool to investigate inner properties of matter and it is used for both fundamental and applied research. If not-zero nuclear spins are embedded in a magnetic field, a detectable magnetization is formed. Its subsequent manipulation allows the study of scientifically interesting microscopic parameters: they can mostly be correlated to macroscopic properties which need to be tuned for industrial applications. On top, polymer science and porous media research exploit NMR peculiarities a lot. Particularly, low-field (LF) time domain (TD) 1H NMR can provide valuable information about bulk, nanostructured and polymer films rapidly, accurately and cheaply. Additionally, NMR-active noble gases combine their almost null reactivity with a high sensitivity to the local environment: they are effective probes to check the presence of pores, their dimensions and degree of accessibility. Firstly, since theories link the NMR-accessible residual dipolar coupling constants (Dres) and their distribution to macroscopic crosslink density (CLD) of vulcanized elastomers, LF TD 1H-NMR was used to evaluate the CLD of polyisoprene/polybutadiene (IR/BR) rubber blends at their optimum curing time. Compared to the ideal case where the two homopolymers evolve independently, small but still significant experimental differences in Dres values suggesting the vulcanizing agents may act differently on the two polymer phases were collected. Introducing new experimental variables (experimental temperature, different vulcanization times) we tried to enhance a single phase only and measure their CLD separately: if ever enhanced, CLD differences in the two phases were however below the technique sensitivity. Additionally, a direct evaluation of the Dres distributions and CLD on IR, BR single-polymer rubber vulcanized at different times in undercuring conditions was performed. The compared analysis of NMR and equilibrium swelling data allowed to propose a new model for rubber network growth with time: the crosslinks are not formed randomly in the sample, but instead islands with a precise morphology are formed and then they merge together. LF TD 1H NMR techniques were applied on polymeric nanostructured systems as well. On top, changes in measured T1 values can be correlated to the activation of different molecular motions. Mostly, we investigated the T1 change in oxygen-free divinylbenzene (DVB)-crosslinked polystyrene (PS) nanoparticles (NPs) due to temperature and different amount of crosslinker: we eventually differentiated the collective motion of the main chain from the PS and DVB phenyl rings ones. Similarly, a precise quantification of the amount of protons which are rigid (fr) and mobile was performed on poly(n-butylacrylate)/polystyrene (PBA/PS) core-shell NPs. A fr temperature-dependent study and its direct comparison with the synthesis conditions at temperatures far away from both PS and PBA glass transition temperatures proved the two phases of PBA@PS NPs behaved as two independent homopolymers. Again, a comparison of the experimental fr values with the theoretical ones of two and three-components BEVA ®731-replacement mixture for cultural heritage applications helped understanding the improved adhesive properties of the three-components mixture over the two-components ones: only in this case a perfect miscibility was obtained. Lastly, high-field 129Xe NMR was applied to study the morphology of differently activated pecan and almond shells-based biochars: on top, 1D conventional and pressure-dependent spectra proved the biochars structure is porous with an average dimensions of around 10Å. T1 and 2D exchange measurements probed the pores accessibility. It strongly depended on the activation conditions: only the pecan-based biochars cured with the higher airflow or the longer-cured, rain-washed almond-based ones showed 129Xe exchange, proving them effective as filtration systems.

The thermal conversion of biomass to biochar has been studied for over 100 years (Laboratory et al., 1978). Over the past two decades it has gained momentum in environmental and energy research (Stavi & Lal, 2013). Concerns over climate change, poverty, declining agricultural production, fertiliser shortage, and fuel generation are all topics that biochar and bio-oils have aimed to address. Optimisation of biochar and bio-oils production, however, has received relatively little attention from a whole-of-system approach. The work undertaken in this thesis aims to address these limitations and provide a system that maximises the conversion of woody biomass to biochar and bio-oils.

Interest in biochar among soil and environment researchers has increased dramatically over the past decade. Biochar initially attracted attention for its potential to improve soil fertility and to uncouple the carbon cycle, by storing carbon from the atmosphere in a form that can remain stable for hundreds to thousands of years. Later it was found that biochar had applications in environmental and water science, mining, microbial ecology and other fields. Beneficial effects of biochar and its environmental applications cannot be fully realised unless the chemical, physical, structural and surface properties of biochar are known. Currently many of the analytical procedures used for biochar analysis are not well defined, which makes it difficult to choose the right biochar for an intended use and to compare the existing data for biochars. Also, in some instances the use of inappropriate procedures has led to erroneous or inaccurate values for biochars in the scientific literature. Biochar: A Guide to Analytical Methods fills this gap and provides procedures and guidelines for routine and advanced characterisation of biochars. Written by experts, each chapter provides background to a technique or procedure, a stepwise guide to analyses, and includes data for biochars made from a range of feedstocks common to all presented methods. Discussion about the unique features, advantages and disadvantages of a particular technique is an explicit focus of this handbook for biochar analyses. Biochar is primarily intended for researchers, postgraduate students and practitioners who require knowledge of biochar properties. It will also serve as an important resource for researchers, industry and regulatory agencies dealing with biochar.

Platelet membrane preparations can be fractionated into two major subpopulations by free flow electrophoresis and these have been shown to correspond to the plasma membrane and the endoplasmic reticulum of the platelet. The plasma membrane fraction can be shown, by two-dimensional electrophoresis, to contain the major surface glycoproteins together with considerable amounts of actin and actin-associated proteins such as the 250 kDa actin-binding protein (filamin), P235 (talin), myosin, α-actinin and tropomyosin (Hack, N. … Crawford, N., Biochem. J. 222, 235 (1984). These cytoskeletal proteins are associated with the cytoplasmic face of the plasma membrane and probably interact with transmembrane glycoproteins. We have raised monoclonal antibodies to the purified plasma membrane preparation in order to investigate the nature of these glycoprotein-cytoskeletal interactions. In two fusion experiments, out of 804 tested, 104 hybrids secreted antibody to the membrane preparation and of these 24 were selected for further study. Initial assays were by ELISA using either the membrane preparation or whole fixed platelets as the target antigen. The specificity of the antibodies was investigated further by immunoblotting of SDS gels of total platelet proteins prepared under reducing and nonreducing conditions, by immunofluorescence, by immunohisto-chemistry and by crossed immunoelectrophoresis. The majority of the antibodies recognise major surface glycoproteins; of these, four bind to glycoprotein Ib under all conditions examined while another seven recognise the glycoprotein IIb/IIIa complex as detected by crossed immunoelectrophoresis. Three antibodies recognise the actin binding protein and these cross-react with the smooth muscle protein filamin in a number of different species. Further characterisation of these antibodies in both structural and functional terms will be presented.We are grateful to the Smith and Nephew Foundation for financial support for these studies

We have identified a family of low molecular weight proteins with cell attachment properties in a variety of soft and mineralised connective tissues (Wong et al., Biochem. J. 232, 119, 1985). For further characterisation of these proteins we extracted porcine bones with 4 M guanidine hydrochloride and purified the proteins on a series of gel filtration columns The purifed SAPs comprise three bands with Mr -14 000 -17 000. All three proteins bound to heparin-sepahrose in both the presence and absence of 4M urea, and when eluted with 2 M NaCl they retained their cell binding capacity. These proteins promoted the adhesion and spreading of a variety of cell types, including normal fibroblasts, osteoblasts, and epithelial cells, and tumour (osteosarcoma) cells. On Western blotting SAPs did not cross-react with antibodies against fibronectin, laminin or type I collagen; however, they were recognised by a monoclonal antibody to human vitronectin, a polyclonal antibody to bovine vitronectin and polyclonal antibody to human somatomedin B. Dose response experiments indicated that maximum attachment of human gingival fibroblasts occurred in the presence or absence of fetal bovine serum on wells precoated with 2.5 μg/cm2 of SAPs. Attachment of cells to these proteins was partially inhibited by the synthetic pentapeptide Gly-Arg-Gly-Asp-Ser. Utilising the nitrocellulose cell binding assay of Hayman et al (J. Cell. Biol. 95, 20, 1982), the cell attachment to these proteins could be completely inhibited by heparin (100 units/mL) whereas up to 1000 units/mL of heparin had no inhibitory effect on cell attachment to fibronectin and vitronectin. The occurrence of these proteins in a variety of connective tissues and their recognition by different cell types may reflect their general biological role in adhesive mechanisms in both hard and soft connective tissues. Currently, we are investigating the relationship between SAPs and vitronectin, since it is possible that SAPs represent a tissue-processed form of vitronectin or may be novel attachment proteins with regions of homology with vitronectin