Legal issues in carbon farming : biosequestration, carbon pricing, and carbon rights

This paper critically analyses the proposed Australian regulatory approach to the crediting of biological sequestration activities (biosequestration) under the Australian Carbon Farming Initiative and its interaction with State-based carbon rights, the national carbon-pricing mechanism, and the international Kyoto Protocol and carbon-trading markets. Norms and principles have been established by the Kyoto Protocol to guide the creation of additional, verifiable, and permanent credits from biosequestration activities. This paper examines the proposed arrangements under the Australian Carbon Farming Initiative and Carbon Pricing Mechanism to determine whether they are consistent with those international norms and standards. This paper identifies a number of anomalies associated with the legal treatment of additionality and permanence and issuance of carbon credits within the Australian schemes. In light of this, the paper considers the possible legal implications for the national and international transfer, surrender and use of these offset credits.

A Bayesian approach for estimating detection times in horses : exploring the pharmacokinetics of a urinary acepromazine metabolite

We describe the population pharmacokinetics of an acepromazine (ACP) metabolite (2-(1-hydroxyethyl)promazine) (HEPS) in horses for the estimation of likely detection times in plasma and urine. Acepromazine (30 mg) was administered to 12 horses, and blood and urine samples were taken at frequent intervals for chemical analysis. A Bayesian hierarchical model was fitted to describe concentration-time data and cumulative urine amounts for HEPS. The metabolite HEPS was modelled separately from the parent ACP as the half-life of the parent was considerably less than that of the metabolite. The clearance ($Cl/F_{PM}$) and volume of distribution ($V/F_{PM}$), scaled by the fraction of parent converted to metabolite, were estimated as 769 L/h and 6874 L, respectively. For a typical horse in the study, after receiving 30 mg of ACP, the upper limit of the detection time was 35 hours in plasma and 100 hours in urine, assuming an arbitrary limit of detection of 1 $\mu$g/L, and a small ($\approx 0.01$) probability of detection. The model derived allowed the probability of detection to be estimated at the population level. This analysis was conducted on data collected from only 12 horses, but we assume that this is representative of the wider population.

1,1,3,3-Tetraethylisoindolin-2-ium chloride

In the structure of the title compound C16H26N+ Cl-, the salt of a precursor in the synthesis of an isoindolin-2-yloxyl free-radical trapping agent, the cations and anions form discrete centrosymetric cyclic dimers through N---H...Cl hydrogen-bonding associations [graph set R2/4(8)].

Hydrothermal syntheses of zeolite N from kaolin

Zeolite N, an EDI type framework structure with ideal chemical formula K12Al10Si10O40Cl2•5H2O, was produced from kaolin between 100oC and 200oC in a continuously stirred reactor using potassic and potassic+sodic liquors containing a range of anions. Reactions using liquors such as KOH, KOH + KX (where X = F, Cl, Br, I, NO3, NO2), K2X (where X=CO3), KOH + NaCl or NaOH + KCl were complete (>95% product) in less than two hours depending on the batch composition and temperature of reaction. With KOH and KCl in the reaction mixture and H2O/Al2O3~49, zeolite N was formed over a range of concentrations (1M < [KOH] < 18M) and reaction times (0.5h < t < 60h). At higher temperatures or higher KOH molarity, other potassic phases such as kalsilite or kaliophyllite formed. In general, temperature and KOH molarity defined the extent of zeolite N formation under these conditions. The introduction of sodic reagents to the starting mixture or use of one potassic reagent in the starting mixture reduced the stability field for zeolite N formation. Zeolite N was also formed using zeolite 4A as a source of Al and Si albeit for longer reaction times at a particular temperature when compared with kaolin as the source material.

Hierarchical robust design optimisation of shock control bump devices for airfoil drag reduction

The paper investigates a detailed Active Shock Control Bump Design Optimisation on a Natural Laminar Flow (NLF) aerofoil; RAE 5243 to reduce cruise drag at transonic flow conditions using Evolutionary Algorithms (EAs) coupled to a robust design approach. For the uncertainty design parameters, the positions of boundary layer transition (xtr) and the coefficient of lift (Cl) are considered (250 stochastic samples in total). In this paper, two robust design methods are considered; the first approach uses a standard robust design method, which evaluates one design model at 250 stochastic conditions for uncertainty. The second approach is the combination of a standard robust design method and the concept of hierarchical (multi-population) sampling (250, 50, 15) for uncertainty. Numerical results show that the evolutionary optimization method coupled to uncertainty design techniques produces useful and reliable Pareto optimal SCB shapes which have low sensitivity and high aerodynamic performance while having significant total drag reduction. In addition,it also shows the benefit of using hierarchical robust method for detailed uncertainty design optimization.

A study of ionic liquids for dissolution of sugarcane bagasse

Over the last decade, Ionic Liquids (ILs) have been used for the dissolution and derivatization of isolated cellulose. This ability of ILs is now sought for their application in the selective dissolution of cellulose from lignocellulosic biomass, for the manufacture of cellulosic ethanol. However, there are significant knowledge gaps in the understanding of the chemistry of the interaction of biomass and ILs. While imidazolium ILs have been used successfully to dissolve both isolated crystalline cellulose and components of lignocellulosic biomass, phosphonium ILs have not been sufficiently explored for the use in dissolution of lignocellulosic biomass. This thesis reports on the study of the chemistry of sugarcane bagasse with phosphonium ILs. Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO4) are obtained using attenuated total reflectance-Fourier Transform Infra Red (FTIR). Absorption bands related to cellulose, hemicelluloses and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalysed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The quantitative measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm-1 has demonstrated utility and greater precision than the conventional Klason lignin method. The cleavage of lignin β-aryl ether bonds in sugarcane bagasse by the ionic liquid [P66614]Cl, in the presence of catalytic amounts of mineral acid. (ca. 0.4 %). The delignification process of bagasse is studied over a range of temperatures (120 °C to 150 °C) by monitoring the production of β-ketones (indicative of cleavage of β-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum delignification is obtained at 150 °C, with 52 % of lignin removed from the original lignin content of bagasse. No delignification is observed in the absence of acid which suggests that the reaction is acid catalysed with the IL solubilising the lignin fragments. The rate of delignification was significantly higher at 150 °C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of β-aryl ethers. An attempt has been made to propose a probable mechanism of delignifcation of bagasse with the phosphonuim IL. All polymeric components of bagasse, a lignocellulosic biomass, dissolve in the hydrophilic ionic liquid (IL) tributylmethylphosphonium methylsulfate ([P4441]MeSO4) with and without a catalytic amount of acid (H2SO4, ca. 0.4 %). The presence of acid significantly increases the extent of dissolution of bagasse in [P4441]MeSO4 (by ca. 2.5 times under conditions used here). The dissolved fractions can be partially recovered by the addition of an antisolvent (water) and are significantly enriched in lignin. Unlike acid catalysed dissolution in the hydrophobic IL tetradecyltrihexylphosphonium chloride there is little evidence of cleavage of β-aryl ether bonds of lignin dissolving in [P4441]MeSO4 (with and without acid), but this mechanism may play some role in the acid catalysed dissolution. The XRD of the undissolved fractions suggests that the IL may selectively dissolve the amorphous cellulose component, leaving behind crystalline material.

ATR-FTIR measurement of biomass components in phosphonium ionic liquids

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO 4), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO 4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed -aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO 4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm 1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process. © 2012 Copyright Taylor and Francis Group, LLC.

The chemistry of acid catalyzed delignification of sugarcane bagasse in the ionic liquid trihexyl tetradecyl phosphonium chloride

This article reports on the cleavage of lignin ß-aryl ether bonds in sugarcane bagasse by the ionic liquid (IL) trihexyl tetradecyl phosphonium chloride [P66614] Cl, in the presence of catalytic amounts of mineral acid fca. 0.4%). The deligniflcation process of bagasse was studied over a range of temperatures (120°C to 150°C) by monitoring the production of ß-ketones (indicative of cleavage of ß-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum deligniflcation was obtained at 150°C, with 52% of lignin removed from the original lignin content of bagasse. No deligniflcation was observed in the absence of acid, which suggests that the reaction is acid catalyzed with the IL solubilizing the lignin fragments. The rate of deligniflcation was significantly higher at 150°C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of ß-aryl ethers. An attempt has been made to propose a probable mechanism of deligniflcation of bagasse with the phosphonuim IL. © Taylor & Francis Group, LLC.

Clinical performance of a new silicone hydrogel contact lens over 6 months of extended wear

Purpose: Silicone hydrogel contact lenses (CLs) are becoming increasingly popular for daily wear (DW), extended wear (EW) and continuous wear (CW), due to their higher oxygen transmissibility compared to hydrogel CLs. The aim of this study was to investigate the clinical and subjective performance of asmofilcon A (Menicon Co., Ltd), a new surface treated silicone hydrogel CL, during 6-night EW over 6 months (M). Methods: A prospective, randomised, single-masked, monadic study was conducted. N=60 experienced DW soft CL wearers were randomly assigned to wear either asmofilcon A (test: Dk=129, water content (WC)=40%, Nanogloss surface treatment) or senofilcon A (control: Dk=103, WC=38%, PVP internal wetting agent, Vistakon, Johnson & Johnson Vision Care) CLs bilaterally for 6 M on an EW basis. A PHMB-preserved solution (Menicon Co., Ltd) was dispensed for CL care. Evaluations were conducted at CL delivery and after 1 week (W), 4 W, 3 M and 6 M of EW. At each visit, a range of objective and subjective clinical performance measures were assessed. Results: N=50 subjects (83%) successfully completed the study, with the majority of discontinuations due to loss to follow-up (n=3) or moving away/travel (n=5). N=2 subjects experienced adverse events; n=1 unilateral red eye with asmofilcon A and n=1 asymptomatic infiltrate with senofilcon A. There were no significant differences in high or low contrast distance visual acuity (HCDVA or LCDVA) between asmofilcon A and senofilcon A; however, LCDVA decreased significantly over time with both CL types (p<0.05). The two CL types did not vary significantly with respect to any of the objective and subjective measures assessed (p>0.05); CL fitting characteristics and CL surface measurements were very similar and mean bulbar and limbal redness measures were always less than grade 1.0. Superior palpebral conjunctival injection showed a statistically, but not clinically, significant increase over time with both CL types (p<0.05). Corneal staining did not vary significantly between asmofilcon A and senofilcon A (p>0.05), with low median gradings of less than 0.5 observed for all areas assessed. There were no solution-related staining reactions observed with either CL type. The asmofilcon A and senofilcon A CLs were both rated highly with respect to overall comfort, with medians of 14 or 15 hours of comfortable lens wearing time per day reported at each of the study visits (p>0.05). Conclusions: Over 6 months of EW, the asmofilcon A and senofilcon A CLs performed in a similar manner with respect to visual acuity, ocular health and CL performance measures. Some changes over time were observed with both CL types, including reduced LCDVA and increased superior palpebral injection, which warrant further investigation in longer-term EW studies. Asmofilcon A appeared to be equivalent in performance to senofilcon A.

2,2-Bis(4-butoxyphenyl)-1,1,1-trichloroethane

In the structure of the title compound C22H27Cl302, which is the p-butoxyphenyl analogue of the insecticidally active p-methoxyphenyl compound methoxychlor, the dihedral angle between the two phenyl rings is 79.61(11)deg. Present also in the structure is an intramolecular aromatic C-H...Cl interaction [3.361(2)Ang].

1,1,1-Trichloro-2,2-bis(4-ethoxyphenyl)ethane

In the title compound, C18H19Cl3O2, which is the 4-ethoxyphenyl analogue of the insecticidally active 4-methoxyphenyl compound methoxychlor, the dihedral angle between the two benzene rings is 60.38(13)deg. An intramolecular aromatic C-H...Cl interaction is present.

I just want to design a sexy flying car! Teaching design-led innovation to designers

Many international management programs have capitalised on the value design can have upon potential business solutions and strategies (Martin, 2009 & Brown, 2008) as well as many international design programs introducing designers to business theory and curriculum (Manzini & Rizzo, 2011). This paper presents the findings from structured interviews with undergraduate design students and design industry professionals. Current literature surrounding design led innovation and the role designers’ play within it is also discussed and the challenges facing designers in this emerging design era are presented. The findings from this study indicate that most designers enter an undergraduate program not wanting to become the business leaders of tomorrow. Instead, they enter in the hope they can humbly help people and to make a difference in the world. There are contentions with this perspective, felt by industry, academia and students around why designers need to be taught business theory content. This paper provides the first step to overcoming this challenge by providing insight into the attitudes, perceptions and challenges designers are facing with this new design era.

Sources of hydrochemical variability and implications associated with CSG water extraction

Coal Seam Gas (CSG) production is achieved by extracting groundwater to depressurize coal seam aquifers in order to promote methane gas desorption from coal micropores. CSG waters are characteristically alkaline, have a neutral pH (~7), are of the Na-HCO3-Cl type, and exhibit brackish salinity. In 2004, a CSG exploration company carried out a gas flow test in an exploration well located in Maramarua (Waikato Region, New Zealand). This resulted in 33 water samples exhibiting noteworthy chemical variations induced by pumping. This research identifies the main causes of hydrochemical variations in CSG water, makes recommendations to manage this effect, and discusses potential environmental implications. Hydrochemical variations were studied using Factor Analysis and this was supported with hydrochemical modelling and a laboratory experiment. This reveals carbon dioxide (CO2) degassing as the principal source of hydrochemical variability (about 33%). Factor Analysis also shows that major ion variations could also reflect changes in hydrochemical composition induced by different pumping regimes. Subsequent chloride, calcium, and TDS variations could be a consequence of analytical errors potentially committed during laboratory determinations. CSG water chemical variations due to degassing during pumping can be minimized with good completion and production techniques; variations due to sample degassing can be controlled by taking precautions during sampling, transit, storage and analysis. In addition, the degassing effect observed in CSG waters can lead to an underestimation of their potential environmental effect. Calcium precipitation due to exposure to normal atmospheric pressure results in a 23% increase in SAR values from Maramarua CSG water samples.

Ionic liquid pre-treatment and fractionation of sugarcane bagasse for the production of bioethanol

Pretretament is an essential and expensive processing step for the manufacturing of ethanol from lignocellulosic raw materials. Ionic liquids are a new class of solvents that have the potential to be used as pretreatment agents. The attractive characteristics of ionic liquid pretreatment of lignocellulosics such as thermal stability, dissolution properties, fractionation potential, cellulose decrystallisation capacity and saccharification impact are investigated in this thesis. Dissolution of bagasse with 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) at high temperatures (110 �‹C to 160 �‹C) is investigated as a pretreatment process. Material balances are reported and used along with enzymatic saccharification data to identify optimum pretreatment conditions (150 �‹C for 90 min). At these conditions, the dissolved and reprecipitated material is enriched in cellulose, has a low crystallinity and the cellulose component is efficiently hydrolysed (93 %, 3 h, 15 FPU). At pretreatment temperatures < 150 �‹C, the undissolved material has only slightly lower crystallinity than the starting. At pretreatment temperatures . 150 �‹C, the undissolved material has low crystallinity and when combined with the dissolved material has a saccharification rate and extent similar to completely dissolved material (100 %, 3h, 15 FPU). Complete dissolution is not necessary to maximize saccharification efficiency at temperatures . 150 �‹C. Fermentation of [C4mim]Cl-pretreated, enzyme-saccharified bagasse to ethanol is successfully conducted (85 % molar glucose-to-ethanol conversion efficiency). As compared to standard dilute acid pretreatment, the optimised [C4mim]Cl pretreatment achieves substantially higher ethanol yields (79 % cf. 52 %) in less than half the processing time (pretreatment, saccharification, fermentation). Fractionation of bagasse partially dissolved in [C4mim]Cl to a polysaccharide rich and a lignin rich fraction is attempted using aqueous biphasic systems (ABSs) and single phase systems with preferential precipitation. ABSs of ILs and concentrated aqueous inorganic salt solutions are achievable (e.g. [C4mim]Cl with 200 g L-1 NaOH), albeit they exhibit a number of technical problems including phase convergence (which increases with increasing biomass loading) and deprotonation of imidazolium ILs (5 % - 8 % mol). Single phase fractionation systems comprising lignin solvents / cellulose antisolvents, viz. NaOH (2M) and acetone in water (1:1, volume basis), afford solids with, respectively, 40 % mass and 29 % mass less lignin than water precipitated solids. However, this delignification imparts little increase in saccharification rates and extents of these solids. An alternative single phase fractionation system is achieved simply by using water as an antisolvent. Regulating the water : IL ratio results in a solution that precipitates cellulose and maintains lignin in solution (0.5 water : IL mass ratio) in both [C4mim]Cl and 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc)). This water based fractionation is applied in three IL pretreatments on bagasse ([C4mim]Cl, 1-ethyl-3-methyl imidazolium chloride ([C2mim]Cl) and [C2mim]OAc). Lignin removal of 10 %, 50 % and 60 % mass respectively is achieved although only 0.3 %, 1.5 % and 11.7 % is recoverable even after ample water addition (3.5 water : IL mass ratio) and acidification (pH . 1). In addition the recovered lignin fraction contains 70 % mass hemicelluloses. The delignified, cellulose-rich bagasse recovered from these three ILs is exposed to enzyme saccharification. The saccharification (24 h, 15 FPU) of the cellulose mass in starting bagasse, achieved by these pretreatments rank as: [C2mim]OAc (83 %)>>[C2mim]Cl (53 %)=[C4mim]Cl(53%). Mass balance determinations accounted for 97 % of starting bagasse mass for the [C4mim]Cl pretreatment , 81 % for [C2mim]Cl and 79 %for [C2mim]OAc. For all three IL treatments, the remaining bagasse mass (not accounted for by mass balance determinations) is mainly (more than half) lignin that is not recoverable from the liquid fraction. After pretreatment, 100 % mass of both ions of all three ILs were recovered in the liquid fraction. Compositional characteristics of [C2mim]OAc treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are opposite to those of chloride IL treated solids. The former biomass characteristics resemble those imparted by aqueous alkali pretreatment while the latter resemble those of aqueous acid pretreatments. The 100 % mass recovery of cellulose in [C2mim]OAc as opposed to 53 % mass recovery in [C2mim]Cl further demonstrates this since the cellulose glycosidic bonds are protected under alkali conditions. The alkyl chain length decrease in the imidazolium cation of these ILs imparts higher rates of dissolution and losses, and increases the severity of the treatment without changing the chemistry involved.

Serine protease inhibition and mitochondrial dysfunction associated with cisplatin resistance in human tumor cell lines : targets for therapy

Indicators of mitochondrial function were studied in two different cell culture models of cis-diamminedichloroplatinum-II (CDDP) resistance: the intrinsically resistant human ovarian cancer cell line CI-80-13S, and resistant clones (HeLa-S1a and HeLa-S1b) generated by stable expression of the serine protease inhibitor—plasminogen activator inhibitor type-2 (PAI-2), in the human cervical cancer cell line HeLa. In both models, CDDP resistance was associated with sensitivity to killing by adriamycin, etoposide, auranofin, bis[1,2-bis(diphenylphosphino)ethane]gold(I) chloride {[Au(DPPE)2]Cl}, CdCl2 and the mitochondrial inhibitors rhodamine-123 (Rhl23), dequalinium chloride (DeCH), tetraphenylphosphonium (TPP), and ethidium bromide (EtBr) and with lower constitutive levels of ATP. Unlike the HeLa clones, CI-80-13S cells were additionally sensitive to chloramphenicol, 1-methyl-4-phenylpyridinium ion (MPP+), rotenone, thenoyltrifluoroacetone (TTFA), and antimycin A, and showed poor reduction of 1-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT), suggesting a deficiency in NADH dehydrogenase and/or succinate dehydrogenase activities. Total platinum uptake and DNA-bound platinum were slightly lower in CI-80-13S than in sensitive cells. The HeLa-S1a and HeLa-S1b clones, on the other hand, showed poor reduction of triphenyltetrazolium chloride (TTC), indicative of low cytochrome c oxidase activity. Total platinum uptake by HeLa-S1a was similar to HeLa, but DNA-bound platinum was much lower than for the parent cell line. The mitochondria of CI-80-13S and HeLa-S1a showed altered morphology and were fewer in number than those of JAM and HeLa. In both models, CDDP resistance was associated with less platinum accumulation and with mitochondrial and membrane defects, brought about one case with expression of a protease inhibitor which is implicated in tumor progression. Such markers may identify tumors suitable for treatment with gold phosphine complexes or other mitochondrial inhibitors.