Process-based modelling of mass transport in the subsurface

Modern societies rely on natural water pathways that include subsurface flow of water and dissolved chemicals. The thesis presents a range of numerical and analytical models for simulating physical, chemical and biological processes in the subsurface, including coastal aquifers, the near-surface vadose zone, and solute transport in biogeochemically active aquifers.

Parameters important in fabricating enzyme electrodes using self-assembled monolayers of alkanethiols

The fabrication of enzyme electrodes using self-assembled monolayers (SAMs) has attracted considerable interest because of the spatial control over the enzyme immobilization. A model system of glucose oxidase covalently bound to a gold electrode modified with a SAM of 3-mercaptopropionic acid was investigated with regard to the effect of fabrication variables such as the surface topography of the underlying gold electrode, the conditions during covalent attachment of the enzyme and the buffer used. The resultant monolayer enzyme electrodes have excellent sensitivity and dynamic range which can easily be adjusted by controlling the amount of enzyme immobilized. The major drawback of such electrodes is the response which is limited by the kinetics of the enzyme rather than mass transport of substrates. Approaches to bringing such enzyme electrodes into the mass transport limiting regime by exploiting direct electron transfer between the enzyme and the electrode are outlined.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc+) as the PF6 - salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc0/+ and Cc+/0 couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 ( 1 °C in each IL determined from measurement on individual Fc and Cc+ solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc+ were simultaneously present, the dc and ac peak currents per unit concentration for the Fc0/+ and Cc+/0 processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc+ were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc0/+ mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu4NPF6), and the double layer capacitance also varied in distinctly different ways when Fc and Cc+ were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the 1H NMR T1 relaxation times for the proton resonance in Cc+ also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

Measuring miscible fluid displacement in porous media with magnetic resonance imaging

The development of new quantitative magnetic resonance imaging (MRI) technologies open new opportunities for measurements of mass transport in porous media. The current work examines a simple miscible displacement process of H2O and D2O in porous media samples. Laboratory measurements of dispersion in porous media traditionally monitor the effluent intensity of an injected tracer. We employ MRI to obtain quantitative water saturation profiles, and to measure dispersion in rock core plugs. The saturation profiles are modeled with PHREEQC, a fluid transport modeling program. We demonstrate how independent magnetic resonance measurements can be employed to estimate three important input parameters for PHREEQC, mobile porosity, immobile porosity, and dispersivity. Bulk Carr Purcell Meiboom Gill (CPMG) T2 distribution measurements were undertaken to estimate mobile and immobile porosity. Bulk alternating-pulsed-gradient-stimulated-echo (APGSTE) measurements were undertaken to measure dispersivity. The imaging method employed, T2 mapping Spin Echo Single Point Imaging (SE-SPI), also provides information about the pore size distributions in the rock cores, and how the fluid occupancy of the pores changes during the displacement process.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

Deploying aptameric sensing technology for rapid pandemic monitoring

The genome of virulent strains may possess the ability to mutate by means of antigenic shift and/or antigenic drift as well as being resistant to antibiotics with time. The outbreak and spread of these virulent diseases including avian influenza (H1N1), severe acute respiratory syndrome (SARS-Corona virus), cholera (Vibrio cholera), tuberculosis (Mycobacterium tuberculosis), Ebola hemorrhagic fever (Ebola Virus) and AIDS (HIV-1) necessitate urgent attention to develop diagnostic protocols and assays for rapid detection and screening. Rapid and accurate detection of first cases with certainty will contribute significantly in preventing disease transmission and escalation to pandemic levels. As a result, there is a need to develop technologies that can meet the heavy demand of an all-embedded, inexpensive, specific and fast biosensing for the detection and screening of pathogens in active or latent forms to offer quick diagnosis and early treatments in order to avoid disease aggravation and unnecessary late treatment costs. Nucleic acid aptamers are short, single-stranded RNA or DNA sequences that can selectively bind to specific cellular and biomolecular targets. Aptamers, as new-age bioaffinity probes, have the necessary biophysical characteristics for improved pathogen detection. This article seeks to review global pandemic situations in relation to advances in pathogen detection systems. It particularly discusses aptameric biosensing and establishes application opportunities for effective pandemic monitoring. Insights into the application of continuous polymeric supports as the synthetic base for aptamer coupling to provide the needed convective mass transport for rapid screening is also presented.

Enhanced thermal energy harvesting performance of a cobalt redox couple in ionic liquid-solvent mixtures

Thermoelectrochemical cells are increasingly promising devices for harvesting waste heat, offering an alternative to the traditional semiconductor-based design. Advancement of these devices relies on new redox couple/electrolyte systems and an understanding of the interplay between the different factors that dictate device performance. The Seebeck coefficient (Se) of the redox couple in the electrolyte gives the potential difference achievable for a given temperature gradient across the device. Prior work has shown that a cobalt bipyridyl redox couple in ionic liquids (ILs) displays high Seebeck coefficients, but the thermoelectrochemical cell performance was limited by mass transport. Here we present the Se and thermoelectrochemical power generation performance of the cobalt couple in novel mixed IL/molecular solvent electrolyte systems. The highest power density of 880 mW m-2, at a ΔT of 70 °C, was achieved with a 31 (v/v) MPN-[C2mim][B(CN)4] electrolyte combination. The significant power enhancement compared to the single solvent or IL systems results from a combination of superior ionic conductivity and higher diffusion coefficients, shown by electrochemical analysis of the different electrolytes. This is the highest power output achieved to-date for a thermoelectrochemical cell utilising a high boiling point redox electrolyte.

Habitual active transport moderates the association of tv viewing time with body mass index

Background: Television viewing time is associated with obesity risk independent of leisure-time physical activity (LTPA). However,
it is unknown whether the relationship of TV viewing time with body mass index (BMI) is moderated by other domains of physical activity. Methods: A mail survey collected height;weight; TV viewing time; physical activity for transportation (habitual transport behavior; past week walking and bicycling), for recreation (LTPA), and in workplace; and sociodemographic variables in Adelaide, Australia. General linear models examined whether physical activity domains moderate the association between BMI and TV viewing time. Results: Analysis of the sample (N = 1408) found that TV time, habitual transport, and LTPA were independently associated with participant’s BMI. The interaction between TV time and habitual transport with BMI was significant, while that between TV time and LTPA was not. Subgroup analyses found that adjusted mean BMI was significantly higher for the high TV viewing category, compared with the low category,
among participants who were inactive and occasionally active in transport, but not among those who were regularly active. Conclusions: Habitual active transport appeared to moderate the relationship between TV viewing time and BMI. Obesity risk associated with prolonged TV viewing may be mitigated by regular active transport.

Earthquake-controlled event deposits and its tectonic significance from the Middle Permian Wandrawandian Siltstone in the Sydney Basin, Australia

The Sydney-Bowen basin in eastern Australia is an elongate back arc-converted foreland basin system situated between the Lachlan Fold Belt in the west and the New England Fold Belt in the east. The Middle Permian Wandrawandian Siltstone at Warden Head near Ulladulla in the southern Sydney Basin is dominated by fossiliferous siltstone and mudstone, with a large amount of dropstones and minor pebbly sandstone beds. Two general types of deposits are recognized from the siltstone unit in view of the timing and mechanism of formation. One is represented by the primary deposits from offshore to subtidal environments with abundant dropstones of glacial marine origin. The second type is distinguished by secondary, soft-sediment deformational deposits and structures, and comprises three layers of mudstone dykes of seismic origin. In the latter type, metre scale, laterally extensive syn-depositional slump deformation structures occur in the middle part of the Wandrawandian Siltstone. The deformation structures vary in morphol-ogy and pattern, including large-scale complex-type folds, flexural stratification, concave-up structures, faulting of small displacements accompanied by folding and brecciation. The slumps and associated syn-sedimentary structures are attributed to penecontemporaneous deformations of soft sediments (mostly silty mud) formed as a result of mass movement of unconsolidated and/or semi-consolidated substrate following an earthquake event. The occurrence of the earthquake event deposits supports the current view that the Sydney Basin was located in a back-arc setting near the New England magmatic arc on an active continental margin during the Middle Permian.

Cost-effectiveness of active transport for primary school children - Walking School Bus Program

Background : To assess from a societal perspective the incremental cost-effectiveness of the Walking School Bus (WSB) program for Australian primary school children as an obesity prevention measure. The intervention was modelled as part of the ACE-Obesity study, which evaluated, using consistent methods, thirteen interventions targeting unhealthy weight gain in Australian children and adolescents.

Methods : A logic pathway was used to model the effects on body mass index [BMI] and disability-adjusted life years [DALYs] of the Victorian WSB program if applied throughout Australia. Cost offsets and DALY benefits were modelled until the eligible cohort reached 100 years of age or death. The reference year was 2001. Second stage filter criteria ('equity', 'strength of evidence', 'acceptability', feasibility', sustainability' and 'side-effects') were assessed to incorporate additional factors that impact on resource allocation decisions.

Results : The modelled intervention reached 7,840 children aged 5 to 7 years and cost $AUD22.8M ($16.6M;$30.9M). This resulted in an incremental saving of 30 DALYs (7:104) and a net cost per DALY saved of $AUD0.76M ($0.23M; $3.32M). The evidence base was judged as 'weak' as there are no data available documenting the increase in the number of children walking due to the intervention. The high costs of the current approach may limit sustainability.

Conclusions : Under current modelling assumptions, the WSB program is not an effective or cost-effective measure to reduce childhood obesity. The attribution of some costs to non-obesity objectives (reduced traffic congestion and air pollution etc.) is justified to emphasise the other possible benefits. The program's cost-effectiveness would be improved by more comprehensive implementation within current infrastructure arrangements. The importance of active transport to school suggests that improvements in WSB or its variants need to be developed and fully evaluated.

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H₃PO₄, were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10⁻² S cm⁻¹. The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H⁺ cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H⁺ diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.

The longitudinal influence of home and neighbourhood environments on children's body mass index and physical activity over 5 years : the CLAN study

Objective: To determine the independent contributions of family and neighbourhood environments to changes in youth physical activity and body mass index (BMI) z-score over 5 years.

Methods: In 2001, 2004 and 2006, 301 children (10–12 years at baseline) had their height and weight measured (BMI was converted to z-scores using Centers for Disease Control and Prevention reference charts; see http://www.cdc.gov/growthcharts) and moderate-to-vigorous physical activity (MVPA) assessed using accelerometers. In 2001, parents reported on the home environment (social support, role modelling, rules and restrictions, physical environment) and perceived neighbourhood environment (local traffic, road safety, sporting venues, public transport), and Geographic Information Systems were used to map features of the neighbourhood environment (destinations, road connectivity, traffic exposure). Generalized estimating equations were used to predict average BMI z-score and MVPA over time from baseline home and perceived and objective neighbourhood environment factors.

Results: Among boys, maternal education and heavy traffic were inversely associated, and sibling physical activity, maternal role modelling of MVPA and the presence of dead-end roads were positively associated with MVPA. Having unmarried parents, maternal MVPA role modelling and number of home sedentary items were positively associated with BMI z-score among boys. Among girls, having siblings, paternal MVPA role modelling, physical activity rules and parental physical activity co-participation were positively associated with MVPA. Having unmarried parents and maternal sedentary behaviour role modelling were positively associated, and number of sedentary behaviour rules and physical activity items were inversely associated with BMI z-score among girls.

Conclusion: The home environment seems more important than the neighbourhood environment in influencing children's physical activity and BMI z-score over 5 years. Physical activity and weight gain programmes among youth should focus on parental role modelling, rules around sedentary and active pursuits, and parental support for physical activity. Intervention studies to investigate these strategies are warranted.

Assessing cost-effectiveness in obesity : active transport program for primary school children— TravelSMART schools curriculum program

Background: To assess from a societal perspective the cost-effectiveness of a school program to increase active transport in 10- to 11-year-old Australian children as an obesity prevention measure.
Methods: The TravelSMART Schools Curriculum program was modeled nationally for 2001 in terms of its impact on Body Mass Index (BMI) and Disability-Adjusted Life Years (DALYs) measured against current practice. Cost offsets and DALY benefits were modeled until the eligible cohort reached age 100 or died. The intervention was qualitatively assessed against second stage filter criteria (‘equity,’ ‘strength of evidence,’ ‘acceptability to stakeholders,’ ‘feasibility of implementation,’ ‘sustainability,’ and ‘side-effects’) given their potential impact on funding decisions.
Results: The modeled intervention reached 267,700 children and cost $AUD13.3M (95% uncertainty interval [UI] $6.9M; $22.8M) per year. It resulted in an incremental saving of 890 (95%UI –540; 2,900) BMI units, which translated to 95 (95% UI –40; 230) DALYs and a net cost per DALY saved of $AUD117,000 (95% UI dominated; $1.06M).
Conclusions: The intervention was not cost-effective as an obesity prevention measure under base-run modeling assumptions. The attribution of some costs to nonobesity objectives would be justified given the program’s multiple benefits. Cost-effectiveness would be further improved by considering the wider school community impacts.