Wet-Dry Cycles and Microstructural Characteristics of Expansive Subgrade Treated with Sustainable Cementitious Waste Materials.

This work presents an experimental study on the physico-mechanical and microstructural characteristics of stabilised soils and the effect of wetting and drying cycles on their durability as road subgrade materials. The durability of expansive road subgrade with a high plasticity index treated with different ratios of ground granulated blast furnace slag (GGBS) and brick dust waste (BDW) was investigated. Treated and cured samples of the expansive subgrade were subjected to wetting-drying cycles, California bearing ratio (CBR) tests, and microstructural analysis. The results show a gradual reduction in the California bearing ratio (CBR), mass, and the resilient modulus of samples for all subgrade types as the number of cycles increases. The treated subgrades containing 23.5% GGBS recorded the highest CBR value of 230% under dry conditions while the lowest CBR value of 15% (wetting cycle) was recorded for the subgrade treated with 11.75% GGBS and 11.75% BDW at the end of the wetting-drying cycles, both of which find useful application in road pavement construction as calcium silicate hydrate (CSH) gel was formed in all stabilised subgrade materials. However, the increase in alumina and silica content upon the inclusion of BDW initiated the formation of more cementitious products due to the increased availability of Si and Al species as indicated by EDX analysis. This study concluded that subgrade materials treated with a combination of GGBS and BDW are durable, sustainable and suitable for use in road construction.

Behaviour and Microstructural Characteristics of Lime-GGBS-Treated Kaolin Clay Contaminated with Gypsum.

In this experimental study, the physico-mechanical and microstructural properties of sulphate-bearing clays have been investigated. Sulphate bearing soils constituted by mixing kaolin and gypsum at 0%, 15%, 25%, and 35% gypsum contents were treated with 12% ordinary Portland cement (OPC) and 4%Lime (L) and 8% ground granulated blast furnace slag (GGBS) and subjected to compaction, swell, unconfined compressive strength (UCS), California bearing ratio (CBR), and scanning electron microscopy (SEM) and energy dispersive spectrometry (EDX) analyses. The results of the study showed that the use of L-GGBS improved the soaked CBRs of the treated samples by over 43% when compared to OPC-treated samples after 7-days curing. A reduction in water absorption by 82% was also observed with L-GGBS treatment after 28-days curing. The UCS results also showed better performance with L-GGBS treatment exceeding 856% at 28 days. The effect of increased cementitious product with increasing gypsum content was negated by simultaneous and rapid growth of ettringite minerals which reduced the strength and increased swelling of OPC treated samples up to 18.92%, exceeding allowable limits of 2.5% as specified in Highway Agency Advice Note HA 74/07. The L-GGBS treated gypseous soil samples meet the strength requirement for stabilised sub-base (CS) and stabilised road-bases (CB1 and CB2) as described in TRL ORN31. Hence, the use of L-GGBS combination was found to be effective in ameliorating sulphate-induced expansion and therefore encouraged in the stabilisation of subgrade and road-base materials with high sulphate contents.

Optimisation of Embodied Carbon and Compressive Strength in Low Carbon Concrete.

To improve the prediction of compressive strength and embodied carbon of low carbon concrete using a program algorithm developed in MATLAB, 84 datasets of concrete mix raw materials were used. The influence of water, silica fume and ground granular base slag was found to have a significant impact on the extent of low carbon concrete behaviour in terms of compressive strength and embodied carbon. While the concrete compressive strength for normal concrete increases with reducing water content, it is observed that the low carbon concrete using lightweight aggregate material increases in compressive strength with an increase in embodied carbon. From the result of the analysis, a function was developed that was able to predict the associated embodied carbon of a concrete mix for a given water-to-cement ratio. The use of an alkaline solution is observed to increase the compressive strength of low carbon concrete when used in combination with ground granular base slag and silica fume. It is further shown that ground granular base slag contributes significantly to an increase in the compressive strength of Low carbon concrete when compared with pulverised fly ash. The optimised mix design program resulted in a 26% reduction in embodied carbon and an R2 value of 0.9 between the measured compressive strength and the optimised compressive strength.

Criteria for Preliminary Risk Assessment of Brownfield Site: An International Survey of Experts.

Comprehensive risk assessment of brownfield sites requires a broad range of knowledge and multi-disciplinary expertise. Whilst the identification of criteria requirements for preliminary risk assessment has received some attention, there appears to be no studies that have specifically examined professional perspectives relating to these requirements. Yet, variations in professional practitioners' assessments may have significant consequences for the assessment of risks, and how the criteria are imparted to stakeholders. This study aims to identify the criteria requirements for preliminary risk assessment, using the pollutant linkage model (Source-Pathway-Receptor), and explores cross-disciplinary professional perspectives related to these requirements. To this end, this study commenced with a systematic review to identify various criteria streams required for the preliminary risk assessment of brownfield sites. Thereafter, a questionnaire survey was design and shared with brownfield site professionals. Quantitative analysis of the survey responses (n = 76) reveals disciplines have markedly different priorities relating to the same hazard. For instance, geophysicists, geochemists, and hydrologists do not raise concerns regarding ground movement that can result from the removal of storage and tanks, whilst the same hazard was considered as having a high importance by other professions (such as geologists and geotechnical engineers). This example, amongst others revealed in the study, underpins potential issues and implications for various stakeholders compiling and/or using preliminary risk assessment criteria. This study clarifies both the key criteria requirements for the preliminary risk assessment of brownfield sites, as well as the importance of recognising how variation in professionals' perceptions plays in the risk assessment process. Although, specialist knowledge is essential for brownfield site investigation, so is the maintaining a broad-based view of other experts coming from different backgrounds, as this renders holistic risk assessment insights.

Strength Predictive Modelling of Soils Treated with Calcium-Based Additives Blended with Eco-Friendly Pozzolans-A Machine Learning Approach.

The unconfined compressive strength (UCS) of a stabilised soil is a major mechanical parameter in understanding and developing geomechanical models, and it can be estimated directly by either lab testing of retrieved core samples or remoulded samples. However, due to the effort, high cost and time associated with these methods, there is a need to develop a new technique for predicting UCS values in real time. An artificial intelligence paradigm of machine learning (ML) using the gradient boosting (GB) technique is applied in this study to model the unconfined compressive strength of soils stabilised by cementitious additive-enriched agro-based pozzolans. Both ML regression and multinomial classification of the UCS of the stabilised mix are investigated. Rigorous sensitivity-driven diagnostic testing is also performed to validate and provide an understanding of the intricacies of the decisions made by the algorithm. Results indicate that the well-tuned and optimised GB algorithm has a very high capacity to distinguish between positive and negative UCS categories ('firm', 'very stiff' and 'hard'). An overall accuracy of 0.920, weighted recall rates and precision scores of 0.920 and 0.938, respectively, were produced by the GB model. Multiclass prediction in this regard shows that only 12.5% of misclassified instances was achieved. When applied to a regression problem, a coefficient of determination of approximately 0.900 and a mean error of about 0.335 were obtained, thus lending further credence to the high performance of the GB algorithm used. Finally, among the eight input features utilised as independent variables, the additives seemed to exhibit the strongest influence on the ML predictive modelling.

Road Pavement Thickness and Construction Depth Optimization Using Treated and Untreated Artificially-Synthesized Expansive Road Subgrade Materials with Varying Plasticity Index.

Road pavement thickness and their depth of construction take a chunk of the overall cost of road construction. This has called for a need for reduced road pavement thickness by improving the engineering properties of subgrade such as the California bearing ratio (CBR). The CBR of road subgrade has been a major determining factor for road pavement thickness, and expansive subgrades generally have a low CBR, resulting in major road defects. In this study, road pavement thickness and construction depth optimization were conducted using the CBR values achieved in this study. Additives proportions of 8% lime and 20% cement were used in expansive subgrade to improve their engineering properties, making them suitable for use in road construction. The study investigated the characteristics, mineral structure, Atterberg limit, compaction, CBR, swell and microstructural properties of expansive subgrade. The results show a reduction in road pavement thickness and a construction depth with an increase in CBR value. All CBR values for treated samples were above 2%, making them usable in road construction. A reduction in swell potential up to 0.04% was observed for treated expansive subgrade. The study concluded that pavement thickness and construction depth can be reduced by enhancing subgrade materials and using cement and lime as binders.

Triquetrohamate Impaction Syndrome: An Unrecognized Cause of Ulnar-Sided Wrist Pain; Its Presentation Further Defined.

BACKGROUND: The aim of this review was to further define the clinical condition triquetrohamate (TH) impaction syndrome (THIS), an entity underreported and missed often. Its presentation, physical findings, and treatment are presented. METHODS: Between 2009 and 2014, 18 patients were diagnosed with THIS. The age, sex, hand involved, activity responsible for symptoms, and defining characteristics were recorded. The physical findings, along with ancillary studies, were reviewed. Delay in diagnosis and misdiagnoses were assessed. Treatment, either conservative or surgical, is presented. Follow-up outcomes are presented. RESULTS: There were 15 male and 3 females, average age of 42 years. Two-handed sports such as golf and baseball accounted for more than 60% of the cases, and these cases were the only ones that involved the lead nondominant hand, pain predominantly at impact. Delay in diagnosis averaged greater than 7 months, with triangular fibrocartilage (TFCC) and extensor carpi ulnaris (ECU) accounting for more than 50% of misdiagnoses. Physical findings of note included pain over the TH joint, worse with passive dorsiflexion and ulnar deviation. Radiographic findings are described. Instillation of lidocaine with the wrist in radial deviation under fluoroscopic imaging with relief of pain helped to confirm the diagnosis. Conservative treatment was successful in 9 of 18 patients (50%), whereas in the remaining, surgical intervention allowed approximately 80% return to full activities without limitation. CONCLUSION: Triquetrohamate impaction syndrome remains an underreported and often unrecognized cause of ulnar-sided wrist pain. In this report, the largest series to date, its presentation, defining characteristics, and treatment options are further elucidated.

Analysis of the jugular foramen in pediatric patients with craniosynostosis.

INTRODUCTION: Intracranial hypertension due to craniosynostosis is a dreaded potential complication that affects the developing brain. We hypothesized that craniosynostotic patients have significantly reduced jugular foramen (JF) when compared with age-matched controls. This may partially account for the observed increase in intracranial pressure (ICP) seen in some of these patients. We also estimated the potential effects on ICP using the Hagen-Poiseuille equation. MATERIALS AND METHODS: Two institutional review board-approved groups were included in this study. Group 1 consists of 14 randomly selected craniosynostotic patients (7 boys and 7 girls; mean age, 9.33 mo; range, 0.6-21 mo). Group 2, the control group, consists of 27 children without craniosynostosis (13 boys and 14 girls; mean age, 8.71 mo; range, 0.23-45 mo). The same neuroradiologist used axial computed tomographic scans to measure the greatest anterior-posterior (AP) and lateral diameters of the jugular bulb. RESULTS: The right JF AP diameter is 23.02% smaller in group 1 than in group 2 (P = 0.0066, 2-tailed t-test). The left JF AP diameter was also smaller for group 1 but was not statistically significant (P = 0.257, 2-tailed t-test). Group 1 also had a nonsignificant increase in both lateral diameters (P > 0.05). DISCUSSION: The study showed a significant decrease (23.02%) in the right JF AP dimension in children with craniosynostosis. On the basis of the Hagen-Poiseuille equation, a 23.02% AP diameter reduction in 1 JF may theoretically increase the ICP 63.5% or 6.35 mm Hg, keeping all other variables, such as blood flow, constant. Although not supported by aspect ratio analysis, the slight increase in the lateral diameters of the patients' JFs may lessen this effect.

Effect of ethanol on the gelation of aqueous solutions of Pluronic F127.

In dilute aqueous solution unimers of copolymer F127 (E(98)P(67)E(98)) associate to form micelles, and in more concentrated solution micelles pack to form high-modulus gels. Cosolvents are known to affect these processes, and ethanol/water mixtures have been of particular interest. Dynamic light scattering from dilute solutions was used to confirm micellization, but major attention was directed towards the gels. Visual observation of mobility (tube inversion) was used to detect gel formation, oscillatory rheometry to confirm gel formation and provide values of the elastic moduli over a wide temperature range, and small-angle X-ray scattering to determine gel structure. The solvents were limited to 10, 20 and 30 wt.% ethanol/water. Critical concentrations for gel formation were similar for 10 and 20 wt.% ethanol/water but were significantly increased for 30 wt.% ethanol/water, e.g. at T=45 degrees C from c approximately 15 wt.% to c approximately 28 wt.%. The elastic moduli reached maximum values at T approximately 50 degrees C: e.g. G' approximately 25 kPa for 25 wt.% F127 in 10 and 20 wt.% ethanol/water and a similar value for 30 wt.% F127 in 30 wt.% ethanol/water. Hard gels of 30 and 35 wt.% F127 in ethanol/water at 25 and 40 degrees C had the body-centered cubic (bcc) structure.

Aqueous gels of mixtures of ionic surfactant SDS with pluronic copolymers P123 or F127.

Gel diagrams based on tube inversion and oscillatory rheometry are reported for Pluronic copolymers F127 (E(98)P(67)E(98)) and P123 (E(21)P(67)E(21)) in mixtures with anionic surfactant sodium dodecyl sulfate (SDS). Total concentrations (c, SDS+copolymer) were as high as 50 wt % with mole ratios SDS/copolymer (mr) in the ranges 1-5 (F127) and 1-7 (P123). Temperatures were as high as 90 degrees C. Determination of the temperature dependences of the dynamic moduli served to confirm the gel boundaries from tube inversion and to reveal the high elastic moduli of the gels, e.g., compared at comparable positions in the gel phase, a 50 wt % SDS/P123 with mr = 7 had G' three times that of a corresponding gel of P123 alone. Small-angle X-ray scattering (SAXS) was used to show that the structures of all the SDS/F127 gels were bcc and that the structures of the SDS/P123 gels with mr = 1 were either fcc (c = 30 wt %) or hex (c = 40 wt %). Assignment of structures to SDS/P123 gels with values of mr in the range 3-7 was more difficult, as high-order scattering peaks could be very weak, and at the higher values of c and mr, the SAXS peaks included multiple reflections.

Solubilisation of griseofulvin, quercetin and rutin in micellar formulations of triblock copolymers E62P39E62 and E137S18E137.

The solubilisation of two poorly soluble flavonoids, quercetin and rutin, in micellar solutions of mixtures of a block copolymer of ethylene oxide and styrene oxide (E(137)S(18)E(137)) with one of ethylene oxide and propylene oxide (E(62)P(39)E(62)) has been studied at 25 and 37 degrees C. Solubilisation capacities were higher than those for the model poorly water-soluble drug griseofulvin and comparable with published values for the solubilisation of rutin by beta-cyclodextrin.

Solubilisation of griseofulvin in aqueous micellar solutions of diblock copolymers of ethylene oxide and 1,2-butylene oxide with lengthy B-blocks.

The influence of hydrophobic-block length on solubilisation capacity was examined for micelles of E(m)B(n) copolymers (E=oxyethylene, B=oxybutylene, subscripts denote number-average block lengths in repeat units) with B-block lengths in the range of 30-76 and with E-blocks of sufficient length to ensure the formation of spherical micelles. Griseofulvin was used as a model poorly-water-soluble drug known to be almost exclusively solubilised in the micellar core. Combination of solubilisation data with those of a previous study has shown that the amount of drug solubilised per gram of hydrophobe is essentially independent of B-block length when this exceeds about 15 B units, suggesting that core size is not a major influence on solubilisation.

Medical waste management in Ibadan, Nigeria: obstacles and prospects.

Quantification and characterization of medical waste generated in healthcare facilities (HCFs) in a developing African nation has been conducted to provide insights into existing waste collection and disposal approaches, so as to provide sustainable avenues for institutional policy improvement. The study, in Ibadan city, Nigeria, entailed a representative classification of nearly 400 healthcare facilities, from 11 local government areas (LGA) of Ibadan, into tertiary, secondary, primary, and diagnostic HCFs, of which, 52 HCFs were strategically selected. Primary data sources included field measurements, waste sampling and analysis and a questionnaire, while secondary information sources included public and private records from hospitals and government ministries. Results indicate secondary HCFs generate the greatest amounts of medical waste (mean of 10,238 kg/day per facility) followed by tertiary, primary and diagnostic HCFs, respectively. Characterised waste revealed that only approximately 3% was deemed infectious and highlights opportunities for composting, reuse and recycling. Furthermore, the management practices in most facilities expose patients, staff, waste handlers and the populace to unnecessary health risks. This study proffers recommendations to include (i) a need for sustained cooperation among all key actors (government, hospitals and waste managers) in implementing a safe and reliable medical waste management strategy, not only in legislation and policy formation but also particularly in its monitoring and enforcement and (ii) an obligation for each HCF to ensure a safe and hygienic system of medical waste handling, segregation, collection, storage, transportation, treatment and disposal, with minimal risk to handlers, public health and the environment.

Magneto-biomonitoring of intra-urban spatial variations of particulate matter using tree leaves.

Preliminary mineral magnetic results from a pilot project investigating the suitability of roadside tree leaves as depositories of vehicular pollution are presented. Tree leaf surfaces (Lime: Tilia europaea; Sycamore: Acer pseudoplatanus) at four roadside and one woodland location in Wolverhampton, UK, have been monitored (July 2003 to November 2003). Mineral magnetic technologies have revealed spatial variations of particulate pollution concentration throughout the conurbation and data analysis indicates that magnetic concentration parameters are suitable proxies for fine particulate pollution, which are particularly hazardous to health. Site-specific traffic management and associated vehicle behaviour appear to be chiefly responsible for the magnetic concentration differences between sites. Magneto-biomonitoring in this way allows the high-resolution spatial mapping of particulate matter (PM) pollution, which may also benefit epidemiology in better assessing exposure to vehicular-derived particulates. Given the speed, measurement sensitivity and non-destructive nature of the technique, it is proposed that this low-cost approach offers some advantages over centralised monitoring stations to monitor urban roadside particulate pollution.

Effect of ethanol on the micellization and gelation of pluronic p123.

In certain applications copolymer P123 (E21P67E21) is dissolved in water-ethanol mixtures, initially to form micellar solutions and eventually to gel. For P123 in 10, 20, and 30 wt % aqueous ethanol we used dynamic light scattering from dilute solutions to confirm micellization, oscillatory rheometry, and visual observation of mobility (tube inversion) to determine gel formation in concentrated solutions and small-angle X-ray scattering (SAXS) to determine gel structure. Except for solutions in 30 wt % aqueous ethanol, a clear-turbid transition was encountered on heating dilute and concentrated micellar solutions alike, and as for solutions in water alone (Chaibundit et al. Langmuir 2007, 23, 9229) this could be ascribed to formation of wormlike micelles. Dense clouding, typical of phase separation, was observed at higher temperatures. Regions of isotropic and birefringent gel were defined for concentrated solutions and shown (by SAXS) to have cubic (fcc and hcp) and hexagonal structures, consistent with packed spherical and elongated micelles, respectively. The cubic gels (0, 10, and 20 wt % ethanol) were clear, while the hex gels were either turbid (0 and 10 wt % ethanol), turbid enclosing a clear region (20 wt % ethanol), or entirely clear (30 wt % ethanol). The SAXS profile was unchanged between turbid and clear regions of the 20 wt % ethanol gel. Temperature scans of dynamic moduli showed (as expected) a clear distinction between high-modulus cubic gels (G'max approximately 20-30 kPa) and lower modulus hex gels (G'max<10 kPa).

Diblock copolymers of ethylene oxide and 1,2-butylene oxide in aqueous solution: formation of unimolecular micelles.

The dependence of log(cmc) on hydrophobic block length n was examined for E(m)B(n) copolymers (E=oxyethylene, B=oxybutylene, subscripts denote number-average block lengths in repeat units) with n in the range 30-76. Combination with published data for E(m)B(n) diblock copolymers with shorter E-blocks shows two changes of slope in the log(cmc)-n plot corresponding to the onset of unimolecular micelle formation at n approximately 12 and completion of this process at n approximately 30. The results are discussed with reference to published data for E(m)L(n) and E(m)CL(n) (L from d,L-lactide; CL from epsilon-caprolactone) copolymers, which show similar behaviour.

Solubilisation of drugs in micellar solutions of diblock copolymers of ethylene oxide and styrene oxide.

The solubilisation of two poorly soluble drugs, furosemide and nabumetone, in micellar solutions of diblock copolymers of ethylene oxide and styrene oxide has been studied at 25 and 37 degrees C and solubilisation capacities compared with published values for griseofulvin and docetaxel. Solubilisation in the micelle core, corrected for the different proportions of poly(styrene oxide) in the copolymers, was similar for all four drugs. The highest solubilisation capacities were found for a copolymer with worm-like micelles.

Solubilisation of drugs in worm-like micelles of block copolymers of ethylene oxide and 1,2-butylene oxide in aqueous solution.

Ethylene oxide and 1,2-butylene oxide were sequentially polymerised to form the diblock copolymer E13B10 (E=oxyethylene, B=oxybutylene, subscripts denote number-average block lengths in repeat units). Dynamic and static light scattering over the temperature range 10-30 degrees C demonstrated a transition from compact (spheroidal) micelles to larger, more elongated (worm-like) micelles with temperature increase above a critical onset temperature of about 20 degrees C. Determination of the solubilisation capacity for griseofulvin, carbamazepine and spironolactone of dilute micellar solutions of this copolymer, together with those of E11B8 and E17B12 block copolymers (which also show the sphere-to-worm transition), allowed investigation of the influence on solubilisation characteristics of hydrophobic block length and temperature. The extent of solubilisation at 25 degrees C of the poorly water-soluble drug spironolactone increased linearly with increase of hydrophobic block length, attributable to a concomitant increase in the proportion of worm-like micelles in solution.

Poly(ethylene oxide) based copolymers: solubilisation capacity and gelation.

It is thought that almost half of potentially useful drug candidates fail to progress to formulation development because of their low aqueous solubility and associated poor or erratic absorption characteristics. A response to this challenge has been the development of a variety of colloidal delivery systems in which the therapeutic agent is encapsulated in nanosized particles. In this review, attention is focussed on colloidal vectors based on amphiphilic block copolymers, the micelles of which can accommodate a wide range of water-insoluble guest molecules, and particularly on copolymers with poly(oxyethylene) as the hydrophilic block and with poly(oxyalkylene) or polyester hydrophobic blocks, taking advantage of the 'stealth' properties of the poly(oxyethylene) corona of their micelles. Although copolymers of this type have been commercially available for several decades in the form of the Pluronic (BASF) polyols, which have a poly(oxypropylene) hydrophobic block, they have not found wide application for drug solubilisation, primarily because of their low solubilisation capacity. In attempts to achieve greater drug loading, recent work has concentrated on copolymers in which the core-forming blocks are designed to be more hydrophobic and more compatible with the drug to be encapsulated. Progress in this area has been reviewed and recent developments in the design of block copolymers of this type that combine high drug loading capacity with thermally reversible gelation characteristics in the temperature range suitable for potential application as in situ gelling vehicles following subcutaneous injection have also been discussed.

Block copolymers for drug solubilisation: relative hydrophobicities of polyether and polyester micelle-core-forming blocks.

Published values of the critical micelle concentration are tabulated for diblock copolymers E(m)P(n), E(m)B(n), E(m)S(n), E(m)L(n), E(m)VL(n) and E(m)CL(n), where E denotes a chain unit derived from ethylene oxide, P from propylene oxide, B from 1,2-butylene oxide, S from styrene oxide, L from dl-lactide, VL from gamma-valerolactone and CL from epsilon-caprolactone, and the subscripts denote average chain lengths. Noting that log(cmc/moldm(-3) is proportional to the standard Gibbs energy of micellisation, the dependence of this quantity on hydrophobic block length (n) is explored for a given E-block length. Superposition of data allows ranking of the hydrophobicities of the chain units. The ratios relative to the least hydrophobic unit are: P : L : B : VL : S : CL = 1 : 4 : 6 : 10 : 12 : 12 Transitions in the slope of log(cmc) versus n are assigned to changes in the unimer-micelle equilibrium and related to the formation of unimolecular micelles and, at high values of n, to the completion of that process. The formation transition is seen in the plots for all the copolymers except the least hydrophobic, E(m)P(n). The completion transition is seen in the plots for E(m)CL(n) and E(m)L(n) copolymers, as these alone include results for copolymers with very lengthy hydrophobic blocks.