Influence of physical and chemical properties of solids on heavy metal adsorption

Partition of heavy metals between particulate and dissolve fraction of stormwater primarily depends on the adsorption characteristics of solids particles. Moreover, the bioavailability of heavy metals is also influenced by the adsorption behaviour of solids. However, due to the lack of fundamental knowledge in relation to the heavy metals adsorption processes of road deposited solids, the effectiveness of stormwater management strategies can be limited. The research study focused on the investigation of the physical and chemical parameters of solids on urban road surfaces and, more specifically, on heavy metal adsorption to solids. Due to the complex nature of heavy metal interaction with solids, a substantial database was generated through a series of field investigations and laboratory experiments. The study sites for the build-up pollutant sample collection were selected from four urbanised suburbs located in a major river catchment. Sixteen road sites were selected from these suburbs and represented typical industrial, commercial and residential land uses. Build-up pollutants were collected using a wet and dry vacuum collection technique which was specially designed to improve fine particle collection. Roadside soil samples were also collected from each suburb for comparison with the road surface solids. The collected build-up solids samples were separated into four particle size ranges and tested for a range of physical and chemical parameters. The solids build-up on road surfaces contained a high fraction (70%) of particles smaller than 150ìm, which are favourable for heavy metal adsorption. These solids particles predominantly consist of soil derived minerals which included quartz, albite, microcline, muscovite and chlorite. Additionally, a high percentage of amorphous content was also identified in road deposited solids. In comparing the mineralogical data of surrounding soil and road deposited solids, it was found that about 30% of the solids consisted of particles generated from traffic related activities on road surfaces. Significant difference in mineralogical composition was noted in different particle sizes of build-up solids. Fine solids particles (<150ìm) consisted of a clayey matrix and high amorphous content (in the region of 40%) while coarse particles (>150ìm) consisted of a sandy matrix at all study sites, with about 60% quartz content. Due to these differences in mineralogical components, particles larger than and smaller than 150ìm had significant differences in their specific surface area (SSA) and effective cation exchange capacity (ECEC). These parameters, in turn, exert a significant influence on heavy metal adsorption. Consequently, heavy metal content in >150ìm particles was lower than in the case of fine particles. The particle size range <75ìm had the highest heavy metal content, corresponding with its high clay forming minerals, high organic matter and low quartz content which increased the SSA, ECEC and the presence of Fe, Al and Mn oxides. The clay forming minerals, high organic matter and Fe, Al and Mn oxides create distinct groups of charge sites on solids surfaces and exhibit different adsorption mechanisms and bond strength, between heavy metal elements and charge sites. Therefore, the predominance of these factors in different particle sizes leads to different heavy metal adsorption characteristics. Heavy metals show preference for association with clay forming minerals in fine solids particles, whilst in coarse particles heavy metals preferentially associate with organic matter. Although heavy metal adsorption to amorphous material is very low, the heavy metals embedded in traffic related materials have a potential impact on stormwater quality.Adsorption of heavy metals is not confined to an individual type of charge site in solids, whereas specific heavy metal elements show preference for adsorption to several different types of charge sites in solids. This is attributed to the dearth of preferred binding sites and the inability to reach the preferred binding sites due to competition between different heavy metal species. This confirms that heavy metal adsorption is significantly influenced by the physical and chemical parameters of solids that lead to a heterogeneity of surface charge sites. The research study highlighted the importance of removal of solids particles from stormwater runoff before they enter into receiving waters to reduce the potential risk posed by the bioavailability of heavy metals. The bioavailability of heavy metals not only results from the easily mobile fraction bound to the solids particles, but can also occur as a result of the dissolution of other forms of bonds by chemical changes in stormwater or microbial activity. Due to the diversity in the composition of the different particle sizes of solids and the characteristics and amount of charge sites on the particle surfaces, investigations using bulk solids are not adequate to gain an understanding of the heavy metal adsorption processes of solids particles. Therefore, the investigation of different particle size ranges is recommended for enhancing stormwater quality management practices.

The exchange: an experiment in environmentally sustainable urban practice for a subtropical climate

The exchange pavilion offers a dialogue between two Expositions: 1998 in Brisbane and 2010 in Shanghai; and a chance to examine the impact that climate change will have on urban best practice outcomes in cities of the future. The Exchange exhibits the proposition that environmentally sustainable buildings need to interact responsively with a range of technical innovations to enable communities (and hence cities) to control and better manage their immediate environment. The 'Exchange' pavilion is a design experiment that integrates 3 key research elements: * An interactive digital exchange * A living green system wall (vertical and temporal) * A public urban star (horizontal and spatial) The proposition argues that the environmentally sustainability of any city is reliant on harnessing the full spectrum of intellectual and creative capital of the winder community (from universities to Government bodies to citizens) - a true knowledge city.

Towards a provably secure DoS-Resilient key exchange protocol with perfect forward secrecy

Just Fast Keying (JFK) is a simple, efficient and secure key exchange protocol proposed by Aiello et al. (ACM TISSEC, 2004). JFK is well known for its novel design features, notably its resistance to denial-of-service (DoS) attacks. Using Meadows’ cost-based framework, we identify a new DoS vulnerability in JFK. The JFK protocol is claimed secure in the Canetti-Krawczyk model under the Decisional Diffie-Hellman (DDH) assumption. We show that security of the JFK protocol, when reusing ephemeral Diffie-Hellman keys, appears to require the Gap Diffie-Hellman (GDH) assumption in the random oracle model. We propose a new variant of JFK that avoids the identified DoS vulnerability and provides perfect forward secrecy even under the DDH assumption, achieving the full security promised by the JFK protocol.

Modeling key compromise impersonation attacks on group key exchange protocols

Two-party key exchange (2PKE) protocols have been rigorously analyzed under various models considering different adversarial actions. However, the analysis of group key exchange (GKE) protocols has not been as extensive as that of 2PKE protocols. Particularly, an important security attribute called key compromise impersonation (KCI) resilience has been completely ignored for the case of GKE protocols. Informally, a protocol is said to provide KCI resilience if the compromise of the long-term secret key of a protocol participant A does not allow the adversary to impersonate an honest participant B to A. In this paper, we argue that KCI resilience for GKE protocols is at least as important as it is for 2PKE protocols. Our first contribution is revised definitions of security for GKE protocols considering KCI attacks by both outsider and insider adversaries. We also give a new proof of security for an existing two-round GKE protocol under the revised security definitions assuming random oracles. We then show how to achieve insider KCIR in a generic way using a known compiler in the literature. As one may expect, this additional security assurance comes at the cost of an extra round of communication. Finally, we show that a few existing protocols are not secure against outsider KCI attacks. The attacks on these protocols illustrate the necessity of considering KCI resilience for GKE protocols.

Anonymity and one-way authentication in key exchange protocols

Key establishment is a crucial cryptographic primitive for building secure communication channels between two parties in a network. It has been studied extensively in theory and widely deployed in practice. In the research literature a typical protocol in the public-key setting aims for key secrecy and mutual authentication. However, there are many important practical scenarios where mutual authentication is undesirable, such as in anonymity networks like Tor, or is difficult to achieve due to insufficient public-key infrastructure at the user level, as is the case on the Internet today. In this work we are concerned with the scenario where two parties establish a private shared session key, but only one party authenticates to the other; in fact, the unauthenticated party may wish to have strong anonymity guarantees. We present a desirable set of security, authentication, and anonymity goals for this setting and develop a model which captures these properties. Our approach allows for clients to choose among different levels of authentication. We also describe an attack on a previous protocol of Øverlier and Syverson, and present a new, efficient key exchange protocol that provides one-way authentication and anonymity.

Breaching the standardised assessment boundary : assessment for learning as a field of exchange

The introduction of the Australian curriculum, the use of standardised testing (e.g. NAPLAN) and the My School website are couched in a context of accountability. This circumstance has stimulated and in some cases renewed a range of boundaries in Australian Education. The consequences that arise from standardised testing have accentuated the boundaries produced by social reproduction in education which has led to an increase in the numbers of students disengaging from mainstream education and applying for enrolment at the Edmund Rice Education Australia Flexible Learning Centre Network (EREAFLCN). Boundaries are created for many young people who are denied access to credentials and certification as a result of being excluded from or in some way disengaging from standardised education and testing. Young people who participate at the EREAFLCN arrive with a variety of forms of cultural capital that are not valued in current education and employment fields. This is not to say that these young people’s different forms of cultural capital have no value, but rather that such funds of knowledge, repertoires and cultural capital are not valued by the majority of powerful agents in educational and employment fields. How then can the qualitative value of traditionally unorthodox - yet often intricate, ingenious, and astute - versions of cultural capital evident in the habitus of many young people be made to count, be recognised, be valuated? Can a process of educational assessment be a field of capital exchange and a space which breaches boundaries through a valuating process? This paper reports on the development of an innovative approach to assessment in an alternative education institution designed for the re-engagement of ‘at risk’ youth who have left formal schooling. A case study approach has been used to document the engagement of six young people, with an educational approach described as assessment for learning as a field of exchange across two sites in the EREAFLCN. In order to capture the broad range of students’ cultural and social capital, an electronic portfolio system (EPS) is under trial. The model draws on categories from sociological models of capital and reconceptualises the eportfolio as a sociocultural zone of learning and development. Results from the trial show a general tendency towards engagement with the EPS and potential for the attainment of socially valued cultural capital in the form of school credentials. In this way restrictive boundaries can be breached and a more equitable outcome achieved for many young Australians.

Towards general capabilities through technology : assessment for learning as a field of exchange

The introduction of the Australian curriculum, the use of standardised testing (e.g. NAPLAN) and the My School website have stimulated and in some cases renewed a range of boundaries for young people in Australian Education. Standardised testing has accentuated social reproduction in education with an increase in the numbers of students disengaging from mainstream education and applying for enrolment at the Edmund Rice Education Australia Flexible Learning Centre Network (EREAFLCN). Many young people are denied access to credentials and certification as they become excluded from standardised education and testing. The creativity and skills of marginalised youth are often evidence of general capabilities and yet do not appear to be recognised in mainstream educational institutions when standardised approaches are adopted. Young people who participate at the EREAFLCN arrive with a variety of forms of cultural capital, frequently utilising general capabilities, which are not able to be valued in current education and employment fields. This is not to say that these young people‟s different forms of cultural capital have no value, but rather that such funds of knowledge, repertoires and cultural capital are not valued by the majority of powerful agents in educational and employment fields. How then can the inherent value of traditionally unorthodox - yet often intricate, ingenious, and astute-versions of cultural capital evident in the habitus of many young people be made to count, be recognised, be valuated?Can a process of educational assessment be a field of capital exchange and a space which crosses boundaries through a valuating process? This paper reports on the development of an innovative approach to assessment in an alternative education institution designed for the re engagement of „at risk‟ youth who have left formal schooling. A case study approach has been used to document the engagement of six young people, with an educational approach described as assessment for learning as a field of exchange across two sites in the EREAFLCN. In order to capture the broad range of students‟ cultural and social capital, an electronic portfolio system (EPS) is under trial. The model draws on categories from sociological models of capital and reconceptualises the eportfolio as a sociocultural zone of learning and development. Results from the trial show a general tendency towards engagement with the EPS and potential for the attainment of socially valued cultural capital in the form of school credentials. In this way restrictive boundaries can be breached and a more equitable outcome achieved for many young Australians.

Turning histories into futures : assessment for learning as a field of exchange

Standardised testing does not recognise the creativity and skills of marginalised youth. Young people who come to the Edmund Rice Education Australia Flexible Learning Centre Network (EREAFLCN) in Australia arrive with forms of cultural capital that are not valued in the field of education and employment. This is not to say that young people‟s different modes of cultural capital have no value, but rather that such funds of knowledge, repertoires and cultural capital are not valued by the powerful agents in educational and employment fields. The forms of cultural capital which are valued by these institutions are measurable in certain structured formats which are largely inaccessible for what is seen in Australia to be a growing segment of the community. How then can the inherent value of traditionally unorthodox - yet often intricate, adroit, ingenious, and astute - versions of cultural capital evident in the habitus of many young people be made to count, be recognised, be valuated? Can a process of educational assessment be used as a marketplace, a field of capital exchange? This paper reports on the development of an innovative approach to assessment in an alternative education institution designed for the re-engagement of „at risk‟ youth who have left formal schooling. In order to capture the broad range of students‟ cultural and social capital, an electronic portfolio system (EPS) is under trial. The model draws on categories from sociological models of capital and reconceptualises the eportfolio as a sociocultural zone of learning and development. Initial results from the trial show a general tendency towards engagement with the EPS and potential for the attainment of socially valued cultural capital in the form of school credentials.

A novel method for the synthesis of monodisperse gold-coated silica nanoparticles

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN)2]?) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]? complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au0) proceeding by an inner sphere mechanism. The residual [Au(MeCN)2]? complex was allowed to react with water, disproportionating into Au0 and Au(III), respectively, with the Au0 adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au0 by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.

A small molecule that walks non-directionally along a track without external intervention

Charge of the light brigade: A molecule is able to walk back and forth upon a five-foothold pentaethylenimine track without external intervention. The 1D random walk is highly processive (mean step number 530) and exchange takes place between adjacent amine groups in a stepwise fashion. The walker performs a simple task whilst walking: quenching of the fluorescence of an anthracene group sited at one end of the track. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Environmental factors controlling temporal and spatial variability in the soil-atmosphere exchange of CO2, CH4 and N2O from an Australian subtropical rainforest

The temporal variations in CO2, CH4 and N2O fluxes were measured over two consecutive years from February 2007 to March 2009 from a subtropical rainforest in south-eastern Queensland, Australia, using an automated sampling system. A concurrent study using an additional 30 manual chambers examined the spatial variability of emissions distributed across three nearby remnant rainforest sites with similar vegetation and climatic conditions. Interannual variation in fluxes of all gases over the 2 years was minimal, despite large discrepancies in rainfall, whereas a pronounced seasonal variation could only be observed for CO2 fluxes. High infiltration, drainage and subsequent high soil aeration under the rainforest limited N2O loss while promoting substantial CH4 uptake. The average annual N2O loss of 0.5 ± 0.1 kg N2O-N ha−1 over the 2-year measurement period was at the lower end of reported fluxes from rainforest soils. The rainforest soil functioned as a sink for atmospheric CH4 throughout the entire 2-year period, despite periods of substantial rainfall. A clear linear correlation between soil moisture and CH4 uptake was found. Rates of uptake ranged from greater than 15 g CH4-C ha−1 day−1 during extended dry periods to less than 2–5 g CH4-C ha−1 day−1 when soil water content was high. The calculated annual CH4 uptake at the site was 3.65 kg CH4-C ha−1 yr−1. This is amongst the highest reported for rainforest systems, reiterating the ability of aerated subtropical rainforests to act as substantial sinks of CH4. The spatial study showed N2O fluxes almost eight times higher, and CH4 uptake reduced by over one-third, as clay content of the rainforest soil increased from 12% to more than 23%. This demonstrates that for some rainforest ecosystems, soil texture and related water infiltration and drainage capacity constraints may play a more important role in controlling fluxes than either vegetation or seasonal variability

Quantum key distribution in the classical authenticated key exchange framework

Key establishment is a crucial primitive for building secure channels in a multi-party setting. Without quantum mechanics, key establishment can only be done under the assumption that some computational problem is hard. Since digital communication can be easily eavesdropped and recorded, it is important to consider the secrecy of information anticipating future algorithmic and computational discoveries which could break the secrecy of past keys, violating the secrecy of the confidential channel. Quantum key distribution (QKD) can be used generate secret keys that are secure against any future algorithmic or computational improvements. QKD protocols still require authentication of classical communication, although existing security proofs of QKD typically assume idealized authentication. It is generally considered folklore that QKD when used with computationally secure authentication is still secure against an unbounded adversary, provided the adversary did not break the authentication during the run of the protocol. We describe a security model for quantum key distribution extending classical authenticated key exchange (AKE) security models. Using our model, we characterize the long-term security of the BB84 QKD protocol with computationally secure authentication against an eventually unbounded adversary. By basing our model on traditional AKE models, we can more readily compare the relative merits of various forms of QKD and existing classical AKE protocols. This comparison illustrates in which types of adversarial environments different quantum and classical key agreement protocols can be secure.

The effect of charge on ultrafine particle deposition : an experimental pilot study

Eepidemiological studies have linked exposure to ultrafine particles (UFPs, <100 nm) to a variety of adverse health effects. To understand the mechanisms behind these effects, it is essential to measure aerosol deposition in the human respiratory tract. Electrical charge is a very important property as it may increase the particle deposition in human respiratory tract (Melanderi et al., 1983). However, the effect of charge on UFP deposition has seldom been investigated. The aim of this study is to investigate the effect of charge on UFP deposition in human lung, by conducting a pilot study using a tube-based experimental system.