Mineralogical characteristics and transformations during long-term operation of a zero-valent iron reactive barrier

Received for publication October 31, 2002. Design and operation of Fe0 permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe0 filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe0 filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe0 section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants. Abbreviations: EDX, energy dispersive X-ray • Fe0, zerovalent iron • PRB, permeable reactive barrier • SEM, scanning electron microscopy • XRD, X-ray diffraction

Mineralogical Characteristics and Transformations during Long-Term Operation of a Zerovalent Iron Reactive Barrier

Design and operation of Fe⁰ permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe⁰ filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe⁰ filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe⁰ section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.

Development of a modified flyash as a permeable reactive barrier media for a former manufactured gas plant site Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (

Ascertainment of cause-specific mortality in COPD - operations of the TORCH clinical endpoint Committee

Background: TORCH (Towards a Revolution in COPD Health) is an international multicentre, randomised, placebo-controlled clinical trial of inhaled fluticasone propionate/salmeterol combination treatment and its monotherapy components for maintenance treatment of moderately to severely impaired patients with chronic obstructive pulmonary disease (COPD). The primary outcome is all-cause mortality. Cause-specific mortality and deaths related to COPD are additional outcome measures, but systematic methods for ascertainment of these outcomes have not previously been described. Methods: A Clinical Endpoint Committee (CEC) was tasked with categorising the cause of death and the relationship of deaths to COPD in a systematic, unbiased and independent manner. The key elements of the operation of the committee were the use of predefined principles of operation and definitions of cause of death and COPD-relatedness; the independent review of cases by all members with development of a consensus opinion; and a substantial infrastructure to collect medical information. Results: 911 deaths were reviewed and consensus was reached in all. Cause-specific mortality was: cardiovascular 27%, respiratory 35%, cancer 21%, other 10% and unknown 8%. 40% of deaths were definitely or probably related to COPD. Adjudications were identical in 83% of blindly re-adjudicated cases ( = 0.80). COPD-relatedness was reproduced 84% of the time ( = 0.73). The CEC adjudication was equivalent to the primary cause of death recorded by the site investigator in 52% of cases. Conclusion: A CEC can provide standardised, reliable and informative adjudication of COPD mortality that provides information which frequently differs from data collected from assessment by site investigators.

Accurate substrate modelling of RF CMOS

The losses within the substrate of an RF IC can have significant effect on performance in a mixed signal application. in order to model substrate coupling accurately, it is represented by an RC network to account for both resistive and dielectric losses at high frequency (> 1 GHz). A small-signal equivalent circuit model of an RF IC inclusive of substrate parasitic effect is analysed in terms of its y-parameters and an extraction procedure for substrate parameters has been developed. By coupling the extracted substrate parameters along with extrinsic resistances associated with gate, source and drain, a standard BSIM3 model has been extended for RF applications. The new model exhibits a significant improvement in prediction of output reflection coefficient S-22 in the frequency range from 1 to 10 GHz in device mode of operation and for a low noise amplifier (LNA) at 2.4 GHz. Copyright (C) 2006 John Wiley & Sons, Ltd.

Extrinsic parameter extraction and RF modelling of CMOS

An analytical approach for CMOS parameter extraction which includes the effect of parasitic resistance is presented. The method is based on small-signal equivalent circuit valid in all region of operation to uniquely extract extrinsic resistances, which can be used to extend the industry standard BSIM3v3 MOSFET model for radio frequency applications. The verification of the model was carried out through frequency domain measurements of S-parameters and direct time domain measurement at 2.4 GHz in a large signal non-linear mode of operation. (C) 2003 Elsevier Ltd. All rights reserved.

Ten Year Performance Evaluation of a Field-Scale Zero-Valent Iron Permeable Reactive Barrier Installed to Remediate Trichloroethene Contaminated Groundwater

The Monkstown Fe0 PRB, Europe’s oldest commercially installed PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is being remediated to below detection limits as the contaminated groundwater flows through the PRB, Ca and Fe carbonates, crystalline and amorphous FeS, and Fe (oxy)hydroxides precipitates are present in the Fe0 filing material within the PRB. A greater variety of minerals are associated with a 1 cm thick slightly cemented crust at the entrance of the Fe0 section of the reactive vessel and the discontinuous cemented Fe0 material directly below it. Also, a greater presence of microbial communities occurred in the upper portion of the PRB compared to the lower section which might be due to less favourable conditions (i.e. high pH, low oxygen) for microbial growth in the lower section of the PRB. Visual estimation suggests that the Fe0 filings in the effluent section of the PRB have life-span of 10+ years compared to the Fe0 filings in the thin influent section of the PRB which may have a life span of only ~2-5 more years. Multi-tracer tests indicated that preferential pathways have formed in this PRB over the 10 years of operation.

Investigation of an electron string ion source with field emission cathode

The string mode of operation for an electron beam ion source uses axially oscillating electrons in order to reduce power consumption, also simplifying the construction by omitting the collector with cooling requirements and has been called electron string ion source (ESIS). We have started a project (supported by INTAS and GSI) to use Schottky field emitting cathode tips for generating the electron string. The emission from these specially conditioned tips is higher by orders of magnitude than the focused Brillouin current density at magnetic fields of some Tesla and electron energies of some keV. This may avoid the observed instabilities in the transition from axially oscillating electrons to the string state of the electron plasma, opening a much wider field of possible operating parameters for an ESIS. Besides the presentation of the basic features, we emphasize in this paper a method to avoid damaging of the field, emission tip by backstreaming ions. (C) 2008 American Institute of Physics.

Steady-State and Transient Performance of Biodiesel-Fueled Compression-Ignition-Based Electrical Generation

This paper investigates the performance characteristics of rapeseed methyl ester, EN 14214 biodiesel, when used for electrical generation in compression ignition engines. The work was inspired by the need to replace fossil diesel fuel with a sustainable low carbon alternative while maintaining generator performance, power quality, and compliance with ISO 8528-5. A 50-kVA Perkins diesel engine generator was used to assess the impact of biodiesel with particular regard to gen-set fuel consumption, load acceptance, and associated standards. Tests were performed on the diesel gen-set for islanded and grid-connected modes of operation, hence both steady-state and transient performance were fully explored. Performance comparisons were made with conventional fossil diesel fuel, revealing minimal technical barriers for electrical generation from this sustainable, carbon benign fuel. Recommendations for improved transient performance are proposed and validated through tests.

Performance Analysis of Novel Randomly Shifted Certification Authority Authentication Protocol for MANETs

The provision of security in mobile ad hoc networks is of paramount importance due to their wireless nature. However, when conducting research into security protocols for ad hoc networks it is necessary to consider these in the context of the overall system. For example, communicational delay associated with the underlying MAC layer needs to be taken into account. Nodes in mobile ad hoc networks must strictly obey the rules of the underlying MAC when transmitting security-related messages while still maintaining a certain quality of service. In this paper a novel authentication protocol, RASCAAL, is described and its performance is analysed by investigating both the communicational-related effects of the underlying IEEE 802.11 MAC and the computational-related effects of the cryptographic algorithms employed. To the best of the authors' knowledge, RASCAAL is the first authentication protocol which proposes the concept of dynamically formed short-lived random clusters with no prior knowledge of the cluster head. The performance analysis demonstrates that the communication losses outweigh the computation losses with respect to energy and delay. MAC-related communicational effects account for 99% of the total delay and total energy consumption incurred by the RASCAAL protocol. The results also show that a saving in communicational energy of up to 12.5% can be achieved by changing the status of the wireless nodes during the course of operation. Copyright (C) 2009 G. A. Safdar and M. P. O'Neill (nee McLoone).

Group Design-Build-Test Projects as the Core of an Integrated Curriculum in Product Design and Development

The School of Mechanical and Aerospace Engineering at Queen’s University Belfast introduced a new degree programme in Product Design and Development (PDD) in 2004. As well as setting out to meet all UK-SPEC requirements, the entirely new curriculum was developed in line with the syllabus and standards defined by the CDIO Initiative, an international collaboration of universities aiming to improve the education of engineering students. The CDIO ethos is that students are taught in the context of conceiving, designing, implementing and operating a product or system. Fundamental to this is an integrated curriculum with multiple Design-Build-Test (DBT) experiences at the core. Unlike most traditional engineering courses the PDD degree features group DBT projects in all years of the programme. The projects increase in complexity and challenge in a staged manner, with learning outcomes guided by Bloom’s taxonomy of learning domains. The integrated course structure enables the immediate application of disciplinary knowledge, gained from other modules, as well as development of professional skills and attributes in the context of the DBT activity. This has a positive impact on student engagement and the embedding of these relevant skills, identified from a stakeholder survey, has also been shown to better prepare students for professional practice. This paper will detail the methodology used in the development of the curriculum, refinements that have been made during the first five years of operation and discuss the resource and staffing issues raised in facilitating such a learning environment.

The structural information content of chemical networks

We present an information-theoretic method to measure the structural information content of networks and apply it to chemical graphs. As a result, we find that our entropy measure is more general than classical information indices known in mathematical and computational chemistry. Further, we demonstrate that our measure reflects the essence of molecular branching meaningfully by determining the structural information content of some chemical graphs numerically.

A Human Rights Perspective on Citizen Participation in the EU's Governance of New Technologies

This article considers the EU’s approach to citizen participation in the governance of new technologies from a human rights perspective. Noting that there is a dearth of insight on the interplay between citizen participation and human rights, the article sketches the essence of its own human rights perspective as being about empowerment. This perspective is brought to bear on EU discourse on citizen participation in the governance of new technologies. Analysis of the discourse—comprising law, citizen participation in EU governance and citizen/science relations, the ‘public understanding of science and technology’, risk and bioethics—reveals a disempowering ‘deficit model’ of citizens in need of education through their participation in governance. The analysis thus suggests that citizen participation in EU governance of new technologies is not truly informed by human rights, but is instead used as a legitimating technique.