Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

The effect of aqueous diffusion on the fractionation of chlorine and bromine stable isotopes

Diffusive isotopic fractionation factors are important in order to understand natural processes and have practical application in radioactive waste storage and carbon dioxide sequestration. We determined the isotope fractionation factors and the effective diffusion coefficients of chloride and bromide ions during aqueous diffusion in polyacrylamide gel. Diffusion was determined as functions of temperature, time and concentration. The effect of temperature is relatively large on the diffusion coefficient (D) but only small on isotope fractionation. For chlorine, the ratio, D-35cl/D-37cl varied from 1.00128 +/- 0.00017 (1 sigma) at 2 degrees C to 1.00192 +/- 0.00015 at 80 degrees C. For bromine, D-79Br/D-81Br varied from 1.00098 +/- 0.00009 at 2 degrees C to 1.0064 +/- 0.00013 at 21 degrees C and 1.00078 +/- 0.00018 (1 sigma) at 80 degrees C. There were no significant effects on the isotope fractionation due to concentration. The lack of sensitivity of the diffusive isotope fractionation to anything at the most common temperatures (0 to 30 C) makes it particularly valuable for application to understanding processes in geological environments and an important natural tracer in order to understand fluid transport processes. (C) 2009 Elsevier Ltd. All rights reserved.

Naturally occurring radioactive material (NORM) from a former phosphoric acid processing plant

In recent years there has been an increasing awareness of the radiological impact of non-nuclear industries that extract and/or process ores and minerals containing naturally occurring radioactive material (NORM). These industrial activities may result in significant radioactive contamination of (by-) products, wastes and plant installations. In this study, scale samples were collected from a decommissioned phosphoric acid processing plant. To determine the nature and concentration of NORM retained in pipe-work and associated process plant, four main areas of the site were investigated: (1) the 'Green Acid Plant', where crude acid was concentrated; (2) the green acid storage tanks; (3) the Purified White Acid (PWA) plant, where inorganic impurities were removed; and (4) the solid waste, disposed of on-site as landfill. The scale samples predominantly comprise the following: fluorides (e.g. ralstonite); calcium sulphate (e.g. gypsum); and an assemblage of mixed fluorides and phosphates (e.g. iron fluoride hydrate, calcium phosphate), respectively. The radioactive inventory is dominated by U-238 and its decay chain products, and significant fractionation along the series occurs. Compared to the feedstock ore, elevated concentrations (<= 8.8 Bq/g) of U-238 Were found to be retained in installations where the process stream was rich in fluorides and phosphates. In addition, enriched levels (<= 11 Bq/g) of Ra-226 were found in association with precipitates of calcium sulphate. Water extraction tests indicate that many of the scales and waste contain significantly soluble materials and readily release radioactivity into solution. (c) 2005 Elsevier Ltd. All rights reserved.

The practice of sustainable facilities management: Design sentiments and the knowledge chasm

The construction industry with its nature of project delivery is very fragmented in terms of the various processes that encompass design, construction, facilities and assets management. Facilities managers are in the forefront of delivering sustainable assets management and hence further the venture for mitigation and adaptation to climate change. A questionnaire survey was conducted to establish perceptions, level of commitment and knowledge chasm in practising sustainable facilities management (FM). This has significant implications for sustainable design management, especially in a fragmented industry. The majority of questionnaire respondents indicated the importance of sustainability for their organization. Many of them stated that they reported on sustainability as part of their organization annual reporting with energy efficiency, recycling and waste reduction as the main concern for them. The overwhelming barrier for implementing sound, sustainable FM is the lack of consensual understanding and focus of individuals and organizations about sustainability. There is a knowledge chasm regarding practical information on delivering sustainable FM. Sustainability information asymmetry in design, construction and FM processes render any sustainable design as a sentiment and mere design aspiration. Skills and training provision, traditionally offered separately to designers and facilities managers, needs to be re-evaluated. Sustainability education and training should be developed to provide effective structures and processes to apply sustainability throughout the construction and FM industries coherently and as common practice.

Discerning policy and drivers for sustainable facilities management practice

Due to the changing nature of the facilities management (FM) profession, facilities managers are increasingly engaged with the evolving sustainability agenda in the UK and the development or uptake of sustainability policies within their organisations. This study investigates how facilities managers are engaging with the sustainability agenda and the drivers, policy issues and information they use to improve their sustainability performance management. A web based self-administered questionnaire survey of facilities managers in the UK was conducted to identify drivers and issues that influence and support good sustainable practices. A total of 268 facilities managers responded. The results indicate that legislation is the most important driver for the implementation of sustainable practices. Corporate image and Organisational ethos are also recognised. However demand for efficient monitoring, management and reporting on environmental impact is not highly rated even though the top three issues of sustainability managed by facilities managers are energy management, waste and recycling management and carbon footprint. In addition, facilities managers are expected to take ownership of activities assigned to the reduction of carbon emission. Government industries and organisation with high turnover are more likely to have a sustainability policy. Financial constraints are the main barriers while legislations are the main driver for implementing sustainability. For non-profit organisations and the charitable sector, financial constraints are no hindrance to implementing a sustainability policy. The conclusion drawn is that sustainability agendas continue to be influenced by regulated environmental issues rather than a balanced approach which takes into consideration the wider social and economic aspects of sustainability. While this scenario is far from ideal, the expectation is that the organisation will trust FM to take a vital role in delivering a comprehensive sustainability policy due to the rising tide of legislation, public scrutiny, as well as the needed business case for genuinely embracing sustainability. However, as the integration of sustainability with core business strategies is continuously evolving the emphasis on different drivers will vary from organisation to organisation as well as the responsibilities of facilities managers.

Facilities management carbon footprints: an audit of critical elements of management and reporting

Concern for the environmental impact of organizations’ activities has led to the recognition and demand for organizations to manage and report on their carbon footprint. However, there is no limit as to the areas of carbon footprints required in such annual environmental reports. To deliver improvements in the quality of carbon footprint management and reporting, there is a need to identify the main elements of carbon footprint strategy that can be endorsed, supported and encouraged by facility managers. The study investigates carbon footprint elements managed and reported upon by facility manager in the UK. Drawing on a questionnaire survey of 256 facility managers in the UK, the key elements of carbon footprints identified in carbon footprint reports are examined. The findings indicate that the main elements are building energy consumption, waste disposal and water consumption. Business travel in terms of using public transport, air travel and company cars are also recognized as important targets and objectives for the carbon footprint strategy of several FM (facilities management) organizations.

Industrial radioactive barite scale: suppression of radium uptake by introduction of competing ions

Incorporation of radioactive isotopes during the formation of barite mineral scale is a widespread phenomenon occurring within the oil, mining and process industries. In a series of experiments radioactive barite/celestite solid solutions (SSBarite-Celcstite) have been synthesized under controlled conditions by the counter diffusion of Ra-226, Ba2+, Sr24+ and SO42- ions through a porous medium (silica gel), to investigate inhibiting effects in Ra uptake associated with the introduction of a competing ion (Sr2+). From characterization studies, the particle size and the morphology of the crystals appear to be related to the initial [Sr]/[Ba] molar ratio of the starting solution. Typically, systems richer in Sr produce smaller sized crystals and clusters characterized by a lower degree of order. The activity introduced to the system is mainly incorporated in the crystals generated from the barite/celestite solid solution as suggested by the activity profiles of the hydrogel columns analysed by gamma-spectrometry. There is a relationship between the initial [Sr]/[Ba] molar ratio of the starting solution and the activity exhibited by the synthesized crystals. An effective inhibition of the Ra-226 uptake during formation of the crystals (SSBarite-Celestite) was obtained through the introduction of a competing ion (Sr2+): the higher the initial [Sr]/[Ba] molar ratio of the starting solution, the lower the intensity of the activity peak in the crystals. (C) 2003 Published by Elsevier Ltd.

Field trial using bone meal amendments to remediate mine waste derived soil contaminated with zinc, lead and cadmium

Bone meal amendments are being considered as a remediation method for metal-contaminated wastes. In various forms (biogenic, geogenic or synthetic), apatite, the principal mineral constituent of bone, has shown promise as an amendment to remediate metal-contaminated soils via the formation of insoluble phosphates of Pb and possibly other metals. The efficacy of commercially available bovine bone meal in this role was investigated in a field trial at Nenthead, Cumbria with a mine waste derived soil contaminated with Zn, Pb and Cd. Two 5 m(2) plots were set up: the first as a control and the second, a treatment plot where the soil was thoroughly mixed with bone meal to a depth of 50 cm at a soil to amendment ratio of 25:1 by weight. An array of soil solution samplers (Rhizon SMS (TM)) were installed in both plots and the soil pore water was collected and analysed for Ca, Cd, Zn and Pb regularly over a period of 2 a. Concurrently with the field trial, a laboratory trial with 800 mm high and 100 mm wide leaching Columns Was conducted using identical samplers and with soil from the held site. A substantial release of Zn, Pb, Cd and Ca was observed associated with the bone meal treatment. This release was transient in the case of the leaching columns, and showed seasonal variation in the case of the field trial. It is proposed that this effect resulted from metal complexation with organic acids released during breakdown of the bone meal organic fraction and was facilitated by the relatively high soil pH of 7.6-8.0. Even after this transient release effect had subsided or when incinerated bone meal was substituted in order to eliminate the organic fraction, no detectable decrease in dissolved metals was observed and no P was detected in solution, in contrast with an earlier small column laboratory study. It is concluded that due to the relative insolubility of apatite at above-neutral pH, the rate of supply of phosphate to soil solution was insufficient to result in significant precipitation of metal phosphates and that this may limit the effectiveness of the method to more acidic soils. (c) 2008 Elsevier Ltd. All rights reserved.

WREN: electronic management system for facilities management

This paper describes a case study of an electronic data management system developed in-house by the Facilities Management Directorate (FMD) of an educational institution in the UK. The FMD Maintenance and Business Services department is responsible for the maintenance of the built-estate owned by the university. The department needs to have a clear definition of the type of work undertaken and the administration that enables any maintenance work to be carried out. These include the management of resources, budget, cash flow and workflow of reactive, preventative and planned maintenance of the campus. In order to be more efficient in supporting the business process, the FMD had decided to move from a paper-based information system to an electronic system, WREN, to support the business process of the FMD. Some of the main advantages of WREN are that it is tailor-made to fit the purpose of the users; it is cost effective when it comes to modifications on the system; and the database can also be used as a knowledge management tool. There is a trade-off; as WREN is tailored to the specific requirements of the FMD, it may not be easy to implement within a different institution without extensive modifications. However, WREN is successful in not only allowing the FMD to carry out the tasks of maintaining and looking after the built-estate of the university, but also has achieved its aim to minimise costs and maximise efficiency.

Extraction behavior of the synergistic system 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine and 2-bromodecanoic acid using Am and Eu as radioactive tracers

In this study, the extraction properties of a synergistic system consisting of 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine (BODO) and 2-bromodecanoic acid (HA) in tert-butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03-12 and 0.003-0.8 have been found for Am(III) and Eu(HI), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO4-, NO3-, and H+. The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log-log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non-linearway. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at similar to1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.

Carbon-encapsulated radioactive Tc-99m nanoparticles

A macroscopic quantity of quasi-spherical fullerene-like shells (see Figure) that encapsulate iron nanoparticles containing radioisotope Tc-99m are prepared for the first time. The nanocomposite is acid-non-leachable, retaining radioactivity at an extremely high level. This method will enable rigorous studies of what are currently theoretical descriptions of nanometer-scale medicinal delivery vehicles for diagnostic and therapeutic purposes.