Development of an Integrated Raman and Turbidity Fiber Optic Sensor for the In-Situ Analysis of High Level Nuclear Waste -13532

ABSTRACT Stored nuclear waste must be retrieved from storage, treated, separated into low-and high-level waste streams, and finally put into a disposal form that effectively encapsulates the waste and isolates it from the environment for a long period of time. Before waste retrieval can be done, waste composition needs to be characterized so that proper safety precautions can be implemented during the retrieval process. In addition, there is a need for active monitoring of the dynamic chemistry of the waste during storage since the waste composition can become highly corrosive. This work describes the development of a novel, integrated fiber optic Raman and light scattering probe for in situ use in nuclear waste solutions. The dual Raman and turbidity sensor provides simultaneous chemical identification of nuclear waste as well as information concerning the suspended particles in the waste using a common laser excitation source

Adding 6 months of androgen deprivation therapy to postoperative radiotherapy for prostate cancer: a comparison of short-course versus no androgen deprivation therapy in the RADICALS-HD randomised controlled trial

Background Previous evidence indicates that adjuvant, short-course androgen deprivation therapy (ADT) improves metastasis-free survival when given with primary radiotherapy for intermediate-risk and high-risk localised prostate cancer. However, the value of ADT with postoperative radiotherapy after radical prostatectomy is unclear. Methods RADICALS-HD was an international randomised controlled trial to test the efficacy of ADT used in combination with postoperative radiotherapy for prostate cancer. Key eligibility criteria were indication for radiotherapy after radical prostatectomy for prostate cancer, prostate-specific antigen less than 5 ng/mL, absence of metastatic disease, and written consent. Participants were randomly assigned (1:1) to radiotherapy alone (no ADT) or radiotherapy with 6 months of ADT (short-course ADT), using monthly subcutaneous gonadotropin-releasing hormone analogue injections, daily oral bicalutamide monotherapy 150 mg, or monthly subcutaneous degarelix. Randomisation was done centrally through minimisation with a random element, stratified by Gleason score, positive margins, radiotherapy timing, planned radiotherapy schedule, and planned type of ADT, in a computerised system. The allocated treatment was not masked. The primary outcome measure was metastasis-free survival, defined as distant metastasis arising from prostate cancer or death from any cause. Standard survival analysis methods were used, accounting for randomisation stratification factors. The trial had 80% power with two-sided α of 5% to detect an absolute increase in 10-year metastasis-free survival from 80% to 86% (hazard ratio [HR] 0·67). Analyses followed the intention-to-treat principle. The trial is registered with the ISRCTN registry, ISRCTN40814031, and ClinicalTrials.gov, NCT00541047. Findings Between Nov 22, 2007, and June 29, 2015, 1480 patients (median age 66 years [IQR 61–69]) were randomly assigned to receive no ADT (n=737) or short-course ADT (n=743) in addition to postoperative radiotherapy at 121 centres in Canada, Denmark, Ireland, and the UK. With a median follow-up of 9·0 years (IQR 7·1–10·1), metastasis-free survival events were reported for 268 participants (142 in the no ADT group and 126 in the short-course ADT group; HR 0·886 [95% CI 0·688–1·140], p=0·35). 10-year metastasis-free survival was 79·2% (95% CI 75·4–82·5) in the no ADT group and 80·4% (76·6–83·6) in the short-course ADT group. Toxicity of grade 3 or higher was reported for 121 (17%) of 737 participants in the no ADT group and 100 (14%) of 743 in the short-course ADT group (p=0·15), with no treatment-related deaths. Interpretation Metastatic disease is uncommon following postoperative bed radiotherapy after radical prostatectomy. Adding 6 months of ADT to this radiotherapy did not improve metastasis-free survival compared with no ADT. These findings do not support the use of short-course ADT with postoperative radiotherapy in this patient population

Duration of androgen deprivation therapy with postoperative radiotherapy for prostate cancer: a comparison of long-course versus short-course androgen deprivation therapy in the RADICALS-HD randomised trial

Background Previous evidence supports androgen deprivation therapy (ADT) with primary radiotherapy as initial treatment for intermediate-risk and high-risk localised prostate cancer. However, the use and optimal duration of ADT with postoperative radiotherapy after radical prostatectomy remains uncertain. Methods RADICALS-HD was a randomised controlled trial of ADT duration within the RADICALS protocol. Here, we report on the comparison of short-course versus long-course ADT. Key eligibility criteria were indication for radiotherapy after previous radical prostatectomy for prostate cancer, prostate-specific antigen less than 5 ng/mL, absence of metastatic disease, and written consent. Participants were randomly assigned (1:1) to add 6 months of ADT (short-course ADT) or 24 months of ADT (long-course ADT) to radiotherapy, using subcutaneous gonadotrophin-releasing hormone analogue (monthly in the short-course ADT group and 3-monthly in the long-course ADT group), daily oral bicalutamide monotherapy 150 mg, or monthly subcutaneous degarelix. Randomisation was done centrally through minimisation with a random element, stratified by Gleason score, positive margins, radiotherapy timing, planned radiotherapy schedule, and planned type of ADT, in a computerised system. The allocated treatment was not masked. The primary outcome measure was metastasis-free survival, defined as metastasis arising from prostate cancer or death from any cause. The comparison had more than 80% power with two-sided α of 5% to detect an absolute increase in 10-year metastasis-free survival from 75% to 81% (hazard ratio [HR] 0·72). Standard time-to-event analyses were used. Analyses followed intention-to-treat principle. The trial is registered with the ISRCTN registry, ISRCTN40814031, and ClinicalTrials.gov , NCT00541047 . Findings Between Jan 30, 2008, and July 7, 2015, 1523 patients (median age 65 years, IQR 60–69) were randomly assigned to receive short-course ADT (n=761) or long-course ADT (n=762) in addition to postoperative radiotherapy at 138 centres in Canada, Denmark, Ireland, and the UK. With a median follow-up of 8·9 years (7·0–10·0), 313 metastasis-free survival events were reported overall (174 in the short-course ADT group and 139 in the long-course ADT group; HR 0·773 [95% CI 0·612–0·975]; p=0·029). 10-year metastasis-free survival was 71·9% (95% CI 67·6–75·7) in the short-course ADT group and 78·1% (74·2–81·5) in the long-course ADT group. Toxicity of grade 3 or higher was reported for 105 (14%) of 753 participants in the short-course ADT group and 142 (19%) of 757 participants in the long-course ADT group (p=0·025), with no treatment-related deaths. Interpretation Compared with adding 6 months of ADT, adding 24 months of ADT improved metastasis-free survival in people receiving postoperative radiotherapy. For individuals who can accept the additional duration of adverse effects, long-course ADT should be offered with postoperative radiotherapy. Funding Cancer Research UK, UK Research and Innovation (formerly Medical Research Council), and Canadian Cancer Society

Sensor development for the nuclear fuel cycle Electrochemistry, spectroelectrochemistry, spectroscopy, and chemometric analysis

Fast, robust, and cost-effective means of detecting various species in complex solution environments are needed throughout the nuclear fuel cycle. Several techniques have the potential to meet this need and this manuscript will cover two spectroscopic based methods for accomplishing this.Spectroelectrochemistry will be the first method discussed, and is a technique that can specifically quantify lanthanides and transition metals by simultaneously monitoring at least two physio-chemical properties. Application of this technique can be limited by both redox chemistry and spectral characteristics of analytes of interest; which is particularly apparent in species like the lanthanides and some free transition metals which have very weak spectral signatures. It is possible to circumvent these limitations and successfully apply spectroelectrochemistry to the analysis of these hard-to-detect species by capturing them in complexes with improved spectral characteristics. This is demonstrated with europium and ruthenium; these elements were chosen due to their spectroscopic and electrochemical characteristics as well as their relevance within the fuel cycle and industrial fields. The electrochemical and the spectroelectrochemical characteristics of Eu(bpy)2 type complexes will be discussed. As will the in situ electrochemical generation of Ru(bpy)3 complexes and their subsequent spectroelectrochemical sensing within a singular spectroelectrochemical sensor device.The second method discussed will be Raman spectroscopy utilized in tandem with chemometric analysis. A novel micro-Raman probe was developed and tested to monitor streams within microfluidic cells, allowing for characterization of small sample sizes either in-line or through grab samples. This system was tested on simple and complex systems containing HNO3, NaNO3, and/or UO2(NO3)2. Chemometric modeling has been paired with this to build predictive models capable of identifying and quantifying these species based on Raman signatures. Initial testing on larger cell path lengths was successful and translates well to preliminary studies with a 250 µm path length microfluidic device.Overall, these two methods have been used to successfully characterize and quantify examples of transition metals (Ru), lanthanides (Eu), and actinides (U) and have significant potential to be applied to other species of interest

Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States

International audienceThe study and development of present and future processes for the treatment/recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. In all of these steps, analysis and instrumentation are key points. For scientific reasons (small-scale studies, control of phenomena, etc.) but also with regard to minimizing costs, risks, and waste, such developments are increasingly carried out on milli- or microfluidic devices. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto–microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid–liquid extraction, precipitation, etc.) have been increasingly designed and developed. In this work, we prove that photonic lab-on-a-chip (PhLoC) technology is fully suitable for all actinides concentration monitoring along the plutonium uranium refining extraction (plutonium, uranium, reduction, extraction, or Purex) process. Several PhLoC microfluidic platforms were specifically designed and used in different nuclear research and development (R&D) laboratories, to tackle actinides analysis in multiple oxidation states even in mixtures. The detection limits reached (tens of µmol·L −1 ) are fully compliant with on-line process monitoring, whereas a range of analyzable concentrations of three orders of magnitude can be covered with less than 150 µL of analyte. Finally, this work confirms the possibility and the potential of coupling Raman and ultraviolet–visible (UV–Vis) spectroscopies at the microfluidic scale, opening the perspective of measuring very complex mixtures

Photonic lab-on-a-chip, a versatile and powerful tool for R&D studies on spent fuel reprocessing

International audienceThe study and development of present and future processes for the recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. Analysis and instrumentation are crucial in all of these steps. These developments are increasingly carried out on milli/microfluidic devices for scientific reasons (small-scale studies, control of phenomena, etc.) and to minimize costs, risks, and waste. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto/microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid/liquid extraction, precipitation, etc.) have been increasingly designed anddeveloped. This communication will review 5 years of photonic lab-on-a-chip (PhLoC) development and show how this technology (cf. Figure 1) can be a suitable and powerful tool to monitor several steps along the PUREX process (Plutonium Uranium Reduction Extraction)

Photonic lab-on-a-chip, a versatile and powerful tool for R&D studies on spent fuel reprocessing

International audienceThe study and development of present and future processes for the recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. Analysis and instrumentation are crucial in all of these steps. These developments are increasingly carried out on milli/microfluidic devices for scientific reasons (small-scale studies, control of phenomena, etc.) and to minimize costs, risks, and waste. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto/microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid/liquid extraction, precipitation, etc.) have been increasingly designed anddeveloped. This communication will review 5 years of photonic lab-on-a-chip (PhLoC) development and show how this technology (cf. Figure 1) can be a suitable and powerful tool to monitor several steps along the PUREX process (Plutonium Uranium Reduction Extraction)

<i>In Situ</i> Quantification of [Re(CO)₃]⁺ by Fluorescence Spectroscopy in Simulated Hanford Tank Waste

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent <i>in situ</i> spectroscopic analysis of [Re­(CO)₃]⁺ species in simulated Hanford tank waste. In this test case, the nonradioactive metal rhenium is substituted for technetium (Tc-99), a weak beta emitter, to demonstrate proof of concept for a method to measure a nonpertechnetate form of technetium in Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the nonemissive [Re­(CO)₃]⁺ species to a developer solution that enables the rapid, quantitative conversion of the nonemissive species to a luminescent species which can then be detected spectroscopically. The [Re­(CO)₃]⁺ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re­(CO)₃]⁺ species was measured to be at a concentration of 38.9 μM, which was a difference of 2.01% from the actual concentration of 39.7 μM

Multivariate Analysis To Quantify Species in the Presence of Direct Interferents: Micro-Raman Analysis of HNO₃ in Microfluidic Devices

Microfluidic devices are a growing field with significant potential for applications to small scale processing of solutions. Much like large scale processing, fast, reliable, and cost-effective means of monitoring streams during processing are needed. Here we apply a novel micro-Raman probe to the online monitoring of streams within a microfluidic device. For either macro- or microscale process monitoring via spectroscopic response, interfering or confounded bands can obfuscate results. By utilizing chemometric analysis, a form of multivariate analysis, species can be accurately quantified in solution despite the presence of overlapping or confounding spectroscopic bands. This is demonstrated on solutions of HNO₃ and NaNO₃ within microflow and microfluidic devices