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Abstract Details

(2020) Pu(IV) Interaction with iron(III) (Oxyhydr)oxide Minerals

Smith K, Balboni E, Moreau L, Zavarin M & Booth C

https://doi.org/10.46427/gold2020.2414

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08b: Room 3, Monday 22nd June 22:15 - 22:18

Listed below are questions that have been submitted by the community that the author will try and cover in their presentation. To submit a question, ensure you are signed in to the website. Authors or session conveners approve questions before they are displayed here.

Submitted by Ruth Tinnacher on Saturday 20th June 21:13
How did you control or monitor Pu oxidation states over the course of your experiments? Thank you.
Hi Ruth. The initial Pu stock solution was manipulated into the +IV state and characterised using UV-VIS before being introduced into the experiments. After this point no further control on oxidation state was attempted. Our XANES data suggest all our samples remained in the +IV state throughout the experiment. We are sure we didn’t oxidise to +V, however, telling +III and +IV apart using Pu L-III XANES is difficult so I wouldn’t want to rule the possibility of reduction out entirely.

Submitted by Xiaofeng Guo on Monday 22nd June 19:26
A very beautiful exafs work! I have two questions: i) do you expect to have charge transfer between Pu and Fe? ii) is the large Debye-Waller factor attributing to spatial or temporal disorder?
It seems I posted my answer to your question in the wrong place...! Hi Xiaofeng. Thankyou, I glad you like it! I would not be surprised if there was charge transfer occurring but really, we have no evidence for or against. Regarding the Debye Waller factors, due to the Pu low concentrations in our samples (and therefore long data collection times) we didn’t collect any temperature dependent EXAFS so it’s impossible for us to split out the spatial and temporal components. However, these systems, especially those involving ferrihydrite, tend to be very messy from a structural perspective. Given that, my money would be on that our high Debye Waller factors being caused by structural disorder around Pu – especially in our experiments where there is evidence for multiple coordination environments.

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