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After gaining a degree in politics from the University of Sussex, she trained as an actress at the Drama Studio in Ealing and was in the musical Evita for a year. She was a magistrate for ten years from the age of thirty in Tottenham.
Arnold joined the BBC Radio Drama Company in 1988. After meeting Peter Donaldson at a party in 1994, she joined Radio 4's presentation team in that year. In 2004 she became a newsreader, and regularly read the afternoon and evening news on Radio 4. In 2005, she featured as a news presenter in BBC Two comedy Broken News. In June 2006, she was promoted to read the news on Radio 4's Today programme. From 2007 to 2011 she co-presented comedian Jon Holmes's show Listen Against, a parody of various programmes on Radio 4.
Arnold gained media attention in May 2012. While returning home, stuck in traffic, she observed an empty plastic bottle being thrown from the car ahead of her and threw it back into the vehicle through an open window. On Twitter, colleague and friend Corrie Corfield said Arnold deserved a damehood for her action.
Towards the end of October 2012, the ending of Arnold's role on Radio 4 emerged. Her final shift ended early on 29 December 2012. During 2013 she worked for the BBC in a training capacity and was involved in the Expert Women's Days where she coached potential female interviewees for Today. Arnold has suggested adopting a smile or frown while talking as appropriate to the context.
Arnold was previously in a relationship with the comedienne, writer, and presenter Sandi Toksvig. She entered into a civil partnership in 2006 with the BBC presenter Clare Balding. They live in Chiswick, London.