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To prepare the peaches, put the white wine, moscatel vinegar and caster sugar into a small pan and gently heat until the sugar has dissolved. Put the peach quarters into a bowl and pour over the hot liquid. Cover to steep for 4 hours while you make the pavlova.
Heat the oven to 150C/fan 130C/gas 2. Put the egg whites into a large, clean bowl and use electric beaters to whisk until light and fluffy. Gradually add the sugar, while whisking, 1 tbsp at a time, until the mixture holds stiff peaks and is shiny and glossy. Carefully whisk in the cornflour and white wine vinegar. Spoon the mixture in a large circle (approximately 28cm in diameter) on a baking sheet lined with baking paper and make a large dip in the middle. Put in the oven and turn the heat down to 140C/fan 120C/gas 1. Bake for 1 hour 50 minutes and then turn off the heat and let the pavlova cool in the oven with the door ajar, for 1 hour. Remove from the oven and cool completely.
Pour the peach juice through a fine sieve into a wide pan with the rum and 100ml of the peach pickling liquid, and reduce over a medium heat until syrupy.
Put the cool pavlova base onto a serving plate and whisk the mascarpone, sugar and double cream together using electric beaters until the mixture holds soft peaks.
Heat a griddle pan to high and drain the peaches. Griddle for 1-2 minutes, cut-sides down, or until they have deep charred marks on them.
Spoon the mascarpone cream onto the base of the pavlova, pile on the charred peaches, drizzle with the peach syrup and scatter with mint and basil. Serve immediately.
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