selectedRowInComponent:
returns the index of the selection made by the user. You can use that value to check which e-mail address you need to use.
NSInteger selectedRow = [self.pickerView selectedRowInComponent:0];
if (selectedRow == 0)
{
// E-mail person 1
}
else if (selectedRow == 1)
{
// E-mail person 2
}
// etc.