You must cast the ConfigrationItem to "System.Configuration.IgnoreSectionHandler" or set the type Attribute in web.conf to an existing Type in your assembly.
<section name="<SectionName>" type="<your type (FQN)>, <Assembly>" />
After that you can access it
YourType o = ((YourType)ConfigurationManager.GetSection("sectionName"));
EDIT:
The Type must derive from ConfigurationSection.