How to read a values from new section in web.config
<configuration>
      <configSections>
        <section name="secureAppSettings" type="System.Configuration.NameValueSectionHandler, System, Version=2.0.0.0, Culture=neutral, PublicKeyToken=b77a5c561934e089" />
      </configSections>
<secureAppSettings>
        <add key="userName" value="username"/>
        <add key="userPassword" value="password"/>
    </secureAppSettings>
    </configuration>

string userName = System.Configuration.ConfigurationManager.secureAppSettings["userName"];
string userPassword = System.Configuration.ConfigurationManager.secureAppSettings["userPassword"];

NameValueCollection section = (NameValueCollection)ConfigurationManager.GetSection("secureAppSettings");
string userName = section["userName"];
string userPassword = section["userPassword"];