I think the answer to this question will do what you want:
how to identify the extension/type of the file using C#?
This will allow you to detect the following mime types:
http://msdn.microsoft.com/en-us/library/ms775147%28VS.85%29.aspx#Known_MimeTypes
Copy/paste from it:
  [DllImport("urlmon.dll", CharSet = CharSet.Unicode, ExactSpelling = true, SetLastError = false)]
    static extern int FindMimeFromData(IntPtr pBC,
          [MarshalAs(UnmanagedType.LPWStr)] string pwzUrl,
         [MarshalAs(UnmanagedType.LPArray, ArraySubType=UnmanagedType.I1, SizeParamIndex=3)] 
        byte[] pBuffer,
          int cbSize,
             [MarshalAs(UnmanagedType.LPWStr)]  string pwzMimeProposed,
          int dwMimeFlags,
          out IntPtr ppwzMimeOut,
          int dwReserved);
Sample usage:
/// <summary>
/// Ensures that file exists and retrieves the content type 
/// </summary>
/// <param name="file"></param>
/// <returns>Returns for instance "images/jpeg" </returns>
public static string getMimeFromFile(string file)
{
    IntPtr mimeout;
    if (!System.IO.File.Exists(file))
    throw new FileNotFoundException(file + " not found");
    int MaxContent = (int)new FileInfo(file).Length;
    if (MaxContent > 4096) MaxContent = 4096;
    FileStream fs = File.OpenRead(file);
    byte[] buf = new byte[MaxContent];        
    fs.Read(buf, 0, MaxContent);
    fs.Close();
    int result = FindMimeFromData(IntPtr.Zero, file, buf, MaxContent, null, 0, out mimeout, 0);
    if (result != 0)
    throw Marshal.GetExceptionForHR(result);
    string mime = Marshal.PtrToStringUni(mimeout);
    Marshal.FreeCoTaskMem(mimeout);
    return mime;
}