A custom attribute to identify netCDF4 files sounds perfectly reasonable as an iteration on the netCDF4 spec.
But I'd like emphasize that it's important to continue to treat netCDF4 as a specification rather than merely whatever libnetcdf knows how to read and write. Doing so keeps you honest and forces more careful design. My project h5netcdf (https://github.com/shoyer/h5netcdf) is one such reimplementation of netCDF4 on top of an HDF5 API, which has exposed a number of bugs and edge cases in the netCDF-C and Python netCDF4 libraries. Cheers, Stephan
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