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The documentation of geometry_msgs/PoseWithCovariance gives some explanation :
# Row-major representation of the 6x6 covariance matrix
# The orientation parameters use a fixed-axis representation.
# In order, the parameters are:
# (x, y, z, rotation about X axis, rotation about Y axis, rotation about Z axis)
float64[36] covariance
For the conversion from quaternions to fixed-axes, see this question and the links therein.