One way of doing it
>>> df.query('TEMPPNUM != 100')
Another way would be with 'mask'
>>> df[df.TEMPPNUM!=100]
Both should produce this output
URN col1 col2 col3 TEMPPNUM
0 100279 24.0 75.8 0.1 99.9
EDIT:
If your TEMPPNUM is NOT float/int, then you'd can either convert it to such or simply do that
>>> df.query('TEMPPNUM != 100')
URN col1 col2 col3 TEMPPNUM
0 100279 24.0 75.8 0.1 99.9
5 123321 91.0 99.0 0.5 100
>>> mask=df['TEMPPNUM'].astype(int) == 100
>>> df[~mask]
URN col1 col2 col3 TEMPPNUM
0 100279 24.0 75.8 0.1 99.9
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