We present ALMA 870-um (345GHz) observations of two sub-millimetre galaxies (SMGs) drawn from an ALMA study of the 126 sub-millimeter sources from the LABOCA Extended Chandra Deep Field South Survey (LESS). The ALMA data identify the counterparts to these previously unidentified sub-millimeter sources and serendipitously detect bright emission lines in their spectra which we show are most likely to be [C II]157.74um emission yielding redshifts of z=4.42 and z=4.44. This blind detection rate within the 7.5-GHz bandpass of ALMA is consistent with the previously derived photometric redshift distribution of SMGs and suggests a modest, but not dominant (<25%), tail of 870-um selected SMGs at z>4. We find that the ratio of L_CII/L_FIR in these SMGs is much higher than seen for similarly far-infrared-luminous galaxies at z~0, which is attributed to the more extended gas reservoirs in these high-redshift ULIRGs. Indeed, in one system we show that the [C II] emission shows hints of extended emission on >3kpc scales. Finally, we use the volume probed by our ALMA survey to show that the bright end of the [C II] luminosity function evolves strongly between z=0 and z~4.4, reflecting the increased ISM cooling in galaxies as a result of their higher star-formation rates. These observations demonstrate that even with short integrations, ALMA is able to detect the dominant fine structure cooling lines from high-redshift ULIRGs, measure their energetics and trace their evolution with redshift.
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