Wikipedia cites a range of 2,000 -- 13,000 km^3.
<https://en.wikipedia.org/wiki/List_of_largest_volcanic_erupt...>
As for the gaseous component of ejecta:
Water vapour is consistently the most abundant volcanic gas, normally comprising more than 60% of total emissions. Carbon dioxide typically accounts for 10 to 40% of emissions.
<https://en.wikipedia.org/wiki/Volcanic_gas>
Citing: H. Sigurdsson et al. (2000) Encyclopedia of Volcanoes, San Diego, Academic Press.
(Late edit: though I note that this seems to discuss percentages of gaseous emissions, not total ejecta. Anyone have a better source here?)
One of the largest volcanic events I'm aware of is the Siberian Traps eruption, about 250 mya, with a volume of about 4 million km^3, another three orders of magnitude greater than Tomba.
This has been linked to the Permian–Triassic mass extinction event, with the mechanism being release of methane clathrates and/or stimulating growth of a microbe which released vast quantities of methane into the atmosphere, killing ~81% of all extant marine species and 70% of terrestrial vertebrate species.
<https://en.wikipedia.org/wiki/Siberian_Traps>
"The level of atmospheric carbon dioxide rose from around 400 ppm to 2,500 ppm with approximately 3,900 to 12,000 gigatonnes of carbon being added to the ocean-atmosphere system during this period."
-- Wikipedia, citing Wu, Yuyang; Chu, Daoliang; Tong, Jinnan; Song, Haijun; Dal Corso, Jacopo; Wignall, Paul B.; Song, Huyue; Du, Yong; Cui, Ying (9 April 2021). "Six-fold increase of atmospheric pCO2 during the Permian–Triassic mass extinction". Nature Communications. 12 (1): 2137. Bibcode:2021NatCo..12.2137W. doi:10.1038/s41467-021-22298-7.
<https://en.wikipedia.org/wiki/Permian%E2%80%93Triassic_extin...>