Let's take a look at the first few....the villains called Vartox, Hellgrammite and Reactron!
Vartox
Vartox got his start in Superman #281 (November, 1974 by Cary Bates and Curt Swan, with a look based on Sean Connery's Zardoz character), as the hero of Valeron, which he protected with his hyper-powers (powers with a psychic base, that include flight, invulnerability, strength, speed, disguise, phasing, energy projection....just to name a few). Vartox lived in relative happiness protecting his home world until his wife, Elyra, mysteriously died. Vartox, using his hyper-senses, found out that she was a "bionic twin" with an Earth woman who was shot and killed in a robbery on Earth by Frank Sykes, and that killed Elyra as well. This led Vartox to come to Earth, where he had a confrontation with Superman (who wouldn't let Vartox just take Frank Sykes off Earth), yet eventually both heroes won, and Frank Sykes paid for his crime.Vartox returns to Earth to recharge his waning hyper-powers in Action Comics #475 and #476 (September and October, 1977, both by Cary Bates and Kurt Schaffenberger), where he uses the alien Karb-Brak to do so...
...along the way triggering Karb-Brak's allergy to super powers, and being turned evil and fighting Superman for a time....
Vartox returned again, in Action Comics #498 and #499 (August and September, 1979 by Cary Bates and Curt Swan), this time, as a refugee, as Valeron had exploded, and Vartox was looking for a new home, with Superman getting him a job as a security officer at Morgan Edge's WGBS as Vernon O'Valeron. But, tragedy seems to follow Vartox, as Earth then seemed set to explode until stopped by Superman and Vartox, with Superman's ex-girlfriend, Lana Lang, falling for the newly relocated hero (who leaves Earth).
Vartox returns again, in Superman #356 and #357 (February and March, 1981, by Cary Bates and Curt Swan), with Vartox relocated to a new planet, but the race on that world, the Tynolans, plan to sacrifice Vartox to their god, Moxumbra...
...with Vartox needing Superman's help to escape the plans and survive...
Vartox did survive and continue on, finding a way for his love, Lana Lang, to survive the poisonous atmosphere of his new homeworld, and join him there as his bride, in Superman #373 (July, 1982 by Cary Bates and Curt Swan), but there are also plans afoot by Syreena (an ex-lover and foe of Vartox's, who also survived the destruction of Valeron). While Vartox and Lana make wedding plans in Superman #374 (August, 1982 by Cary Bates and Curt Swan), Syreena tricks Vartox into thinking Superman wants Lana back, and a fight ensues between Superman and Vartox. The battle between Superman and Vartox continues in Superman #375 (September, 1982 by Cary Bates and Curt Swan), at least until Syreena turns Lana Lang into stone, but eventually the heroes prevail and save Lana, and Syreena meets her end with the petrification being transferred to her.
Vartox's tale gets more epic, starting in Superman #389 (November, 1983, by Cary Bates, Paul Kupperberg and Curt Swan), starting by returning to Earth while Clark Kent was undergoing some turmoil...but as Vartox arrives on Earth in Superman #390 (December, 1983 by Cary Bates, Eliot S! Maggin and Curt Swan), finds himself attacking Superman!
The battle between Superman continues into Superman #391 (January, 1984 by Cary Bates, Eliot S! Maggin and Curt Swan), with Vartox kidnapping Lana Lang, and then in Superman #392 (February, 1984 by Cary Bates), it is revealed that Vartox is being controlled by Srakka, an amoebic lifeform, and Superman throws down with it to save Lana Lang and Vartox!
Vartox briefly appeared in Action Comics #583 (September, 1986) with Alan Moore and Curt Swan's "Whatever Happened To the Man of Tomorrow?", a tale that might have been the end of the Silver Age Superman, and, like Superman, Vartox was revived with a new history (that tied to Brainiac) in Superman #148 (September, 1999 by Dan Jurgens and Steve Epting) and Superman #150 (November, 1999, by Dan Jurgens and Steve Epting), and returned looking a little more like his classic version, facing Power Girl in Power Girl #7 and #8 (February and March, 2010 by Justin Gray, Jimmy Palmiotti and Amanda Conner), and Vartox continues to vex Power Girl to this day.
Hellgrammite
Hellgrammite got his start in Brave and the Bold #80 (October-November, 1968) in the tale "And Hellgrammite Is His Name!" by Bob Haney and Neal Adams, with entomologist Roderick Rose trying to turn Gotham mob bosses into insects like himself, with only Batman and relatively new at the time hero, the Creeper, around to stop him.Hellgrammite then briefly fought Green Arrow and Black Canary in World's Finest Comics #248 and #249 (mostly 1978) in an odd pair of stories that will get coverage later (mostly because they also dealt with Green Arrow dressing as Batman....).
Hellgrammite didn't return again until Action Comics #673 (January, 1992) by Roger Stern and Bob McLeod, with "Friends In Need", and the Hellgrammite as a pawn of Lex Luthor, to clear the streets of Metropolis...
...which he continued to do in Action Comics #674 (February, 1992, by Roger Stern and Bob McLeod).
Hellgrammite then met the current Supergirl, as Luthor recruited her to be his bodyguard after Hellgrammite attempted to kill him in Action Comics #676 (April, 1992 by Roger Stern and Jackson Guice), and breaking into S.T.A.R. Labs in Action Comics #681 (September, 1992, by Roger Stern and Jackson Guice), taking a bit of a backseat to all the other Superman action going on....
Hellgrammite continued to bug Supergirl and Luthor in the Lex Luthor/Supergirl Special #1 of April 1993 by Roger Stern, June Brigman and Jackson Guice, with Luthor manipulating Supergirl to get the world to believe that George Markham was the man who hired Hellgrammite to kill him. Hellgrammite was one of many of Earth's super-villains to be recruited by the demon, Neron, in Underworld Unleashed #1 (November, 1995 by Mark Waid and Howard Porter), becoming more bug-like and the ability to make others into larvae, and attacking the Metropolis Special Crimes Unit (Metropolis S.C.U.) in Adventures of Superman #530 (December, 1995) while Superman and Supergirl were off-planet.
Hellgrammite returned with groups of villains in Green Lantern #79 (October, 1996) and JLA #18 (May, 1998), as well as being one of the villains affected by the morphing Joker gas in Joker's Last Laugh of 2001, spilling over into Birds of Prey #36 (December, 2001, battling Black Canary along with Copperhead) and Robin #95 (December, 2001, mostly featuring Killer Croc).
Hellgrammite was one of many foes in Adventures of Superman #608 (November, 2002), returned again with Superman #652 (July, 2006) and Action Comics #839 (July, 2006) with villains like the Puzzler, Live Wire and Silver Banshee, all as part of groups of attackers, and needing to be rounded up by Atom, Green Arrow, Green Lantern, Shazam! and Supergirl in Justice League: Cry For Justice #2 and #3 of October and November, 2009 as an ally of Prometheus and finally being caught by Donna Troy in Justice League of America #43 (May, 2010).
Reactron
In the next issue, it is revealed that Reactron was contemporary of Tempest's (and Krullen's attack on a Vietnamese village triggered the powers of Joshua Clay, resulting in him becoming Tempest). Supergirl defeated Reactron, but absorbed too much radiation, with the Doom Patrol taking her for help in the Daring New Adventures of Supergirl #10 (August, 1983, also by Kupperberg and Infantino).
When Reactron next returns, he is treated as a Power Girl foe (thanks to the Crisis On Infinite Earths wiping out Supergirl...
...explained a bit in Secret Origins Annual #1 of 1987), and fights the Doom Patrol in Doom Patrol #10 and #11 (July and August, 1988 by Paul Kupperberg and Erik Larsen; and oddly guesting Superman and the matrix Supergirl as Lana Lang in the first issue, with Superman and the Doom Patrol going to face Metallo in Superman #20 of August, 1988), with Larry Trainor trying to use Reactron to get the Negative Being back from Negative Woman (with Reactron being assumed to be dead again...and his history being slightly altered, with his name now being Benjamin Martin Krull).
Dying this many times made Reactron a great candidate for the villainous Suicide Squad, and he served during Suicide Squad #6 through #8 (April to June, 2002 by Keith Giffen and Medina) along with Major Disaster, Deadshot, the second Killer Frost and Blackstarr..
...with Reactron being shot to end his association with the Suicide Squad!
Reactron returned next in Crisis Aftermath: The Battle For Bludhaven #1 (Early June 2006) as a member of the Nuclear Legion (a group of radioactive villains like Neutron, Professor Radium, Geiger, Nuclear and Mister Nitro), but didn't stay long, going to fight Supergirl in Supergirl #25 and #26 (March and April, 2008 by Kelley Puckett and Drew Johnson).
Reactron returned again, popping up next to fight Supergirl in Supergirl #35 (January, 2009 by Sterling Gates and Jamal Igle) as part of a larger battle, with Kryptonians battling to take Earth, running as a part of Supergirl's title, as well as issues of Action Comics like Action Comics #872 and #880 in 2009, working with Metallo, and getting a new power source, that of a variation of Gold Kryptonite, that only removes Kryptonians' powers for 15 seconds, resolving in Superman: War of the Superman #1 in July, 2010 (and his history being slightly altered, with his name now being Benjamin Martin Krull).
That battle also featured General Zod (and others from the Phantom Zone), who will come to menace Supergirl in the future....
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