I doubt TIG welding would work. Welding copper properly demands “de-oxidised” quality copper, and anyway the silver-solder would contaminate the weld.
Comsol ought be satisfactory if you can get it into the joint, but your friendly local boiler-inspector might be wary of it. He or she might wonder about the state of the rest of the joint.
If the locomotive has not been run much, worn piston-rings seem rather unlikely, but silicon O-rings may be “weaker” than iron ones. Such rings should of course be of a grade suitable for reciprocating seals. Or one was damaged in its installation.
I’d investigate the valves first as requiring less dismantling for inspection.
Leaky surfaces apart, the main source of possible blow-by with a slide-valve is the valve unable to “float” properly in its mounting arrangement on the spindle. Either by excessive tightness, or a design flaw. So once you’ve lifted the covers, test for that float first.
I add the latter reason having encountered a Winston’s Kit steam-wagon that had no way of stopping it, we discovered due to a design weakness compounded by poor manufacturing, of its slide-valve regulator!