I am not a lawyer; I am an environmental engineer with 20+ yrs of experience with the clean up of contaminated sites. So I am comfortable speaking to what I am seeing actually happen with these sites, but not to the underlying legal principals.
As to the protection an LLC offers to you personally, that is a lawyer question. I have seen this fail to protect for several reasons.
I can tell you that under Superfund you can but probably won't be held liable by EPA for clean up, if the contamination is clearly not coming from and could not reasonably have come from any operations on your site. There are some old horror stories, cases in which EPA pursued and ruined truly innocent landowners in the 80’s and 90’s, but less so today. I am less familiar with how NY DEC would handle this.
If your operations or past operations you were aware of on your property could have contributed to the contamination you may have a problem. The EPA is not consistent or entirely predictable, but in recent years I have seen less interest on their part in going after clearly innocent landowners. Your best bet might be to try and figure out where the contamination came from, and if it is not from your property give all that information to the EPA and NY DEC, focus their attention where it needs to be focused. If it did or may have come from your property keep your head down, sometimes regulators loose interest (this comment only applies if no one is being exposed to the contamination and it is not migrating; if their is or could be exposure or migration do something right away to limit it).
Unfortunately some of what the regulators will focus on depends on depth of pocket; they will want to go after someone who can pay; sometimes even if it is not really the right entity to go after.
This is a complex question, you really need professional advice, both from an environmental lawyer and an engineer.
Good luck,
Buzz