We've assayed unsulfated matter by both HPLC and high-temperature capillary GC. There's even been a publication on the high-temperature GC assay of unsulfonated (analogous to unsulfated) matter in linear alkybenzenesulfonates. Journal of Surfactants and Detergents
Volume 8, Number 2, 199-202.
http://www.springerlink.com/content/7q2u847j5nw10747/
There are also well-loved extraction procedures....
We've assayed for Kathon CG in materials by HPLC for 30 years, pretty much use the suppliers procedure (gradient, H2O-acetic acid plus methanol, on C18 column, UV detection). Both the methylisothiazolinone and the methylchloroisothiazolinone peaks are measured independently.