How about ammonia? See http://www.nrcs.usda.gov/Internet/FSE_DOCUMENTS/stelprdb1253871.pdf page 226 ff. Is there any reason why it wouldn't work with biochar? You can analyse ammonia photometrically or even distill and titrate it if you like.
BTW, formerly people precipitated Ba with SO4 and weighed it. So this might be a socond option.
Thank you Thomas Fischer sir. I am just trying to find out the method which can be easily applicable without using more sophisticated instrument. I will surely try it.