Hi,
They may have been married in Nova Scotia. The 1871 census has the family in Quebec. James is 39, born in England and W. Methodist. Catharine is 32, born in Nova Scotia, Presbyterian with an Irish background (I think there are other census references which say her background is Irish). Kids are Martha 10, born in Nova Scotia, Harriet 9, Alfred 7, Mary 6 - all born in Ontario, Sarah 3 born in Newfoundland, and Sophia 8 months, born in Ontario.
Billow thinks they were married about 1860, and this certainly makes sense. I don't see them on the 1861 census yet, but I will keep looking.
RK