(a) Comparative anatomy - by studying any shared structures between the two organisms, like the arrangement of beak bones, Darwin would determine if indeed the organisms are closely related. The more there would be shared characteristics, the closely related they would be.
Fossil records - Darwin could also observe the fossils of the ancestors of both birds to see if he can establish a link between them. A study on the oldest penguin and albatross fossils could reveal when the two species diverged.
(b) Molecular genetics is the modern tool that can be used to support this relationship. We know that mutations accumulate in genes at fairly steady rates, hence the variations observed between species can act as some sort of molecular clock. This information can then be used to approximate the exact dates (in millions of years) ago the two species diverged. Such data would then be used to determine if indeed penguins and albatrosses belong to any old lineage.
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