It really depends on how the shelf is mounted to your wall. If you're into numbers, you can use the formula:
$$\text{Load Capacity = (Material Strength × Width × Thickness × Thickness) / (8 × Length)}$$
But I suppose material strength values aren't that easily available, and specific shelfs can be more complicated, so you'll have to resort to experimental tests.
An aquarium is a stationary load. If your shelf can hold it for a few seconds without bending, it can hold it for an indefinite period of time (hopefully). So I suggest you just keep the aquarium on top of it and be ready to hold it if the shelf falls. Testing with smaller loads will only prove that the shelf can handle those smaller loads; the behaviour is unpredictable for larger loads as shelf-failure is an abrupt event with no observable signs beforehand.
Better to just go off of your intuition and install additional supports if required.