Because the pH of a reef aquarium goes through a daily cycle the best time of the day to test it is at the same time of day. That way you are always comparing the reading for the system at the same stage and you will get a more accurate indicator if there are some problems.

The reason that the pH fluctuates is due to the fluctuation of photosynthesis and respiration. All non-photosynthetic organisms respire 24 hours a day, which uses up oxygen and releases carbon dioxide. On the other hand, photosynthetic organisms perform the opposite during daylight hours, using up carbon dioxide and releasing oxygen. So the net effect is during daylight carbon dioxide is used up faster than it is produced, increasing the pH. And the converse occurs at night, with only carbon dioxide being generated, decreasing the pH.

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