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It depends; there are two types of film that might develop, and neither necessarily mean that the olives have spoiled.

A clear film on top of the brine is a layer of Olive Oil that has solidified due to changes in temperature. Simply remove the jar from the refrigerator for 30 minutes and the olive oil will dissolve and return to its liquid state. A little "olive jar shake" won't hurt either.

A white film however, is the result of a reaction (oxidation) that occurs between the vinegar and the air in the jar. Simply remove the layer of white film with a spoon. Then remove and rinse any olives that may have come in contact with the film. The olives are most always safe for consumption and may be placed back in the brine.

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12y ago
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Q: When a bottle of olives in a brine spoil a film may develop on the liquid surface what is it?
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