There is evidence that the toothpick has been around in various forms since 1600 BC and that our modern day toothbrushes actually evolved from them! In early times, things like porcupine quills and chicken bones and wood splinters were used to clean teeth. Here are some excerpts from an article I found that has some great information about when the toothpick originated.
"The skulls of Neanderthals, as well as Homo sapiens, have shown clear signs of having teeth that were either flossed with blades of grass or picked with rudimentary toothpick tools. Similar markings have been found in the fossilized teeth of both American Indians and Australian Aborigines."
Source: Smithsonian Magazine
Here is another excerpt I found particularly interesting...
"At one time, you could tell a person's status by what they used to pick their teeth. Kings, queens, and lords picked their teeth with designer toothpicks made from gold, silver, or ivory. Often, they were inlaid with precious stones. Twigs and porcupine quills were most often used by the "lower classes." By the 17th century, the toothpick was the latest fad for the educated classes in Europe they were even included in traveling sets together with a knife and spoon."
Source: http://members.aol.com/acalendar/February/toothpick.html
Here's a closing fact just for fun:
Did you know?
"One cord of wood (logs 8' in length, stacked 4' high, and 4' wide) can be turned into 7.5 million toothpicks." Source: amusingfacts.com
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