ANSWERS: 5
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Possibly. But there were lots of Smiths and without documentation it is simply an old powder horn, though it could have value.
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You could send a picture and info to the Jamestown Project and ask them: http://www.apva.org/resource/index.html You might be interested in doing some research, if you haven't already. This would be a good place to start, with several external links at the bottom of the article: http://en.wikipedia.org/wiki/John_Smith_of_Jamestown
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Another immediate kicker. Of what animal is the horn? Remember Captain Smith was only in Virginia from 1607 to 1609. If he is connected, it would be far more probable from his Massachussets expedition in 1614. As a long time gun collector I will add that powder horns were used by the very poor. I would expect tjat Smith would have carried a brass powder horn. Why? Well Smith did have a wheellock pistol well advanced at the time. Wheellocks were very expensive. And lastly Smith died in England. As such, my bet is anything of meaning would have returned there with him. Unless you can trace the item to the Ambler, Barney or Travis families, I don't think you can make any connection. Probably the owner was a very generic John Smith.
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Something else. If the powder horn is steer or buffalo horn, It would have considerable cracking and very yellow after 400 years. In fact without very careful keeping it would likely fall apart. Horns don't last long unless cased. In the wild you will not likely find deer, elk and other antlers older than a year. Rodents and other animals eat them for the calcium. And water will decompose and leach it into the soil.
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here are a few photos
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