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When the Potomac arrived in Boston, Maury applied for leave of absence and went directly to Fredericksburg, Virginia, where he was married to Ann Herndon on July 15, 1834. In this charming old Virginia town he established his residence for the next seven years, living on Charlotte Street in a two-story frame house with a large old-fashioned garden, which he rented from a Mr. Johnston. He had always been generous with his money to different members of his family, and it is related that, as a consequence, he had but twenty dollars of ready money at the time of his marriage, all of which he gave as a fee to Parson E. C. McGuire. In the same generous way he shared his home for a considerable time with his brother John's widow and her two sons.

With some leisure at his command, Maury determined to become an author, under the encouragement of the recent appearance in the American Journal of Science and Arts of his first scientific article, "On the Navigation of Cape Horn". This, the first fruit of his sea experience, described forcefully the dangers of the passage of Cape Horn, and gave specific information concerning the winds and the peculiar rising and falling of the barometer in those latitudes. In the same number of this journal there appeared another article describing Maury's "Plan of an Instrument for Finding the True Lunar Distance", the instrument in question having been invented by him. With these beginnings, he ambitiously set to work to finish a book on navigation, which he had commenced