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At the age of ten, the Shadd's moved to West Chester, Pennsylvania where Mary attended a Quaker School for the next six years. This experience influence dMary later in life, whereby she returned to this location and opened a school for Black children in 1840.
During her youth, Daly loved to read, especially about science. After graduating from Hunter College High School, she went on to attend Queens College where she earned her B.S in Chemistry in 1942 (graduating magna cum laude). Daly then went on to attend New York University and earned her Master's degree there in 1944.