A fascinating question. Queen Elizabeth I was often depicted wearing a full, even masssive, ruff without ever having been married. Bess of Hardwick is usually shown wearing a full ruff, and she was married several times. I am aware of a half-dozen portraits of Bess, but none with a brooch in her hair. On the other hand, the famous portrait of Arbella Stuart at about age 13 (and unmarried) shows here without a ruff, but with a brooch in her hair ... but it is in the middle of her head! I do know that wedding rings were usually specifically shown on the left hand of married women in portraits from the last half of the sixteenth century, so I suspect that acts as a more reliable indicator of marital status than does ruffs or hair attachments. But I'd have to do further research to be more certain.
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