The liturgical use of ashes was introduced during the Old Testament times. Ashes means mourning, mortality, and penance. For instance, in the Book of Esther, Mordecai put on sackcloth and ashes when he heard the announcement of King Ahasuerus (or Xerxes, 485-464 B.C.) of Persia to kill all the Jewish people in the Persian Empire (Esther 4:1). Also Job (whose story was written between the 7th and 5th centuries B.C.) repented in sackcloth and ashes (Job 42:6). Daniel (c. 550 B.C.), when prophesying the Babylonian captivity of Jerusalem, wrote, “I turned to the Lord God, asking in earnest prayer, with fasting, sackcloth, and ashes” (Daniel 9:3).

The town of Nineveh proclaimed a fast and put on sackcloth, and the king covered himself with sackcloth and sat in the ashes In the 5th century B.C. And this was after Jonah’s preaching of conversion and repentance, (Jonah 3:5-6). These Old Testament instances gave evidence to both a recognized practice of using ashes and a common understanding of their symbolism.
Jesus Himself also referred to ashes when he referred to towns that refused to repent of sin although they had witnessed the miracles and heard the gospel, our Lord said in (Matthew 11:21), “If the miracles worked in you had taken place in Tyre and Sidon, they would have reformed in sackcloth and ashes long ago”.

In the Middle Ages (The time of the eighth century), those who were at the edge of death were laid on the ground on top of sackcloth sprinkled with ashes. The priest would bless the person who is at the point of death with holy water, saying, “Remember that from dust you are and to dust you shall return”. After sprinkling the ash, the priest would ask, “Are you content with sackcloth and ashes in testimony of thy penance before the Lord in the day of judgment?” To which the dying person would reply “I am content”. In all of these examples, the symbolism of ashes as mourning, mortality, and penance is clear.

The early Church continued the usage of ashes for this same symbolic reasons. The famous early Church historian, recounted in his book “The History of the Church” how an apostate named Natalis came to Pope Zephyrinus clothed in sackcloth and ashes begging forgiveness. Also during this time, for those who were supposed to do public penance, the priest sprinkled ashes on the head of the person leaving confession.

Eventually, the use of ashes upon our head was adapted to signify the beginning of Lent, the 40-day preparation period (not including Sundays) for Easter to signify that we ought to turn away from our sins during the Lenten fast. A story was told of a man who refused to go to Church on Ash Wednesday and receive ashes, the man was killed a few days later in a boar hunt.
Since the Middle Ages, the Church has been using ashes to mark the beginning of the penitential season of Lent, when we remember our mortality and mourn for our sins.

On the Ash Wednesday, the priest would bless the ashes and impose them on the foreheads of the faithful, making the sign of the cross and saying, “Remember, that you are dust and unto dust, you shall return,” or “Turn away from sin and be faithful to the Gospel”. When we begin the holy season of Lent which is a way we prepare for Easter, we must remember the significance of the ashes we have received. We are reminded to mourn and do penance for our sins. We again turn our hearts to the Lord, who suffered, died, and rose for our salvation. We make again the promises made at our baptism when we died to an old life and rose to a new life with Christ.

Finally, be mindful that the kingdom of this world passes away, we strive to live the kingdom of God now and look forward to its fulfillment in heaven.

Source: https://yeahcatholic.com/the-origin-of-ash-wednesday/

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