Silver has been known since ancient times and as such, no one knows exactly how it was discovered. The major centers of silver production have shifted throughout history.
Silver has been mined, since at least 3000 BCE. Slag heaps dating back to that time period have been discovered near silver mines in Anatolia, in modern-day Turkey. It was refined by heating silver in a shallow vessel until it melted, then blowing a strong draft of air over the top. This would eliminate other materials, like copper and lead, leaving pure silver. The Chaldeans, a people who inhabited modern-day southern Iraq, developed this process.
Mining of silver has been central in the development of ancient empires. Around 1200 BCE, Greece's Laurium mines became the center of silver production and remained prominent until 100 CE, when Spain became a major producer of the precious metal. Spain supplied silver to the burgeoning Roman Empire. Later, silver mining moved north to Germany and other parts of Central and Eastern Europe, where major operations took place between 750 and 1200 CE.
When Christopher Columbus arrived in the New World, in 1492, a major shift in silver production took place. Between 1500 and 1800, South American countries, including Bolivia, Peru and Mexico, accounted for most of the world's silver mining.