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Silver has been used for thousands of years for ornaments, utensils, and trade, and as the basis for many monetary systems. Its value as a precious metal was long considered second only to gold. The word "silver" appears in Anglo-Saxon in various spellings, such as seolfor and siolfor. A similar form is seen throughout the Germanic languages (compare Old High German silabar and silbir). The chemical symbol Ag is from the Latin word for "silver", argentum (compare Ancient Greek ἄργυρος, árgyros), from the Proto-Indo-European root *h₂erǵ- (formerly reconstructed as*arǵ-), meaning "white" or "shining". Silver has been known since ancient times; it is mentioned in the Book of Genesis. Slag heaps found in Asia Minor and on the islands of the Aegean Sea indicate silver was being separated from lead as early as the 4th millennium BC using surface mining. One of the earliest silver extraction centres in Europe was Sardinia in early Chalcolithic.

The stability of the Roman currency relied to a high degree on the supply of silver bullion, which Roman miners produced on a scale unparalleled before the discovery of the New World. Reaching a peak production of 200 t per year, an estimated silver stock of 10,000 t circulated in the Roman economy in the middle of the second century AD, five to ten times larger than the combined amount of silver available to medieval Europe and the Caliphate around 800 AD. Financial officials of the Roman Empire worried about the loss of silver to pay for silk from Sinica (China), which was in high demand. Mines were worked in Laureion during 483 BC.

In the Gospels, Jesus' disciple Judas Iscariot is infamous for having taken a bribe of 30 coins of silver from religious leaders in Jerusalem to turn Jesus of Nazareth over to soldiers of the High Priest Caiaphas.

The Chinese Empire during most of its history used primarily silver as a means of exchange. In the 19th century, the threat to the balance of payments of the United Kingdom from Chinese merchants who required payment in silver for tea, silk, and porcelain led to the Opium War; Britain addressed the imbalance of payments by selling opium from British India to China.

In the Americas, high temperature silver-lead cupellation technology was developed by pre-Inca civilizations as early as AD 60–120.

While Greeks and Muslims were known for striking gold coins (such as bezants and dinars) silver, alongside copper, iron and salt, formed the principal mineral wealth of mediaeval Europe, and for a higher-level currency, silver was sufficient in quantity and quality, extracted from mines in eastern Europe or from Sardinia, whose ore fed the purse of the Pisan republic. Silver also has anti-bacterial properties and was also sought by apothecaries as well — tradition in Korea holds that the best chopsticks are made of pure silver.

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