Which of the following matter are first discovered by man?

Which of the following matter are first discovered by man?

مندرجہ ذیل میں سے کون سا مادہ سب سے پہلے انسان نے دریافت کیا؟
Explanation

 Copper was first used by man over 10,000 years ago

The period following the use of copper is sometimes referred to as the Copper Age or Chalcolithic Age.