Smelting

In the case of sulfides and carbonates, a process called "roasting" removes the unwanted carbon or sulfur, leaving an oxide, which can be directly reduced. Roasting is usually carried out in an oxidizing environment. A few practical examples:

• Malachite, a common ore of copper, is primarily copper carbonate hydroxide Cu₂(CO₃)(OH)₂.[4] This mineral undergoes thermal decomposition to 2CuO, CO₂, and H₂O[5] in several stages between 250 °C and 350 °C. The carbon dioxide and water are expelled into the atmosphere, leaving copper(II) oxide, which can be directly reduced to copper as described in the following section titled Reduction.
• Galena, the most common mineral of lead, is primarily lead sulfide (PbS). The sulfide is oxidized to a sulfite (PbSO₃), which thermally decomposes into lead oxide and sulfur dioxide gas. (PbO and SO₂) The sulfur dioxide is expelled (like the carbon dioxide in the previous example), and the lead oxide is reduced as below.

Reduction is the final, high-temperature step in smelting, in which the oxide becomes the elemental metal. A reducing environment (often provided by carbon monoxide, made by incomplete combustion in an air-starved furnace) pulls the final oxygen atoms from the raw metal. The required temperature varies over a very large range, both in absolute terms and in terms of the melting point of the base metal. Examples:

• Iron oxide becomes metallic iron at roughly 1250 °C (2282 °F or 1523.15 K), almost 300 degrees below iron's melting point of 1538 °C (2800.4 °F or 1811.15 K).
• Mercuric oxide becomes vaporous mercury near 550 °C (1022 °F or 823.15 K), almost 600 degrees above mercury's melting point of -38 °C (-36.4 °F or 235.15 K).

Flux and slag can provide a secondary service after the reduction step is complete: they provide a molten cover on the purified metal, preventing contact with oxygen while still hot enough to readily oxidize. This prevents impurities from forming in the metal.

Metal workers use fluxes in smelting for several purposes, chief among them catalyzing the desired reactions and chemically binding to unwanted impurities or reaction products. Calcium oxide, in the form of lime, was often used for this purpose, since it could react with the carbon dioxide and sulfur dioxide produced during roasting and smelting to keep them out of the working environment.

In the Old World, the first metals smelted were tin and lead. The earliest known cast lead beads were found in the Çatal Höyük site in Anatolia (Turkey), and dated from about 6500 BC, but the metal may have been known earlier.

Since the discovery happened several millennia before the invention of writing, there is no written record about how it was made. However, tin and lead can be smelted by placing the ores in a wood fire, leaving the possibility that the discovery may have occurred by accident.

Lead is a common metal, but its discovery had relatively little impact in the ancient world. It is too soft to use for structural elements or weapons, though its high density relative to other metals makes it ideal for sling projectiles. However, since it was easy to cast and shape, workers in the classical world of Ancient Greece and Ancient Rome used it extensively to pipe and store water. They also used it as a mortar in stone buildings.

Tin was much less common than lead and is only marginally harder, and had even less impact by itself.

After tin and lead, the next metal smelted appears to have been copper. How the discovery came about is debated. Campfires are about 200 °C short of the temperature needed, so some propose that the first smelting of copper may have occurred in pottery kilns. The development of copper smelting in the Andes, which is believed to have occurred independently of the Old World, may have occurred in the same way.[6] The earliest current evidence of copper smelting, dating from between 5500 BC and 5000 BC, has been found in Pločnik and Belovode, Serbia.[7][8] A mace head found in Can Hasan, Turkey and dated to 5000 BC, once thought to be the oldest evidence, now appears to be hammered native copper.[9]

Combining copper with tin and/or arsenic in the right proportions produces bronze, an alloy that is significantly harder than copper. The first copper/arsenic bronzes date from 4200 BC from Asia Minor. The Inca bronze alloys were also of this type. Arsenic is often an impurity in copper ores, so the discovery could have been made by accident. Eventually arsenic-bearing minerals were intentionally added during smelting.

Copper–tin bronzes, harder and more durable, were developed around 3200 BC, also in Asia Minor.

How smiths learned to produce copper/tin bronzes is unknown. The first such bronzes may have been a lucky accident from tin-contaminated copper ores. However, by 2000 BC, people were mining tin on purpose to produce bronze—which is amazing given that tin is a semi-rare metal, and even a rich cassiterite ore only has 5% tin. Also, it takes special skills (or special instruments) to find it and locate richer lodes. However early peoples learned about tin, they understood how to use it to make bronze by 2000 BC.

The discovery of copper and bronze manufacture had a significant impact on the history of the Old World. Metals were hard enough to make weapons that were heavier, stronger, and more resistant to impact damage than wood, bone, or stone equivalents. For several millennia, bronze was the material of choice for weapons such as swords, daggers, battle axes, and spear and arrow points, as well as protective gear such as shields, helmets, greaves (metal shin guards), and other body armor. Bronze also supplanted stone, wood, and organic materials in tools and household utensils—such as chisels, saws, adzes, nails, blade shears, knives, sewing needles and pins, jugs, cooking pots and cauldrons, mirrors, and horse harnesses. Tin and copper also contributed to the establishment of trade networks that spanned large areas of Europe and Asia, and had a major effect on the distribution of wealth among individuals and nations.

Casting bronze ding-tripods, from the Chinese Tiangong Kaiwu encyclopedia of Song Yingxing, published in 1637.

The earliest evidence for iron-making is a small number of iron fragments with the appropriate amounts of carbon admixture found in the Proto-Hittite layers at Kaman-Kalehöyük and dated to 2200–2000 BCE.[10] Souckova-Siegolová (2001) shows that iron implements were made in Central Anatolia in very limited quantities around 1800 BCE and were in general use by elites, though not by commoners, during the New Hittite Empire (∼1400–1200 BCE).[11]

Archaeologists have found indications of iron working in Ancient Egypt, somewhere between the Third Intermediate Period and 23rd Dynasty (ca. 1100–750 BCE). Significantly though, they have found no evidence for iron ore smelting in any (pre-modern) period. In addition, very early instances of carbon steel were in production around 2000 years ago (around the first century CE.) in northwest Tanzania, based on complex preheating principles. These discoveries are significant for the history of metallurgy.[12]

Most early processes in Europe and Africa involved smelting iron ore in a bloomery, where the temperature is kept low enough so that the iron does not melt. This produces a spongy mass of iron called a bloom, which then must be consolidated with a hammer to produce wrought iron. The earliest evidence to date for the bloomery smelting of iron is found at Tell Hammeh, Jordan (), and dates to 930 BCE (C14 dating).

From the medieval period, an indirect process began to replace direct reduction in bloomeries. This used a blast furnace to make pig iron, which then had to undergo a further process to make forgeable bar iron. Processes for the second stage include fining in a finery forge and, from the Industrial Revolution, puddling. Both processes are now obsolete, and wrought iron is now rarely made. Instead, mild steel is produced from a bessemer converter or by other means including smelting reduction processes such as the Corex Process.

Wastewater pollutants discharged by iron and steel mills includes gasification products such as benzene, naphthalene, anthracene, cyanide, ammonia, phenols and cresols, together with a range of more complex organic compounds known collectively as polycyclic aromatic hydrocarbons (PAH).[17]

Pollutants generated by other types of smelters varies with the base metal ore. For example, aluminum smelters typically generate fluoride, benzo(a)pyrene, antimony and nickel, as well as aluminum. Copper smelters typically discharge cadmium, lead, zinc, arsenic and nickel, in addition to copper.[18]

The smelter in Flin Flon, Canada was one of the largest point sources of mercury in North America in the 20th century.[19][20] Even after smelter releases were drastically reduced, landscape re-emission continued to be a major regional source of mercury.[19] Lakes will likely receive mercury contamination from the smelter for decades, from both re-emissions returning as rainwater and leaching of metals from the soil.[19]

Labourers working in the smelting industry have reported respiratory illnesses inhibiting their ability to perform the physical tasks demanded by their jobs.[21]