Smelting

Electric phosphate smelting furnace in a TVA chemical plant (1942)

Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. ^[1] It is a form of extractive metallurgy that is used to obtain many metals such as iron, copper, silver, tin, lead and zinc. Smelting uses heat and a chemical reducing agent to decompose the ore, driving off other elements as gases or slag and leaving the metal behind. The reducing agent is commonly a fossil-fuel source of carbon, such as carbon monoxide from incomplete combustion of coke—or, in earlier times, of charcoal. ^[1] The oxygen in the ore binds to carbon at high temperatures, as the chemical potential energy of the bonds in carbon dioxide (CO₂) is lower than that of the bonds in the ore.

Sulfide ores such as those commonly used to obtain copper, zinc or lead, are roasted before smelting in order to convert the sulfides to oxides, which are more readily reduced to the metal. Roasting heats the ore in the presence of oxygen from air, oxidizing the ore and liberating the sulfur as sulfur dioxide gas.

Smelting most prominently takes place in a blast furnace to produce pig iron, which is converted into steel.

Plants for the electrolytic reduction of aluminium are referred to as aluminium smelters.

Process

Copper smelter, Chelyabinsk Oblast, Russia

Electrolytic cells at an aluminum smelter in Saint-Jean-de-Maurienne, France

Smelting involves more than just melting the metal out of its ore. Most ores are the chemical compound of the metal and other elements, such as oxygen (as an oxide), sulfur (as a sulfide), or carbon and oxygen together (as a carbonate). To extract the metal, workers must make these compounds undergo a chemical reaction. Smelting, therefore, consists of using suitable reducing substances that combine with those oxidizing elements to free the metal.

Roasting

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. ^[2] This mineral undergoes thermal decomposition to 2CuO, CO₂, and H₂O ^[3] 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

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 carbon source acts as a chemical reactant to remove oxygen from the ore, yielding the purified metal element as a product. The carbon source is oxidized in two stages. First, carbon (C) combusts with oxygen (O₂) in the air to produce carbon monoxide (CO). Second, the carbon monoxide reacts with the ore (e.g. Fe₂O₃) and removes one of its oxygen atoms, releasing carbon dioxide (CO₂). After successive interactions with carbon monoxide, all of the oxygen in the ore will be removed, leaving the raw metal element (e.g. Fe). ^[4] As most ores are impure, it is often necessary to use flux, such as limestone (or dolomite), to remove the accompanying rock gangue as slag. This calcination reaction emits carbon dioxide.

The required temperature varies 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 K), almost 300 degrees below iron's melting point of 1538 °C (2800 °F or 1811 K). ^[5]
• Mercuric oxide becomes vaporous mercury near 550 °C (1022 °F or 823 K), almost 600 degrees above mercury's melting point of -38 °C (-36.4 °F or 235 K), and also above mercury's boiling point. ^[6]

Fluxes

Fluxes are materials added to the ore during smelting to catalyze the desired reactions and to chemically bind to unwanted impurities or reaction products. Calcium carbonate or calcium oxide in the form of lime are often used for this purpose, since they react with sulfur, phosphorus, and silicon impurities to allow them to be readily separated and discarded, in the form of slag. Fluxes may also serve to control the viscosity and neutralize unwanted acids.

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.

Sulfide ores

Cowles Syndicate of Ohio in Stoke-upon-Trent England, late 1880s. British Aluminium used the process of Paul Héroult about this time.

The ores of base metals are often sulfides. In recent centuries, reverberatory furnaces have been used to keep the charge being smelted separately from the fuel. Traditionally, they were used for the first step of smelting: forming two liquids, one an oxide slag containing most of the impurities, and the other a sulfide matte containing the valuable metal sulfide and some impurities. Such "reverb" furnaces are today about 40 meters long, 3 meters high, and 10 meters wide. Fuel is burned at one end to melt the dry sulfide concentrates (usually after partial roasting) which are fed through openings in the roof of the furnace. The slag floats over the heavier matte and is removed and discarded or recycled. The sulfide matte is then sent to the converter. The precise details of the process vary from one furnace to another depending on the mineralogy of the ore body.

While reverberatory furnaces produced slags containing very little copper, they were relatively energy inefficient and off-gassed a low concentration of sulfur dioxide that was difficult to capture; a new generation of copper smelting technologies has supplanted them. ^[8] More recent furnaces exploit bath smelting, top-jetting lance smelting, flash smelting, and blast furnaces. Some examples of bath smelters include the Noranda furnace, the Isasmelt furnace, the Teniente reactor, the Vunyukov smelter, and the SKS technology. Top-jetting lance smelters include the Mitsubishi smelting reactor. Flash smelters account for over 50% of the world's copper smelters. There are many more varieties of smelting processes, including the Kivset, Ausmelt, Tamano, EAF, and BF.

History

Of the seven metals known in antiquity, only gold regularly occurs in nature as a native metal. The others – copper, lead, silver, tin, iron, and mercury – occur primarily as minerals, although native copper is occasionally found in commercially significant quantities. These minerals are primarily carbonates, sulfides, or oxides of the metal, mixed with other components such as silica and alumina. Roasting the carbonate and sulfide minerals in the air converts them to oxides. The oxides, in turn, are smelted into the metal. Carbon monoxide was (and is) the reducing agent of choice for smelting. It is easily produced during the heating process, and as a gas comes into intimate contact with the ore.

In the Old World, humans learned to smelt metals in prehistoric times, more than 8000 years ago. The discovery and use of the "useful" metals – copper and bronze at first, then iron a few millennia later – had an enormous impact on human society. The impact was so pervasive that scholars traditionally divide ancient history into Stone Age, Bronze Age, and Iron Age.

In the Americas, pre-Inca civilizations of the central Andes in Peru had mastered the smelting of copper and silver at least six centuries before the first Europeans arrived in the 16th century, while never mastering the smelting of metals such as iron for use with weapon craft. ^[9]

Copper and bronze

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

Copper was the first metal to be smelted. ^[10] 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. ^[11] (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. ^[9] )

The earliest current evidence of copper smelting, dating from between 5500 BC and 5000 BC, has been found in Pločnik and Belovode, Serbia. ^{[12] [13]} A mace head found in Turkey and dated to 5000 BC, once thought to be the oldest evidence, now appears to be hammered, native copper. ^[14]

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.^{[ citation needed ]}

Copper–tin bronzes, harder and more durable, were developed around 3500 BC, also in Asia Minor. ^[15]

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 remarkable as tin is a semi-rare metal, and even a rich cassiterite ore only has 5% tin.^{[ citation needed ]}

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.^{[ citation needed ]} 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.^{[ citation needed ]}

Tin and lead

The earliest known cast lead beads were thought to be in the Çatalhöyük site in Anatolia (Turkey), and dated from about 6500 BC. ^[16] However, recent research has discovered that this was not lead, but rather cerussite and galena, minerals rich in, but distinct from, lead. ^[17]

Since the discovery happened several millennia before the invention of writing, there is no written record of 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.^{[ citation needed ]} Recent scholarship however has called this find into question. ^[18]

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. ^{[19] [20]}

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

Early iron smelting

Main article: Ferrous metallurgy

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 BC. ^[21] Souckova-Siegolová (2001) shows that iron implements were made in Central Anatolia in very limited quantities around 1800 BC and were in general use by elites, though not by commoners, during the New Hittite Empire (~1400–1200 BC). ^[22]

Archaeologists have found indications of iron working in Ancient Egypt, somewhere between the Third Intermediate Period and 23rd Dynasty (ca. 1100–750 BC). Significantly though, they have found no evidence of 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.) in northwest Tanzania, based on complex preheating principles. These discoveries are significant for the history of metallurgy. ^[23]

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. Some of the earliest evidence to date for the bloomery smelting of iron is found at Tell Hammeh, Jordan, radiocarbon-dated to c. 930 BC. ^[24]

Later iron smelting

Main article: Blast furnace

From the medieval period, an indirect process began to replace the 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. In the 13th century during the High Middle Ages the blast furnace was introduced by China who had been using it since as early as 200 b.c during the Qin dynasty. Puddling was also introduced in the Industrial Revolution.

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.

Environmental and occupational health impacts

Smelting has serious effects on the environment, producing wastewater and slag and releasing such toxic metals as copper, silver, iron, cobalt, and selenium into the atmosphere. ^[25] Smelters also release gaseous sulfur dioxide, contributing to acid rain, which acidifies soil and water. ^[26]

The smelter in Flin Flon, Canada was one of the largest point sources of mercury in North America in the 20th century. ^{[27] [28]} Even after smelter releases were drastically reduced, landscape re-emission continued to be a major regional source of mercury. 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. ^[27]

Air pollution

Air pollutants generated by aluminium smelters include carbonyl sulfide, hydrogen fluoride, polycyclic compounds, lead, nickel, manganese, polychlorinated biphenyls, and mercury. ^[29] Copper smelter emissions include arsenic, beryllium, cadmium, chromium, lead, manganese, and nickel. ^[30] Lead smelters typically emit arsenic, antimony, cadmium and various lead compounds. ^{[31] [32] [33]}

Wastewater

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). ^[34] Treatment technologies include recycling of wastewater; settling basins, clarifiers and filtration systems for solids removal; oil skimmers and filtration; chemical precipitation and filtration for dissolved metals; carbon adsorption and biological oxidation for organic pollutants; and evaporation. ^[35]

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. ^[36] Lead smelters may discharge antimony, asbestos, cadmium, copper and zinc, in addition to lead. ^[37]

Health impacts

Labourers working in the smelting industry have reported respiratory illnesses inhibiting their ability to perform the physical tasks demanded by their jobs. ^[38]

Regulations

In the United States, the Environmental Protection Agency has published pollution control regulations for smelters.

• Air pollution standards under the Clean Air Act ^[39]
• Water pollution standards (effluent guidelines) under the Clean Water Act. ^{[40] [41]}

See also

• Cast iron
• Ellingham diagram, useful in predicting the conditions under which an ore reduces to its metal
• Copper extraction techniques
• Clinker
• Cupellation
• Lead smelting
• Metallurgy
• Metallurgy in pre-Columbian America
• Pyrometallurgy
• Wrought iron
• Zinc smelting

References

1. "Smelting". Encyclopedia Britannica. Retrieved 23 February 2021.
2. "Malachite: Malachite mineral information and data". mindat.org. Archived from the original on 8 September 2015. Retrieved 26 August 2015.
3. "Copper Metal from Malachite | Earth Resources". asminternational.org. Archived from the original on 23 September 2015. Retrieved 26 August 2015.
4. "Blast Furnace". Science Aid. Retrieved 13 October 2021.
5. Eisele, T.C. (2005). Direct Biohydrometallurgical Extraction of Iron from Ore. doi:10.2172/877695.
6. "Mercury processing - Extraction and refining". Encyclopedia Britannica. Retrieved 23 February 2021.
7. Minet, Adolphe (1905). The Production of Aluminum and Its Industrial Use. Leonard Waldo (translator, additions). New York, London: John Wiley and Sons, Chapman & Hall. p.  244 (Minet speaking) +116 (Héroult speaking). OL   234319W.
8. W. G. Davenport (1999). "Copper extraction from the 60s into the 21st century". In G. A. Eltringham; N. L. Piret; M. Sahoo (eds.). Proceedings of the Copper 99–Cobre 99 International Conference. Vol. I—Plenary Lectures/Movement of Copper and Industry Outlook/Copper Applications and Fabrication. Warrendale, Pennsylvania: The Minerals, Metals and Materials Society. pp. 55–79. OCLC   42774618.
9. "releases/2007/04/070423100437". sciencedaily.com. Archived from the original on 9 September 2015. Retrieved 26 August 2015.
10. McGeough, Joseph. "Early metals and smelting". Brittanica.
11. Tylecote, R F (1986). The Prehistory of Metallurgy in the British Isles. London: The Institute of Metals. pp. 16–17.
12. "Stone Pages Archaeo News: Ancient metal workshop found in Serbia". stonepages.com. Archived from the original on 24 September 2015. Retrieved 26 August 2015.
13. "201006274431 | Belovode site in Serbia may have hosted first copper makers". archaeologydaily.com. Archived from the original on 29 February 2012. Retrieved 26 August 2015.
14. Sagona, A.G.; Zimansky, P.E. (2009). Ancient Turkey. Routledge. ISBN   9780415481236. Archived from the original on 6 March 2016.
15. "History of Bronze Infographic | About | Website | Makin Metal Powders (UK)". www.makin-metals.com. Archived from the original on 8 November 2020. Retrieved 23 February 2021.
16. Gale, N.H.; Stos-Gale, Z.A. (1981). "Ancient Egyptian Silver". The Journal of Egyptian Archaeology. 67 (1): 103–115. doi:10.1177/030751338106700110. S2CID   192397529 – via Sage Journals.
17. Radivojević, Miljana; Rehren, Thilo; Farid, Shahina; Pernicka, Ernst; Camurcuoğlu, Duygu (1 October 2017). "Repealing the Çatalhöyük extractive metallurgy: The green, the fire and the 'slag'". Journal of Archaeological Science. 86: 101–122. Bibcode:2017JArSc..86..101R. doi:10.1016/j.jas.2017.07.001. ISSN   0305-4403.
18. Radivojević, Miljana; Rehren, Thilo; Farid, Shahina; Pernicka, Ernst; Camurcuoğlu, Duygu (2017). "Repealing the Çatalhöyük extractive metallurgy: The green, the fire and the 'slag'". Journal of Archaeological Science. 86: 101–122. Bibcode:2017JArSc..86..101R. doi:10.1016/j.jas.2017.07.001.
19. Browne, Malcolm W. (9 December 1997). "Ice Cap Shows Ancient Mines Polluted the Globe (Published 1997)". The New York Times. ISSN   0362-4331 . Retrieved 23 February 2021.
20. Loveluck, Christopher P.; McCormick, Michael; Spaulding, Nicole E.; Clifford, Heather; Handley, Michael J.; Hartman, Laura; Hoffmann, Helene; Korotkikh, Elena V.; Kurbatov, Andrei V.; More, Alexander F.; Sneed, Sharon B. (December 2018). "Alpine ice-core evidence for the transformation of the European monetary system, AD 640–670". Antiquity. 92 (366): 1571–1585. doi: 10.15184/aqy.2018.110 . ISSN   0003-598X.
21. Akanuma, Hideo (2008). "The significance of Early Bronze Age iron objects from Kaman-Kalehöyük, Turkey" (PDF). Anatolian Archaeological Studies. 17. Tokyo: Japanese Institute of Anatolian Archaeology: 313–320.
22. Souckova-Siegolová, J. (2001). "Treatment and usage of iron in the Hittite empire in the 2nd millennium BC". Mediterranean Archaeology. 14: 189–93..
23. Peter Schmidt, Donald H. Avery. Complex Iron Smelting and Prehistoric Culture in Tanzania Archived 9 April 2010 at the Wayback Machine , Science 22 September 1978: Vol. 201. no. 4361, pp. 1085–1089
24. Veldhuijzen, Xander; Rehren, Thilo (2007). "Slags and the city: early iron production at Tell Hammeh". In La Niece, Susan; Hook, Duncan; Craddock, Paul (eds.). Metals and Mines: Studies in Archaeometallurgy. Archetype, British Museum. pp. 189–201. ISBN   978-1904982197. OCLC   174131337.
25. Hutchinson, T.C.; Whitby, L.M. (1974). "Heavy-metal pollution in the Sudbury mining and smelting region of Canada, I. Soil and vegetation contamination by nickel, copper, and other metals". Environmental Conservation. 1 (2): 123–13 2. Bibcode:1974EnvCo...1..123H. doi:10.1017/S0376892900004240. ISSN   1469-4387. S2CID   86686979.
26. Likens, Gene E.; Wright, Richard F.; Galloway, James N.; Butler, Thomas J. (1979). "Acid Rain". Scientific American. 241 (4): 43–51. Bibcode:1979SciAm.241d..43L. doi:10.1038/scientificamerican1079-43. JSTOR   24965312.
27. Wiklund, Johan A.; Kirk, Jane L.; Muir, Derek C.G.; Evans, Marlene; Yang, Fan; Keating, Jonathan; Parsons, Matthew T. (15 May 2017). "Anthropogenic mercury deposition in Flin Flon Manitoba and the Experimental Lakes Area Ontario (Canada): A multi-lake sediment core reconstruction". Science of the Total Environment. 586: 685–695. Bibcode:2017ScTEn.586..685W. doi:10.1016/j.scitotenv.2017.02.046. ISSN   0048-9697. PMID   28238379.
28. Naylor, Jonathon (21 February 2017). "When the smoke stopped: the shutdown of the Flin Flon smelter". Flin Flon Reminder. Retrieved 6 July 2020.
29. "Primary Aluminum Reduction Industry". National Emission Standards for Hazardous Air Pollutants (NESHAP). Washington, D.C.: U.S. Environmental Protection Agency (EPA). 25 May 2022.
30. "Primary Copper Smelting". NESHAP. EPA. 1 February 2022.
31. "Primary Lead Processing". NESHAP. EPA. 7 April 2022.
32. Jeong, H.; Choi, J. Y.; Ra, K. (2021). "Potentially toxic elements pollution in road deposited sediments around the active smelting industry of Korea". Scientific Reports. 11 (1): 7238. doi:10.1038/s41598-021-86698-x. PMC   8012626 . PMID   33790361.
33. Jeong, Hyeryeong; Choi, Jin Young; Ra, Kongtae (2021). "Heavy Metal Pollution Assessment in Stream Sediments from Urban and Different Types of Industrial Areas in South Korea". Soil and Sediment Contamination. 30 (7): 804–818. Bibcode:2021SSCIJ..30..804J. doi:10.1080/15320383.2021.1893646. S2CID   233818266.
34. "7. Wastewater Characterization". Development Document for Final Effluent Limitations Guidelines and Standards for the Iron and Steel Manufacturing Point Source Category (Report). EPA. 2002. pp. 7–1ff. EPA 821-R-02-004.
35. Development Document for Effluent Limitations Guidelines, New Source Performance Standards and Pretreatment Standards for the Iron and Steel Manufacturing Point Source Category; Vol. I (Report). EPA. May 1982. pp. 177–216. EPA 440/1-82/024a.
36. EPA (1984). "Nonferrous Metals Manufacturing Point Source Category." Code of Federal Regulations, 40 CFR 421 .
37. Development Document for Effluent Limitations Guidelines and Standards for the Nonferrous Metals Manufacturing Point Source Category; Volume IV (Report). EPA. May 1989. pp. 1711–1739. EPA 440/1-89/019.4.
38. Sjöstrand, Torgny (12 January 1947). "Changes in the Respiratory Organs of Workmen at an Ore Smelting Works1". Acta Medica Scandinavica. 128 (S196): 687–699. doi:10.1111/j.0954-6820.1947.tb14704.x. ISSN   0954-6820.
39. "Clean Air Act Standards and Guidelines for the Metals Production Industry". EPA. 1 June 2021.
40. "Iron and Steel Manufacturing Effluent Guidelines". EPA. 13 July 2021.
41. "Nonferrous Metals Manufacturing Effluent Guidelines". EPA. 13 July 2021.

Bibliography

• Pleiner, R. (2000) Iron in Archaeology. The European Bloomery Smelters, Praha, Archeologický Ústav Av Cr.
• Veldhuijzen, H.A. (2005) Technical Ceramics in Early Iron Smelting. The Role of Ceramics in the Early First Millennium Bc Iron Production at Tell Hammeh (Az-Zarqa), Jordan. In: Prudêncio, I.Dias, I. and Waerenborgh, J.C. (Eds.) Understanding People through Their Pottery; Proceedings of the 7th European Meeting on Ancient Ceramics (Emac '03). Lisboa, Instituto Português de Arqueologia (IPA).
• Veldhuijzen, H.A. and Rehren, Th. (2006) Iron Smelting Slag Formation at Tell Hammeh (Az-Zarqa), Jordan. In: Pérez-Arantegui, J. (Ed.) Proceedings of the 34th International Symposium on Archaeometry, Zaragoza, 3–7 May 2004. Zaragoza, Institución «Fernando el Católico» (C.S.I.C.) Excma. Diputación de Zaragoza.