Environmental Pollution 129 (2004) 341–343 www.elsevier.com/locate/envpol Invited Paper Heavy metals—geochemical bogey men? Mark E. Hodson* Department of Soil Science, School of Human and Environmental Sciences, University of Reading, Reading RG6 6DW, UK Received 30 October 2003; accepted 10 November 2003 ‘‘Capsule’’: Serveral alternatives are presented for poorly defined term ‘‘heavy metals’’. ‘‘When I use a word,’’ Humpty Dumpty said in rather a scornful tone, ‘‘it means just what I choose it to mean—neither more nor less.’’ Lewis Carroll, Alice through the looking glass. Abstract Heavy metals is a loose term usually used to indicate environmentally ‘‘bad’’ metals. It is poorly defined with a multitude of often contradictory definitions based on density, atomic weight, atomic number or other properties of the elements or their compounds. Alternative, scientifically rigorous definitions exist for subgroups of metals and should be used instead. # 2003 Elsevier Ltd. All rights reserved. Keywords: Heavy metals; Pollution; Environment; Terminology 1. Introduction Heavy metals is a popular term in the environmental literature. Web of Science, a Web based reference tool, records 293 articles with the term ‘‘Heavy metal’’ in the title published in 2002, 308 in 2001 and 270 in 2000. This tails off to 107 articles in 1981 when the coverage of Web of Science is less good. But what are heavy metals and is the term used consistently or, as in the case of Lewis Carroll’s Humpty Dumpty does the word mean what we, rather than someone else, choose it to mean at any particular moment? Use of the word heavy metals calls to mind the case of the man who has heard much about elephants but never seen one—he can’t describe an elephant, but would know one when he saw it. The difference is that whilst most of us would quite like to see an elephant the majority view is that heavy metals are synonymous with pollution and toxicity. Heavy metals are regarded as bogey men, responsible for all manner of evils in the environmental world. Thus * Tel.: +44-118-378-6974; fax: +44-118-378-6660. E-mail address: [email protected] (M.E. Hodson). 0269-7491/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2003.11.003 whenever I see a paper titled ‘‘Distribution of heavy metals in. . ...’’, ‘‘Effects of heavy metals on. . ..’’ or ‘‘Uptake of heavy metals by. . ..’’ I know that I am in for a paper on pollution, environmental impact or anthropogenic influences. But, just like bogey men, do heavy metals really exist? 2. What are heavy metals? The above preamble has a serious point. In 2002, John Duffus published an excellent article ‘‘Heavy metals—a meaningless term?’’ in Pure and Applied Chemistry which is an official IUPAC journal (Duffus, 2002). IUPAC is the International Union of Pure and Applied Chemistry and amongst other things ‘‘IUPAC has long been recognized as the world authority on chemical nomenclature, terminology, standardized methods for measurement, atomic weights and many other critically evaluated data’’ (IUPAC, 2003). In terms of chemical nomenclature, what IUPAC says goes. In his article, Duffus (2002) acknowledged that some form of classification beyond ‘‘metal’’ is useful to science, rather like the group classifications ‘‘alkanes’’ and ‘‘alkynes’’ etc. in the field of organic chemistry. 342 M.E. Hodson / Environmental Pollution 129 (2004) 341–343 However, he argues heavy metals is an ill defined term that means many different things to many different people. There are a host of different definitions of the term in the literature many of which are contradictory. You may know what you mean when you talk about a heavy metal but someone else may mean something entirely different. At the end of his paper Duffus provides a variety of other metal/element classification schemes that are chemically defensible and which illustrate that the heavy metal apologists’ main argument ‘‘There are no alternative terms’’ is simply untrue. What follows is a brief summary of the Duffus paper. I would recommend that (1) people stop using the term heavy metal in their papers and (2) people read the article by Duffus (2002) and then act upon it. According to the Oxford English Dictionary the oldest scientific use of the term heavy metal is to be found in the 3rd Danish edition of Bjerrum’s Inorganic Chemistry (Bjerrum, 1936) where heavy metals are described as those metals with an elemental density above 7 g cm 3. Before this time the term was used to mean ‘‘guns or shot of large size’’ or ‘‘great ability’’ (Ogilvie, 1884; Williams, 1930). From 1936 onwards heavy metals are referred to within chemistry textbooks and articles. However, the definition of the phrase varies wildly. Interested readers are referred to Duffus’ 2002 article for a whole string of definitions which are summarised in Table 1. As Duffus points out, the various definitions are not internally consistent or based on any obvious logical scheme. For example, on the basis of some of the definitions using atomic weight as a marker Mg would be classified as a heavy metal; however some definitions that use atomic weight as a marker specifically exclude the alkaline earth metals and therefore would not classify Mg as a heavy metal. Similarly, definitions based on atomic number would include Sc as a heavy metal and yet the density of Sc is 3 g cm 3 (at an unspecified temperature and pressure: Sharp, 1990) excluding it from many density-based definitions. Duffus (2002) also makes the point that even if one were to accept heavy metals as a valid term, its use in the literature as a synonym for ‘‘bad’’ metals is unjustified given that toxicity is a function of the chemical properties of the element/compound and the biological properties of the organism at risk. Also as Paracelsus (1493– 1541) points out, toxicity is always dependent on dose. Given all of the above there is no a priori reason to assume that the presence of a heavy metal will cause harm or is a bad thing. To illustrate this point Duffus quotes two examples in which the same element may be present in either a toxic or relatively non-toxic form— tin (relatively non-toxic) and tributyltin (highly toxic to shell fish) (WHO, 1980) and chromium in stainless steal (relatively non-toxic) and the chromate ion that has been associated with causing lung cancer (relatively toxic) (WHO, 1988). Similarly much work on the in situ remediation of heavy metal contaminated soils seeks to convert the metals into inert, non-toxic forms (e.g. much work has been carried out investigating the conversion of lead compounds into lead phosphates: Cotter-Howells and Caporn, 1996; Hodson et al., 2001, 2000; Laperche et al., 1997; Ma et al., 1994; Xu et al., 1994). Incidentally the above is a good reason for not adopting potentially toxic metal/element as a heavy metal alternative. All metals/elements are toxic in certain forms and in sufficiently high doses. 3. There is an alternative Many heavy metal apologists amongst the environmental science community defend their use of the term Table 1 Range of definitions for the term heavy metals (summarised from Duffus, 2002) Property forming basis of definition Range of values characterising a ‘‘heavy metal’’ Metal density Atomic weight 3.5–5 g cm 3, >4 g cm 3, >4.5 g cm 3, >5 g cm 3, 55 g cm 3, 55 g cm 3, >6 g cm 3, >7 g cm 3 ‘‘high’’, >22.99 (Na, i.e. heavy metals are from Mg onwards), >40 (Ca, i.e. heavy metals are from Sc onwards) Some definitions also specifically include (e.g. common transition metals) or exclude (e.g. alkaline earth metals, lanthanides and actinides) groups of elements and also add caveats such as ‘‘can damage living things at low concentrations’’, ‘‘cannot be processed by living organisms’’, ‘‘are toxic’’ ‘‘moderate to high’’, ‘‘high’’, > 20 (Ca), the range 21 (Sc)–92 (U) Atomic number Other definitions Elements in the block defined by Ti, Hf, As and Bi plus Se and Te Very dense alloys used for radiation screening or balancing purposes Intermetallic compound of Fe and Sn Pb, Zn and alkaline earth metals that react with fatty acids to form soaps Any metals that react with dithizone (C6H5N) Elements commonly used in industry and generically toxic to animals and to aerobic and anaerobic processes Pb, Cd, Hg and some other elements which are relatively toxic in nature. . .also sometimes refers to compounds containing these elements M.E. Hodson / Environmental Pollution 129 (2004) 341–343 with the statement ‘‘I know it is a terrible term but everyone knows what it means and there aren’t any alternatives’’. Having laid the lie that everyone knows what heavy metal means (they may do but it means something different to every one of us), Duffus (2002) proceeds to detail some of the alternatives for categorising metals. The alternatives he suggests are well established in the literature and are based on scientifically defensible chemical principles. There is absolutely no reason why they should not be used. The best established chemically-based classification of metals, and all elements, is the periodic table. Phipps (1981) discussed the biologically significant properties of s-, p-, d- and f-block elements. d-block elements are particularly important in enzymes, whilst higher atomic number p-block elements bind strongly to sulphur, often leading to a toxic effect. An alternative classification was suggested by Lewis (1923), and further developed by authors such as Nieboer and Richardson (1980). This classification applies to ions and places them into either Class A/hard, Class B/soft, or Borderline/Intermediate class ions. The scheme is not absolute but there is general agreement between authors as to which class different ions belong. Typically Class A metal ions preferably form ionic bonds and are easily displaced and mobile, whilst Class B form covalent bonds, show strong affinity to soft ligands such as sulphide or sulphur donors, and tend to accumulate in organisms with resultant toxicity. As Duffus (2002) and Nieboer and Richardson (1980) point out, the differing toxicities of Class A and B metal ions hints at a way of developing a classification of metals that is based on chemical properties and also has biological, toxicological and environmental relevance. These alternatives may seem unfamiliar or nonintuitive to environmental scientists used to the term heavy metals. This is no excuse for not using them! Over time the terms will become normal and accessible. If, on reading this, you still feel that you will have an aversion to using such terms, I suggest you stick to the straight forward term ‘‘metal’’. 4. Conclusion Heavy metals is a poor scientific term and alternatives exist. As scientists we should use them. 343 Acknowledgements I would like to thank John Duffus for giving freely of his time in discussing his paper and Steve Robinson (Soil Science) for commenting on an earlier version of this text. The current contribution was largely written at the Natural History Museum, London, where I am a Scientific Associate and am provided with a desk away from the distractions of University students. References Bjerrum, N., 1936. Bjerrum’s Inorganic Chemistry, 3rd Danish Edition. Heinemann, London. Cotter-Howells, J., Caporn, S., 1996. Remediation of contaminated land by formation of heavy metal phosphates. Ap. Geochem. 11, 335–342. Duffus, J.H., 2002. Heavy metals—a meaningless term? Pure Appl. Chem. 74, 793–807. Available on the IUPAC website at: http:// www.iupac.org/publications/pac/2002/7405/7405x0793.html. Hodson, M.E., Valsami-Jones, E., Cotter- Howells, J.D., Dubbin, W.E., Kemp, A.J., Warren, A., 2001. Effect of bone meal (calcium phosphate) amendments on metal release from contaminated soils— a leaching column study. Environ. Pollut. 112, 233–243. Hodson, M.E., Valsami-Jones, E., Cotter- Howells, J.D., 2000. Bone meal additions as a remediation treatment for metal contaminated soil. Environ. Sci. Technol. 34, 3501–3507. IUPAC, 2003. http://iupac.chemsoc.org/dhtml_home.html (accessed August, 2003). Lewis, G.N., 1923. Valence and the Structure of Molecules. The Chemical Catalogue Company, New York. Laperche, V., Logan, T.J., Gaddam, P., Traina, S.J., 1997. 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