ELSEVIER 8 TIONAL (ODETERIORATION & (ODEGRADATION International Biodsteioaton & Bindoyratation 48 (2001) 5-11 THE BIODETERIORATION OF MATERIALS —AN APPRAISAL HJ. HUECK Centraal Laboratorium TNO, Delft, The Netherlands Summary The biodeterioration of materials is one of the oldest problems of mankind, as testified by Homer, the pyramids, the Bible and other venerable sources of knowledge. Empirical knowledge of the phenomenon and of ways to cope with it are common knowledge. As a branch of science, however, the study of the biodeterioration of materials is still in its infancy. Though the deteriora- tion of wood as a branch of phytopathology and the control of fouling on ships’ hulls as a branch of technology dated already from the 19th century it is only in the last few decades that a more general appreciation of the problem has come to the fore. It is worthwhile to consider the biodeterioration of materials, rooted in applied biology and technology of materials, as to its place among the sciences, ‘A comparison of the concepts ‘biodegradation’ and ‘biodeterioration™ leads to a consideration of the manifold relations between organisms and materials and to a systematization of these fields of science. By inverting the problem and posing the question, ‘Why do not all materials suffer from diodeterioration?’ its limits may be appreciated. INTRODUCTION A modern zoologist’s view on the nature of Man holds that he is a naked ape and essentially a killer, using tools for his hunting techniques (Morris, 1967). Even Australopithecus, a most probable forebear of Homo sapiens, living 1 to 2million years ago must have used tools according to the Oldoway-diggings. ‘As raw materials for these tools, wood, bone, ivory, horn and stone may have been used, Because he was naked, it may be supposed that hides, bark and fibrous materials were used for a covering, which materials gradually developed into leather and natural textile fibres. We do know that wood, leather and cellulosic fibres are easily attacked by micro-organisms while insects can and do damage horn, wool and also wood. It may be inferred, therefore, that the biodeterioration of materials, the subject we are studying today inthis symposium, must have been one of the earliest troubles of mankind. Taking this for granted, it is not surprising that in early written history we find evidence of deterioration-phenomena apparently important enough to be recorded. Herfs (1936) has drawn the attention to a verse in the Odyssey, apparently referring to larvae of carpet beetles (Song 21, verse 395). It reads (in trans- lation by E. V. Rieu), “Odysseus now had the bow in kis hands and was twisting it about, testing it this way and that, for fear that the worms might have eaten into the horn in the long absence of its owner” (964.8305I018 se foot mater 1969 Published by Psevoe Skene PU SoH 8305101 UG T-DMilenio issue: International Biodeeronaion & Bidegradaion 48 (200) 5 The Biodeterioration of Materials—An Appraisal 7 The elder Pliny, in his Narural History, Book XI, gives, in chapter 38, description of wood being attacked by insects, and in chapter 4 refersto math larvae living in wool. In chapter 21, the wax-moth is described as a vile animal eating wax. The full citations, in a translation by Rackham (1940) are: Book XI chapter XXI (On enemies of bees) “Even the moth, that cowardly and ignoble creature that flutters up to lamps when they are lit, bring disaster, and not in one way only, for it both devours the comb itself and leaves excrement from which gruts are pro- duced; also wherever it walks it weaves 2 covering of cobwebs chiefly made from the down on its wings. Moreover moths are born in the wood itself that specially attack the combs.” Book XI chapter XXXVII (On modes of generation of insects). “In this way some creatures are generated from rain in the earth and some even in wood. For not only is the goatmoth caterpillar born in wood, but also the horse-fly springs from wood, and other creatures wherever there is excessive damp, just as tape-worms thirty feet in length, sometimes even more, grow inside a human being.” Book XI chapter XLI (On clothes moths). “Similarly, dust in woollens and in clothes breeds moths, especially if a spider is shut up with them; for being thirsty and sucking up all the moisture it increases the dryness. This is also noticed in papers. There is a kind of moths that carry their own coats in the same Way as snails; but the moths have visible feet.” Insects, being visible with the naked eye, were easily associated with the damage they did, though it is clear from Pliny that the acceptance of organisms as the cause of the damage is not self-evident. Spontaneous generation of organisms from decaying materials has long been an interesting subject for discussion among scientists. It is all the more remarkable in this respect that Plutarch (cit. Laidlaw, 1952) already held the fouling of ships’ hulls was directly responsible for the slowing down of ships and not the small fish, Echeneis, the ‘ship-stopper’ which is associated in Mediterranean regions with fouling. Though less easy of interpretation, mention of damage to materials by micro-organisms also can be found in ancient writings. The Bible states, Leviticus 13: 47-49 (King James version), “The garment also, that the plague of Ieprosie is in, whether it bee a woollen garment, or a linnen garment, whether it bee in the warpe, or woofe of linnen or of woollen, whether in a skin, or in anything made of skinne: And ifthe plague be greenish or reddish in the garment, or in the skin, either in the warpe, or in the woofe, or in anything, of skinne, it is a plague of leprosie, and shall be shewed unto the Priest’ ‘A more direct evidence of early occurrence of deterioration by micro- organisms was pointed out by Bunker (1946). During the excavation of Tut, Anch Amon’s tomb the paint on the walls of the inner chamber was found to bbe damaged by mildew. The shrine dates from about 1350 BC. An interesting peculiarity was that the mold had apparently avoided spots where a yellow pigment had been employed, which turned out to contain arsenic sulphide. ‘One wonders whether empirical means of preventing the biodeterioration of materials were already known at that time, Laidlaw (1952) quotes evidence that the Phoenicians and Carthagenians used pitch and possibly copperMilouniam sve: Intemational tneterionation & Biodegradation 48 (2001) 5-11 8 Fundamentals of Biodeterioration sheathing to prevent fouling, Wax, tar and asphaltum are also mentioned in this respect. In a description of the construction of the hanging gardens of Babylon (Alleau, 1967) they are said to have been constructed with layers of asphaltum with reed and cemented brick, separated from the garden soil by a thin sheet of lead in order ‘to guard it against moisture’. From these quotations it is clear that many elements of the science of biodeterioration of materials, as we sec it today, were already present or known in the days. Of course, progress could be made only after recognition of the role of organisms, especially in the processes of rotting and fermentation. Indeed, in the age of the great microscopists interesting references are made to micro-organisms on common commodities. In his first letter to the Royal Academy, Anthonie yan Leeuwenhoek (1676) begins with a discussion of mold on leather in which he diflers in view with Robert Hooke, who has given the first microscopic picture of a mold in his Micrographia, Scheme XII, page 125 (1665). A truly scientific approach, however, became only possible in the era of Pasteur and Koch, who established the cause-effect relationship between micro-organismsand disease or putrefaction beyond reasonabledoubt. Especially the knowledge of wood decay grew rapidly, perhaps benefiting from the rise of phytopathology as a science. In the field of textiles Thaysen and Bunker (1927) and Burgess (1928) gave evidence of a growing awareness of the problem. It was not, however, until the Second World War that the extent of the problem became clear to a wider public. The war experience has been compiled by Siu (1951) and by Greathouse and Wessel (1954) in their well-known books which leave no doubt about the amazingly large number of commodities that can be attacked by a wide array of organisms, giving rise to considerable economic losses. Hueck-v.d. Plas (1965) estimates these losses in the more important industrial countries at about one billion dollars annually, From the summary of Greathouse and Wessel it is clear that the bio- deterioration of materials relies heavily on empirical knowledge, though their unifying treatment of the deterioration of different materials must be praised as being important for the development of biodeterioration into a special branch of science. In 1938, Schulze pleaded for the establishment of ‘Werk- stoffbiologie’, i. ‘Materials-biology’ or ‘Hylobiology” as a special branch of biology. I have tried to present a systematic approach to this subject (Hueck, 1965, 1967), developing the biodeterioration of materials as a special branch of hylobiology and will try to summarize this in this introductory lecture. ancient THE NATURE OF BIODETERIORATION OF MATERIALS, According to the definition given in Webster's New International Dictionary (1949), a material is ‘the substance or matter of which anything is made or to be made’. Apparently it is human use, or intended use, which turns ‘matter’ into ‘material’, Between organisms and materials many relations exist. It is appropriate to consider these relations with reference to their usefulness to humans, materials being what they are, viz. an anthropocentric notion derived from the neutral word ‘matter’ This being granted we may consider organisms and matter both as neutral entities; but their interrelationships may be either harmful or beneficial, fromMillenium Ieue:tnernaiona Beterionaton & Biedegradation #8 (2001) 5-12 The Biodeterioration of Materials—An Appraisal 9 the point of view of man, We can then draw up the following scheme showing relations with neighbouring fields of science. ORGANISMS noxious useful toxic pest control toxicology matter, non-toxic biodeterioration biosynthesis From the human viewpoint, not all breakdown of materials by organisms is undesirable. The biodegradability of detergents, for example, is a highly desirable feature of these substances. Depending on the circumstances, one and the same process may be called harmful or beneficial. When mineral oil ‘was spilled from the Torrey Canyon on to the sea, the biodegradation of it was certainly welcome, if the same process, however, occurs in fuel or cooling fluids we call it “biodeterioration’. Thus we arrive at the following definition, of biodeterioration of materials as ‘any undesirable change in the properties of a material caused by the vital activities of organisms’ {In the foregoing, we have considered biodeterioration as being a process, linking cause and effect. As such, it has much in common with infectious diseases as we know them in human- and plant-pathology. A detailed com- parison of pathology and biodeterioration might lead us too far, although interesting parallels can be found (Hueck, 1965). Biodeterioration and pathology of organisms differ in that they describe phenomena occurring in systems of a different degree of complexity. Apart from this, qualitative differences exist due to the fact that materials as a substrate for biodeteriora- tion, are non-living matter, in contrast to living organisms which react ‘actively’ to the noxious disease agent. It depends, however, on the philo- sophical outlook of the investigator, whether he will rate such reactions in chemical or physical terms only, or adds a metaphysical plus, Table I SYSTEMATICS OF PATHOLOGY AND BIODETERIORATION Question Pathology ‘Biodeterioration What phenomena can be Symptomatology, Symptomatology, observed” including diagnosis including diagnosis What is the cause of the E phenomena? Slory Etiology “How do the phenomena Pathogens develop? Under what external ‘Epidemiology ‘Ecology circumstances does the ‘process occur? “How ean the process be Medicine Control of biodeterioration checked? (3) curative {@) curative control (rare) {(&)preventive —_(@) prevention of biodeteriorationMillennium Iau: International Bladterioation & Blodegnaation 48 2001) 5-11 10 Fundamentals of Biodeterioration At any rate, all essential features of disease, viz. the impairment of normal function due to a process released by the interaction of noxious agent and subject may be taken to be present in principle (although it may be in a very simple form) in all cases of biodeterioration of materials. This being so, it may be worthwhile to consider whether the basic questions, which have led to such fertile systematic investigations of disease, are valid also in biodeteriora- tion. In my opinion this is possible (Table 1), Not all these aspects of biodeterioration have, as yet, received the same attention, This will have to be remedied if the desire is to advance from mere empiricism to truly scientific approach in the study of biodeterioration THE EXTENT OF BIODETERIORATION Biodcterioration, as defined, covers a wide field of study, The popular notion that biodeterioration is equal to rotting or mildewing is certainly not true. There is no reason why mechanical damage and functional impairment of materials should not be included: they are valid manifestations of the inter- action of organisms and materials. A simple classification of biodeterioration processes is the following (Table U0). Table IL CLASSIFICATION OF BIODETERIORATION PROCESSES Process Examples 1, The material is damaged mechanically. 1, Rodent and insect damage to non- rutvitive materials 2, The material is attacked chemically. 2. (a) By organisms which use the material "" (a) Breakdown of cellulose by micro- as a food (assimilation). organisms. Damage to wool by cloth moths. (b) By excretion products or vital (8) Corrosion of iron by sulphate reducing phenomena other than nutrition bacteria (dissimilarion). Damage to calcareous rocks by lichens 3, The function of the material is impaired 3. Fouling of ships’ hulls by barnacles and by the presence of organisms. algae. Clogging of pipelines by iron bacteria, In viewing this broad approach to the problem, one wonders whether perhaps all materials su(fer from biotic attack at one time or another. Though, indeed, the range of materials suffering from such attack is very wide, wider than the layman suspects, the field covered by biodeterioration is not un- bounded. Alexander (1965) has contributed much to an appreciation of microbiological degradation of chemical compounds by inverting the question and asking why are not all organic compounds degraded by micro-organisms, Much of his argument is relevant in the case of the interrelation of organisms and materials, It must be recalled that a material is not a thing per se, but becomes a material only by human use, which means that the material must be considered together with its temporary environment. Alexander's categories of resistance to biodegradation can be adapted to our problem as follows:=Milerninm tse: International Bindteiortion & Bindgradaron 48 (2001) 5-11 The Biodeterioration of Materials—An Appraisal n 1. The material is inaccessible to organisms—This is a phenomenon of com- mon occurrence in technical structures. Cables fall in this category and termite proofing of building relies on it. Prevention of deterioration by canning is a practical application, 2. An essential factor for growth of organisms is absent. —Particulacly if water is absent, materials may appear to be rather resistant to biodeterioration: every housewife knows that dampness induces rotting. Yet it is not always appreciated sufficiently when materials such as rubber possess, in themselves, hydrophobic qualities. It is well-known that hydrocarbons are essentially biodegradable, yet the higher paraffins are often thought virtually inert. Though the slow degradation by elimination of endgroups may be one part of the story, the hydrophobic character of such commodities certainly is another. As this is often not realized by technologists, it frequently gives the impression that materials are being dealt with which in themselves are in- vulnerable and hence there may be some surprise when this turns out to be a fallacy. 3. The environment is toxic—Certain types of Wood possess toxic inhibitors for insects or fungi, Artificially induced toxicity is the most popular means for the prevention of biodeterioration, as we all know. 4, The damaging agent is inactivated.—Alexander quotes the adsorption of enzymes to clay minerals, but more likely is the occurrence of environmental factors such as heat, cold or drought which prevent biodeterioration by inactivating the causal organisms. Wool kept at temperatures below 1 practically invulnerable to insect damage; textiles in the dry Egyptian desert have withstood the ages; and mammoths have been preserved in the frozen Siberian soil 5, The chemical or physical composition of the material is unsuitable for biotic aitack —Cellulose is biodegradable whereas acetylated cellulose is not. Straight hydrocarbons are biodegradable, branched ones are not. Polyethy- lene with the same hydrocarbon chains untit now has not yielded to attack by micro-organisms. On the other hand, it is not resistant to mechanical damage by rodents, although a diameter > 22 mm may prevent them from gnawing (Neuhaus, 1957). In this category of invulnerability we have still much to learn 6. When no organism exists which might attack the material in question. — Alexander postulates the absence of appropriate enzymes. Admittedly it is rather obvious that, if no organism exists that can attack a certain material, the material, by definition, is not liable to biodeterioration. As biodeteriora- tion essentially is an interaction between material and organism, it has no practical implication to attribute the absence of a relation to such a negative factor which cannot be proved if taken in an absolute sense Relatively speaking, however, we must admit the possibility. It is by virtue of a very special enzyme system that clothes-moths and carpet beetles can damage wool. Suppose these insects were to die out, then wool would become fully invulnerable to insect attack of this kind. It is futile to attribute this cither to the many sulphur bonds in keratin, making it inert to proteolysis like other proteins, or to the absence of an appropriate enzyme. For all practical purposes, therefore, this category is identical with the foregoing one which supports Alexander's speculations showing that we must be careful making absolute statements about the vulnerability or inertiness of materials in relation to organisms.Millom tse: International Biodeterianation & Biokegradation 48 (2001) 5-1 R Fundamentals of Biodeterioration Let me conclude this survey of the biodeterioration of materials by stating that apparently we are only at the beginning of the exploration of a vast field of study where many aspects of the problem have hitherto received only scant attention. In years to come it will be an attractive task to fill in thegaps inour knowledge. REFERENCES ALEXANDER, M. (1965), “Biodegradation: Problems of molecular recalcitrance ‘and microbial fallibility."" Advances in Applied Microbiology, 7, 35-80. ALLEAU, R. (1967). "Geschiedenis van de grote bouwwerken” (rad. “Histoire des Grands batiments”). Amsterdam: Scheltema & Holkema N.V. BUNKER, H. J. (1946). “Moulds and bacteria in paint, from the point of view of @ microbiologist." J. Oil & Colour Chem. Assoe., 29, 201-214. BURGESS, R. (1928). “A contribution to the study of the microbiology of wool.” J. Text. Insta, 19, T31S. GREATHOUSE, G. A., and WESSEL, C. J. (1954). Deterioration of Materials New York: Reinhold Publ. Co. HERFS, A. (1936). “Ockologisch-physiologische Studién an Anthrenus fasciatus”. Zoologica, 34, Heft 90. HUECK-VAN DER PLAS, E. H. (1965). “Cooperative:research in biodeteriora- tion.” Int. Biodet, Bull, 1-7 HUECK, H. J. (1965). “The biodeterioration of materials as a part of hylobiology.” Material und Organismen, Vy 5-34. HUECK, H. J. (1967). “Some aspects of biodeterioration research in the Nether- lands.” TNO-Niews (the Hague, Netherlands), 22, 243-247, LAIDLAW, F. B. (1952). “The history of the prevention of fouling” in Marine Fouling and its Prevention edited by Woods Hole Oceanographic Institution. U.S, ‘Naval Institute, Annapolis, Maryland. LEEUWENHOEK, ANTONIE VAN (1676). Alle de brieven van Antonie van Leeuwenhoek. Uitgegeven door een Commissie van Nederlandsche Geleerden. ‘Amsterdam (1939, 1941), LITTRE, H. E. (1848). Histoire Naturelle de Plene, Paris: (Eds.) Dubochet, Le Chevalier & Cie. MORRIS, D. (1967). The Naked Ape, a Zoologist’s Study of the Human Animal. London: Jonathan Cape. SCHULZE, B. (1938). “Das Arbeitsgebiet Werkstoff-Biologie.” Angewandte Botanik, 20, 381-387. SIU, R. G. H. (1951). Microbial Decomposition of Cellulose, New York: Reinhold Publ. Co. THAYSEN, A. C., and BUNKER, H. J. (1927). The Microbiology of Cellulose, Hemicellulases, Pectin and Gums. Oxford University Press.