Page 82 - Copper and Bronze in Art: Corrosion, Colorants, Getty Museum Conservation, By David Scott
P. 82

I  BIOLOGICAL  FACTORS  Many artifacts  recovered  from  the  sea
            are  associated with  shipwrecks. At such  sites, marine  life,  algae, rotting timbers, coral, and  so
            on, may strongly influence the local environment of submerged  bronzes;  as a result, such  arti­
            facts may be heavily covered with concretions. The fact that copper is a natural biocide does not
            necessarily  stop copper  alloys from becoming heavily encrusted.
                Microbially influenced corrosion (MIC)  is an important aspect of the environmental attack
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            on  metals,  but it is  seldom  considered n detail. In natural  environments,  bacteria  attach  to
            solids, including metals,  where  they colonize the  surface  and produce  a biofilm. Microorgan­
            isms within the biofilm are capable of producing an environment at the surface  of the object that
            is radically different from the bulk solution in terms of pH, dissolved oxygen, and other organic
            and inorganic species. The sulfate-reducing  bacteria  are  a particularly important group in the
            corrosion of metals, since the production of the sulfide ion is usually damaging to metal surfaces
            and can initiate a number of corrosion events at the metal surface. McNeil and Little  (1992) note
            that in natural environments, various types of bacteria  may grow in conjunction with oxygen-
            using microorganisms  that  can  deplete  the  local environment of oxygen, driving  the  biofilm
            layer toward Eh values  that  are  more electronegative  and providing conditions for the growth
            of sulfate-reducing bacteria. These biofilms may then produce elevated levels of sulfide ions and
            shift pH levels toward the acid regions,  as well  as scavenge for chloride ions to maintain elec-
            troneutrality. Under these conditions, the microbial corrosion of copper, silver, and their alloys
            becomes an important event; this may be applicable both to aqueous environments  and to land
            burials, f microbiological activity is very active at the site.
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                Leidheiser  (1979) pointed out that  copper  concentrations  of 10~ 5  to 10~  molar  stimulate
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            marine bacterial communities in a seawater-agar gel containing 0.5% peptone and  0.1% yeast
            extract. In some cases, these colonies tolerate copper  concentrations  as high  as 10"  molar. It is
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            known that certain fungi  are very resistant  to both high hydrogen-ion concentration  and high
            copper-ion  concentrations;  in particular, Acontium velatum Morgan and  a dark green  organ­
            ism belonging to the Dematiaceae family can happily thrive at pH 0.1 in a medium saturated in
            copper  sulfate.
                A  study by Rogers (i948)  on the  corrosion of copper  pipes in which  sewage effluent  was
            used for  cooling water  showed  that  bacteria  and  molds growing in contact  with  70Cu30Zn
            brass accelerated  corrosion, resulting in the formation of deep pits below the  colonies. Some
            bacteria tolerated high concentrations  of copper  salts, and several nonsporing microorganisms
            withstood copper  concentrations  higher than  100 ppm. One of these was a nonsporing, gram-
            negative rod living in large reddish brown colonies; the microorganism appeared similar to oth­
            ers previously isolated from  seawater. In another  culture, a spore-forming organism  removed
            from  copper  exposed  to infected seawater resisted 2000 ppm of copper. The attack on the brass
            was invariably intercrystalline, and bacterial nutrients  such  as mannitol and asparagine accel­
            erated the rate of attack. Samples of seawater known to produce rapid pitting of brass contained



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