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The nature of cleaning: physical and chemical

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The Nature of Cleaning: Physical and Chemical Aspects of Removing
Dirt, Stains and Corrosion
Gordon Turner-Walker
Department of Cultural Heritagr Conservation
National Yunlin University of Science & Technology

Abstract
Cleaning is one of the basic procedures in conservation. However, there is considerable
misunderstanding about the meaning of “cleaning” and even the nature of “dirt” amongst
museum curators and non-conservators. In its simplest form, dirt can be considered to be
simply “stuff in the wrong place”. For example, soil is good in a farmer’s field but not good on
your silk carpet. “Dirt” may be classified into three broad categories – soiling; staining and
corrosion. Soiling may be considered as solid particulate matter sitting on (or bonded to) the
surface of an object, whereas staining occurs when liquid matter (such as oil, coffee or ink) is
carried into a porous substrate by capillary action, darkening or discolouring the surface.
Corrosion is a special case in which the original composition of the surface is altered by
chemical processes – either external processes or internal processes. Often, “dirty” surfaces are
a combination of two, or all three, of these processes. The cleaning method is usually
determined by the type of dirt but can be again roughly divided into four categories –
mechanical cleaning, wet cleaning, chemical cleaning and chemical modification of the altered
(corroded) surface. In this paper the different kinds of dirt and various alternative cleaning
strategies are described and illustrated by case histories involving ceramics, metals artefacts
and historic bones.

Introduction
The Oxford English Dictionary defines the verb to clean as “to free from dirt, filth, or impurity”.
It goes on to define dirt as “unclean matter, such as (something that) soils any object by
adhering to it”. Wikipedia describes dirt as follows “unclean matter, especially when in contact
with a person's clothes, skin or possessions when they are said to become dirty”. These
definitions are a little too imprecise to be useful in the conservation profession and therefore
conservators must define their terms before any real discussion of different cleaning strategies
and methodologies can take place. Caple (2000) describes cleaning as the removal of soiling
and decay products from the surface of an object. He goes on to stress that soiling in the form
of soil from burial, dust from storage and adhering mud, and grease, oil, dirt, sweat or blood
acquired from use is detrimental to the preservation of cultural objects. Dirt and dust obscure
the surface, soiling on paper, textiles, etc. can act as a food source for microorganisms, and
particulate matter acts as an attractant and reservoir for moisture.
According to Caple (2000) the impulse to clean an object arises from an unconscious idea that
cleanliness is the correct or appropriate state for the human environment. Of course this can
be a hazard in the conservation of ancient cultural objects because of the potential unconscious
impulse to return an object to an assumed pristine state. When we talk about cleaning we most
often think in terms of the surface appearance of an object but when dealing with ancient or
historic objects the question must arise – what is the original surface and can we reveal it? In
some cases the original surface may not longer be there to reveal. On a painted object if the
paint has fallen away then the original surface is irretrievably lost. Alternatively, the chemistry
and structure of the original surface may have been sufficiently altered by degradation
processes (e.g. corrosion of metals or glass) that cleaning will never reveal the appearance the
object may have had in the past. Overcleaning in search of an assumed original surface can
seriously damage a museum object and may also remove valuable historical, scientific or
technical evidence in the process. It is essential that the nature of the “dirt” and the way the
object’s surface and interior have been altered with the passage of time are understood before
any attempt is made to “clean” an object.
Here I propose that there are three broad categories of dirt:

 Soiling, that may be considered as solid particulate matter sitting on the surface of an
object. Soiling includes dust accumulated over time in storage or use. It also
encompasses particulate mineral and other matter that was previously suspended in
liquid (often water but also possibly oil or grease) and hardened by evaporation after
having come into contact with the object. Soiling may be bonded to the surface either
mechanically or via electrostatic attraction, hydrogen bonding or Van der Waal’s forces.
This definition would also describe the intentional application of a paint layer – i.e. a
finely ground mineral pigment suspended in water or a drying oil. Soiling on the other
hand is normally considered as an accidental process.

 Staining occurs when liquid matter is carried into a porous substrate by capillary action,
darkening or discolouring the surface. Again, staining is distinguished from intentional
dyeing by being an accidental event. Staining differs from soiling in that any particulate
matter must generally be very small in order to penetrate the pores of the substrate.
Staining an also be caused by liquids, either because the liquids are themselves
coloured – e.g. ink or coffee – or because the liquid changes colour because of a
chemical reaction with the substrate or due to subsequent degradation of the liquid –
e.g. oxidation and yellowing of an oil or fat.

 Corrosion is a general term that can describe alteration and degradation of the original
composition of the surface, either by external or internal chemical processes. Corrosion
is often used to describe the degradation of inorganic materials such as metal, glass or
stone. In the corrosion of metals water, oxygen or other corrosive gasses react with
the surface, which is transformed from a metallic state to a mineral, usually an oxide,
carbonate or sulphate – although sulphides may be produced by reaction with
atmospheric H2S. Corrosion may take place above ground or within the soil for an
archaeological object and the thickness of the corrosion layer will depend upon the
environment as well as the type of metals involved.

Corrosion usually involves the migration of charged ions into and out of the metal
surface. As a result, the outer layers of the object are transformed into an oxide while
the surface becomes covered with a mixed layer of corrosion products depending upon
the environment. These transformations are necessarily accompanied by significant
changes in volume. Thus, the internal corrosion becomes more porous but may also be
distorted by blisters and pits. If the corrosion takes place in the soil then the external
corrosion incorporates soil, grit and any other material that is in close proximity to the
corroding metal. The extent of the resulting concreted mass depends upon the type of
metal – in bronzes the corrosion crust may be quite thin and the surface of the object
may be quite obvious. In the case of ferrous metals the corrosion crust may be several
millimetres thick and the shape of the object may be totally obscured – requiring X-
rays to reveal the form and identity of the artefact hidden within (Lang & Middleton
2005; Turner-Walker 2008). Cleaning such an object involves considerable judgement
and care since the original surface is represented by the interface between the internal
and external corrosion, both of which are considerably more fragile than the underlying
un-corroded metal.

The Nature of Cleaning

For the purposes of this discussion I propose that there are four broad categories of cleaning.
Although in most conservation work any cleaning is really a combination of one or more
methods:

 Mechanical cleaning is the term used when foreign matter or corrosion is physically
removed from the surface of an object using an external force. There is no
requirement that a machine is used and most mechanical cleaning is done by hand
using small tools with no moving parts. The simplest act of mechanical cleaning is the
removal of superficial dust or particulate matter using a soft, dry cloth. No chemical
interaction takes place between the cloth and the object’s surface, nor between the
 cloth and the particulate matter. Table 1 shows that there are many different ways of
applying an external force to remove unwanted surface contamination and some are
more gentle or aggressive than others (Turner-Walker 2008).

Table 1: Methods of mechanical cleaning ranked by increasing energy input.

(Methods in bold are described in the case histories)

Method Tools
Air movement Rubber bulb
Breath
Vacuum cleaner
Compressed air jet
Brushing Natural bristle (watercolour brush)
Nylon bristle
Glass bristle brush
Brass wire brush
Steel wire brush
Peeling/Pulling Adhesive tapes
Latex poultice

 INCREASING ENERGY INPUT 

Rubbing/Polishing Cotton swabs
Cotton swabs with a polishing compound
Soft pencil eraser
Hard pencil eraser
Scraping/Scratching Bamboo sticks
Needle Probe
Scalpel
Cutting Scalpel
Abrading/Grinding Polishing compounds
Sandpaper
Rotary grindstone
Thermal shock Laser ablation
Impact Air-abrasion
Vibrotool
Solid CO2 blasting
Sandblasting
Hammer & chisel

 Wet cleaning, which involves the use of a liquid “wetting agent” to dislodge soiling
from a porous or non-porous substrate. Wet cleaning of a surface is usually done in
combination with an absorbent swab into which the “dirty” liquid is drawn by capillary
attraction. Alternatively it can be “washed” in an excess of water, as in the wet-
cleaning of textiles. Wet cleaning is often undertaken using a soap or detergent to
increase the attractive forces between the particulate matter and the liquid and hold
the dirt in suspension (Hofenk-de Graaff 1968). At other times the liquid may simply
act as a solvent for the dirt or contaminant and therefore the properties of the wetting
agent – e.g. polar solvent, non-polar solvent – are selected according to the nature of
the material to be dissolved (Rice 1964). In wet cleaning there is no chemical
interaction between the solvent and either the dirt or the substrate.

 Chemical cleaning is obviously related to wet cleaning but in this case implies a
chemical reaction between the applied liquid (usually water-based) and the dirt to be
removed. This reaction may be obtained quite simply by adjusting the pH of the water
or the reaction may be more sophisticated. A chelating agent such as oxalic acid or
ethylendiaminetetraacetic acid (EDTA) may be used to surround and solubilise
(sequester) specific cations, thus removing them from a compact or porous surface.
Both EDTA and oxalic acid will sequester Fe 3+ ions and are used in removing rust or
iron staining from paper, ceramics, wood and leather, and wrought iron (Selwyn &
Argyropoulos 2005). Watson (1985) also used EDTA in the cleaning and conservation
 of archaeological lead objects. Alternatively, a dissolved species that forms a soluble
complex with an otherwise insoluble contaminant may be used to remove stubborn
stains or corrosion crusts. Sometimes a water-soluble oxidising or reducing agent may
be used to change the oxidation state of a metal corrosion product, thus rendering it
more soluble. Example would include the use of thiourea (Stambolov 1966);
ammonium thiosulphate (Bhowmik 1968); or alkaline dithionite (MacLeod & North 1979)
to remove tarnishing and corrosion from silver, or the use of hydrogen peroxide to
bleach stains out of paper and textiles (Annis & Reagan 1979).

 The chemical or electrochemical modification of the altered (corroded) surface is

sometimes used in the cleaning and consolidation of severely corroded metals. Here
the corrosion products on a metal object are transformed chemically, either by
exposure to a reducing aqueous solution, a reducing gas or plasma, or under the
influence of an external electrical current. Many of these methods have been applied to
the extremely challenging problem of stabilising archaeological iron, either excavated
from land sites or recovered from marine shipwrecks. Treatment of archaeological iron
has a very long history, being notorious for catastrophic post-excavation corrosion and
its instability has generally been attributed to chloride ions trapped within the internal
corrosion products. Thus many treatment regimes have been devised with the aim of
removing these chlorides. Treatments using aqueous solutions of reducing reagents –
e.g. alkaline sulphite produce what are thought to be the following reactions (North &
Pearson 1975, 1977; Burshneva & Smirnova 2010):
2SO32- + O2 » 2SO42-
Fe3+ + SO32- » SO42- + Fe2+
Or in alkaline solutions:
2Fe3+ + SO32- + 6OH- » SO42- + 2Fe(OH)2 (solid)+ H2O
i.e. Fe3+ ions are reduced to Fe2+ ions – a situation which favours the formation of
magnetite Fe3O4 according to the following reaction.
2Fe(OH)2+ + SO32- + Fe(OH)+ + 5OH- » Fe3O4 + SO42+ + 5H2O
For the transformation from chloride-containing oxyhydroxides magnetite to take place,
however, there must be Fe2+ ions already available in the corrosion products.
High temperature, gas phase transformation of unstable chloride-containing corrosion
crusts has a long history in conservation – the first experiments taking place in 1966
(Eriksen & Thegel 1966). The method was developed by Arrhenius et al (1973) and
later Barkman (1977) and North and Pearson (1977). Heavily corroded iron objects are
heated to high temperature (400-1000oC) in a pressure vessel filled with dry hydrogen
gas. This has been principally used for marine cast iron objects but has also seen
success in terrestrial wrought iron. The following reactions (among others) are thought
to occur:
FeOCl + ½ H2 » FeO + HCl
FeO + H2 » Fe + H2O
FeOCl + 2HCl » FeCl2 + H2O
FeCl2 + H2 » Fe + 2HCI
2FeO.OH » Fe2O3 + H2O
Thus, the corrosion products are converted from chemically unstable and mechanically
weak FeOCl and FeO.OH to more compact and stable haematite and metallic iron. Of
course both the external and internal corrosion products will be reduced, so that if
there is a heavy crust of corrosion the final conserved object will no longer have its
original surface profile. Because high temperature reduction of iron objects will
effectively destroy their metallographic and technological evidence, low temperature
methods using gas plasmas have also been explored with limited success (Daniels et al
1979; Daniels 1981; Patscheider & Veprek 1986; Schmidt-Ott & Boissonnas 2002).
 The reduction of metal corrosion to the original metallic state can also be achieved by
driving electrons into the system using an external electric current. This is most often
employed in the reductive consolidation of extremely fragile lead object with finely
detailed surfaces (Schotte & Adriaens 2006; Schotte 2007) Corrosion products can also
be transformed to more stable, compact or aesthetically pleasing forms using chemical
transformations. These methods include the treatment of corroded iron objects with
phosphates or tannates (Farrer et al 1953) or something as simple as the final rinsing
of cleaned lead objects in dilute sulphuric acid to decompose the powdery (and
poisonous) lead carbonates and leave a deposit of highly insoluble lead sulphate on the
surface. The lead sulphate is dark grey and gives an aesthetically pleasing leaden look
to the objects.

Case Studies
The following case studies illustrate several of the cleaning methodologies described above.
The case studies involve three very different classes of materials, metals, ceramics and bone
and all three are drawn from the author’s personal professional experience. In the case of the
whale skeletons discussed in the last case study several different cleaning methods were
tested – some proving to be unsuitable and some to be very successful. To be considered a
successful method any cleaning regime must satisfy several requirements – it must be cheap,
simple, not damage the future integrity of the object, require the minimum of expensive
equipment, and pose minimal hazard to the environment and to the health of the conservators
using it. Some of the methodologies described involved some very expensive equipment but
often the most successful approaches are the most simple. In each case history the nature of
the objects and their problems are described, the mechanism of action of the treatment is
explained and the degree of success evaluated.

Case 1: Cleaning of Archaeological Ironwork

Archaeological iron presents conservators with some extremely difficult challenges. Once it is
removed from a relatively stable environment in the soil it is frequently extremely unstable in
anything but the driest air (RH<15%). It is frequently encrusted in a thick layer of soil particles
concreted with iron corrosion products which may easily crack, delaminate and separate from
the remaining metal core (Figure 1).

Figure 1: Iron object excavated in Vietnam. Note the exfoliating layers of

external corrosion and exposed metal core where corrosion has been lost.
Apart for the question of the stability of archaeological ironwork, the cleaning of heavily
corroded objects is a major headache. The corrosion layers include both the internal corrosion
(seen as dark blue/black magnetite in Figure 1) and external concreted corrosion (the
orange/brown layer). Both layers are very hard and intimately bonded to one another but often
they are very loosely attached to the remaining iron core. That means that is too much force is
applied to the corrosion crust then it is likely that the whole corrosion layer will break away for
the core and the object is irretrievably damaged. That means that vibrotools and hand tools
such as scalpels have little success in cutting through the corrosion crust without destroying
the object. If dental drills and burrs are used then these will also put too much pressure and
vibration into the corrosion crust and potentially cause disintegration of the object. In addition,
dental drills generate large quantities of dust which obscure the surface being cleaned –
making precise work impossible.
The most successful approach to cleaning archaeological ironwork, and one that has been
almost universally adopted in the West is the use of micro-airabrasion. Here a fine jet of
pressurised air carrying micron-sized abrasive powders is directed at the surface of the
corroded object. The nozzle is ~0.5 mm diameter and both the pressure and the volume of
powder released can be carefully controlled. Aluminium oxide with a particle size of ~50
microns is generally used for cleaning iron objects, although other abrasive powders are
available for more delicate work (Turner-Walker 1998, Einarsdóttir 2012). Work is undertaken
in a vacuum extracted glove box and a microscope is generally used while working. The work is
extremely fine but painstakingly slow. As a result only small objects are cleaned by airabrasion
and very often only small windows are opened in the external corrosion to reveal fine details
that cannot be seen and understood from X-radiography alone. Sometimes a window will be
opened to allow XRF identification of an inlayed metal (see Figure 2: Right).

Figure 2 Left: A partly cleaned group of 2nd century AD Roman iron writing styli from
Wroxeter (U.K.). Note the heavy encrustation of sand and stones and the orange/brown
FeO.OH overlying the blue/black Fe3O4. Right: Close up showing how airabrasion can
reveal the finest constructional details without destroying the original surface. The inlayed
metal is brass and the stylii are no more than 4 mm in diameter.
Images courtesy of English Heritage (AML)

Removing the external corrosion from archaeological ironwork does nothing to stabilise the
objects against further corrosion. In fact, removing the hard corrosion can greatly weaken the
object and make it more prone to breakage. In removing a thick layer of compact corrosion it
also allows water vapour and oxygen easier access to the chloride-containing corrosion
products close to the surviving metal core. Thus cleaned objects must be always stored in a
suitable environment – one with either very low RH or one that is scrubbed of both oxygen and
water vapour such as the Mitsubishi Gas Chemical America, Inc. RP system™ A-type (formerly
known as the “RPA system”). The RP system™ A-type utilizes an oxygen scavenger and a
desiccant to provide an oxygen depleted and low relative humidity microenvironment. This
differs from Mitsubishi's previously developed low-oxygen system (Ageless) in that it also
maintains a desiccated environment (Mathias et al 2004; Einarsdóttir 2012).
Case 2: Cleaning of Calcium-encrusted Terracottas
Terracotta (literally baked earth) is a class of low-fired, porous ceramic that was commonly
produced in prehistory throughout the civilized world. Terracotta was used to make utilitarian
vessels, votive figurines and statures throughout the Mediterranean lands during Classical
Antiquity. The terracottas described below were excavated during the Princeton University
Cyprus Expedition at Polis Chrysochous, Cyprus (1984-present). Conservation work was
undertaken by the author in 1987 and 1989. All the terracottas were recovered from a very fine
silt-loess soil, loosely cemented with calcium carbonate. Cyprus is typical of Southern Europe
and the Mediterranean region in having long dry summers in which the movement of water in
the topsoil is predominantly driven by evaporation. In other words, soil water moves from the
water table deep below the ground up towards the surface, where evaporation takes place in
the top several centimetres of the topsoil. Because terracottas are porous these salt-rich
groundwater also pass through the body of the ceramic but because of a change in pore size
distribution between the ceramic and the surrounding sediment, slightly soluble salts such as
calcium carbonate (CaCO3) tend to precipitate out on the surfaces of the object. This has the
result of cementing and consolidating the soil particles onto the surface and obscuring any
painted decoration (Figure 3).

Figure 3: Two terracotta vessels excavated in from Polis in Cyprus in 1986. The surfaces
are encrusted in CaCO3 which obscures part of the painted decoration, especially the pot
on the left.

This calcareous encrustation is technically known as efflorescence and is similar in compactness

and hardness to the underlying terracotta and considerably harder than the paint layer. Hidden
within the pores of the terracotta there is also a precipitation of slightly soluble salts know as
cryptoflorescence. Any attempt to mechanically remove the efflorescence will almost certainly
damage the painted decoration and also runs the risk of scratching the soft ceramic body. Here,
the most suitable strategy was to use some kind of chemical cleaning method. There were two
possible options – use of a chelating agent such as EDTA or use of an acid to decompose the
CaCO3 to a soluble calcium salt and CO2.

EDTA, which also sequesters iron and other divalent ions, would be slow acting and the time
necessary to dissolve the calcareous crust would also allow the EDTA to penetrate into the
interior and weaken the structure. Furthermore, EDTA might also sequester iron or manganese
ions from any painted decoration, thus altering the colour. A dilute mineral acid, however
rapidly decompose carbonates as follows:
CaCO3 (solid) +HCl (aqueous) » CaCl2 (soluble) + CO2 (gas)
The evolved gas helps to remove any clay and silt particles adhering to the surface of the
ceramic. In this case hydrochloric acid is a more suitable choice than sulphuric acid because
calcium sulphate is only slightly soluble in water, whereas calcium chloride is very soluble. The
pottery to be cleaned must be soaked in water for several hours to flood the internal porosity
with water before immersing them in dilute acid. If the acid were able to penetrate inside the
fabric of the ceramic then any CO2 produced in the pores would expand and break up the
structure. In the case of the terracottas from Cyprus the ceramics were soaked for several
hours in tap water and then gently immersed in a 2.5% solution of HCl until no further bubbles
were seen being produced at the surface. The diffusion of H+ and Cl- ions into the ceramic
body is much slower than the decomposition of CO 32- ions to CO2 gas. Therefore, acid does not
penetrate into the ceramic body because the porosity is already flooded with water. After
treatment the ceramic was rinsed in running tap water for 24 hours followed by a final distilled
water rinse. The cleaned terracottas were allowed to dry slowly in air.

Figure 4: A life-sized head from a terracotta statue of a Nubian immediately after

excavation. Note the white crust of soil and carbonate obscuring the surface detail.

Figure 5: The terracotta statue head during treatment.

Note how the colours are more vivid when the ceramic is wet.

Figure 4 shows the head of a Nubian statue immediately after excavation. The fresh damage
shows that the terracotta is a dark orange colour but much of the colour and detail is hidden
beneath a layer of carbonaceous concretion. Figure 5 shows the head being rinsed in clean
water after acid cleaning and figure 6 shows the finished head after limited restoration of the
nose, while Figure 7 shows some of the pots seen in Figure 3 after treatment.
Figure 6: The finished head after cleaning, partial restoration and mounting.

Figure 7: The pots shown in Figure 3 after acid cleaning.

Case 3: Cleaning of Historic Whale Skeletons
The Bergen Museum was founded in 1825 and today is part of the University of Bergen and is
divided between the Natural History Collections (DNS) and the Cultural History Collections. DNS
has one of the world’s largest collections of whale skeletons – some of which have been on
continuous display since 1865 when the Museum hosted the International Fisheries Exhibition.
There are currently 22 articulated skeletons hanging from the ceiling and two crania in the
whale hall. The specimens represent 18 different species ranging from the 24 meter blue whale
down to the smallest porpoise. At the start of 2010 conservation work began on the ten largest
whale skeletons. The goals of the two-year conservation project were to return the hanging
skeletons to their original appearance if possible, and secure them for the future, while
retaining as much of the original materials, character and scientific potential as was practical.

In its scale, the work often had more in common with building restoration than normal
conservation, certainly in terms of the surface area to be cleaned. The blue whale skeleton
alone was estimated to have a total surface area of almost 95 m2 and the area cleaned on all
ten skeletons added up to hundreds of square metres. Because whales spend their entire lives
in the sea with their bodies supported by water their bones are very much lighter and more
porous than those of land mammals. The greater porosity of whale bones means that they
have a high storage capacity of oil while the animal is alive, and that they retain a high
proportion of that oil even after death. Whale bones contain a very high proportion of oil (or
lipids) although the exact values vary from one bone to another and from one species to
another. The bones of the skull and mandible, and the lower vertebrae and tail bones have the
highest oil contents (~40-55% by weight), whilst the central vertebrae have the lowest (~10-
25%). Bergen’s whale bones matched this pattern and the tail vertebrae are markedly more
disfigured by oil than the thoracic vertebrae. Over the past 100 years the oil had migrated to
the surfaces of the bones and in some cases could clearly be seen running down some of the
bones (Figure 8A). Sometimes the oil had been drawn into the smallest pore spaces by
capillary action rather than falling under gravity (Figures 8B & 8C). On the upper horizontal
surfaces where a thick layer of dust had accumulated the oil had also seeped into the dust,
sticking it firmly to the bone surfaces (Figure 8D).

Figure 8A Figure 8B
Oil that has run down the surfaces of two Oil accumulation in the spongy areas of the
whale rib (note also the fungal growth). distal radius and humerus of the humpback

Figure 8C Figure 8D
Oil has collected in the upper margin of Oil wicked into the thick layer of dust on fin
this whale scapula. Note the oily patch on whale vertebrae (note white paint spots).
the lateral surface.

The composition of whale oils varies considerably between species but like all oils derived from
marine animals it is characterised by a high proportion of triacylglycerols and esters of
unsaturated fatty acids – i.e. the fatty acids containing one or more C=C double bonds. The
proportion of unsaturated fatty acids in a lipid determines several of its properties, including
whether it is a liquid (oil) or solid (fat) at room temperature. Several of the fatty acids in whale
oils are polyunsaturated containing two or more double bonds, with some highly unsaturated
fatty acids, including acids of the C18, C20 and C22 series having 4, 5 and 6 double bonds.

Both saturated and unsaturated lipids are susceptible to oxidation by a number of mechanisms.
Hydrolytic rancidity is when water splits the fatty acid from the glycerol backbone of a
triacylglycerol (triglyceride). Technically the chemical term for this is ester hydrolysis. The
resultant free fatty acid is released into the remaining bulk of the lipid and may alter its
properties such as smell, colour and viscosity. Some of the shorter chain fatty acids released
may be volatile and escape into the air. Generally as the free fatty acid content increases the
colour becomes darker, passing from a pale honey colour to dark brown. This picture is also
seen in the whale skeletons hanging in University Museum of Bergen with the visible oil drips
varying from light brown to dark brown (see Figure 8 above). The reduction in C=C bonds and
accumulation of free fatty acids also makes the oil thicker and stickier as the longer chain fatty
acids accumulated in the oily residues. The whale bones also had a distinctive “acid” or rancid
smell to them.
Polyunsaturated marine oils fall under the classification of drying oils. Drying oils are those that
form tough, solid films when exposed to the air. Drying oils have traditionally been used in the
manufacture of paints and varnishes where the film forming mechanism is a cross-linking or
polymerisation action by atmospheric oxygen. The best known application of a drying oil is in
oil paints where linseed oil is used as the binding medium. Other drying oils include walnut oil,
poppy seed oil, sunflower oil and – in the Orient – tung oil. Thus, as oil slowly migrated to the
surface of the bones it reacted with the air and formed a drying film that combines with dust,
soot and grit to form a dark, hard but still sticky mass. This reaction was catalysed by light.
Figure 9 shows the total lipid extract of a northern right whale that hangs in the front windows
of the whale gallery. Lipid extracts from the whale oil residues were dominated by C18, C20
and C22 free fatty acids. There were relatively small amounts of mono-acyl and di-acyl
glycerides with C18:2 (linoleic acid), C20:2 (eicosadienoic acid) and C22:2 (docosadienoic acid)
acyl groups being the dominant acyl groups, and consistent with the likely chemical
composition of the original whale oil. In addition to these whale oil hydrolysis products, the
extracts displayed lipid oxidation products, i.e. oxidised free fatty acids, as major components
of the whale oil residues. The 9-hydroxy- and 10-hydroxy- mono-unsaturated fatty acid isomers
were significantly abundant, with very little 8-hydroxy- and 11-hydroxy mono-unsaturated fatty
acids. This is indicative that photo-oxidation by UV radiation played a significant role in the
degradation of the whale oils.

ION TRACE. Flagging=Area. Max.Scan=4301#48:00.80. Integ=[Det:50%, Hgt:0.01V, Wid:3-50, Res:90%].

Total Ion Current. Max.Int.=30.72366. 100% Int.=30.72366.
100
1.48450E09 1.25319E09
90
80 1.04991E09
Intensity (%age)

70
60 3.15797E08
50
40
30
20
10
0
5:00 10:00 15:00 20:00 25:00 30:00 35:00 40:00
Retention Time

Figure 9: GC-MS trace of total lipid extract from whale BM 15.

Test Cleaning
Because of the huge scale of the cleaning job it was important to identify the most effective
cleaning methods for the whale bones. A number of high-tech non-aqueous cleaning methods
were tested, including:
 Laser cleaning
 Solid carbon dioxide blasting
 Airabrasion
 Sandblasting
 Hammer and chisels
 Latex peels
In addition, several tests were made using solvent cleaning and chemical cleaning.
 Mixed organic solvents
 Aqueous ammonia cleaning

Laser Cleaning
Several tests were made using a Compact Phoenix conservation laser loaned by Lynton Lasers
(U.K.). The Compact Phoenix is a Q-switched Nd:YAG laser with an output energy of 100mJ per
10 ns pulse and a repetition rate of 1-25 Hz. I can deliver laser light at two wavelengths – 532
nm and 1064 nm. Laser cleaning works via a combination of thermal decomposition, thermal
shock and the shock wave produced by the rapid transformation of solid to gas at the object’s
surface. Laser cleaning is most effective when removing a dark, light absorbing layer of dirt
form a hard, white substrate. The effectiveness of laser cleaning can be increased by darkening
the dirt layer by spraying with water or ethanol. Laser cleaning seemed like a good option for
working in difficult spaces because the ”dirt” is effectively vapourised and there is no powder or
other residue to collect, although for health reasons efficient air extraction is necessary.

Figure 10: Test cleaning with the Compact Phoenix laser system.

Figure 10 shows test laser cleaning of a whale scapula at 532 nm. The laser was very good at
removing surface dust, grime and mould from the surface of the bones but did not remove the
degraded oil and fat running down the surface of the bone. It was also very slow – taking
several minutes to clean an area of only 10 square centimetres. In the end laser cleaning was
not adopted for cleaning the whale skeletons.

Solid CO2 Blasting

Another cleaning method tested was particle blasting using solid carbon dioxide. In this
technique small particles are shaved off a block of “dry ice” or solid CO2 and delivered at high
pressure through a special nozzle. The system is used in industry for removing grease and
grime fron machinery and food processing equipment. It also has applications in paint removal
and the cleaning of smoke-damaged buildings. Theoretically, dry ice blasting is an attractive
method: it is non-toxic to work with, it involves no direct contact with the surface of the object
being cleaned and it leaves no working residues other than the dirt that has been removed.
The equipment tested on the whalebones was a Cold Jet Microclean system powered by a large
compressor parked outside the museum.

Figure 12: Test cleaning with the Cold Jet solid CO2 cleaning system.

The performance of solid CO2 blasting was disappointing. In order to achieve any cleaning
effect on the oily bones the air pressure had to be turned up so high that the air penetrated
into the porous bone structure and detached the surface in places (Figure 13). This approach
was also abandoned as a cleaning method for historic whale bones.
Figure 13 Left: The author testing the solid CO2 system on a killer whale scapula. Right:
The high pressure jet has damaged the surface of this whale vertebra (white spots) but
failed to remove the soiling.

Airabrasion
Airabrasion has been used with considerable success in the cleaning of fossil bones and ivory
(Turner-Walker 1998). This approach was tested on a loose whale rib using a variety of
abrasive powders (Figure 14).

Figure 14: Test cleaning of a broken rib fragment using

different abrasive powders and different pressures and
powder flow settings.

The method proved to be extremely slow and, in common

with the solid CO2 blasting, with the less aggressive abrasive
powders the pressure had to be turned up so high that the
surface was damaged by the air jet. This approach was also
abandoned as impractical.

Sandblasting
Sandblasting is used for the removal or paint and corrosion from large pieces of machinery. It
is normally carried out in large glove boxes in inside purpose-built rooms where the operator
wears protective clothing and special breathing apparatus. For the whale project a closed-
system sandblaster was used in which in integrated vacuum cleaner collects the used abrasive
powder and re-circulates it back to the pressure nozzle. A circular nylon brush surrounding the
pressure nozzle forms a seal and prevents abrasive powder form leaking out into the working
environment. This system proved to be very effective in removing old restorations (paint,
plaster etc.) from large flat surfaces such as the underside of the blue whale skull and much
time was saved from not having to wet clean these areas (Figure 15).
Figure 15: Cleaning the underside of the blue whale skull using the re-circulating
sandblasting system.

Mechanical cleaning with chisels

On the blue whale skull there were a lot of early restorations using cardboard, wood, plaster of
Paris and paint. Where the plaster was thin it could be removed by covering the surface in a
layer of paper poultice and hot water for several minutes to siften the plaster, which could then
be scrubbed off with stiff nylon brushes. Where the plaster was thich, however, this was not
practical. Thge simplest solution was to mechanically remove the thick plaster using hammer
and chisels. By carefully selecting the correct angle between the chisel and the bone surface it
was quite simple to remove the hard plaster. The cleaning effect depends upon a difference in
Young’s modulus (hardness and flexibility) between the plaster of Paris and the underlying
bone. If this difference is large enough the plaster will flake away cleanly from the surface
below.

Figure 16: Using a hammer and small chisel, and then a screwdriver, to remove an old
plaster restoration from the blue whale skull (before sandblasting).

Latex Peel
Monuclean™ is a combination of natural latex and clay-complexes as a dirt-absorbent filler,
combining in this way the adhesive capacity of the latex and the absorbing capacity of the clay.
This ‘latex and clay’ paste is painted on the surface with a brush to create a film of 0.5 to 1 mm
thick and peeled off after ~24 hours. The first attempt on a whale vertebra proved probematic
because the latex penetrated the slightly porosus surface and adhered too well. When it was
removed the cured latex film was fagile and had to be removed in small fragments. On a
second attempt a thicker application of Monuclean™ was used and two layers of absorben
paper were added on top of the painted latex as a reinforcement. This pealed off much more
cleanly (Figure 16). However, there only a slight cleaning effect and what dirt and grease was
removed was probably due to the small amount of ammonia used as a stabiliser in the latex.
Figure 17: Testing Monuclean™ on the vertical processes of the humpback whale. The
middle bone is partly cleaned while the bone on the left is wet cleaned using ammonia and
the right bone is uncleaned. The Monuclean™ is only slightly effective.

Solvent Cleaning
The tail bones of some of the whales, especially the sei whale, were vey greasy with a thick
layer of sticky, dark brown fat on the surfaces (Figure 18). This could be removed using a
cocktail of mixed solvents comprising:
100 ml RO water
100 ml ethanol
100 ml acetone
5 ml aqueous ammonia
1 ml Triton-X100 (non-ionic detergent)

Figure 18: Cleaning with a mixed solvent (water:acetone:ethanol) applied as a paper

poultice. The before and after images (lower right) are very dramatic.

After several tests this solvent mixture proved to have the same cleaning ability as a non-polar
solvent but at lower cost and fewer associated health and safety issues than with a solvent
such as 1,1,1,trichloroethane. The solvent power was increased by applying the cocktail as a
paper poultice and wrapping it tightly in plastic. After approximately 30 minutes the paper
could be unwrapped and the paper used to clean off the dirty grease. Several applications of
solvent poultice were necessary and final cleaning was undertaken using cotton wool swabs
and solvent.

Ammonia cleaning
Aqueous ammonia is used in the saponification of a number of natural resins and oils. It has
been used in the production of linseed oil soaps and shellac soap. In general, surfactants
produced from the reaction of fatty acids with ammonia have a lower surface tension that
those using sodium and potassium (Averko-Antonovich et al., 2004) and this should facilitate
their removal from porous substrates.

Aqueous ammonia reacts with fatty acids in the bone to form an ionic soap via a saponification
reaction. In water ammonia disproportionate as follows:
NH3 + H2O ↔ NH4+ + OH-
This is an equilibrium reaction and the ammonia dissolved in the water is only weakly
hydrolysed to give hydroxyl ions (OH-). At room temperature a 25% solution (~ 13 M) has a pH
value of around 12.5 but only a small percentage (<1%) of the ammonia is hydrolysed. When
spread over an open surface the pH falls quickly to below 11.0 as gaseous ammonia escapes
from the liquid. As the pH falls the proportion of ammonia in the form of NH 4+ increases in
accordance with Le Chatelier's principle.

The hydroxyl ion released by the dissociation of water reacts with fats in a hydrolysis reaction
to give free fatty acids which bind to the ammonium ion to give soluble salts.
NH4+ + OH- + (R-OOH) → (R-OO- • NH4+) + H2O
(insoluble) → (soluble)

Where R-OOH is any fatty acid.

The ammonium ion will also bind to some of the cross-linked fatty acids and any that that may
be bound to calcium ions in the bone mineral since the ammonium ion forms stronger ligands
that Ca2+ ions. As the hydroxyl ions are consumed in these reactions more are released by
further dissociation of the dissolved ammonia (again in accordance with Le Chatelier's principle).
Any excess ammonia will slowly off-gas, leaving no residues and any ammonium salts of low
molecular weight carboxylic acids are also likely to sublime and escape from the spongy matrix
of the bone.

In practice, cleaning fat-soiled bones with aqueous ammonia involved painting a 25% solution
of ammonia directly onto the greasy surface, forming a foam with a soft brush and water, and
then removing the foam and any particulate matter from the porous substrate with a wet-
vacuum cleaner. Suitable safety equipment was worn by conservators at all times – overalls,
goggles, respirator masks and neoprene gloves (latex gloves disintegrate with ammonia). Best
results were achieved by working in small areas (c. 10 cm x 10 cm) and using several
applications as necessary. Final drying of the surface was achieved by spraying the surface
with absolute ethanol and wiping with a micro-fibre cloth. Ammonia is considerably less soluble
in ethanol than water (solubility in water at 25 ºC = 34% w/w; solubility in ethanol at 25 ºC =
10% w/w, Budavari et al. 1996) as so any excess ammonia was driven off when the ethanol
was applied.

It was necessary that the vacuum cleaners were cleaned once a week to remove the dark
residues that accumulated in the chamber. These foul smelling deposits contained volatile,
short-chain fatty acids such as butyric (butanoic) acid (which gives the smell of rancid butter
and vomit) valeric (pentanoic) or caproic (hexanoic) acid (which smells like goats). These
smelly vapours were exhausted from the vacuum cleaner during use and made the whale hall
smell very bad for museum visitors.
Figure 19: Cleaning with aqueous ammonia and a wet vacuum cleaner. Note the before and
after pictures (lower right)

The cleaning of ten whale skeletons took a team of four conservators two years in total to
clean and conserve. Figure 20 shows before and after images of one of the smaller whales
(minke). The original ironwork holding the lower jaw in place was corroded and unsafe. It was
replaced by a stainless steel system (right hand image). On each skull a small section of the
surface was left uncleaned as a reference. In the image on the right it is indicated by the red
oval. Figure 21 shows a view of the whale hall in September 2012 with all the whales cleaned
and the scaffolding removed. The whole room is much lighter and much more pleasant – the
dirty. Musty smell has disappeared.

Figure 20: Skull and jaw of a minke whale before and after cleaning and restoration. The
uncleaned reference surface is indicated by the red oval.
Figure 21: The whale hall as it appeared in September 2012, after the completion of the
whale project.

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