CASE STUDY ON COPPER CORROSION

ABSTRACT
Corrosion of copper plumbing tubes indicated by either the
formation of 'blue water' or pitting corrosion, is a phenomenon
which randomly affects large parts of the east coast of Australia,
as well as New Zealand, USA and Europe. It is characterised by
the production of voluminous blue/green corrosion products in the
tube bores and is primarily associated with cold, soft unbuffered
waters of high pH and negligible levels of disinfectant residual.
The history and causes for this type of corrosion are described,
with some emphasis placed on the various erroneous statements
that have been advanced to explain the problem. The corrosion
mechanisms whilst by no means well understood are shown to be
associated primarily with water chemistry factors together with a
contribution from copper tube surface condition.
Management of the corrosion problem is shown to be achievable,
using two case studies recently completed from regional NSW.
Key words: Copper tube, corrosion, water quality, remedial
measures.
Theoretical

Corrosion can only take place if certain elements are present; iron,
oxygen and water, in the form of Moisture in the air. If a section is
hermetically sealed the moisture in the entrapped air will allow
only a limited amount of corrosion to take place. As the oxygen is
used up oxidation will cease, since the entrapped air cannot be
replenished.
Practical.

On the basis of this theory it seems obvious that the protection of

hollow sections is simply a question of air tightness. Thus the
general outlines of the investigation are clearly defined; the
inspection of structures which have been standing for many years
must prove that the normal methods of fabrication are sufficient to
prevent internal corrosion.

This report investigates the problems presented by the welding of

hollow sections used in structures and in particular the protection
given to the interior of sections when closed by welding.
On the basis of his own observations and on foreign experience,
he reaches the conclusions which we reproduce in full below.
1) Sealed hollow sections require no internal protective coating
and may be regarded as essentially immune from corrosive attack.
2) Condensation in a sealed section is impossible, and when found
upon inspection is evidence of an opening having developed
-possibly a small opening that is drawing surface water in through
capillary action.
3) Adding a "pressure equilibrium hole" at any point in a hollow
structure where water cannot enter by gravity will prevent
aspiration in an imperfectly sealed system. (If the engineer has
qualms about condensation, he might as well put the hole at a low
point where it would serve for drainage also - merely to satisfy his
peace of mind.')
4) An "open" system should generally be kept as tight as feasible
with rubber gaskets used at manholes and such closures positioned
so as to avoid water accumulation and the possibility of its
entrance by capillarity action or aspiration. A strategically placed
pressure equilibrium hole might be advisable. Such Systems
should be protected with an interior coating.
5) A ventilated hollow structure should be internally protected and
have adequate ventilation holes at each end and in the sides.
6) Bolt and rivet holes should be avoided where-ever possible;
they create conditions conduciveb to water entrance by capillarity
action. In general, good design and good practice should eliminate
concern about corrosion in hollow steel sections. The
overwhelming mass of evidence, scientific analysis, and European
experience suggest that it is - as the Englishman said - more of a
"bogey" than a serious engineering problem.

INTRODUCTION
Background to Copper Corrosion
L & T has performed fabrication surveys on 10 copper
corrosion, at three different fabrication yards. In the interest of
protecting our client, names of the installations or fabrication
yards are not revealed in this paper. Typically, fabrication surveys
would include the following to identify future (when operational)
integrity and inspect ability issues

Although copper tubes for carrying potable water are known

to have existed 4,500 years ago (Nicholas, 1994), it is only with
the post-WWII introduction of thin-walled capillary tubing that
copper has become the default plumbing material used in virtually
all first-world countries, including Australia.
Figure 1:Membrane Theory (Lucey, 1967)
Whilst this theory was originally generated for relatively cold hard
waters on tubes often associated with carbon surface films, called
Type 1 pitting, Lucey himself (Lucey,1982) suggested a
commonality with all types of pitting, including hot waters and
cold, soft waters. However, aspects of Lucey's membrane theory
have been questioned (Edwards et al, 1994) and the mechanism of
both nucleation and growth of pits are now unresolved.
Excellent reviews of pitting corrosion of copper tubes have been
published (Edwards et al, 1994, Sequeria 1995) but although the
quantity of published literature is voluminous the precise
mechanisms are still not well understood. However, work on
pitting corrosion continues, with a significant component of this
being carried out in Australia and New Zealand.
These corrosion events, themselves often associated with pitting
failures, are observed in soft, cold unbuffered water supplies that
predominate along the east coast of Australia. The NSW Land
and Water Conservation report itself detailed the results of a
survey across the whole of NSW and, given a 52% response rate,
the results showed that about 30% of Councils that responded
recognised a significant problem.
A central question in all of these studies is why, after so much
research, are the prime causes and solutions to both 'blue water'
and pitting corrosion poorly understood? Primarily, this is due to
both the complexity of the phenomenon and the large number of
variables that may be involved. Another principal factor is the
randomness of corrosion: there is rarely more than a few percent
of buildings in a particular location involved, and it is often found
that failures have a tendency to cluster in certain suburbs or even
streets.
The situation is rendered even more complex by the tendency for
interested parties in the corrosion issues - often but by no means
restricted to the actual building owners - to attempt to identify
spurious and almost invariably misleading causes for copper
corrosion. These are usually single issue variables which often
attempt to both discredit the local water authority and apportion
blame for the incidents.
In fact, the issues are quite complex enough and the following
listing may assist in identifying some of these spurious causes that
are often erroneously quoted as causing copper corrosion.
Non-contributory issues
• Stray Electrical Currents - Stray currents do exist and can
readily be measured on copper tubes as they are usually
connected to the earth of the Electricity M.E.N. distribution
network. Unfortunately, these currents have nothing to do with
internal corrosion as demonstrated by a number of studies
(Moss and Potter, 1984). It is still regularly quoted as a source
of corrosion.
• Sources of Water - Recently, there was community concern at
one corrosion site that 'blue water' was caused solely by the use
of bore water. In fact, both surface and underground sources
are involved with copper corrosion.
• Fluoride - Shown in a 1980 report to have absolutely no
influence on corrosion (Bensley, 1980).
• Grade of Copper - All copper tube has been manufactured
from phosphorus deoxidised copper since before WWII. In
itself it has no influence, but the surface condition of the tubes
is another matter and has a significant role.

BASIC CRITERIA FOR COPPER CORROSION

All potential explanations of copper corrosion, either pitting or
'blue water', must encompass the following observations:
• Failure is almost never found in relatively hard water areas such
as Adelaide and Brisbane. It is confined to soft, poorly buffered
water supplies.
• 'Blue Water', and the majority of pitting cases, are only found in
cold water.
• Tube surface conditions have clearly been shown to have an
effect on copper corrosion, with some temper conditions worse
than others (Taylor et al, 1998). However, corrosion has been
frequently identified with all forms of tubing and surface
condition (Page, 1973; Nicholas, 1980).
• It is very random in occurrence even in areas where water
characteristics and tube surface condition might predicate
copper corrosion. In terms of incidents per 100 properties it
rarely exceeds 5%.
• In any given distribution system, copper corrosion incidents are
more likely to occur at the extremities of the network.
Several factors have been put forward as direct causal
explanations of these observations. These can roughly be divided
into water chemistry factors and tube surface condition factors:
Condition of Tube
The original work on copper pitting in the UK firmly identified
so-called 'carbon films' as the basis for tube pitting (Campbell,
1950). These were glassy, black coherent films of carbon
produced by a furnace anneal prior to the final drawing process -
so called 'half hard' or bendable quality (BQ) tubes. The remedy
was to remove the films using abrasive cleaning.
During the 'blue water' episodes investigated in Australasia in the
1970's (Page, 1973., Nicholas, 1980) it was clear that the mainly
hard-drawn tubes involved in these corrosion incidents did not
have these carbon films, and the influence of tube surface became
less of an issue. Nicholas, (1980) claimed that carbon films were
present to a degree on all tube surfaces and a causal relationship
between the presence of carbon and corrosion could not be
established.
More recently, extensive laboratory trials at the CSIRO have
indicated that tubes of different temper do give different results in
simulated 'blue water' tests (Taylor et al, 1998) although the
precise reasons are not at all clear and continue to be under
investigation. It can be said, however, that tubes with a thermal
history (i.e. annealed or BQ) show a greater tendency to corrode
when compared with hard drawn tubes, at least in the controlled
testing carried out by the CSIRO.

Water Chemistry
Regardless of the possible influence of tube surfaces in copper
corrosion, in Australia it has been found that for corrosion to
occur, the prevailing water chemistry must have certain
characteristics. Tubes, of whatever surface condition, simply do
not cause 'blue water' or pitting to perforation in either Adelaide,
Brisbane or wherever the source water is moderately hard.
Cuprosolvency or minor surface pitting can be found in these
waters, but rarely is this a serious corrosion problem.
The extent of copper corrosion on the east coast of Australia,
Perth, Tasmania, New Zealand and elsewhere encompasses a
range of 'soft' water chemistries. All areas of failure, however,
seem to share significant characteristics:
• Soft, with Total dissolved solids <300mg/L
• Low alkalinity (typically, <30mg/L)
• Ability to leach lime from cement lined cast iron pipes leading
to relatively high pH at the end of the distribution system.
• Almost invariably cold water, or <50°c if warm water involved.
• Varying levels of chloride and sulfate, but corrosion is known
to occur with both these analytes <7mg/L.
• Low residual disinfectant.
Anecdotal arguments can be advanced, largely from these simple
observations coupled with the randomness and previous factors
discussed in section 1.3., that the prime cause of 'blue water' is
Microbiologically Induced Corrosion (MIC).
This mechanism postulates the colonisation of newly installed
tubes by various strains of copper tolerant bacteria (Wells, 1999)
which themselves produce acidic interfacial layers on the tube
surface, thus lowering surface pH and altering the protective
qualities of the oxide film. Whilst this mechanism is by no means
universally accepted it has been shown (Taylor et al, 1998; Wells,
1999) that chlorine or chloramine disinfectant is highly successful
in controlling 'blue water'. Nevertheless, alternative chemical
explanations for the beneficial effects of disinfectant residuals are
possible, if currently not well-explained, and definitive
experiments are planned in the near future.
Further, the MIC theories currently only exist for 'blue water'
events, not for pitting corrosion. Given the clear links between the
two types of corrosion, it would be unusual if some commonality
of cause did not exist, but this is unproven and also under active
investigation.
Case Study I
Shoalhaven Council has experienced significant pitting corrosion
in a relatively isolated community at Sussex Inlet. Investigation
showed that the soft, unbuffered water supplying Sussex Inlet was
at the end of a long cement mortar lined distribution system with
subsequent long retention times. Consequently, water supplied
was at elevated pH and negligible disinfection residual.
Relatively high levels of pitting corrosion were reported and most
significantly, this was not reported from population centres
upstream with ostensibly the same copper tubing and the same
basic water chemistry. Detailed surveys of the Sussex Inlet
showed a total tube failure rate of about 5%-7%, which included
cases of 'blue water' previously unreported.
Experience here and elsewhere shows that actual failures or
incidents are usually many times higher than those reported to the
relevant utility. The outcome here is the introduction of full-scale
calcium bicarbonate dosing of the bulk supply together with the
maintenance of effective disinfectant residual.
Case Study II
Rouse Water, a bulk water supplier to a number of Northern NSW
Councils, received complaints of 'blue water' from the Evans Head
community in May, 1998. As with case Study I, the water caused
few if any failures at the major population centre (Lismore) but
significant incidents when the same supply finally reached
downstream at Evans Head. The 'blue water' complaints were
relatively numerous, but still tended to cluster at key streets within
Evans Head itself. Large parts of the community were
unaffected.
A very comprehensive corrosion management plan has been
implemented by Rous Water, perhaps the most significant field
trials yet attempted to alleviate 'blue water'. It can best be
summarised through Figure 3 below:
One of the early attempts to control corrosion on an individual
premises basis was to carry out hot water flushing. This was
highly successful in immediately lowering copper levels, but
gradually these returned in the majority of cases to the previous
high levels. Whilst a chemical theory explaining these
observations is possible, the alternative MIC explanation of a
bacteria kill-off from the hot water treatment followed by
gradualre colonisation and thus increases in copper levels is
arguably a more attractive theory.
Whilst carbon dioxide dosing on its own successfully dropped pH
levels in the distribution system from around 9.5 to 8.0, Figure 3
clearly shows that there was no concurrent or consistent drop in
copper levels. The combined use of line/carbon dioxide, however,
shows a relatively immediate drop in average copper levels,
indicating that controlling pH alone does not necessarily control
copper corrosion. The added buffering of lime/CO2 may control
corrosion by simply making localised changes in pH on the copper
surface (from whatever mechanism) harder to achieve.
Finally, the re chloramination introduced in April, 1999 achieved
another significant drop in copper such that average levels are now
below 0.2 mg/L, an order of magnitude less than the
recommended guideline limit of 2mg/L.
Figure 3 shows that it took over a month for the secondary
disinfection to significantly lower copper levels. This is due to the
deliberately low levels (<0.1 mg/L) achieved at the customer tap
so as to minimise taste and odour complaints. Nevertheless, 'blue
water' has been controlled.
Whilst the beneficial effects of these management processes on
the 'blue water' phenomena can readily be assessed through
chemical analysis of the 'first flush' water samples, this does not
necessarily indicate that corrosion processes are not continuing on
the tube surface in the form of pitting corrosion and/or build-up of
blue/green corrosion product on the surface, both of which were
known to occur at Evans Head.
To investigate these possibilities, a number of 19mm OD tube
samples, of different tempers and various experimental surface
treatments, were installed in 2 metre lengths in series at a site in
Evans Head that had previously experienced pitting corrosion.
The tubes were installed about a month before lime/carbon
dioxide dosing came on line (see Figure 3) and thus had exposure
to undoes water for this initial period. 300mm lengths of each
tube were removed after 1 month, 3 months and 6 months
exposure respectively for sectioning and subsequent examination.
Whilst this examination is so far incomplete, some general
observations can be reported:
• Some tube samples, in broad confirmation of the previous
CSIRO trials, (Taylor et al, 1998) are far more susceptible to
corrosion than others.
• Many of the susceptible tubes were showing clear signs of
surface corrosion after only one (1) month exposure in undoes
water.
• The onset of bicarbonate dosing was not successful in
preventing the growth of pits, or the formation of corrosion
product, on susceptible tubes after a further two months of
exposure.
• It is not clear-cut that tubes with higher levels of carbonaceous
films automatically suffer most from corrosion.
• When comparing the appearance of tube surfaces after three and
six months exposure, there are indications that the corrosion
rate has generally been slowed down by a significant
margin.This trial is now being extended to assess the longer
term performance of these tubes. The samples previously
removed are currently being subjected to a range of physical
and chemical surface analysis techniques in order to reach some
quantitative conclusions as to the basic reasons for the differing
performance.
Further, in order to assess the performance of these susceptible
tubes when exposed in their unused state to calcium bicarbonate
dosed and rechloraminated water, a second series of tubes have
recently been installed at the same site. This second round of
trials also have a parallel loop in which a duplicate set of new
tubes have been fitted which are connected to an activated carbon
filter to remove the disinfectant. In this way the effects of
secondary disinfection can be assessed.

CONCLUSIONS
• Corrosion of copper plumbing tubes can occur in an
unpredictable manner whenever soft waters predominate. It is
encouraged when the supplies are at the extremities of
distribution systems where relatively high pH and low residual
disinfection is found.
• The mechanisms of 'blue water' and pitting corrosion are not
well understood, although an MIC mechanism can be
tentatively argued, at least for 'blue water'.
• The tube surface has a secondary but important role to play in
the corrosion process, although the precise factors are also not
understood.
• Regardless of the mechanisms involved, 'blue water' at least can
be controlled by a corrosion management program that provides
buffering of the supply on either a localised or global basis
together with maintenance of an adequate disinfectant residual.

REFERENCES
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