INVITED CRITICAL REVIEW
A Critical Review on Corrosion and Runoff
from Zinc and Zinc-Based Alloys in
Atmospheric Environments
I. Odnevall Wallinder* and C. Leygraf,*
ABSTRACT
This critical review aims at addressing important issues
concerning zinc corrosion and zinc runoff processes of zinc or
zinc alloyed with aluminum or magnesium exposed to at-
mospheric environments. The evolution of the corrosion product
(patina) layer is very important for both processes. While
corrosion largely is controlled by electrochemical reactions at the
metal/patina interface, runoff is predominantly governed by
chemical reactions at the patina/atmosphere interface. The
gradual evolution of compounds in zinc patina follows one of
two main routes: one in more sulfur-dominated and one in
more chloride-dominated environments. Because of climatic
changes and reduction of sulfur-containing atmospheric species
in many parts of the world, the chloride-route is expected to
dominate over the sulfur-route. Alloying with aluminum and
magnesium results in substantial improvement in corrosion
protection, whereby several mechanisms have been proposed.
The released amount of zinc is highly dependent on the
amount of rainfall, also on sulfur dioxide concentration or
deposition, and to only a low extent on chloride deposition.
Based on all runoff data, a model is presented which predicts
70% of all observed zinc runoff rates within 40% from their
measured value.
KEY WORDS: atmospheric corrosion, atmospheric environment,
chloride, metal runoff, sulfur dioxide, zinc, zinc alloys
Submitted for publication: March 27, 2017. Revised and accepted:
May 4, 2017. Preprint available online: May 4, 2017, http://
dx.doi.org/10.5006/2458.
Corresponding author. E-mail: chrisl@kth.se.
*
KTH Royal Institute of Technology, Division of Surface and Corrosion
Science, School of Chemical Science and Engineering, SE 10044
Stockholm, Sweden.
ISSN 0010-9312 (print), 1938-159X (online)
1060 17/000175/$5.00+$0.50/0 2017, NACE International
INTRODUCTION
Because of its anticorrosive properties, its bonding
ability to other metals, its use in many production
technologies, and its importance as an essential
metal for humans, animals, and plants, zinc is number
four among the most consumed metals worldwide
(after iron, aluminum, and copper).1 The most impor-
tant use of zinc is in zinc-galvanizing to protect iron
and steel from rusting. As such, with and without
applied organic coatings, it nds much use in, e.g.,
architectural, infrastructural, and automotive applica-
tions. In second place comes zinc in zinc-containing
alloys for electrical components, vehicles, and house-
hold xtures, and in third place zinc in zinc oxide
(ZnO) for protective skin ointment and for rubber
manufacturing. But zinc is not only one of the most
important construction materials but also an essential
metal, necessary for the proper growth and health of
humans, animals, and plants.1
In view of its technical importance, atmospheric
corrosion of zinc and galvanized steel has been studied
extensively over several decades. Numerous eld and
laboratory studies of zinc in atmospheric environments
have resulted in the ISO classication system,2 which
is used for practical purposes in order to predict the
corrosion rates of zinc in different corrosiveness
classes. Zinc has also been extensively studied for
a better fundamental understanding and is today
probably the most investigated metal from an atmo-
spheric corrosion perspective.
The last two to three decades have seen an in-
creased environmental concern regarding the use and
CORROSIONSEPTEMBER 2017

concomitant diffuse emission of metals into the
surrounding environment. Since the beginning of the
1970s, international programs have been inaugu-
rated (e.g., WHOs Environmental Health Criteria [EHC]
program and the International Programme on
Chemical Safety [IPCS]) in order to increase the
scientic-based knowledge on stocks and ows of
chemicals, including metals, in the society and how they
may induce adverse effects on humans and the
environment. The rst assessments were primarily
focusing on human health aspects, whereas envi-
ronmental effects were not fully addressed until 1989.
The rst EHC for zinc was published in 2001 followed
by a full environmental risk assessment of zinc in 2006
and a chemical safety report in 2010 within the
framework of REACH (Registration, Evaluation, Autho-
risation, and Restriction of Chemicals).3 A summary
on ows of metals, including zinc, in society and in
the environment was published in 2004.4
In this critical review the intent is to present im-
portant aspects on the corrosion and dispersion (runoff) of
zinc from zinc and selected zinc-based alloys of rele-
vance in outdoor constructions. Corrosion and runoff are
processes of different physicochemical nature.5 The
review seeks to identify the most important parameters
which inuence the corrosion and runoff processes,
respectively. To place the data in a broader perspective,
the review also briey discusses how zinc runoff data
can be used in environmental risk assessments and
which additional data need to be considered.
DIFFERENT FUNCTIONALITIES CAN BE
ATTRIBUTED TO THE ZINC CORROSION
PRODUCT LAYER
The fact that the corrosion and runoff processes
are of different nature and are governed by different
parts of the corrosion product layer (herein often
referred to as patina) is discussed rst. Figure 1 (left)
25
20
Rate (g/m2.y)
Corrosion
15
10
Runoff
5 metal
0
0 50 100 150 200
Exposure Period (d)
FIGURE 1. Left: Corrosion and runoff rates of bare zinc sheet during exposure in the urban site Stockholm, Sweden.
Right: Schematics of cross section of a zinc patina to illustrate where the corrosion and runoff processes take place, respectively.
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
shows the corrosion rate and runoff rate of pure zinc
during the rst year of exposure in an urban site
(Stockholm, Sweden).5 While the corrosion rate is
slowly decaying, the runoff rate is fairly constant
throughout the whole rst year of exposure. These
different time-dependences are caused by different
physicochemical processes that govern corrosion and
runoff processes, respectively. Figure 1 (right) displays
schematically that the corrosion process, which is
electrochemically driven, takes part at the interface
between the metal and the corrosion product layer.
The runoff process, on the other hand, is largely gov-
erned by chemical dissolution as the patina gradually
develops in contact with the atmosphere, and
takes place at the atmosphere/patina interface.5
Hence the role of the patina is two-fold, with
different parts taking place during corrosion and runoff,
respectively. To describe this dual role further the
so-called GILDES-formulation of the interfacial regime
between the zinc metal and the atmosphere is intro-
duced. GILDES is a computer model which was devel-
oped to explore the interfacial regime between an
oxide-covered metal and the atmosphere.6 It contains six
parts (Gas, the Interface between gas and liquid, the
Liquid, the Deposition layer, the Electrodic region
near the solid surface, and the Solid), and has been
developed for the exploration of the chemistry of metal or
metal oxide surfaces covered by a layer of water and
exposed to the atmosphere. The aim of GILDES is to use
all chemical information available and then apply the
model to predict the phases formed during atmospheric
corrosion and their formation rate. It has been suc-
cessfully applied to zinc in a few laboratory atmospheres
representing both outdoor7 and indoor8 atmospheric
environments. To exemplify the GILDES formulation,
Figure 2 (left) shows the sequence of compounds
detected during exposure of zinc in a typical marine
environment.9
It starts with the instant formation of a very thin
layer of zincite (ZnO), which is present already before the
Corrosion Corrosion
Patina
Zinc
runoff
Zinc
Interface
250 300 350
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INVITED CRITICAL REVIEW
Time
NaZn4Cl(OH)6SO4.6H2O
Zn5Cl2(OH)8.H2O
Zn5(CO3)2(OH)6
ZnO/Zn(OH)2
Zn/galvanized
FIGURE 2. Left: The sequence of compounds detected during exposure of zinc in a marine atmosphere at sheltered
conditions, starting with the instant formation of ZnO/Zn(OH)2 and ending with NaZn4ClSO4(OH)66H2O after extended
exposure times. Right: A schematic picture of the interfacial regime according to the GILDES-formulation when zinc is
exposed in a marine atmosphere.
marine exposure, continues with a thin layer of
hydrozincite (Zn5(CO3)2(OH)6) that evolves to simon-
kolleite (Zn5Cl2(OH)8H2O), and ends with gordaite
(NaZn4Cl(OH)6SO46H2O)10 as the nal compound after
extended exposure times. Figure 2 (right) shows
schematically the main species and compounds that
can be detected in each GILDES-region during
marine exposure of zinc.
It is evident from Figure 2 that the patina consists
of two regions with different functionalities, the inner
electrodic and the outer deposition region. According
to GILDES, the electrodic region is a very thin region at
the interface between the patina and the solid that
incorporates all electrochemistry governing the corrosion
process. The deposition region, on the other hand, has
been formed through a broad spectrum of chemical
rather than electrochemical reactions, including
equilibria reactions (gas-solid reactions, hydration
chemistry reactions, acid-base reactions, surface
complex formation, and solubility equilibria) and irre-
versible reactions (redox reactions involving oxygen
and hydrogen, zinc oxidation, reduction reactions, and
irreversible ligand- or proton-promoted dissolution).5
The important point to be made herein is that the
corrosion process largely is inuenced by the electrodic
region, to some extent also by the deposition region,
while the runoff process mainly occurs in the outermost
part of the deposition region, where patina dissolu-
tion takes place in contact with the liquid region.
Evidence for this dual or multi-role of the corrosion
product layer can easily be observed on other metals,
such as passivating metals, or on copper. On pas-
sivating metals, the observation of an inner barrier layer
and an outer porous layer with different functional-
ities is well established, see, e.g., Macdonald, et al.,11
and Chu, et al.12 Also, copper exhibits a patina which
usually contains two different sublayers:13-14 an inner
cuprite (Cu2O) layer, which largely governs the pro-
tection ability of the patina layer, and an outer layer,
which commonly contains brochantite (Cu4SO4(OH)6
in sulfur-dominating environments) or atacamite
(Cu2Cl(OH)3 in chloride-dominating environments)
1062
G (Gas) O2 H2O NaCl SO2 CO2
I (Interface)
L (Liquid) 2 2
OH H+ Cl SO4 CO3
NaZn4Cl(OH)6SO4.6H2O
D (Deposition)
Zn5(CO3)2(OH)6 Zn5Cl2(OH)8.H2O
E (Electrodic) ZnO Cathode Anode
S (Solid) Zn/galvanized
and which determines the runoff rate of copper during
its interaction with the surrounding atmosphere.15-16
As opposed to copper, the protective inner layer
on zinc is more difcult to detect. However, detailed
analysis of the corrosion products on zinc by trans-
mission electron microscopy (TEM) revealed an inner
layer of ZnO, having a thickness in the range 20 nm to
70 nm.17 Detailed analyses of self-repairing properties
of the corrosion products formed on zinc show that
this inner barrier layer is compact and dense, and that
the barrier properties may improve with exposure
time.18
Following the GILDES-formulation, it is con-
cluded that the corrosion process is largely governed by
the electrodic region at the metal/patina interface, to
some extent also by the deposition region, while the
runoff process mainly is governed by the deposition
region at the patina/atmosphere interface. Differences
between corrosion and runoff data of zinc will be
further discussed in a later section.
INFLUENCE OF CORROSIVE SPECIES ON THE
ATMOSPHERIC CORROSION PROCESS OF ZINC
The atmospheric corrosion of zinc is an electro-
chemical process, and the standard electrode reduction
potential of zinc at 25C is 0.76 VSHE. The metal
dissolves as Zn2+ in the aqueous adlayer, which acts as
the medium for electrochemical reactions on zinc
during atmospheric corrosion. The stability domain of
the Zn2+ ion in the Zn-H2O system is relatively large
and ranges from around pH 8 to lower pH values. Zn2+ is
an intermediate Lewis acid, and when following the
Lewis hard and soft acid-base (HSAB) principle one
expects the ion to coordinate with a broad range of
Lewis bases, such as OH, O2, SO2 2
4 , SO3 , NO3 , NO2 ,
5
and CO23 . These and many other ions have shown to
be reactants during the atmospheric corrosion process,
which is evidenced by the relatively broad composi-
tional range of corrosion products observed in both
outdoor and indoor atmospheric environments.5
CORROSIONSEPTEMBER 2017

Zinc is one of the base metals on which the
standardized ISO corrosiveness classication is based.2
In this classication there are a few atmospheric
parameters that are more inuential than others for
predicting the corrosion behavior of zinc in different
outdoor atmospheric environments. These include
sulfur dioxide (SO2) concentration or deposition,
chloride ion (Cl) deposition, temperature, and time of
wetness (TOW, the time during which the tempera-
ture is >0C, and the relative humidity [RH] > 80%).2
This standard was originally based on corrosion rate
data mainly from the temperate region. Extended in-
ternational exposure programs were therefore initi-
ated. The rst was ISOCORRAG,19 which included more
than 50 test sites in other climatic regions than the
temperate region, located in Europe, Argentina,
Canada, Japan, New Zealand, and the United States.
Later, the MICAT project was established to perform
corrosiveness mapping in 12 Ibero-American coun-
tries and in Spain and Portugal.20 An important
outcome of these exposure programs was the estab-
lishment of corrosiveness categories of all environ-
ments, from C1 to CX, as explained in ISO 9223 and
briey described in Table 1.
Another important outcome of the international
exposure programs was the exploration of the combined
effect of temperature and RH. It turned out that in
atmospheric environments dominated by SO2, the
corrosion rate of the investigated metals increases
with temperature up to a certain maximum value and
thereafter decreases, corresponding to the drying out
of the aqueous adlayer and concomitant reduction in
corrosion rate. In atmospheric environments domi-
nated by Cl, on the other hand, the decrease at higher
temperature values is never observed. The hygro-
scopic salt particles can retain the aqueous adlayer even
at higher temperatures, resulting in extremely high
corrosion rates (Category CX in Table 1).
In the period between 1960 and 2000, the SO2
levels decreased substantially in many parts of Europe,
and it was soon realized that the relative contribution
of SO2 and other sulfur-containing pollutants were not
any longer dominating. Instead, the focus was on
TABLE 1
Corrosiveness Categories According to ISO 9223 Showing Ranges of Zinc Corrosion Attack During the First Year of
Exposure, and Examples of Environments in Each Category2
Category Corrosiveness Zn Corrosion Attack (m)
C1 Very low 0-0.1
C2 Low 0.1-0.7
C3 Medium 0.7-2.1
C4 High 2.1-4.2
C5 Very high 4.2-8.4
CX Extreme 8.4-25
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
other pollutants that could contribute, especially par-
ticulate matter and nitric acid (HNO3). The overall
result of all these international efforts is seen in the
dose-response functions developed for zinc:5
R = 0.49 0.066SO2 0.22 e0.018RHf T
0.0057 RainH  0.192HNO3  (1)
Here, R denotes the average corrosion effect in m after
1 y of exposure. The corrosion effect has four major
contributions. The rst is a constant and corresponds to
the background atmospheric condition. The second is
the overall contribution of dry deposition effects and
is expressed as a combined effect of SO2, RH, and
temperature (T), where f(T) = 0.062(T 10) when
T < 10C, otherwise f(T) = 0.021(T 10). These con-
ditions describe the complex temperature behavior of
the atmospheric corrosion of zinc, with a maximum in
corrosion rate at 10C. The third contribution is from
wet deposition, and includes the amount (in mm/y)
and concentration ([H+] = 10pH) of rain. The fourth
contribution is from HNO3, which turns out to have a
very strong corrosion effect on zinc, as has been shown
both in laboratory and eld based exposures.21-22
[SO2] and [HNO3], nally, represent annual average
concentrations in g/m3.
A consequence of the historical development in
many parts of Europe with a steadily decreasing SO2
concentration is the increasing relative importance of
salt aerosols. Predictions have been made in the
European region showing that the atmospheric cor-
rosion of zinc and other metals will be dominated by
Cl deposition in coastal and near-coastal areas, an
effect which will increase further when the temperature
is expected to increase because of climate changes.23
The situation is, however, different in other parts of the
world which still do not experience any SO2 reduction
or only limited reduction of this and other acidifying
gaseous pollutants.
Given the importance of Cl deposition at high
humidity conditions in combination with or without
SO2, an exposure program was undertaken to explore
Example of Environments
Offices, schools, museums
Storage, sport halls, low polluted rural areas
Medium polluted inland areas or coastal areas with low
deposition of chlorides
High polluted inland areas or coastal areas without direct influence of
spray of salt water
Very high polluted inland areas or coastal areas with significant
effects of chlorides
Coastal areas with significant effect of chlorides in subtropical and tropical
zones with very high TOW
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INVITED CRITICAL REVIEW
the atmospheric corrosion of zinc in 18 tropical sites in
Asian countries and Australia.24 Regression analysis
of corrosion and environmental data indicated that the
most important factors to control zinc corrosion were
the climatic parameters temperature and rainfall, and
also time of wetness. However, no signicant inu-
ence of any gaseous pollutants on zinc corrosion rate
could be discerned, despite large variations in SO2
concentration between the sites. The result shows that
dose-response functions obtained from one or several
programs may not necessarily be valid in other
programs, because of differences in environmental
conditions between the programs.
Of particular concern is the natural and an-
thropogenic emission of aerosol particles, originating
from, e.g., sea spray (from breaking ocean waves),
mineral dust (from windblown surface soil), biomass
burning, industrial processes, and vehicle trafc. The
interaction of these particles and zinc or zinc-alloy
surfaces is quite complex. Upon adsorption most
particles sorb water whereby they transform from
agglomerated solid particles to droplets. This del-
iquescence process follows the variations in RH and
generally results in highly complex chemical species,
which may undergo further changes when emitted gases
in the atmosphere interact with the wetted aerosol
particles. Local emission variations, the complex aerosol
chemistry, and lack of predicted emission data makes
it very difcult to give some general prediction of the
corrosion effect of aerosol particles on zinc and zinc-
alloys. However, when limiting the effect to NaCl particles
alone, one can expect a signicant increase in corro-
sion effect as a result of the combined effect of temper-
ature, RH, and Cl concentration on zinc.25
INFLUENCE OF ALLOYING ELEMENTS (AL AND
MG) ON THE ATMOSPHERIC CORROSION
PROCESS OF ZINC
Zinc-based coatings on steel in general corrode
two orders of magnitude slower than conventional cold
rolled steel in many types of environments. By adding
Zn4SO4(OH)6.nH2O
ZnO/
Zn5(CO3)2(OH)6
Zn(OH)2
Seconds Hours
FIGURE 3. Schematic sequence for corrosion product formation on zinc sheet (or galvanized steel) at sheltered conditions in
ambient atmospheres dominated by sulfur pollution (upper sequence) and chloride pollution (lower sequence).
1064
magnesium, aluminum, or a combination of both, the
corrosion rate may decrease another order of mag-
nitude.26-27 Considering the technical importance for,
e.g., the automotive industry, the last decade has
seen a large number of investigations aiming at ex-
ploring the role of these two alloying elements for the
corrosion resistance of zinc. In this section, an effort is
made to summarize major ndings. The authors start
by presenting important investigations on pure zinc. It
should be emphasized that the zinc-containing layer
on steel in, e.g., hot-dip galvanized steel in reality
consists of a series of intermetallic Fe-Zn alloy layers,
each characterized by a decrease in Fe content when
going from the steel substrate toward the outer zinc-
rich phase.28-29 Each layer has a unique electrochem-
ical nobility which makes the corroding system quite
complex when deducing mechanistic information from
hot-dip galvanized or other zinc-coatings on steel. For
simplifying reasons, many fundamental studies have
therefore been performed on pure zinc rather than on
galvanized steel.
During the decades between 1970 and 2000, the
fundamental and practical understanding of the
atmospheric corrosion of pure zinc and other metals
was largely based on the exposure of metal plates in
both laboratory and eld exposure conditions. Based
on data generated, the present authors were able
to deduce main sequences for corrosion product
formation on zinc sheet or galvanized sheet in atmo-
spheric environments.9 Despite large variations in
gaseous and aerosol pollutants, RH, time of wetness,
and solar radiation, two main sequences were iden-
tied: one in more sulfur-dominated environments and
one in more chloride-dominated environments. These
sequences are shown schematically in Figure 3 for
sheltered conditions. Both sequences start with the
instant formation of zinc oxide (ZnO) and zinc hydroxide
Zn(OH)2 and subsequent formation of hydrozincite,
Zn(CO3)2(OH)6, during time scales indicated in the
gure. This compound, together with Zn(OH)2, is the
whitish corrosion product formed on zinc during wet
storage or exposure in low polluted environments.
Zn4Cl2(OH)4SO4.5H2O
2
SO2/SO4
NaCl/Cl
Zn5Cl2(OH)8.H2O NaZn4Cl(OH)6SO4.6H2O
Days Weeks Months Years
CORROSIONSEPTEMBER 2017

In environments dominated by SO2 or other
sulfur-containing pollutants, the upper sequence of
compounds is formed with zinc hydroxysulfate con-
taining different amounts of water (Zn4SO4(OH)6nH2O).
The phases are commonly seen in rural, urban, and
industrial environments, and can remain as end
product in these environments. If chloride aerosols
are present in the atmosphere, such as in certain
industrial or road environments, the Cl ions can
become incorporated into the lattice and eventually
form Zn4Cl2(OH)4SO45H2O. This is the end product
in many highly corrosive atmospheres characterized by
high deposition rates of SO2, sulfates, and
chlorides.5,30
In marine environments, or other environments
dominated by aerosols containing NaCl or other chlor-
ides, the corrosion products formed instead include
Zn5Cl2(OH)8H2O and later NaZn4Cl(OH)6SO46H2O,
a result of the incorporation of S-containing aerosols
from the ocean. Characteristic for the formation of these
compounds is their gradual formation through a
number of principal steps, facilitated by the structural
resemblance of several of the compounds
involved.5,10
The interaction of NaCl aerosols on zinc have
been described in quite some detail in a series of papers.
Such investigations are of particular relevance in view
of the increasing importance of aerosols relative to
gaseous pollutants, as explained above. Signicant
progress has been made in the understanding of
corrosion phenomena under aqueous droplets pro-
duced by wetting of salts.31-36 The droplet is usually
formed around a single salt crystal which is exposed
to increasing RH until the point of deliquescence is
reached and the crystal transforms into a droplet.
Although the droplets formed under these experimental
conditions are much larger than those formed as
natural marine aerosols, it is nevertheless believed that
fundamental information has been gained which can
help to understand the atmospheric corrosion in marine
environments.
Figure 4 helps to depict some of the major pro-
cesses found for pure zinc with a single NaCl droplet.
A characteristic feature is the well-separated anodic
and cathodic regions. The anode in the central part
has been formed as a pit through chloride- or acid-
promoted dissolution of the ZnO covered surface. If the
conditions for maintaining the pit are fullled, driven
by high enough zinc dissolution and local acidication
in the pit, a pH gradient is formed across the surface
from the anode (acid) to the peripheral cathodic region
(basic) through the cathodic reaction with dissolved
oxygen forming hydroxyl ions. Zn2+ and Zn(OH)+ ions
formed in the pit will migrate out of the pit, react with
Trade name.
(1)
UNS numbers are listed in Metals and Alloys in the Unied Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
Droplet
CO2 CO32 Cl
OH Zn5(CO3)2(OH)6 Zn5Cl2(OH)8.H2O
O2 Zn(OH)+ Zn(OH)2
ZnO Cathode Cathode ZnO
+
Zn 2+ H
Zn
Anode
FIGURE 4. Schematic model of the atmospheric corrosion of zinc in
marine environments. Adopted from Cole, et al.,24 and Chen, et al.34
Characteristic features are the central anode (acid) and peripheral
cathodic (basic) areas, and the formation of Zn(CO3)2(OH)6 and
Zn5Cl2(OH)8H2O at various parts of the surface.
CO23 (from dissolved CO2 into the droplet) and Cl . This
creates conditions to form both Zn(CO3)2(OH)6 and
Zn5Cl2(OH)8H2O at various parts, depending on pH and
Cl ion concentration.
It should be emphasized that this depicted model
is simplied and becomes more complicated when
adding SO2 or sulfate-containing aerosols, for more
details see, e.g., Cole and coworkers,24,37 and Chen,
et al.34 Another important phenomenon not seen in
the gure is the so-called secondary spreading effect,
which is observed during single droplet experiments
when the moisture lm spreads out from the central
droplet after certain stages of exposure and alters the
local electrochemical and chemical conditions for the
corrosion processes.38
Nevertheless the schematic gure can act as a
platform when discussing the role of the alloying ele-
ments magnesium and aluminum on galvanized steel
sheet. Such efforts have been based mostly on labora-
tory exposures, less often on eld exposures. The
improvement of hot-dip galvanized steel sheets by alu-
minum has a history which goes back to the early
1970s with the development of Galvalume (Zn + 55 wt%
Al + 1.6 wt% Si, from here on denoted Zn55Al)39 and
Galfan (Zn + 5 wt% Al; UNS Z38510(1), from here on
denoted Zn5Al).40 Later came the development of even
more corrosion resistant coatings through addition of
magnesium. It resulted in several commercial Mg-Al
coatings by Nippon Steel Corporation around the year
2000, such as ZAM (Zn + 6.0 wt% Al + 3.0 wt% Mg)
and Super Dyma (Zn + 11.0 wt% Al + 3.0 wt% Mg +
0.2 wt% Si).41 Driven by mainly European industries,
numerous investigations have been implemented dur-
ing the last decade to further explore the benecial
role of the elements aluminum and magnesium. The
way to produce the alloy coatings has been through
hot-dipping in Zn-Al-Mg baths or by physical vapor
deposition of Zn-Mg alloy coatings.41 Magnesium has
usually been added in the range from 0.2 wt% to 11 wt%
and aluminum in the range from 0.1 wt% to 3 wt%,
and both elements result in a highly complex micro-
structure, which includes different phases besides
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INVITED CRITICAL REVIEW
the main phase Zn: MgZn2, binary eutectic MgZn2-Zn,
binary eutectic Zn-Al, and ternary eutectic phases.
These additions have resulted in layers on steel which
clearly represent alternatives to hot-dipped zinc and
electrogalvanized zinc coatings, and with signicantly
improved corrosion protection ability in the neutral
salt spray test or in cyclic automotive corrosion
tests.27,41-44 However, the improvements reported
very much depend on the actual laboratory exposure
conditions. They are expected to vary even more when
considering actual differences in natural eld exposure
conditions. Critical parameters in this context are
Cl-load, pH of electrolyte introduced, RH, and
temperature.
Because of the variations of these critical para-
meters, it has so far been difcult to develop a universal
mechanism for the benecial role of the alloying
elements magnesium and aluminum alone or in combi-
nation on the corrosion resistance of zinc coatings,
despite a substantial amount of studies on this topic. The
new mechanistic insight that has been generated
during the last decade has been based on a few novel
fundamental approaches: the inuence of the complex
microstructure on atmospheric corrosion initiation, the
possibility for in situ measurements of the dissolution
of alloying elements, and the detailed compositional
analysis of corrosion products formed. Within this
context it is hard to give full justice to all investigations
made, and this survey therefore will be limited to some
key investigations. The present authors begin by
explaining the role of magnesium alone, which is largely
based on the comprehensive study of Hosking, et al.42 In
doing so, refer to Figure 5, which is a modication of the
gure shown for bare zinc sheet (Figure 4).
As for pure zinc, an important prerequisite is the
creation of anodic (center) and cathodic (periphery)
areas. Mg2+ and Zn2+ ions anodically dissolve from
the MgZn2 phase in the Zn-Mg matrix and enter into the
electrolyte. In the initial stage, ZnO covers the sub-
strate outside the anodic area where the cathodic
reaction can proceed. When the magnesium ions
reach close to the cathodic area they form stable
Droplet
CO2 CO32 Cl
OH Zn5Cl2(OH)8.H2O + (LDH)
O2 Mg(OH)2 Zn(OH)+ Zn(OH)2 Mg(OH)2
H+ (Al2O3) Cathode ZnO
ZnO Cathode (Al2O3)
Al3+
Zn2+ H+
Zn-Mg(-Al)
Anode
FIGURE 5. Schematic model of the atmospheric corrosion of Zn-Mg
and Zn-Mg-Al alloys in chloride-containing environments. The
compounds shown within parentheses are detected upon exposure
of Zn-Mg-Al coatings, but not of Zn-Mg coatings. LDH is a layered
double Zn-Al hydroxide, Zn6Al2(OH)16(CO3)4H2O.
1066
precipitates of Mg(OH)2 on the cathodic area. This
suppresses the cathodic reaction rate and facilitates
the formation of Zn5Cl2(OH)8H2O, either directly
from chloride complexes at the anodic region or via
the transformation of zinc oxide. Zn5Cl2(OH)8H2O is
a relatively compact compound and improves the
corrosion protective ability of the system. It will
continue to form as long as the oxygen reduction
process at the cathode is reduced through formation
of Mg(OH)2 on the cathodic area. Hence, a main bene-
cial role of alloying zinc coatings with magnesium is
the reduction of the cathodic reaction through precip-
itation of Mg(OH)2 and the formation of protective
Zn5Cl2(OH)8H2O.45-46 Studies have shown that the
benecial effect of magnesium has an optimum
Mg-concentration range of 4 wt% to 8 wt%, when
exposed to pre-deposited NaCl and humidied
air.45 By adding aluminum to the Zn-Mg coating
a few additional benecial effects can be seen
(Figure 5), primarily the formation of a layered double
hydroxide (shortened LDH in the gure) of type
Zn6Al2(OH)16(CO3)4H2O,43 and also the formation of
a thin lm of Al2O3 with barrier properties (see below
for Zn-Al coatings). Several studies provide evidence
for the combined effect of Mg and Al, based on both
eld and laboratory conditions.27,44,47
For Zn-Al coatings on steel, there exists today a
substantial amount of information on corrosion rates
and long-term corrosion product formation, both for
Zn55Al48-51 and Zn5Al.52-53 Zn55Al possesses a rela-
tively simple microstructure with an aluminum-rich
dentritic phase (often denoted the -phase) and a zinc-
rich interdentritic phase (the -phase). This is seen in
Figure 650 displaying an atomic-force microscope (AFM)
in image (a) and a corresponding Volta potential
image in (b). After slight diamond polishing of the
as-received Zn55Al surface, the initial Al2O3-lm
covering all parts of the surface was removed revealing
the two-phase structure underneath. The Volta
potential on dendritic parts (Al-rich) of the surface
turn out to be higher than on interdendritic parts
(Zn-rich), from which is expected that interdendritic
parts are more susceptible to corrosion initiation than
dendritic parts, at least initially.50
Figure 7 is a compilation of all compounds found
in corrosion products formed on zinc,9 Zn5Al,53 and
Al54-56 upon unsheltered exposure in marine
environments.
On all three materials, oxides and/or hydroxides
of zinc or aluminum are instantaneously formed
whenever they are exposed to moist-containing
atmospheres. In the presence of CO2, Zn(OH)2 reacts
to form hydrozincite (Zn5(CO3)2(OH)6) and Zn6Al2-
CO3(OH)164H2O. Sufciently high Cl-deposition rates
also result in the formation of hydroxychlorides, such
as simonkolleite (Zn5Cl2(OH)8H2O) on bare zinc and
Zn5Cl2(OH)8H2O and/or Zn2AlCl(OH)6H2O on the
Zn-Al coating. Because of biological activity in the
CORROSIONSEPTEMBER 2017
 INVITED CRITICAL REVIEW

(a) 200
(b) 200

Z (nm) P (mV)
FIGURE 6. AFM image (a) and a corresponding Volta potential image (b) of a Zn55Al surface. Lighter areas in (a) and (b)
correspond to Al-rich dendritic areas, darker to Zn-rich interdendritic areas.50

Zn/galvanized steel Zn-Al alloys Al

ZnO/Zn(OH)2 ZnO/ZnAl2O4/Al2O3 Al2O3

Zn5(CO3)2(OH)6 Al(OH)3 Al2O3.2H2O

Zn6Al2CO3(OH)16.4H2O

Zn5Cl2(OH)8.H2O/Zn2AlCl(OH)6.H2O AlxSO4(OH)y
Zn5Cl2(OH)8.H2O
NaZn4Cl(OH)6SO4.6H2O

NaZn4Cl(OH)6SO4.6H2O Al(OH)3

FIGURE 7. Generalized evolution scheme of corrosion products for bare zinc sheet (left), Zn5Al (middle), and bare Al sheet
(right) exposed to unsheltered marine atmospheric exposure.53

oceans, marine environments are also characterized
by signicant sulfate emission rates. This is a
main reason for the frequent detection of gordaite
(NaZn4Cl(OH)6SO46H2O) on both bare zinc and on
Zn5Al in marine environments.
As originally proposed for zinc,9 several com-
pounds in corrosion products bear structural resem-
blance. They consist of layered structures with
octahedral or tetrahedral building blocks in which the
layers are held together by, e.g., CO2 2
3 , SO4 , or Cl
5
ions. Such compounds, which are characterized
by layered structures, include Zn5(CO3)2(OH)6,
Zn5Cl2(OH)8H2O, NaZn4Cl(OH)6SO46H2O, Zn2AlCl
(OH)6H2O, and Zn6Al2CO3(OH)164H2O, whereby the
former three form on bare zinc and the latter two on
Zn-Al alloys. During the cycling weathering condi-
tions the slow transformation from one compound
into another can proceed through replacement of,
e.g., CO2 2
3 or OH ions with, e.g., SO4 or Cl ions. This
sequential process of the gradual buildup of corrosion
products can successively result in more protective
corrosion products in many atmospheric environ-
ments, see Leygraf, et al.,5 for more details.
Several of the compounds seen in the corrosion
product sequences displayed in Figure 7 have been
detected upon exposure of zinc and Zn-Al alloys in
different Cl-containing atmospheres, including labo-
ratory exposures (the new revised VDA Corrosion Test
Method, Standard SEP 1850 VDA 621-415 B, for
automotive applications, and the single drop-test
discussed above) as well as marine eld exposures.41,53
The similarity in detected compounds for both labo-
ratory and eld tests suggests that laboratory exposures
can reproduce the same or similar compounds as in
marine environments, although in different
proportions.53
It should emphasized that the different
mechanisms presented above for the role of magnesium
and aluminum in Zn-Mg-Al coatings are highly de-
pendent on actual physicochemical conditions, and
can only be expected to operate to a varying extent
depending on actual exposure. One obvious example of
an inuential parameter is the Cl-deposition rate
which determines to what extent the Cl-containing
compounds in Figure 7 are formed at the expense of
CO23 -containing compounds. Another important
parameter is the concentration of CO2, which may be
dramatically reduced in geometrically conned
volumes. The reduction or absence of this gaseous
constituent has been shown to signicantly increase the

CORROSIONVol. 73, No. 9 1067

INVITED CRITICAL REVIEW
corrosion rate of hot-dip ZnMgAl coatings compared
with ambient CO2 concentrations. At low levels of
CO2, the main corrosion products detected were the
layered double hydroxide Zn6Al2CO3(OH)164H2O and
Zn5Cl2(OH)8H2O, whereas Zn5(CO3)2(OH)6 and
Zn5Cl2(OH)8H2O were detected at ambient CO2 levels.57
In addition to all mechanisms presented above, which
largely are based on the detection and distribution of
different compounds in the corrosion products, the
corrosion protective ability may depend on compounds
which have actually not been detected but, never-
theless, may play a decisive role. One example could be
the very thin (less than 100 nm) layer of ZnO that has
been shown to form a protective inner barrier layer on
bare zinc and only could be detected with highly
sensitive TEM.18
ATMOSPHERIC CORROSION RATES AND
RUNOFF RATES ARE NOT EQUAL
As discussed in a previous section, corrosion is
primarily an electrochemical process in which the metal
is oxidized in the anodic reaction, whereas metal
runoff with time predominantly is governed by chemical
processes taking place at the interface between the
patina and the environment (Figure 1). There are several
reasons why atmospheric corrosion rates and runoff
rates are not equal. The total amount of corroded metal
contains two parts: one part which retains in the
corrosion product layer and one part which dissolves
from the patina by the action of precipitation (metal
runoff) or possibly via aking or wear processes
(e.g., Leygraf, et al.,5 and Oesch and Heimgartner58).
From this follows that metal corrosion rate data cannot
directly be used to assess metal release rate data;
such an assumption would highly overestimate the
extent of metal release. Available corrosion rate data
(a) 12
Average corrosion rate
Calculated runoff rate
10
Measured runoff rate
8
Rate (g/m2.y)
6
4
2
0 0
0.5 1 2 4
Exposure Period (y)
FIGURE 8. (a) Corrosion rates and zinc runoff rates (measured and calculated) for zinc sheet exposed in Dbendorf,
Switzerland up to 4 y (adapted from Leuenberger-Minger, et al.62), and (b) annual runoff/corrosion rate ratios for zinc sheet
exposed during 1 y at a marine site in Brest, France72 and during 15 months at the marine site of Valparaiso, Chile.63 Note:
calculated runoff data deduced from the difference between the mass loss and the zinc content of adhering corrosion
products (assuming Zn5(CO3)2(OH)6 as the dominating patina constituent).
1068
or dose-rate predictions5,59 are often based on 1 y
measurements or on corrosion rates averaged over a
few years. During this time, the corrosion rates are
signicantly higher compared with long-term condi-
tions, when the patina is established and acts as an
efcient barrier that hampers the corrosion process.
As a result of substantial reductions in corrosive
pollutant levels (e.g., SO2) seen in several parts of the
world (e.g., Europe, North America), available literature
data on corrosion rates are furthermore often con-
siderably higher than more contemporary rates.60
Differences in short-term corrosion rates and runoff
rates of zinc and galvanized steel are therefore expected,
and directly measured annual average runoff rates
are typically 50% to 90% of the corresponding annual
average corrosion rates up to 5 y of exposure61-74 at
sites characterized by different corrosiveness and an-
nual rainfall quantities (in the range 500 mm to
1,000 mm). Similar results have been observed for zinc
sheet exposed up to 4 y at seven different sites in
Switzerland58,62 for which the zinc runoff rate was
calculated, rather than measured, by subtracting
the amount of zinc in adhering corrosion products
(assuming Zn5(CO3)2(OH)6 as the main corrosion
product) from the total measured mass loss. These
calculated release rates of zinc were on an average
49% and 69% of the corrosion rates after 1 y and 4 y of
exposure. Comparative runoff rate measurements at
one of the sites (Dbendorf) showed that such calcu-
lations highly overestimate the runoff rate, see
Figure 8(a), as the patina also contained other corrosion
products not considered in the calculations. At more
polluted sites and for more complex patina composi-
tions, this effect will be even more pronounced.
Nevertheless, this approach can provide conservative
and more realistic estimates of runoff rates, rather
than using corrosion rates directly. Lower runoff rates
(b) 1
Annual Rate: Runoff/Corrosion
0.8
0.6
0.4
0.2
Brest, France Valparaiso, Chile
CORROSIONSEPTEMBER 2017

compared with corrosion rates (84% lower) during
short-term exposures are further illustrated in Figure 8(b)
for zinc sheet exposed during 1 y at a marine site
(Brest) in France72 and for galvanized steel (99% lower)
exposed for 15 month in Valparaiso, Chile.63 As
discussed below, the differences depend on factors such
as the corrosiveness of the test site, the formation rate
and composition of corrosion products, and on climatic/
environmental conditions. At sites of low or minor
annual rainfall quantities (<250 mm/y), such as the site
in Valparaiso, Figure 1(c), the difference can be even
larger as the partial dissolution of zinc from the patina
during daily repeated cyclic wet/dry periods is not
washed from the surface to any larger extent but will
rather re-precipitate and gradually build up the
patina.
THE RUNOFF PROCESS IS TIME DEPENDENT
AND GOVERNED BY PREVAILING EXPOSURE
AND ENVIRONMENTAL CONDITIONS
Even though different mechanisms govern at-
mospheric corrosion and metal runoff, both phenomena
are highly intertwined and inuenced by the same
environmental and exposure conditions. Whereas the
corrosion rates often rapidly decrease with time,
resulting from the formation of a protective patina, long-
term runoff rates seem to be relatively constant or
even reduced with time as the barrier properties of the
patina improve (Figure 8[a] and discussion below).
The metal release process of single rain events is
time dependent and strongly dependent on actual
pollutant levels and environmental conditions, both
prior to and during a rain episode. The predominating
corrosion products that form on zinc at most atmo-
spheric conditions are usually poorly soluble and ad-
here strongly to the surface where they act as efcient
barriers that reduce the corrosion rate. These corrosion
products should not be mistaken for soluble, poorly
adhering zinc salt particles that rapidly dissolve in the
presence of water/humidity. Some zinc in the cor-
rosion products will be dissolved into the thin aqueous
surface layer (in which pollutants and deposits dis-
solve) and be released (washed) from the surface by
the action of impinging rainwater. This fraction is
denoted the zinc runoff or zinc release and inuences
only marginally the adherent patina. In the absence of
rainwater, dissolved zinc will re-precipitate as corrosion
products. The amount of released zinc that can be
dissolved and released from the corrosion products
depends not only on the patina composition and
action of rain water, but also on parameters such as
exposure site and environmental/pollutant condi-
tions, environmental conditions prior to a rain event,
surface orientation, degree of sheltering, and surface
inclination, rain characteristics/intensity, and sam-
pling period (e.g., see literature63,70,75-80). Several
investigations have concluded that most metal is
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
released in the rst portion (rst ush) of the runoff
volume (e.g., see literature63,70,75,79,81-83), where after it
is reduced to lower, relatively constant, levels upon
extended rain duration. The part of metal runoff in the
rst ush portion of a rain event is strongly related to
the ow rate (or rain intensity) passing over a surface. At
a given total rainfall volume, more zinc is released per
surface area during a longer low intensity rain episode
than during a shorter high intensity rain episode.
As a consequence, large variations in released
concentrations of zinc are reported both during and
between different rain episodes. For example, zinc
concentrations between 0.3 mg/L and 30 mg/L, with a
volume weighted mean concentration of 4.9 mg/L,
have been reported for 38 different rain events sampled
during 1 y in Munich, Germany.75 Data from con-
tinuous measurements of released zinc from bare
zinc sheet during a 15 y urban exposure in Stock-
holm, Sweden showed a mean concentration (225
sampling periods of several rain events) of 4.1 mg/L
Zn (min: 1.3 mg/L, max: 11.9 mg/L) for the whole time
period.84-85 Corresponding data generated during
10 y at marine conditions ranged between 1.6 mg/L and
6.9 mg/L (mean value 3.7 mg/L).71,85 Similar results
(1.1 mg/L Zn to 12.2 mg/L Zn) have been observed,86-90
whereas other studies reported signicantly lower
concentrations, ranging from 0.03 mg/L to 0.5 mg/L,91
or higher concentrations (8.0 mg/L Zn to 38.1 mg/L
Zn).87,92 However, any direct use or comparison
between runoff concentrations of different sites or
events may lead to erroneous conclusions as the mea-
sured concentrations of released metals in, e.g., roof
and faade runoff strongly depend on the surface area
exposed to precipitation, the duration and intensity of
the rainfall event, the actual rain volume impinging the
surface of interest, dilution effects, etc.63,75,78,93-95
Implications on the environmental risk assessment are
discussed below.
Normalization of observed released concentra-
tions of zinc to the nominal surface area and inclination,
the rainfall quantity (in mmdifferent from the col-
lected runoff volume because of surface inclination and
wind direction) and time period must be made to
enable comparison of results from, e.g., sites of different
rainfall quantities or between different rain events.2,61
In order to quantify the extent of zinc release from
corroded surfaces it is also essential to correct for
background levels of deposited metals. Relatively high
background deposition rates of zinc from the atmo-
sphere96 or from industrial plants have been observed
in the literature.64,76,90,97 The methodology on how
to determine and report metal runoff rates at atmo-
spheric conditions is described in ISO Standard
17752:2012.98
As a consequence of the successive buildup of
more insoluble corrosion products, the runoff rate of
zinc from zinc sheet and galvanized steel is gradually
reduced with time on a long-term perspective. As long as
1069
INVITED CRITICAL REVIEW

5 Relatively few studies exist that have performed

long-term zinc runoff rate measurements from bare zinc
Average Runoff Rate (Zn g/m2.y)

sheet at outdoor eld conditions. These investigations

4
3 Reported annual zinc runoff rates from bare zinc and
2 malized to a surface inclination of 45. The data in
1
0 exposure conditions. The runoff rates range from
0 2
FIGURE 9. Changes in zinc runoff rates released from bare zinc
sheet per surface area versus time exposed for almost 16 y at urban
unsheltered conditions (Stockholm, Sweden) with 45 inclination
from the horizontal, facing south.
the prevailing environmental and meteorological
conditions (e.g., SO2, pH, rainfall quantity) do not show
any signicant variations on an annual perspective,
the long-term runoff rate reaches a relatively constant
(or slightly diminishing) level.62,79 This effect is
illustrated in Figure 9 for bare zinc sheet exposed for
15 y at urban conditions during which a patina,
predominantly consisting of a basic zinc hydroxide
(Zn5(CO3)2(OH)6), gradually is built up.5,61 Similar
ndings and trends (based on shorter exposure periods)
have been reported also for other exposure condi-
tions, e.g., Leuenberger-Minger, et al.,62 and
Veleva, et al.69
are usually performed using model surfaces of different
size, orientation, and surface inclination.65,99
galvanized steel in the literature are compiled in
Figure 10(a) whereby the runoff rates have been nor-
Figure 10(a) include 117 different annual rates and
originate from 33 investigated sites with different
rainfall quantities (220 mm/y to 2,200 mm/y), envi-
ronmental characteristics, exposure length, and
4 6 8 10 12 14 16
0.6 g/m2y to 25.3 g/m2y (mean value 4.97 g/m2y;
Exposure Period (y)
50% of all rates are between 2 g/m2y and 6.4 g/m2y).
The highest zinc runoff rates are observed in indus-
trial sites characterized by high pollutant levels.
Because observed differences in runoff rates reect
differences in both exposure and environmental condi-
tions, reported runoff rates have been normalized to
the corresponding annual rainfall quantity (when
available), Figure 10(b). More than 85% of the reported
data show runoff rates between 0.002 g/m2mm
and 0.010 g/m2mm (amount of metal runoff [g] per
surface unit [m2] and annual rain amount [mm]) without
any differences between marine, rural, or urban sites
with low levels of SO2. The amount of released zinc per
given rainfall unit increases as the SO2 concentration
exceeds 10 g/m3. The results clearly show that the
amount precipitation is a major factor that determines
the zinc runoff rate and that the effect of chlorides seems
less important compared with SO2. This is consistent
with both eld and laboratory investigations that show
the importance of SO2 deposition on the runoff process
(e.g., see literature64,80,97,99-102).

(a) 30 (b) 0.035

n = 117 Marine
Normalized Annual Zinc Runoff

Rural/urban (SO2: <5 g/m3)

Reported Annual Runoff Rate

25 0.03
Urban/industrial (SO2: 5 g/m3 to 10 g/m3)
0.025
20 Urban/industrial (SO2: 11 g/m3 to 80 g/m3)
(Zn g/m2.y)

(g/m2.mm)

0.02
15
0.015
10
0.01
5 0.005

0 0
0 20 40 60 80 100 120
Data No.
FIGURE 10. (a) Reported annual zinc runoff rates (g/m2y) (in total 117 datasets) of bare zinc sheet or galvanized steel
exposed at 33 exposure sites with data normalized to 45 surface inclination from the horizontal. The box encompasses 50% of
all data with the top line representing the upper quartile (25% of data > this value), the bottom line the lower quartile (25% of all
data < this value), and the median value displayed as a line in the box. The maximum and minimum values excluding outliers
(dots, dened as values larger than or less than 1.5 times the upper and the lower quartile, respectively) are illustrated by the
error bar. (b) The corresponding annual amount of zinc runoff normalized to the annual rainfall quantity (mm/y). The data
originate from exposure sites with increasing SO2 concentration representing marine, rural/urban, and urban/industrial sites.

1070 CORROSIONSEPTEMBER 2017


PREDICTIVE MODELING OF ZINC RUNOFF
RATES POSSIBLE AT ATMOSPHERIC
EXPOSURE CONDITIONS
Models to predict zinc runoff resulting from at-
mospheric corrosion were elaborated during the 1990s
in which the importance of rainfall quantities (surface
wetness), rain pH, and wet and dry deposition of weak
and strong acids (including gaseous concentrations
and deposition velocities of SO2, HNO3, and HCl) and of
particles on the solubility of corrosion products were
explored.80,101 Later on, an equation could be deduced:
R = 1.36 0.16SO2 
in which observed zinc runoff rates (R, in g/m2y) at
sites of similar annual rainfall quantities were corre-
lated to SO2 concentration (g/m3).99 Because of
scarce availability of literature data, the correlation was
only based on limited data. Nevertheless, the model
illustrated the importance of SO2 on the zinc runoff
process. Based on detailed eld and laboratory
investigations on the importance and inuence of
(a) 25
y = 0.86x
Predicted Runoff Rate (g/m2.y)
20
15
10
0
0 5
Observed Runoff Rate (g/m2.y)
(b)
1980
FIGURE 11. (a) Relation between observed and predicted annual runoff rates of zinc based on Equation (3). (b) Predictive
annual zinc runoff rate maps for 1980, 1990, 2000, and 2005 for zinc sheet exposed at a surface inclination of 45 from the
horizontal. Maps of pH, SO2, mm rain based on European Monitoring and Evaluation Programme (EMEP) available in
Odnevall Wallinder, et al.104
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
surface inclination, rainfall quantity, and rain pH on
the zinc runoff rate,66,70 a more elaborate model was
established. However, this model did not include the
importance of SO2 deposition or concentration, previ-
ously known to inuence the runoff rate. As a result of
the lack of sufcient data highlighting the effect of SO2,
runoff rates were instead calculated based on mass
balances (zinc runoff = zinc mass loss zinc in adhering
corrosion products) from gravimetric data on mass
loss and on the assumption that Zn5(CO3)2(OH)6 is the
predominating corrosion product. As previously dis-
cussed and shown in Figure 8,62 such a calculation
may overestimate the importance of SO2 on the
(2) runoff rate and provide a conservative measure of its
effect. Based on the same approach as previously
used for copper103-104 and on data from bare zinc sheet
and galvanized steel after 1, 2, and 4 y of unsheltered
exposure within the ICP Materials research program,105
the following model was established (Equation [3]):
R = 1.2 SO2 0.5 0.4 Rain 100.45pH
cos= cos45 (3)
1:1 ratio
10 15 20 25
Zn runoff
0.0 g/m2
2.0 g/m2
4.0 g/m2
6.0 g/m2
8.0 g/m2
1990 2000 2005
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INVITED CRITICAL REVIEW

Here R is the predicted annual runoff quantity of zinc improved corrosion resistance (lower corrosion
per surface unit area (g/m2y), [SO2] the annual rate) compared with galvanized steel and zinc
average value of the SO2 concentration (g/m3), and sheet.50-51,71,107-108 The amount of zinc runoff from
[Rain] the total amount of rain per year (mm/y). these (and other) coatings is strongly related to the
Predicted versus observed zinc runoff rates from zinc presence and surface coverage of zinc-rich corrosion
sheet or galvanized steel are presented in Figure 11. products (similar as formed on zinc sheet and gal-
The model predicts 70% of all observed rates (panels of vanized surfaces) and of aluminum-rich, or aluminum-
different age, zinc sheet, hot-dipped galvanized zinc-rich corrosion products of low solubility and/or
sheet, electrogalvanized sheet) within 40% from their with efcient barrier properties. The formation of
measured value. However, it should be noted that corrosion products is also strongly related to the
quite a few environmental datasets added into the microstructure, as discussed above. From an increased
model are uncertain because of lack of information formation of poorly soluble corrosion products and
(in particular for rain pH). the presence of aluminum-rich corrosion products follows
Calculated zinc runoff maps of Europe are pre- a reduced zinc runoff rate from Zn-Al coatings com-
sented in Figure 11(b) based on annual average values pared with zinc sheet and galvanized steel. As illustrated
of rainfall quantities and SO2 taken from the coop- in Figure 12 for Zn55Al (containing 43.3 wt% Zn) and
erative program for monitoring and evaluation of the Zn5Al (containing 95 wt% Zn), the amount of zinc runoff
long-range transmission of air pollutants in Europe106 from alloy coatings cannot be calculated based on their
and rain pH data compiled as annual average values bulk composition and knowledge on zinc runoff rates
for the period 19802000. Maps of rain pH, SO2, and from bare zinc sheet. Long-term eld data shows that
rainfall and details on how they were generated are the annual runoff rate of zinc from Zn55Al is 64% lower
given in Odnevall Wallinder, et al.104 The maps clearly (after 1 y) and 95% lower (after 10 y) than the corre-
show that the amount of zinc runoff has decreased sponding data for bare zinc sheet exposed in urban
signicantly over the time span investigated, a con- conditions, Figure 12(a). In marine conditions the zinc
sequence of reduced SO2 concentrations and rain runoff from Zn55Al is 80% (after 1 y) and 90% (after 5 y)
acidity over most parts of Europe. lower50 than for bare zinc sheet. For Zn5Al, observed
annual zinc runoff rates were 40% to 50% lower than for
THE EXTENT OF ZINC RUNOFF IS STRONGLY zinc sheet in urban conditions and remained at rela-
DEPENDENT ON THE PROPERTIES OF THE tively stable levels up to 10 y, Figure 12(b).51 Also in
CORROSION PRODUCTS LAYER, AND NOT marine exposures the zinc runoff rate was 40% to 60%
POSSIBLE TO PREDICT FROM THE BULK lower than for bare zinc sheet up to 5 y of exposure.53
ALLOY CONTENT These results are consistent with literature ndings at
an industrial/marine site with approximately 40% and
Depending on the area of application, the given 20% lower runoff rates of zinc from Galvalloy (a similar
exposure condition, the intended service life, and the alloy as Zn5Al) and Zalutite (a similar alloy as Zn55Al),
requirement to hinder cut-edge corrosion, zinc-based respectively, after 1 y of exposure.78 The efciency of
coatings on steel sheet are commonly used in outdoor aluminum-rich corrosion products to hinder zinc runoff
constructions and outdoor applications. The Zn-Al has also been shown for Zn-Al-Mg alloys.109 The extent
alloys Zn5Al and Zn55Al are two frequently used of aluminum runoff from Zn-Al alloys or magnesium from
coatings that, at similar exposure conditions, possess Zn-Al-Mg alloys has not been reported in the literature,

(a) Zn55Al (43.4% Zn) (b) Zn5Al (95% Zn)

1.2 2.5
Annual Runoff Rate (Zn g/m2.y)
Annual Runoff Rate (Zn g/m2.y)

Calculated Calculated
1 2 Observed
Observed
0.8
1.5
0.6
1
0.4

0.2 0.5

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Exposure Period (y) Exposure Period (y)
FIGURE 12. Observed annual runoff rates of zinc from two Zn-Al alloys, Zn55Al (a) and Zn5Al (b) exposed up to 10 y at urban
conditions compared with calculated rates based on bulk alloy composition and annual zinc runoff rates of bare zinc sheet
exposed in parallel. All data from surfaces inclined 45 from the horizontal.

1072 CORROSIONSEPTEMBER 2017

 INVITED CRITICAL REVIEW

with a few exceptions. Long-term studies of Zn55Al most years less or signicantly less than 5% com-
exposed up to 10 y at urban and up to 5 y at marine pared with the bare surface except for the fourth
unsheltered conditions show 20 to 30 times lower release year (less than 9%). Similar results are reported up to
rates of aluminum compared with zinc.50 Even lower 10 y at urban conditions.61,85 Very low levels of zinc
levels of released aluminum compared with zinc have have also been shown to be intermittently released
been determined for Zn5Al exposed at similar from coatings due to the presence of zinc-rich
conditions.53,85 pigments.61,78
Some runoff data also exist for other coatings
such as spray-coated zinc and zinc-aluminum alloys,
e.g., Bertling, et al.,84 and for pre-weathered zinc ENVIRONMENTAL FATE
sheet.64,71,94,97,110 Runoff rates from these surfaces are
Reported runoff rates reect total amounts of
in the same order of magnitude, or lower, compared
released zinc without considering the chemical specia-
with bare zinc sheet. The release of zinc from cut-edges
tion of zinc or how it changes upon environmental
of Zn-Al and Zn-Al-Mg alloys has been shown to be of
interaction. This kind of data can be used to assess
minor importance and, furthermore, to be reduced with
the total amount of dispersed zinc from an outdoor
time.109
application but cannot be used directly to assess any
The presence of different additional surface
potential environmental risks.4 Such an assessment
treatments and organic coatings (of different composi-
requires additional knowledge on the chemical specia-
tion and thickness) will reduce the released amount of
tion (chemical form) of released zinc, which depends
zinc further as long as they remain intact, but will
on the chemistry of actual dispersion conditions, and
gradually (often locally) lose their barrier properties
which governs the bioavailability. Further aspects
with time upon environmental exposure (e.g., resulting
that need to be considered and that inuence both the
from UV radiation, chloride deposition, gaseous pol-
total amount of dispersed zinc and its speciation
lutants, etc.).61,71-72,78,84,94,109 Thin (10 nm) chromate-
include dilution effects of zinc runoff with other storm
based surface treatments on galvanized steel have as
water sources and the retention and interaction with
an example shown barrier effects up to 5 y of exposure at
different solid surfaces and with dissolved organic
urban conditions and thin organic coatings (100 nm)
matter upon environmental entry via different aquatic
on the same material to maintain their barrier proper-
settings. Reported total released zinc concentrations are
ties also after 10 y.61 Similar observations, though
measured at the immediate release situation (often
more rapid coating degradation, have been made at
directly at the rooftop) and vary signicantly with time
marine conditions up to 5 y.72 More efcient and long-
and between different rain episodes, with levels
term barrier effects of top-coatings with time are illus-
related to differences in rain characteristics, rain
trated in Figure 13 for hot-dipped galvanized steel
amount, and prevailing environmental and pollutant
with and without an organic coating (duplex, 60 m
conditions. At the immediate release situation at the
thick) exposed up to 9 y at marine conditions. The
rooftop, zinc is predominantly present as the free
amount of zinc runoff from the coated surface was for
hydrated Zn2+ ion and some weakly bonded (labile) zinc
complexes, all in a bioavailable form.71,78,84,111-113
0.7
These ndings are supported by chemical speciation
HDG modeling considering the pH of the zinc runoff water,
0.6 which typically varies between 5.8 and 7.1 for galva-
Zinc Runoff (g/m2.100 mm)

HDG + duplex coating

nized steel78 and between 4.5 and 7.2 for different
0.5 bare and coated zinc-based materials and with low
levels of organic matter at the rooftop.84 However,
0.4 when dispersed via downspouts, through urban storm
water systems, or directly into an aquatic setting, the
0.3
free Zn2+ ion will rapidly react with organic and inor-
0.2
ganic species in the water forming different labile or
strongly bonded complexes with OH, CO2 3 , or dissolved
0.1 organic matter of low bioavailability and reduced
toxicity,114 or be retained to different extent on sur-
0 rounding solid surfaces. Surfaces in the near vicinity
1 2 3 4 5 6 7 8 9
of a building, such as concrete in pavement and in storm
Year of Exposure
water systems, and sewage piping and soil have
FIGURE 13. Observed annual zinc runoff rates normalized to the shown to act as efcient sinks for released zinc
annual rainfall quantity (g/m2100 mm) for hot-dipped galvanized with and to reduce the bioavailable fraction, e.g., see
and without an organic coating (duplex) exposed at 45 from the
literature.61,84,94,115-119 Laboratory investigations at
horizontal at the marine site of Brest, France up to 9 y. (Data up to 3 y
realistic rain and runoff water conditions using slabs
published in Lindstrm and Odnevall Wallinder61).
of pavement concrete revealed a retention capacity of

CORROSIONVol. 73, No. 9 1073

INVITED CRITICAL REVIEW

Zinc runoff

Zn2+

Zn2+
2.5 m
Zinc runoff
Concre
te

7% to 25%
retained Fic
tive
raction sc
95% to 100% Soi l inte en
ari
retention o
Non-retained zinc

Zn2+ Concentration (g/L)

100 0.05
Zn2+
Zinc Species (%)

80 0.04

60 0.03
Background 40 Znorg 0.02
concentrations 20
Znother 0.01
0 Zntot < EbC50 (algae)
0
0 20 40 60 80 100 120
Distance in Storm Drain (m)

FIGURE 14. Schematic illustration of the capacity of soil and concrete to retain zinc dispersed from outdoor constructions as
a consequence of atmospheric corrosion.

zinc which varied between 7% and 25% per contact
meter depending on ow rate. Such ndings suggest
that most zinc in the runoff water is retained within
20 m from the building, Figure 14.61
These observations are supported by literature
ndings on porous pavement cement, e.g., Dierkes,
et al.,120 and Legret and Colandini.121 Efcient (>90%)
long-term retention of zinc in storm water runoff has
recently been reported for porous Portland cement
concrete.122 Long-term zinc retention investigations on
soil of different characteristics (pH, cation exchange
capacity, composition) clearly show a high capacity
of all soils to retain all zinc in runoff water (95%
to 100%) and to strongly bind released zinc to organic
matter. Zinc in the pore water was present in a non-
bioavailable form (non-toxic toward algae) and
strongly bonded to complexes with organic matter,
Figure 14.84 Similar ndings have been observed for
zinc retained in constructed wetlands.123
These results and literature ndings suggest that
zinc to a large extent is retained by different solid
surfaces already in the near vicinity of a building and
that the concentration (and bioavailability) of dispersed
zinc becomes substantially reduced upon environ-
mental entry.
CONCLUDING REMARKS
v In this review some critical issues have been
addressed that concern the corrosion and dispersion
(runoff) from zinc and zinc alloyed with aluminum
and magnesium when exposed to atmospheric
environments.
v Corrosion and runoff are intertwined processes
inuenced by the same environmental and exposure
conditions. Yet, the underlying physicochemical
mechanisms that inuence the processes are different.
Corrosion is largely controlled by electrochemical
reactions at the metal/patina interface, whereas runoff
predominantly is governed by chemical reactions at
the patina/atmosphere interface.
v For both processes, the evolution of the patina layer
is crucial. The corrosion rate is often observed
to slowly decrease with time, resulting from the for-
mation of a successively more protective patina. The
runoff rate, on the other hand, is more constant on a
long-term perspective (not during individual rain events)
but may also exhibit a slow long-term reduction, as the
barrier properties of the patina eventually may improve.
v Despite large environmental variations between
exposure sites, there exist two main sequences for the
gradual evolution of compounds in zinc patina: one in
more sulfur-dominated and one in more chloride-
dominated environments. Because of climatic
changes and the reduction of sulfur-containing atmo-
spheric species in many parts of the world, the
chloride sequence is expected to gradually dominate
over the sulfur sequence.
v The atmospheric corrosion of bare zinc sheet in
chloride-containing atmosphere is relatively well under-
stood. Characteristic features are separated anodic and
cathodic areas, the instant formation of a thin layer of zinc

1074 CORROSIONSEPTEMBER 2017


oxide, and the subsequent formation of hydrozincite
(Zn5(CO3)2(OH)6), simonkolleite (Zn5Cl2(OH)8H2O), and
gordaite (NaZn4Cl(OH)6SO46H2O) at various parts of
the zinc surface with different corrosion protective func-
tions. Even though the deposition of chlorides increases
the rate of corrosion of zinc, its effect on the extent of zinc
runoff is minor.
v Successful efforts to improve the corrosion prop-
erties of zinc by alloying with magnesium and alumi-
num have resulted in zinc layers with more complex
microstructure and also a broader range of mechanisms
responsible for the improved protective ability. The
role of the alloying elements has been attributed to
several mechanisms, such as the precipitation of
magnesium hydroxide at cathodic areas to reduce the
oxygen reduction rate, the increased formation of
protective simonkolleite and of aluminum oxide, and a
layered double hydroxide, the latter two with signif-
icant barrier properties. No universal mechanism
exists, as the proposed mechanisms most likely are
dependent on actual exposure conditions.
v By compiling a large body of reported zinc runoff
data, it is concluded that the amount of released zinc is
highly dependent on the amount of rainfall. Per
rainfall unit, the zinc release increases when the SO2
concentration exceeds 10 g/m3, while the effect of
chloride deposition is less important compared
with SO2.
v Based on all runoff data a model is presented for
bare zinc sheet that predicts 70% of all observed runoff
rates within 40% from their measured value. Corre-
sponding predictions of Zn alloys cannot be based on
the bulk alloy content, but need to consider actual
properties of the corrosion product layer.
v In order to perform an assessment of potential
environmental risks of zinc-containing outdoor surfaces
it is necessary to consider not only the total amount of
dispersed zinc in a given exposure situation, but also
the chemical speciation (chemical form) of zinc in
different environmental settings of varying chemistry,
the dilution effects, and the capacity of different solid
surfaces to retain dispersed zinc.
ACKNOWLEDGMENTS
The authors are most grateful to Docent Johan
Tidblad, Swerea Kimab, Sweden for invaluable contri-
butions in the elaboration of the predictive zinc runoff
model and for producing zinc runoff maps. We also wish
to acknowledge Dr. Clara Anghel for her initial efforts
to establish a zinc runoff model and M.Sc. Tingru Chang
for technical assistance with the manuscript
preparation.
REFERENCES
1. S.J. Kropschot, J.L. Doebrich, Zinc-the Key to Preventing Cor-
rosion, U.S. Geological Survey Fact Sheet, 2327-6932, 2011.
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
2. ISO 9223:2012, Corrosion of Metals and AlloysCorrosivity of
AtmospheresClassication, Determination and Estimation
(Geneva, Switzerland: International Organization for Standardi-
zation, 2012).
3. Regulation (EC) No. 1907/2006 of the European Parliament and
of the Council of 18 December 2006 Concerning the Registration,
Evaluation, Authorisation and Restriction of Chemicals (REACH),
Establishing a European Chemicals Agency, EU-OSHA, 2006.
4. L. Landner, R. Reuther, Metals in Society and in the Environment.
A Critical Review of Current Knowledge on Fluxes, Speciation,
Bioavailability and Risk for Adverse Effects of Copper, Chromium,
Nickel and Zinc (Dordrecht, The Netherlands: Kluwer Academic
Publishers, 2004).
5. C. Leygraf, I. Odnevall Wallinder, J. Tidblad, T. Graedel, Atmo-
spheric Corrosion (Hoboken, NJ: John Wiley & Sons, 2016).
6. T. Graedel, Corros. Sci. 38 (1996): p. 2153-2180.
7. L. Farrow, T. Graedel, C. Leygraf, Corros. Sci. 38 (1996):
p. 2181-2199.
8. H. Gil, C. Leygraf, J. Tidblad, J. Electrochem. Soc. 159 (2012):
p. C123-C128.
9. I. Odnevall, C. Leygraf, Reaction Sequences in Atmospheric
Corrosion of Zinc, STP 1239 (West Conshohocken, PA: ASTM
International, 1995).
10. I. Odnevall, C. Leygraf, Corros. Sci. 34 (1993): p. 1213-1229.
11. D.D. Macdonald, K.M. Ismail, E. Sikora, J. Electrochem. Soc. 145
(1998): p. 3141-3149.
12. S.Z. Chu, K. Wada, S. Inoue, S. Todoroki, J. Electrochem. Soc. 149
(2002): p. B321-B327.
13. A. Krtschmer, I. Odnevall Wallinder, C. Leygraf, Corros. Sci. 44
(2002): p. 425-450.
14. K. FitzGerald, J. Nairn, G. Skennerton, A. Atrens, Corros. Sci. 48
(2006): p. 2480-2509.
15. I. Odnevall Wallinder, C. Leygraf, Corros. Sci. 39 (1997):
p. 2039-2052.
16. J. Sandberg, I. Odnevall Wallinder, C. Leygraf, N. Le Bozec, Corros.
Sci. 48 (2006): p. 4316-4338.
17. S. Thomas, I. Cole, N. Birbilis, J. Electrochem. Soc. 160 (2013):
p. C59-C63.
18. S. Thomas, N. Birbilis, M. Venkatraman, I. Cole, Corros. Sci. 69
(2013): p. 11-22.
19. D. Knotkova, K. Kreislova, S.W. Dean, ISOCORRAG, International
Atmospheric Exposure Program: Summary of Results: Developed by
ISO/TC 156/WG 4, Atmospheric Corrosion Testing and Classi-
cation of Corrosivity of Atmosphere (West Conshohocken, PA:
ASTM International, 2010).
20. M. Morcillo, Atmospheric Corrosion in Ibero-America: The MICAT
Project, in Atmospheric Corrosion, eds. W.W. Kirk, H.H. Lawson,
STP 1239 (West Conshohocken, PA: ASTM International, 1995).
21. F. Samie, J. Tidblad, V. Kucera, C. Leygraf, J. Electrochem. Soc.
154 (2007): p. C249-C254.
22. F. Samie, J. Tidblad, Corros. Eng. Sci. Technol. 43 (2008):
p. 117-122.
23. J. Tidblad, Atmos. Environ. 55 (2012): p. 1-6.
24. I.S. Cole, W. Ganther, S. Furman, T. Muster, A. Neufeld, Corros.
Sci. 52 (2010): p. 848-858.
25. A. Mikhailov, J. Tidblad, V. Kucera, Prot. Met. 40 (2004):
p. 541-550.
26. P. Volovitch, T. Vu, C. Allly, A.A. Aal, K. Ogle, Corros. Sci. 53
(2011): p. 2437-2445.
27. T. Prosek, D. Persson, J. Stoulil, D. Thierry, Corros. Sci. 86 (2014):
p. 231-238.
28. A.P. Yadav, A. Nishikata, T. Tsuru, Corros. Sci. 46 (2004): p. 169-
181.
29. A. Yadav, H. Katayama, K. Noda, H. Masuda, A. Nishikata,
T. Tsuru, Corros. Sci. 49 (2007): p. 3716-3731.
30. I. Odnevall, C. Leygraf, Corros. Sci. 36 (1994): p. 1551-1559.
31. A.K. Neufeld, I.S. Cole, A.M. Bond, S.A. Furman, Corros. Sci. 44
(2002): p. 555-572.
32. T. Tsuru, K.-I. Tamiya, A. Nishikata, Electrochim. Acta 49 (2004):
p. 2709-2715.
33. E. Dubuisson, P. Lavie, F. Dalard, J.-P. Caire, S. Szunerits,
Corros. Sci. 49 (2007): p. 910-919.
34. Z.Y. Chen, D. Persson, C. Leygraf, Corros. Sci. 50 (2008):
p. 111-123.
35. I. Cole, T. Muster, S. Furman, N. Wright, A. Bradbury, J. Elec-
trochem. Soc. 155 (2008): p. C244-C255.
36. S. Li, L. Hihara, J. Electrochem. Soc. 161 (2014): p. C268-C275.
37. I. Cole, N. Azmat, A. Kanta, M. Venkatraman, Int. Mater. Rev. 54
(2009): p. 117-133.
1075
INVITED CRITICAL REVIEW
38. I. Cole, T. Muster, D. Lau, N. Wright, N.S. Azmat, J. Electrochem.
Soc. 157 (2010): p. C213-C222.
39. A. Borzillo, J. Crowley, J. Horton, Non-Ferrous Metal Coated
Products and Method of Production Thereof, Canadian patent CA
899729, 1972.
40. S.F. Radtke, D. Coutsouradis, J. Pelerin, Zinc-Aluminum Alloys
and Coatings, WIPO patent WO8102748, 1981.
41. S. Schuerz, M. Fleischanderl, G. Luckeneder, K. Preis,
T. Haunschmied, G. Mori, A. Kneissl, Corros. Sci. 51 (2009):
p. 2355-2363.
42. N. Hosking, M. Strm, P. Shipway, C. Rudd, Corros. Sci. 49 (2007):
p. 3669-3695.
43. S. Schrz, G. Luckeneder, M. Fleischanderl, P. Mack, H. Gsaller,
A. Kneissl, G. Mori, Corros. Sci. 52 (2010): p. 3271-3279.
44. T. Prosek, N. Larch, M. Vlot, F. Goodwin, D. Thierry, Mater.
Corros. 61 (2010): p. 412-420.
45. T. Prosek, A. Nazarov, U. Bexell, D. Thierry, J. Serak, Corros. Sci.
50 (2008): p. 2216-2231.
46. P. Volovitch, C. Allely, K. Ogle, Corros. Sci. 51 (2009): p. 1251-1262.
47. D. Persson, D. Thierry, N. LeBozec, T. Prosek, Corros. Sci. 72
(2013): p. 54-63.
48. A.R. Moreira, Z. Panossian, P. Camargo, M.F. Moreira, I. Da Silva,
J.R. De Carvalho, Corros. Sci. 48 (2006): p. 564-576.
49. D. Persson, D. Thierry, N. Le Bozec, Corros. Sci. 53 (2011):
p. 720-726.
50. P. Qiu, C. Leygraf, I. Odnevall Wallinder, Mater. Chem. Phys. 133
(2012): p. 419-428.
51. X. Zhang, T.-N. Vu, P. Volovitch, C. Leygraf, K. Ogle, I. Odnevall
Wallinder, Appl. Surf. Sci. 258 (2012): p. 4351-4359.
52. T. Vu, M. Mokaddem, P. Volovitch, K. Ogle, Electrochim. Acta 74
(2012): p. 130-138.
53. X. Zhang, C. Leygraf, I. Odnevall Wallinder, Corros. Sci. 73 (2013):
p. 62-71.
54. I. Odnevall, Characterization of Corrosion Products Formed on
Rain Sheltered Aluzink and Aluminum in a Rural and an Urban
Atmosphere, 14th Int. Corrosion Congress (Cape Town, South
Africa: ICC, 1999).
55. T. Graedel, J. Electrochem. Soc. 136 (1989): p. 204C-212C.
56. J. Friel, Corrosion 42 (1986): p. 422-426.
57. N. Le Bozec, D. Thierry, M. Rohwerder, D. Persson, G. Luckeneder,
L. Luxem, Corros. Sci. 74 (2013): p. 379-386.
58. S. Oesch, P. Heimgartner, Mater. Corros. 47 (1996): p. 425-438.
59. J. Tidblad, A. Mikhailov, V. Kucera, Unied Dose-Response
Functions after 8 Years of Exposure, Proceedings UN/ECE
Workshop on Quantication of Effects of Air Pollutants on
Materials (Berlin, Germany: Umweltbundesamt, 1998), p. 77-86.
60. J. Tidblad, Atmospheric Corrosion of Heritage Metallic Artefacts:
Processes and Prevention, in Corrosion and Conservation of
Cultural Heritage Metallic Artefacts, eds. P. Dillmann, D. Wat-
kinson, E. Angelini, A. Adriaens (Amsterdam, The Netherlands:
Elsevier, 2013), p. 37-52.
61. D. Lindstrm, I. Odnevall Wallinder, Environ. Monit. Assess. 173
(2011): p. 139-153.
62. A. Leuenberger-Minger, M. Faller, P. Richner, Mater. Corros. 53
(2002): p. 157-164.
63. R. Vera, F. Guerrero, D. Delgado, R. Araya, J. Braz. Chem. Soc. 24
(2013): p. 449-458.
64. P. Verbiest, H. Waeterschoot, R. Racek, M. Leclerq, Prot. Coat. Eur.
9 (1997): p. 47-58.
65. B. Lehmann, Freibewitterungsverhalten Von Dchern Mit
Metalldeckung Untersuchung Zur Zinkabgabe Von Dachdeck-
ungen Mit Titanzink (Ph.D. diss., Universitt Hannover, 1995).
66. S.D. Cramer, L.G. McDonald, Atmospheric Factors Affecting the
Corrosion of Zinc, Galvanized Steel, and Copper, STP 1000 (West
Conshohocken, PA: ASTM International, 1990).
67. L. Veleva, E. Meraz, M. Acosta, Mater. Corros. 58 (2007): p. 348-352.
68. L. Veleva, M. Acosta, E. Meraz, Corros. Sci. 51 (2009): p. 2055-2062.
69. L. Veleva, E. Meraz, M. Acosta, Corros. Eng. Sci. Technol. 45
(2010): p. 76-83.
70. W. He, I. Odnevall Wallinder, C. Leygraf, Water Air Soil Pollut.
Focus 1 (2001): p. 67-82.
71. J. Sandberg, I. Odnevall Wallinder, C. Leygraf, N. Le Bozec,
J. Electrochem. Soc. 154 (2007): p. C120-C131.
72. D. Lindstrm, Y. Hedberg, I. Odnevall Wallinder, Environ. Sci.
Technol. 44 (2010): p. 4322-4327.
73. D. Reiss, B. Rihm, C. Thni, M. Faller, Water Air Soil Pollut. 159
(2004): p. 101-113.
74. M. Faller, R. Richner, Polysurface 39 (1998): p. 7-11.
1076
75. A. Schriewer, H. Horn, B. Helmreich, Corros. Sci. 50 (2008):
p. 384-391.
76. S. Jouen, B. Hannoyer, A. Barbier, J. Kasperek, M. Jean, Mater.
Chem. Phys. 85 (2004): p. 73-80.
77. M. Chang, C.M. Crowley, J. Amer. Water Res. Assoc. 29 (1993):
p. 777-783.
78. J. Sullivan, D. Worsley, Br. Corros. J. 37 (2002): p. 282-288.
79. M. Faller, D. Reiss, Mater. Corros. 56 (2005): p. 244-249.
80. S. Cramer, J. Carter, P. Linstrom, D. Flinn, Environmental Effects
in the Atmospheric Corrosion of Zinc, STP 965 (West Consho-
hocken, PA: ASTM International, 1987).
81. J. Frster, Water Sci. Technol. 39 (1999): p. 137-144.
82. S.D. Cramer, S.A. Matthes, G.R. Holcomb, B. Covino Jr.,
S.J. Bullard, Precipitation Runoff and Atmospheric Corrosion,
CORROSION 2000, paper no. 452 (Houston, TX: NACE Interna-
tional, 2000).
83. J. Zobrist, S. Mller, A. Ammann, T. Bucheli, V. Mottier, M. Ochs,
R. Schoenenberger, J. Eugster, M. Boller, Water Res. 34 (2000):
p. 1455-1462.
84. S. Bertling, I. Odnevall Wallinder, C. Leygraf, D. Bergren Kleja, Sci.
Total Environ. 367 (2006): p. 908-923.
85. I. Odnevall Wallinder, unpublished work, 2017.
86. J.C. Good, Water Sci. Technol. 28 (1993): p. 317-321.
87. U. Quek, J. Frster, Water Air Soil Pollut. 68 (1993):
p. 373-389.
88. P. Thomas, G. Greene, Water Sci. Technol. 28 (1993): p. 291-299.
89. K. Lamprea, V. Ruban, Micro Pollutants in Atmospheric Depo-
sition, Roof Runoff and Storm Water Runoff of a Suburban
Catchment in Nantes, France, 11th Int. Conf. Urban Drainage
(Scotland, United Kingdom: IAHR/IWA, 2008).
90. S.A. Matthes, S.D. Cramer, S.J. Bullard, B. Covino Jr., G.R.
Holcomb, Atmospheric Corrosion and Precipitation Runoff from
Zinc and Zinc Alloys Surfaces, CORROSION 2003, paper no.
3598 (Houston, TX: NACE, 2003).
91. Y. Mason, A.A. Ammann, A. Ulrich, L. Sigg, Environ. Sci. Technol.
33 (1999): p. 1588-1597.
92. M. Gromaire, G. Chebbo, A. Constant, Water Sci. Technol. 45
(2002): p. 113-122.
93. I. Odnevall Wallinder, P. Verbiest, W. He, C. Leygraf, Corros. Sci.
42 (2000): p. 1471-1487.
94. P. Robert-Sainte, M.-C. Gromaire, B. De Gouvello, M. Saad,
G. Chebbo, Environ. Sci. Technol. 43 (2009): p. 5612-5618.
95. W. He, I. Odnevall Wallinder, C. Leygraf, Corros. Sci. 43 (2001):
p. 127-146.
96. J.N. Rauch, J.M. Pacyna, Global Biogeochem. Cycles 23 (2009):
p. 1-16.
97. P. Verbiest, C. Janssen, I. Odnevall Wallinder, C. Leygraf, En-
vironmental Effects of Zinc Runoff from Phosphated Zinc Sheets
Used for Building Applications, 14th International Corrosion
Congress (Cape Town, South Africa: ICC, 1999).
98. ISO 17752, Corrosion of Metals and AlloysProcedures to
Determine and Estimate Runoff Rates of Metals from Materials as
a Result of Atmospheric Corrosion (Geneva, Switzerland:
International Organization for Standardization, 2012).
99. I. Odnevall Wallinder, P. Verbiest, W. He, C. Leygraf, Corros. Sci.
40, 11 (1998): p. 1977-1982.
100. J.W. Spence, E.O. Edney, F.H. Haynie, D.C. Stiles, E.W. Corse,
M.S. Wheeler, S. Cheek, Advanced Laboratory and Field Exposure
Systems for Testing Materials, STP 1000 (West Conshohocken, PA:
ASTM International, 1990).
101. J. Spence, F. Haynie, F. Lipfert, S. Cramer, L. McDonald, Corro-
sion 48 (1992): p. 1009-1019.
102. V. Kucera, M. Collin, Atmospheric Corrosion with Special Regard
to Short-Term VariationsAn Investigation Using Electrochemi-
cal and Weight Loss Methods, 6th European Congress on Metallic
Corrosion (London, United Kingdom: Society of Chemical
Industry, 1977), p. 189.
103. I. Odnevall Wallinder, S. Bertling, C. Leygraf, Metall. 58 (2004):
p. 717-720.
104. I. Odnevall Wallinder, B. Bahar, C. Leygraf, J. Tidblad, J. Environ.
Monit. 9 (2007): p. 66-73.
105. ICP Materials, International Co-Operative Programme on Effects
on Materials, Including Historic and Cultural Monuments, April
7, 2016, http://www.corr-institute.se/icp-materials/web/page
.aspx (September 20, 2016).
106. EMEP, European Monitoring and Evaluation Programme,
August 24, 2016, http://www.emep.int/ (September 20, 2016).
107. H.E. Townsend, MP 32, 4 (1993): p. 68-71.
CORROSIONSEPTEMBER 2017

108. J. Zoccola, H. Townsend, A. Borzillo, J. Horton, Atmospheric
Corrosion Behavior of Aluminum-Zinc Alloy-Coated Steel, STP 646
(West Conshohocken, PA: ASTM International, 1978).
109. A. Belghazi, S. Bohm, J. Sullivan, D. Worsley, Corros. Sci. 44
(2002): p. 1639-1653.
110. J. Hedberg, N. Le Bozec, I. Odnevall Wallinder, Mater. Corros. 64
(2013): p. 300-308.
111. I. Odnevall Wallinder, C. Leygraf, C. Karlen, D. Heijerick,
C. Janssen, Corros. Sci. 43 (2001): p. 809-816.
112. D.G. Heijerick, C. Janssen, C. Karln, I. Odnevall Wallinder,
C. Leygraf, Chemosphere 47 (2002): p. 1073-1080.
113. C. Karln, I. Odnevall Wallinder, D. Heijerick, C. Leygraf,
C. Janssen, Sci. Total Environ. 277 (2001): p. 169-180.
114. I. Gnecco, J. Sansalone, L. Lanza, Water Air Soil Pollut. 192 (2008):
p. 321-336.
115. C. Dierkes, W. Geiger, Water Sci. Technol. 39 (1999): p. 201-
208.
CORROSIONVol. 73, No. 9
INVITED CRITICAL REVIEW
116. J. Gasperi, M.-C. Gromaire, M. Ka, R. Moilleron, G. Chebbo,
Water Res. 44 (2010): p. 5875-5886.
117. M.-C. Gromaire, S. Garnaud, M. Saad, G. Chebbo, Water Res. 35
(2001): p. 521-533.
118. G. Chebbo, M. Gromaire, M. Ahyerre, S. Garnaud, Urban Water 3
(2001): p. 3-15.
119. K.V. Brix, J. Keithly, R.C. Santore, D.K. DeForest, S. Tobiason,
Sci. Total Environ. 408 (2010): p. 1824-1832.
120. C. Dierkes, L. Kuhlmann, J. Kandasamy, G. Angelis, Pollution
Retention Capability and Maintenance of Permeable Pavements,
9th Int. Conf. on Urban Drainage (9ICUD) (Reston, VA: ASCE,
2002), p. 1-13.
121. M. Legret, V. Colandini, Water Sci. Technol. 39 (1999): p. 111-117.
122. L. Haselbach, C. Poor, J. Tilson, Constr. Build. Mater. 53 (2014):
p. 652-657.
123. P. Lim, K. Mak, N. Mohamed, A.M. Noor, Water Sci. Technol. 48
(2003): p. 307-313.
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