Heavy Metals

TD Jickells and AR Baker, University of East Anglia, Norwich, UK

Ó 2015 Elsevier Ltd. All rights reserved.

Synopsis

Metals, other than mercury (0), travel in the atmosphere associated with aerosols. Emission sources include soil dust and sea
spray, as well as anthropogenic emissions. Source strength estimates are presented and these show that the relative
importance of anthropogenic and natural sources are very different for different metals. This difference, along with atmo-
spheric cycling discussed, leads to differences in aerosol size distribution, atmospheric residence time, solubility in rainwater
and environmental impacts. Hg(0) is gaseous, behaves very differently to other metals with a much longer atmospheric
residence time.

Introduction changed by human activities such as the formation of wind-

‘Heavy metals’ is a widely used but poorly defined term. This
article will consider all metallic elements in the periodic table
except those in groups 1 and 2. This definition will include
metals, such as aluminum, which are not heavy in terms of
their atomic weight but are emitted, transported, transformed,
and deposited via the atmosphere in a similar way to other true
heavy metals. Mercury is the only metal to behave very differ-
ently since it exists in the atmosphere in the gas phase rather
than on aerosols. In the context of global biogeochemical
cycling, atmospheric transport of heavy metals is a major
transport route and one that has for some metals been signif-
icantly perturbed by human activity. The following sections
will briefly describe the sources of some heavy metals to the
atmosphere, their transport and cycling through the atmo-
sphere, and their subsequent deposition, and will also consider
the biogeochemical significance of the atmospheric transport
rate. Because of its fundamentally different behavior, a separate
section is devoted to mercury.
Sources
Metals are emitted to the atmosphere from a wide range of
sources. Some of these emissions are entirely natural, such as
from volcanoes or from biological emissions from land and the
oceans. Others arise from natural processes that may have been
blown dust or biomass burning. Similarly, sea salt formation is
a natural process, but its significance as a source of metals to the
atmosphere may have been modified by human perturbation
of the concentrations of these metals in seawater, as will marine
gaseous mercury emissions. Other sources of metals to the
atmosphere are essentially entirely anthropogenic, arising from
combustion processes and industrial activity.
Table 1 lists best estimates of fluxes to the atmosphere from
the known sources for a group of metals whose fluxes are
thought to have been significantly modified by human activity.
In general fossil fuel combustion and metal production
dominate the anthropogenic emission sources of these metals.
The table is not intended to represent a comprehensive list of
sources. Indeed, for many metals we do not know sources well.
Furthermore, fluxes from human activity can change dramati-
cally with time. This is particularly evident in the case of lead.
Emissions of lead worldwide, for instance, have increased more
than 25-fold. Even in remote areas of Europe, it is possible to
show increasing lead concentrations in sediments dating back
2000 years, associated with its use by the Romans. Concen-
trations increased further as populations and industrialization
developed over the last 1000 years. The biggest increase, from
the 1950s, was predominantly due to the use of lead additives
in automobile fuels. This source has declined very rapidly from
the 1980s onward as a result of the removal of such additives.
Measurements of the isotopic composition of lead have been
a particularly powerful tool for tracing the changes in lead

Table 1 Worldwide emissions of trace metals (109 g per year)

Source Arsenic Cadmium Copper Lead Selenium Zinc

Wind-blown soil 2.6 0.2 8 3.9 0.2 19

Sea spray 1.7 0.1 3.6 1.4 0.5 0.4
Volcanoes 3.8 0.8 9.4 3.3 0.9 9.6
Forest fires 0.2 0.1 3.8 1.9 0.3 7.6
Continental biogenic emissions 1.6 0.2 2.9 1.5 3.7 5.1
Marine biogenic emissions 2.3 0.05 0.4 0.2 4.7 3.0
Total natural emissions 12 1.3 28 12 10.3 45
Total anthropogenic emissions in the mid-1990s 5 3 26 119 4.6 57

Natural emissions based on Nriagu, J.O., 1989. A global assessment of natural sources of atmospheric trace metals. Nature 338, 47–49 and anthropogenic emissions on
Pacyna, J.M., Pacyna, E.G., 2001. An assessment of global and regional emissions of trace metals to the atmosphere from anthropogenic sources worldwide. Environmental
Reviews. 9, 269–298.

Encyclopedia of Atmospheric Sciences 2nd Edition, Volume 1 http://dx.doi.org/10.1016/B978-0-12-382225-3.00018-9 201

202 Biogeochemical Cycles j Heavy Metals
sources. The use of isotopic measurements in other metals, to
trace their sources, transport, and transformation processes, is
beginning to be developed, with recent results published for Fe,
Nd, and Hf.
Thus Table 1 serves only to estimate the wide range of
specific natural sources that are important for at least some
elements, and the scale of perturbations of the total fluxes
arising from human activity. The elements listed in Table 1
have been selected to represent those for which we know that
human perturbations are large. For many other metals such as
iron, aluminum, and manganese, perturbations appear to be
much smaller. This is illustrated in Table 2. Here the data are
based on direct measurements of the metals in the atmosphere,
which are expressed as enrichments of the observed concen-
trations over those predicted, if soil dust was the only source. As
is evident from Table 1, this assumption of a soil source is
simplistic, but large enrichments such as seen in Table 2 for As,
Cd, Cu, Pb, Se, and Zn do demand that there are large sources
in addition to soil dust. In the case of a few metals such as
selenium, it is likely that other natural sources, such as bio-
logical emissions of alkylated selenium compounds from
seawater, are responsible for the enrichments. However, in
most cases it is generally accepted that the large enrichments
reflect the fact that anthropogenic emissions are now of
comparable magnitude to natural sources for some metals as
illustrated in Table 1.
Transport and Transformation
Metals emitted to the atmosphere with soil dust retain this
association and hence, like soil dust itself, are associated with
relatively large aerosols of an equivalent aerodynamic mass
median radius of 0.5–2 mm during long-range atmospheric
transport. Large-sized particles will be found close to sources or
occasionally during highly energetic long-range transport.
Metals derived from bursting of bubbles in seawater are asso-
ciated with sea salt particles that typically are again associated
with larger aerosol particles and have radii of 1–5 mm. By
Table 2 Average enrichments of metals in
aerosols over the value expected, if soil dust is the
dominant source based on samples collected
from many sites around the world
Metal Enrichment
Aluminum 1
Arsenic 190
Cadmium 1100
Cobalt 1.9
Copper 25
Iron 1.3
Lead 320
Manganese 1.5
Selenium 3500
Silicon 0.8
Zinc 50
Based on Wiersma, G.B., Davidson, C.I., 1986. Trace
metals in the atmosphere of rural and remote areas. In:
Nriagu, J.O., Davidson, C.I. (Eds.), Toxic Metals in the
Atmosphere. Wiley, New York.
contrast to these metals associated with aerosol particles
formed directly by physical processes, metals released as gases
(either of biogenic origin or arising from hot combustion
processes) condense onto existing particles on the basis of
surface area. Hence, such metals will be associated with finer
modes of aerosol.
During aerosol transport, cloud cycling can induce changes
in size distribution, as different aerosol particles are incorpo-
rated into cloud droplets that subsequently evaporate to
produce a mixed aerosol particle. Despite this complication, it
is remarkable that the aerosol size distribution appears to be
very effectively retained over very long transport distances, as
illustrated by data from Enewetak Atoll in the central Pacific
Ocean shown in Table 3, where the size distributions of metals
with predominantly crustal and anthropogenic origins are still
clearly different from each other, but similar to those of these
metals close to sources, even at this remote location, thousands
of kilometers from their terrestrial sources.
During atmospheric transport, aerosols containing metals
will become hydrated and the metals may become solubilized.
This solubilization process is highly pH-dependent, with all
metals being more soluble at low pH. Crustal aerosol itself is
often alkaline and hence high dust loadings may suppress
solubility. In contrast, anthropogenic emissions of gases such
as SO2 and NO/NO2 can acidify atmospheric aqueous solu-
tions and thus promote solubility. Indeed, some trace metals
are known to be able to catalyze oxidation of SO2, and hence
a positive feedback enhancing solubility is possible. During
long-range transport, aerosols will be cycled through clouds
a number of times, thereby encountering a range of pH values
that may include highly acidic cloud waters. There is evidence
to suggest that such pH cycling is not completely reversible and
that repeated cycles enhance the solubility of metals at
a particular final pH relative to the initial aerosol solubility at
the same pH.
In the case of iron, photochemical reactions can lead to the
formation of OH radicals (eqn [I]), which are powerful
oxidizing agents that link these metals to the cycling of many
other components in the atmosphere. These reactions can also
modify iron solubility because of the much greater solubility of
Fe(II) compared to Fe(III).
 2þ light  2þ
FeðIIIÞðOHÞðH2 OÞ5 þ H2 Oƒƒ! FeðIIÞðH2 OÞ6 þ OH
[I]
Table 3 Mass median radius of some aerosol trace
metals at Enewetak in the remote North Pacific
Metal Mass median radius (mm)
Sodium 4.3
Aluminum 1.0
Iron 1.1
Manganese 1.3
Copper 0.3–0.4
Lead 0.3–0.6
Zinc 0.5–1.0
Based on Arimoto, R., Duce, R.A., Ray, B.J., Unni, C.K., 1985.
Atmospheric trace elements at Enewetak Atoll: 2. Transport to the
ocean by wet and dry deposition. Journal of Geophysical Research.
90, C22391–C22408.
 Biogeochemical Cycles j Heavy Metals 203

A further process that may significantly modify the behavior

of trace metals during atmospheric transport and trans-
100
formation is organic complexation. This process has been
known to be important for many years in soil, freshwaters, and 80

Solubility (%)
marine waters. It is now becoming clear that organic material
represents a substantial component of many aerosols. This 60
organic material is poorly characterized, but it is clear that some
of the organic compounds, including relatively simple organic 40
molecules such as oxalic acid as well probably as some more
20 Zn
complex organic material, can chemically bind metals and Cu
significantly modify the metals’ solubility, bioavailability, and Pb
0
photochemistry. 3 4 5 6 7
pH

Deposition Figure 1 Effect of pH on the solubility (mass/mass) of copper, lead,

Trace metal removal processes from the atmosphere are similar
to those of other aerosol species, and involve wet and dry
deposition processes. These are discussed elsewhere in this
Encyclopedia and will not be described in detail here. However,
a few important points arise that are of specific relevance to
metals. First, wet and dry deposition processes are dependent
on aerosol particle size. Metals associated with coarser material
will therefore be removed more rapidly from the atmosphere
than metals associated with finer aerosol particles. The
component of the metals in aerosol arising from gas-to-particle
conversion, predominantly the anthropogenic component, is
therefore less efficiently removed than those components
associated with soil dust or sea spray. Thus anthropogenic
emissions in general not only increase emissions of metals to
the atmosphere but also promote their long-range transport.
This is probably one reason why the enrichments seen in
Table 2 are greater than predicted from the ratio between
natural and anthropogenic emissions (Table 1).
The effect of pH on metal solubility was noted earlier. This
results in marked changes in solubilities of metals over rather
narrow pH ranges that vary for all metals (Figure 1). This is
important because the impact of the metals on the environ-
ment varies markedly depending on whether the metal is
soluble or insoluble. However, this solubility will also depend
on the pH of the receiving media, which will generally be less
acidic than rainwater.
Mercury
Mercury is unique among metals because it exists predomi-
nantly in the gas phase in the atmosphere as Hg0. In this form it
has long residence time of about 1 year compared to only a few
and zinc in rainwater. Based on Jickells, T.D., 1997. Atmospheric inputs
of some chemical species to the North Sea. Ger. J. Hydrogr. 49,
111–118.
days for aerosol-bound metals (including oxidized forms of
mercury). Mercury has substantial, natural, terrestrial, biolog-
ical (2.5  109 g per year), and marine (2.7  109 g per year)
sources, together with a large anthropogenic emission
(2.3  109 g per year). Atmospheric oxidation reactions slowly
convert Hg0 to Hg(II), in which form it is essentially nonvol-
atile and is removed rapidly to aerosols and deposited.
Biogeochemical Significance of Atmospheric
Transport of Trace Metals
As noted earlier, the emissions of many metals to the atmo-
sphere have been estimated to be increased markedly by
human activity and are now a major route for global transport
(Table 4). Atmospheric emissions, particularly fine-mode
aerosols, lead to very effective long-range transport, as is
evident from the enrichment of several trace metals in even the
remote atmosphere (Table 2). The complex record of
increasing atmospheric concentrations arising from industri-
alization is preserved in the ice caps, particularly of the
Northern Hemisphere, and in corals in central ocean regions
remote from riverine sources (Figure 2). Thus it is clear that
atmospheric transport has resulted in contamination of remote
environments by trace metals, though the evidence for delete-
rious effects arising from their contamination, and hence for
pollution, is equivocal. Recent studies have documented that
measures to reduce emissions of lead via its elimination from
vehicle fuels have been very successful with concentrations now

Table 4 A comparison of atmospheric and riverine fluxes (109 g per year) of some trace metals to the oceans

Metal Fluvial dissolved flux Fluvial particulate flux Atmospheric dissolved flux Atmospheric particulate flux

Iron 1100 110 000 3200 29 000

Copper 10 1500 14–45 2–7
Lead 2 1600 80 10
Zinc 6 3900 33–70 11–60

Note particulate material is deposited in estuaries and hence the best measure of comparison in terms of impacts on the open ocean is probably of the total atmospheric
flux and the riverine dissolved flux.
Based on Duce, R.A., Liss, P.S., Merrill, J.T., et al., 1991. The atmospheric input of trace species to the world ocean. Global Biogeochemical. Cycles 5, 193–259.
204 Biogeochemical Cycles j Heavy Metals
1.0
Pb concentration (nmol l −1)
0.75
0.50
0.25
0
(a) 1750 1800 1850 1900 1950
2.0
(nmol Cd per mole CaCO3 )
Cd concentration
1.5
1.0
0.5
0 Geosci. 3, 675–682.
1850 1870 1890 1910 1930 1950 1970 1990
(b)
Year
Figure 2 (a) Concentration of lead in Greenland snow. (Reproduced
from Wolff, E., 1995. In: Wolff, E., Bales, R.C. (Eds.), Chemical
Exchange between the Atmosphere and Polar Snow. Springer-Verlag,
Berlin, pp. 1–18.) (b) Concentration of cadmium in coral from Bermuda
in the Sargasso Sea, Central Atlantic. (Reproduced from Shen, G.T.,
Boyle, E.A., Lea, D.W., 1987. Nature 328, 794–796.) Note high concen-
trations during the early twentieth century associated with industrializa-
tion with limited emission abatement then reduced emissions following
basic emission control with a subsequent rise with increasing industri-
alization before a fall post-1970 with improved emission control.
falling to levels, which are equivalent to those of the early
1900s. For other metals such as cadmium, which do not have
a dominant single source, as was the case for lead, there is
evidence of reducing concentrations as a result of improving
emission control at source, although this is balanced against
increasing societal use of resources.
While atmospheric transport of some trace metals has
increased due to societal emissions, that of others such as iron
has been little changed. Iron fluxes have changed on longer
timescales, being higher during the last glaciation owing to
increased aridity and stronger winds. Over the last few years the
role of atmospheric iron transport has attracted increasing
interest as it has become clear that iron is a key nutrient for
phytoplankton in the oceans and that in some areas remote
from desert regions (the dominant sources of dust), phyto-
plankton growth may be limited by iron availability. Higher
dust loadings during the last glaciation may have promoted
high marine productivity and contributed to the lower atmo-
spheric CO2 levels and hence to a cooler climate. Furthermore,
higher productivity may increase emissions of dimethyl sulfide
from the oceans, which would increase the acidity of clouds
and promote increasing bioavailability of iron as well as
increase global albedo and hence influence climate. This
emphasizes the interconnected nature of global cycles and it
has become clear over recent years that atmospheric cycling of
trace metals is a very important component of the global
biogeochemical cycle.
See also: Aerosols: Aerosol Physics and Chemistry.
Hydrology, Floods and Droughts: Deserts and Desertification.
2000 Paleoclimatology: Ice Cores. Tropospheric Chemistry and
Composition: Mercury.
Further Reading
Arimoto, R., Duce, R.A., Ray, B.J., Unni, C.K., 1985. Atmospheric trace elements at
Enewetak Atoll: 2. Transport to the ocean by wet and dry deposition. J. Geophys.
Res. 90, C22391–C22408.
Boyd, P.W., Ellwood, M.J., 2010. The biogeochemical cycle of iron in the ocean. Nat.
Duce, R.A., Liss, P.S., Merrill, J.T., et al., 1991. The atmospheric input of trace
species to the world ocean. Global Biogeochem. Cycles 5, 193–259.
Jickells, T.D., 1985. Atmospheric inputs of metals and nutrients to the oceans: their
magnitude and effects. Marine Chem. 48, 199–201.
Jickells, T.D., 1997. Atmospheric inputs of some chemical species to the North Sea.
Ger. J. Hydrogr. 49, 111–118.
Jickells, T.D., et al., 2005. Global iron connections between desert dust, ocean
biogeochemistry and climate. Science 208, 65–71.
Kelly, A.E., Reuer, M.K., Goodkin, N.F., Boyle, E.A., 2009. Lead concentrations and
isotopes in corals and water near Bermuda, 1780–2000. Earth Planet. Sci. Lett.
283, 93–100.
Majestic, B.J., Anbar, A.D., Herckes, P., 2009. Stable isotopes as a tool to apportion
atmospheric iron. Environ. Sci. Technol. 43, 4327–4333.
Nriagu, J.O., 1989. A global assessment of natural sources of atmospheric trace
metals. Nature 338, 47–49.
Pacyna, J.M., Pacyna, E.G., 2001. An assessment of global and regional emissions of
trace metals to the atmosphere from anthropogenic sources worldwide. Environ.
Rev. 9, 269–298.
Pirrone, N., et al., 2010. Global mercury emissions to the atmosphere from anthro-
pogenic and natural sources. Atmos. Chem. Phys. 10, 5951–5964.
Renberg, I., Brännvall, M.L., Bindler, R., Emteryd, O., 2000. Atmospheric lead
pollution during four millennia (2000 BC to 2000 AD) in Sweden. Ambio 29,
150–156.
Rickli, J., Frank, M., Baker, A.R., Aciego, S., de Souza, G., Georg, R.B., Halliday, A.N.,
2010. Hafnium and neodymium isotope distribution in surface waters of the
eastern Atlantic Ocean: implications for sources and inputs of trace metals to the
ocean. Geochim. Cosmochim. Acta 74, 540–557.
Spokes, L.J., Jickells, T.D., 2002. Speciation of metals in the atmosphere. In:
Ure, A.M., Davidson, C.M. (Eds.), Chemical Speciation in the Environment, second
ed. Blackwell, Oxford, pp. 161–187.
Turner, D.R., Hunter, K.A. (Eds.), 2001. The Biogeochemistry of Iron in Seawater.
Wiley, Chichester.
Wiersma, G.B., Davidson, C.I., 1986. Trace metals in the atmosphere of rural and
remote areas. In: Nriagu, J.O., Davidson, C.I. (Eds.), Toxic Metals in the Atmo-
sphere. Wiley, New York.
Zhuang, G., Yi, Z., Duce, R.A., Brown, P.R., 1992. Link between iron and sulphur
suggested by detection of Fe(II) in remote marine aerosols. Nature 355,
537–539.