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-

blown dust or biomass burning. Similarly, sea salt formation is
‘Heavy metals’ is a widely used but poorly defined term. This a natural process, but its significance as a source of metals to the
article will consider all metallic elements in the periodic table atmosphere may have been modified by human perturbation
except those in groups 1 and 2. This definition will include of the concentrations of these metals in seawater, as will marine
metals, such as aluminum, which are not heavy in terms of gaseous mercury emissions. Other sources of metals to the
their atomic weight but are emitted, transported, transformed, atmosphere are essentially entirely anthropogenic, arising from
and deposited via the atmosphere in a similar way to other true combustion processes and industrial activity.
heavy metals. Mercury is the only metal to behave very differ- Table 1 lists best estimates of fluxes to the atmosphere from
ently since it exists in the atmosphere in the gas phase rather the known sources for a group of metals whose fluxes are
than on aerosols. In the context of global biogeochemical thought to have been significantly modified by human activity.
cycling, atmospheric transport of heavy metals is a major In general fossil fuel combustion and metal production
transport route and one that has for some metals been signif- dominate the anthropogenic emission sources of these metals.
icantly perturbed by human activity. The following sections The table is not intended to represent a comprehensive list of
will briefly describe the sources of some heavy metals to the sources. Indeed, for many metals we do not know sources well.
atmosphere, their transport and cycling through the atmo- Furthermore, fluxes from human activity can change dramati-
sphere, and their subsequent deposition, and will also consider cally with time. This is particularly evident in the case of lead.
the biogeochemical significance of the atmospheric transport Emissions of lead worldwide, for instance, have increased more
rate. Because of its fundamentally different behavior, a separate than 25-fold. Even in remote areas of Europe, it is possible to
section is devoted to mercury. 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
Sources developed over the last 1000 years. The biggest increase, from
the 1950s, was predominantly due to the use of lead additives
Metals are emitted to the atmosphere from a wide range of in automobile fuels. This source has declined very rapidly from
sources. Some of these emissions are entirely natural, such as the 1980s onward as a result of the removal of such additives.
from volcanoes or from biological emissions from land and the Measurements of the isotopic composition of lead have been
oceans. Others arise from natural processes that may 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 contrast to these metals associated with aerosol particles
trace their sources, transport, and transformation processes, is formed directly by physical processes, metals released as gases
beginning to be developed, with recent results published for Fe, (either of biogenic origin or arising from hot combustion
Nd, and Hf. processes) condense onto existing particles on the basis of
Thus Table 1 serves only to estimate the wide range of surface area. Hence, such metals will be associated with finer
specific natural sources that are important for at least some modes of aerosol.
elements, and the scale of perturbations of the total fluxes During aerosol transport, cloud cycling can induce changes
arising from human activity. The elements listed in Table 1 in size distribution, as different aerosol particles are incorpo-
have been selected to represent those for which we know that rated into cloud droplets that subsequently evaporate to
human perturbations are large. For many other metals such as produce a mixed aerosol particle. Despite this complication, it
iron, aluminum, and manganese, perturbations appear to be is remarkable that the aerosol size distribution appears to be
much smaller. This is illustrated in Table 2. Here the data are very effectively retained over very long transport distances, as
based on direct measurements of the metals in the atmosphere, illustrated by data from Enewetak Atoll in the central Pacific
which are expressed as enrichments of the observed concen- Ocean shown in Table 3, where the size distributions of metals
trations over those predicted, if soil dust was the only source. As with predominantly crustal and anthropogenic origins are still
is evident from Table 1, this assumption of a soil source is clearly different from each other, but similar to those of these
simplistic, but large enrichments such as seen in Table 2 for As, metals close to sources, even at this remote location, thousands
Cd, Cu, Pb, Se, and Zn do demand that there are large sources of kilometers from their terrestrial sources.
in addition to soil dust. In the case of a few metals such as During atmospheric transport, aerosols containing metals
selenium, it is likely that other natural sources, such as bio- will become hydrated and the metals may become solubilized.
logical emissions of alkylated selenium compounds from This solubilization process is highly pH-dependent, with all
seawater, are responsible for the enrichments. However, in metals being more soluble at low pH. Crustal aerosol itself is
most cases it is generally accepted that the large enrichments often alkaline and hence high dust loadings may suppress
reflect the fact that anthropogenic emissions are now of solubility. In contrast, anthropogenic emissions of gases such
comparable magnitude to natural sources for some metals as as SO2 and NO/NO2 can acidify atmospheric aqueous solu-
illustrated in Table 1. 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
Transport and Transformation
long-range transport, aerosols will be cycled through clouds
Metals emitted to the atmosphere with soil dust retain this a number of times, thereby encountering a range of pH values
association and hence, like soil dust itself, are associated with that may include highly acidic cloud waters. There is evidence
relatively large aerosols of an equivalent aerodynamic mass to suggest that such pH cycling is not completely reversible and
median radius of 0.5–2 mm during long-range atmospheric that repeated cycles enhance the solubility of metals at
transport. Large-sized particles will be found close to sources or a particular final pH relative to the initial aerosol solubility at
occasionally during highly energetic long-range transport. the same pH.
Metals derived from bursting of bubbles in seawater are asso- In the case of iron, photochemical reactions can lead to the
ciated with sea salt particles that typically are again associated formation of OH radicals (eqn [I]), which are powerful
with larger aerosol particles and have radii of 1–5 mm. By 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
Table 2 Average enrichments of metals in Fe(II) compared to Fe(III).
aerosols over the value expected, if soil dust is the  2þ light  2þ
dominant source based on samples collected FeðIIIÞðOHÞðH2 OÞ5 þ H2 Oƒƒ! FeðIIÞðH2 OÞ6 þ OH
from many sites around the world [I]
Metal Enrichment
Table 3 Mass median radius of some aerosol trace
Aluminum 1
metals at Enewetak in the remote North Pacific
Arsenic 190
Cadmium 1100 Metal Mass median radius (mm)
Cobalt 1.9
Copper 25 Sodium 4.3
Iron 1.3 Aluminum 1.0
Lead 320 Iron 1.1
Manganese 1.5 Manganese 1.3
Selenium 3500 Copper 0.3–0.4
Silicon 0.8 Lead 0.3–0.6
Zinc 50 Zinc 0.5–1.0

Based on Wiersma, G.B., Davidson, C.I., 1986. Trace Based on Arimoto, R., Duce, R.A., Ray, B.J., Unni, C.K., 1985.
metals in the atmosphere of rural and remote areas. In: Atmospheric trace elements at Enewetak Atoll: 2. Transport to the
Nriagu, J.O., Davidson, C.I. (Eds.), Toxic Metals in the ocean by wet and dry deposition. Journal of Geophysical Research.
Atmosphere. Wiley, New York. 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 and zinc in rainwater. Based on Jickells, T.D., 1997. Atmospheric inputs
to those of other aerosol species, and involve wet and dry of some chemical species to the North Sea. Ger. J. Hydrogr. 49,
111–118.
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 days for aerosol-bound metals (including oxidized forms of
metals. First, wet and dry deposition processes are dependent mercury). Mercury has substantial, natural, terrestrial, biolog-
on aerosol particle size. Metals associated with coarser material ical (2.5  109 g per year), and marine (2.7  109 g per year)
will therefore be removed more rapidly from the atmosphere sources, together with a large anthropogenic emission
than metals associated with finer aerosol particles. The (2.3  109 g per year). Atmospheric oxidation reactions slowly
component of the metals in aerosol arising from gas-to-particle convert Hg0 to Hg(II), in which form it is essentially nonvol-
conversion, predominantly the anthropogenic component, is atile and is removed rapidly to aerosols and deposited.
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 Biogeochemical Significance of Atmospheric
the atmosphere but also promote their long-range transport. Transport of Trace Metals
This is probably one reason why the enrichments seen in
Table 2 are greater than predicted from the ratio between As noted earlier, the emissions of many metals to the atmo-
natural and anthropogenic emissions (Table 1). sphere have been estimated to be increased markedly by
The effect of pH on metal solubility was noted earlier. This human activity and are now a major route for global transport
results in marked changes in solubilities of metals over rather (Table 4). Atmospheric emissions, particularly fine-mode
narrow pH ranges that vary for all metals (Figure 1). This is aerosols, lead to very effective long-range transport, as is
important because the impact of the metals on the environ- evident from the enrichment of several trace metals in even the
ment varies markedly depending on whether the metal is remote atmosphere (Table 2). The complex record of
soluble or insoluble. However, this solubility will also depend increasing atmospheric concentrations arising from industri-
on the pH of the receiving media, which will generally be less alization is preserved in the ice caps, particularly of the
acidic than rainwater. 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
Mercury environments by trace metals, though the evidence for delete-
rious effects arising from their contamination, and hence for
Mercury is unique among metals because it exists predomi- pollution, is equivocal. Recent studies have documented that
nantly in the gas phase in the atmosphere as Hg0. In this form it measures to reduce emissions of lead via its elimination from
has long residence time of about 1 year compared to only a few 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 from the oceans, which would increase the acidity of clouds

Pb concentration (nmol l −1)

and promote increasing bioavailability of iron as well as
increase global albedo and hence influence climate. This
0.75
emphasizes the interconnected nature of global cycles and it
has become clear over recent years that atmospheric cycling of
0.50 trace metals is a very important component of the global
biogeochemical cycle.
0.25
See also: Aerosols: Aerosol Physics and Chemistry.
Hydrology, Floods and Droughts: Deserts and Desertification.
0
(a) 1750 1800 1850 1900 1950 2000 Paleoclimatology: Ice Cores. Tropospheric Chemistry and
Composition: Mercury.
2.0
(nmol Cd per mole CaCO3 )
Cd concentration

1.5

Further Reading
1.0
Arimoto, R., Duce, R.A., Ray, B.J., Unni, C.K., 1985. Atmospheric trace elements at
0.5 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.
0 Geosci. 3, 675–682.
1850 1870 1890 1910 1930 1950 1970 1990
(b) Duce, R.A., Liss, P.S., Merrill, J.T., et al., 1991. The atmospheric input of trace
Year
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
Figure 2 (a) Concentration of lead in Greenland snow. (Reproduced magnitude and effects. Marine Chem. 48, 199–201.
from Wolff, E., 1995. In: Wolff, E., Bales, R.C. (Eds.), Chemical Jickells, T.D., 1997. Atmospheric inputs of some chemical species to the North Sea.
Exchange between the Atmosphere and Polar Snow. Springer-Verlag, Ger. J. Hydrogr. 49, 111–118.
Berlin, pp. 1–18.) (b) Concentration of cadmium in coral from Bermuda Jickells, T.D., et al., 2005. Global iron connections between desert dust, ocean
in the Sargasso Sea, Central Atlantic. (Reproduced from Shen, G.T., biogeochemistry and climate. Science 208, 65–71.
Boyle, E.A., Lea, D.W., 1987. Nature 328, 794–796.) Note high concen- Kelly, A.E., Reuer, M.K., Goodkin, N.F., Boyle, E.A., 2009. Lead concentrations and
trations during the early twentieth century associated with industrializa- isotopes in corals and water near Bermuda, 1780–2000. Earth Planet. Sci. Lett.
283, 93–100.
tion with limited emission abatement then reduced emissions following
Majestic, B.J., Anbar, A.D., Herckes, P., 2009. Stable isotopes as a tool to apportion
basic emission control with a subsequent rise with increasing industri- atmospheric iron. Environ. Sci. Technol. 43, 4327–4333.
alization before a fall post-1970 with improved emission control. 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
falling to levels, which are equivalent to those of the early trace metals to the atmosphere from anthropogenic sources worldwide. Environ.
1900s. For other metals such as cadmium, which do not have Rev. 9, 269–298.
a dominant single source, as was the case for lead, there is Pirrone, N., et al., 2010. Global mercury emissions to the atmosphere from anthro-
evidence of reducing concentrations as a result of improving pogenic and natural sources. Atmos. Chem. Phys. 10, 5951–5964.
Renberg, I., Brännvall, M.L., Bindler, R., Emteryd, O., 2000. Atmospheric lead
emission control at source, although this is balanced against pollution during four millennia (2000 BC to 2000 AD) in Sweden. Ambio 29,
increasing societal use of resources. 150–156.
While atmospheric transport of some trace metals has Rickli, J., Frank, M., Baker, A.R., Aciego, S., de Souza, G., Georg, R.B., Halliday, A.N.,
increased due to societal emissions, that of others such as iron 2010. Hafnium and neodymium isotope distribution in surface waters of the
eastern Atlantic Ocean: implications for sources and inputs of trace metals to the
has been little changed. Iron fluxes have changed on longer
ocean. Geochim. Cosmochim. Acta 74, 540–557.
timescales, being higher during the last glaciation owing to Spokes, L.J., Jickells, T.D., 2002. Speciation of metals in the atmosphere. In:
increased aridity and stronger winds. Over the last few years the Ure, A.M., Davidson, C.M. (Eds.), Chemical Speciation in the Environment, second
role of atmospheric iron transport has attracted increasing ed. Blackwell, Oxford, pp. 161–187.
interest as it has become clear that iron is a key nutrient for Turner, D.R., Hunter, K.A. (Eds.), 2001. The Biogeochemistry of Iron in Seawater.
Wiley, Chichester.
phytoplankton in the oceans and that in some areas remote Wiersma, G.B., Davidson, C.I., 1986. Trace metals in the atmosphere of rural and
from desert regions (the dominant sources of dust), phyto- remote areas. In: Nriagu, J.O., Davidson, C.I. (Eds.), Toxic Metals in the Atmo-
plankton growth may be limited by iron availability. Higher sphere. Wiley, New York.
dust loadings during the last glaciation may have promoted 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,
high marine productivity and contributed to the lower atmo-
537–539.
spheric CO2 levels and hence to a cooler climate. Furthermore,
higher productivity may increase emissions of dimethyl sulfide