GLOBAL BIOGEOCHEMICAL CYCLES, VOL. 23, GB2001, doi:10.

1029/2008GB003376, 2009

Earth’s global Ag, Al, Cr, Cu, Fe, Ni, Pb, and Zn cycles
Jason N. Rauch1 and Jozef M. Pacyna2,3
Received 11 September 2008; revised 6 January 2009; accepted 23 January 2009; published 2 April 2009.

[1] The stocks and flows of the global silver, aluminum, chromium, copper, iron, nickel,
lead, and zinc cycles quantify over 98% of the total mass of metal mobilized by human
activity at the turn of the 21st century. Iron and aluminum, representing >95% by mass of
all metals mined, are for the first time assessed for global anthropogenic emissions to
air, water, and land. Anthropogenic activity has significantly perturbed Earth’s natural
biogeochemical cycles, attested by the ‘‘grand nutrient’’ cycles of carbon, nitrogen,
phosphorous, and sulfur and further revealed here by the ‘‘anthrobiogeochemical’’ cycles
of metals. We demonstrate that humans today mobilize about half the metal mass of these
global elemental metal cycles.
Citation: Rauch, J. N., and J. M. Pacyna (2009), Earth’s global Ag, Al, Cr, Cu, Fe, Ni, Pb, and Zn cycles, Global Biogeochem.
Cycles, 23, GB2001, doi:10.1029/2008GB003376.

1. Introduction ated uncertainty illustrates potential priority areas for future

research. The cycles presented can be a useful tool for
[2] Though metals serve as ‘‘technological nutrients’’ assessing the apportionment of metals when analyzing their
without which modern society could not function, they have amounts in the environment. One may assess the changes
not received the same attention on the global scale as the to the environment caused by any change of anthropogenic
‘‘grand nutrients’’ C, N, S, and P [Falkowski et al., 2000; drivers, such as industry production, population increase, or
Galloway et al., 2004; Rodhe, 1992; Smil, 2000]. Only a full increased demand for energy and food production. The results
global cycle of copper, inclusive of natural and anthropogenic reported here also integrate, update, and expand upon previ-
stocks and flows, has been constructed quantitatively [Rauch ous anthropogenic and natural global emission inventories
and Graedel, 2007]. Rather, previous studies have addressed [Nriagu and Pacyna, 1988].
particular metal stocks and flows, the most holistic of which
have examined natural atmospheric trace metal emissions
[Lantzy and Mackenzie, 1979; Nriagu, 1989], anthropogenic 2. Quantification
trace metal emissions to land, air, and water [Nriagu and [5] Given the scope of the analysis, various literature, data
Pacyna, 1988], and movement of metal through the industrial sources, and methods of calculation are required to quantify
ecosystem [Graedel et al., 2005; Johnson et al., 2005, 2006; each metal cycle. Many of the methods and sources we use
Wang et al., 2007]. herein are presented in further detail in an analysis of the
[3] These works suffer from narrow system boundaries, global copper cycle for the mid-1990s [Rauch and Graedel,
failing to fully illustrate relative anthropogenic and natural 2007]. We define the system boundary as Earth and its orbital
flow magnitudes, natural reservoirs that are not in mass bal- bodies. All flows >1 Mg/a between reservoirs are explicitly
ance, and the degree to which human activity has perturbed quantified. Mass balance of atmospheric, water, and biomass
the natural cycling of metals. The intent of our analysis is reservoirs, assuming no net accumulation due to high turn-
to both highlight these gaps in knowledge and to provide a over rates, was applied to estimate flow magnitudes. Results
comprehensive view of Earth’s metal systems. Al, Fe, Zn, are for the year 2000, except where comprehensive data are
and Cu are chosen for analysis as these metals represent over not available, as is for Ag (1997) and Al (2002). Estimated
95% of the total metal mass mined for human consumption. uncertainties are absolute errors calculated by propagation of
This analysis also includes Pb, Cr, Ag, and Ni, the only other the estimated or standard errors associated with the source
metallic elements for which enough data are presently avail- data. Averages are arithmetic unless otherwise noted. Al-
able for constructing comprehensive global cycles. though certain results are limited by informed approxima-
[4] Quantifying Earth’s metal cycles provides an under- tions, the values and methods to calculate these values
standing of the comparable magnitudes of metal appropriated represent the present state of understanding. The entire
by humans and by the natural environment, and the associ- exercise provides a diagrammatic representation of Earth’s
global metal cycles, combining the endogenic reservoirs of
1
Yale School of Forestry and Environmental Studies, Yale University, the core, mantle, and consolidated crust, the natural exogenic
New Haven, Connecticut, USA. cycles of the pedosphere, hydrosphere, and biosphere, the
2
3
Norwegian Institute of Air Research, Kjeller, Norway. anthropogenic exogenic reservoirs from production to waste
Chemistry Faculty, Gdansk University of Technology, Gdansk, Poland. management, and Earth’s atmosphere and orbit. Note that
this study builds upon the methodology and framework of
Copyright 2009 by the American Geophysical Union.
0886-6236/09/2008GB003376 a previous review of Earth’s mid-1990s global copper cycle

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Table 1. Global Mean Metal Concentrationsa

Reservoir Cu Zn Fe Pb Ag Ni Cr Al Source(s)b
Core 125 0 822000 0.4 0.15 50400 8400 0 1,2
Mantle 30 56 62700 0.03 0.006 1960 2500 11300 3,4,5
Bulk continental crust 27 72 52000 11 0.056 59 140 42000 6
Upper continental crust 28 67 39000 17 0.053 47 92 41000 6
Oceanic crust 78 78 70000 0.49 0.04 150 320 83000 7,8,9
Continental sediment 40 65 40000 17 1.1 40 74 71000 10,11
Oceanic sediment 75 86 40000 20 0.13 71 79 32000 10,12
Loess 21 63 24000 13 - 27 59 67000 11,13
Soil 39 48 33000 27 2.6 25 130 62000 10,14
Coal 12 29 9100 14 0.23 14 16 12000 10,15,16,17
Crude oil 0.091 0.32 2.5 0.30 0.0001 10 0.19 0.5 15,18
Rivers (particulate) 100 250 48000 35 0.07 90 100 89000 19,20,22,23
Rivers (dissolved) 0.0015 0.0006 0.053 0.000055 0.0003 0.00065 0.00085 0.081 19,20,21
Freshwater lakes (dissolved) 0.00058 0.0003 0.0011 0.000036 0.000012 0.0006 0.00025 0.0036 24,25,26,27
Groundwater (dissolved) 0.0046 0.014 6.8 0.001 0.0000018 0.003 0.0007 0.012 28,29,30,31
Greenland ice 0.00006 0.00022 0.015 0.000028 0.0000006 0.000058 0.000038 0.12 32,33,34,35,62,63
Antarctic ice 0.000008 0.000030 0.0071 0.000005 0.0000002 0.00015 0.000007 0.026 36,37,38,39,40,41,42,64,65,66
Ocean (dissolved) 0.00016 0.00035 0.00011 0.000002 0.0000025 0.0005 0.00026 0.00086 23,43,44,45
Terrestrial biomass (dry weight) 4.8 36 193 9.4 0.094 1.1 0.94 166 46,47,53,54,55,56,57,58,59,60,61
Agricultural crops (dry weight) 5.1 26 60 1.1 0.053 0.91 0.066 42 46,47,52
Marine organisms (dry weight) 12 39 160 8.7 0.22 1.4 1.8 62 43
Atmosphere 0.0000008 0.000002 0.0004 0.000001 0.00000002 0.0000005 0.0000009 0.0006 67
Micrometeorites 93 52 300000 4.5 0.082 19000 3300 9300 48,49
Moon 6.4 3.1 110000 0.000037 0.009 6500 1700 39000 50
Man-made satellites 69000 27000 76000 86 9000 8000 23000 456000 51
a
Concentration are in mg/g.
b
Notation is as follows: 1, McDonough [1998]; 2, Allegre et al. [1995]; 3, Salters and Stracke [2004]; 4, Rehkamper and Hofmann [1997]; 5, Workman and
Hart [2005]; 6, Rudnick and Gao [2003]; 7, Wedepohl and Hartmann [1994]; 8, Hofmann [1988]; 9, McDonough and Sun [1995]; 10, IAEA Database of
Natural Matrix Reference Materials; 11, McLennan [1995]; 12, Plank and Langmuir [1998]; 13, Poulton and Raiswell [2000]; 14, Han et al. [2002]; 15,
Bertine and Goldberg [1971]; 16, Clarke and Sloss [1992]; 17, Finkelman [1999]; 18, Stigter et al. [2000]; 19, Martin and Whitfield [1983]; 20, Martin et al.
[1993]; 21, Gaillardet et al. [2003]; 22, Poulton and Raiswell [2002]; 23, Lisitsyn et al. [1982]; 24, Nriagu et al. [1996]; 25, Rossmann and Barres [1988]; 26,
Sterner et al. [2004]; 27, Beaubien et al. [1994]; 28, Hussam et al. [2003]; 29, Minnesota Pollution Control Agency [1999]; 30, Page [1981]; 31, Sanudo-
Wilhelmy et al. [2002]; 32, Barbante et al. [1997]; 33, Hong et al. [1996a]; 34, Osterberg et al. [2006]; 35, Snyder-Conn et al. [1997]; 36, Batifol et al. [1989];
37, Boutron and Patterson [1986]; 38, Boutron et al. [1990]; 39, Gabrielli et al. [2005]; 40, Hanappe et al. [1968]; 41, Hong et al. [2005]; 42, Planchon et al.
[2001]; 43, Li [1991]; 44, Nozaki [1997]; 45, Quinby-Hunt and Turekian [1983]; 46, Adriano and Adriano [2001]; 47, Kabata-Pendias and Pendias [1984];
48, Kaye and Laby [1995]; 49, Richardson et al. [2001]; 50, Morgan et al. [1978]; 51, Opiela [2008]; 52, Sujari and Bowen [1987]; 53, Watmough et al.
[1998]; 54, Harju et al. [1997]; 55, Wolterbeek et al. [1996]; 56, Reimann et al. [2007]; 57, Madejon et al. [2004]; 58, Tyler [2004]; 59, Demirbas [2003]; 60,
Nissen and Lepp [1997]; 61, Smith and Siccama [1981]; 62, Hong et al. [1994]; 63, Hong et al. [1996c]; 64, Planchon et al. [2002]; 65, Van de Velde et al.
[2005]; 66, Marteel et al. [2008]; 67, Calculated from this paper.

[Rauch and Graedel, 2007]. Only those quantification meth- total mass of the oceanic crust (6.6  1021 kg) has also been
ods with significant revision are outlined here. estimated [Mackenzie et al., 2004]. Metal concentrations in
the upper, middle, and lower continental crust were taken
2.1. Data from [Rudnick and Gao, 2003]. The concentration of metal in
[6] Many calculations are simply a generally accepted the oceanic crust is available for most metals [Wedepohl and
global mass multiplied by a global average metal concentra- Hartmann, 1994]. However, Pb concentration is taken as an
tion, though deriving these underlying two values can be N-MORB average [Hofmann, 1988], and Ag concentration
complex. Generally accepted masses used or derived have is taken from basalt compositions [McDonough and Sun,
been reported previously [Rauch and Graedel, 2007]. A 1995]. The consolidated crust contains potentially recover-
summary of the metal concentrations used in these calcula- able resources of metal, most size estimates of which come
tions is presented in Table 1. from the United States Geological Survey commodity reports,
with the exception of Cu [Gordon et al., 2006] and Ag
2.2. Select Revised Methods [Reese, 1992].
2.2.1. Natural Reservoirs of Metal Stocks [8] While many estimates exist for total global living bio-
[7] For Earth’s crust, we divide crust into consolidated mass [Smil, 2002], we use 1800 Pg [Whittaker, 1975]. This
(igneous, metamorphic, and sedimentary bedrock) and un- living biomass can be disaggregated between terrestrial
consolidated (regolith) rock, subdividing consolidated crust phytomass (800 Pg C) [Falkowski et al., 2000] and marine
further into oceanic and continental crust. The mass totals phytomass (3 Pg C) [Holmen, 1992]. We convert Pg C to Pg
of the subdivided continental crust were taken to be 5.1  using a 2.22 conversion ratio [Smil, 2000]. Since trees con-
1015 Gg (upper), 4.9  1015 Gg (middle), and 8.1  1015 Gg stitute 80% of the world’s biomass [Kindermann et al., 2008],
(lower), derived from bulk crust mass estimates and aver- metal concentrations in terrestrial plant dry matter are derived
age depth and density estimates of each section of crust as a biomass weighted mean of the metal concentrations
[Christensen and Mooney, 1995; Mackenzie et al., 2004; in foliage (4%), twigs and branches (8%), bark (8%), wood
Rudnick and Gao, 2003; Taylor and McLennan, 1995]. The (60%), and roots (20%) [Adriano, 2001; Demirbas, 2003;

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Harju et al., 1997; Kabata-Pendias and Pendias, 1984; manufacturers and fabricators that purchase refined metal
Madejón et al., 2004; Nissen and Lepp, 1997; Reimann from ‘‘producers.’’ Cu at the fabrication stage is that which is
et al., 2007; Smith and Siccama, 1981; Tyler, 2004; Wolterbeek reported as at ‘‘consumers’’ and is added to Cu at merchants
et al., 1996; Watmough et al., 1998]. This approach is and exchanges [International Copper Study Group, 2004].
necessitated by the uneven distribution of metal content in Pb and Zn follow a similar approach, with stocks at ‘‘con-
trees, where lower concentrations exist in the majority of the sumers’’ (adjusted estimate from reported value to account
biomass contained in wood, but can be overwhelmed by the for ‘‘other countries’’ not reporting, as based upon previous
minority of biomass in other tree parts that contain higher years estimates) added to merchant and exchange stocks
metal concentrations, as has been observed for Pb [Smith [International Lead and Zinc Study Group, 2003]. Global
and Siccama, 1981]. Average metal concentrations in marine Fe stocks at fabrication are scaled from reported ‘‘consumer’’
organisms are applied separately [Li, 1991]. In our analysis, stocks in Japan (Japan Iron and Steel Federation), Europe
all dead biomass is considered part of the soil mass. (European Confederation of Iron and Steel Industries), and
[9] We adopt here the theory that the Moon is depleted in South Africa (South African Steel and Iron Institute) on the
volatile elements and enriched in refractory elements, and basis of the apparent consumption of iron and steel in these
utilize the resulting estimated bulk average elemental concen- countries relative to global apparent consumption (statistics
trations [Morgan et al., 1978]. These values are multiplied by from the International Iron and Steel Institute). Ni fabrication
the generally accepted mass of the Moon (7.4  1022 kg). and market stocks are those reported at ‘‘consumers’’ plus the
2.2.2. Anthropogenic Reservoirs of Metal Stocks inventory on the London Metal Exchange [International
[10] We report the mass of metal residing in the anthropo- Nickel Study Group, 2003]. Ag manufacturing stocks are
genic life cycle stage of metal production either directly from those reported as industry inventory [CPM Group, 1998] less
industry statistics or calculated from available data. Govern- that which is already accounted for in production stocks.
ment stockpiles, being relatively illiquid, are grouped here Market exchange bullion and other bullion repositories
with producer stocks for many metals. All values are for the [CPM Group, 1998] are added to these Ag manufacturing
year 2000 except Ag (1997) and Al (2002). Cu stocks in stocks. We sum scrap, process, and semifab stocks and dis-
production include those reported at ‘‘producers’’ and in gov- tributor inventories as reported by the International Alumi-
ernment stockpiles of refined copper [International Copper num Institute, then subtract out our independent estimate
Study Group, 2004] plus unrefined copper (blister anode, of Al stock in waste management to arrive at the stock of Al
ores, and concentrates) [World Bureau of Metal Statistics, in fabrication. We then add this value to Al market stocks,
2002]. Zn and Pb stocks in production include refined Zn and as reported by the International Aluminum Institute for the
Pb at ‘‘producers’’ plus government stockpiles [International London Metal Exchange (end of year inventory) and the New
Lead and Zinc Study Group, 2003]. Production stocks of York Mercantile Exchange (warehouse stocks), and by mar-
Fe available for the United States (USGS iron ore statistics), ket analysts for Japanese port stocks (L. T. O’Carroll and
Japan (Japan Iron and Steel Federation), Europe (European T. P. Hayes, Monthly aluminum update: September 2004,
Confederation of Iron and Steel Industries), and South Africa 26 pp., BB&T Capital Markets, 2004).
(South African Steel and Iron Institute) are scaled to a global [12] All values for in-use metal stocks are for the year 2000
stock estimate on the basis of relative iron and steel produc- except Ag (1997) and Al (2002). The global in-use stocks of
tion statistics available from the International Iron and Steel Cu and Zn were calculated from the accumulated difference
Institute. Ni stocks include those at ‘‘producers’’ plus govern- over time between inflows (new purchases) and outflows
ment stockpiles [International Nickel Study Group, 2003]. (discards). We adopt this top-down methodology that is
Government stockpiles of Cr exist for Japan (estimated from explained and applied in depth elsewhere [Gordon et al.,
a stated 60 day supply) and the United States (USGS sta- 2006; Kapur, 2004; Spatari et al., 2005], applying it here to
tistics) and are added to an estimate of Cr stocks at producers. Cu [Lifset et al., 2002] and Zn [Gordon et al., 2004] global
We estimate Cr stocks at producers by averaging (1) a scaled consumption data and utilizing estimated average categorical
estimate of global Cr producer stocks based upon U.S. lifetimes [van Beers and Graedel, 2007]. The summation
producer stocks and relative global Cr production (USGS of the annual net accumulation (or depletion) of Cu and Zn
statistics) and (2) an assumed average 10 week supply of begins in 1700, capturing essentially all the Zn and Cu in
chromite ore at producers and statistics of global annual contemporary use. With a start date of 1900, global Pb in-use
chromite ore consumption [Pariser, 2002]. Ag stocks include stocks have also been estimated [Mao and Graedel, 2009].
reported global end of year refinery stocks [American Bureau This top-down methodology is fairly accurate despite metal
of Metal Statistics, 2001] plus government stockpiles [CPM consumption in ancient times [e.g., Hong et al., 1996b], as
Group, 1998]. Al (unwrought) inventory at producers is the combination of product lifetimes measured in decades
reported by the International Aluminum Institute. with the different uses of metals in the modern industrial era
[11] We combine metal stocks at fabrication and manufac- result in the vast majority of preindustrial age metal having
turing facilities with metal in the market. The metal market been discarded through recycling, landfilling, or environ-
includes metal exchanges, merchants, and treasury stock- mental dissipation. The global in-use stock of Fe is linearly
piles. A formalized metal market exists for all metals exam- interpolated from estimates made for 1985 [Baccini and
ined except Cr and Fe. Again, we derive values directly from Brunner, 1991] and 2005 [Müller et al., 2006]. Al in-use
industry statistics or calculated from available data; all values stocks have been estimated by the European Aluminum
are for the year 2000 except Ag (1997) and Al (2002). Note Association [European Aluminum Association, 2004]. Al-
that ‘‘consumers’’ in metal industry statistics refers to the though a global estimate of in-use stocks was made for Ag in

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

1991 [Charles River Associates, 1992], the estimate for Japan overall consolidated crust mass balance between weathering
appears to be eight times larger than a subsequent estimate and lithification, the mass of metal weathered into regolith
made for the year 2000 [Murakami, 2006]. Given the can also be estimated.
magnitude of disagreement of in-use silver stocks, here we [15] We adjust a rough estimate of sediment mass mobi-
average the two estimates for Japan and then scale to a global lized by freshwater, 60 Pg/a, of which about 40 Pg/a is
value on the basis of the proportion of in-use silver stocks redeposited [Stallard, 1998], to 65 Pg/a to agree with recent
represented in Japan in 1991. Although the result is applied estimates of about 25 Pg/a of sediment deposited to the
for 1997, it essentially stands as an estimate for the end of the oceans. These total mass flows are multiplied by estimated
20th century. We take studies conducted in New Haven, average metal concentrations in sediment [McLennan, 1995].
Connecticut [Rostkowski et al., 2007] and Stockholm, We add to the continental regolith mass mobilized by
Sweden [Sörme et al., 2001] and extrapolate per capita Ni freshwater the difference between the mass of continental
and Cr in-use stocks to the globe on the basis of the ratio of crust weathered and that lithified. The sediment redeposited
Pb per capita in-use stocks in the developing and developed onto terrestrial land is adjusted according to an assumed mass
regions of the world [Mao and Graedel, 2009] and global balance (inputs = outputs) of the freshwater reservoir.
population. Ag, Ni, and Cr values thus exist as rough order of [16] It has been estimated that about 20% of sediment
magnitude estimates and further in-depth studies are required entering the ocean makes its way to the deep ocean seafloor,
to accurately assess these global in-use stocks. the remainder being deposited in estuaries and continental
2.2.3. Natural Flows of Metal margins [McLennan, 1995]. This ratio is applied to the metal
[13] Yearly sulfur emissions from energetically (explosive) flow inputs to the ocean. The values for continental margin
and quiescently degassing volcanoes [Bluth et al., 1993] and and seafloor deposition are adjusted for (see relevant sections
average metal to sulfur ratios from quiescently degassing for these calculations) sewage sludge dumping, net atmo-
basaltic and andesitic volcanoes are the data used to estimate spheric influx, and hydrothermal emissions, assuming the
global emissions of metals [Hinkley et al., 1999]. Because of metal stocks in the ocean reservoir itself are in steady state.
the present uncertainty as to how these metal to sulfur ratios [17] Atmospheric emissions from biomass occur owing
apply to energetic degassing, we average available estimates to biogenic emission or combustion. We multiply average
of global volcanic metal emissions to the atmosphere [Hinkley terrestrial biomass metal concentrations by the total estimated
et al., 1999; Lambert et al., 1988; Lantzy and Mackenzie, global emission of biogenic particulates (1000 Tg/a) [Jaenicke,
1979; Le Cloarec and Marty, 1991; Nriagu, 1989; Pacyna, 2005] to arrive at the mass of metals emitted. Utilizing the
1986; Patterson and Settle, 1987; Schmidt and Andren, 1980; methodology and data available in an analysis of metal
Zoller, 1984] (adjusting for noted errors [Mather et al., 2003; emissions from burning in savanna and tropical rain forests
Patterson and Settle, 1988]) for our reported estimate of [Yamasoe et al., 2000], we compute and scale Cu, Zn, Fe, Ni,
global emissions. Metal emissions into the oceans also occur Cr, and Al emissions to the total amount of vegetative matter
owing to degassing and hydrothermal fluids [Rubin, 1997]. on the basis of total global dry matter mass burned [Andreae
Emissions of Fe and Al into the oceans have also been exam- and Merlet, 2001]. We proceed with the same approach but
ined [Le Cloarec and Marty, 1991]. use different data sources for metal concentrations in partic-
[14] The flow of metal in subducting oceanic sediments ulate emitted for Ag [Vincze et al., 2002] and Pb [Battye and
has been quantified [Plank and Langmuir, 1998], with the Battye, 2002]. This independent calculation is averaged with
exception of Ag. Utilizing the same methodology [Plank and other available estimates (scaled to total biomass burned where
Langmuir, 1998], we calculate Ag in regolith subduction necessary) to produce a best estimate [Klee and Graedel,
utilizing Ag oceanic sediment concentrations from the Inter- 2004; Lantzy and Mackenzie, 1979; Nriagu, 1989; Pacyna,
national Atomic Energy Agency (IAEA) Database of Natural 1986; Richardson et al., 2001; Schmidt and Andren, 1980;
Matrix Reference Materials. The total mass of subducting Zoller, 1984]. We subtract from this total biomass burned that
consolidated crust, 60 Pg/a [Mackenzie et al., 2004], is multi- which is estimated to be burned owing to agricultural activity
plied by the typical metal concentrations of ocean crust. to arrive at metal emitted from natural biomass burning.
60 Pg/a of oceanic crust and 4.5 Pg/a of continental crust are [18] Certain metals are known to become enriched in sea
estimated to be produced from the mantle each year [Reymer spray (Cu, Zn, Pb [Richardson et al., 2001] and Fe, Al [Weisel
and Schubert, 1984]. Metal concentrations utilized are those et al., 1984]) while others are not (Ni [Richardson et al.,
aforementioned for crustal metal stock estimation. Lithifica- 2001], Cr [Schneider, 1985], and Ag [Arimoto et al., 1990]).
tion of continental and oceanic regolith also produces crust. While we report what has been calculated from observations,
For our purposes we assume constant freeboard with no note that the extent of enrichment remains a matter of some
change in crustal volume [Schubert and Reymer, 1985] and debate, given contamination concerns and the variability due
that 75 ± 20%, or the majority of sedimentary rocks, are of to sampling techniques [Hunter, 1997]. Following the calcu-
marine origin [Blatt, 1992]. With these two assumptions we lation outlined elsewhere [Richardson et al., 2001], we utilize
construct a mass balance calculation wherein the mass of metal enrichment factors, seawater concentrations derived
sediment deposited to the seafloor and continental margins, previously for estimating ocean metal stocks, sea-salt [Weisel
less the sedimentary mass that is subducted into the mantle, et al., 1984] and seawater [Duce et al., 1976] Na concentra-
is equal to the mass of regolith lithified. We employ our tions, and total sea-salt emissions [Gong et al., 2002] to cal-
assumption that this mass flow accounts for 75% of the culate metal emission in sea spray. We average our results for
sedimentary rock production, with the other 25% occurring Cu, Zn, Pb, Fe, and Al with other estimates [Weisel et al.,
owing to lithification of continental regolith. Assuming 1984] to arrive at a best estimate. The total sea salt flow to the

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atmosphere is about 1  1013 kg/a, of which 98.5% is de- of the relative consumption of total fungicides in the year
posited back into the ocean, with only the remaining 1.5% 2000 [Fishel, 2007].
deposited onto land [Gong et al., 2002]. [21] We determine the uptake of metal by crop growth
2.2.4. Anthropogenic Flows of Metal by assuming the total agricultural biomass stock turns over
[19] For fossil fuel combustion, atmospheric emissions once per year. One of the major caveats of this assumption
from mobile sources such as diesel and gasoline are consid- concerns the difficulty in assessing how much of metal
ered negligible for the metals under analysis, with the uptake occurs from the soil and how much from applied
exception of Pb [von Storch et al., 2003]. Rather, the vast fertilizers. It appears that on average 10% of Cu, 28% of Zn,
majority of emissions arise from stationary coal combustion and 5% of Pb in agricultural crops is derived from artificial
sources. We estimate the total global emission of metals using fertilizer input [Moolenaar, 1999]. We are unaware of other
global coal consumption and the average metal concentra- studies from which these fractions can be determined, so we
tions in coal used in the stock estimate. Our results can be average the above fractions together as an approximation for
compared with other recent estimates [Klee and Graedel, other metals. These percentages can be interpreted as repre-
2004]. Although most of this emission is collected in pollu- senting that fraction of fertilizer applied that is taken up by
tion control equipment and/or disposed of as bottom ash, a agricultural crops. Consumption of crops by human ingestion
fraction is emitted to the atmosphere. Utilizing the same results in a flow of metal into use; we use the estimate that 8%
approach for Cu, Zn, Ni, Pb, and Cr emission estimates made of agricultural biomass is actually consumed [Wirsenius,
for the mid-1990s [Pacyna and Pacyna, 2001], we update 2003]. For Cu, Zn, and Pb we average this result with con-
atmospheric emissions to the year 2000. Pb emissions in- sumption estimates from Dutch [Moolenaar and Lexmond,
clude that from petroleum combustion by mobile sources. 2000] and Finnish [Moolenaar, 1999] studies that we scale
For Ag, total emissions are fractionated between air and land to global values on the basis of total cropland. The metal
emissions using data from an Ag emission study [Eckelman returned to the soil is determined by a mass balance of the
and Graedel, 2007]. Fe and Al emissions assume 10% of overall flows of inputs and outputs.
total emissions enter the atmosphere given the emission [22] Quantified technological cycles (flows such as min-
controls [Lantzy and Mackenzie, 1979]. ing, production to fabrication, consumption into use, dis-
[20] In our analysis framework for flows related to agri- cards) for the year 2000 exist for Pb [Mao et al., 2008], Fe
cultural crops, manure fertilizer is an internal cycle within [Wang et al., 2007], Ni [Reck et al., 2008], Cu [Gerst and
agricultural stock, so is not quantified explicitly. However, Graedel, 2007], and Cr [Johnson et al., 2006]. Ag [Johnson
artificial fertilizers and pesticides contain trace amounts of et al., 2005] data are available for the year 1997. We also
metals which flows we do quantify. We treat the source of this obtained global cycle data for Al (year 2002 from the
flow as arising from production, although it could be argued European Aluminum Association) and derived Zn data on
that artificial fertilizers and pesticides should be sourced from the basis of the preceding technological cycle methodologies.
fabrication and manufacturing. For artificial fertilizers, we [23] The masses of metal mined, metal released back to the
assume the global yearly consumption is applied to agricul- environment in the forms of tailings and slag, and metal sent
tural use in the same year. Armed with this assumption, we to fabrication have been determined in former assessments of
use global consumption statistics for major nitrogen, phos- the global technological cycles of metals [European Aluminum
phorous, and potash fertilizers as provided by the Interna- Association, 2004; Gerst and Graedel, 2007; Graedel et al.,
tional Fertilizer Association. We arithmetically average 2005; Johnson et al., 2005, 2006; Mao et al., 2008; Reck
fertilizer metal concentrations obtained from a literature et al., 2008; Wang et al., 2007] (where Zn has been updated to
review [Adriano, 2001; Bowhay et al., 1997; Franklin et al., 2000 values). Atmospheric emissions occur both from min-
2005; Iskander, 1994; McBride and Spiers, 2001; Moolenaar ing activity itself and from the smelting production phase of
and Lexmond, 2000; Rauf et al., 2002; Raven and Loeppert, metal ore processing. For atmospheric mining emissions, we
1997; Senesi and Polemio, 1981; Weinberg Group, 2000; aggregate recorded (all metals but Fe) mining metal emis-
Environmental Protection Agency (EPA), 1999]. We esti- sions for the United States (Toxic Release Inventory (TRI)),
mate the metal flow in each individual fertilizer (urea, triple Canada (National Pollutant Release Inventory (NPRI)), and
superphosphate, potassium chloride, etc.) and then sum. A Australia (National Pollutant Inventory (NPI); Al and Ag not
review of the Pesticide Action Network (PAN) database recorded). We scale by employment these emissions to the
reveals that only Al, Cu, and Zn had significant application total mining sector in each country using the ratio of
volumes as of the year 2000, all in fungicides. No global emissions to number of employees, a ratio derived from
statistics exist regarding consumption of individual pesti- Canada’s NPRI data. We then scale to global emissions on the
cides, and the only data available for the United States are for basis of total global employment in mining as published by
the years 1992 and 1997 from the National Center for Food the International Labour Organisation. Although likely an
and Agricultural Policy pesticide use database. We employ underestimate given the better pollution controls in devel-
the 1997 U.S. data for pesticide consumption, and use pes- oped countries, the emissions calculated from this approach
ticide molecular weights to estimate Al, Cu, or Zn mass are within the range of previous global emission estimates
contained. Al is a major constituent of fosetyl aluminum, Cu [Nriagu and Pacyna, 1988]. This same method is used to
is used mostly in copper sulfate and copper hydroxide, and estimate water emissions from mining and metal production
Zn is a component of ziram, metiram, and mancozeb. We activity. Atmospheric emissions for Ag and Al from produc-
scale the U.S. metal mass flow to a global value on the basis tion also use this approach. However, for atmospheric emis-
sions from production of Cu, Cr, Zn, Pb, and Ni we are able to

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use a more robust methodology [Pacyna and Pacyna, 2001], management result from municipal solid waste (MSW) and
updating results to the year 2000. For total atmospheric sewage sludge (SS) incineration. For emissions for the year
emissions of Fe from mining and production, we scale to 2000 we assume little change in emission controls, resulting
the year 2000 an estimate for the year 1980 of global in an increase of emissions by 10% over mid-1990s levels
production emissions [Malakhov and Makhon’ko, 1990] on [Pacyna and Pacyna, 2001]. For Al, Fe, and Ag we estimate
the basis of the average relative change of emissions of the emissions using average emission factors for MSW [Law and
other seven metals in our analysis. No previous estimates for Gordon, 1979] and SS [EPA, 1995] incineration, utilizing our
global water emissions of Fe could be found, so we estimate adjusted estimates for total MSW (85 Tg/a) and SS (8 Tg/a)
water emissions on the basis of the average relative propor- incinerated [Pacyna and Pacyna, 2001]. Water emissions
tion of water emissions to mass of metal ore mined of the result from sewage sludge management and domestic waste-
other seven metals we assess. water discharge. Dumping occurs to both oceans and fresh-
[24] The masses of metal sent to use, recycled back to water. We estimate 50 Tg/a dry weight of total sewage sludge
production, and discarded from fabrication have been deter- production globally on the basis of a review of regional
mined in the previous global technological cycles of metals estimates [Chang et al., 2002; Epstein, 2002; Krauss and
[European Aluminum Association, 2004; Gerst and Graedel, Page, 1997] scaled up by population and previous global
2007; Graedel et al., 2005; Johnson et al., 2005, 2006; Mao estimates [Eckelman and Graedel, 2007; Nriagu and
et al., 2008; Reck et al., 2008; Wang et al., 2007] (where Zn Pacyna, 1988]. Metal concentrations in sewage sludge are
has been updated to 2000 values). Scrap produced at this obtained from an arithmetic average of published literature
stage is also often recycled in a recursive, internal flow of values [Alonso et al., 2006; Berrow and Webber, 1972; Feiler,
metal back into fabrication and manufacturing, but this flow 1980; Furr et al., 1976a, 1976b; Georgopoulos et al., 2001;
is not required by our framework. Fabrication emissions to Gutenmann et al., 1994; Karvelas et al., 2003; Lisk et al.,
air, land, and water are calculated using the same approach as 1992; Mumma et al., 1983, 1984; Scancar et al., 2000;
production emissions, on the basis of TRI, NPRI, and NPI Spiegel et al., 1985]. To apportion sewage sludge discharge
data. Air emissions for Cr, Cu, Ni, Pb, and Zn again utilize a between freshwater and ocean reservoirs, we use an ocean
more robust methodology [Pacyna and Pacyna, 2001], with dumping rate of of 12 Pg/a dry weight [Ross, 1995]. We
updated 2000 data. Fe emissions to land and water are estimate domestic wastewater use as ‘‘withdrawal’’ minus
estimated on the basis of the relative ratio between metal ‘‘consumption’’ as reported in available world regions esti-
emissions and metal mass flow into fabrication averaged mates [Shiklomanov, 1999]. Metal discharge in wastewater is
across the other seven metals in our analysis. For atmospheric the difference between the metal mass influent to wastewater
emissions of Fe in fabrication, we assume the proportion of treatment and metal mass effluent discharge. Influent water
mass emitted relative to Al is the same as the proportion of metal concentrations are taken from a collection of studies for
mass emitted between Fe and Al in production. Europe [Busetti et al., 2005; Lesage et al., 2007; Rule et al.,
[25] Discards from use are either managed (to waste 2006; Sörme and Lagerkvist, 2002], the United States [Shafer
management) or unmanaged (emissions). Metal discards to et al., 1998; EPA, 1991], Africa [Odiyo et al., 2005], and Asia
waste management have been assessed [European Aluminum [Chino et al., 1991; Lim et al., 2006; Yadav et al., 2002] with
Association, 2004; Gerst and Graedel, 2007; Graedel et al., care that only wastewater from domestic sources is consid-
2005; Johnson et al., 2005, 2006; Mao et al., 2008; Reck ered. For regions for which data are not available we use a
et al., 2008; Wang et al., 2007] (where Zn has been updated to global average of all available data. We calculate metal
2000 values). Emissions from use are often described as removal in wastewater treatment using UN statistics on the
dissipative losses; these losses are very difficult to quantify, country distribution of wastewater treatment types (no treat-
let alone disaggregate among air, water, and land media. Until ment, primary, secondary, tertiary) and associated metal
further research expands our understanding of these dis- removal efficiencies [Busetti et al., 2005; Grafton Water
sipative losses, we believe we should only make a general Pollution Control Facility, 2003; Isaac et al., 1997; da Silva
emission estimate for each metal, where emissions to various Oliveira et al., 2007; Oliver and Cosgrove, 1974; EPA,
media are not disaggregated. This general emission estimate 2004]. The resulting mass flows are available for between
is represented in our model by a flow to land. On the basis of two and seven regions on all 6 continents, as defined by the
preliminary evidence with copper [Rauch and Graedel, original UNESCO data, and are summed for reporting global
2007], we estimate that no more than about 1% of the flow emissions. Emission to oceans versus freshwater are divided
of metal into use is dissipated. We apply this assumption to according to the same fraction as sewage sludge emissions.
all metals in our analysis except Fe, Al, and Pb. For these
metals, independent estimates of dissipative emissions exist 3. Results
[European Aluminum Association, 2004; Mao et al., 2008;
Wang et al., 2007]. [27] The results in Gigagrams (Gg) (a thousand metric
[26] Recycling of metal from waste management back to tonnes) are presented in global cycle diagrams, colored to
fabrication, to production, and that metal sent to landfill have reflect the estimated uncertainty (Figures 1 and 2). Numerical
been quantified in the technological cycle of these metals values of the uncertainty are available in the rainbow plots
[European Aluminum Association, 2004; Gerst and Graedel, located in the auxiliary material affiliated with this paper
2007; Graedel et al., 2005; Johnson et al., 2005, 2006; Mao (Figures S1 and S2).1
et al., 2008; Reck et al., 2008; Wang et al., 2007] (where Zn
1
has been updated to 2000 values). Air emissions from discard Auxiliary materials are available in the HTML. doi:10.1029/
2008GB003376.

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Figure 1. Earth’s global metal cycles for (a) aluminum (Al), (b) iron (Fe), (c) copper (Cu), and (d) zinc
(Zn). These four metals constitute over 95% of the total mass of all metals extracted annually for human
utilization. Anthropogenic data are for the year 2000 except for Al (2002). The line thicknesses are
logarithmically proportional to the flow magnitude, and colors indicate the percent uncertainty.

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Figure 1. (continued)

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Figure 2. Earth’s global metal cycles for (a) chromium (Cr), (b) nickel (Ni), (c) lead (Pb), and (d) silver
(Ag). These four metals are the additional metals for which global cycles could be constructed given the
available data. Anthropogenic data are for the year 2000 except for Ag (1997). The line thicknesses are
logarithmically proportional to the flow magnitude, and colors indicate the percent uncertainty.

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

Figure 2. (continued)

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

[28] Although Fe and Al undergo crustal subduction and global demand for stainless steel in durable products. Deple-
production at the same mass flow rate (4 – 5  106 Gg/a), Fe tion of crustal ore resources contributes to this net in-use
becomes increasingly more abundant with depth (Figures 1a stock accumulation. Whereas flood control and hydroelectric
and 1b). Cu exceeds Pb abundance in the crust by a factor of dams reduce denudation rates, and agricultural activity and
five (Figures 1c and 2c), yet the subduction and production urban run off increase such rates [Syvitski et al., 2003], a net
mass flow rate of Pb (70– 80 Gg/a) is almost 2 orders of accumulation of metal mass in continental margin sediments
magnitude less due to the much lower concentrations of Pb occurs for all metals except Fe. This result assumes no net
in the oceanic basalts that dominate the mass of crustal pro- change in crustal mass during the Phanerozoic. Previous
duction and subduction. estimates agree, suggesting total mass flow in the Holocene
[29] Groundwater (1  1013 Gg) [Gleick, 2000] contains was 50% of what it is with today’s human impacts [Milliman
the majority of metal mass in freshwater bodies, despite and Syvitski, 1992].
relatively lower concentrations. Metal masses contained in
rivers, lakes, ice, wetlands, and soil moisture are all relatively 4. Discussion and Conclusion
insignificant. Al is the most abundant of the studied metals in
the oceans (1.4  106 Gg), followed by Ni, Cr, Zn, and Cu, [34] Comparison to previous research focused upon par-
with Fe (4.8  104 Gg) relatively depleted given the oxidative ticular stocks or flows indicates general agreement with our
conditions (Figures 1a – 1d and 2a and 2b). results. The atmospheric mass of metals, calculated from
[30] Nature mobilizes metal mass on Earth’s surface mass balance of inputs and outputs and average residence
mostly by water transport, biomass growth and death, and times, agrees with previous estimates [Lantzy and Mackenzie,
eolian action. Note that potential biogenic emissions of 1979], though Pb has been reduced owing to significant
metals by volatile natural hydrocarbons are not included in reductions in its use in gasoline combustion. The minor
our analysis, as there is no experimental evidence that natural reduction in Cu and Zn atmospheric stock can be attributed
volatile organic compounds of isoprene and derivative ter- to advances in pollution control technology in production;
penes complex with metal ions to act as a significant vector of the trend in atmospheric emission is evident over time
metal emissions, despite past extrapolation of plausible [Nriagu and Pacyna, 1988; Pacyna and Pacyna, 2001].
assumptions to global estimates [Nriagu, 1989]. Groundwa- The atmospheric metal concentrations derived from this work
ter has a large standing mass, but flows slowly enough that (Table 1) are on the lower end of the range of measured
river mass transport (25 Pg/a) [Syvitski et al., 2003] domi- atmospheric concentrations [Wiersma and Davidson, 1986].
nates movement of material to the oceans. Although wind- Despite successful reductions in hydrologic and atmospheric
blown dust is the largest medium for atmospheric metal emissions, society’s increasing consumption of metal has
transport [Jickells et al., 2005], volcanic emissions are larger increased both in-use stocks and waste stream discards. As
than natural biomass combustion for Fe, Ni, Cr, and Al, but a result, metal emissions to land have increased by a factor
smaller for Cu, Pb, Ag, and Zn (Figures 1 and 2). Much more of 1.5 to 3 since 1983 [Nriagu and Pacyna, 1988].
Fe than Al is released directly into the oceans (700x) and [35] While the process of translocating metal from below
atmosphere (2x) by mantle-derived outgassing. Sea spray ground to human built infrastructure has seen an overall
emission is also a significant flux for Cu, Pb, Ag, and Zn reduction over the past few decades in the wasteful and
(Figures 1c and 1d and 2c and 2d). potentially harmful dissipative emissions to environmental
[31] Metals constitute less mass in most anthropic reser- media, the continued increase in mass movement from ore
voirs than in natural reservoirs. However, U.S. Geological to in-use stocks has repercussions for the future of environ-
Survey estimates of global resources for Ag, Cu, Ni, and Zn mental emissions. Though dissipative emissions from in-use
are only 1 order of magnitude larger than derived estimates of stocks have traditionally been minor relative to upstream
global in-use metal stocks [Gerst and Graedel, 2008]. All emissions, the chances of increased emissions from in-use
metals examined are more abundant in global in-use stocks stocks is greater with the increasing size of this reservoir. This
than in Earth’s living biomass. trend necessitates continued work in measuring and moni-
[32] Significant (>1 Mg/a) flows of metal from anthropic toring nonpoint metal emissions, with information on loca-
sources to natural sinks occur through emissions to air, water, tions, sources, and sinks of emissions related to the in-use life
and land from metal production, fabrication, and discard stage of metals.
management, and emissions to air and land from fossil fuel [36] The increasing size of the in-use stock reservoir also
combustion, agricultural biomass, and metal use. Our results has repercussions on the future sources of metal resources, as
indicate that the largest anthropogenic emissions to air arise more metal will likely be sourced from the discards of in-use
from fossil fuel combustion for Al, Fe, and Pb (Figures 1a and stocks through recycling. This recovery will not necessarily
1b and 2c). For Ag, Cr, Cu, Ni, and Zn, the largest air reduce the burden on raw ore extraction, for most raw ores
emissions are from metal production (Figures 1c and 1d and remain highly concentrated relative to in-use stocks, and ore
2a, 2b, and 2d). is required to provide for increasing levels of consumption
[33] Coincident with these pollution flows, we find that and compensate for dissipative losses. However, stabilization
large imbalances exist in both the natural and anthropogenic of the world’s population will likely provide the first step
parts of these metal cycles. The yearly growth rates of in-use toward bringing the world’s metal cycles into balance.
metal stocks at the turn of the 21st century range from around Emphasis on understanding the amounts, forms, and spatial
2% for Zn and Fe to around 6% for Ni and Cr. The higher rate distributions of in-use metal stocks will be important as this
of accumulation of Ni and Cr can be attributed to the high

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GB2001 RAUCH AND PACYNA: GLOBAL METAL CYCLES GB2001

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