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How a century of ammonia synthesis changed


the world

Article in Nature Geoscience · September 2008


DOI: 10.1038/ngeo325

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FEATURE

How a century of ammonia synthesis


changed the world
On 13 October 1908, Fritz Haber filed his patent on the “synthesis of ammonia from its elements”
for which he was later awarded the 1918 Nobel Prize in Chemistry. A hundred years on we live in a
world transformed by and highly dependent upon Haber–Bosch nitrogen.

Although over 78% of the atmosphere


is composed of nitrogen, it exists in its
chemically and biologically unusable
gaseous form. Haber discovered how
ammonia, a chemically reactive, highly
usable form of nitrogen, could be
synthesized by reacting atmospheric
dinitrogen with hydrogen in the presence
of iron at high pressures and temperatures.
Today, this reaction is known as the
Haber–Bosch process: Fritz Haber was the
inventor who created the breakthrough
and laid the foundations for high-
pressure chemical engineering, but it was
Carl Bosch who subsequently developed
it on an industrial scale, for which he
was awarded a Nobel Prize in 1931. The

Gert van duinen


importance of Haber’s discovery cannot
be overestimated — as a result, millions of
people have died in armed conflicts over
the past 100 years, but, at the same time,
billions of people have been fed. Agricultural production for food and fuel has increased in the past few years; for example, oilseed rape as
In his Nobel lecture, Haber explained shown here.
that his main motivation for synthesizing
ammonia from its elements was the
growing demand for food, and the and the course of modern history, has natural reservoirs of reactive nitrogen,
concomitant need to replace the nitrogen literally changed the world. particularly Peruvian guano, Chilean
lost from fields owing to the harvesting What Fritz Haber could not saltpeter and sal ammoniac extracted
of crops: “it was clear that the demand foresee, however, was the cascade of from coal. Early attempts to fix nitrogen
for fixed nitrogen, which at the beginning environmental changes, including the from the atmosphere were inefficient and
of this century could be satisfied with a increase in water and air pollution, the energetically expensive. The Haber–Bosch
few hundred thousand tons a year, must perturbation of greenhouse-gas levels and process has significantly lower energy
increase to millions of tons”1. We now the loss of biodiversity that was to result requirements and was therefore
know that his vision was right: the current from the colossal increase in ammonia substantially cheaper, allowing it to form
worldwide use of fertilizer nitrogen is production and use that was to ensue3. the basis of an alternative expanding supply
about 100 Tg N per year. Here we reflect on the influence that of reactive nitrogen. Haber’s nitrogen has
Haber’s other motivation, not Haber’s invention has had on society since boosted the production of many
mentioned in his lecture, was to provide over the last century, both the benefits previously expensive or rare compounds,
the raw material for explosives to be used and unintended consequences. And, such as dyes and artificial fibres, but it has
in weapons, which requires large amounts based on different scenarios of future had its greatest impact on the production
of reactive nitrogen. Haber’s discovery has nitrogen fertilizer use, we discuss some of explosives and fertilizers2.
therefore had a major influence on both of the challenges likely to be faced by our
World Wars and all subsequent conflicts. ‘nitrogen economy’ in the next 100 years. Explosives
In addition, the large-scale production
of ammonia has facilitated the industrial Economic and security benefits The central role that nitrogen has in the
manufacture of a large number of manufacture of explosives is reflected
chemical compounds and many synthetic Up until the first decades of the not only in the Nobel prizes awarded to
products. Thus the Haber–Bosch process, twentieth century, many industrial Haber and Bosch, but in the very origin
with its impacts on agriculture, industry processes were dependent on limited of the Nobel Prize itself. Alfred Nobel’s

636 nature geoscience | VOL 1 | ADVANCE ONLINE PUBLICATION | www.nature.com/naturegeoscience


FEATURE
wealth was built on the development of 7,000
World population
safe methods for using nitroglycerine,
50
and his patents for dynamite and gelignite World population
eventually financed the Nobel Foundation. 6,000
(no Haber Bosch nitrogen)
As a German patriot, Haber was keen to
develop explosives and other chemical 5,000
% World population 40
weapons, which to his mind were more fed by Haber Bosch nitrogen

Average fertilizer input (kg N ha–1 yr –1)/


Meat production (kg person–1 yr –1)
World population (millions)
humane, because they “would shorten the
war”4. The need to improve munitions 4,000 Average fertilizer input

% World population/
30
supplies was in reality a central motivation
for industrial ammonia production.
With the blockade of Chilean saltpeter 3,000 Meat production
supplies during the First World War, the 20
Haber–Bosch process provided Germany
2,000
with a home supply of ammonia.
This was oxidized to nitric acid and 10
used to produce ammonium nitrate, 1,000
nitroglycerine, TNT (trinitrotoluene) and
other nitrogen-containing explosives.
Haber’s discovery therefore fuelled the 0 0
First World War, and, ironically, prevented 1900 1950 2000
what might have been a swift victory for
the Allied Forces. Since then, reactive
nitrogen produced by the Haber–Bosch Figure 1 Trends in human population and nitrogen use throughout the twentieth century. Of the total world
process has become the central foundation population (solid line), an estimate is made of the number of people that could be sustained without reactive
of the world’s ammunition supplies. As nitrogen from the Haber–Bosch process (long dashed line), also expressed as a percentage of the global
such, its use can be directly linked to population (short dashed line). The recorded increase in average fertilizer use per hectare of agricultural land
100–150 million deaths in armed conflicts (blue symbols) and the increase in per capita meat production (green symbols) is also shown.
throughout the twentieth century5.

Fertilizers
to produce — this is partly reflected in Together with the role of reactive
At the same time, the Haber–Bosch the global increase in per capita meat nitrogen in ammunition supplies, these
process has facilitated the production of consumption (Fig. 1). In contrast, the figures provide an illustration of the
agricultural fertilizers on an industrial latest Food and Agriculture Organization huge importance of industrial ammonia
scale, dramatically increasing global report shows that approximately 850 production for society, although, on
agricultural productivity in most regions million people remain undernourished8. balance, it remains questionable to what
of the world7 (Fig. 1). We estimate that the Overall, we suggest that nitrogen extent the consequences can be considered
number of humans supported per hectare fertilizer has supported approximately as beneficial.
of arable land has increased from 1.9 to 27% of the world’s population over
4.3 persons between 1908 and 2008. This the past century, equivalent to around Unintended consequences
increase was mainly possible because of 4 billion people born (or 42% of the
Haber–Bosch nitrogen. estimated total births) since 1908 (Fig. 1). Of the total nitrogen manufactured by
Smil estimated that at the end of For these calculations, we assumed the Haber–Bosch process, approximately
the twentieth century, about 40% of that, in the absence of additional 80% is used in the production of
the world’s population depended on nitrogen, other improvements would agricultural fertilizers10. However, a large
fertilizer inputs to produce food2,6. have accounted for a 20% increase in proportion of this nitrogen is lost to the
It is difficult to quantify this number productivity between 1950 and 2000. environment: in 2005, approximately
precisely because of changes in cropping Consistent with Smil6, we estimate, 100 Tg N from the Haber–Bosch
methods, mechanization, plant breeding that by 2000, nitrogen fertilizers were process was used in global agriculture,
and genetic modification, and so on. responsible for feeding 44% of the world’s whereas only 17 Tg N was consumed
However, an independent analysis, based population. Our updated estimate for by humans in crop, dairy and meat
on long-term experiments and national 2008 is 48% — so the lives of around products11. Even recognizing the other
statistics, concluded that about 30–50% of half of humanity are made possible by non-food benefits of livestock (for
the crop yield increase was due to nitrogen Haber–Bosch nitrogen. example, transport, hides, wool and so
application through mineral fertilizer7. In addition, fertilizer is required on), this highlights an extremely low
It is important to note that these for bioenergy and biofuel production. nitrogen-use efficiency in agriculture
estimates are based on global averages, Currently, bioenergy contributes 10% (the amount of nitrogen retrieved in
which hide major regional differences. of the global energy requirement, food produced per unit of nitrogen
In Europe and North America, increases whereas biofuels contribute 1.5%. These applied). In fact, the global nitrogen-
in agricultural productivity have been energy sources do not therefore have a use efficiency of cereals decreased
matched by luxury levels of nitrogen large influence on global fertilizer use9. from ~80% in 1960 to ~30% in 200012,13.
consumption owing to an increase in the However, with biofuel production set to The smaller fraction of Haber–Bosch
consumption of meat and dairy products, increase, the influence of Haber–Bosch nitrogen used in the manufacture of
which require more fertilizer nitrogen nitrogen will only grow. other chemical compounds (~20%) has

nature geoscience | VOL 1 | ADVANCE ONLINE PUBLICATION | www.nature.com/naturegeoscience 637


FEATURE

Efficiency additional carbon stored per kilogram


250
A1 + biofuel Diet optimization of nitrogen deposited range from 40
A2 Biofuels to 400 kilograms of carbon, although
B1 Food equity
200
B2 Population growth the most recent estimates suggest that
Tilman et al . 27 the largest values are unlikely18–20. In
Tubiello and Fischer 28
150 FAO (baseline)26
the meantime, further efforts are being
directed to understand the overall effect
Tg N

FAO (improved)26
100 of reactive nitrogen on the greenhouse
gas balance, including its interactions
with nitrous oxide, methane, ozone
50
and aerosols21,22.
0
1900 1950 2000 2050 2100 A1 A2 B1 B1 The next century of Haber–Bosch

We project global nitrogen fertilizer


demand over the next century on the
Figure 2 Global nitrogen fertilizer consumption scenarios (left) and the impact of individual drivers on 2100 basis of the four storylines developed for
consumption (right). This resulting consumption is always the sum (denoted at the end points of the respective the Intergovernmental Panel on Climate
arrows) of elements increasing as well as decreasing nitrogen consumption. Other relevant estimates26,27,28 are Change Special Report on Emission
presented for comparison. The A1, B1, A2 and B2 scenarios draw from the assumptions of the IPCC emission Scenarios (SRES)23. The storylines reflect
scenario23 storylines as explained in the text. varying economic, demographic and
technological developments. The A1
storyline assumes a world of very rapid
economic growth, a global population
an uncertain fate, with its escape into the biodiversity. Similarly, the transfer that peaks mid-century, and rapid
environment depending on the life-cycle of reactive nitrogen from terrestrial introduction of new and more efficient
of the product. to coastal systems has doubled since technologies. B1 describes a convergent
A recent study suggested that pre-industrial times16. As with terrestrial world, with the same global population
approximately 40% of fertilizer nitrogen ecosystems, many of the coastal as A1, but with more rapid changes in
lost to the environment is denitrified back ecosystems receiving increased nitrogen economic structures towards a service
to unreactive atmospheric dinitrogen14. loadings are nitrogen-limited, leading to and information economy. B2 describes
In principle this loss is environmentally algal blooms and a decline in the quality a world with intermediate population
benign, although it represents a waste of surface and ground waters. and economic growth, emphasizing
of the energy used in the Haber–Bosch In addition to these ecosystem-level local solutions to economic, social
process equivalent to at least 32 MJ kg–1 N disturbances, reactive nitrogen alters and environmental sustainability.
fixed, or about 1% of the global primary the balance of greenhouse gases, A2 describes a very heterogeneous
energy supply. However, the rest enhances tropospheric ozone, decreases world with high population growth,
of the excess nitrogen escapes into stratospheric ozone, increases soil slow economic development and slow
environmental reservoirs, where it acidification and stimulates the technological change. We consider the
cascades through atmospheric, terrestrial, formation of secondary particulate following five parameters to be the
aquatic and marine pools before matter in the atmosphere, all of which main drivers of the estimated trends
eventually being denitrified or stored as have negative effects on people and in fertilizer use, and we apply a subset
fossil reactive nitrogen. In principle, one the environment. of these parameters to the respective
molecule of reactive nitrogen can have The effects of reactive nitrogen scenarios (see Fig. 2).
multiple effects during its lifetime in the on the environment can be mitigated
cascade. Understanding this cascade is through several intervention strategies, (1) Population growth is the main driver
therefore essential for the development of which should focus on reducing the behind the increase in nitrogen fertilizer
effective abatement measures15. creation of reactive nitrogen, increasing use. The SRES population projections
The influence of Haber–Bosch the efficiency with which it is used, range between 7 (B1) and 15 billion people
nitrogen on the global nitrogen cycle or converting it back to atmospheric (A2) in 2100. Recent research suggests
can be seen in present-day atmospheric dinitrogen. Such strategies could include that global fertility rates will continue to
and aquatic nitrogen pools. Emissions increasing the efficiency of nitrogen use decrease. As a consequence, population
of NO and NH3 to the atmosphere in food production, altering human diets growth is expected to eventually halt24,25.
have increased about fivefold since and improving the treatment of human
pre-industrial times14. Atmospheric and animal waste10. (2) The potential for increasing
nitrogen deposition in the absence of Another unintended, but positive, yield per hectare is large, and could
human influence is ~0.5 kg N ha−1 yr−1 environmental consequence of the allow food output to keep pace with
or less, but in large regions of the world, Haber–Bosch process may be an increase population increases, without requiring
average atmospheric deposition rates in the amount of carbon sequestrated an increase in cropping area. At the same
exceed 10 kg N ha−1 yr−1, exceeding in non-agricultural ecosystems, due to time, an increase in fertilizer efficiency
natural rates by more than an order an increase in atmospheric nitrogen is expected. In agreement with Smil2, we
of magnitude. Much of this reactive deposition. Recent debate has focused assume that nitrogen management can
nitrogen is deposited in nitrogen-limited on the response of forests17–20, where be improved, resulting in a 50% increase
ecosystems, leading to unintentional the strength of this fertilization effect is in nitrogen-use efficiency, thus reducing
fertilization and loss of terrestrial contentious. Estimates of the amount of nitrogen application.

638 nature geoscience | ADVANCE ONLINE PUBLICATION | www.nature.com/naturegeoscience


FEATURE
3) Further demand on agriculture may the future nitrogen ECONOMY 3. Erisman, J. W., Bleeker, A., Galloway, J. N. & Sutton, M. A
be posed by biofuel production, calling Environ. Pollut. 150, 140–149 (2007).
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for an expansion of crop land as well It is appropriate to mark a century of German, Jew. (Chemical Heritage Press, Philadelphia, 2004)
as an increase in nitrogen demand. Haber’s invention. Given its multiple roles 5. White, M. Historical Atlas of the Twentieth Century (2003);
In the technology-oriented ‘global’ in military security, food production, available at <http://users.erols.com/mwhite28/warstat1.
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Development estimate of the maximum considered dependent on a nitrogen-based Agron. J. 97, 1–6 (2005).
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Organization of the United Nations, Rome, Italy, 2006).
(0.74 Gha), which represents an that the benefits of Haber–Bosch nitrogen 9. Biofuels: Is the Cure Worse Than the Disease?
extension equal to half the current are not available to all people of the world, (OECD Paris, France, 2007).
cropland area9. owing to financial, geographical and 10. Galloway, J. N. et al. Science 320, 889–892 (2008).
political constraints. It is therefore essential 11. Reactive Nitrogen in the Environment: Too Much or Too Little of
a Good Thing (UNEP, WHRC, Paris, 2007).
(4) Large parts of the world population to provide the infrastructure to supply 12. Sustainable Management of the Nitrogen Cycle in Agriculture
are deprived of valuable animal protein. nitrogen where it is needed, and to use it in a and Mitigation of Reactive Nitrogen Side Effects (International
We assume that food equity will increase sustainable way. Fertilizer Association, Paris, France, 2007).
worldwide meat consumption to the Fritz Haber aimed to influence the 13. Tilman, D., Cassman, G. K., Matson, P. A., Naylor, R. &
Polasky, S. Nature 418, 671–677 (2002).
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Increased meat production will increase advantages for his country in terms of food 15. Galloway, J. N. et al. Bioscience 53, 341–356 (2003).
nitrogen usage because of the additional and military security. His invention for 16. Gruber, N. & Galloway, J. N. Nature 451, 293–296 (2008).
17. Magnani, F. et al. Nature 447, 848–851 (2007).
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use in meat-based diets relative to course of the planet throughout the doi:10.1111/j.1365–2486.2008.01636.x (2008).
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Nature Geosci. 1, 430–437 (2008).
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(5) We assume that human diets will be that the unintended environmental Atmos. Chem. Phys. 8, 389–395 (2008).
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efficiency in the production cycle. the coming decades. Each of the main 23. Nakicenovic, N. et al. Special Report on Emissions Scenarios.
Working Group III of the Intergovernmental Panel on Climate
Specifically, we assume that the ratio of human drivers, such as growth in the Change (Cambridge Univ. Press, Cambridge, UK, 2000).
meat protein to milk protein (currently population, improvement of the world’s 24. UN Department of Economic and Social Affairs.
about 2:1) will be reversed (1:2), as the food supply and the use of biomass World population to 2300 (United Nations Publications,
New York, 2004)
nitrogen-to-protein conversion ratio is to provide energy, will lead to further 25. Lutz, W., Sanderson, W. & Scherbov, S. Nature
higher in milk than meat. increases in the demand for nitrogen, and 451, 716–719 (2008).
will more than compensate for expected 26. Fertilizer Requirements in 2015 and 2030 (FAO, Rome, 2000).
Our projections are well within the improvements in efficiency. In the 27. Tilman, D. et al. Science 292, 281–284 (2001).
28. Tubiello, F. N. & Fischer G. Technol. Forecast Soc.
low estimates provided by the Food and worst-case scenario, we will move towards 74, 1030–1056 (2007).
Agriculture Organization26, and some a nitrogen-saturated planet, with polluted
higher estimates in scientific literature27,28, air, reduced biodiversity, increased human Acknowledgements
which suggest a two- to threefold increase health risks and an even more perturbed We acknowledge financing from the European Commission
in nitrogen fertilizer use by the second greenhouse-gas balance. for the NitroEurope Integrated Project, the European Science
Foundation for the NinE programme and the COST programme
half of the twenty-first century, assuming Food and military security were the (European Cooperation in the field of Scientific and Technical
continuation of past practices. In all our key objectives for Haber. For us, global Research) for COST 729. This article was prepared as a
scenarios, anticipated improvement in environmental sustainability must surely contribution to the International Nitrogen Initiative and the
Task Force on Reactive Nitrogen of the United Nations Economic
efficiency will compensate for much of the be the main driver for future innovation. Commission for Europe.
increase in fertilizer demand. Furthermore, Examples of key advances to aim for include
we do not expect global protein supply improving nitrogen-use efficiency and
to improve towards ‘food equity’ in the reducing dependency on nitrogen-intensive Jan Willem Erisman1*, Mark A. Sutton2,
scenarios predicting high population biofuels, as well as developing a James Galloway3, Zbigniew Klimont4
growth (A2 and B2 projections). Thus the comprehensive supply of protein and and Wilfried Winiwarter4, 5
drivers towards high nitrogen use will not amino acids with greatly improved 1
Energy Research Center of the Netherlands,
occur simultaneously, leading to smaller efficiency compared with traditional ECN, PO Box 1, 1755 ZG Petten,
differences in annual nitrogen demand agricultural systems. the Netherlands;
(100–150  Tg N) than would be expected It will be interesting to look back a 2
Centre for Ecology and Hydrology,
from population projection alone. Only century from now: will another patent have Edinburgh Research Station, Bush Estate,
when bioenergy calls for a large increase changed the world to the same extent as the Penicuik, Midlothian, EH26 0QB, UK;
in crop production is fertilizer nitrogen one Fritz Haber filed a hundred years ago? 3
Environmental Sciences, University
demand expected to double to nearly of Virginia, PO Box 400123,
200 Tg N per year. Despite the uncertainty Published online: 28 September 2008. 291 McCormick Rd, Charlottesville,
and the many important drivers not Virginia 22904, USA;
References
included, all scenarios point towards an 1. Haber, F. The Synthesis of Ammonia from its
4
International Institute for Applied Systems
increase in future production of reactive Elements Nobel Lecture (1920); available at Analysis (IIASA), Schlossplatz 1,
nitrogen. This will further increase the www.nobelprize.org/nobel_prizes/chemistry/laureates/ A-2361 Laxenburg, Austria;
1918/haber-lecture.pdf.
nitrogen pressures on the environment, 2. Smil, V. Enriching the Earth: Fritz Haber, Carl Bosch
5
Austrian Research Centers, Donau-City Str. 1,
with uneven distribution only exacerbating and the Transformation of World Food Production A-1220 Vienna, Austria.
the problem regionally. (MIT Press, Cambridge, Massachusetts, 2001). *e-mail: [email protected]

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