N
Native Minerals
Satoshi Matsubara
Department of Geology and Paleontology, National Museum
of Nature and Science, Tokyo, Japan
Synonyms
Native elements
Definition
Native minerals are basically the natural substances that occur
in the state of chemical elements or their alloys.
Classification
The term “native minerals” is not used but “native elements”
or simply “elements” in the field of mineralogy, and some
minerals that occur as carbides, nitrides, silicides, and phos-
phides as well as chemical elements or their alloys are tradi-
tionally classified into the class of “native elements and
alloys” (Gaines et al. 1997) or simply “elements” (Strunz
and Nickel 2001). As of 2014, the mineral names including
native minerals are summarized in Fleischer’s glossary of
mineral species (Back 2014).
Native minerals are divided to the following three groups.
1. Metals and intermetallic alloys
A few native metals have nearly pure composition, but
almost all of them are under the state of solid solution, e.g.,
between Au and Ag (Fig. 1) (referred as electrum), which are
isostructural, and among Os, Ir, and Ru (referred as iridos-
mine) in case of different structure in pure metals, respec-
# Springer International Publishing AG, part of Springer Nature 2018
W. M. White (ed.), Encyclopedia of Geochemistry,
https://doi.org/10.1007/978-3-319-39312-4
tively, or intermetallic alloys, e.g., between Hg and other
metals (referred as amalgam). In this group, 33 minerals are
recognized as native elements composed of 25 elements such
as Al, Ti, V, Cr, Fe, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, In,
Sn, Sb, W, Os, Ir, Pt, Au, Hg, Pb, and Bi. Intermetallic alloys
are recognized as 50 species. Among them, Al63Cu24Fe13 and
Al71Ni24Fe5 discovered from meteorites have unusual quasi-
crystalline structure with quasiperiodic fivefold or tenfold
rotation symmetry and were approved as new minerals
under the name of icosahedrite in 2012 and of decagonite in
2015, respectively, by the Commission on New Minerals,
Nomenclature and Classification, IMA.
2. Nonmetals
In this group, five native elements are recognized such
as C, Si, S, As, and Te. Carbon and sulphur minerals have
nearly pure composition, and four polymorphs (diamond,
graphite, chaoite, and lonsdaleite) and three polymorphs
(sulphur, sulphur-b, and rosickýite) exist, respectively. Arse-
nic minerals generally have solid solution between Sb, e.g.,
stibarsen (Sb0.5As0.5); in addition, three polymorphs (arsenic,
arsenolamprite, and pararsenolamprite) exist.
3. Metallic and nonmetallic carbides, nitrides, silicides, and
phosphides
In the field of mineralogy, these compounds traditionally
are classified as native elements. Many minerals of this group
have been discovered from extraterrestrial materials and two
species are known as carbides (e.g., cohenite, (Fe,Ni,Co)3C),
four species as nitrides (e.g., osbornite, TiN), six species as
silicides (e.g., hapkeite, Fe2Si), and eight species as phos-
phides (e.g., barringerite, (Fe,Ni)2P).
The occurrences of the native elements are divided into
nine types: (1) in terrestrial rocks, (2) in ultramafic rocks
(including kimberlite and lamproite) (account for about
38%), (3) in mafic rocks, (4) in felsic rocks, (5) in
958 Native Minerals

metamorphic or metasomatic rocks, (6) in hydrothermal veins

(account for about 18%), (7) in others (oxidation products,
volcanic sublimate, etc.) and (8) in placer deposits (unknown
original rocks), and (9) in extraterrestrial materials
(meteorites, cosmic dusts, lunar rocks, etc.) (account for
about 21%).
The mineral names of the native elements, chemical com-
positions, crystal system, and main occurrences are demon-
strated in Table 1.

Summary

136 mineral species are classified into groups of native min-

Native Minerals, Fig. 1 Photomicrograph of native gold crystals in
hydrothermal quartz vein from the Nakase mine, Hyogo Prefecture,
Japan. Field view: approximately 3.5
4.0 mm
erals (native elements) such as chemical elements or their
alloys, carbides, nitrides, silicides, and phosphides
(CNMNC 2016).

Native Minerals, Table 1 Mineral names of native elements. Mineral (8) ET. Also crystal systems are as follows: cubic, cub; tetragonal, tet;
names are arranged alphabetically in every group. Abbreviations are as hexagonal, hex; trigonal (rhombohedral), trig; orthorhombic, orth;
follows: (1) UL, (2) MF, (3) FL, (4) MT, (5) HY, (6) OT, (7) PL, and monoclinic, mon; triclinic, tric
Mineral name Composition Crystal system Main occurrence
(Native metals)
Aluminum Al Cub MF, HY, OT
Antimony Sb Trig HY
Awaruite Ni2Fe ~ Ni3Fe Cub UL
Bismuth Bi Trig HY
Cadmium Cd Hex MF
Chromium Cr Cub PL (inclusions in diamond)
Copper Cu Cub OT, MT
Gold Au Cub HY, PL
Garutite (Ni,Fe,Ir) Hex UL
Hexaferrum (Fe,Os,Ru,Ir) Hex UL
Hexamolybdenum (Mo,Ru,Fe) Hex ET
Indium In Tet FL
Iridium Ir Cub UL, PL
Iron (kamacite = Ni-bearing iron) Fe Cub MF, ET
Lead Pb Cub MT, HY
Mercury Hg Trig (<38.9  C) HY
Nickel Ni Cub UL, MT
Osmium Os Hex UL, PL
Palladium Pd Cub UL, OT
Platinum Pt Cub UL, MF, HY, PL
Rhodium Rh Cub UL
Rutheniridosmine (Ir,Os,Ru) Hex UL
Ruthenium Ru Hex UL, PL
Silver Ag Cub HY, OT
Stibarsen Sb0.5As0.5 Trig HY
Taenite (Fe,Ni) Cub ET
Tetrataenite FeNi Tet ET
Tin Sn Tet FL
Titanium Ti Hex UL
Tungsten W Cub PL (inclusions in yttriaite-(Y))
(continued)
Native Minerals 959

Native Minerals, Table 1 (continued)

Mineral name Composition Crystal system Main occurrence
Vanadium V Cub OT
Wairauite CoFe Cub UL
Zinc Zn Hex OT
(Intermetallic alloys)
Anyuiite Au(Pb,Sb)2 Tet UL, PL
Atokite (Pd,Pt)3Sn Cub UL
Auricupride Cu3Au Cub UL
Belendorffite Cu7Hg6 Trig HY
Bogdanovite (Au,Te,Pb)3(CuFe) Cub OT
Bortnikovite Pd4Cu3Zn Tet UL
Cabriite Pd2CuSn Orth UL
Chengdeite Ir3Fe Cub UL, PL
Chromferide Fe1.5Cr0.2 Cub HY
Cupalite (Cu,Zn)Al Orth UL
Damiaoite PtIn2 Cub HY
Danbaite CuZn2 Cub UL
Decagonite Al71Ni24Fe5 Decagonal ET
Eugenite Ag11Hg2 Cub HY
Ferchromide Cr1.5Fe0.2 Cub HY
Ferronickelplatinum Pt2FeNi Tet UL
Hongshiite (Pt,Fe)Cu Trig UL
Hunchunite Au2Pb Cub PL
Icosahedrite Al63Cu24Fe13 Icosahedral ET
Jedwabite Fe7(Ta,Nb)3 Hex PL
Khatyrkite (Cu,Zn)Al2 Tet UL
Kitagohaite Pt7Cu Cub PL
Kolymite Cu7Hg6 Cub HY
Leadamalgam Pb0.7Hg0.3 Tet HY N
Luanheite Ag3Hg Hex PL
Maldonite Au2Bi Cub HY
Moschellandsbergite Ag2Hg3 Cub HY
Nielsenite PdCu3 Tet UL
Niggliite PtSn Hex UL, MF
Nisnite Ni3Sn Cub UL
Norilskite (Pd,Ag)2-xPb (x = 0.08–0.11) Trig MF
Novodneprite AuPb3 Tet HY
Paolovite Pd2Sn Orth UL, MF
Paraschachnerite Ag1.2Hg0.8 Orth HY
Plumbopalladinite Pd3Pb2 Hex UL, MF
Potarite PdHg Tet UL, PL
Rustenburgite (Pt,Pd)3Sn Cub UL, MF
Schachnerite Ag1.1Hg0.9 Hex HY
Skaergaardite CuPd Cub UL, MF
Sorosite Cu1-x(Sn,Sb) (x = 0.1–0.2) Hex PL
Stannopalladinite Pd3Sn2 Orth UL MF
Taimyrite-I (Pd,Cu,Pt)3Sn Orth UL
Tatyanaite (Pt,Pd,Cu)9Cu3Sn4 Orth UL
Tetra-auricupride CuAu Tet UL
Tulameenite Pt2FeCu Tet UL
Weishanite (Au,Ag)1.2Hg0.8 Hex HY
Yixunite Pt3In Cub MT
Yuanjiangite AuSn Hex PL
Zhanghengite CuZn Cub ET
(continued)
960 Native Minerals

Native Minerals, Table 1 (continued)

Mineral name Composition Crystal system Main occurrence
Zvyagintsevite (Pd,Pt,Au)3(Pb,Sn) Cub UL, MF
(Native nonmetals)
Arsenic As Trig HY, MT
Arsenolamprite As Orth HY
Chaoite C Hex MT
Diamond C Cub UL, MT,PL
Graphite C Hex, trig MT, MF
Lonsdalite C Hex ET
Pararsenolamprite As Orth HY
Rosickýite S Mon OT
Silicon Si Cub UL (inclusions in gold), MT
Sulfur S Orth OT
Sulfur-b S Mon OT
Tellurium Te Trig HY
(Metallic and nonmetallic carbides)
Cohenite (Fe,Ni,Co)3C Orth ET, MF
Haxonite (Fe,Ni)23C6 Cub ET
Isovite (Cr,Fe)23C6 Cub PL
Khamrabaevite (Ti,V,Fe)C Cub MF
Moissanite SiC Hex, trig UL, ET
Niobocarbide (Nb,Ta)C Cub PL
Qusongite WC Hex UL
Tantalcarbide TaC Cub PL
Tongbaite Cr3C2 Orth UL
Yarlongite Cr4Fe4NiC4 Hex UL
(Metallic and nonmetallic nitrides)
Carlsbergite CrN Cub ET
Nierite Si3N4 Trig ET
Osbornite TiN Cub ET
Qingsongite BN Cub UL
Roaldite (Fe,Ni)4N Cub ET
Siderazot Fe5N2 Hex OT
(Metallic silicides)
Brownleeite MnSi Cub ET
Gupeiite Fe3Si Cub ET
Hapkeite Fe2Si Cub ET
Linzhiite FeSi2 Tet UL
Luobusaite Fe0.83Si2 Orth UL
Mavlyanovite Mn5Si3 Hex UL
Naquite FeSi Cub UL
Palladosilicide Pd2Si Hex UL
Perryite (Ni,Fe)8(Si,P)3 Trig ET
Suessite Fe3Si Cub ET
Xifengite Fe5Si3 Hex ET
Zangboite TiFeSi2 Orth UL
(Metallic phosphides)
Allabogdanite (Fe,Ni)2P Orth ET
Andreyivanovite FeCrP Orth ET
Barringerite (Fe,Ni)2P Hex ET
Florenskyite FeTiP Orth ET
Halamishite Ni5P4 Hex MT
Melliniite (Ni,Fe)4P Cub ET
Monipite MoNiP Hex ET
(continued)
Natural Gas 961

Native Minerals, Table 1 (continued)

Mineral name Composition Crystal system Main occurrence
Murashkoite FeP Orth MT
Negevite NiP2 Cub MT
Nickelphosphide (Ni,Fe)3P Tet ET
Schreibersite (Fe,Ni)3P Tet ET, MF
Transjordanite Ni2P Hex MT
Zuktamrurite FeP2 Orth MT

Cross-References Gaines RV, Skinner HCW, Foord EE, Mason B, Rosenzweig A (1997)
Dana’s new mineralogy, 8th edn. Wiley, New York, pp 1–36
Strunz H, Nickel EH (2001) Strunz mineralogical tables, 9th edn.
▶ Aluminum E. Schweizerbart’sche Verlagsbuchhandlung (Nägele u. Obermiller),
▶ Antimony Stuttgart, pp 33–55
▶ Arsenic
▶ Bismuth
▶ Cadmium
▶ Chromium Natural Gas
▶ Cobalt
▶ Copper Giuseppe Etiope
▶ Elements: Metalloids Sezione Roma 2, Istituto Nazionale di Geofisica e
▶ Gold Vulcanologia, Rome, Italy
▶ Indium
▶ Iridium
▶ Iron Definitions
▶ Lead
▶ Mercury Natural gas is a mixture of gaseous hydrocarbons and non-
▶ Meteorites hydrocarbon gases typically produced in subsurface sedimen-
▶ Mineralogy tary rocks, frequently associated with crude oil or coal beds.
▶ Molybdenum Hydrocarbon gases are almost exclusively alkanes, N
▶ Nickel dominantly methane (CH4, generally from 70 to 90 vol.%),
▶ Osmium and, subordinately, ethane (C2H6, 1 to 10 vol.%), propane
▶ Palladium (C3H8, generally <5 vol.%), and butane (C4H10 < 1–2 vol.
▶ Platinum %). Nonhydrocarbon gases, such as CO2, N2, He, H2, and
▶ Platinum Group Elements H2S, are generally present as minor constituents. Natural gas
▶ Rhenium is formed through microbial or thermal degradation of organic
▶ Rhodium matter in sedimentary rocks, typically shale or limestone
▶ Ruthenium (source rocks), in coal-beds, and through oil cracking and
▶ Selenium biodegradation. The gas can move inside the porous source
▶ Silicon rocks (primary migration), migrate to external rocks
▶ Silver and accumulate in trapped permeable “reservoir” rocks
▶ Sulfur (secondary migration), and move from a reservoir to another,
▶ Tellurium or seep to the Earth’s surface (tertiary migration and seepage;
▶ Tin Fig. 1) (Hunt 1996; Etiope 2015).
▶ Titanium In the petroleum geology literature, the term “natural gas”
▶ Zinc does not refer to geothermal or volcanic H2O- or CO2-rich gas
where hydrocarbons are a minor component. The term can
however include hydrocarbon-rich gas originated abiotically,
References in considerable concentrations (up 90 vol.%), in some igne-
ous rocks (see “Origin”).
Back ME (2014) Fleischer’s glossary of mineral species 2014. The The methane produced in subsurface source rocks is typ-
Mineralogical Record Inc., Tucson
Commission on New Minerals, Nomenclature and Classification, Inter-
ically “fossil,” i.e., radiocarbon (14C) free (carbon older than
national Mineralogical Association (2016) Available via IMA 50,000 years BP) and can be termed “geological methane.”
CNMNC. http://nrmima.nrm.se//. Accessed 18 Feb 2016 Modern microbial methane is instead produced and dispersed
962
Natural Gas, Fig. 1 Scheme of the main natural gas occurrences
within shallow sediments and bottom waters in estuaries,
deltas, bays, lakes, marshes, wetlands, and shallow perma-
frost. Although this modern gas could also be broadly called
“natural gas,” it does not represent a fossil-fuel source for
petroleum industry and literature.
Origin
The natural gas currently exploited as energy source origi-
nates through the microbial or thermal degradation of organic
matter, coal, or oil in sedimentary rocks, typically shale
and limestone. Microbial and thermogenic gases are
cumulatively termed biotic because of the derivation from
biologic compounds, mainly lipids and carbohydrates, in
marine (sapropelic) and terrestrial (humic) organic matter.
Microbial (or biogenic) gas is mainly produced during
diagenesis of sediments (Hunt 1996) by specialized microor-
ganisms that decompose organic matter and form CH4 at
relatively low temperatures (typically up to 60–80  C; or
above 100  C by extremophiles in special hydrothermal sys-
tems). Although the term “bacterial methane” is also used in
the literature, it should be remembered that Bacteria do not
produce methane, only Archaea do it. After organic matter is
decomposed, methane is formed through two main biochem-
ical pathways: CO2 or carbonate reduction (CO2 + 8H+ + 8e
➔ CH4 + 2H2O), and acetate fermentation (CH3COOH ➔
CH4 + CO2), depending on burial depth and organic matter
(e.g., Whiticar et al. 1986). In special conditions, trace
amounts of ethane and propane can be formed (Formolo
2010). Microbial methane is also produced in coal-beds, in
Natural Gas
early and late stages of coalification (Rice 1993) and by oil
biodegradation (secondary microbial methanogenesis), via
carbonate reduction. This secondary microbial gas may con-
stitute large gas resources (Milkov 2011). Microbial gas is
very dry, i.e., it consists almost entirely of methane. Generally
(but not always), it indicates relatively shallow gas source
rocks and reservoirs.
Thermogenic gas is produced in deeper sedimentary rocks
by the thermal degradation (catagenesis) of organic matter,
kerogen, coal (primary cracking), or oil (secondary cracking)
at higher temperatures, typically up to 250  C. Organic matter
maturation includes a series of intermediate products, such as
geopolymers (kerogen), bitumen, then converted into hydro-
carbons, as described in classic petroleum geochemistry lit-
erature (e.g., Tissot and Welte 1984; Hunt 1996). Vitrinite
reflectance is the main parameter to define thermal maturity
(Hunt 1996). Thermogenic gas can be independent from or
associated with oil reservoirs and can have variable amounts
of ethane, propane, butane, and heavier (C5+) hydrocarbons.
It also frequently contains measurable quantities of non-
hydrocarbon gases.
Abiotic hydrocarbon-rich gas can be produced in special
geological conditions by chemical reactions that do not require
the presence of organic matter. These reactions include gas-
water-rock reactions (for example, Fischer-Tropsch type reac-
tions, like the Sabatier reaction between carbon dioxide and
hydrogen) occurring at relatively low temperatures, often
below 150  C, in mafic and ultramafic rocks (Etiope and
Sherwood Lollar 2013). Abiotic methane is also produced,
in low concentrations (typically parts per billion to parts per
million), by magmatic and high temperature (>250  C) reac-
tions in geothermal systems (Etiope and Sherwood Lollar
2013) but, as anticipated above, it is not typically termed
“natural gas.”
Nonhydrocarbon gases (mainly CO2, N2, H2S, H2, and He)
are often associated with hydrocarbons as they can originate
through organic or inorganic processes that can occur within,
beneath, or in proximity to the petroliferous sedimentary
rocks (Hunt 1996). The organic processes are mainly thermo-
genic, e.g., kerogen decarboxylation (producing CO2 during
catagenesis), thermochemical sulfate reduction (producing
mainly H2S), thermal degradation of organic N-containing
compounds (producing N2), and oil biodegradation
(producing mainly CO2 after hydrocarbon production).
Bacterial sulfate reduction can also produce H2S and CO2.
Inorganic reactions include kaolinite-carbonate reactions
(producing CO2), metamorphism of ammonium-rich clays
(producing N2), thermo-methamorphism of limestone
(CO2), radioactive decay of U and Th (producing He), and
magma degassing (mainly CO2 and He).
The identification of natural gas origin may start observing
the relative abundance of methane (C1), ethane (C2), and
propane (C3) (i.e., the Bernard ratio C1/(C2 + C3), or the gas
Natural Gas
Natural Gas, Fig. 2 Stable C and H isotope values of methane (CH4) in
different geological systems and related genetic mechanisms (biotic and
abiotic). Biotic (microbial and thermogenic) gas data are from a global
inventory of natural gas in conventional (reservoir) and unconventional
(shale-gas, coal-gas) petroleum systems (Sherwood et al. 2017), and
wetness, expressed as SC2–5/SC1–5). Microbial gas gener-
ally has a Bernard ratio > 1000. But this diagnostic tool may
be misleading as it fails to detect post-genetic alterations of
the molecular composition of the gas (molecular fraction-
ation of thermogenic gas leading to high Bernard ratios) and
secondary genetic processes (secondary microbial methane).
The critical step for identifying the origin of natural gas is
the analysis of the stable isotope composition of carbon
(13C/12C) and hydrogen (2H/1H) in methane (expressed as
d13C and d2H in ‰ (per mil) relative to Vienna Pee Dee
Belemnite, VPDB, and Vienna Standard Mean Ocean Water,
VSMOW, standards; e.g., Schoell (1980)). The isotopic data
are typically plotted in a d13C vs. d2H diagram, an empirical
diagram that differentiates the genetic fields of microbial,
thermogenic, and abiotic methane (Fig. 2). Worldwide
occurrences of thermogenic and microbial gases have a
well-defined distribution in regards to carbon and hydrogen
isotopes. Microbial methane is generally characterized by
d13C values lower than 50‰. Thermogenic methane is
typically in the range between 50 and 30‰; but highly
mature source rocks can provide methane with d13C values
up to 20‰, and low maturity rocks (early thermogenesis)
can lead to values as low as 70‰. Abiotic CH4 has a wide
range of d13C and d2H values and, although overlapping
with part of the thermogenic field, is characterized by an
overall shift towards more 13C–enriched and more
2
H–depleted values (Fig. 2).
963
from Coleman et al. (1988), Whiticar et al. (1986) and Tazaz et al.
(2013). Abiotic gas data are from Etiope and Sherwood Lollar (2013),
Etiope et al. (2016), and Etiope (2017a, b). Abiotic gas must be consid-
ered as “dominantly abiotic,” as it may be mixed with variable amounts
of biotic gas
Use of d13C in relation to the Bernard ratio is beneficial for
determining the mixing between microbial and thermogenic
gas and the source rock maturity. The changes in the molec- N
ular and stable isotopic composition of natural gas with
increasing thermal maturity are a direct result of the kinetics
of the formation mechanisms. During the first stages of
catagenesis, at relatively low temperatures (low maturity),
gas is “wet” (i.e., rich in alkanes heavier than methane).
Wetness (defined above) can range between 10 and 100.
With increasing maturity (time and temperature) gas becomes
“dry,” less rich in C2–C5 due to the thermal cracking of heavy
alkanes. Wetness can drop to values below one. If the carbon
isotopic composition is not evaluated, this type of dry ther-
mogenic gas can be confused with microbial gas, which
generally has wetness <0.1. Additional interpretative tools
use the isotopic composition of nonhydrocarbon gases
(especially CO2 and N2).
Occurrences
Natural gas occurs in porous, sedimentary, organic-rich
source rocks (shales, marls, and limestones), and coal-beds,
where it is initially generated, and in more permeable sedi-
mentary rocks (sandstones, fractured limestones) and, not
rarely, even in igneous and metamorphic rocks (fractured
volcanic or crystalline basement rocks; e.g., Farooqui 2009),
964
where it accumulated. Permeable reservoir rocks represent
“conventional” gas resources. Scarcely permeable reservoirs
(e.g., tight-gas sandstones) and source rocks (shale-gas) rep-
resent “unconventional” resources, as they require stimula-
tion methods to improve economic recovery rates. Gas
hydrates and coal-beds (coal-bed methane, CBM; or coal
seam gas, CSG) are also unconventional gas resources.
More than 50% of conventional reservoired oil and gas
was generated by source rocks formed within two relatively
short geological time periods, between 144 and 169 Myrs ago
(Upper Jurassic) and between 88 and 119 Myrs ago (Aptian-
Turonian) (Klemme and Ulmishek 1991). From the reservoir
rocks, natural gas can migrate through faults to the Earth’s
surface (seepage), entering shallow aquifers, soil, and the
atmosphere via diffuse exhalation (microseepage), springs
and seeps (macroseeps), such as mud volcanoes, and oil or
gas seeps, including natural “eternal” fires (Etiope 2015).
Natural gas source rocks, reservoirs, and seeps are distributed
throughout the petroliferous sedimentary basins of all conti-
nents. The largest gas reservoirs are located in Russia, Iran,
Qatar, and Algeria.
In ocean bottom sediments, microbial or thermogenic
natural gas can occur as gas hydrates or clathrates, ice-like
crystalline solids stable under specific pressure and temper-
ature conditions, composed of rigid cages of water mole-
cules that enclose guest gas molecules. Methane hydrates
generally occur in deep-sea sediments or shallow seabed in
Arctic regions, and likely contain one order of magnitude
more methane than the 220 Gt of carbon estimated to occur
in all conventional gas reservoirs (Milkov 2004). Permafrost
on land, in subpolar regions, may also host significant
amounts of methane clathrates, either microbial or
thermogenic.
Abiotic natural gas has been widely reported, in
concentrations reaching orders of 80–90 vol.%, in deep
boreholes in crystalline shields in Canada, South Africa,
and Finland (Sherwood Lollar et al. 1993), and in surface
seeps and springs in serpentinized ultramafic rocks
(peridotites) of continental ophiolites, peridotite massifs,
and igneous intrusions, in at least 17 countries in North
America, Europe, Asia, and Oceania (Etiope and Sherwood
Lollar 2013; Etiope and Schoell 2014; Etiope 2017b). Vol-
umes of this gas in the rocks are not known but the high gas
flux, observed at the surface in some cases, suggests the
presence of pressurized pools.
Energy Resource
Natural gas in conventional and unconventional petroleum
systems is a nonrenewable resource. Thermogenic gas accu-
mulations account for approximately 80% of the world’s
natural gas resources (Rice 1993). Shale-gas represents an
Natural Gas
increasingly important source of gas in the United States,
Canada, and China. Commercial accumulations of abiotic
methane have not been identified by the petroleum industry,
so far; less than 1% of the CH4 in most oil and gas fields was
estimated to be abiotic (Jenden et al. 1993). The recent dis-
coveries of abiotic gas in continental ultramafic rocks and
Precambrian crystalline shields could, however, represent
new resource prospects for the future.
In total, natural gas accounts for about 24% of the world’s
energy consumption. Global natural gas production, con-
sumption, and reserves have been estimated (end of 2015) at
approximately 3539, 3469, and 186,900 billion cubic meters,
respectively (BP 2016).
Summary
Natural gas is a mixture of hydrocarbons (methane, ethane,
propane, butane) and nonhydrocarbon gases (CO2, N2, H2S,
H2, and trace amounts of noble gases) originated in sedimen-
tary source rocks (shales, marls, and limestones) and stored in
reservoir rocks (sandstones, limestones, and subordinately
igneous/metamorphic rocks). The gas is produced biotically
by microbial or thermal degradation of marine (sapropelic) or
terrestrial (humic) organic matter in marine sediments and
coal formations (coal-bed gas), and by oil cracking and bio-
degradation. Abiotic natural gas, generated by gas-water-rock
chemical interactions (e.g., Fischer-Tropsch type reactions),
has been increasingly discovered in recent years in Precam-
brian shields and serpentinized ultramafic rocks in ophiolites
and peridotite massifs. Microbial and thermogenic gas can
also be stored as hydrates in marine sediments and onshore
permafrost. From source rocks and reservoirs, the gas can
migrate along faults to the Earth’s surface, where it exhales to
the atmosphere through gas seeps and mud volcanoes.
Reservoired natural gas presently accounts for one fourth of
the world’s energy consumption.
Cross-References
▶ Biogenic Methane
▶ Black Shales and Sapropels
▶ Carbon
▶ Carbon Isotopes
▶ Coal
▶ Gas Hydrates
▶ Geochemical Exploration
▶ Hydrocarbons
▶ Kerogen
▶ Organic Geochemistry
▶ Petroleum
▶ Surface Geochemistry
Neodymium 965

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Neodymium
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statisticalreview#BPstats
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Paleozoic sediments and glacial deposits of Illinois, U.S.A. Chem Earth and Ocean Sciences, University of South Carolina,
Geol 71:23–40 Columbia, SC, USA
Etiope G (2015) Natural gas seepage. The Earth’s hydrocarbon
degassing. Springer, Switzerland, 199 pp
Etiope G (2017a) Methane origin in the Samail ophiolite. Comment on
“modern water/rock reactions in Oman hyperalkaline peridotite aqui-
fers and implications for microbial habitability” by Miller et al. 2016.
Geoch Cosm Acta 197:467–470
Element Data
Etiope G (2017b) Abiotic methane in continental serpentinization sites: Atomic Symbol: Nd
an overview. Procedia Earth Plan Sci 17:9–12 Atomic Number: 60
Etiope G, Schoell M (2014) Abiotic gas: atypical but not rare. Elements Atomic Weight: 144.242 g/mole
10:291–296
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Isotopes and Abundances:
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Geophys 51:276–299 Nd: 27.153%
143
Etiope G, Vadillo I, Whiticar MJ, Marques JM, Carreira PM, Tiago I, Nd: 12.173%
Benavente J, Jiménez P, Urresti B (2016) Abiotic methane seepage in 144
Nd: 23.798%
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66:101–113
Nd: 8.293%
146
Farooqui MY and 11 coauthors (2009) Evaluating volcanic reservoirs. Nd: 17.189%
148
Oil field Review 21: 36–47 Nd: 5.756%
Formolo M (2010) The microbial production of methane and other 150
Nd: 5.638%
volatile hydrocarbons. In: Kenneth N (ed) Timmis handbook of
hydrocarbon and lipid microbiology. Springer, New York,
1 Atm Melting Point: 1294 K
pp 113–126 1 Atm Boiling Point: 3347 K
Hunt JM (1996) Petroleum geochemistry and geology. W.H. Freeman Common Valences: 3+
and Co, New York, 743 pp Ionic Radii: 112 pm (eightfold coordination)
Jenden PD, Hilton DR, Kaplan IR, Craig H (1993) Abiogenic hydro-
carbons and mantle helium in oil and gas fields. In: Howell
Pauling Electronegativity: 1.14
D (ed) Future of energy gases, USGS professional paper, First Ionization Potential: 5.5250 eV
vol 1570, pp 31–35 Chondritic (CI) Abundance: 0.475 ppm
Klemme HD, Ulmishek GF (1991) Effective petroleum source rocks of N
Silicate Earth Abundance: 1.25 ppm
the world: stratigraphic distribution and controlling depositional
factors. AAPG Bull 75:1809–1851
Crustal Abundance: 20 ppm
Milkov AV (2004) Global estimates of hydrate-bound gas in marine Seawater Abundance: 2–60 pmol/kg
sediments: how much is really out there? Earth Sci Rev 66:183–197 Core Abundance: ~0
Milkov AV (2011) Worldwide distribution and significance of secondary
microbial methane formed during petroleum biodegradation in con-
ventional reservoirs. Org Geochem 42:184–207
Rice DD (1993) Biogenic gas: controls, habitats, and resource potential.
In: Howell DG (ed) The future of energy gases – U.S, Geological Properties
survey professional paper, vol 1570. United States Government
Printing Office, Washington, pp 583–606 Neodymium (Nd) is a silvery-white-yellow metal with an
Schoell M (1980) The hydrogen and carbon isotopic composition of
methane from natural gases of various origins. Geochim Cosmochim atomic number (Z) of 60, electronic configuration of [Xe]
Acta 44:649–661 4f46s2, and atomic weight of 144.242(3) (Meija et al. 2016a, b).
Sherwood OA, Schwietzke S, Arling VA, Etiope G (2017) Global It is a group IIIB inner transition element and one of the lantha-
inventory of gas geochemistry data from fossil fuel, microbial and nide and rare-earth elements. Neodymium is a refractory element,
biomass burning sources, version 2017. Earth Syst Sci Data Discuss.
https://doi.org/10.5194/essd-2017-20 with a melting point of 1294 K, boiling point of 3347 K, and
Sherwood Lollar B, Frape SK, Weise SM, Fritz P, Macko SA, Welhan JA density of 7.01 g/cm3. It is a lithophile element under the
(1993) Abiogenic methanogenesis in crystalline rocks. Geochim Goldschmidt classification, and it is dominantly found in the
Cosmochim Acta 57:5087–5509 trivalent state, with Nd3+ ionic radius of ~1.12
1010 m at
Tazaz AM, Bebout BM, Kelley CA, Poole J, Chanton JP (2013) Redefining
the isotopic boundaries of biogenic methane: methane from endo- eightfold coordination.
evaporites. Icarus 224:268–275
Tissot BP, Welte DH (1984) Petroleum formation and occurrence.
Springer, New York History and Use
Whiticar MJ, Faber E, Schoell M (1986) Biogenic methane formation
in marine and freshwater environments: CO2 reduction versus ace-
Nd was discovered in 1885 by Austrian chemist Carl F. Auer
tate fermentation – isotope evidence. Geochim Cosmochim Acta
50:693–709 von Welsbach and is named from the Greek word neos
966
didymos (new twin) (Holden 2001). The usage of neodymium
has increased significantly in the last three decades after the
discovery of neodymium-boron-iron alloys that make very
strong permanent magnets. These magnets have found its use
in a wide variety of electronics and electric motors. Nd is also
used in the manufacturing of crystals for lasers and didymium
glass used for glass blowing and welder’s goggles. As Nd is
incompatible in all major rock-forming minerals, it concen-
trates in late-stage highly differentiated melts and accessory
minerals, like phosphates. The main commercial sources of
Nd are currently rare-earth element-rich carbonatite deposits,
where the key mineral is bastnaesite (REE)CO3F, monazite
(REE)PO4, and some carbonate-bearing iron oxide deposits
(Kiruna type, Sweden, Bayan Obo, Mongolia). In all cases,
Nd is found together with other light rare earths (La, Ce, Pr,
Sm).
Geochemical Behavior
The major importance of Nd is that it is one of the larger
trivalent rare-earth elements, among the most useful trace
elements in all areas of geochemistry and cosmochemistry
due to their coherent and systematic behavior as a group.
143
Nd is also the decay product of 147Sm, and 142Nd is the
decay product of 146Sm. Nd has two radioactive isotopes,
144
Nd with a half-life (T1/2) of 2.4
1015 years (McSween
and Huss 2010) and 150Nd with a half-life of 9.11
1018
years (Argyriades et al. 2009), both too long to have any
practical applications in geochronology and are thus consid-
ered effectively stable.
As a lithophile element, Nd is thought to wholly partition
in the silicate portion of the Earth with effectively no Nd in the
Earth’s core. Primitive CI-chondrite meteorites, thought to
represent the initial composition of the solar nebular for
refractory elements, have an estimated 0.457–0.474 ppm Nd
concentration (McDonough and Sun 1995; Palme and
O’Neill 2003). The Nd concentration of the primitive mantle
(or bulk silicate earth) is estimated at 1.25–1.37 ppm
(McDonough and Sun 1995; Palme and O’Neill 2003). Due
to its relatively large ionic radius and 3+ charge, Nd is mod-
erately to highly incompatible in upper mantle mineralogy
(olivine, pyroxene, spinel, and garnet). Of these minerals,
clinopyroxene has the highest Nd concentrations (typically
in the order of several ppm or less), where Nd substitutes for
Ca in the M2 crystallographic site that is of similar size
(~1
1010m) as the Nd ionic radius in eightfold coordina-
tion, likely through a coupled substitution of Al3+ for Si4+ or
Na1+ for Ca2+ (Wood and Blundy 2001). As an incompatible
element, Nd is preferentially concentrated in melts from the
mantle, and its concentration in the continental crust is near
20 times than of the primitive mantle, between 16 and
27 ppm, with an average of 20 ppm (Rudnick and Gao
Neodymium
2003), the range being largely due to the uncertainty of the
proportions of upper, middle, and lower crust in
reconstructing the bulk continental crust composition. In
turn, the upper mantle source of mid-oceanic ridge volcanism
and the presumed residue of continental crust extraction is
depleted in Nd relative to the primitive mantle with Nd
concentration estimated between 0.71 and 0.58 ppm (Salters
and Stracke 2004; Workman and Hart 2005). The mean Nd
concentration of mid-oceanic ridge basalts, the most volumi-
nous volcanism on Earth sourced from this depleted mantle, is
12  0.78 ppm (Gale et al. 2013).
Due to the different compatibility of Sm and Nd in most
petrogenetically important minerals, melting and crystalliza-
tion processes create variable Sm/Nd ratios in minerals and
melts that over time generate variable amounts of radiogenic
143
Nd over the stable 144Nd, denoted by the 143Nd/144Nd ratio,
making the 147Sm/143Nd decay system, one of the most
important geochronological and isotope tracer systems.
142
Nd, the decay product of now extinct 146Sm with a some-
what uncertain half-life of 68 Ma (Kinoshita et al. 2012) to
103 Ma (Marks et al. 2014), is an increasingly important tracer
in evaluating the evolution of the terrestrial mantle during the
first 300 hundred million years of Earth’s history (Rizo et al.
2012), and the terrestrial 142Nd/144Nd isotope systematics are
central in the discussion of whether Earth evolved with a
chondritic composition or not (Carlson and Boyet 2009).
In typical seawater composition and pH = 8.2, Nd exists
primarily as a carbonate ion species Nd(CO3)2 and NdCO3+.
In the absence of strong organic complexing ligands, like
humic acids (Sonke and Salters 2006), Nd is highly particle
reactive and readily adsorbed in hydrated Fe and Mn oxide
phases and particulate surfaces (Schijf et al. 2015), resulting
in very low concentrations in seawater on the order of
2–60 pmol/kg (Goldstein and Hemming 2003). In the pelagic
ocean setting, Nd concentration increases with depth, which
appears to be controlled by processes involving sinking par-
ticles. Despite the nutrient-like behavior of Nd concentra-
tions, Nd isotopes vary with salinity (e.g., von
Blanckenberg 1999) suggesting a residence time shorter
than ocean mixing (~1500 years, Broecker and Peng 1982).
The residence time of Nd in seawater ranges from 200 to 1000
years (Tachikawa et al. 1999; Arsouze et al. 2009; Rempfer
et al. 2011).
Biological Utilization and Toxicity
Nd does not appear to have a specific biological function,
likely due to its extremely low concentration in natural waters
that prevented organisms for developing a use for it. Yet,
some evidence suggests that under acidic conditions where
Nd becomes increasingly soluble, methanotrophic microbes
can utilize Nd and other light rare earths to stimulate growth
Neodymium Isotopes
(Pol et al. 2014). Neodymium is thought as moderately toxic
in humans, although specific data is scarce. Neodymium
dusts and salts are considered as irritating to the eyes and
mucus membranes and moderately irritating to the skin (Rim
et al. 2013). However, as Nd concentrations are low in the
environment, any health effects are mostly anecdotal and
appear isolated to those with occupational exposure either
closely related to mining or processing of the ore (Pagano
et al. 2015).
Cross-References
▶ Chondrites
▶ Earth’s Continental Crust
▶ Lanthanide Rare Earths
▶ Lithophile Elements
▶ Mantle Geochemistry
▶ Mid-Ocean Ridge Basalts (MORB)
▶ Neodymium Isotopes
▶ Ore Deposits
▶ Samarium
References
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ography, paleoceanography, and ice-sheet dynamics. Treatise
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Neodymium Isotopes
Michael Bizimis and Howie D. Scher
Earth and Ocean Sciences, University of South Carolina,
Columbia, SC, USA
Introduction
Isotope ratios of Nd are key geochemical tracers for
unraveling the compositional evolution of terrestrial planets,
as well as an important geochronometer. Neodymium has
seven natural isotopes: 142Nd (27.153%), 143Nd (12.173%),
968 Neodymium Isotopes

144
Nd (23.798%), 145Nd (8.293%), 146Nd (17.189%), 148Nd
(5.756%), and 150Nd (5.638%) (Meija et al. 2016). 147Sm
decays to 143Nd through a-decay with a half-life of
1.06
1011 year that corresponds to a decay constant
(lSm147) of 6.54
1012 year1. 146Sm decays to 142Nd
through a-decay and a half-life estimated between 68
106
year (Kinoshita et al. 2012) and 103
106 year (Meissner
et al. 1987; Marks et al. 2014). Due to its slightly lower ionic
radius, Sm is generally more compatible than Nd in the
Earth’s mantle. The fractionation of Sm from Nd during
melting and crystallization processes changes the Sm/Nd
ratios in minerals, which, over time, will change the relative
abundance of 143Nd and 142Nd. These changes in Nd isotopes
are important for understanding the evolution of different
terrestrial reservoirs and the processes that influence their
chemical evolution.
Nd Isotope Ratio Determinations
Neodymium is chemically isolated from other elements by
cation-exchange chromatography (Richard et al. 1976; Pin
and Zalduegui 1997). Neodymium isotope ratios are deter-
mined by thermal ionization mass spectrometry (TIMS) or
by multicollector inductively coupled mass spectrometry
(MC-ICPMS). During ionization and/or transmission
through the mass spectrometer, the Nd isotope ratios frac-
tionate relative to their true value as a function of their
mass. This instrument-induced mass fractionation is typi-
cally described by an exponential mass law and can thus
be corrected for if one (stable) ratio is known a priori. The
ratio 146Nd/144Nd = 0.7219 is conventionally used for this
fractionation correction (Hamilton et al. 1983). Additional
instrument bias can be corrected by measuring a widely
available pure Nd standard, typically the “La Jolla” stan-
dard with accepted 143Nd/144Nd = 0.511858 (Lugmair
and Carlson 1978) or the JNdi-1 with accepted
143
Nd/144Nd = 0.512115 (Tanaka et al. 2000). When
data from different laboratories is compared, care should
be taken that measurements are normalized to the same
standard value to avoid interlaboratory bias. Table 1
shows typical high-precision Nd isotope ratio determina-
tions by TIMS for the La Jolla and JNdi-1 standards
(Carlson et al. 2007).
The 147Sm-143Nd Decay System
For a closed system where the parent and daughter isotopes
remain undisturbed from any process other than radioactive
decay, 143Nd/144Nd will increase over time due to the decay of
147
Sm to 143Nd according to the decay equation:

143 
143
Nd Nd 147
Sm  lSm t 
144 Nd
¼ 144 Nd
þ 144 e 1 ; (1)
i Nd
where 143Nd/144Nd is the measured (i.e., present day) isotope
ratio of the sample, 147Sm/144Nd is the measured parent-
daughter ratio, 143Nd/144Ndi is the initial ratio of the sample
at the time that the Sm-Nd system became closed to mass
exchange, and t is the time since system closure.
The 147Sm/144Nd parent-daughter atom ratio is calculated
from the Sm and Nd concentrations as


147
Sm ½Sm=SmAtW  NA  147 SmAtAb
¼ ; (2)
144 Nd ½Nd=NdAtW  NA  144 NdAtAb
where [Sm] and [Nd] are concentrations, SmAtW and NdAtW
are element atomic weights, 147SmAtAb and 144NdAtAb are the
abundance of the two isotopes, and NA is Avogadro’s number.
For a set of cogenetic samples with identical 143Nd/144Ndi
and variable 147Sm/144Nd, for example, rocks from a common
source or minerals from within a single rock, their
143
Nd/144Nd ratios will increase over time proportionally to
their 147Sm/144Nd and will fall along a straight line on a
143
Nd/144Nd vs. 147Sm/144Nd plot, called the isochron. The
slope of this line (elt 1) allows calculation of the age of the
samples, i.e., the time since the Sm-Nd system closed. As Sm
and Nd are generally immobile in fluids and low-temperature
alteration, the Sm-Nd isotope system is well suited to date
ancient rocks. This is especially useful for mafic rocks that
generally have a greater range in Sm/Nd ratios than felsic
rocks. An example of dating of Archean mafic rocks is shown
in Fig. 1 for a series of ancient lavas with island arc affinities
(rhyolites, basalts, boninites) from the Gadwal greenstone
terrane, Dharwar craton, India, where 143Nd/144Nd versus
147
Sm/144Nd values form a well-defined isochron of 2.7 Ga
(Khanna et al. 2014).
Of the common petrogenetic minerals, garnet most
strongly fractionates the Sm/Nd ratio. Sm is significantly

Neodymium Isotopes, Table 1 Example of measured Nd isotope ratios

142
Nd/144Nd 143
Nd/144Nd 145
Nd/144Nd 146
Nd/144Nd(m) 148
Nd/144Nd 150
Nd/144Nd
La Jolla 1.1418444 0.511871 0.348413 0.7221844 0.2415826 0.2364560
JNdi-1 1.1418444 0.512126 0.348414 0.7225158 0.2415803 0.2364489
The 146Nd/144Nd ratio is the measured ratio. The other ratios are corrected for fractionation relative to 146
Nd/144Nd = 0.7219. After Carlson
et al. (2007)
Neodymium Isotopes 969

Neodymium Isotopes,
Fig. 1 An example of a Sm-Nd
isochron constructed by island
arc-related metavolcanics from
Gadwal greenstone terrane,
Dharwar, India. After (Khanna
et al. 2014). The best-fit line
defined by these rocks has an age
of 2.701  0.028 Ga. The
intercept defines the initial
143
Nd/144Ndi of the source of the
volcanics with a calculated
eNd(2,701) = 1.85. This positive
value suggests that the source of
these volcanics is a depleted
mantle that evolved over time with
a time-integrated Sm/Nd ratio
greater than CHUR. Isochron age
was calculated with the program
ISOPLOT (Ludwig 2003)

more compatible than Nd in garnet, leading to high Sm/Nd «Nd Notation

ratios and significant ingrowth of 143Nd over time, making
garnet geochronology an important tool for dating metamor- The comparison between different reservoirs and CHUR is
phic processes (Baxter and Scherer 2013). Recent advances facilitated best with the eNd notation, which is the normalized
in sample manipulation and mass spectrometry allow age difference of the sample’s 143Nd/144Nd ratio relative to
143
determinations of separate domains within single garnet Nd/144NdCHUR in parts per 10,000:
crystals by the Sm/Nd isochron method, providing high
0 143
1
spatial and temporal resolution of growth rates and meta- Nd
morphic reaction rates (Ducea et al. 2003; Pollington and B 144 Nd rock C N
eNd ¼B
@143 Nd  1C
A
10000 (3)
Baxter 2011).
144 Nd
CHUR

The Nd Isotopic Evolution of the Earth and the
CHUR Reservoir
The Nd isotopic evolution of the Earth is thought to be
described by the “chondritic uniform reservoir” or CHUR
(DePaolo and Wasserburg 1976). This assumes that the mate-
rial from which Earth was accreted had Sm/Nd and
143
Nd/144Ndi similar to chondritic meteorites. This assump-
tion is justified, as both Sm and Nd are refractory elements
with similar condensation temperatures. Sm and Nd are also
lithophile, hence exclusively incorporated in silicate minerals
and Earth’s silicate reservoirs (crust and mantle). The CHUR
composition is 143Nd/144NdCHUR = 0.512630 and
147
Sm/144NdCHUR = 0.1960 leading to a solar system initial
composition of 143Nd/144NdSSI = 0.506686  0.000070 at
4.5685
109 year (Bouvier et al. 2008). The bulk silicate
Earth is generally thought to have the same 143Nd/144Nd
evolution as CHUR (but see below for the 142Nd), thereby
making the CHUR values a useful reference point for evalu-
ating the time-integrated Sm/Nd evolution of different terres-
trial reservoirs.
Rocks with 143Nd/144Nd higher than 143Nd/144NdCHUR have
positive eNd and those with lower 143Nd/144Nd than
143
Nd/144NdCHUR, negative eNd. For example, mid-oceanic
ridge basalts have a mean 143Nd/144Nd = 0.513074 (Gale
et al. 2013) and eNd = 8.5 (typical range of eNd 5 to 12),
consistent with a derivation from the depleted mantle with
greater time-integrated Sm/Nd ratio than CHUR. Crustal
rocks have negative (and also highly variable) eNd consistent
with an origin from a reservoir with low time-integrated
Sm/Nd ratio compared to CHUR (Fig. 2). Rocks with eNd
between that of the depleted mantle and the crust, for exam-
ple, some ocean island basalts or arc lavas, are often thought
to originate from a source that contains crustal material that
was recycled back into the mantle (Hofmann 1997). The
positive eNd of mid-oceanic ridge magmas and negative eNd
of crustal rocks have led to the generally accepted paradigm
that extraction of continental crust left behind a melt-depleted
mantle that is now the source of mid-oceanic ridge volcanism.
From the decay Eq. 1, the initial 143Nd/144Ndi ratio of a
rock at the time of its formation can be calculated from its
measured 143Nd/144Nd and 147Sm/144Nd, provided that its age
970
Neodymium Isotopes, Fig. 2 (a) Schematic evolution of the
143
Nd/144Nd ratio of the depleted mantle and continental crust relative to
the chondritic uniform reservoir (CHUR), here taken as equivalent to the
primitive mantle. This example assumes a depleted mantle and continental
crust reservoirs with present-day 143Nd/144Nd of 0.5132 and 0.5116,
respectively, and single-stage evolution from CHUR 3
109 ago. The
depicted depleted mantle has higher 147Sm/144Nd = 0.225 and the crust
is known. The eNd notation can be used to compare the initial
143
Nd/144Ndi of a rock at some time t in the past, to that of
CHUR at the same time t, (CHURt), by calculating
143
Nd/144NdCHUR(t) at time t using the present-day CHUR
values above and substituting in Eq. 3.
Time-Integrated Sm/Nd Ratios of Terrestrial
Reservoirs and Model Ages
The 143Nd/144Nd of a rock, or any reservoir, effectively
records the time-integrated fractionation of the Sm/Nd ratio
in that rock. As Sm is more compatible than Nd in the Earth’s
mantle, melting creates residual rocks with relatively high
Sm/Nd that generate over time higher, i.e., more radiogenic,
143
Nd/144Nd than the bulk silicate Earth (primitive mantle)
with CHUR composition. In turn, melts generated from the
mantle, for example, melts giving rise to the continental crust,
have lower Sm/Nd and evolve over time toward relatively
lower, or less radiogenic, 143Nd/144Nd than CHUR. This con-
cept is shown schematically in Fig. 2, where the 143Nd/144Nd
evolution of three reservoirs, namely, CHUR, depleted man-
tle, and continental crust, is plotted as a function of time.
147
Sm/144Nd (and therefore Sm/Nd) of the depleted mantle
reservoir is calculated assuming it was extracted from CHUR
at a single event some time t in the past. If a younger age of
extraction from CHUR is chosen, the 147Sm/144Nd of that
reservoir will be higher, and the 143Nd/144Nd versus time
evolution curve will be steeper to reach the present-day
143
Nd/144Nd of the reservoir, demonstrating the concept of
time-integrated fractionation.
Neodymium Isotopes
lower 147Sm/144Nd = 0.144 ratios than CHUR and evolve to more radio-
genic and unradiogenic 143Nd/144Nd ratios, respectively, than CHUR over
time. (b) Same data as in (a) but the 143Nd/144Nd isotope compositions of
these reservoirs are compared using the eNd notation. CHUR, by definition,
has eNd = 0. The depleted mantle with higher 147Sm/144Nd ratio than
CHUR has increasingly positive eNd over time, and the continental crust
with lower 147Sm/144Nd ratio than CHUR has increasingly negative eNd
Conversely, if the parent-daughter ratio of the rock or
reservoir is known, and it has not changed over time due to
secondary processes like alteration, then the time of extraction
of that rock from bulk silicate Earth (or any other reservoir)
can be calculated. In other words, this “model age” is effec-
tively the time when the rock had the same isotopic compo-
sition as its parental reservoir. The concept of model age has
been proven useful for estimating the age and rate of extrac-
tion of continental crust from bulk silicate Earth or the
depleted mantle (Allègre and Rousseau 1984; Arndt and
Goldstein 1987; Hawkesworth and Kemp 2006).
This initial Nd isotope composition, or eNd(i), allows track-
ing the Nd isotopic evolution of mantle reservoirs and the
crust-mantle system over time. The generally robust behavior
of the Sm/Nd system during alteration allows precise dating
of Archean rocks and has been central in the investigation of
the Earth’s early silicate differentiation history. Mafic
Archean rocks as old as about 3.7–3.8 Ga have positive
eNd(i) (Bennett et al. 1993; Frei et al. 2004; Blichert-Toft and
Puchtel 2010; Hoffmann et al. 2011). This requires that by
3.7 Ga, there already existed a mantle reservoir with higher
Sm/Nd ratio than CHUR, suggesting an early differentiation
of the Earth. This further requires the formation of a comple-
mentary enriched reservoir with lower Sm/Nd than CHUR.
The 146Sm-142Nd System
Excess 142Nd (i.e., high 142Nd/144Nd) in some ~3.8 Ga old
rocks from Isua, Greenland, compared to modern terrestrial
samples, requires that a depleted reservoir with high Sm/Nd
Neodymium Isotopes
ratio had already formed while 146Sm was still extant,
between 4.53 and 4.42 Ga (Caro et al. 2006; Bennett et al.
2007; O’Neil et al. 2008; Rizo et al. 2011). This early,
depleted reservoir must have survived convective mixing in
the early Archean-Hadean time for about 700 Ma after for-
mation of the Earth, in order to become the source of these
Isua rocks at 3.8 Ga. The lack of 142Nd excesses in terrestrial
samples after 2.7 Ga (Debaille et al. 2013) requires subse-
quent destruction of that early depleted reservoir, possibly due
to convective stirring and mixing in the mantle (Caro 2011).
A puzzling aspect of the 142Nd isotope systematics is that
chondrite meteorites have a variable 142Nd deficit (average
20 ppm) compared to terrestrial samples (Boyet and Carlson
2005; Carlson and Boyet 2009; Gannoun et al. 2011). To
explain this discrepancy, it was originally proposed that the
Earth begun with a chondritic composition, followed by early
differentiation and isolation of an incompatible element-
enriched, low Sm/Nd reservoir from the rest of the convecting
planet (a so-called “hidden” reservoir) within the first 30 My
of the Earth’s history (Bourdon et al. 2008; Carlson and Boyet
2009). An alternative is that the Earth formed from material
with higher Sm/Nd ratio than CHUR, i.e., the Earth is
non-chondritic (Caro and Bourdon 2010). Yet, the observa-
tion that meteorite 142Nd anomalies also correlate with
145,148.150
Nd anomalies points to nucleosynthetic Nd hetero-
geneity in the early solar nebula (Gannoun et al. 2011;
Burkhardt et al. 2016; Fukai and Yokoyama 2016), which
would eliminate the need for a hidden reservoir or a signifi-
cantly non-chondritic Earth.
Seawater
The distribution of Nd in seawater is closely correlated with
salinity (von Blanckenburg 1999) leading to its use as a
conservative tracer of ocean circulation (Goldstein and Hem-
ming 2003). As the Sm-Nd isotope system is not appreciably
disturbed during weathering and transport, the Nd isotope
signature of the weathering flux into the oceans reflects the
age and lithology of crustal sources (Roy et al. 2007). Due to
the short residence time of Nd in seawater and the fortuitous
distribution of ancient and juvenile crustal material over the
Earth’s surface, major water masses can be traced using Nd
isotopes as they mix in the thermohaline circulation with deep
waters. Pioneering work in this field first illustrated ocean
basin scale Nd isotope variations (Piepgras and Wasserburg
1980; Piepgras and Wasserburg 1982; Shaw and Wasserburg
1985; Piepgras and Wasserburg 1987) and highlighted the use
of seawater Nd as a water mass tracer in the modern and
ancient oceans. In general, the North Atlantic waters have
low 143Nd/144Nd and highly negative eNd (<13), while
Pacific waters have more radiogenic 143Nd/144Nd and less
negative eNd (<3), and Indian and Southern Ocean waters
971
fall in between. The low eNd of North Atlantic waters is
explained by the North Atlantic basin being surrounded by
old, highly unradiogenic crustal rocks (e.g., the Canadian
shield), while the Pacific basin is surrounded by younger
volcanic systems with contributions from the depleted man-
tle. Critically, the conservative behavior of Nd isotopes is not
compatible with observations of nutrient-like behavior of Nd
concentrations, which has been termed as the “Nd paradox”
(Goldstein and Hemming 2003) and points to a missing flux
of Nd into the oceans. Detailed depth profiles of seawater Nd
isotopes also revealed significant deviations from conserva-
tive behavior along continental margins (Jeandel et al. 2007),
pointing to some possible sources of Nd to the oceans. Recent
work to resolve this paradox has focused on submarine
groundwater discharge (Johannesson and Burdige 2007)
pore fluid flux at the margins (Abbott et al. 2015) and eolian
inputs (Greaves et al. 1999). During planning for the interna-
tional GEOTRACES (www.geotraces.org) program, Nd iso-
topes were identified as a key parameter that will be measured
at every GEOTRACES station. Nd isotope results from inter-
national GEOTRACES cruises in the Atlantic Ocean, Ross
Sea, Pacific Southern Ocean, and Bay of Bengal highlight the
importance of advection of water masses in the Nd isotope
systematics of seawater (Stichel et al. 2012; Amakawa et al.
2013; Basak et al. 2015; Stichel et al. 2015; Lambelet et al.
2016).
Summary N
The radioactive decay of 147Sm into 143Nd and 146Sm into
142
Nd through time has produced variations in Nd isotope
ratios in terrestrial and extraterrestrial materials. As Sm is
more compatible than Nd during melt extraction from the
mantle and during crystallization of mafic minerals, there
are significant differences in the Sm/Nd ratio and Nd isotopic
composition of rocks and minerals on and within the Earth.
As a result, variations in Nd isotopes have proved to be
extraordinarily useful in geochronology, igneous and meta-
morphic petrology, and terrestrial and marine provenance
studies.
Cross-References
▶ Chondrites
▶ Earth’s Continental Crust
▶ Formation and Evolution of the Earth
▶ Geochronology and Radiogenic Isotopes
▶ Lanthanide Rare Earths
▶ Lithophile Elements
▶ Mantle Geochemistry
▶ Mid-Ocean Ridge Basalts (MORB)
972
▶ Neodymium
▶ Ocean Biochemical Cycling and Trace Elements
▶ Samarium
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Neon
Manuel Moreira
Institut de Physique du Globe de Paris, Sorbonne Paris Cité,
UMR CNRS 7154, Université Paris Diderot, Paris, France
Element Data
Atomic Symbol: Ne
Atomic Number: 10
Atomic Weight: 20.179 g/mole
Isotopes and Abundances:
20
Ne: 90.48%
21
Ne: 0.27%
22
Ne: 9.25%
Common Valence: 1 s2 2 s2 2p6
Atomic Radius: 0.51 A
1 atm Melting Point: 24.56 K
1 atm Boiling Point: 27.07 K
First Ionization Energy: 21.565 eV
(continued)
973
Sun Abundance (Solar photosphere) [Calculated]:
Ne/H = 6.9 105 (Alecian et al. 2005)
Bulk Solar Wind Abundance [Measured]: Ne/H = 6.6
105 (Heber et al. 2012)
Chondrites CI Abundance: 360  160 ppt (Mazor
et al. 1970)
Phase Q Abundance: 30–1400 ppt (Busemann
et al. 2000)
Atmosphere Abundance: 18.18 ppm (volume)
Depleted Mantle Abundance: 0.1–0.5 ppt (weight)
(Moreira and Kurz 2013)
Core Abundance: Unknown
Seawater (Pacific) Abundance: ~18 108 cm3 g1 at
STP (e.g., (Bieri et al. 1966).
Properties
Neon is the second noble gas, the family of elements of the
last column of the periodic table. It is chemically inert.
History and Use
Neon was discovered a few years after argon, in 1898, by
Ramsay and Travers (1898). Its atomic number is 10 and it
has three stable isotopes 20Ne, 21Ne, and 22Ne. Its atomic N
mass is 20.179, which reflects the relative proportion of the
three isotopes (90.48, 0.27, and 9.25%, respectively
(Eberhardt et al. 1965)). The neon isotopes 20Ne and 22Ne
were discovered by Thomson (1913), whereas the existence
of the less abundant neon isotope 21Ne was suggested by
Aston (1920) and later proved by Hogness and Kvalnes
(1928). Neon is a gas at normal pressure and temperature
conditions. It has a low solubility in silicates
(k ~ 2.5
10–4 cm3 STP/g/bar at 1400  C) and in water
(k ~ 10–2 cm3 STP/g/bar at 7.5  C) (Jambon et al. 1986;
Lux 1987; Potter and Clynne 1978; Sano and Takahata
2005). Neon is atmophile and one of the most volatile
elements in the solar nebula (half-temperature of condensa-
tion of 9.1 K (Lodders 2003)). The main budget of terrestrial
neon is the atmosphere where it represents ~18.18 ppm in
volume, the second most abundant noble gas on Earth, after
argon.
Industrial neon can be extracted from air by distillation.
Air is compressed and cooled to remove water, CO2, and
other impurities. The purified air is then cooled again until
the gases turn into liquids. Then, in distillation towers, neon is
separated from other gases. There are not many industrial uses
of neon. Neon is mainly employed as filler in lamps and signs
(with argon) and in lasers. Neon is a noble gas, rare, so no
974
mineral is formed by neon. It is not toxic and not used in
biological utilization.
Neon is extracted from geological samples in different
ways depending of the sample type. For mantle-derived sam-
ples, crushing under vacuum is common to release neon
contained in fluid or melt inclusions such as minerals or
silicate glasses. Heating and melting under vacuum is also
used for all solids in order to fully degas the samples. UV laser
allows in situ analyzes with ablation spots with a diameter of
~50 mm. Small samples (~0.1 mg) can be degassed using lasers
of appropriate power (e.g., Yb-doped laser). All these extrac-
tion techniques have in common that they are performed under
vacuum to avoid air contamination in the samples.
The neon dissolved in water can be extracted by vaporiz-
ing water under vacuum, which allows the noble gases to
leave the liquid phase because of their low solubility. After the
extraction phase from the samples, the gas purification con-
sists generally in the exposure to hot titanium sponge and/or
to nonevaporable getters (made of Zr, Al, V, Fe) at high
temperatures (>600  C) in order to crack all the reactive
molecules and to trap all the atoms except those of noble
gases. Hydrogen is trapped at room temperature on these
getters. Once the gas has been purified, noble gases are
generally separated on activated charcoal at different temper-
atures. He is separated from other noble gases at ~20 K
whereas neon will be introduced from heavy noble gases at
~70 K. Neon is then expended into the mass spectrometer for
analysis. Due to its low abundance in mantle-derived samples
(e.g., less than a ppt in mid-ocean ridge basalts), neon is
difficult to analyze and the analytical blanks are often a
major issue. This is less critical for more gas rich samples
such as meteorites or water samples. The very low abun-
dances also require the measurement of neon by mass spec-
trometry in static mode (no pumping) and most often,
detection on electron multipliers instead of faraday cups.
Although one of the most abundant elements in the Solar
System (the 5th) (Alecian et al. 2005), neon is very rare in
chondrites and in terrestrial planets (less than 1 ppb in CI
(Mazor et al. 1970), and 11 ppt in Earth in g/g of planet). This
reflects its highly volatile behavior during condensation in the
solar nebula. Its origin on Earth is debated as it is for other
volatiles, and it can be threefold: chondritic (late veneer or
during late accretion) (Marty 2012; O’Brien et al. 2014), solar
(dissolution of solar gases of a primary solar atmosphere into
a molten primitive Earth followed by its degassing after the
loss of this primary atmosphere (Sasaki 1999)), and cometary
(Bar-Nun and Owen 1998). The neon isotopic composition in
the Earth’s mantle suggests a contribution of solar neon
during accretion (solar wind implantation or dissolved solar
gases) (Honda et al. 1991; Sarda et al. 1988), but the neon
isotopic composition of the atmosphere requires either a neon
loss from the atmosphere with isotopic fractionation (Hunten
et al. 1987) or a chondritic addition (Marty 2012).
Neon
Summary
Neon, the second noble gas, was discovered in 1898 by
Ramsay and Travers. On Earth, it is the second noble gas in
abundance due to its very high volatility. Its origin on Earth is
still debated, but it is generally proposed that it involves a
mixture of chondrites, comets, and solar gases either by a
dissolution of a primordial atmosphere into a magma ocean or
by solar wind implantation in planetary precursors formed
closed to the Sun.
Cross-References
▶ Argon
▶ Earth’s Atmosphere
▶ Helium
▶ Krypton
▶ Neon Isotopes
▶ Noble Gases
▶ Xenon
References
Alecian G, Richard O, Vauclair S, Grevesse N, Asplund M, Sauval A
(2005) The new solar chemical composition. Eur Astron Soc Publ Ser
17:21–30. https://doi.org/10.1051/eas:2005095
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6 39:449–455
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Neon Isotopes
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gen and noble gases on Earth. Earth Planet Sci Lett 313-314:56–66
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chondrites. Geochim Cosmochim Acta 34:781–824
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geochemical tracers. Springer, Berlin, pp 371–391
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seawater using a quadrupole mass spectrometer. J Oceanogr
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R Soc Ser A 89:1–20
Neon Isotopes
Moreira Manuel
Institut de Physique du Globe de Paris, Sorbonne Paris Cité,
UMR CNRS 7154, Université Paris Diderot, Paris, France
Definition
Neon, the second element of the noble gas family, has three
stable isotopes: 20Ne, 21Ne, and 22Ne.
Introduction
The two most abundant isotopes (20Ne and 22Ne) were dis-
covered in 1913 by Thomson using the first “mass spectrom-
eter” ever built (Thomson 1913). They are the first stable
isotopes of the same element that have been discovered. In
1920, Aston suggested the existence of the 21Ne (Aston
1920), which was later confirmed in 1928 by Hogness and
Kvalnes (1928). The relative abundance in the atmosphere of
the three neon isotopes has been estimated by several authors
(Dibeler et al. 1947; Nier 1950; Vaughan et al. 1934), and the
commonly adopted values are those of Eberhardt et al. (1965),
who determined the following abundances: 90.50  0.07%
20
Ne, 0.268  0.002% 21Ne, and 9.23  0.07% 22Ne. This
corresponds to isotopic ratios of 9.80  0.08 and
0.0290  0.0003 for 20Ne/22Ne and 21Ne/22Ne, respectively,
for the Earth’s atmosphere.
975
The Primordial Composition: The Solar Neon
The determination of the neon isotopic ratio of the Sun has
been the subject of many works on meteorites and lunar
samples returned by the Apollo and the Luna missions.
Early in the 1960s, noble gas measurements on primitive
meteorites have suggested that the solar 20Ne/22Ne ratio is
30% higher than the atmospheric one (Zähringer 1962).
A 20Ne/22Ne ratio above 13 for the solar wind, higher
than the Earth’s atmosphere ratio of 9.80, was confirmed
by the analyzes of lunar soil grains (Eberhardt et al. 1970)
and of metal foils exposed to the solar wind for a few hours
during the Apollo 11 and 12 landings (Geiss et al. 1970).
The solar wind isotopic ratios have been precisely esti-
mated on the Genesis targets exposed to the solar wind
for 850 days after their return (e.g., Grimberg et al. 2006;
Heber et al. 2009; Pepin et al. 2012). The solar wind is
isotopically fractionated compared to the photosphere and
therefore does not provide the composition of the Sun.
Heber et al. (2009) have corrected for this isotopic frac-
tionation and proposed that the 20Ne/22Ne ratio of the Sun
is 13.36  0.09 (Heber et al. 2012), whereas the solar wind
ratio is above 13.7 (Grimberg et al. 2006; Heber et al. 2009;
Pepin et al. 2012).
Reactions Producing Neon Isotopes in Solids
Although the three neon isotopes mostly have a primordial N
origin, two processes can alter the neon isotopic compositions
in crustal and mantle rocks, as well as in extraterrestrial
materials. Neon isotopes are produced by cosmogenic and
nucleogenic reactions. Cosmogenic isotopes are produced
during spallation reactions on major elements induced by
either high-energy protons in space or by secondary neutrons
and muons produced in the atmosphere reaching the surface
(the first meters) on Earth. The production ratios in meteorites
are ~0.8 and ~0.9 for 20Ne/22Ne and 21Ne/22Ne, respectively
(from the stony meteorites compilation of Schultz and Franke
2000) and ~1 and ~0.8 in terrestrial quartz (Niedermann et al.
1993). The cosmogenic isotopes are used in geomorphology
and in cosmochemistry to determine exposure ages. In addi-
tion to spallation processes, nucleogenic reactions can also
alter the trapped neon isotopic compositions. The major
nucleogenic reactions producing neon isotopes are 17O(a,
n)20Ne, 18O(a,n)21Ne, and 25Mg(n,a)22Ne with production
ratios of ~0.3 and ~3.5 for 20Ne/22Ne and 21Ne/22Ne, respec-
tively (Leya and Wieler 1999; Yatsevich and Honda 1997).
This process is significant in U and Th rich materials, which is
the case of crustal minerals and rocks. Nucleogenic neon is
also observed in the mantle-derived rocks and allows expla-
nation of the variation of the 21Ne/22Ne ratio in oceanic
basalts sources (Honda et al. 1991; Sarda et al. 1988). These
976
secondary reactions producing neon isotopes tend to decrease
the 20Ne/22Ne and increase the 21Ne/22Ne.
Neon in Chondrites: The Neon Alphabet
Neon isotopes show the existence of mainly four components
in variable proportions in chondrites. These components are
the implanted solar wind, presolar grains (diamonds, SiC,
graphites), the cosmogenic end-member discussed above
and the phase Q, and a carbonaceous phase mainly carrying
the heavy noble gases (Fig. 1). These components can be
found in the literature with various names, leading to the
concept of the “neon alphabet” (Q, P1, Ne-A1; e.g., Ott
2014). Neon-B refers to implanted solar wind. This compo-
nent has a 20Ne/22Ne of ~12.5–13.0 and is observed in gas-
rich meteorites and lunar soil grains (Black 1972; Black and
Pepin 1969). Before 2007, Neon-B was proposed to represent
a mixture between the “normal” implanted solar wind and
implanted neon from solar flares (Solar Energetic Particles,
SEP). However, this has been challenged after the analyzes of
Genesis probe targets (Wieler et al. 2007). Neon-B rather
characterizes the implanted solar wind at steady state coupled
with sputtering since it has been shown that neon isotopes are
fractionated during solar wind implantation (Grimberg et al.
2006). A scenario able to explain the neon isotopic composi-
tion of neon B proposes that the heavy isotopes are implanted
deeper than the light ones, leading to a surface of the grains
enriched in light isotopes. When sputtering occurs, it
Neon Isotopes, Fig. 1 Neon
isotopes in chondrites, in the solar
wind and of the probable Sun neon
isotopic ratios. The red triangle
shows the isotopic compositions
of oceanic basalts (MORB and
OIB). Neon end-member (A, Q, E,
and cosmogenic) are also
represented. The figure is
modified from Moreira (2013)
Neon Isotopes
produces an isotopic composition heavier than that of the
solar wind itself (Raquin and Moreira 2009). Presolar grains
have neon isotopic compositions different from those of the
Sun. They show 20Ne/22Ne ratios of 8.5–8.9 for presolar
diamonds, with values down to 0.01 for presolar SiC and
graphite, the later suggesting a pure 22Ne component either
deriving from the radioactive decay of 22Na or from the direct
nucleosynthetic production of pure 22Ne. This later compo-
nent has however little influence of the global budget of neon
in chondrites, which is mainly dominated by Neon-B, pre-
solar diamonds, and cosmogenic neon.
Solar-Like Neon in the Earth’s Mantle
Since the pioneering works of Craig and Lupton (1976),
Kyser and Rison (1982), Poreda and Radicati di Brozolo
(1984), and Sarda et al. (1988), it is clearly established that
the mantle shows a solar-like composition, different from the
atmospheric composition and from carbonaceous chondrites.
Neon in Midocean-Ridge Basalts (MORB) and Oceanic
Island basalts (OIB) show a mixture between the atmospheric
component and a component having a 20Ne/22Ne ratio higher
than 12.5, which can only reflect a solar origin (Honda et al.
1991 1993; Moreira et al. 1995 2001; Sarda et al. 2000;
(Porcelli et al. 2001; Sasaki 1999; Yokochi and Marty 2004;
Mukhopadhyay 2012). The exact origin of the solar compo-
nent in the mantle is still matter of debates because three
origins are possible. The subduction of cosmic dust
Neon Isotopes
(interplanetary dust, or IDP) having implanted solar wind
into the OIB and MORB sources has been proposed as a
possible origin for the solar-like neon in the mantle (Allègre
et al. 1993; Anderson 1993). However, only the smallest IDPs
(<10 mm) contribute to the He and Ne budget in sediments
because they do not suffer significant heating during the
entry into the atmosphere (Farley et al. 1997). The largest
ones reach temperatures high enough to degas them. There-
fore only a very small fraction (~0.5%) of the extraterrestrial
material falling onto Earth contributes to solar helium and
neon in sediments that could be subducted, which is
not enough to explain the neon budget of the Earth’s mantle.
Moreover, it appears difficult for the implanted solar
neon to survive subduction due to its relatively high diffusiv-
ity (Hiyagon 1994; Schwarz et al. 2005). Therefore, it seems
unlikely that the solar-like neon observed in the mantle
is derived from the subduction of cosmic dust. A primordial
origin deriving either from the dissolution of solar gases
captured by the planet (Porcelli et al. 2001; Sasaki 1999;
Yokochi and Marty 2004; Mukhopadhyay 2012) or
from the solar wind irradiation of planetary precursors is
therefore proposed and still matter of discussion (Raquin
and Moreira 2009; Tolstikhin and Hofmann 2005; Trieloff
et al. 2000).
Atmospheric Neon: Late Veneer or
Atmospheric Loss?
The difference between the atmospheric and solar 20Ne/22Ne
observed in the mantle has been explained in two ways. The
neon in the mantle has a solar-like isotopic composition
(Honda et al. 1991; Sarda et al. 1988). Therefore, if the
atmosphere was degassed from the mantle, its Ne composi-
tion should have been solar, different from the present-day
composition of the atmosphere. Neon loss from the atmo-
sphere with a preferential loss of 20Ne compared to 22Ne can
explain the atmospheric 20Ne/22Ne (Hunten et al. 1987). On
the other hand, late addition of chondrites with a Neon-A
signature can also explain the atmospheric composition by
mixing between solar neon degassed from the mantle and
chondritic neon, corresponding to ~1% of late veneer material
(Marty 2012).
Summary
Neon has three stable isotopes. In geochemistry and cosmo-
chemistry, neon isotopes are mainly used either to date
exposure ages using the cosmogenic production or as a
tracer of the origin of volatiles on Earth. They provide
significant constraints on the origin and evolution of the
Earth’s atmosphere.
977
Cross-References
▶ Argon Isotopes
▶ Helium Isotopes
▶ Krypton
▶ Neon
▶ Noble Gases
▶ Xenon Isotopes
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Neutron Activation Analysis
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Neutron Activation Analysis
James R. Budahn
U.S.Geological Survey, Denver, CO, USA
Definition
Neutron activation analysis (NAA), discovered in 1936, is an
analytical technique that relies on the measurement of gamma
rays emitted from a sample that was irradiated by neutrons.
The rate at which gamma rays are emitted from an element in
a sample is directly proportional to the concentration of that
element. The major advantages of NAA are that (1) it is a
multielement technique capable of simultaneously determin-
ing up to about 50 elements in many materials; (2) it is
nondestructive and therefore does not suffer from the errors
associated with sample preparation, the most important
source of error in most analytical techniques; (3) it has very
high sensitivities for most of the elements that can be deter-
mined by NAA, most detection limits range from 0.05 to
50 ppm; (4) it is highly precise and accurate, overall errors
of less than 2% relative standard deviation can be achieved for
many elements; and (5) samples as small as a few micrograms
can be analyzed by NAA.
Principle
The process for analyzing samples by NAA involves irradi-
ating them at or near a neutron source. Neutrons are captured
by naturally occurring elements in the sample to produce
unstable radioactive isotopes (radionuclides). Beta particles,
and in some cases gamma rays, are emitted from the radionu-
clides to produce stable nuclei. The energies of these gamma
rays are, in general, distinct for a specific nuclide, and the rate
at which these photons are emitted with a particular energy
can be measured using high-resolution semiconductor detec-
tors. Because the production and decay rate of gamma-ray
radiation are dependent on the half-life of the nuclide, ele-
mental measurements can be optimized by varying the irradi-
ation and the decay times (i.e., how long the sample is near a
neutron source and when the sample is counted).
Neutron Activation Analysis
Procedure
The most common procedure for NAA involves encapsulat-
ing the samples and suitable standards in heat-sealed polyeth-
ylene or quartz vials and simultaneously irradiating them in a
research nuclear reactor. Typical research nuclear reactors
have neutron fluxes ranging between 1010 and 1015 n/cm2/s.
Ideally, the samples are irradiated in a “lazy susan” facility
that revolves around the core of the reactor, thereby ensuring
that the samples and standards experience the same neutron
fluence (i.e., flux multiplied by time). Alternatively, samples
can be irradiated by neutron point sources, such as
californium-252, that have neutron fluxes ranging between
105 and 1010 n/cm2/s. Following sequential decay periods,
each standard and sample is counted utilizing high-resolution
germanium detectors coupled to a multichannel analyzer sys-
tem. Counting of samples over sequential decay periods opti-
mizes the determination of 35–50 elements in various types
of samples. The analyzer system converts the signals that
result from gamma-ray photons impinging the detector into
digital electronic pulses and stores this information into a
few energy-related channels (i.e., an energy region).
Gamma-ray counts accumulated in an energy region above
the background counts produce photopeaks. After the
counting is complete, these data are processed using sophis-
ticated computer programs that smooth the spectral data and
determine the net areas of the gamma-ray photopeaks and
translate the area data into count rates (e.g., cpm). These
programs are capable of resolving overlapping and complex
photopeak energy regions. Final data reduction procedures
involve correcting the count rate data for decay time differ-
ences, electronic deadtime losses, and unresolved interfer-
ences and comparing the sample data (e.g., cpm/weight) to
the standard data (e.g., cpm/mg) to calculate elemental abun-
dances in the sample. In some cases, especially when it is not
practical to irradiate multiple standards, elemental abun-
dances can be determined using the k0 method which is
based on activities (i.e., cpm/ug) calculated from activation
equations.
Errors In Analysis
The principal error in the analysis of materials by NAA is the
counting statistic error, which is based on the signal-to-
background ratio at the gamma-ray energy region of interest.
A one-sigma error for a photopeak area determination is
approximately equal to the square root of the total counts
(i.e., background plus net counts) divided by the net counts.
For example, a peak area determination with 2000 total counts
and a net area of 1000 counts produces a counting error of
about 4.5%. An additional error for some elemental determi-
nations is due to unresolved interferences. The most serious
interferences are those that result when identical radionu-
clides are produced from different nuclear reactions: for
979
example, high concentrations of U fission products can
significantly interfere with the accurate determination of
La, Ce, Nd, Mo, and Zr abundances. In addition, the deter-
minations of some elements can suffer because the photo-
peaks produced by gamma rays emitted by two or more
radionuclides are not readily resolved. In these cases, empir-
ical corrections are integrated into the data reduction
procedure.
Self-shielding is a phenomenon that occurs when the neu-
tron flux experienced by a sample is attenuated, thereby
reducing the neutron activation of the nuclides in self-
shielded samples. This effect occurs when a sample contains
extremely high concentrations of elements with very high
probabilities that a neutron will be captured, which is mea-
sured in terms of a neutron capture cross section.
Other errors can result from inhomogeneous neutron
fluxes and not maintaining the identical distance between
the samples and the detector.
Detection Limits
Elemental detection limits for NAA are variable because of
variations in nuclear parameters. Specifically, the production
of a radionuclide depends on the neutron capture cross
section of the target isotope of the specific element. In
general, elements that have cross sections less than 2 barns
(a barn being equal to 1024 cm2) have detection limits
greater than 2 ppm, whereas elements with cross sections
greater than 5 barns have detection limits less than 1 ppm.
Also important is the number of gamma rays emitted by a N
radionuclide (i.e., the branching intensity). In some cases,
only a small fraction of the total emissions from a specific
nuclide is in the form of gamma rays. Another important
nuclear parameter affecting detection limits is the isotopic
abundance of the target nuclide. Detection limits are also
matrix dependent. Samples with high concentrations of
readily activated elements and that emit a considerable num-
ber of high-energy gamma rays, such as Na and Sc, can
generate high background count rates, which raise the detec-
tion limits. Some of these emissions can blocked from
detection by electronic anticoincidence techniques, thereby
reducing the background rates.
Summary
Neutron activation analyses remain at the forefront of tech-
niques for the quantitative multielement analyses of major,
minor, and trace elements in hundreds of different types of
materials. NAA is especially important in the analyses of
geochemical reference materials because of the nondestruc-
tive nature of the technique. The following list includes some
materials that have been readily analyzed by NAA: fish, teeth,
bones, chemicals, bird feathers, wheat, metal, alloys, rocks,
980 Nickel

animal shells, wood, tree needles, soil, rocks, lunar samples,

meteorites, minerals, water, hair, fingernails, fossils, bullets, Pauling Electronegativity: 1.91
paint, silica glass, and biomass fuel oils. First Ionization Energy: 737.1 kJ/mol
Chondritic (CI) Abundance: 1.091%
Silicate Earth Abundance: 0.186%
Cross-References
Crustal Abundance: 47 ppm
Seawater Abundance: ~2–10 nM/kg
▶ Analytical Techniques
Core Abundance: ~5.2%
▶ Geochemical Reference Materials
▶ Trace Elements

Properties
References

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3:385
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Wiley, New York, p 836
Friedlander G, Kennedy JW, Macias ES, Miller JM (1981) Nuclear and
radiochemistry. Wiley, New York, p 684
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Explor Spec Issue Geoanalysis 44:297–320
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materials. Wiley, New York, p 421
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reactor neutron-activation analysis. J Radioanal Chem 24:31–46
Nickel
William L. Griffin1 and Mathieu Chassé2
1 [Ar]3d84s2; consequently it shows both siderophile (iron-
Earth and Planetary Sciences, Macquarie University, North
Ryde, NSW, Australia
2 and upper mantle, it normally occurs as Ni2+, whereas in the
Institut de minéralogie, de physique des matériaux, et de
cosmochimie (IMPMC), Sorbonne universités – UPMC,
Paris, France
Nickel has an atomic number of 28, an atomic weight of
58.69, and a density of 8.9 g/cm3. It is a silvery metal that
melts at 1455  C and boils at 2913  C; it is magnetic, mallea-
ble, and ductile and conducts electricity (www.rsc.org/
periodic-table).
Ni has five naturally occurring stable isotopes and up to
18 radioactive isotopes, all long extinct. Up to 0.4 permil
difference in Ni-isotope composition is observed between
coexisting kamacite and taenite in iron meteorites and is
ascribed to diffusion during exsolution and cooling (Lazar
et al. 2012). However, the isotopic composition of Ni in
chondritic meteorites and Earth is probably identical within
current analytical capabilities (Lazar et al. 2012). Significant
fractionation of Ni isotopes can occur in low-temperature
processes such as lateritic weathering of ultramafic rocks;
progressive weathering leads to isotopically lighter soils
(D60NiSoil-Bedrock = 0.47 ‰) (Ratié et al. 2015).
Ni is a transition element, with the electronic configuration
loving) and lithophile (silicate-loving) behavior. In the crust
Earth’s core, it is alloyed with iron.
History and Use

Nickel (Ni) was first isolated from NiAs (niccolite) and

Element Data named by A. F. Cronstedt in 1751. The name derives from
Atomic Symbol: Ni the Saxon “nickel,” a malicious sprite (“Kupfernickel”) who
Atomic Number: 28 prevented them from extracting copper from niccolite, which
Atomic Weight: 58.69 they had mistaken for chalcopyrite (CuFeS2). Its properties
Isotopes and Abundances: 58Ni 68.0769%, 60Ni were determined by J.B. Richter in 1804.
26.2231%, 61Ni 1.1399%, 62Ni 3.6345%, 64Ni The main use of Ni (ca 65%) is for the production of
0.9256% stainless steel, with demand increasing by ca 5%/annum
1 Atm Melting Point: 1455  C (International Nickel Study Group; www.insg.org). It is also
1 Atm Boiling Point: 2913  C used in the production of nonferrous alloys or so-called
Common Valences: 2+ “superalloys” which show better resistance to corrosion and
Ionic Radii: fourfold, 55 pm; fourfold square, 49 pm; are widely used in jet engines and turbines. Smaller propor-
fivefold, 0.63 pm; sixfold, 9 pm tions are used in various surface treatments such as electro-
(continued) plating and as hydrogenation catalysts.
Nickel
Ores and Production
World usage of Ni amounts to between 1.8 and 2 million
tonnes/year (2014–2015).
Nickel is mined almost entirely from two types of deposit,
magmatic sulfides and lateritic horizons, developed through
the weathering of ultramafic rocks, usually in tropical areas
(e.g., New Caledonia, Venezuela, the Dominican Republic,
Brazil, Madagascar, and eastern Australia). Magmatic sul-
fides occur in ultramafic lava flows (komatiites; Fig. 1) in
Archean cratons, in large intrusions of layered gabbros, and in
the Sudbury giant impact crater. In all of these, the major ore
mineral is pentlandite (Ni,Fe)9S8, but Ni also forms a range of
other sulfides, arsenides, and antimonides. While magmatic
sulfide ores are important resources, >70% of the world’s
supply of Ni is mined from lateritic deposits. During
weathering, Ni concentrates in Ni-bearing limonite
(Fe oxyhydroxide) and garnierite (referring to a group of
green Ni-bearing magnesium phyllosilicates including ser-
pentine, talc, sepiolite, smectite, and chlorite) in the middle-
upper parts of the weathering profile, providing a resource
that is easily mined and processed.
Geochemistry
The cosmic abundance of Ni estimated from carbonaceous
chondrites is 10,910 ppm (Palme et al. 2014); estimates for its
abundance in Earth lie between 17,000 and 19,000 ppm. Most
of this is concentrated in the Earth’s core; analyses of iron
meteorites suggest the core contains ca 5 wt% Ni
Nickel, Fig. 1 Distribution of Ni
concentration in various lithotypes
(Data from GEOROC, Sarbas and
Nohl (2008); 18,359 analyses).
The boxes represent the first and
third quartiles of the data
distribution. The horizontal line
represents the median, and the
width of the adjacent notches
shows the 95% confidence interval
about the median. The “whiskers”
represent 1.5 x midrange
(arithmetic mean of maximum and
minimum values) beyond the first
or third quartile
981
(McDonough 2014), leaving ca 1860 ppm in the mantle
(Palme and O’Neill 2014) and 47 ppm in the continental
crust (Rudnick and Gao 2014). Ni substitutes readily into the
Mg-rich minerals of the mantle and is largely retained in the
residue during partial melting. Ni concentrations in the crust
are correspondingly quite low. The worldwide distribution
of Ni in different rock types is shown in Fig. 1; Fig. 2 pro-
vides more detail on its distribution in mantle rocks. The
variability shown in Fig. 2 is easily understood in terms of
the relative abundance of Ni in the important minerals of
mantle rocks (Fig. 3). This behavior is related to the charge
and ionic radii of Ni. Under crustal and upper mantle con-
ditions, the most common oxidation state of nickel is Ni(II).
The effective ionic radius of Ni(II) depends on its coordina-
tion number ([4]Ni, 0.55 Å; [4]Ni square, 0.49 Å; [5]Ni,
0.63 Å; and [6]Ni, 0.69 Å). The identical charge and simi-
larity in ionic radii between [6]Ni and [6]Mg allow significant
substitution of Mg by Ni in olivine, the main Ni bearer
among mantle-related minerals (Fig. 3). In addition, these
distributions reflect mineral-mineral partitioning. Ni can
substitute for Mg but not for Ca, which explains the higher
Ni concentration in orthopyroxene compared to
clinopyroxene (Fig. 3). Ni substitution may also be favored
in the Mg site of spinel, which is smaller than the Mg site of
garnet.
The solubility of Ni in pure water is low (<2 mg/L), but in
the presence of dissolved organic compounds, it can form
complexes that are soluble. In anoxic conditions, it precipi-
tates in sulfide phases (NiS, pyrite). Atmospheric concentra- N
tions of Ni are dominated by anthropogenic pollution,
principally from the burning of oil, and have increased by
982 Nickel

Nickel, Fig. 2 Distribution of Ni

concentration in various mantle-
related lithotypes. (Data from
GEOROC, Sarbas and Nohl
(2008); 5,403 analyses.)

Nickel, Fig. 3 Distribution of Ni

concentration in various mantle-
related minerals. (Data from
GEOROC, Sarbas and Nohl
(2008) and authors’ unpublished
data; 105,630 analyses.)

a factor of >500 since the beginning of the Industrial Revo-
lution (Pacyna and Pacyna 2001). Contributions to atmo-
spheric Ni from smelting operations account for ca 10% of
the total; they have declined in recent years due to better
emission controls, but previously devastated large areas in
the vicinity of smelters at, e.g., Sudbury in Canada and the
Kola Peninsula in arctic Russia.
Biological Utilization and Toxicity
Ni is known to be toxic in high doses, but they are reached
only in special situations. However, Ni contamination of
groundwater can represent a hazard, especially in acidic con-
ditions where it can be leached from soils (Nieminen et al.
2007).
Niobium
Nickel is an important micronutrient in the oceans, and
dissolved Ni is variably enriched (ca 10 nM/kg) in deeper
waters and depleted (ca 2 nM/kg) in surface waters, following
the pattern of other micronutrients such as Fe and Zn, as well
as P and Si. This distribution suggests that diatoms actively
control the distribution of Ni in ocean waters (Twining et al.
2012). The methanogenic bacteria that dominated Archean
life appear to have been addicted to Ni. It has been proposed
that a decline in the Ni contents of banded iron formations late
in the Archean reflects a decrease in the availability of Ni in
ocean water. This “nickel famine” may have led to the rise of
the cyanobacteria, and their production of oxygen led in turn
to the Great Oxidation Event at the end of the Archean (Saito
2009; Konhauser et al. 2009), allowing the evolution of
multicellular life.
Summary
Nickel shows a very diverse range of geochemical behavior,
being both a siderophile and a lithophile element. It has been
important to mankind since the Bronze Age and is a mainstay
of modern industrial society. It also is an essential element in
the biogeochemistry of the oceans.
Cross-References
▶ Iron Meteorites
▶ Lithophile Elements
▶ Mantle Geochemistry
▶ Ore Deposits
▶ Periodic Table
▶ Siderophile Elements
▶ Sulfide Minerals
▶ Transition Elements
References
Konhauser KO et al (2009) Oceanic nickel depletion and a
methanogen famine before the Great Oxidation Event. Nature
458:750–753
Lazar C, Young ED, Manning CE (2012) Experimental determina-
tion of equilibrium nickel isotope fractionation between metal
and silicate from 500  C to 950  C. Geochim Cosmochim Acta
86:276–295
McDonough WF (2014) 3.16 – compositional model for the Earth’s core
A2. In: Turekian KK, Holland HD (eds) Treatise on geochemistry,
2nd edn. Elsevier, Oxford, pp 559–577
Nieminen TM, Ukonmaanaho L, Rausch N, Shotyk W (2007) Biogeo-
chemistry of nickel and its release into the environment. Met Ions
Life Sci 2:1–30
Pacyna EC, Pacyna JM (2001) An assessment of global and regional
emissions of trace metals to the atmosphere from anthropogenic
sources worldwide. Environ Rev 9:269–298
983
Palme H, O’Neill HSC (2014) 3.1 – cosmochemical estimates of mantle
composition. In: Turekian KK, Holland HD (eds) Treatise on geo-
chemistry, 2nd edn. Elsevier, Oxford, pp 1–39
Palme H, Lodders K, Jones A (2014) 2.2 – solar system abundances of
the elements A2. In: Holland HD, Turekian KK (eds) Treatise on
geochemistry, 2nd edn. Elsevier, Oxford, pp 15–36
Ratié G, Jouvin D, Garnier J, Rouxel O, Miska S, Guimaraes E, Cruz VL,
Sivry Y, Zelano I, Montarges Pelletier E, Thil F, Quantin C (2015)
Nickel isotope fractionation during tropical weathering of ultramafic
rocks. Chem Geol 402:68–76
Rudnick RL, Gao S (2014) 4.1 – composition of the continental crust. In:
Holland HD, Turekian KK (eds) Treatise on geochemistry, 2nd edn.
Elsevier, Oxford, pp 1–51
Saito M (2009) Less nickel for more oxygen. Nature 458:714–715
Sarbas M, Nohl U (2008) The GEOROC database as part of a growing
geoinformatics network. In: Geoinformatics conference, Postdam
Twining BS, Baines SB, Vogt S, Nelson D (2012) Role of diatoms in
nickel biogeochemistry in the ocean. Glob Biogeochem Cycles 26.
https://doi.org/10.1029/2011GB004233
Niobium
Carsten Münker
Institut für Geologie und Mineralogie, Universität zu Köln,
Köln, Germany
Element Data
Atomic Symbol: Nb N
Atomic Number: 41
Atomic Weight: 92.90637
Isotopes and Abundances: 93Nb, 100%
1 Atm Melting Point: 2477  C
1 Atm Boiling Point: 4744  C
Common Valences: 5+
Ionic Radii: 6-fold: 64 pm
Pauling Electronegativity: 1.6
First Ionization Potential: 652 kJ/mol
Chondritic (CI) Abundance: 283 ppb
Silicate Earth Abundance: 595 ppb
Crustal Abundance: 8 ppm
Seawater Abundance: 1–4 pmol/kg
Core Abundance: 450–500 ppb
Properties
Niobium is a transition metal of low toxicity with the atomic
number of 41. Niobium has one stable isotope (93) with an
atomic mass of 92.90637(2) (CIAAW 2015) The now extinct
isotope 92Nb with a half-life of 34.7 Ma is currently being
investigated as a potential chronometer in cosmochemistry
984
(e.g., Münker et al. 2000, Schönbächler et al. 2000), decaying
to 92Zr by electron capture. In nature, Nb occurs in +5 valence
state, although lower valence states are known from synthetic
systems. Its atomic radius is 146 pm and its ionic radius in +5
valence state and sixfold coordination is 64 pm (Shannon
1976). Due to its high ratio of charge to ionic radius, Nb is
classified in geochemistry as high field strength element.
History and Use
Niobium was first discovered in 1801 by the English chemist
C. Hatchett (1802), which he named columbium. In 1845, the
German chemist Heinrich Rose (1845) discovered that
Ta-rich minerals contained a second element he named nio-
bium, after Niobe, the daughter of Greek mythological figure
Tantalus, reflecting the extreme geochemical similarity
between Nb and Ta. It was subsequently discovered that
columbium and niobium are identical. Not until 1949 was
the name niobium adopted as official name for the element,
but since then columbium had been used frequently in the
North American literature, in particular in metallurgy.
Economically important Nb deposits are hosted by
carbonatites or pegmatitic granites that in most cases exhibit
a paired enrichment of both Nb and Ta to ore grade level.
Important economical grade minerals include pyrochlore and
columbite/tantalite, the latter mineralization is often referred to
as COLTAN. Countries with the world’s largest Nb deposits
include Brazil, Canada, Australia, and some African countries,
with Brazil presently supplying most of the industrially used
Nb (USGS 2015). Technically, Nb is mainly used as steel alloy,
for instance, in gas pipelines, jet and rocket engines, heat-
resisting equipment, and superconducting alloys.
Geochemical Behavior
Niobium is a highly refractory element with a 50% conden-
sation temperature of 1559K (Lodders 2003) and has tradi-
tionally been regarded as behaving lithophile during Earth’s
differentiation. Ratios of Nb and similarly refractory elements
like Ta or Zr are nearly constant in most groups of chondrites,
and only CV chondrites rich in refractory components deviate
from this general pattern (Münker et al. 2003). The solar
system abundance of Nb as estimated from CI chondrites is
283 ppb; the estimated abundance in the bulk silicate Earth is
595 ppb (Münker et al. 2003 in Palme and O’Neill 2014). The
estimate for the bulk silicate Earth takes into account recent
findings that, in contrast to its entirely lithophile geochemical
twin Ta, Nb behaved moderately siderophile at the low oxy-
gen fugacities prevailing during early core formation on Earth
(Wade and Wood 2001). This provides a viable explanation
why silicate Earth’s Nb/Ta is significantly lower (14.0  0.3)
Niobium
than the chondritic Nb/Ta of 19.9  0.6 (Münker et al. 2003).
The corresponding concentration of Nb in the core is between
450 and 500 ppb, assuming that all of the missing Nb in the
silicate Earth has indeed been sequestered into the core (Wade
and Wood 2001). There are suggestions that some of the
missing Nb is stored via subduction zone processes in silicate
reservoirs in the deep Earth and not in the core (e.g., Rudnick
et al. 2000; Kamber and Collerson 2000). However, the
observation that Nb/Ta in early Archean mafic rocks is indis-
tinguishable from values in Phanerozoic rocks (Münker et al.
2003) argues against this view.
During silicate melting on Earth, Nb behaves highly
incompatible in mantle minerals and is therefore depleted in
the mantle and enriched in the crust. In the continental crust,
the Nb content is estimated to 8 ppm with a content of 12 ppm
and an Nb/Ta between 12 and 13 in the upper crust (Barth
et al. 2000; Rudnick and Gao 2014). Relative to similarly
incompatible elements like La or U-Th, however, Nb is mark-
edly depleted in the continental crust, mirroring its selective
depletion in subduction zone magmas that contributed to the
bulk of the continental crust. The selective depletion of Nb in
subduction-related lavas and the continental crust is caused
by its lower solubility in subduction zone fluids and by its
retention in Ti-rich phases like rutile in subducting oceanic
crust and possibly in subducting sediments (e.g., Zack et al.
2002; Hermann and Rubatto 2009). Together with its geo-
chemical twin Ta, Nb is therefore a viable tracer for elemental
mass balances in subduction zone systems, and it is now
known that Nb can be soluble in subduction zones to some
extent at high pressures and in Cl- and F-rich environ-
ments, leading to distinct Nb/Ta fractionation patterns (e.g.,
Münker et al. 2004; König et al. 2010; Kirchenbaur and
Münker 2015). Hence, employing Nb/Ta ratios in igneous
and metamorphic rocks has now become an important tool
to better understand the role of residual phases such as rutile,
titanite, or amphibole during silicate melting.
Due to its high valence state, Nb tends to hydrolize easily
and is not very soluble in seawater, with an estimated con-
centration between 1 and 4 pmol/kg (Firdaus et al. 2011;
Bruland et al. 2014). Notably, elevated Nb/Ta in seawater as
high as 85 (Firdaus et al 2011) indicate that Nb can be highly
fractionated from its geochemical twin Ta in aqueous sys-
tems, likely due to their different complexing behaviors. Once
more data will become available for aqueous systems, com-
bined Nb and Ta studies may have great potential to better
understand weathering processes and ocean circulation.
Biological Utilization and Toxicity
Niobium has no known biological role. Niobium salts have
been shown to be toxic, but only at very high doses (Haley
et al 1962).
Nitrogen 985

Summary Münker C, Wörner G, Yogodzisnki G, Churikova T (2004) Behaviour of

high field strength elements in subduction zones: constraints from Kam-
chatka-Aleutian arc lavas. Earth Planet Sci Lett 224(3–4):275–293
Niobium is a highly refractory incompatible element and one Palme H, O’Neill HSC (2014) Cosmochemical estimates of mantle
of the high field strength elements. Although generally con- composition. In: Carlson RW (ed) The mantle and core, Treatise on
sidered lithophile, it has some siderophile tendency, and up to geochemistry, vol 3. Elsevier, Amsterdam, pp 1–39
500 ppb, Nb may be in the core. It has low solubility and is Rose H (1845) On two new metals, pelopium and niobium, discovered in
the bavarian tantalites. Philos Mag Ser 3 26(171):179–181
generally considered immobile. Compared to elements of Rudnick RL, Barth M, Horn I, McDonugh MF (2000) Rutile-bearing
similar incompatibility, it is depleted in the Earth’s crust and refractory eclogites: missing link between continents and depleted
in subduction zone magmas. mantle. Science 287:278–281
Rudnick RL, Gao S (2014) Composition of the continental crust. In:
Rudnick RL (ed) The crust, Treatise on geochemistry, vol 4. Elsevier,
Amsterdam, pp 1–51
Cross-References Schönbächler M, Rehkämper M, Halliday AN, Lee DC, Bourot-Denise M,
Zanda B, Hattendorf B, Günther D (2000) Niobium-zirconium chro-
nometry and early solar system development. Science 295:1705–1708
▶ High Field Strength Elements Shannon RD (1976) Revised effective ionic radii and systematic studies
▶ Incompatible Elements of interatomic distances in halides and chalcogenides. Acta
▶ Ore Deposits Crystallogr A32:751–767
▶ Periodic Table Wade J, Wood BJ (2001) The Earth’s ‘missing’ Nb may be in the core.
Nature 409:75–78
▶ Subduction Zone Geochemistry Zack T, Kronz A, Foley SF, Rivers T (2002) Trace element abundances
▶ Tantalum in rutiles from eclogites and associated garnet mica schists. Chem
▶ Transition Elements Geol 184:97–122

References

Barth MG, McDonough WF, Rudnick RL (2000) Tracking the budget of Nitrogen
Nb and Ta in the continental crust. Chem Geol 165:197–213
Bruland KW, Middag R, Lohan MC (2014) Controls of trace metals in Pierre Cartigny
seawater. In: Mottl MJ, Elderfield H (eds) The oceans and marine Institut de Physique du Globe de Paris, Sorbonne Paris Cité,
geochemistry, Treatise on geochemistry, vol 8. Elsevier, Amsterdam,
pp 19–51 Université Paris Diderot, Paris, France N
CIAAW (2015) Commission on isotopic abundances and atomic
weights. http://ciaaw.org/atomic-weights.htm
Firdaus ML, Minami T, Norisuye K, Sohrin Y (2011) Strong elemental
fractionation of Zr-Hf and Nb-Ta across the Pacific Ocean. Nat
Geosci 4:227–230 Element Data
Haley TJ, Komesu N, Raymond K (1962) Pharmacology and toxicology
Atomic Symbol: N
of niobium chloride. Toxicol Appl Pharmacol 4(3):385–392
Hatchett C (1802) An analysis of a mineral substance from North Atomic Number: 13
America, containing a metal hitherto unknown. Philos Trans R Soc Atomic Weight: 14.0067 g/mol
Lond 92:49–66 Isotopes and Abundances: 15N (0.36%), 14N (both stable)
Hermann J, Rubatto D (2009) Accessory phase control on the trace
Dinitrogen (78 molar percent of atmosphere) is gaseous
element signature of sediment melts in subduction zones. Chem
Geol 265:512–526 at standard Pressure and Conditions.
Kamber BS, Collerson KD (2000) Role of ‘hidden’ deeply subducted Common Valences: primarily 3 (nitride, ammoniac),
slabs in mantle depletion. Chem Geol 166:241–254 0 (dinitrogen) and +5 (nitric acid)
Kirchenbaur M, Münker C (2015) The behaviour of the extended HFSE
Chondritic (CI) Abundance: ~2500 ppm
group (Nb, Ta, Zr, Hf, W, Mo) during the petrogenesis of mafic
K-rich lavas: the Eastern Mediterranean case. Geochim Cosmochim Silicate Earth Abundance: 2–20 ppm
Acta 165:178–199 Crustal Abundance: 83 ppm
König S, Münker C, Schuth S, Luguet A, Hoffmann JE, Kuduon J (2010) Core Abundance: –
Boninites as windows into variable trace element mobility in sub-
duction zones. Geochim Cosmochim Acta 74(2):684–704
Lodders K (2003) Solar system abundances and condensation tempera-
tures of the elements. Astrophys J 591:1220–1247
Münker C, Weyer S, Mezger K, Rehkämper M, Wombacher F, Bischoff Properties
A (2000) 92Nb-92Zr and the early differentiation history of planetary
bodies. Science 289:1538–1542
Münker C, Pfänder JA, Weyer S, Büchl A, Kleine T, Mezger K (2003)
Nitrogen is the 5th element of the periodic table. With an
Evolution of planetary cores and the earth – moon system from Nb/Ta electronic structure [He] 2s2 2p3, nitrogen can either lose or
systematics. Science 301:84–87 gain up to five and three electrons, respectively, and can
986
therefore occur under a wide range of redox states from 3 to
+5. The main reduced to oxidized species include nitride (N3
in diamond, ammonium, and ammoniac), atmospheric
dinitrogen gas (N0 in N2) to oceanic dissolved nitrate (N5+
in NO3).
Nitrogen has 16 isotopes, two are stable
(14N ~ 99.64%, 15N ~ 0.36%), the 14 others being radio-
active with too short half-lives (<10 min) to have any
potential geochemical application. Resulting atomic mass
of nitrogen of 14.0067 (Coplen 2001) and variations in its
stable isotope ratio is a central tool in stable isotope
geochemistry.
Nitrogen is the fifth most abundant element in the solar
system (~1105 ppm N, Lodders 2003) and is comparatively
depleted on Earth with estimated Bulk Earth of ~3 to
~28 ppm N (Cartigny and Marty 2013). On Earth, nitrogen
is unevenly distributed. The atmosphere is a nitrogen-rich
reservoir where N2 gas represents 78.084% mole fraction
(~3.9
1021 g N) together with minor but significant green-
house gases such as nitrous oxide (N2O), other nitrogen
oxides (NOx, 100 ppt–1 ppm), ammonia (NH3, 10 ppt–1 ppb),
and particulate nitrate and ammonium (1 ppt–10 ppb) occur-
ring in aerosols (Brasseur et al. 1999). The crust and sedi-
ments typically contain 100–1000 ppm levels (Busigny and
Bebout 2013), the Earth’s mantle is N-poor with estimated
N-contents of 0.26–36 ppm. The nitrogen content of the
Earth’s core remains unknown with contradicting experimen-
tal evidence.
The main source of nitrogen to the hydrosphere is atmo-
spheric in origin being massively cycled by biological activity
(at a rate of ~2
1014 g N/y; Galloway 2003), particularly by
primary producers (e.g., phytoplankton and cyanobacteria).
Without a strong return flux (denitrification and anaerobic
ammonium oxidation), present-day atmospheric nitrogen
(~4
1021 gN) would be entirely sequestered within less
than 100 million years (My).
Unlike other elements, crustal nitrogen is originally
sourced from the atmosphere by biological activity (i.e.,
mantle nitrogen contribution and abiotic atmospheric reduc-
tion are negligible). Nitrogen enters the rock cycle as organic
matter matures releasing nitrogen as ammonium ion (NH4+).
Having similar charge and ionic radius to potassium, ammo-
nium then substitutes for – and follows the fate
of – potassium in potassic minerals (e.g., clays, feldspars,
and micas; Busigny and Bebout 2013). The occurrence of
ammonium in crustal rocks is therefore primarily of atmo-
spheric origin.
Very few N-forming minerals exist in nature; they occur
in very specific environments such as volcanic fumerolles,
evaporitic systems, atmospheric deposits (Atacama desert),
or meteorites (see Table 1 in Holloway and Dahlgren 2002).
Ammonium is generally only a substitutional impurity,
buddingtonite the ammonium feldspar (NH4AlSi3O8)
Nitrogen
being a noticeable case. Nitrate-forming minerals are rare
as well (nitrate is a very soluble species), but it is worth
mentioning that nitre (KNO3, the word nitrogen coming
actually from nitre-forming) and saltpetre were important
sources of nitrogen entering the composition of gun-powder
and fertilizers.
Nowadays, since the advent (1909–1913) of industrial
abiotic dinitrogen reduction into ammoniac through the
so-called Haber-Bosch process where N2 + 3H2 ! NH3
(Bosch 1966), the main source of nitrogen entering fertil-
izers is actually atmospheric with over 1.4
1014 gNH3
produced every year, i.e., close to the flux of biological
nitrogen fixation. Present-day nitrogen cycle is thus a good
example of a heavily anthropized cycle. Nearly 100% of
world production of synthetic ammonia relies on the
Haber-Bosch process and the resulting massive production
(and use) of fertilizers is generally described as the detona-
tor of the population explosion (Smil 1999). With only half
of fertilizers being fixed by plants, nitrate pollution of
groundwaters, rivers, and estuaries leads to biological
blooming which results in anoxic waters during their subse-
quent degradation.
Cross-References
▶ Biogeochemistry
▶ Nitrogen Cycle
▶ Nitrogen Isotopes
References
Bosch C (1966) The development of the chemical high pressure method
during the establishment of the new ammonia industry (1931 Nobel
Lecture). In: Nobel lectures, chemistry 1922–1941. Elsevier,
Amsterdam. Available at http://www.nobelprize.org/nobel_prizes/
chemistry/laureates/1931/bosch-lecture.html
Brasseur GP, Orlando JJ, Tyndall GS (1999) Atmospheric chemistry and
global change. Oxford University Press, Oxford
Busigny V, Bebout GE (2013) Nitrogen in the silicate earth: speciation
and isotopic behavior during mineral-fluid interactions. Elements
9:353–358
Cartigny P, Marty B (2013) Nitrogen isotopes and mantle geodynamics:
the emergence of life and the atmosphere-crust-mantle connection.
Elements 9:359–366
Coplen TB (2001) Atomic weights of the elements 1999. Pure Appl
Chem 73:667–683
Galloway JN (2003) The global nitrogen cycle. In: Holland HD,
Turekian KK (eds) Treatise on geochemistry. Pergamon, Oxford,
pp 557–583
Holloway JM, Dahlgren RA (2002) Nitrogen in rock: occurrences
and biogeochemical implications. Global Biogeochem Cycles
16:1118
Lodders K (2003) Solar system abundances and condensation tempera-
tures of the elements. Astrophys J 591:1220–1247
Smil V (1999) Detonator of the population explosion. Nature
400:415
Nitrogen Cycle 987

into inorganic forms of nitrogen that have varying biological

Nitrogen Cycle availability and reactivity. The largest pool of nitrogen on
Earth is the atmosphere, where the dominant form of nitrogen
Monica M. Palta1 and Hilairy Ellen Hartnett2 is N2 gas. The formidable energy required to break the triple
1
Department of Environmental Studies and Science, Pace bond in N2 gas means this large pool of nitrogen is predom-
University, New York, NY, USA inantly unavailable biologically. However, two to three bil-
2
School of Earth and Space Exploration and School of lion years ago, both photosynthesis and the microbial process
Molecular Sciences, Arizona State University, Tempe, of N2 fixation, which converts one mole of N2 to two moles of
AZ, USA ammonia (NH3) using nitrogenase, evolved. Photosynthesis
and N2 fixation created larger pools of organic carbon and
bioavailable nitrogen in terrestrial and aquatic systems; these
Definition molecules were now available for processing and recycling
by other organisms. Of the 203 Tg of reactive (biologically
The nitrogen cycle describes the biogeochemical transforma- available) nitrogen generated annually from natural sources,
tion of the element nitrogen into a variety of chemical species one-third is terrestrially derived and two-thirds are marine-
within ecosystems the transfer of those nitrogen-containing derived (Table 1; e.g., Fowler et al. 2013). Most organisms
species among atmospheric, terrestrial, and aquatic ecosystems. cannot fix nitrogen, but rather obtain nitrogen as NH4+,
NO3 (which is then converted to NH4+ through assimila-
tory NO3 reduction), or as organic nitrogen (Fig. 1). The
Pools in the Nitrogen Cycle latter is the form in which many heterotrophs (including
animals and fungi) obtain nitrogen, while plants and some
The vast majority of global nitrogen (N) is in a form or setting heterotrophs (including bacteria) are able to use inorganic
that makes it unavailable to organisms for their uptake and forms of nitrogen. Bioavailable forms of inorganic nitrogen
metabolism. Atmospheric nitrogen (in the form of N2) makes range from fully reduced to fully oxidized forms and include
up roughly 50% of the total nitrogen on Earth; the remaining NH3, NH4+, NO, NH2OH, N2O, NO2, and NO3 (Fig. 1,
nitrogen is primarily in rocks of Earth’s mantle and crust and Table 2).
is highly unavailable biologically (Canfield et al. 2010). A number of different reactions govern fluxes of nitro-
Nitrogen in rocks is generally in the form of NH4 in silicates gen between different types of bioavailable forms and
(clays), although a few NO3 bearing minerals are known. In between terrestrial, aquatic, and atmospheric pools of N
igneous rocks, N content is usually <0.1 wt%. Nitrogen in
sedimentary rocks can be much higher (up to ~2 wt%). Due to
the low reactivity of rock-derived nitrogen, nitrogen in the Nitrogen Cycle, Table 1 Global nitrogen fluxes (Table modified from
Fowler et al. 2013)
mantle and crust of the Earth is typically excluded from
consideration in the nitrogen cycle. Atmospheric nitrogen Nitrogen fluxes Tg N year1
thus holds roughly 90% of the nitrogen relevant to the global Sources of fixed nitrogen
Anthropogenic
nitrogen cycle, with nearly all of that nitrogen in the form of
Fertilizer production 100
N2 (Chapin et al. 2011). The ocean holds the second largest
Chemical production 20
pool of nitrogen (roughly 9%), but a sizeable portion of this
N2 fixation, agricultural 60
nitrogen (99.98%) is located in ocean sediments and deep
Combustion to NOx 40
water (Chapin et al. 2011) and thus has a very low turnover Natural
time relative to other terrestrial and aquatic pools. In the Lightning 5
terrestrial pool of the nitrogen cycle, soils hold roughly N2 fixation, marine 140
23 times the total nitrogen found in terrestrial biomass N2 fixation, terrestrial 58
(Chapin et al. 2011). Most soil nitrogen is in organic form, Sinks for fixed nitrogen
due to the rapid uptake of nitrogen by organisms; the pool of Denitrification, marine 100–280
inorganic nitrogen in soil at any given time is very small N burial, marine 20
(Schlesinger and Bernhardt 2013). Nitrogen fluxes between pools
Wet and dry atmospheric deposition 100
NH3 emissions, terrestrial 60
Overview of Nitrogen Cycle NH3 emissions, marine 9
N2O emissions, marine 5.5
The nitrogen cycle involves incorporation of nitrogen into NO emissions from soil 5
biological molecules and the breakdown of those molecules N2O emissions from soil 13
988 Nitrogen Cycle

Nitrogen Cycle, Fig. 1 The more oxidized NO3–

major biological nitrogen

n)
transformation pathways and the

io
ct
relative oxidation state at which

du

Ni
NO2– NO2– NO2–

re
they occur

t ri
3 –

fic
O

at
(N

io
n

n
As
io

(N
at

sim
N2O N2O

H4
fic

Nitrate reduction

ilat
tri

ox
ion
ni

DNRA

id
De

a
NO

tio
n)
Anammox NH2OH
N2

N
2 fixa
tion
NH4+ PON NH4+
more reduced
Assimilation Remineralization

DON

Nitrogen Cycle, Table 2 Redox state of common environmentally
relevant nitrogen species
Species Valence state
NH3, NH4+ III
NH2OH I
N2 0 ical transformations (i.e., microbial respiration and plant pro-
N2O +1
NO +II
NO2 +III
NO3 +V
nitrogen (Figs. 1 and 2). Nitrogen is cycled internally in
terrestrial and aquatic systems primarily via the metabolic
processes of microbes and plants (assimilation, mineraliza-
tion, nitrification, and dissimilatory nitrate reduction to
ammonium (DNRA)). These processes are especially sensi-
tive to oxygen and pH and are typically highly coupled with
one another. A subset of microbial processes in terrestrial and
aquatic systems (i.e., denitrification, anammox, and, to a
lesser extent, nitrification) returns nitrogen to the atmosphere
in the form of nitrogen gas (NO, N2O, N2).
Humans have radically altered the global nitrogen cycle.
The invention of the Haber-Bosch process (a synthetic nitro-
gen fixation reaction) in the early 1900s allowed the industrial
production of NH4+ for fertilizer. This process has radically
altered the nitrogen cycle by more than doubling the amount
of bioavailable nitrogen in terrestrial systems (Table 1). The
dramatic increase of bioavailable nitrogen in both aquatic and
terrestrial systems has had large impacts on ecosystems, alter-
ing both internal fluxes of nitrogen and feedbacks between the
atmosphere and biosphere. Human activities, including com-
bustion of fossil fuels, changes in land use, and inputs of
inorganic nitrogen to terrestrial and aquatic systems in the
form of fertilizer, have greatly increased fluxes of nitrogen
(NO2, NO, N2O) to the atmosphere.
Fluxes in the Nitrogen Cycle
Major fluxes in the nitrogen cycle are either internal to terres-
trial, aquatic, or atmospheric pools or move nitrogen between
these pools (Fig. 2). Fluxes are mediated primarily by biolog-
duction); less common are a few abiotic phenomena that
convert nitrogen from one molecular form to another. The
key flux in the nitrogen cycle, nitrogen fixation, is a microbial
process that moves atmospheric nitrogen (N2) into a form
useable by plants and other microbes (NH4+). Although not
typically considered a major component of the nitrogen cycle,
abiotic chemical reactions can convert some forms of nitrogen
gas into forms that enter terrestrial and aquatic pools. For
example, lightning strikes are responsible for a small amount
of nitrogen fixation (~2% of annual nitrogen fixation;
Galloway et al. 2008), and various forms of nitrogen gas are
miscible (NH3) or reactive (NOx) with water, which moves
nitrogen from the atmosphere to aquatic and/or terrestrial
systems. Current models suggest that in the early Earth’s
atmosphere, long prior to the evolution of nitrogen fixation,
lightning and high-energy meteorite impacts were primarily
responsible for producing NO that would be converted to
NO3 and NO2 through photochemical and aqueous phase
reactions (Canfield et al. 2010).
Internal cycling of nitrogen within terrestrial and aquatic
systems largely involves conversion of nitrogen between
various inorganic, biologically reactive forms and between
inorganic and organic forms of nitrogen. Figure 2 shows an
example of internal cycling within a coastal marine ecosystem
(labeled “Ecosystem N cycle”), where nitrogen moves
between different inorganic and organic forms, as well as
gaseous (g) and aqueous (aq) forms. Ecosystem cycling
includes the following major fluxes: nitrification (microbial
oxidation, over several intermediary steps, of NH4+ to NO3),
Nitrogen Cycle 989

g Atmosphere
r nin
Bu
NOx as
s
om n
io
Bi sit Co

Deposition
NOx n
ep
o tio m
D ns Fixa bu
st
issio al
N 2 io
n
Em g ic
o
ol
Bi
Fossil Fuel
Vegetation

Emissions
Soils
Detritus

Emiss

ea al
ions

oc ast
ns
co Marine Biota
Fertil Agriculture
izers
New or Export
Production
Crop N
Fixatio 2
Runoff
n
Surface Ocean Mixing from deep ocean

Reactive N NH3(g) NO(g) N2O(g)

Particulate Organic N

N2(g) Organic N NH4(aq)

+
NH3(aq) NO2(aq)
–
NO–3(aq)

Ecosystem N cycle
N2O(g) NO(g) NO2(aq) N
–

Nitrogen Cycle, Fig. 2 The nitrogen cycle. Fluxes occur between
major global pools (atmospheric, terrestrial, and aquatic ecosystems) and
between pools within these ecosystems. An example of internal ecosys-
tem cycling is shown for a coastal marine ecosystem (labeled “Ecosys-
tem N cycle”), where nitrogen moves between different types of
molecules, including inorganic and organic, and gaseous (g) and aque-
ous (aq) forms. Human activities, including agricultural practices, fossil
fuel combustion, and biomass burning, have heavily influenced the
nitrogen cycle. Anthropogenic influence includes increased inorganic
(reactive) flux from the terrestrial to aquatic pool through runoff, and
increased nitrogen flux (of nitrogen gases) from the terrestrial to atmo-
spheric pool. Atmospheric deposition of reactive nitrogen onto terrestrial
ecosystems has also increased due to human activities

NO3 reduction (to NO2), dissimilatory nitrate reduction
to ammonium (DNRA) (microbial reduction of NO2 to
NH4+), assimilation (NH4+ to organic nitrogen), and mineral-
ization or ammonification (organic nitrogen to NH4+) (Fig. 1).
Denitrification and ammonia oxidation (anammox) by
microbes convert NO3 and NH4+, over a few intermediary
steps, to nitrogen gas, returning nitrogen to the atmosphere
(Fig. 1). The terminal form of nitrogen in both these processes
is N2. Microbial nitrification and abiotic NH4+ volatilization can
also result in the production of N2O and NH3+ gas, respectively
(Fig. 1).
The concentration of oxygen (redox status) in water, soil,
and sediments strongly influences which processes related to
nitrogen cycling can occur in a given system at a given point
in time (Fig. 1, Table 2). Nitrogen loses and gains electrons
during abiotic and biotic chemical transformation, with the
oxidation state of nitrogen ranging from 3 to +5 (an eight
electron difference). Nitrification is an oxidizing reaction that
requires the largest transfer of electrons (oxidation state
change of 3 to +5) in the nitrogen cycle and thus requires
high oxygen availability. This process is carried out in several
steps that transfer oxygen to the nitrogen molecule: first,
bacteria (primarily Nitrosomonas species) convert NH4+ to
NH2OH using the enzyme ammonium monooxygenase and
NH2OH to NO2 using hydroxylamine oxidoreductase.
Nitrobacter species are then primarily responsible for
990
converting NO2 to NO3 using the enzyme nitrite oxido-
reductase. Most other fluxes in the nitrogen cycle
(denitrification, nitrogen fixation, DNRA, and anammox)
are reduction reactions that occur under anaerobic condi-
tions. Anammox does involve an increase in oxidation state
for its final step (i.e., N2H4 to N2, catalyzed by hydroxyl-
amine oxidoreductase), but this reaction is anaerobic
nonetheless.
Coupling of Fluxes and Flux Balances
Because the products of one process involving nitrogen are
often the inputs for another, fluxes in the nitrogen cycle are
coupled with and balance one another. For example, denitri-
fication relies on nitrification in the absence of external NO3
inputs, which leads to a predominance of coupled
nitrification-denitrification in many ecosystems. Nitrogen
assimilation is tightly coupled to mineralization and is con-
trolled by nutrient limitations. If organisms in an ecosystem
are limited in their metabolic processes by nitrogen relative to
other needed nutrients (e.g., carbon and phosphorus), nitro-
gen assimilation will constitute a larger flux than nitrogen
mineralization, and organic nitrogen will constitute a larger
pool within that system than those of biologically available
(inorganic) nitrogen species. The nitrogen cycle is thus tightly
coupled with that of phosphorus and carbon, globally and
within ecosystems. Finally, the balance between N2 fixation
and denitrification in terrestrial and aquatic ecosystems deter-
mines total global terrestrial and marine pool sizes (see
Table 1).
Fluxes of nitrogen between different pools is also tightly
linked with fluxes of water, both because the presence of
water in a terrestrial system can influence redox status of
soils, and therefore internal cycling, and because water can
transport nitrogen in the form of dissolved gas and ions.
Because NO3 is highly soluble in water compared to
NH4+, for example, and less readily adsorbed to charged
surfaces in soil, NO3 tends to be the dominant form of
inorganic nitrogen that is transported between terrestrial and
aquatic systems.
Anthropogenic Alterations to the Nitrogen Cycle
Human activities have had both direct and indirect effects on
pools and fluxes in the nitrogen cycle, but never so much as in
the last century. One of the most seminal changes by humans
in the nitrogen cycle has been perpetuated by the invention of
the Haber-Bosch process, or industrial-scale N fixation. The
invention of this process was a tremendous boon for global
food supply and resulted in increased population growth
worldwide. However, it has also doubled the production of
Nitrogen Cycle
reactive N in terrestrial ecosystems (Fowler et al. 2013).
Inadvertent N fixation also occurs through other anthropo-
genic activities, i.e., fossil fuel combustion and industrial
processes (e.g., electricity production). Nitrogen-fixing agri-
cultural crops cultivated by humans also contribute significant
amounts of reactive N to terrestrial ecosystems (Fowler et al.
2013) (Table 1). The result of these large anthropogenic
sources of reactive N has been doubling in global N cycling
over the last century (Fowler et al. 2013). Further, reactive
N is accumulating in the environment, because although
roughly 20%, by some estimates, of N fertilizer is lost to the
atmosphere as N2 in croplands, gaseous nitrogen emissions
cannot keep pace with N fertilizer applications (Wang
et al. 2017).
Hydrologic and atmospheric transport processes disperse
reactive N widely outside of where it is formed, and this
dispersal can have large-scale, cascading environmental con-
sequences (Galloway et al. 2003). For example, urban and
agricultural runoff transports inorganic nitrogen (especially
NO3) deposited as fertilizer in terrestrial systems to fresh-
water aquatic systems; this reactive nitrogen eventually
makes its way to estuaries. Although a great deal of reactive
N is denitrified when it reaches marine systems (Table 1),
excess reactive nitrogen in surface water causes eutrophica-
tion, hypoxia, loss of biodiversity, and habitat degradation in
aquatic systems in general and coastal ecosystems in particu-
lar on a global scale (Galloway et al. 2003; McCrackin et al.
2017). NO3 is also a ubiquitous contaminant in aquifers
worldwide due to fertilizer use; NO3 in drinking water can
cause a number of human health problems (Spalding and
Exner 1993). The emissions of nitrogenous trace gases
(NH3, NOx, N2O) have increased exponentially from pre-
industrial emissions, with the source being primarily terres-
trial soils (Table 1); this is largely due to conversion of
nitrogen fertilizer by microbes into gaseous forms of nitrogen
(Galloway et al. 2003). Fossil fuel combustion is the primary
source of NOx gases to the atmosphere, however (Table 1).
Reactive nitrogen in the atmosphere in the form of NOx is
linked to the oxidizing capacity of the atmosphere, and plays a
key role in the photochemical production of ozone, which in
turn increases pollution (smog) in and the greenhouse poten-
tial of the troposphere (Galloway et al. 2003; Fowler et al.
2013). N2O is a potent greenhouse gas with 298 times the
atmospheric heat-trapping ability of carbon dioxide (CO2)
over a 100-year period, on a per-molecule basis. It is relatively
inert in the troposphere, but plays a role in stratospheric ozone
destruction (Portmann et al. 2012). Finally, NHx, NOy (all
oxidized forms of nitrogen other than N2O), and organic
nitrogen can fall from the atmosphere onto terrestrial and
aquatic systems as dry or wet deposition, resulting in ecosys-
tem acidification, fertilization, and eutrophication (Galloway
et al. 2003). Atmospheric transport and subsequent deposition
of reactive nitrogen was estimated to be 34 Tg N year1
Nitrogen Isotopes
during the preindustrial area, but had increased to 100 Tg
N year1 in 1995; in 2050, this process is estimated to
increase to 200 N year1 (Galloway et al. 2008).
Summary
Nitrogen is an essential element for all life, yet the vast
majority of nitrogen on the Earth exists as N2 gas – a form
that is unavailable to most organisms. Nitrogen has a wide
range of redox states, and life has evolved many complex
nitrogen cycling metabolisms to obtain and retain this most
valuable element. Reactions that convert nitrogen among
different species, including (but not limited to) N2, NH4+,
NO3, and organic nitrogen, are present in all domains
of life. These reactions are generally coupled to energy-
yielding metabolisms; however, nitrogen fixation
(N2 + 6H+ ! 2NH3) requires significant energy input, and
16 ATP are needed for this reaction. Because nitrogen is
often the limiting nutrient in both aquatic and terrestrial
ecosystems, the nitrogen cycle is necessarily tightly coupled
to the global cycles of phosphorus and carbon. The pre-
anthropogenic global nitrogen budget was essentially in
balance between N2 fixation (predominantly by microbes)
and microbial denitrification. In the twentieth century, how-
ever, human activity has had a profound impact on the
nitrogen cycle, second only to the human impact on the
carbon cycle. Anthropogenic nitrogen fixation, primarily
through the Haber-Bosch process, which produces NH3
from atmospheric N2, has disrupted the balance between
nitrogen sources and nitrogen sinks. Nitrogen sources now
exceed nitrogen sinks by more than 40% and perhaps as
much as a factor of three (see Table 1). This excess reactive
nitrogen from anthropogenic inputs has caused eutrophica-
tion, hypoxia, increases in greenhouse gases (e.g., N2O),
loss of biodiversity, and habitat degradation in aquatic
coastal ecosystems.
Cross-References
▶ Acid Deposition
▶ Atmospheric Evolution
▶ Biogeochemistry
▶ Carbon Cycle
▶ Earth’s Atmosphere
▶ Nitrogen
▶ Nutrients
▶ Oxidation-Reduction Reactions and Eh-pH (Pourbaix)
Diagrams
▶ Oxygen
▶ Ozone and Stratospheric Chemistry
▶ Phosphorus
991
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century. Philos Trans R Soc B-Biol Sci 368(1621). https://doi.org/
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depletion due to nitrous oxide: influences of other gases. Philos Trans
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N
Nitrogen Isotopes
Pierre Cartigny and Vincent Busigny
Institut de Physique du Globe de Paris, Sorbonne Paris Cité,
Université Paris Diderot, Paris, France
Introduction
Together with those of carbon, nitrogen stable isotopes (14N
and 15N) represent one of the most widely applied tracers in
isotope geochemistry, with over 120 articles published
every year having “nitrogen isotopes” in their title. Nitro-
gen is cycled between the different envelopes of the
Earth – hydrosphere, atmosphere, crust, and mantle – and
can occur as various species depending on pressure, temper-
ature, and redox conditions. The origin and fate of nitrogen
between these pools can be constrained using its isotope
composition.
Nitrogen isotopes are primarily used in the fields of envi-
ronment and paleoenvironment studies, sediment diagenesis,
soil formation and evolution, and archeological and paleo-
diet studies. There are comparatively less applications in the
992
field of cosmochemistry and high-temperature geochemistry
(i.e., mantle and crustal environments), and this reflects the
need to use more complex analytical techniques compared
with the former.
This entry provides a brief overview of questions that have
been addressed using natural variations of N stable isotopes. It
will omit studies that used either artificially 15N–enriched
compounds; these are commonly used in plant physiology
and agriculture to establish detailed biogeochemical mecha-
nisms (e.g., identify and quantify the biological and chemical
pathways between these N pools). It is however worth men-
tioning that the semiconservative DNA replication – rejecting
the conservative and dispersive hypotheses – was demon-
strated using 15N–enriched (Meselson and Stahl 1958).
Nitrogen Stable and Unstable Isotopes
Nitrogen has two stable isotopes, 14N (~99.632%) and 15N
(~0.368%), leading to an atomic mass of 14.0067. Fourteen
radioactive isotopes have been identified but have too short
half-lives to be useful in geochemistry. Note however that 13N
(half-life ~9.92 min) is used in medical studies for positron
emission tomography (PET). It requires 13N to be made
on-site in a cyclotron, 13NH3 being synthesized and injected
to the patient for PET imaging to deduce a large number of
cardiac parameters (blood flux, volume of the ventricles) and,
if any, cardiac abnormalities. In the following, the term “N
isotopes” will refer only to N stable isotopes (14N and 15N).
The two stable isotopes of nitrogen are neither radioactive
nor radiogenic. Therefore, on a bulk Earth scale, their abun-
dance did not change through time. The relative abundance of
N isotopes on Earth is grossly speaking that of our solar
system, and they were produced in stars as part of the
so-called C-N-O cycle (see Furi and Marty 2015 for a more
subtle assessment). Atmospheric 14N is the main source of
C( N + n ! 14C + 1p), which decays back to 14N with a
14 14
half-life of 5730  40 years. This reaction in particular
(14N ! 14 N) and other reactions (e.g., 14C production from
17
O) are not significant enough to change the abundance of
terrestrial 14N through time. The same applies to 15N; its
abundance did not change through time.
Stable isotope variations of terrestrial nitrogen originate
from vibrational effects and are therefore quite limited.
Terrestrial 15N/14N ratios range mostly between 3.356
and 3.750
103, and these variations are expressed
using the conventional delta notation where d15Nsample =
[(15N/14Nsample)/(15N/14Natmospheric nitrogen)  1]
1000
with 15N/14Natmospheric nitrogen = 0.0036764  0.0000041
(Junk and Svec 1958; Mariotti 1983). In cosmochemical
studies, the variations are much larger (15N/14N from 1.838
to 22.059
103), and these result from stable iso-
tope fractionation processes, nuclear reactions, and
Nitrogen Isotopes
nucleosynthetic anomalies. In the literature, these large vari-
ations are expressed using either 15N/14N or 14N/15N ratios
and/or d15N notation.
Analytical Techniques
Nitrogen isotopes are almost exclusively measured using N2
as an analyte and electron-impact gas-source ion-ratio mass
spectrometers (IRMS) operating in dynamic pumping mode
(i.e., the sample is either ionized, accelerated, and detected or
immediately pumped away). Historically, nitrogen was extra-
cted from its matrix, quantitatively converted to N2 gas,
purified using offline vacuum extraction techniques before
being analyzed by dual-inlet mass spectrometry. Sample
size is typically >5 micromoles and precision on d15N better
than 0.1‰ (1s). The historical method for solid sample
analysis (e.g., rocks, minerals, soils) – generally referred to
as Dumas combustion – consists in oxidizing the sample in a
sealed tube at ~900  C, nitrogen oxides (if any) being reduced
by copper at ~600  C and CO2, SO2, and H2O being separated
from N2 using either liquid nitrogen or calcium oxide (e.g.,
Kendall and Grim 1990). Presently, nitrogen can be extracted
using various methods, including crushing, laser ablation, and
laser or furnace heating (either in oxidized, inert, or reducing
conditions), and purified using gas chromatography and/or
chemical and cryogenic techniques. It is also worth mention-
ing that N and O isotopes of nitrate are commonly analyzed
using cultured denitrifying bacteria releasing N2O.
The coupling of elemental analyzers to IRMS (EA-IRMS)
in the early 1980s opened the path to online, nearly fully
automated, analyses of N content and isotope composition
(Preston and Owens 1983). The sample loaded in tin capsule
is combusted (flash combustion) in a stream of helium. This
releases C, N, S, and H, which are converted to CO2, N2, SO2,
and H2O using various chemical compounds (including Cu at
~600  C) and are subsequently separated using gas chroma-
tography. This method does not require prior vacuum
N extraction and purification, is slightly more sensitive than
the abovementioned method, and can produce several dozen
of analyses per day, still with very good precisions on d15N
better than 0.15‰ (1s).
These two techniques account for the majority of applica-
tions of d15N in geochemistry. Both of them require sub-
micromole N amount, and, in most cases, data are obtained
together with C isotope composition. Yet for smaller samples
size (sub-nano to even picomole of N), these techniques are
not sensitive enough and require other types of instrumenta-
tion such as static vacuum mass spectrometers (as used in
noble gas geochemistry). In this case, the sample gas is
entirely introduced, expanded, and analyzed in the mass
spectrometer, leading to an increase of sensitivity by
several orders of magnitude but a decrease of precision to
Nitrogen Isotopes 993

typically 1‰ (Wright et al. 1988; see analytical boxes in
Cartigny and Marty 2013; Furi and Marty 2015). Offline
extraction and purification methods are the same as above,
nitrogen being also analyzed as N2, but special care is
required to monitor atmospheric contamination. To date, this
type of technique has been limited to less than ten laboratories
in the world.
Secondary ion mass spectrometry (SIMS) provides alter-
native to determine N isotope composition on small samples.
This method is almost nondestructive and can operate at high
spatial resolution (typically ~ 20 mm), the isotope analysis
being determined from secondary CN ions. This method is
precise but requires standards having the same composition
than the investigated samples, so that precision and accuracy
vary as a function of both matrix and N concentration (~1‰
for d15N in diamonds, to 20‰ for the analysis of solar wind
nitrogen, Marty et al. 2011). High-resolution SIMS are quite
expensive instruments and therefore restricted to few labora-
tories (and even less are involved in the analysis of d15N).
Remote analysis of comets or molecular clouds can be deter-
mined using high-resolution spectroscopy for molecules/ions
such as HCN, NH2, and NH3 but not N2. The precision is
typically of several tens of per mil. Similar methods (high-
resolution IR spectroscopy) are presently being developed for
the analysis of non-symmetric terrestrial gaseous N-bearing
molecules such as N2O. Finally, the development of site-
specific N isotope composition is emerging with applications
in forensic (Aranda et al. 2011, a field outside the scope of this
overview) and atmospheric (Toyoda and Yoshida 1999; Heil
et al. 2014) sciences.
Cosmochemistry
Nitrogen isotope composition varies greatly among extrater-
restrial materials (sometimes even within a single object),
and, for many years, no clear understanding of the mecha-
nisms driving N isotope variability was achieved. A long-
standing hypothesis was that N isotope variability of meteor-
ites reflects isotopic heterogeneity of the solar nebula. Indeed,
N isotopes are synthesized by two distinct astrophysical
processes (14N during hydrostatic hydrogen burning and
15
N during explosive hydrogen and helium burning), and
the isotope variability could thus reflect variable influx from
different stars to the solar system. At present, the role of
chemical, likely photochemically induced, reactions is
emerging (Furi and Marty 2015), i.e., with a view rather
similar to that deduced from O isotope cosmochemistry.
The key observation is that the Sun (and therefore the
primitive solar nebula) is enriched in light N isotope
(d15N ~ 400‰, Marty et al. 2011, Fig. 1) with respect to
meteorites and planets, a result strikingly similar to what is
observed for O isotopes. Such 15N–depleted compositions are
also found only in rare refractory nitride minerals (TiN) and
the atmosphere of giant planets, including Jupiter and
Saturn (Fig. 1). The former are described as representing
N

0
Inner Solar System Outer Solar Syste m Interstellar medium
5000
Comets Local Galactic
100 Isheyevo 2000
hotspots HC N
Mars atm (N 2) Titan atm. 1000
(N 2) NH 3
IOM CN
200 Wild2
IDPs (Stardust) HC N
Earth atm (N 2)
δ15 N (‰)
Venus 0
CN
N/ N

atm (N 2) Moon Terrestrial

15

300 Earth int. OC CC HC N

Mars int.
14

–200
Inner planets Meteorites Giant
planets
400 TiN NH 3
–400
Solar wind Jupiter (NH 3) Saturn (N 2)
500 (Genesis)
–500

600

Nitrogen Isotopes, Fig. 1 Nitrogen isotope variations in solar system atmospheres of the giant planets: all other solar system objects are
objects and reservoirs. The value of the protosolar nebula (blue shading) comparatively significantly enriched in 15N (From Furi and Marty
is defined by the measurement of solar wind nitrogen, TiN, and the 2015, reproduced with permission)
994
high-temperature solar nebula condensate, whereas the latter
acquired their N isotope composition by accretion of the gas
left from the Sun accretion and/or trapped nitrogen flushed
from the inner disk by the protosun.
All other objects including primitive and differentiated
meteorites are comparatively enriched in 15N (Fig. 1), typi-
cally by 400  50‰ (d15N ~ 0  50‰). Significant differ-
ences exist among primitive meteorites classes and within a
group of meteorites. The most reduced (enstatite chondrites)
are more depleted in 15N (d15N from 50 to 0‰, average ~
25‰; Grady et al. 1986) than the more oxidized carbona-
ceous CI and CM chondrites (d15N ~ +40‰; Kerridge 1985).
Other carbonaceous chondrites display a large range, with CV
and CO being characterized by the more negative d15N values
of this group (d15N ~20 and 10‰, respectively). Ordinary
chondrites show average d15N values close to that of the
Earth’s atmosphere (~0‰; Hashizume and Sugiura 1995).
Various reservoirs of telluric planets including Earth, Mars
interior, Venus atmosphere, and the Moon have mostly similar
N isotope compositions, consistent with their formation
within the inner part of the accretion disk. Interestingly, both
Mars and Earth show atmospheric 15N enrichment compared
to their mantle of ~600 and ~5‰, respectively, and this
originates from two different processes. For Mars, atmo-
spheric 15N enrichment reflects hydrodynamic escape or
pickup charge exchange with solar wind ions and subsequent
nonthermal escape with preferential loss of 14N to space.
Given that there is neither evidence for recent tectonic activity
nor biological fixation, N exchange and re-equilibration
between Mars inner and outer reservoirs appear unlikely. In
contrast, owing to its larger size, the occurrence of life, and
plate tectonics, the case for Earth is fundamentally distinct
from Mars and discussed hereafter. Finally, it is worth noting
that Earth is comparatively depleted in 15N compared with
most primitive meteorites, including carbonaceous chon-
drites. The only class of meteorites with d15N values
matching those of bulk silicate Earth is enstatite chondrites.
Together with O isotopes, nitrogen was one of the first recog-
nized elements to share similarities with this class of meteor-
ites. Since then, such similarity has been extended to many
elements such as Zn, Mo, Ru, Cr, Sr, Ti, and Ca (Javoy
et al. 2010).
In detail, a single meteorite can display strong N isotope
heterogeneity, reflecting a multitude of processes and origins.
For example, the Isheyevo carbonaceous chondrite shows a
range > 5000‰ (Fig. 1). Presolar grains carry tremendous
isotope anomalies (15N/14N from ~0.2  100
103, Zinner
et al. 2007), but the low concentration of this component in
meteorites induces limited isotope variability on bulk sam-
ples. Spallation reactions can produce significant amount of
light elements, including nitrogen. They are most recogniz-
able on the rare isotopes (i.e., 15N enrichment) and can be
easily targeted using exposure proxies (e.g., 38Ar/36Ar). More
Nitrogen Isotopes
importantly for this overview, d15N variability also reflects
photochemically induced isotope fractionation effects, and
the large isotope fractionation between N-bearing molecules
(HCN and NH3, Fig. 1) is a likely illustration (next section
also reports a case for photochemical effects on Earth). By
analogy with the so-called mass-independent fractionation of
O isotopes, N isotope variations could result from photo-
chemistry during interactions with UV light originating
from the forming Sun and/or other stars. For instance, N2
could react and form molecules such as ammonia or cyanide
that would then be transferred/condensed to ice and dust and
subsequently to meteorites and planets. As for O isotopes, the
exact mechanism remains unclear and UV photochemical
effects could result from isotope selective reactions or reflect
self-shielding effects. Accordingly, compared with heavy ele-
ments that are commonly used to trace solar nebula heteroge-
neity, light elements such as N bear the potential to highlight
chemical processes that occurred in the solar nebula.
Atmospheric Nitrogen Species and Deposits
The main (i.e., 78% molar fraction) gaseous species of Earth
atmosphere is diatomic nitrogen (N2). The isotope composi-
tion of atmospheric N2 is homogeneous and used as the
international reference for d15N notation, i.e., d15Natmosphere
 0‰ (Mariotti 1983). Several other N-bearing gas and/or
aerosols occur in the atmosphere such as NH4, N2O, NOX, or
HNO3, and their origin and fate can be studied from their
N isotope composition.
A good example of photochemically induced isotope frac-
tionation is illustrated by nitrate recorded in Antarctic snow/
ice, which shows large range of d15N values from 0 to +300‰
(Savarino and Morin 2011, Fig. 2). This range results from
the photolysis of nitrate in snow, leading to the release of
15
N–depleted NOx and the accumulation of residual
15
N–enriched nitrate. This process can be modeled using a
Rayleigh distillation (with a fractionation factor a ~ 0.94, i.e.,
60‰) and seems to be only expressed where snow accu-
mulation rates are low. For other locations such as Greenland,
where accumulation rates are higher and for which photo-
chemical processing of nitrate is accordingly less important,
the N isotope composition of nitrate is consistently less var-
iable, although very negative d15N values can be reached
(down to 60‰). In contexts where accumulation rates are
the largest (e.g., Greenland Summit), the secular evolution of
d15N values from ~ +10 down to ~ 0‰ in preindustrial times
to present (Fig. 3) was suggested to reflect the anthropogenic
influence on the N cycle (Hastings et al. 2009). Along with
the development of industrial N fixation at the beginning
of the twentieth century, the N cycle became massively
anthropogenized, with present-day industrial nitrogen fixa-
tion close to biological flux (~2
1014 gN.yr.1, Galloway
Nitrogen Isotopes 995

2003, with d15N ~0‰, Michalski et al. 2015), consistent with composition because N2 and Ar have long residence times.
the trend of decreasing d15N through time (Fig. 3). However, Two combined effects contribute to d15N variability. The first
the observed trend is challenged by the lack of known values effect corresponds to gravitational fractionation in the first
at ~ + 10‰ for preindustrial sources and could instead relate ~100 m of the ice sheet, which behaves as a porous media, and
to an increase in anthropogenic atmospheric acidity, the iso- the second effect is thermal fractionation resulting from
tope variation reflecting the resulting change in nitrate abrupt temperature warming (Severinghaus et al. 1998).
partitioning between gas and particles (Geng et al. 2014). After an abrupt increase in air temperature – as illustrated by
Another application of N isotopes consists in quantifying the so-called Dansgaard-Oeschger events in Greenland ice
abrupt temperature changes from gas bubbles trapped in ice. cores – the resulting temperature gradient leads to heavier
The variability does not reflect changes in atmosphere gas species (15N14N, 40Ar, 18O16O) in the colder, i.e., deeper
part of the firn. When used together with Ar isotopes, it allows
deducing both the magnitude of temperature increase
[NO3- ] (ng.g-1) (typically >10  C with precision of ~2.5  C) and duration
δ15N (‰)
(typically <100 years) for most of the Dansgaard-Oeschger
0 500 1000 1500 0 200 400
0 events (Landais 2011).
Among atmospheric compounds, nitrous oxide (N2O,
5 half-life of 120 years) receives peculiar attention because it
10 is a powerful atmospheric greenhouse gas (~ 300 times more
efficient than CO2) and is a cause of ozone layer depletion.
15
The concentrations of N2O in the atmosphere have
20 increased from 270 to 330 ppm since preindustrial times.
Depth, cm

The average d15Nbulk of tropospheric N2O is 6.5‰, yet vary-

25
ing with location and time and decreasing by 0.040‰/yr
30 (Rockmann and Levin 2005). Emissions are biotic, with the
majority (~2/3) being produced in soils from bacterial and
35
fungal anaerobic denitrification and aerobic nitrification pro-
40 cesses (see next section). The other part is produced in the
ocean, but N2O origins, fluxes, and fate are still poorly
45
constrained in this environment. In soils, N2O emissions N
50 depend upon a large number of parameters including agricul-
tural practices (N application rate, crop type, fertilizer type)
Nitrogen Isotopes, Fig. 2 Typical snow pit profiles in central Antarc-
and soil conditions (soil moisture, soil organic C content, soil
tica (Dome C) showing the strong denitrification of the snow in a very
short depth accompanied by a strong 15N enrichment of nitrate (Modified pH, and texture) resulting in a large variability on both spatial
from Savarino and Morin 2011) and temporal scales (Thomson et al. 2012). To better address

Nitrogen Isotopes, 800

Fig. 3 Secular evolution of d15N 15
of nitrate (solid circles) and nitrate
CO2 emissions from fossil fuels (1012 g C)
700
concentration (open triangles) in a
100 m ice core from Summit,
Greenland, spanning ~1718 to 600
δ15N(NO3-) (‰ vs. air)

2006 together with global CO2 10

emissions from fossil fuels. The 500
trend was originally suggested to
Nitrate (ppb)

reflect a change in d15N emissions

(Hastings et al. 2009) but was 400
5
recently suggested to reflect a
change in atmospheric acidity 300
(Geng et al. 2014) (Modified from
Hastings et al. 2009)
0 200

100

-5 0
1700 1750 1800 1850 1900 1950 2000
996
this issue, studies now commonly include site-specific analy-
sis of nitrogen (the isotope composition of internal and exter-
nal nitrogen atoms within N2O). Notably, there is a strong site
preference of ~18.7‰ for the central N atom (Yoshida and
Toyoda 2000) with temporal trends being ~0.064 and
0.014‰/yr. for terminal and central N atom, respectively
(Rockman and Levin 2005). Clearly, N isotope geochemistry
is central for understanding the global N2O cycle.
Finally, the analysis of N isotope composition of urban
and rural aerosols is developing, but its interpretation is
generally simplified to isotope fingerprinting, i.e., N isotope
composition reflecting the characteristics of their source,
neglecting therefore secondary processes that can be signifi-
cant (Widory 2007 and see above). Much remained to be done
in this field.
Paleoenvironment and Paleo-Ecosystem
Reconstruction
Nitrogen in sedimentary rocks initially derives from the atmo-
sphere, and in the absence of life, there would be no nitro-
gen in sediments. Moreover, without a strong return flux,
atmospheric nitrogen would be fixed by biological activity
within 100 My (1.4 1014gN/yr., Galloway 2003). In sedi-
ments, nitrogen is mostly carried by organic matter and detri-
tal K-bearing minerals such as clays or feldspars, in which
ammonium (NH4+) enters by substitution with potassium
(K+) due to similar charge and ionic radius. The nitrogen
Nitrogen Isotopes,
Fig. 4 Schematic diagram of the
principal biogeochemical
processes driving the modern
N cycle. Nitrogen isotope
fractionations are expressed using
the e-notation where ereactant-
product ~ ™reactant–dproduct
(Reproduced from Ader et al.
(2016) with permission)
Nitrogen Isotopes
isotope signature of bulk sedimentary rocks reflects mostly
primary organic matter composition and is often used as a
proxy of marine paleoenvironments and paleo-ecosystems.
There are two main reasons for studying N in sedimentary
rocks. First, N is a major nutrient, essential to all kinds of
biological activity/organisms on Earth. It constitutes the basis
of molecules such as amino acids, DNA, RNA, and proteins,
and therefore the N isotope signature can provide constrains
on specific metabolic activity, probing traces of life in the
sedimentary record (Honma 1996). Second, N is a redox-
sensitive element, with diverse chemical species (e.g., N2,
NO3, NH4+) controlled by local redox conditions. The nitro-
gen isotope composition will depend on the fate and recycling
of nitrogen compounds in the ocean and can shed light on the
redox structure of the ocean, which is of particular interest for
Precambrian environment reconstruction but also for under-
standing changes in the Phanerozoic such as those related to
Cretaceous oceanic anoxic events (OAE). The modifications
of sedimentary N isotope composition through time can thus
be used as a proxy of biological evolution and varying envi-
ronmental conditions (see reviews by Ader et al. 2016;
Stueken et al. 2016).
Nitrogen enters the oceanic biogeochemical cycle through
N2 fixation by aerobic or anaerobic autotrophs (such as phy-
toplankton and cyanobacteria) in which N2 is reduced to
NH4+ and assimilated with minimal isotope fractionation
(2 to +1‰; e.g., Wada et al. 1975, Fig. 4). This reaction is
based on nitrogenase enzyme, which requires molybdenum as
a cofactor. Recent experimental study demonstrated that
Nitrogen Isotopes
alternative cofactors such as Fe and V can also be used and
produce larger isotope fractionation with organic matter
depleted in 15N down to 8‰ relative to N2 (Zhang et al.
2014). After their death, organic matter mineralization
releases N as ammonium (NH4+), with very little isotopic
fractionation. In the presence of free O2, NH4+ is oxidized to
nitrate (NO3) during a two-step process called nitrification,
which is associated with significant N isotope fractionation
>20‰ (Sigman et al. 2009, Fig. 4). This fractionation is
rarely expressed in modern marine environments since the
transformation of NH4+ to NO3 is generally complete. In
O2-depleted environments such as oxygen minimum zones or
anoxic sediments, nitrates are partially reduced by denitrifi-
cation or anammox (i.e., anaerobic ammonium oxidation)
into gaseous N2 or N2O (for N2O see atmospheric section).
During denitrification, 14N is preferentially released relative
to 15N, leaving residual marine NO3 enriched in heavy
isotope (average marine d15NNO3 ~ +5‰, Fig. 4). The
heavy isotope signature of NO3 is transferred by assimila-
tion to organisms living in the water column and then
recorded in sedimentary organic matter. Accordingly, assum-
ing a steady-state system, the N isotope composition of
organic matter in modern marine environment reflects mainly
the relative proportion of N denitrification and fixation. In
O2-free environments such as the Archean oceans, nitrifica-
tion and thus subsequent denitrification are unlikely, and
amphibolite bulk hydrothermal bulk
greenschist kerogen sub-greenschist bulk
35
30
25
20
δ15N [‰]
15
10
-5
-10
4.0 3.5 3.0 2.5
Nitrogen Isotopes, Fig. 5 Secular trends in nitrogen isotope of marine
samples, separated by metamorphic grade. Note that sub-greenschist and
green schist facies kerogens (evolved organic matter) and bulk rock
samples typically overlap, suggesting limited metamorphic alteration.
However, amphibolite facies rocks tend to be characterized by
997
dissolved N species are probably dominated by NH4+
(Beaumont and Robert 1999). Ammonium can be assimilated
by living organisms with an isotope fractionation up to
27‰, favoring 14N in organic matter (Pennock et al.
1996). In the case of quantitative NH4+ consumption, this
fractionation is, again, not expressed, and the d15N of
dissolved NH4+ is readily recorded in sedimentary organic
matter. For instance, ammonium assimilation has been
invoked from negative d15N down to 5‰ recorded in sed-
iments from the ~2.2Ga Aravalli Supergroup, India (Papineau
et al. 2009, Fig. 5).
Postdepositional Modifications of Sedimentary
N Isotope Composition
An important aspect of ancient sedimentary rock studies is the
evaluation of possible d15N modifications related to diagene-
sis and metamorphism (Ader et al. 2016, Fig. 4). Organic
matter degradation occurs in water column and near
sediment-water interface during early diagenesis and during
thermal maturation associated with burial diagenesis and
metamorphism. In oxic environments, early diagenesis can
impart a shift in d15N values toward more positive values, up
to ~3‰ (Lehmann et al. 2002). In contrast, organic matter
degradation under anoxic and suboxic conditions either pre-
serves original nitrogen isotope values or slightly lowers d15N
values down to 1‰ (Lehmann et al. 2002). Metamorphism
hydrothermal kerogen greenschist bulk
N
sub-greenschist kerogen
2.0 1.5 1.0 0.5 0.0
Age [Ga]
15
N–enriched compositions compared with samples of lower metamor-
phic grade. The large variations of d15N-values through time emphasized
from low metamorphic grade samples therefore highlight profound
changes in the nitrogen cycle (Modified from Stueken et al.
(2016) with the very kind help of the first author)
998
associated with sediment burial induces only minor modifi-
cations (< 1‰) for metamorphic grade lower than greenschist
facies (see review in Ader et al. 2016; higher metamorphic
grade is discussed below).
Selected Applications of N Isotopes to the Sedimentary
Record
One of the most important changes in the Earth history is the
oxygenation of the ocean and atmosphere. The oxygenation of
the atmosphere occurred about 2.4 Gy as recorded by mass-
independent fractionations of S isotopes; for the ocean the
situation is not so clear, and, over the last 20 years, N isotopes
have been used to discuss this issue (Beaumont and Robert
1999; Zerkle et al. 2017 and ref. therein). The rationale is that
N forms NO3 in the presence of dissolved O2, and due to
subsequent partial denitrification, the residual NO3 becomes
increasingly enriched in heavy isotopes, thus imparting posi-
tive d15N values in organic matter deposited in sediments. The
compilation of all data available places the onset of marine
dissolved NO3 in the Neoarchean and Paleoproterozoic
(Stueken et al. 2016). Extremely positive d15N values, up to
+50‰ (Thomazo et al. 2011; Stueken et al. 2015a, Fig. 5),
were observed in sedimentary rocks from the 2.7 Ga Tumbiana
Formation and could correspond to the first oxidative distilla-
tion of the NH4+ reservoir (Thomazo et al. 2011). An alterna-
tive interpretation suggested that volatilization of NH3 in an
alkaline lake could leave residual NH4+ enriched in heavy
isotope (Stueken et al. 2015a) but such high values have not
yet been found even in the most alkaline modern lakes.
In parallel to the reconstruction of ocean redox structure,
N isotopes of the sedimentary record have been used as
tracers of metabolic activity. For instance, d15N values near
0‰ measured in 3.2–2.75 Ga sedimentary rocks of low
metamorphic grade (Fig. 5) indicate that the biomass was
dominated by N2-fixing autotrophic organisms (Stueken
et al. 2015b). This finding places a minimum age constraint
of 3.2 Ga on the origin of biological N2 fixation. If we
consider that the occurrence of nitrogen in sedimentary
rocks attests for the occurrence of life, then the minimum
age constraint becomes 3.8 Gy (Honma 1996).
In the Phanerozoic, low d15N values (7 to 0‰, Fig. 5) are
systematically observed in sediments deposited during Creta-
ceous OAE and are associated with high concentration of total
organic carbon (up to 20%). These low d15N values are
interpreted as evidence for N2-fixing organisms thriving in a
water column highly depleted in oxygen, which would be
related to warm and wet greenhouse climate periods and asso-
ciated thermohaline stratification of the ocean (e.g., Rau et al.
1987; Zhang et al. 2014). Intense denitrification would in this
case limit any contribution of residual nitrate to the bulk d15N
signature of the biomass. A compilation through the entire
Phanerozoic shows that low and high d15N values correspond
to greenhouse and icehouse climate periods, respectively,
Nitrogen Isotopes
thus suggesting that long-term d15N variations are controlled
by climate rather than redox variations (Algeo et al. 2014).
Sedimentary denitrification would dominate during green-
house periods owing to higher eustatic (global sea-level)
elevations and greater on-shelf burial of organic matter,
whereas water-column denitrification would dominate dur-
ing icehouse modes owing to lower eustatic elevations.
Nitrogen Chemical Geodynamics
Biological activity does not only mediate transfers from the
atmosphere to sediments (see above) but also to the crust and
the mantle. Nitrogen is a unique element because it originally
requires living organisms to enter the rock record (abiotic
reactions exist but are negligible, see below). It thus repre-
sents a unique tracer of chemical geodynamics. In this context
too, N isotopes have been successfully applied. For instance,
they have been used to constrain and quantify the loss of
nitrogen and other fluid-mobile elements during subduction.
Nitrogen isotopes were also used to trace the presence of
subducted surface material in the Earth’s mantle because a
significant difference exists between mantle and surface
N isotope signatures, being, respectively, 15N–depleted and
15
N–enriched relative to the atmosphere (see Cartigny and
Marty 2013).
As mentioned above, the introduction of N into the rock
record arises from maturation of organic matter, which
releases ammonium ions. Ammonium is then substituted for
potassium, thus following the fate of potassic minerals:
mainly clays at low P-T conditions and micas under higher
metamorphic grade (Busigny and Bebout 2013 for review).
As temperature increases, metamorphic reactions can induce
fluid devolatilization. The release of 15N–depleted fluids (N2
and/or NH3) produces an increase of d15N value in the resid-
ual rock, typically from d15N ~ +5 up to +15‰ (Bebout and
Fogel 1992). The nitrogen budget can be derived from Ray-
leigh model, based on theoretical fractionation factors,
ammonium content, and correlations with large ion lithophile
elements (K, Rb, and Cs). An important result is that N in
subduction zones can either be preserved or released during
metamorphism, depending on geothermal gradient. In cold
(e.g., 8  C/km) subduction zones, N is stable and preserved in
potassic minerals (e.g., phengitic micas), and d15N remains
constant. Nitrogen is thus massively subducted to depths in
excess of 90 kilometers. In contrast, significant amounts of
N are devolatilized in warm subduction zones (> 15  C/km).
At present, the average fluxes of N input in subducted slab
and output from volcanic arcs by degassing are 9.6
1011 and
0.7
1011 gN/yr., respectively (Busigny et al. 2011). There-
fore about 80% of N buried in subduction zones is recycled to
the deep mantle and is characterized by a majority of positive
d15N values (Fig. 6).
Nitrogen Isotopes 999

Modern sediments
0.7% of
The Earth mantle contains little nitrogen (likely between
δ15N = 7.2 ± 3.3‰ (1σ) 0.26 and 36 ppmN), and its study remains limited to few

Modern
values above

samples such as diamonds, basaltic glasses (and their gas

vesicles), and volcanic fumaroles. Nitrogen isotopes remain
Sediments

difficult to investigate primarily owing to atmospheric con-

Archaean kerogen 10% of tamination (although this can be quantified using Ar isotopes)
Ancient

δ15N = 6.0 ± 6.7‰ (1σ) values above

and assimilation. The exception is diamond since N is the
main diamond impurity (with an average concentration of
150 ppmN) but for which genesis ages and depth of formation
Nitrogen in metasediments remain often under-constrained. The d15N values of samples
warm geothermal gradients
from the Earth mantle are scattered but are primarily negative.
< 90 km

(>15 °C)
Subducted Material

Importantly, both the so-called diamond coats and fibrous

diamonds and mid-ocean ridge basalts (all <500 My) distinc-
tively point to a present-day mantle d15N ~ 5‰ (Fig. 6).
Nitrogen in metasediments
< 90 km

cold geothermal gradients Older diamonds (possibly Archean) with silicate inclusions
~ 8°C/km
pointing to peridotitic composition display more scattered
d15N values with two third being negative. This makes
> 120 km

Metamorphic
diamonds
N isotope a powerful tracer of recycled material and was
used to discuss the origin of eclogitic (i.e., basaltic) compo-
sition, their 13C–depleted isotope composition being often
Fibrous diamonds
Subcontinental

attributed to recycling of organic matter in the mantle. Yet

their d15N are strikingly similar to peridotitic diamonds and
Present-Day Mantle

do not emphasize a recycled origin for most of them (Cartigny

and Marty 2013 for review). However consistent evidence for
Mid-ocean ridge
basalts
deep recycling of nitrogen was found from the study of
Oceanic

metamorphic diamonds formed in crustal rocks subducted to

ultrahigh pressures (> 3.5 GPa), some lamproïtes, ocean
island basalts, and some deep diamonds (Cartigny and
Marty 2013 for review). N
The average flux of N in modern subduction zones, sub-
Deep, Possibly

Carbonatites
Subducted

from Kola
tracted from N loss in volcanic arcs, is seven times larger than
Nitrogen

mantle degassing flux (Busigny et al. 2011). This implies that

Ocean island basalts
crustal N is preferentially recycled to the mantle, likely induc-
ing secular evolutions of atmospheric, crustal, and mantle
Peridotitic N contents. Given their isotope characteristics, the exchanges
diamonds
between 15N–enriched surface materials and 15N–depleted
Old (mostly Archaean)

2 diamonds mantle also predict secular evolutions of their N isotope com-

Upper Mantle

down to -40‰
positions which have been searched in crustal and mantle
records. Although there is no consensus yet, addressing this
Eclogitic question is fundamental. If the Archean atmosphere had ~2 to
diamonds
3 present nitrogen atmospheric levels (NAL), it would result
in N2 radiative forcing (i.e., N2 as a greenhouse gas), resulting
from pressure broadening and Rayleigh scattering. It could
explain why the Earth remained warm despite the faint young
sun, i.e., without requiring high amounts of greenhouse gases
The Deepest

such as CO2 or methane (Goldblatt et al. 2009; Wordsworth

Diamonds from the lower mantle
Mantle

(peridotitic compositions) and Pierrehumbert 2013). Considering an average N content

of the continental crust of 83 ppmN (Rudnick and Gao 2003)
-24 -18 -12 -6 0 +6 +12 +18
environments), present-day convective mantle, ancient mantle and lower
mantle, and magmas possibly sampling nitrogen recycled to mantle
Nitrogen Isotopes, Fig. 6 Comparative histograms of d15N values for depths. Note that modern and ancient sediments do not reveal any obvious
modern and ancient sediments, subducted nitrogen (warm and cold secular isotopic trends (but see Fig. 5) (From Cartigny and Marty 2013)
1000
with a d15N value of +6‰ and that crustal N is of atmospheric
origin, without biological activity, present nitrogen atmospheric
level (NAL) would be 20% higher with a d15N > 1.2‰. These
are minimum values as some nitrogen was recycled in the
Earth’s mantle. Yet, the study of fluid inclusions and crustal/
sedimentary (Archean and Proterozoic) rocks led, so far, to
contradicting conclusions. Studies of several Archean
crustal rocks (giant quartz veins) and 2.7 Gy kerogens sug-
gest significant d15N evolution of atmospheric nitrogen from
> + 40‰ to present value of 0‰ (Jia and Kerrich 2004)
when others evidenced rather constant d15N values (Marty
et al. 2013). Similarly, NAL may have decreased (from
3 NAL, Goldblatt et al. 2009) or increased (from 0.5 NAL,
Marty et al. 2013) through time. Mantle d15N values could
have evolved from more negative values (e.g.,
from < 40‰), but the evidence presently relies on a few
samples, and if any, this evolution happened early in the
Earth history, Archean samples pointing to d15N
values ~ 5‰ (Cartigny and Marty 2013). Here, further
studies are needed for reaching a consensus.
The Neglected Role of Abiotic Reactions
In the modern oxic world, atmospheric nitrogen fixation is
primarily driven by biological activity, but in the ancient
anoxic world, the role of abiotic atmospheric nitrogen reduc-
tion might have been significant. This is a fundamental issue
as it raises the question of abiotic amino acids genesis (see
discussion in Stueken et al. 2016). By analogy with the
Miller’s experiments (Miller 1953), we need to understand
whether present and ancient deep hydrothermal systems
could represent favorable environments where significant
abiotic nitrogen reduction might occur. In this case, high
concentration of ammonium in clays or micas would not
necessarily represent an indirect evidence for life. At present,
abiotic nitrogen reduction remains little investigated (see the
experimental work by Brandes et al. 1998). Such reactions
have been suggested in hydrothermal systems and were char-
acterized by very negative d15N values down to ~16‰
(Li et al. 2014). Much work remains to be done in this field,
and N isotopes of future studies may provide fingerprints of
biotic vs. abiotic processes.
“You Are What You Eat”: Paleo-Diet and
Archeological Investigations
The application of N isotopes to paleo-diet and archeological
investigations (this section) and in forensics science (next
section) is primarily a fingerprinting approach. This kind of
approach involved generally multi-isotope systems (C, H,
O, B, Sr, Pb, etc.) but is restricted here to N isotopes.
Nitrogen Isotopes
Application of N isotopes to determine paleo-diets relies
on two observations. First, as N is cycled through the body of
animals/humans, 14N is preferentially lost, leading to 15N
enrichment of tissues (DeNiro and Epstein 1981). This is
also illustrated by 15N depletion of urine relative to the diet.
Throughout the trophic chain, the predators gain the N isotope
composition of their preys, which is then further
15
N–enriched, typically by 3‰ (Minagawa and Wada 1984;
Fig. 7). Therefore N isotope composition indicates the trophic
level position of both marine and continental organisms
(Fig. 7). Second there is a difference between continental
(grass, wheat, fruits) and marine (seashells, fish, algae)
diets, the former being 15N–depleted relative to the latter.
This difference also exists for carbon and can be jointly
used with N isotopes. Therefore, although there are some
overlaps, a vegetarian will be more 15N–depleted than some-
one being omnivore or eating only meat.
These applications extend beyond the field of geochemistry
but provide a good example of interdisciplinary interactions
with the field of human sciences. Typically undertaken with the
analysis of C isotopes (e.g., to constrain the proportion of C3
and C4 plant species in the diet of herbivores), N isotopes
revealed when agriculture was introduced in the diet and
more generally when a group changed their subsistence strat-
egy. Nitrogen isotopes demonstrated that Neanderthals had
large herbivores on their diet, therefore implying that they
were top-level predators and accomplished hunters (Richards
and Trinkausc 2009). Similarly, the zonation of tooth can help
archeologists determine when animals or humans weaned their
babies and, again, what kind of food they had.
Forensics Science with a Focus on Nitrate
Pollution
Nitrogen isotopes remain less used than carbon and hydrogen
isotopes in forensics science, which are collectively used as a
Primary producers
Primary consumers
Secondary consumers
Tertiary consumers
0 5 10 15 20
δ15N (‰)
Nitrogen Isotopes, Fig. 7 Illustration of the stepwise enrichment of
d15N along food chains (Modified from Minagawa and Wada 1984)
Nitrogen Isotopes 1001

Nitrogen Isotopes, 100

Fig. 8 Typical values of d15N and Atmospheric NO 3−
d18O of nitrate derived or nitrified 90 (Denitrifier method)
from various N sources.
80
Atmospheric. The two arrows
indicate typical expected slopes 70
for data resulting from
denitrification of nitrate with 60
initial d15N = +6‰ and

δ18 O NO3 (‰)

d18O = 9‰. The typical ranges 50 Atmospheric NO 3−
of ™18ONO3 values produced by (AgNO 3 method)
nitrification of ammonium and 40
organic matter are denoted by
“nitrification” (Modified from 30
Kendall et al. 2007)
20 NO3− fertilizerr
Marine NO 3− 1:1
10

Nitrification
NH 4+ in n 2:1
Soil
rif icatio
0 fertilizer and
NH4+ Denit
precipitation
–10 Manure and
Septic Waste
–20
–20 –15 –10 –5 0 5 10 15 20 25 30 35

δ15N NO3 (‰)

fingerprint to distinguish genuine products from counterfeits. 80

In this section, we will specifically focus on a very important
application that arises from the anthropization of the N cycle. ε=-15.9‰
60
With only half of fertilizers being fixed by crop plants and
δ15N (‰)

owing to nitrate (NO3) release from intensive agriculture,

nitrate concentrations in drinking water supplies have risen
above acceptable levels in many areas of the world (Kendall
et al. 2007). Increase in nitrate levels of groundwaters, rivers,
and estuaries induces biological blooming which leads, due to
the subsequent degradation of organic matter, to eutrophic
waters in many locations. Monitoring nitrate levels and deter-
mining their sources and fate and the role and rate of (bio-)
remediation are key data to understand and subsequently
change common practices (although sometimes the good
practice could consist in stopping pumping water of a con-
taminated aquifer !). Understanding the origin and fate of
nitrate can be complex because various sources exist
(Fig. 8): fertilizers which contain both ammonium (d15N
from 10 to +5‰ that will get oxidized to nitrate) and
nitrate (d15N from 10 to +5‰), animal and septic manure
(d15N from 0 to +25‰), and atmosphere deposits (but
also organic nitrogen) and owing to isotope effects that
occur through biotic denitrification mechanisms (see
paleoenvironments and paleo-ecosystems section). How-
ever, in most cases, the sources are known (Fig. 8) and
studied, and mixing processes can be modeled and distin-
guished from isotope variations related to other physico-
chemical reactions. Denitrification isotope effects can be
recognized from the slope ~1 to ~2 between d15N and d18O
evolving toward 15N- and 18O–enriched isotope
40 N
20
0
0.01 0.05 0.1 0.5 1.0 2.0
residual fraction of NO3 (‰)
Nitrogen Isotopes, Fig. 9 Dependence between nitrogen isotope ratio
and the fraction of residual nitrate in a sandy aquifer. Note the linear trend
between the two parameters when the nitrate concentration is displayed
in logarithmic scale: this is typical of open-system process (Rayleigh
distillation) here typified for nitrate reduction (Modified from Böttcher
et al. 1990)
compositions (see Fig. 8). This relationship allows both a
quantitative modeling and forecasting the evolution of
nitrate concentration (Böttcher et al. 1990; Fig. 9). Extrapo-
lation of d15N and d18O values to their likely origin allows to
recognize the source of nitrate pollution. It is worth noting
that N isotopes can only develop their full potential in
conjunction with other geochemical parameters, including
boron, strontium, and oxygen (both d18O and d17O) isotopes
(Kendall et al. 2007; Widory et al. 2004). Finally, because
1002
residual nitrate evolves toward 15N–enriched compositions
(modulo the isotope fractionation during assimilation and
processes through the animal body), inputs of nitrate into
estuaries or coastal ecosystems can easily be recognized by
increasing d15N through time.
Conclusion
Despite being unevenly distributed on Earth and in extrater-
restrial samples, several methods have been developed to
analyze accurately N content and isotope composition. In
modern and primitive Earth, the cycling of atmospheric nitro-
gen to the silicate Earth requires biological activity, and this
makes nitrogen a unique tracer of life in the rock record. In
every overviewed contexts, N isotopes have brought unique
constraints that could hardly be deduced from other geochem-
ical systems. It is however worth mentioning that N isotopes
can only reach their full potential when considered together
with other systematics.
Cross-References
▶ Archeological Geochemistry
▶ Biogeochemistry
▶ Nitrogen
▶ Nitrogen Cycle
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Noble Gases
Chris J. Ballentine and Peter H. Barry
Department of Earth Sciences, University of Oxford,
Oxford, UK
Definition
The noble gases occupy Group 0 (column 18) of the periodic
table, comprised of the following elements: helium, neon,
argon, krypton, xenon, and radon (not discussed here). They
are colorless, odorless, monatomic, and unreactive gases at
standard temperature and pressure.
Introduction: History and Uses
Helium: The spectral signature of helium was first observed
from the Sun by Janssen and Lockyer in 1868, with Lockyer
1004
credited for proposing this as a new element. Helium was first
isolated and identified in clevite, a uranium-rich mineral, by
both Cleve and Langlet and independently by Ramsay in
1895.4He is formed by alpha particles during the decay of
natural uranium and thorium in the crust, with commercial
sources provided in rare natural gas fields containing helium
at concentrations between ~0.1 and 0.3%.
Helium is used in many cryogenic applications, most
notably as a liquid in the cooling of superconducting mag-
nets used in medical MRI scanners, but is also used for
pressurizing and gas purging in many industrial applica-
tions, controlled atmospheres, specialist welding, leak
detection, and breathing mixtures. In 2006, total global
proven reserves and probable resources were estimated to
be 51.9 billion standard cubic meters. In 2014, global helium
production/use was estimated to be 180 million standard
cubic meters (USGS 2015).
Neon: Discovered in air by Ramsay and Travers in 1898,
the main source of commercial neon today is through cryo-
genic fractional distillation of liquid air. Best known for its
use as a lighting source in neon discharge tubes, it is also a
vital component in excimer laser gas mixes used by semicon-
ductor manufacturers. Semiconductor lithography applica-
tions using excimer lasers account for 70% of neon demand
with global production in 2014 at ~400 million liters liquid
neon (Corbett et al. 2015).
Argon: Cavendish first observed argon in 1785 as a resid-
ual gas after removing all chemically active species from air.
It was later confirmed as a component of air and subsequently
named by Ramsey and Rayleigh in 1894. Like neon, the main
source of commercial argon today is obtained through cryo-
genic fractional distillation of liquid air. This process pro-
duces ~700,000 tonnes of argon globally each year (2001).
Argon is used as an inert blanket gas in the microchip and
food industries and in cryogenics when the less expensive but
more reactive nitrogen is not an appropriate coolant. Addi-
tional uses of argon include laser applications, to generate
high energy plasma and – in liquid phase – as a scintillation
target for neutrino and dark matter detectors (Acosta-Kane
et al. 2008).
Krypton: Discovered in 1898 by Ramsay and Travers in
air, commercial krypton is also produced by cryogenic frac-
tional distillation of air. Krypton gas finds use in lasers, as a
filling for double glazing, incandescent lights, and specialist
cryogenic uses as a liquid.
Xenon: Also discovered in 1898 by Ramsay and Travers.
Commercial xenon is produced by cryogenic fractional
distillation of air. Global production is about 10,000 m3 at
standard pressure and temperature (6 tonnes) of which 15% is
used in medical applications as an anesthetic. In addition,
xenon gas is used in modern flash bulbs; in the liquid
form, it is used as a supercritical solvent, as a scintillation
target for dark matter detectors, and as fuel for ion propulsion
Noble Gases
engines used in satellite positioning (Royal Society of
Chemistry 2016).
Cosmochemistry
The isotopic compositions and abundances of the noble gases
in the Sun are referred to as the solar composition. This pro-
vides the reference point for chemically differentiating
between meteoritic, cometary, and planetary materials. The
best analog for the solar composition is solar wind, and its
noble gas composition has been successfully determined by
the recent NASA Genesis return mission, which trapped solar
wind implanted into a variety of target materials (Wiens et al.
2007; Meshik et al. 2014; Crowther and Gilmour 2013) and
returned them to Earth for analysis.
The observed differences between solar and terrestrial
compositions are used to identify the various origins and
processes that trap volatile elements during meteorite and
planetary formation (Marty 2012; Halliday 2013). Some
noble gases are produced by radioactive decay and cosmo-
genic reactions; excess abundances in these isotopes are used
to provide temporal constraints on these trapping and forma-
tion processes.
Similar to other highly volatile elements such as nitrogen
and carbon, the noble gas composition of the most primitive
meteorites and carbonaceous chondrites are depleted by sev-
eral orders of magnitude relative to the solar abundance of
silicon; solar volatiles are not efficiently captured in rock-
forming bodies. Superimposed upon this general depletion,
light noble gases are more depleted than heavy gases
(He < Ne < Ar < Kr < Xe). Furthermore, lighter isotopes
of the same element are more depleted than heavier isotopes
relative to the solar reference (Huss et al. 1996; Busemann
et al. 2000; Ott 2014).
Noble gases in meteorites are trapped in different solid
phases. For example, most of the Ar, Kr, and Xe found in
meteorites are found in a carbonaceous residue that remains
after Hf/HCl acid treatment (i.e., “Q-phase”). In addition to
Q-phase gases, noble gases are found in silicon, carbon,
graphite, and nano-diamonds formed before the collapse of
the solar nebula. The latter “pre-solar grains” provide isotopic
compositions of Kr and Xe that are formed by s-, r-, and
p-nucleosynthetic processes occurring in stars and super-
novae (Ott 2014).
In addition to Q-phase and pre-solar noble gases, signifi-
cant sources of noble gas, particularly He and Ne, include ion
implantation of solar wind and noble gases produced by the
high energy impact of cosmogenic rays. The latter provide a
crucial temporal history of meteorite breakup exposing fresh
surfaces (Wieler et al. 2016) and the travel time of Martian
meteorites between ejection from Mars and impact on Earth
(Nyquist et al. 2001).
Noble Gases
Cometary activity and meteorite breakup deliver 3He-rich
material to Earth in the form of interplanetary dust particles
(IDPs). These provide a significant cosmogenic flux to
Earth, as IDPs retain solar wind implanted 3He, which can
be resolved in ocean floor sediments. Over periods of
known IDP deposition, 3He concentrations provide a measure
of sedimentation rate. In areas of known sediment
accumulation, variance in IDP flux can be attributed to, for
example, high levels of cometary activity (McGee and
Mukhopadhyay 2013).
Mantle Geochemistry
Three dominant sources of noble gases exist in the Earth’s
mantle: (i) those trapped during the accretionary process,
(ii) noble gases recycled from the planetary surface into the
mantle, and (iii) those produced by the decay of extinct (244Pu
and 129I) and extant radionuclides (U, Th, and K) within the
mantle. The first work on mantle materials soon identified a
dichotomy; all samples from mid-ocean ridges exhibit a very
narrow range in 3He/4He (7–9 RA) (where RA = the 3He/4He
of air = 1.4
106), whereas most plume-influenced samples
from intraplate volcanics have 3He/4He values significantly
higher (>9 RA) and some lower than those from the mid-
ocean ridges. Due to the fact that 3He is dominantly sourced
during accretion and 4He through the radioactive decay of
U and Th, this ratio provides a proxy for 3He/U ratios in
different mantle domains. The resulting layered mantle
model dominated the community understanding of mantle
structure and evolution for a quarter of a century, a mantle
in which a well-mixed upper mantle, above the 660 km seis-
mic discontinuity, was lithophile depleted (see lithophiles)
and degassed compared to a less depleted, heterogeneous,
and more volatile rich lower mantle (Kurz et al. 1982; Allègre
et al. 1983; O’Nions and Oxburgh 1983; Moreira 2013). Later
improvements in seismic observation of the mantle and
numerical simulation of mantle convection found significant
mass transfer between upper and lower mantle and a far more
complex picture than the two layered mantle model (Van Der
Hilst et al. 1997; Van Keken et al. 2002).
The Ne isotopic composition of mid-ocean ridge source
mantle is indistinguishable from the solar-wind-irradiated
trapped component found in meteorites (Trieloff et al. 2002;
Ballentine et al. 2005; Ballentine and Holland 2008). In
contrast, there is some evidence in plume-derived Ne isotopes
of a solar nebular signature (Yokochi and Marty 2004;
Mukhopadhyay 2012), although this interpretation remains
contested (Moreira 2013). Similarly, the primordial MORB-
source mantles Kr and Xe are also consistent with delivery of
a trapped component within accreting material (Holland et al.
2009; Caracausi et al. 2016). This result precludes models in
which the dominant sources of volatiles in Earth’s mantle are
1005
derived from equilibration of an early magma ocean with a
massive early (solar) atmosphere.
Xe isotopic values approaching solar values have never-
theless been found in some plume-derived samples, and this
may suggest an early accretionary role for solar nebula gases
(Yokochi and Marty 2004; Mukhopadhyay 2012). Because
129
I decays to 129Xe (t½ = 15.7 Ma), 129Xe/130Xe isotopic
compositions can be used to infer source I/Xe compositions in
the earliest Earth history. Results from the Iceland plume
show that volatiles from this source have lower I/Xe than
mid-ocean ridge samples, and that this signature has been
preserved since 129I became extinct in the first ~100 Ma of
Earth history. This data is also used to argue that mixing of
noble gases from the Iceland plume mantle source with mid-
ocean ridge sourced volatiles does not occur at any significant
level (Mukhopadhyay 2012).
The primordial heavy noble gases in the mid-ocean ridge
basalt source mantle are accompanied by atmosphere noble
gases with an elemental composition consistent with subduc-
tion of an ocean/pore-fluid signature into the mantle (Holland
and Ballentine 2006). This oceanic pore-fluid signature is
observed in both halogens and noble gases in fluids subducted
to ~100 km depth (Sumino et al. 2010), demonstrating pres-
ervation of the pore-fluid signal to depths at which transfer
into the deeper mantle can be envisaged. Linking subduction
flux of the noble gases to volatile species such as carbon and
nitrogen (Marty and Jambon 1987; Barry and Hilton 2016)
has provided a powerful tool to trace major volatile subduc-
tion into the mantle (Hilton et al. 2002). N
The location and processes, recorded by the noble gases,
that enable preservation of different accretionary volatile
components in the mantle since the formation of Earth and
the superposition of radiogenic and recycled noble gases
remain at the frontier of the current research effort.
Earth’s Atmosphere
The noble gas composition of Earth’s atmosphere is well
mixed and provides the reference abundance and isotopic
composition for most noble gas terrestrial studies (e.g., Sano
et al. 2013). With the exception of 40Ar and He, the atmo-
sphere contains >98–99% of all terrestrial noble gases. The
pattern of the non-radiogenic noble gas isotopes is, similar to
chondrites, strongly depleted in both light elements and light
isotopes relative to solar. Xe abundances are, however,
depleted by an order of magnitude more than would be
expected using the chondritic pattern as a reference, and
very strongly isotopically fractionated. This is often referred
to as the “missing xenon” paradox (Marty 2012).
Xe isotopes derived from the extinct radioisotopes 129I and
244
Pu can be resolved in the atmosphere. These are highly
depleted relative to predicted amounts and are used to argue
1006
that the earliest atmosphere was not retained until “closure” at
~40–100 Ma after the Earth formed (Pepin and Porcelli 2006;
Avice and Marty 2014). The proportion of radiogenic noble
gas isotopes from extant radionuclides has increased in the
atmosphere over geological time due to Earth degassing. This
is most notably seen in 40Ar relative to 36Ar and is a key
measure of mantle outgassing efficiency and continental
crustal growth (Allègre et al. 1996; Pujol et al. 2013). Anal-
ysis of fluids trapped in ancient minerals and free fracture
fluids shows a light isotope enrichment in shielded Xe iso-
topes (124,126,128Xe) (Pujol et al. 2011; Holland et al. 2013). It
is argued that this is evidence of xenon loss from Earth’s
atmosphere that provides one explanation for the missing
xenon (Pujol et al. 2011; Marty 2012).
Over the last 1Ga, changes in the isotopic composition and
partial pressure of the noble gases in the terrestrial atmosphere
have been small and implicitly assumed negligible in work
using the modern atmosphere as a reference.
Ice, Oceans, and Crustal Fluids
The physical processes of diffusion and solubility which fix
atmosphere-derived noble gases into ice and water are well
understood. Small differences in environmental conditions
such as temperature and salinity provide measurable changes
in the noble gas content of ice and water, preserving temporal
records of environmental change.
Transient temperature gradients fractionate air trapped
within firn through thermal diffusion which is then preserved
in air bubbles in ice. Ice cores therefore provide a
temporal record of both temperature change and rate of
change (Severinghaus and Brook 1999; Winckler and
Severinghaus 2013).
Similarly, when water equilibrates with the atmosphere,
the concentration of noble gases in the water phase is deter-
mined by the temperature and salinity of the water as well as
the partial pressure of the noble gases. Dynamical features of
air dissolving into water can introduce nonequilibrium air
concentrations into the water, but these are reasonably well
understood.
In ocean environments, noble gas concentrations that devi-
ate from equilibrium are used to diagnose and quantify ice
formation, melting, and/or bubble injection through increased
wave activity. Argon can be used to provide a baseline for N2
and O2 activity, allowing differentiation between physical and
biogeochemical activity and thus identification of the pro-
cesses controlling biologic production and denitrification.
Non-atmosphere input occurs in the form of 3He from mid-
ocean ridges and atmosphere tritium decay (t½ = 12.3 years).
The former provides a tool for deriving basin-scale mixing,
global model verification, and trace element addition to dif-
ferent ocean bodies through hydrothermal activity. The latter
Noble Gases
provides information about the age and extent of recent sur-
face water incursion (Schlosser and Winckler 2002; Stanley
and Jenkins 2013).
On the continents for a known location (altitude) and
freshwater recharging an aquifer (near zero salinity), local
temperatures at recharge can typically be determined from
the noble gas concentrations in water to better than
0.3–0.5  C (Ballentine and Hall 1999). With knowledge
of the mean residence time of the water in a given aquifer,
changes in the local paleoclimate can be reconstructed (Kipfer
et al. 2002; Aeschbach-Hertig and Solomon 2013).
Like ocean water, tritium-3He can be used to provide a
mean residence time (MRT) for young (<50 years) ground-
waters. 85Kr (t½ = 10.76 years) released into the atmosphere
by anthropogenic nuclear activity has similar potential but
requires large sample volumes and specialized atom trap trace
analysis (ATTA) techniques. Cosmogenically produced 39Ar
(t½ = 269 years) is formed in the atmosphere and has the
potential to significantly extend the capability to trace young
groundwater. It also requires ATTA technology for analytical
determination; however, recent advances in the technique has
allowed for smaller sample quantities to be accurately mea-
sured (Yang et al. 2013; Ritterbusch et al. 2014).
With the development of ATTA, cosmogenic 81Kr can now
also be determined in groundwater and ice. With a half-life of
229,000 years., 81Kr extends the ability to date water MRTs
and ice core ages beyond the limit of 14C dating to over ~1 Ma
(Aggarwal et al. 2015). For fluids with MRTs >1 Ma, the
radiogenic noble gases (4He, 21,22Ne, 40Ar, 131,132,134,136Xe)
can be used if the accumulation rate is known (Ballentine and
Burnard 2002). For a closed system which releases all noble
gases into the fluid phase, this is given by the concentration of
radioelements and has been used to identify fluids in the crust
>1 Ga (Holland et al. 2013). When an aquifer is open to flux
into the system, the external flux rate needs to be determined;
this may be from local proximal formations with high radio-
element concentrations (Tolstikhin et al. 2011) or by using
flux estimates based on the steady-state release of radiogenic
noble gases from the whole crust (Torgersen 2010).
When a second fluid phase such as natural gas, oil, or
carbon dioxide passes through the groundwater system, the
noble gases equilibrate between phases as a function of local
conditions (temperature, pressure, and salinity) and fluid vol-
ume ratio, and/or whether the process is open or closed
system (Zhou et al. 2005; Barry et al. 2016). In well-behaved
systems, the resulting noble gas content of either phase pre-
serves a quantitative record of this phase interaction. This has
been used to identify the role of groundwater in oil and gas
migration to trap and identify sources and sinks of non-
hydrocarbon gases such as CO2, N2, and commercial helium
accumulation (Ballentine et al. 2002; Gilfillan et al. 2009;
Prinzhofer 2013, Byrne et al. 2016). Similar principles apply
in hydrothermal systems where boiling or other phase
Noble Gases
separation processes can be traced (Sano and Fischer 2013)
and their role in mineral deposition investigated (Kendrick
et al. 2001).
Geochronology
Noble gas accumulation rates within minerals provide a
wealth of information for geochronological applications
throughout cosmochemistry and the Earth sciences. Arguably
the largest impact has been the exploitation of K decay to 40Ar
(t½ = 1250 Ma). Early development of K-Ar was very rapidly
superseded by reactor neutron conversion of K to 39Ar, with
simultaneous measurement of 40Ar-39Ar providing accuracy
and a temporal range applicable “from archaeology to plane-
tary sciences” (Kelley 2002; Jourdan et al. 2016).
A related offshoot to 40Ar-39Ar chronology is the conver-
sion of halogens (F, Cl, Br, I) by neutron reaction to noble gas
isotopes, providing a powerful analytical tool for halogen
determination in samples where other techniques
(particularly for Br and I) do not provide the necessary sensi-
tivity (e.g., Ruzié-Hamilton 2016).
Cosmogenic nuclides provide surface exposure ages on
meteorites and terrestrial surfaces alike (Niedermann 2002;
Dunai et al. 2007; Wieler et al. 2016), while (U-Th)/He takes
advantage of the low closure temperature in minerals (e.g.,
apatite) and provides a thermochronological history that
can delineate the cooling history of rocks in a temperature
range unobtainable by other techniques (Farley 2002, Reiners
et al. 2004).
Summary and Conclusions
Noble gases have a wide array of terrestrial geochemical
applications in addition to great utility in cosmochemistry.
Due to the unique sources of different isotope species, the
noble gases can be readily exploited to differentiate between
atmospheric, mantle, crustal, and extraterrestrial volatile
sources. Furthermore, radiogenic noble gas species can be
used to provide temporal constraints on the timing of geologic
closure events. Together, noble gases form a unique and
extremely diverse set of geochemical tracers that have far-
reaching applications in Earth and planetary sciences.
Cross-References
▶ Cosmogenic Nuclides
▶ Earth’s Continental Crust
▶ Fluid–Rock Interaction
▶ Geothermal Systems
▶ Geochronology and Radiogenic Isotopes
1007
▶ Mantle Geochemistry
▶ Periodic Table
▶ Radon
▶ Water
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Nuclear Magnetic Resonance
Nuclear Magnetic Resonance
Corey D. Pilgrim
Department of Chemistry, University of California, Davis,
Davis, CA, USA
Synonyms
Continuous wave NMR (CW-NMR); Fourier transform NMR
(FT-NMR); Magnetic resonance; NMR; Solid-state NMR
(SSNMR)
Definition
Nuclear magnetic resonance (NMR) is a powerful analytical
tool to both elucidate structure and measure dynamics of
chemical systems. Using a powerful magnet and radio-
frequency (RF) pulses, the spins of nuclei are perturbed and
allowed to relax, generating signals specific to the chemical
environment the nuclei are contained within. A broad range of
nuclei are NMR active (most notably 1H, 13C, and 29Si).
Chemical analysis can be performed on both liquid and
solid samples, with sample volumes ranging from microliters
to milliliters. Analysis can also be performed at variable
temperatures and pressures using specialized probe designs.
Governing Physics
NMR relies principally on the idea that every nucleus has an
inherent spin, which is a type of angular momentum that is not
defined in the classical sense. Classical spin deals with the
rotation of a particle around a central axis – with this rotation
comes an angular momentum vector that points orthogonally
to the direction of the rotation. Nuclear spin has no basis in
rotational motion, yet it still acts as an angular momentum
vector – it is an intrinsic property of the nucleus. Wolfgang
Pauli theorized that electrons have spin of one-half, and it has
since been shown that neutrons and protons also have spin of
one-half (Levitt 2008). Here it can be noted that particles with
half-integer spin (like the electron, proton, and neutron) are
known as “fermions” and particles with integer spin (such as
the photon) are known as “bosons.”
Nuclear spin (also referred to as I) manifests itself in
different isotopes depending on the amount of neutrons and
protons in the nucleus. The two main isotopes of hydrogen,
1
H and 2H, are chemically identical because they share the
same number of protons and electrons (one each), but they
differ by one neutron – this causes the nuclear spin to be
different (I = ½ and 1, respectively). As NMR is the
1009
measurement of species with nuclear spin, I must be greater
than 0 for the nuclei to be considered “NMR active.” I is equal
to 0 when the number of protons and the number of neutrons
in the nucleus are even numbered, such as the case with 32S
(16 protons and 16 neutrons). In all other instances (odd/odd,
odd/even, and even/odd pairings of protons and neutrons), the
nuclei are NMR active (Hore 1995). Nuclei with spin one-half
(1H, 13C, 31P, 29Si, etc.) are the simplest to understand, but
quadrupolar nuclei (I > ½, such as 2H, 17O, 27Al, etc.) exist
and are of great importance in the field of NMR spectroscopy.
There are 2I + 1 degenerate spin states associated with I, as in
the case of classical angular momentum. Thus, for a spin
I = ½ nuclei, there are 2(½) + 1 = 2 degenerate spin states.
NMR spectroscopy probes what is known as the Zeeman
effect. The Zeeman effect occurs when identical spin states
are placed in a magnetic field and split into distinct energy
levels. Particles with angular momentum have a magnetic
moment such that M = gℏI, and these magnetic moments
will align with the strong static field. Here, g is the gyromag-
netic ratio. For a spin one-half system, this causes the spins to
align either parallel or antiparallel to the external magnetic
field, with enough thermal energy in the system (via a
Boltzmann distribution of spins) to cause an almost even
population in each energy level, though there are slightly
more spins in the parallel state – this is why NMR is known
as an insensitive measurement. The slight excess of spin in the
parallel state leads to a magnetic moment, which does not
align perfectly with the external magnetic field (due to the
quantization of the energy levels from the Zeeman effect). N
There is thus some magnetization in the xy-plane, but this
averages to zero due to the precession of the magnetic
moment. The skewed nuclear magnetic moment in the static
field experiences a torque, which will change the direction of
the angular momentum of the nucleus. This torque causes the
spin to move and is known as Larmor precession. This pre-
cession occurs at what is known as the Larmor frequency
(with g the gyromagnetic ratio and B0 the strength of the
external magnetic field):
oL ¼ gB0 (1)
The magnetic moment can be interpreted as a stationary
vector by using the rotating frame approximation, where the
frame of reference for the moment is rotating with the same
frequency and direction as the Larmor frequency in the
xy-plane. This approximation allows the z-magnetization to
be seen as a stationary, vertical vector.
The Larmor frequency equates the strength of the static
magnetic field to the frequency of precession. This frequency
is also the frequency of light that is needed to excite the spins
in the lower energy state to the higher energy spin state,
following Planck’s equation. This excitation is the central
phenomenon in NMR, probing the different energy levels of
1010
the spin states. In large external magnetic fields, the Larmor
frequency of the proton (1H) lies in the range of radio-
frequency (RF) along the electromagnetic spectrum. Thus,
RF waves are used to excite the nuclear spins to probe the
chemical environments of the analytes at hand.
The NMR Experiment
A typical NMR experiment follows this formula:
1. An ensemble of spins is placed inside a static magnetic
field.
2. The sample is irradiated with an RF pulse to focus the
spins.
3. The spins are allowed to relax back to the original orien-
tation, and the induced current is measured.
4. The irradiation is repeated many times to enhance the net
signal.
5. The data is analyzed after the “free induction decay” is
transformed from the time domain to a frequency domain
via a Fourier transform.
Starting off with the first step in the sequence, it is neces-
sary to place the sample into a strong static field such that the
spins split by the Zeeman effect, leading to a net magnetiza-
tion parallel the external field, and the magnetic moments of
the spins precess as previously described.
An RF pulse is sent through a resonant circuit (with
the coil centered on the sample) to start the second step.
This pulse effectively applies a magnetic field (generally
called B1) to the z-directional magnetization vector, Mz,
to focus it into the xy-plane. The pulse is tuned in both
duration and power such that Mz is shifted 90 onto
either the x- or y-axis, which yields the following equa-
tion for the magnetization under the rotating frame
approximation:
M x ðt Þ ¼ M z , 0 (2)
With the magnetization tipped into the x-direction (in the
case above), the pulse is turned off, and the spectrometer is
turned to the receive mode and thus begins the third step. The
magnetic moments start to relax back to their original direc-
tions in the static magnetic field, B0. The magnetization in the
x-direction is given by
Mx ðtÞ ¼ Mz, 0 cos ðoL tÞet=T 2 (3)
Without the magnetic field B1, the magnetic moments
oscillate around the z-axis with the Larmor frequency. The
cosine wave is at a maximum at t = 0, and the exponential is
added as a damping factor to account for the relaxation
Nuclear Magnetic Resonance
(in this case, the damping factor is spin-spin relaxation
which accounts for the T2 constant) back to where the mag-
netization is in the z-direction. As the magnetic moments
oscillate, they induce a current in the coil (as a moving
magnetic field will always induce an electric current). This
current is then measured by the coil that surrounds the
sample and leads to the “free induction decay” or FID,
mentioned above.
Steps 1–3 are repeated multiple times to increase the
signal, as each successive FID builds upon the last to create
one superimposed FID. The signal-to-noise ratio scales with
the square root of the number of scans. Once the desired
signal-to-noise ratio (and signal amplitude) has been
achieved, data collection is finished, and a Fourier transform
of the FID from the time domain (t) into the frequency domain
(O) is implemented:
ð
1
Sð O Þ ¼ sðtÞeiOt dt (4)
0
The Fourier transform is a complex function, as it con-
sists of real and imaginary parts. The real portion of the
spectrum is known as the absorption spectrum, while the
imaginary portion is known as the dispersive spectrum. The
absorption spectrum is the spectrum associated with
FT-NMR analysis, and it is a plot of the different Larmor
frequencies of the nuclei in the ensemble (and the molecule
overall), measured along the x-axis as a difference from the
carrier frequency that was pulsed through the sample. The
Larmor frequency of each nucleus depends on the chemical
environment it experiences – thus, separate signals that
show up on the spectrum indicate separate magnetic envi-
ronments. This fact helps to elucidate the structure of the
chemicals under consideration since the structural settings
give rise to differences in the magnetic environments. Func-
tional groups can be identified; bond distances, bonding,
conformations, and rates of interconversion can all be
measured.
Instrument Design
The NMR instrument can be separated into two main compo-
nents, the magnet and the spectrometer.
The magnet is generally a high-field superconducting coil
that takes liquid helium and liquid nitrogen to maintain the
currents necessary to produce the large magnetic field. Per-
manent magnets do exist, but are lower field and do not
provide as high a resolution as superconducting magnets.
The field strengths of superconducting magnets range from
7 to 23.5 T. The large cylindrical magnet also houses the
sample probe. The probe is usually a tunable LC-type circuit
Nuclear Magnetic Resonance 1011

the data. The receiver splits the signal from the probe into
real and imaginary phases, converts the analog signal to a
digital signal, and compares the signal to a reference fre-
quency. This data is then manipulated, and the spectrum is
analyzed.

The Bloch Equations

The Bloch equations are a description of how the magnetic

moment of the nuclear spins (M) interacts with a static mag-
netic field (B) after the influence of a strong RF pulse, follow-
ing the torque equation (Bloch 1946) and using the vector
cross product:

t¼MxB (5)

The equation is modified to show how the magnetic

moments are changed in the magnetic field, knowing that
M ¼ gℏI (g is once again the gyromagnetic ratio of the
nuclei):

dI ℏ dM 1 dM dM
t¼ℏ ¼ ¼ ! ¼ gm x B (6)
dt ℏg dt g dt dt

Describing the torque in the laboratory frame of reference,

the vectors are defined in three dimensions such that
Nuclear Magnetic Resonance, Fig. 1 A simple solenoid sample coil 0 1 0 1 0 1
M Mx Bx N
d @ xA
M y ¼ g @ M y A x @ By A (7)
dt
that provides the irradiation to the sample nuclei. This Mz Mz Bz
coil is also sensitive enough to measure the induced
current of the nuclei once they start to relax after being The overall magnetic field B is given by a combination of
perturbed (Fig. 1). To achieve the best resolution, the magnetic fields during the NMR experiment. At the initial
magnetic field must be homogeneous around the sample. point in the experiment, there is a strong static magnetic field
Electromagnets, called “shimming coils,” are used to B0 in the z-direction and a smaller R-induced magnetic field
homogenize the magnetic field around the actual sample. B1 in the xy-plane. If the B1 pulse is directed in the
Magnetic fields are generated by the application of cur- x-direction, the B vector becomes
rent to these electromagnets, which constructively or
0 1 0 1
destructively alter the local magnetic field around the Bx B1 cos orf t
sample. The homogenization of the local field leads to @ By A ¼ @ B1 sin orf t A (8)
sharper linewidths and more symmetric peaks. Bz B0
The second half of the instrument, the spectrometer, is
where the RF synthesizers, duplexers, receivers, and con- Substituting Eq. (8) into the torque equation, Eq. (7),
trollers reside. A high-power electrical pulse is sent from the yields
spectrometer to the coil to perturb the nuclei and then is
0 1 0 1 0 1
turned off quickly. One of the most important parts to an M Mx B1 cos orf t
d @ xA
NMR spectrometer is the high-speed duplexer, which is a My ¼ g@ My A x @ B1 sin orf t A (9)
dt
very fast switch that protects the sensitive receiving elec- Mz Mz B0
tronics from high-power pulses. The electronics must be
able to function in rapid succession, as experiments can The g is a scalar, and the Larmor and Rabi frequencies are
occur within microseconds of one another. The modern defined as oL¼ gB0 and oR¼ gB1. Substituting these definitions
receiver relies on digital quadrature detection to process into Eq. (9) yields
1012 Nuclear Magnetic Resonance

0 1
dMx magnetization if one were sitting on a packet rotating at the
B dt C 0 1 0 1 Larmor frequency in the xy-plane.
B C Mx gB1 cos orf t
B dMy C @
B C ¼ My A x @ gB1 sin orf t A Bloch noticed the phenomenon of relaxation when deriv-
B dt C ing these equations (signals decaying along a first-order path
@ dMz A Mz gB0
versus time) and coined the terms longitudinal (T1 or spin-
dt
0 1 0 1 lattice) and transverse (T2 or spin-spin) relaxation times. The
Mx oR cos orf t longitudinal relaxation time T1 is the time that it takes for the
¼ @ My A x @ oR sin orf t A (10) Mz signal to relax back to its original state after being
Mz oL perturbed by the RF pulse. The mechanism for this relaxa-
tion, for the I = 1/2 case, is due to the interaction of the nuclei
which simplifies to with its surrounding rotational and vibrational environ-
0 1 ments. The energy contained in the excited state is dissipated
dMx to neighboring electric and magnetic fields. Quadrupolar
B dt C 0 oL My þ Mz oR sin orf t
1
B C nuclei as well as paramagnetic ions also allow for fast
B dMy C @ A (11)
B C¼ Mz oR cos orf t  oL Mx dissipation of this energy. The transverse relaxation time,
B dt C
@ dMz A Mx oR sin orf t  My oR cos orf t T2, is the time that it takes for the spins to dephase and lose
dt coherence in the xy-plane. This dephasing is an adiabatic
process where the energy is dissipated between spins, and
Equation (11) is the set of coupled differential equations information is lost. As the net magnetization is regained in
known as the Bloch equations in the lab frame. This set is the z-direction but lost in the xy-plane, T1 is always greater
conveniently transformed into the rotating frame of reference, than, or equal to, T2.
where the z-magnetization is stationary, and the frame of The relaxation pathway that yields T1 is a first-order pro-
reference rotates with the Larmor frequency, by applying a cess that affects only Mz:
rotation matrix:
  t
0 1 Mz ðtÞ ¼ Mz, eq  Mz, eq  Mz ð0Þ e T 1 (15)
cos orf t sin orf t 0
Trot ¼ @  sin orf t cos orf t 0A (12) T2 is also a first-order process for Mx and My, so the two
0 0 1 magnetizations are defined as

Redefining new magnetization vectors (u, v, and Mz), Tt Tt

Mx ðtÞ ¼ Mx ð0Þe 2 and My ðtÞ ¼ My ð0Þe 2 (16)
Bloch derived
0 1 0 1 Substituting these into Eq. (14), the rotating Bloch equa-
u Mx tions, with relaxation effects:
@ v A ¼ Trot @ My A
Mz Mz 0 1 0   u 1
0 1 du v orf  oL 
Mx cos orf t þ My sin orf t B dt C B T2 C
B C  
¼ @ Mx sin orf t þ My cos orf t A (13) B dv C B B u o  o  o 
v C
C
B C ¼ M (17)
B dt C B T2 C
rf L z R
Mz @ dMz A @ Mz  M0 A
voR 
dt T1
After substituting in u, v, and Mz to the torque equation and
solving for the derivatives of these new functions, the end
These equations have since been modified to deal with the
result is
kinetics of chemical reactions (McConnell 1958). This
0 1 McConnell formalism has been widely used to determine
du the rates of exchange reactions in solution, typically in the
B dt C 0   1
B C v orf oL case where a complexed ligand around a solvated metal ion
B dv C @ 
B C ¼ u orf  oL  Mz oR A (14) replaces itself with a free ligand in solution. The rate of
B dt C
@ dMz A voR exchange for bound water molecules in solution has also
dt been studied for a myriad of metal centers (Helm and
Merbach 1999). McConnell postulated that on the NMR
This set of coupled differential equations is known as the timescale, magnetization would not only transfer due to relax-
Bloch equations for a rotating frame of reference and accounts ation mechanisms but that nuclei would exchange between
for the perceived oscillation of three directions of sites and affect magnetization transfer as well. For this to
Nuclear Magnetic Resonance 1013

0 1
occur, he made a series of assumptions. The first was that the duB
rate of exchange of magnetization was directly proportional to B dt C
B C
B dvB C
the rate of chemical exchange. The second was that the B C
B dt C
process could either be described as a set of elementary @ dMz, B A
(one-step) reactions. Thus, for a two-site exchange reaction 0dt 1
  uB
between sites A and B (depicting first-order or pseudo-first- vB orf  oL   kB uB þ kB PB uA
B T 2, B C
order reaction conditions), it was formulated that the follow- B   C
B uB orf  oL  Mz, B oR  vB  kB vB þ kB PB vA C
ing equations can be used to depict chemical exchange, ¼B C
B T 2, B C
with the rates of the forward and reverse reaction given by @ M z, B  M 0 , B A
vB oR   kB Mz, B þ kB PB Mz, A
kA and kB, respectively, and from the law of detailed balance, T 1, B

kB ¼ XA ¼ PB where “Xi” is the mole fraction of site “i” and PB

kA XB
(19)
is the ratio of mole fractions.
Now the system of equations is split into two, one set for These equations look daunting but can be easily solved
each of the exchanging sites: using desktop mathematical software to yield spectra, or even
to fit experimental spectra and extract rate parameters.
0 1
duA
B dt C
B C
B dvA C Application to Geochemistry
B C
B dt C
@ dMz, A A
NMR has been used to determine chemical speciation and
0dt   uA 1
vA orf  oL   kA uA þ kA PA uB elucidate the phase and characteristics of minerals (specifically
B T 2, A C using solid-state NMR as a complementary technique to X-ray
B   C
B uA orf  oL  Mz, A oR  vA  kA vA þ kA PA vB C
¼B C crystallography) and has been used to measure reactions that
B T 2, A C
@ M z, A  M 0 , A A occur in the geosphere. The probes have also been engineered to
vA oR   kA Mz, A þ kA PA Mz, B
T 1, A measure systems under extreme environments. Specifically,
(18) high-pressure NMR measurements are now used to understand
the chemistry of the deep Earth. Diamond-anvil cells are most
widely used with solid-state NMR measurements and can reach
N
Nuclear Magnetic Resonance,
Fig. 2 The complexation of boric
acid by catechol as a function of
pressure, leading to coalescence at
pressures of 0.8 GPa
1014
up to 20 GPa in pressure (Meier et al. 2014). Piston cylinder cells
are typically used for solution-state NMR and can reach up to
2.0 GPa in pressure. Solution chemistry at higher pressure is
dominated by solvent effects, although the kinetics of reaction
can sometimes be measured due to coalescence of signals
(Pautler et al. 2014) (Fig. 2).
Conclusion
Nuclear magnetic resonance is an analytical method with
profound potential for geochemistry, both in solid and solu-
tion state. It is sensitive to molecular structure and chemical
dynamics and samples those dynamics at the most important
timescales (microseconds to seconds). It is a relatively insen-
sitive, yet nondestructive, technique that is widely pervasive
in academia and industry. Although solid-state NMR is rela-
tively common in the geochemical and mineralogical litera-
ture, less common is the solution state at geochemical
conditions of high temperatures and pressures, though con-
stant advances are being made in this field.
Cross-References
▶ Analytical Techniques
References
Bloch F (1946) Nuclear induction. Phys Rev 70:460–474
Meier T, Herzig T, Haase J (2014) Moissanite anvil cell design
for giga-pascal nuclear magnetic resonance. Rev Sci Instrum 85:043903
Helm L, Merbach AE (1999) Water exchange on metal ions: experiments
and simulations. Coord Chem Rev 187:151–181
Hore PJ (1995) Nuclear magnetic resonance. Oxford University Press,
Oxford
Levitt MH (2008) Spin dynamics, 2nd edn. Wiley, Chichester
McConnell HM (1958) Reaction rates by nuclear magnetic resonance. J
Chem Phys 28:430–431
Pautler BG, Colla CA, Johnson RL, Klavins P, Harley SJ, Ohlin CA,
Sverjensky DA, Walton JH, Casey WH (2014) A high-pressure NMR
probe for aqueous geochemistry. Angew Chem Int Ed 53:9788–9791
Nucleosynthesis
Jitendra Nath Goswami
Physical Research Laboratory, Ahmedabad, India
Definition
Nucleosynthesis is the creation of all the atomic nuclides
known to us through a variety of processes that started with
Nucleosynthesis
an explosive event, the so-called “Big-Bang” and followed by
nuclear processes that include fusion, neutron capture, proton
capture, energetic particle interactions, and spallation. Fusion
of protons and neutrons led to formation of deuterium,
helium, and very little of lithium. It continues today with
fusion, neutron, and proton capture in large stars, supernova
explosions as well as spallation resulting from collisions
between preexisting nuclei and cosmic rays.
Origin and Abundances of the Elements
The elements and their isotopes, present in our solar system,
and in other stellar systems, are products of nuclear and
energetic processes taking place in various astrophysical
environments, starting with the “Big-Bang,” that marks the
beginning of our universe. The term “Nucleosynthesis”
broadly refers to the various energetic astrophysical processes
involved in the formation of the nuclides known to us.
There are 81 naturally occurring stable elements, starting with
Hydrogen (Z = 1) to Bismuth (Z = 83), along with two unstable
elements, Technetium (Z = 43) and Promethium (Z = 61). In
addition, there are nine other unstable elements that include
Thorium (Z = 90) and Uranium (Z = 92). The total number of
nuclides, both stable and long-lived, is more than 300.
Studies of early solar system solids, present in meteorites,
revealed fossil records of nearly a dozen short-lived,
now-extinct nuclides (e.g., 41Ca, 26Al, 60Fe, 129I, 244Pu) that
are now identified as products of stellar nucleosynthesis. Injec-
tion of these nuclides from an exploding stellar source into the
proto-solar cloud is generally considered as the trigger for the
collapse of the cloud leading to formation of the proto-Sun and
some of the first solar system solids (Goswami and Vanhala
2000). Fossil records (decay products) of these now-extinct
radionuclides are preserved in early solar system solids.
Formation of the First Nuclides
Synthesis of the nuclides, in particular, H and He, dates back to
the beginning of our universe, following the so-called “Big-
Bang” event. The extremely high energy density during the
very early stages of our universe provided a high temperature
(>1010 K) radiation environment dominated by energetic
gamma ray photons. The equivalence of energy and matter
(E = mc2) led to formation of a rapidly changing populations
of subatomic particles, in particular, protons and neutrons, as
well as mu-meson, electron, and their antiparticles in such an
environment. Although formation and destruction reactions are
in equilibrium at this stage, protons will be more abundant
because of their lower mass. The formation of deuterons (2H)
took place after temperature dropped significantly and
followed by formation of 3H, 3He, and 4He. This led to a
Nucleosynthesis
Nucleosynthesis, Fig. 1 Hydrogen Burning (PP1 & PP2 Chains)
decrease in abundance of neutrons resulting in lower abun-
dances of 7Li and 7Be. Formation of the first nuclides in the
early universe followed two dominant pathways, designated
PP1 and PP2 chains and, a minor one, the PP3 chain.
A proposal made by George Gamow and his colleagues in late
1940s (Alpher et al. 1948) suggested that neutrons will constitute
a significant fraction of matter following the big-bang event and
facilitate production of elements, starting with deuteron, through
successive neutron capture. The absence of stable nuclides with
mass 5 and 8 made the suggestion untenable.
It was also realized at that time that the energy radiated by
the Sun, attributed to its gravitational collapse, cannot sustain
solar luminosity for more than tens of millions years, an
extremely small duration compared to the age of the Sun,
inferred to be in excess of 4 billion years, based on geological
evidences. The suggestion that nuclear reactions in stellar
interior can replenish energy radiated by the star was based
on studies on nuclear transmutation by Hans Bethe (1939),
who also proposed the reactions responsible for energy gen-
eration in stars and for the Sun in particular (Fig. 1).
Synthesis of Nuclides in Stellar Interior
Two seminal papers in the field of nucleosynthesis, published
in 1957 by Burbidge, E. M. et al. and A. G. W. Cameron,
provided a broad outline of the nuclear processes taking place
in stellar interior and also during explosive stellar events (e.g.,
supernova) leading to formation of the nuclides. This was
preceded by the suggestion that nuclear reactions in stars can
lead to formation of chemical elements heavier than helium
(Hoyle 1946 1954). It was also established that a few of the
low mass nuclides (lithium, beryllium, and boron) are prod-
ucts of energetic particle interactions in space environment
(Reeves 1994). These early studies of nucleosynthesis were
followed by a large volume of work taking into account the
finer details of various stellar sites and nucleosynthesis
1015
processes. Explaining the abundances of the elements as
well as their isotopes in our Solar System was the main
focus and these are now known with very high accuracy
(see e.g., Anders and Grevesse 1989; Lodders 2010). The
Nobel lectures by Penzias (1979) and Fowler (1984) provide
a very engrossing description of the development in the field
of nucleosynthesis.
Even though a variety of stellar sources have contributed
towards the formation of the Solar System, the very uniform
elemental and isotopic composition of solar system matter
suggest an extremely well-mixed proto-solar cloud whose
collapse led to formation of our Solar System. An explosive
stellar event, a supernova, is the most probable trigger for this
collapse (Goswami and Vanhala 2000).
A new dimension was added to the field of stellar
nucleosynthesis following the identification of “stardust”
(microscopic interstellar grains), refractory in nature, in prim-
itive meteorites (Anders and Zinner 1993). These grains,
nano- to micrometer in size, reveal large isotopic anomalies,
relative to average solar system composition and host records
of stellar environments in their formation sites (Asymptotic
Giant Branch (AGB) star, Novae, Supernovae). This provides
a gateway for studies of nucleosynthesis processes in specific
stellar environment, beyond the realm of the Solar System
(see also, Meyer and Zinner 2006).
Synthesis of the naturally occurring elements and their iso-
topes present in the Solar System solids may be divided into
three broad segments: primordial nucleosynthesis (H, He),
energetic particle (cosmic ray) interactions (Li, Be, B), and N
stellar nucleosynthesis (C and heavier elements). A concise
description of these processes is presented in the following.
Primordial Nucleosynthesis
Our ideas of primordial nucleosynthesis are based on the
standard Big-Bang model of our universe that suggests for-
mation of hydrogen and nearly all of helium within the first
few minutes following this explosive event. The agreement
between the predicted relative abundances of the first nuclides
(1H, 2H, 3He, 4He) that formed in the early universe, with their
observed abundances at present, in regions of our universe,
which have not experienced much of chemical evolution,
supports this view (Peebles 1971). A very refreshing discus-
sion is also provided by S. Weinberg (1977).
Cosmic Ray Spallation
The next group of elements, Li, Be, and B, are not primary
product of stellar nucleosynthesis. These elements are
destroyed easily in energetic nuclear processes taking place
in stellar interiors. They are produced by interaction of
1016
energetic particles present in interstellar space (Galactic Cos-
mic Rays) with ambient interstellar matter. Collisions of ener-
getic carbon and oxygen ions in cosmic rays with hydrogen
atoms in interstellar medium lead to production of these three
elements (see, e.g., Reeves 1994). The source of energetic
cosmic rays could be an exploding star (a supernova) or
interstellar matter accelerated by supernova shocks. A small
fraction of Li is also contributed from primordial nucleosyn-
thesis, while stellar nucleosynthesis adds to the inventory of
both 7Li and 11Be.
Stellar Nucleosynthesis
Energy generation in the interior of a star is driven by “nuclear
fusion,” starting with fusion of hydrogen to form helium
(4He), the dominant mode of energy production in stars
(Bethe 1939). The fusion chain of exothermic reactions con-
tinues with successive burning of He, C, O, and Si in stellar
interior, leading to formation of iron (56Fe), beyond which
fusion become an endothermic reaction.
Formation of elements beyond the iron group takes place
through capture of neutrons by preexisting nuclides and fol-
lows two distinct paths, the “s” (slow) or “r” (rapid) process.
The proton-rich nuclides that are away from the line of beta-
stability are produced by photo-nuclear reactions, the “p”
process. An outline of the various nucleosynthesis processes,
involving burning of seed nuclides, starting with Hydrogen, is
presented in the following.
Hydrogen Burning
There are several pathways for fusion of hydrogen to form
helium when the internal temperature of the star exceeds
107 K, sufficient to overcome the coulomb barrier. In solar
mass stars, it proceeds via the proton-proton (PP-I) chain:
1
Hþ1 H ! 2 H þ g;2 Hþ1 H ! 3 He þ g;3 Heþ3 He! 4 He þ 21 H
Even though produced in small amount, 3He can react
through different channels (PP-II and PP-III), yielding 7Be,
7
Li, and 8B as intermediate products that finally end up as
4
He. In massive star with higher core temperature, conversion
of H to He can proceed via C─N─O cycle with 12C, present
initially in the star acting as a catalyst. 14N is a major product of
the CNO cycle along with minor amounts of 13C,15N and 17O.
Helium Burning
Gradual exhaustion of hydrogen in the core of the star will
make hydrogen burning weaker, leading to contraction of the
Nucleosynthesis
core, and make it dense enough to raise the temperature of the
Helium-rich core to ~108 K that can initiate Helium burning.
The most important reaction at this stage is the “triple-alpha”
reaction that converts 4He to 12C. Several other important
nuclides, 16O, 18O, 22Ne, 25Mg, are also produced during
this stage via successive exothermic alpha capture by 14N,
an end product of hydrogen burning through C─N─O cycle:
4
He þ 4 He þ 4He ! 12 C þ g;
12
C þ 4 He ! 16 Oþ4 He;
14
N þ4 He ! 18 F þ g;
18
F !18 O þ eþ þ n;
18
O þ4 He ! 22 Ne þ g;
22
Ne þ4 He ! 25 Mg þ n
Successive capture of alpha particles by 14N, end product
of hydrogen burning through the CNO cycle, also leads to
production of 18O and 22Ne. For stars with mass less than
8 solar mass, He burning marks the last stage of energy
generation process that leads to a stellar core enriched in
carbon and oxygen.
Carbon and Oxygen Burning
Nuclear burning in stars with mass less than 8 solar mass
cannot raise the core temperature needed for nuclear burning
beyond helium. They end their life as a cool and dense white
dwarf. However, in more massive stars, the core temperature
is high enough (109 K) to initiate He burning, followed by
successive burning of carbon and oxygen. This leads to pro-
duction of 20Ne, 23Na, and 24Mg via carbon burning, while
28
Si, 31P, and 32Si are products of oxygen burning. Synthesis
of elements at this stage can also follow production via
capture of alpha (4He) particle and proton by carbon and
oxygen that can lead to synthesis of nearly all the elements
between Ne and Ar.
Silicon Burning and the “e” (Equilibrium) Process
Silicon burning, the last stage of nuclear fusion in stellar
interior, takes place when the core temperature reaches
~3
109 K. The high temperature environment leads to
endothermic photo-disintegration of preexisting nuclei
around silicon via (g, a) reaction, prior to initiation of the
fusion process. This provides a copious source of alpha
particles that are captured by nuclides having intermediate
masses leading to formation of precursors of the iron group
nuclides. Interactions among the nuclides – alpha particles,
Nucleosynthesis
proton, and neutrons – lead to formation of the iron group
nuclides with equilibrium abundances; the nuclides having
higher binding energy being more abundant. The relative
abundances of the iron group nuclides during the “e”
(equilibrium) process depend on the nature of both strong
and weak nuclear interactions, in particular, electron capture
and neutrino emission.
Explosive Nucleosynthesis
The end of silicon burning will leave a massive star with a
core composed primarily of Fe-group elements that will be
surrounded by layers enriched with elements (H, He, C, O,
Ne, Si) that are products of earlier evolutionary stages of the
star. Exhaustion of nuclear energy source in the interior of the
star will lead to collapse of the stellar core that will trigger an
explosion (a supernova event) resulting in expulsion of the
outer layers of the star as well as further processing of material
in the inner layers of the star. This transient phase of nuclide
processing is termed as “explosive nucleosynthesis.” The
nonequilibrium nature of this phase leads to synthesis of
nuclides with very different abundance pattern than those
produced in the slow hydrostatic burning inside a stellar
object, even though the seed nuclides are the same. The
abundance of a sizable number of intermediate mass nuclides
in the solar system can be explained as products of “explosive
nucleosynthesis.”
A low mass star, which generally ends its life as a white
dwarf, may also suffer a catastrophic end. This happens if the
white dwarf has a companion from which it accretes matter
and its mass exceeds a critical mass and become unstable and
explodes. Such an explosion is termed as a Type-I supernova
to distinguish it from the explosion of high mass massive
stars, termed as Type-II supernova. White dwarfs are primar-
ily left over carbon- and oxygen-rich cores of low mass stars,
and their explosive end primarily leads to synthesis of iron
group of nuclides (Fe, Co, Ni).
Nucleosynthesis,
Fig. 2 Pathways for S (slow: red)
and R (rapid: blue) processes for
synthesis of elements (isotopes)
beyond the iron group
1017
Elements Beyond the Iron Group
Synthesis beyond the iron group of elements follows two
processes that are termed as r-process, involving rapid neu-
tron capture, and the s-process, characterized by slow neutron
capture.
r-Process
The r-process is effective when the neutron densities are high
enough to facilitate build-up of heavier elements beyond iron
via successive neutron capture by the Fe group as well as
other heavy elements. Even though these elements will be far
removed from the line of b-stability, as long as neutron
capture rate exceed the beta decay rates, they will eventually
suffer successive beta decay and end up as stable high mass
nuclide (Fig. 2).
s-Process
Unlike the relatively fast r-process, the slow neutron capture
takes place in stellar environments that provide relatively low
flux of neutrons over a significant period of time. In such a
setting, the neutron capture timescales could be longer than or
comparable to beta decay timescales and bypassing unstable
neutron-rich nuclide is not possible as in the r-process. The
main sources of neutrons for the s-process are the two reac-
tions: 13C (a, n) 16O and 22Ne (a, n) 25Mg; 22Ne is a product of
successive alpha capture by 14N. Thus, both the seed nuclides
(13C and 14N) are products of hydrogen burning via C─N─O
cycle. These reactions take place in low mass stars during the N
red-giant phase of their evolution, following H and He burn-
ing, when nuclear burning takes place in a thin He shell
between the carbon- and oxygen-rich core and the H-rich
outer envelope. He-burning in massive stars is another plau-
sible site for s-process synthesis. Spectroscopic evidence for
the presence of the unstable element Technetium in low mass
stars (red giant; Merrill 1952) also makes them a plausible site
for s-process synthesis providing an important link in the
s-process path around mass 100.
1018
1.E+11
Primordial
Nucleosynthesis
1.E+9
1.E+7
1.E+5
(Si = 106)
1.E+3
1.E+1
Cosmic ray
spallation
1.E-1
1.E-3
0 25 50 75 100
Mass Number
Nucleosynthesis, Fig. 3 Abundances of nuclides
p-Process
A group of proton-rich stable nuclides having very low abun-
dances cannot be produced by the nucleosynthesis processes
outlined above. These are stable neutron-deficient nuclides,
heavier than iron, which are observed only in solar system
matter and grouped as product of p-process, as they were
initially thought to be product of proton capture. However,
there is no suitable astrophysical site where proton capture
(p, g) may dominate over photonuclear reaction like (g, n) or
(g, p). These nuclides are generally considered to be products
of photonuclear reaction involving s- and r-process nuclides
that lead to formation of proton-rich isotopes which finally
end up as proton-rich stable nuclides via (g, p) and (g, a)
reactions (Arnould and Goriely 2003) (Fig. 3).
Summary
Our understanding of stellar nucleosynthesis processes, since
the time of the early work by Burbidge et al. (1957) and
Cameron (1957), that attempted to explain the solar system
abundances of nuclides compiled by Suess and Urey (1956),
based on studies of meteorites as well as spectroscopic
observation of the Sun, has improved significantly. It is now
possible to identify specific nucleosynthesis processes
Nucleosynthesis
Odd Mass
Even Mass
125 150 175 200 225 250
responsible for synthesis of nuclides present in the solar
system and also understand the lower abundances of the odd
mass nuclides.
Advances in studies of nucleosynthesis allow one to predict
abundance pattern of the Fe-group nuclei and beyond, with a
fair degree of accuracy, by considering contributions from both
Type-I and type II supernova (Timmes et al. 1995). The
s-process systematics can lead to the abundance peaks beyond
the iron group, at mass numbers around 84, 138, and 208, with
magic neutron numbers 50, 82, and 126, respectively. Another
group of heavy nuclides, at mass numbers, 80, 130, and
195, preceding the s-process peaks, can be explained by con-
sidering r-process systematics (Fowler 1984). A general dis-
cussion of various nucleosynthesis processes and their
connection to solar system abundances of nuclides is provided
by Cox (1989). Several other areas related to field of nucleo-
synthesis include chemical evolution of our galaxy that deals
with star formation rates, stellar evolution models and stellar
nucleosynthesis (see, e.g., Clayton 1988) and cosmo-chronol-
ogy (Symbalisty and Schramm 1981), timescales of nucleo-
synthesis of the radioactive nuclides present in the early solar
system and, also present day solar system.
A major impetus for studies in Stellar nucleosynthesis
came following the discovery of microscopic grains of silicon
carbide, graphite, and diamonds in primitive meteorites with
Nutrients 1019

large isotopic anomalies, relative to solar system solids (see Peebles PJ (1971) Physical cosmology. Princeton University Press,
e.g., Meyer and Zinner 2006). The stellar origin of these Princeton
Penzias AA (1979) The origin of the elements. Science 205:549–554
grains can be inferred from the very different abundance Reeves H (1994) On the origin of the light elements (Z < 6). Rev Mod
pattern of H and C isotopes, relative to solar system matter, Phys 66:193–216
thus hosting nucleosynthesis records that are not homoge- Suess HE, Urey HC (1956) Abundances of the elements. Rev Mod Phys
nized as in the case of our solar system. 28:53–74
Symbalisty EMD, Schramm DN (1981) Nucleocosmochronology. Rep
Prog Phys 44:293–328
Timmes FX, Wooseley SE, Weaver TA (1995) Galactic chemical evolu-
tion: helium through Zinc. Astrophys J 98(Suppl):617–658
Cross-References Weinberg S (1977) The first three minutes, 1993rd edn. Basic Books,
New York, 203 pp
▶ Atomic Number, Mass Number, and Isotopes
▶ Carbon Isotopes
▶ Cosmic Elemental Abundances
▶ Cosmogenic Nuclides Nutrients
▶ Hydrogen Isotopes
▶ Meteorites J. A. Brandes
▶ Presolar Grains Skidaway Institute of Oceanography and Department
▶ Stable Isotope Geochemistry of Marine Science, University of Georgia, Savannah,
GA, USA

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Synonyms
Alpher RA, Bethe HA, Gamow G (1948) The origin of chemical ele-
ments. Phys Rev 73:803
Anders E, Grevesse N (1989) Abundances of the elements: meteoritic Bioessential compounds; Essential elements
and solar. Geochim Cosmochim Acta 53:197–214
Anders E, Zinner E (1993) Interstellar grains in primitive meteorites.
Meteoritics 28:490–514
Arnould M, Goriely S (2003) The p-process of stellar nucleosynthesis:
Definition
astrophysics and nuclear physics status. Phys Rep 384:1–84 N
Bethe HA (1939) Energy production in stars. Phys Rev 55:103 Nutrients are elements or compounds used by organisms in
Burbidge EM, Burbidge GR, Fowler WA, Hoyle F (1957) Synthesis of the production of biomass, cellular function, or related struc-
the elements in stars. Rev Mod Phys 29:547–650
Cameron AGW (1957) Stellar evolution, nuclear astrophysics and
tural material.
nucleogenesis. Chalk River Report, Atomic Energy of Canada Ltd.,
CRL-41; see also Publ Astron Soc Pacific 69:201–222
Clayton DD (1988) Stellar nucleosynthesis and chemical evolution
of the solar neighbourhood. In: Kerridge JF, Matthews MS (eds)
Introduction
Meteorites and the early solar system. Arizona University Press,
Tucson, pp 1021–1062 Nutrients are elements or compounds used by organisms in
Cox PA (1989) The elements: their origin, abundances and distributions. the production of biomass, cellular function, or related struc-
Oxford University Press, Oxford, 207 pp
Fowler WA (1984) The quest for the origin of the elements. Science
tural material (Odum 1959). Nutrients that are required for
226:922–935 proper cellular functioning are described as essential nutri-
Goswami JN, Vanhala HAT (2000) Extinct nuclides and the formation of ents. Traditionally, major essential nutrients (utilized by
the solar system. In: Mannings V, Boss A, Russell S (eds) Protostar & organisms in approximate percentage or greater abundances
planets IV. Arizona University Press, pp 965–996
Hoyle F (1946) The synthesis of the elements from hydrogen. Mon Not
in biomass) have been considered to be N, P, and S. However,
R Astron Soc 106:343–383 essential trace nutrients are also required for growth and
Hoyle F (1954) On nuclear reactions occurring in very hot proper cellular function; these include Fe, Co, Zn, Ni, V,
STARS. I. The synthesis of elements from carbon to nickel. and many others (see Fig. 1). Part of what defines an element
Astrophys J Suppl 1:121–146
Lodders K (2010) Solar system abundances of the elements. In:
as a nutrient is its potential for limitation, which is the reason
Goswami A, Reddy BE (eds) Principles and perspective in cosmo- that O and H are not typically defined as nutrients, even
chemistry. Springer, Berlin, pp 379–417 though they are required for the production of biomass, and
Merrill PW (1952) Spectroscopic observations of stars of class water is a requirement for all known life. In addition to
S. Astrophys J 116:21–26
Meyer BS, Zinner E (2006) In: Lauretta DS, McSween HY Jr (eds)
elements used in biomass, inorganic ions such as Cl,
Meteorites and the early solar system II. University of Arizona Mg2+, Na+, and K+ are also required for cellular function
Press, Tucson, pp 69–108 and may be considered essential nutrients. Finally, some
1020 Nutrients

Nutrients, Fig. 1 Shaded

elements are those identified as 1 H 2 He
nutrients or involved in cellular
function 3 Li 4 Be 5 B 6 C 7 N 8 O 9 F 10 Ne

11 Na Mg12 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar

19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr Mn Fe Co Ni
25 26 27 28 29 Cu Zn Ga Ge As Se
30 31 32 33 34 35 Br 36 Kr

37 Rb Sr38 39 Y 40 Zr Nb Mo Tc
41 42 43 44 Ru Rh Pd Ag Cd
45 46 47 48 49 In 50 Sn Sb Te
51 52 53 I 54 Xe

55 Cs Ba56
* 71 Lu 72 Hf 73 Ta 74 W 75 Re Os
76 77 Ir 78 Pt 79 Au Hg
80 81 Tl 82 Pb 83 Bi 84 Po 85 At Rn 86

87 Fr 88 Ra ** 103 Lr 104 Rf Db Sg Bh Hs Mt Ds Rg Cn
105 106 107 108 109 110 111 112 113
Uut 114
Uuq 115
Uup 116
Uuh 117
Uus 118
Uuo

57 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho
58 59 60 61 62 63 64 65 66 67 68 Er Tm Yb
69 70

**

89 Ac Th Pa
90 91 92 U 93 Np Pu Am Cm Bk Cf
94 95 96 97 98 99 Es Fm Md No
100 101 102

organisms require Si to form inorganic shells and will be
growth limited in silicate-depleted environments.
Another important aspect of a nutrient is its chemical form
and consequent bioavailability. Different species may have
very different abilities to access the nutrients in their environ-
ment and may require that a nutrient be in a specific form. For
example, ocean waters contain over half a millimole per liter
of nitrogen, far in excess of need if all were available for
marine organisms. However, most of this N is in the form of
dissolved N2 gas, which, with a very strong triple bond, is not
accessible by most organisms for their growth needs. Only
organisms with specialized enzymatic systems that can
reduce N2 and form organic nitrogen forms can access this
pool (Sohm et al. 2011). Furthermore, not all primary pro-
ducers can access N in its oxidized forms (e.g., NO3 or
NO2). Similarly, much of the supply of Fe to the ocean
away from continental margins is in the form of insoluble
iron oxides that are considered unavailable to primary pro-
ducers without chemical reduction to more soluble com-
pounds (Norman et al. 2014). Several significant taxa of
marine primary producers require Co in the organically
bound form of cobalamin (vitamin B-12) in order to use it
(Moore et al. 2013).
Nutrient Limitation
The concept of nutrient limitation dates back to the “law of the
minimum” developed by Justus von Liebig and expanded
upon by FF Blackman (von Liebig 1840; Blackman 1905;
Odum 1959). Von Liebig postulated that growth of plants was
limited by the scarcest resource and not by total resources.
This has been refined to indicate that scarcity is in relation to
the relative availability of other nutrients. The most famous of
such relationships is the “Redfield ratio” developed by Alfred
Redfield (1934). Redfield found that the proportions of
carbon to nitrogen to phosphorus used by marine primary
producers were 106C:16N:1P. As there is typically less than
a 16:1 stoichiometry in bioavailable N vs bioavailable P, N is
thought to be the primary limiting major nutrient over long
time scales in the ocean. However, there are major regions of
the surface ocean (where primary productivity takes place)
that contain significant amounts of both bioavailable N and
P. These are described as “high-nutrient low-chlorophyll”
(HNLC) waters and are limited by the trace nutrient Fe
(Moore et al. 2013). In freshwater environments, P is gener-
ally thought of as the primary limiting nutrient, especially
since the implementation of P-limiting policies to combat
eutrophication (Schindler et al. 2016).
There is also considerable evidence for nutrient co-limitation
in the environment, where two or more nutrients are found in
limiting concentrations. Several regions of the global surface
ocean are nearly as depleted in P as N. Addition of only N to
these environments results in only a small increase in biomass
as compare to addition of both N and P. Other co-limiting
nutrient pairs found in the environment have been N, P and
Fe, N and Co, Fe and Si, and Fe and Zn (Moore et al. 2013).
Nutrient availability can differ greatly between environ-
ments. While Ca and S are plentiful in marine ecosystems,
they can be limiting in terrestrial forests and croplands. Such
limitation can be exacerbated by enhanced leaching caused by
acid rain (St. Clair et al. 2008) and also by the release of toxic
elements such as Al during leaching events that may prevent
the uptake of Ca (Schaberg et al. 2001).
Organisms can in some cases ameliorate nutrient limitation
in their environment. Although the Redfield ratio appears
remarkably robust over most of the ocean (Anderson and
Sarmiento 1994), individual organisms have shown a wide
range of nutrient uptake ratios under simulated limiting con-
ditions (Bertilsson et al. 2003), either by proportional reduc-
tion in the cellular production of high N content proteins or
P-rich phospholipids or by the substitution of metals in
Nutrients
enzymatic systems (e.g., Co for Zn) (Moore et al. 2013). Over
longer time scales, some organisms can evolve to reduce their
relative requirements for certain elements (e.g., substituting
S for P in membrane lipids) (van Mooy et al. 2009). In
addition, organisms employ a wide range of strategies for
collecting, storing, and concentrating scarce nutrient
resources. These include storage as insoluble intracellular
pools (polyphosphates) (Diaz et al. 2016), production of
extracellular organic compounds to chelate and solubilize
metals (Hopkinson and Morel 2009), and physical movement
to gather nutrients from subsurface regions.
Nutrient Proxies
Patterns of nutrient availability in the surface ocean have been
investigated using proxies as indicators of past biological
productivity and CO2 uptake (Deutch and Weber 2012).
Commonly used proxies include Cd:Ca ratios in foraminifera
shells (for P) (Boyle 1988) and the 15N of organic N in
sediments, biomarkers, and encased in diatom frustules (for
bioavailable N and N-cycling processes) (Ren et al. 2012).
Such studies have indicated significant shifts in global nutri-
ent patterns during glacial maxima (Straub et al. 2013). The
present-day environment is experiencing a large (2–3
pre-
industrial levels) anthropogenic input of N and P from agri-
cultural and industrial sources (Codispoti 2007). This is
subsequently exported through runoff and riverine transport
to coastal oceanic environments, resulting in the shift of
several from oligotrophic (primary producer growth rates
and biomass limited by nutrient availability) to eutrophic
(containing high primary producer growth rates and biomass
limited by light availability or other factors) states (Fulweiler
et al. 2012).
Summary
Nutrients comprise a subset of elements and compounds
required for life. Environments typically have one or more
nutrients that may be considered as limiting or potentially
limiting to organism growth. However many organisms can
mitigate such limitations by adjustment of required nutrient
ratios or substitution of a more abundant nutrient for a more
limiting one.
Cross-References
▶ Biogeochemistry
▶ Biological Pump
1021
▶ Carbon
▶ Iron
▶ Nitrogen
▶ Paleoproductivity
▶ Phosphorus
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