Geochrmrca n Cosmochlmrca Acfa Vol. 51, pp. 1727-1741 0016-7037/87/$3.

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0 Pergamon Journals Ltd.1987. Printedin U.S.A.

The systematics of lithium abundances in young volcanic rocks*

JEFFREY G. RYAN and CHARLESH. LANGMUIR
Lament-Doherty Geological Observatory, Palisades, NY 10964, U.S.A.

(Received August 22, 1986; accepted in revised form April 1, 1987)

Abstract-Lithium is a moderately incompatible trace element in magmatic systems. High precision analyses
for lithium conducted on well characterized suites of MORB and ocean island basalts suggest a bulk distribution
coefficient of 0.25-0.35 and behavior which is similar to Yb during low pressure fractionation and V during
melting, as long as garnet is not an important residual phase. Data for peridotites and basalts suggest a
mantle lithium content of about 1.9 ppm and show that significant concentrations of lithium reside in
olivine and orthopyroxene, resulting in unusual inter-mineral partitioning of Li and complex relationships
between lithium and other incompatible trace elements.
The lithium abundances of arc basaits are similar to those of MORB, but their Li/Yb ratios are considerably
higher. The high Li/Yb suggests the addition of a Li-rich component to arc sources; relatively low Yb
abundances are consistent with the derivation of some arc magmas by larger extents of melting or from a
more depleted source than MORB. Although Li is enriched at arcs, K is enriched more, leading to elevated
K/Li ratios in arc volcanics. The high K/Li and relatively low La/Yb of primitive arc basalts requires either
incorporation of altered ocean crust into arc magma sources, or selective removal of K and Li from subducted
sediments. Bulk incorporation of sediments alone does not explain the Li systematics.
Data from primitive MORB indicate a relatively low (3-4 ppm) Li content for new oceanic crust. Thus,
the Li flux from the ocean crust is probably <l X 10” p/yr, and the oceanic crust may not be an important
net source in the oceanic budget of lithium.

INTRODUCTION ing magmatic processes and of its general distribution

ONE OFTHE MAJORproblems of interest to geochemists
is determining what processes control the chemical
variations observed in young volcanic rocks, and dis-
cerning how these processes relate to the plate tectonic
cycle. Trace element data are useful in this regard as
they can help to distinguish among the various pro-
cesses. In Fig. 1, elements are categorized in terms of
their incompatibility with respect to crystal/liquid
equilibria, their solubility in hydrothermal fluids and
their concentrations in sediments. Elements with dis-
tinctive sets of properties are necessary to identify those
components or processes that have contributed signif-
icantly to the composition of a volcanic rock. For ex-
ample, concentrations of elements of consistently high
mobility, such as potassium and rubidium, cannot by
themselves distinguish between the effects of crystal/
liquid enrichment processes, addition of fluids, or ad-
dition of sediments.
In this context lithium, the lightest of the alkali met-
als, possesses a set of geochemical properties that are
potentially useful. Like K and Rb, Li is concentrated
in sediments relative to mafic igneous rocks and is sol-
uble in hydrothermal fluids. In contrast to these ele-
ments, Li may partition strongly into crystals during
crystal/liquid fractionation because of its small ionic
radius. Thus a ratio such as K/Li may be a sensitive
indicator of the relative importance of a given process
in the petrogenesis of igneous rock suites. Because of
lithium’s potential utility, we have analyzed rocks from
a variety of regions and tectonic settings to gain a
quantitative understanding of lithium’s behavior dur-
* LDGO contribution No. 4144.
1727
in the mantle and the crust.
PREVIOUS WORK
A substantial data base exists for lithium in meteorites, par-
ticularly for chondrites and eucrites (NICHIPORUK and
MOORE, 1970, 1974; MURTV et al. 1983; TERA et al., 1970).
In terrestrial samples JAGOUTZet al. (1979) measured up to
2 ppm Li in primitive ultramafic nodules. Thompson
(THOMPSON,1973; THOMPSON et al., 1972; BRYAN et al.,
1979; FREY et al.. 1974) and BAILEY and GWOZDZ (1978)
have published lithium data on both fresh and altered oceanic
hasalts and gabbros. The median Li content of MORBs ex-
amined in these studies lay between 5 and 6 ppm.
The behavior of lithium during hydrothermal processes has
been investigated experimentally and inferred from measure-
ments at hot springs. SEYFFUED et al. (1984) showed that Li.
like K, is highly soluble at temperatures in excess of 350°C.
MICHARD et al. (I 984) measured lithium concentrations of
up to 5 ppm in hydrothermal vent waters at 13”N on the East
Pacific Rise, and VON DAMM et al. (1985) observed over 9
ppm Li in 350°C vent waters from 21”N on the EPR. The
K/Li ratios of these vent waters average about 150, similar
to values observed in fresh MORB. Altered oceanic basalts
and spilites can contain 75 ppm Li or more (SHAW et al.,
1977; DONNELLYet al., 1980), though the upper 500 m of
old ocean crust on average probably contains only about IO
ppm Li (DONNELLYet al., 1980; EMMERMANN and PUCHELT,
1980). Lithium has also been measured extensively in sedi-
ments. For example, DEAN and PARDUHN( 1983) report lith-
ium concentrations for marine sediments ranging between 10
and 150 ppm. Based on a survey of sedimentary Li data,
HOLLAND(1980) showed lithium to be significantly enriched
in sediments relative to average igneous rock. K/Li ratios in
both sediments and altered crust average around 500, higher
than those observed in hot spring waters. Clearly rock alter-
ation processes other than hydrothermal interactions are frac-
tionating K from Li on the seafloor, and enriching them both
relative to fresh basalt. Differential incorporation of K over
Li during clay formation or late stage interactions with seawater
1728 J. G. Ryan and C. H. Langmuir

LOW MODERAfE HIGH in contact with the sample solution were replaced by parts
used exclusively for lithium analyses. As a final check on po-
tential contamination, a scan of ultra&an distilled water was
made around the lithium wavelength at the most sensitive
settings. These extensive precautions successfully eliminated
HYDROTHERMAL the contamination problem.
SOLuBILITY The analytical wavelength was 6708 A. The detection limit
for our procedure is 0.05 ppm Li in the rock. AS determined
by replicate analyses, the precision is +2%. When compared
SEDIMENTARY
to atomic absorption determinations of Li at LDGO, DCP
data are the same within 4% save at the lowest Li concentra-
tions. For a variety of samples and rock standards (Table I),
DCP lithium data are identical within error to neutron acti-
FIG. 1. Chart of elemental behavior in crystal/liquid, hy-
vation and the USGS star&d values tabulated in FLANAGAN
drothermal, and sedimentary systems.
(1973). Our data differ substanWly from conventional emis-
sion spectrometry data.

(K/Li > 2000) are both possible causes, but little data exists
to support either possibility.
In mineral/melt systems, however, lithium may not behave
like other alkalis. The ionic radius of Li+ is similar to that of
Mg’+, (0.76 A)making it theoretically capable of substituting
into mal% mineral phases. NAGASAWAand SCHNETZLER
(1971), MATSUI ef al. (1977), and YURIMOTOand SUENO
(1984) have published multi-element partitioning studies of
basaits and andesit& which include data for the mineral/melt
partitioning of lithium in olivine, piagioclase, pyroxene, and
other phases. The results of these studies seem to support the
idea that Li is more compatibk in basalt& minerals than other
alkalis, although published plutition coefficients for olivine
show a substantial range (.03-0.5).
ANALYTICAL CONSIDERATIONS
AND TECHNIQUES
Because the total range of lithium contents in basalts is
small, a high precision analytical technique is essential to study
its behavior. All samples in this study were analyzed using the
direct current plasma emission spectrometer at Lamont-Do-
herty; some comparisons are made to earlier data obtained at
Lament by atomic absorption. Powdersweredissolved using
a concentrated HF:HClO, mixture. Care was necessary during
dissolution because lithium forms insoluble fluorides, even in
the presence of small amounts of HQO,. Small amounts of
such residue can cause up to a factor of two decmase in mea-
sured lithium. To assure 100% dissolutions, an HCIO,-rich
solvent (5: I HF:HCIO, for MORB, 4: I for alkalic rocks) was
Used.
Because complete recovery of Li was essential, we tested
three of the samples by a method of double additions. Three
aliquots of a sample powder were prepared, two spiked with
di&rent amounts oflithium. A&r dissolution of each aliquot,
lithium contents of each of the solutions were measured by
method of additions. The Li contents of each set of nine so-
lutions should be linear on a plot of gm/ml of Li added versus
signal intensity, and the intercept should yield the lithium
contents of the rocks. Consistency among all the values de-
pends upon 100% sample recovery. Values obtained by this
method demonstrated IO@%recovery for our technique.
After dissolution, samples were dried, redissolved in 4 N
HNO, plus a few drops of perchloric acid, then diluted in 0.8
N HNO, for analysis. Normal sample size was 250 mg. For
REsULls
The samples selected represent a variety of com-
positions, geographic areas, and tectonic settings. Fig-
ure 2 shows sample locations. For oceanic rocks we
chose fresh, zero age glasses for analysis. In the case of
subaerial volcanics for which glass was not available,
we selected fresh whole rocks. A large number of sam-
ples came from well characterized volcanic and ultra-
mafic suites. Table 2 lists the data, the sample locations,
and references to other work on the same powders.
MID-OCEAN RIDGE BASAIXS (MORB)
AND ANDESITES
The mid-ocean ridge voicanics analyzed for lithium
ranged from incompatible element enriched (E-type)
to depleted (N-type), and from basalt to dacite. Basalts
from all the ocean basins have lithium contents in the
range 3 to 17 ppm, but only highly evolved FeTi basalts
have values exceeding 8 ppm. Andesites and dacites
from the East Pacific Rise range up to 30 ppm. The
Li data form a good negative correlation with MgO
(Fig. 3), showing that lithium increases with differen-
tiation, and hence must have a bulk distribution coef-
ficient (D) of less than 1 during low pressure fiaction-
ation. This qualitative conclusion was also apparent
in the study of BRYAN et al. (1979). The limited range
of lithium contents in MORB samples shows that lith-
ium cannot have a D near zero, however.
TABLE I:
Li.FFm
L-DGO BMISS.
SAMPLE DCPM INM’ SPEc. REC.

all samples containing more than 2 ppm Li, the linal dilution BHVOI 4.w 4.9 4.54
was 100: 1. !?ampks with less than 2 ppm Li (20 ppb Li in Bat-l 13.3 12.3 182 12.11
solution) fell near the limit of the linear dynamic range of the MS-1 1.90 2.6 25
spectrometer, so they were n-run at a 50: I dilution. In almost PCC-1 1.19 0.9 25
ADK 53 7.65 7.8
all cases the values obtained were identical within crcor to the
FAMOUS 527-1-l 3.70 23
1oO:l values. FAMOUS 52743 5.70 53
Since routine major and trace element analyses in our lab-
oratory involve using large amounts of LiB02 and L&CO>, 1) BAlLJZYdOWOpa.1978
WCperfbnned all sample dissolutions for lithium in the isotope :,’ TMwPSoN. 1973
BRYAN. THOWSON. m6 MICHAEL. 1979
clean labomtory in an adjoining building. Before each run on 4) 0l.AlxaYm6cKxIDE.1961
the plasma spectrometer all parts of the machine which come 5) FLANAOAN et J.. 1976
 Lithium in volcanic rocks
FIG. 2. Map of sample localities.
Three different approaches can be used to obtain
more precise estimates of the distribution coefficient
for lithium (&i) during melting and crystallization in
MORB. The first is to use liquid line of descent cal-
culations to estimate the amount of crystallization
leading to the major element variations (Fig. 3), and
then use the Rayleigh fractionation equation to find
the D that explains the Li-MgO correlation. The second
is to see if the behavior of lithium is analogous to that
of another trace element whose behavior is well un-
derstood (e.g. see ETOUBLEAUet al., 1983). The third
is to use well documented suites of glasses to obtain
& by trace element inversion techniques (e.g. MIN-
ESTERand ALL&GRE,1978).
1: Liquid line of descent
Before using major element data to constrain DL~,
the data need to be examined more closely. Figure 4
shows Li plotted against SiOz. FeTi basalts and the
andesites lie on different trends, and must therefore
have distinct fractionation histories. Returning to Fig.
3, the two basalt sample sets with the largest range in
MgO (59% wt.), that is, the suites from the Juan de
Fuca Ridge and the East Pacific Rise (EPR) between
8 and I3”N, show trajectories different from one an-
other and from the more primitive MORB samples,
suggesting that they should each be considered sepa-
rately. Liquid line of descent calculations using the
method of WEAVERand LANGMUIR(1986) show that
fractionation from 9 to 5 wt.% MgO (8 to 14% FeO)
requires 65 to 70% fractional crystallization (i.e. F
= 0.3-0.35). Taking these estimates for F and using
measured Li concentrations from each ofthe two suites,
solution of the Rayleigh equation (CdCo = F’““) leads
1729
to an estimated range in DLi of 0.2 to 0.35 for low
pressure fractional crystallization.
2: Covariation behavior
The second approach involves comparing the vari-
ations in lithium contents to those of other trace ele-
ments with better known partitioning behavior. Figure
5 compares Li with Y, Yb, and V, which during melting
and crystallization processes in MORB have progres-
sively increasing distribution coefficients.
In Fig. Sa, Li vs. Y, most MORB glasses plot as a
single array that intersects the Li axis, showing lithium
to have a higher distribution coefficient than Y. Whole
rock E-MORB samples from the Oceanographer Frac-
ture Zone do not plot on the same trend. These sam-
ples, among the most enriched ever recovered from
the ocean ridges, have low Li relative to Y. which would
seem to preclude alteration as the cause of their anom-
alous position and scatter in Fig. Sa. Differentiated
samples from both the East Pacific Rise and the Juan
de Fuca Ridge define separate trends that intersect the
yttrium axis, which suggest that for these samples Y is
more compatible than Li. Thus for basalts related by
melting and small extents of crystallization, it appears
that DL, is larger than I&. But for greater extents of
crystallization, the relationship reverses.
In Fig. 5b, Li vs. Yb, both basalts and andesites ap-
pear to plot as a single array which intersects at the
origin. This general correlation would seem to imply
that the dist~bution coefficient of lithium is similar to
that of ytterbium, and that the Li/Yb ratio of all
MORBs is 1.7. Examination of specific sample sets,
however, show that this is not quite the case. Glass
suites from the FAMOUS area on the MAR and the
 1730 J. G. Ryan and C. H. Langmuir

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1) LAIGIIOIII.1910 13) J*EDusm .I al.. 1978

2) LsmKR1.L al., 1977 14) zInnI& l r al.. 1979
3) 9aYAllad mG%JL i977 A51 FLUWM, * &..I%')(
4) =fdn, nialF9Cs‘ ud nxC4wL. 1979 lb) yxIas2. 1971
5) B *t II.. 19u 173 WklGnT. 9snwsGu md wYYlcui. 1975
4) JBRE,I9a5 1%) m l t d.. 1964
7) tnukumG l L al., 1913 l9f WXGVWS. 196h
0 wlmlxn .t bl,. la prrp. 20) muJImEL. 1981
9) MI .t ti.. *n p**t. 21) K4T. 1980
10) -a, SrmwEI ad %Arxl*. 1916 22) Yuauar, 19.3
11) ~wxT l t J., ieu4 233 m urd CASJSIGIIAEL. 1973
123 UCX .r *I.. two w PtRssadcAmscIIu1L, 1969
 Lithium in volcanic rocks 1731

30 . zo- EPRDIFFERENTIATES
\
. 7 15-
. a
I ,a
_I IO-
-z 20. jd
JUAN DE FUCA FE-T,
iii \*
.-
-I
$- ef OFZ

I I I 1 I
50 100
IO-
Y (ppm)

”
.a

1 I I I I I 1
2 4 6 8 IO I2

MqO (wt %)

FIG. 3. Lithium versus MgO diagram for ocean ridge basalt

glasses. Error bars equivalent to point size. Open diamonds
mark the Juan de Fuca Ridge sample suite; open circles mark
basalts from 8-l 3”N on the East Pacific Rise.

Tamayo Fracture Zone region of the EPR form trends

that extend toward the Li axis. Previous workers have
described both the FAMOUS and Tamayo suites as
showing trace element variability due to varying extents
of partial melting (LANGMUIR et al., 1977; BENDER et
Yb (mm)
al., 1984). It therefore appears that during melting DLi
is slightly larger than Dyb. However, when magmas
fractionate at low pressure, the two elements show the
same D value.
In Fig. 5c, Li vs. V, the FAMOUS and Tamayo ba-
salts form a trend that extends toward the V axis. Ex-

MT. RECHESNOI FE-TI BASALTS

40

)
100 200 300 400

V (ppm)

FIG. 5. Lithium-trace element covariation diagrams for

ocean ridge basalts. Dots signify MORB glasses; open circles
mark the MORB glass suites from the FAMOUS area and
I 1 I I the Tamayo Fracture Zone; stars are whole rock samples from
50 56 60 65 70 the Oceanographer Fracture Zone. A) Li vs. Y. B) Li vs. Yb.
SiO, (wf %) Mid-ocean ridge volcanics form a single trend that intersects
the origin, while the suites from the FAMOUS area and the
FIG. 4. Lithium versus silica diagram. Dots mark MORB Tamayo Fracture Zone form separate trends that extend to
and differentiates; crosses mark arc volcanic samples. The the Li axis. (See inset). C) Li vs. V. The FAMOUS samples
various arc volcanic suites are distinct from one another, line up to form a trend that intersects the V axis, while the
ranging from the low Li/SiO? trend observed for the Izu Arc Tamayo suite forms a trend that extends to the origin. Ex-
suite to the substantial Li increases observed at Okmok volcano tremely differentiated basalts and andesites show an inverse
and Mt. Rechesnoi. relationship.
1732 J. G. Ryan and C. H. Langmuir
amining the suites separately, the Tamayo trend comes
close to intersecting the origin, while the FAMOUS
correlation clearly intersects the vanadium axis. The
mean Li/V ratio of the Tamayo correlation is about
0.020, similar to the average Li/V of 0.02 1 in the prim-
itive ultramafic nodules examined by JAGOUTZ et al.
(1979). Thus it seems that DL~is similar to or slightly
less than DV during melting. The OFZ samples form
a scattered trend below the other MORB samples, but
ihis trend also intersects the V axis. The EPR and Juan
de Fuca differentiates define inverse correlations,
showing that while L)v increases significantly with ad-
vanced fractionation, 4j remains less than one.
Thus, comparing Li variations with those of other
elements in MORB shows that lithium’s partitioning
behavior may be similar to that of Yb during shallow
level fractionation, and is perhaps like that of vanadium
during melting. No lithophile element matches the be-
havior of Li in both processes, which suggests relative
differences in its mineral/melt partitioning. Lithium’s
greater compatibility during melting is probably due
to its having significant olivine/liquid and orthopyrox-
ene/liquid partition coefficients, while Yb is highly in-
compatible in these minerals. The Li/Yb ratio of fertile
upper mantle samples is about 4.5 (JAGOUTZ et al.,
1979), as compared to the MORB ratio of 1.7, sug-
gesting a significant difference in the partitioning of Li
and Yb during melting. In shallow level fractionation,
however, plagioclase dominates the crystallizing as-
semblages, and this mineral apparently does not dis-
criminate between Li and Yb as effectively as olivine
or orthopyroxene. Thus lithium appears to be relatively
more compatible during melting of the mantle than it
is during low pressure fractionation.
In the OFZ samples the behavior of lithium appears
to be different. Although there is not enough variation
in Li to be definitive, Li appears to be much less com-
patible than V, and may have about the same D value
as Y. The relative behaviors of Li, V, and Y change
significantly for ocean andesites and FeTi basal& Much
of that change appears to be due to increased com-
patibility of V and Y in differentiated magmas. Li and
Yb vary almost identically, however, up to dacitic
compositions.
TABUI:
REGION
TNUTO mCTDFtC 0.207 2.02 0.329 2.21 0.259 1.81
znn
FAHOUS REIols 0.246 1.13 0.312 1.00 0.304 1.77
JDARDBllJCA 0.2a2 ---- _---- ___- _____ --__
RIDGE
PllIlWF ISIMDS 0.316 ---- 0.556 ---- O.bO2 ----
: In PP.
D'% - 0.04, cmo, - .256
'Dy - O.O3Ob, 8." - 1.196 pp~
' D- - 0.0374. Gem - .3Sb pp~
IO -
REYKJANES
-z PRIBILOF IS.
B
ov 1 1 1
0 2 4 6
Yb (ppm)
FK 6. Li vs. Yb diagram for ocean island basalt% REE
data from Z~NDLER et al. (1979), HOFMANN et ui. (1984), and
KAY (1980).
3: Inverse modeling
The value of inverse modeling is that it permits one
to assign a numerical value to &. The success of this
approach depends on two factors. First, the chosen
sample suites must be related by different extents of
melting or fractional crystallization. Second, one must
choose reference elements that are highly incompatible
and well documented in terms of distribution coeffi-
cients and source abundances. Table 3 displays the
results of inverse modeiing calculations, using the
equations of MINSTER and ALL~GRE (1978). for
MORB melting suites from the FAMOUS area and
from the Tamayo Fracture Zone. Using reasonable
values for the D’s of several reference elements which
have mantle concentrations that are reasonably well
constrained, the calculated values for&j range between
0.25 and 0.33, averaging .29. We have also inverted
data for Juan de Fuca Ridge samples that are believed
to be related by low pressure crystallization (KAPPEL,
1985). Applying methods based on MINSTER et al.
( 1977) yields a &i value of 0.28, similar to those ob-
tained from liquid line of descent calculations. Thus,
based on the collected MORB data, lithium appears
to be a moderately incompatible element, with a bulk
distribution coefficient between 0.25-0.35.
OCEAN ISLAND AND ALKALI BASALTS
The ocean island tholeiites analyzed for lithium
come from Kilauea volcano and from the Reykjanes
Peninsula of Iceland; the alkali basalts come from Ha-
waii, Iceland, the Canary Islands, the Pribilof Islands,
and continental sites in the western U.S. and Mexico.
For samples ranging from picrite to trachyte the range
in lithium content is similar to that seen in MORB (3-
15 ppm); basalts generally contain less than 8 ppm Li.
Figure 6 is a plot of Li vs. Yb for ocean island sam-
ples. The different ocean islands have variable Li/Yb
ratios, but all are higher than the typical MORB ratio
of I .7. Inverse modeling of a set of alkali basalts from
 Lithium in volcanic rocks
PRIBILOF IS.
Dy/Yb
FIG.7.Li/Yb versus Dy/Yh for ocean island suites. REE
data sources same as Fig. 6.
the Pribilof Islands that are probably related by crys-
tallization suggests a DLi of 0.3-0.6 for low pressure
fractionation (Table 3).
HOFMANN et al.(1984) attributed chemical varia-
tions in the Mauna Ulu lavas of Kilauea to a 20%
increase in the extent of partial melting over the life
of the eruption. After correction for olivine fraction-
ation, the concentrations of incompatible elements in
the Mauna Ulu samples decrease as the flows become
younger. The heavy REE contents change only slightly
over the life of the eruption, implying that a phase in
the source with high HREE partition coefficients (such
as garnet) is controlling their distribution (HOFMANN
et al., 1984). Ten Mauna Ulu basalts erupted between
1969 and 1970 are identical in their Li content within
analytical uncertainty, averaging 4.65 f 0.1 ppm. The
maximum observed variation in these samples (+4%
relative) is comparable to the range observed for the
heavy REE, from dysprosium to ytterbium (HOFMANN
etal.,1984). No discernible systematic change in lith-
ium concentration occurs with time at Mauna Ulu.
Based on data from the Mauna Ulu samples, &i
during melting at ocean islands is much like that of
the HREE. In order to have enough range in concen-
tration to find out which rare earth the behavior of Li
most resembles, the ocean islands must be considered
together. Figure 7 plots Li/Yb versus Dy/Yb for ocean
_I E I. .
a)
3 .
l--l-l-L- 15
FIG. 8. Li versus SC, V, and Yb in samples from the Ronda peridotite massif. Trace element data from
FREY et al. (1985).
1733
island suites. Samples from the Reykjanes peninsula,
Kilauea, and the Pribilof islands form a slightly scat-
tered trend that extends toward the origin, implying
that Li behaves most like Dy during melting at ocean
islands. This change in Li-HREE relationships is con-
sistent with the increase in Dm expected at ocean is-
lands due to the presence of mantle garnet. and implies
that lithium does not partition as strongly into garnet
as do the HREE, SC, and V.
PEIUDOTITES AND MANTLE ROCKS
The analyzed peridotites came from several ultra-
mafic localities in North America, Europe, and Africa.
Lithium in these peridotites ranges from 1 to 3 ppm.
In samples from the Ronda ultramafic body of Spain
(FREY et al., 1985) lithium varies regularly with a va-
riety of other trace elements (Fig. 8). Using calculated
melt fraction values for the Ronda samples obtained
by the approach outlined in FREY et al. (1985), and
the measured lithium contents, one can determine dis-
tribution coefficients for Li during melting events in
the Ronda ultramafic body. Table 4 lists the results of
these calculations for two Ronda samples. While an
equilibrium melting model yields reasonable DLival-
ues, the calculated liquid concentrations are too high
for MORB. This may be due to increasing lithium
concentration during partial serpentinization, but the
Li concentrations do not correlate with the extent of
serpentinization. Alternatively, the peridotite may not
be residual to MORB, or the samples are not related
by different amounts of melt extraction.
To examine the affinity of the different ultramafic
phases for lithium, we analyzed mineral separates from
two different ultramafic rocks, one a spine1 peridotite
from San Carlos, New Mexico, and the other a garnet
peridotite from the Western Gneiss Region of Norway.
The samples were crushed to 200-250 microns,
washed, separated magnetically, and handpicked. The
separates were then leached in dilute HCl (24 hours
for pyroxene and garnet, 2 hours for olivine), and an-
alyzed at a 50: 1 dilution. All major phases save spine1
b) cl
. .
. .
L
.
.
25 50
V (ppm)
75
F .I5 .3
Yb (porn)
.45
1734 J. G. Ryan and C. H. Langmuir
R6S6 0.21 0.250 7.36 99.
1693 0.29 0.213 6.61 ppa
were analyzed for lithium. For comparative purpmes suites form well defined linear trends that intersect the
whole rock samples from each peridotite were also an-
alyzed (Table 2).
AU the silicate phases present in both peridotites
contained significant amounts of L& with concentra-
tions ranging between 1.4 and 4 ppm. Assuming these
minerals represent equilibrium assemblages, the ratios
of their lithium contents can be used to estimate inter-
mineral partition coefficients (Table 5). The lithium
content of the San Carlos nodule is distributed rather
evenly among the silicate phases, yielding inter-mineral
coefficients in the range of 1.0-1.3. However, in the
garnet peridotite lithium is concentrated in the clino-
pyroxene and to a lesser extent in the garnet relative
to the olivine. This difference in Li partitioning between Mt. Rechesnoi to 3 ppm at Ixu, suggesting differences
the garnet and spinel bearing nodules may imply
changes in the L& for melting with depth, but the data
are insuflicient to draw firm conclusions. In both cases
estimates of whole rock lithium content based on min-
eral modes agree well with measured whole rock values,
suggesting that all the Li in these rocks is retained in
the minerals (Table 5).
These data from ultrama6c samples demonstrate
intermineral relations for lithium which are dissimilar
to those of most other lithophile elements. Lithium is
moderately incompatible, yet it partitions similarly into
all silicate phases in a spine1 peridotite. The data also
show that the similarity of lithium to Yb during crys-
tallization and V during melting in MORB is probably
fortuitous. The distribution coefficients of Yb and V
are controlled by the amount of residual clinopyroxene
and garnet. 4j, on the other hand, is relatively inde-
pendent of residual phase abundances, as lithium ap
pears to partition evenly among the major mineral
phases of the shallow upper mantle. Thus, Li will show
variable relationships to Yb and V depending on how
much clinopyroxene and garnet are residual to a par-
ticular melting process.
ARC VOLCANIC ROCK!3
The arc volcanic samples analyzed for this study
come from the Aleutians (Mt. Rechesnoi and Okmok
volcano on Umnak island, Adak island, Mt Katmai),
Central America, the cascades, and two islands in the
Izu Arc south of Japan. Some of the more differentiated
arc samples contain as much as 67 ppm Li, though at
60% SiOr the average lithium content is 10-30 ppm
(Fig. 4). Arc basalts have lithium concentrations com-
parable to those observed in theii oceanic counterparts,
ranging from 3 to 10 ppm. Like many other incom-
patible trace elements, lithium varies mgularly and
positively with increasing silica in arc suites, although
the slopes of the variation curves differ considerably
from suite to suite (Fig. 4).
Figure 9a is a Li vs. Yb diagram comparing am suites
to MORBs. Like ocean island basal& arc samples plot
above the MORB correlation line, but none of the
origin. Figures 9b and c. show Li vs. Y and V for am
samples. Two different fractionation paths am apparent
on both diagrams: the low LiJY and LijV trends of the
tholeiitic Okmok and Izu samples, and the steep slopes
of the c&-alkaline Adak and Mt. Rechesnoi suites.
Figure 9 makes it evident that relative to Y and Yb,
lithium is enriched in arc magmas, but the magnitude
of that enrichment appears to vary with the path of
differentiation and from one volcano to the next. The
Li/V ratios of arc rocks show considerable range, even
reaching values lower than the MORB melting ratio
of 0.020. The lithium contents of the most primitive
samples from each area range widely, from 9 ppm at
in source contents or extent of melting as well as dif-
ferentiation path.
ARCHEAN CRUETAL ROCKS
To gain an understanding of lithium variations in
continental rocks, Li contents were determined for Ar-
chean gneisses and greenstones from the Granite Falls
and Morton units of Minnesota. Li contents in the
greenstones range from 13 to 20 ppm, abundances far
greater than those of fresh basal&, suggesting that dur-
ing metamorphism the greenstones were enriched in
Li. For the gneisses the situation is not as clear: they
have variable Li contents (8 to 37 ppm) and show no
systematic variations with any analyzed elements.
About half the gneisses contain 8-12 ppm Li, though
they range from 53% to 72% Siq. In their study of
chemical trends in high grade metasediments of the
Alps, SIGHINOLFI and G~RCXJNI(1978) noted an 80%
TUU ,:
PAKTIIIOKCoEF!J1c1KtmS LItxmmNT.PPK
SAMPLE OL/CPK OWPK mm noMLcAu.'AnN..
___._
sm CAKLDS 1.15 1.27 1.72-1.76 1.77
SPiMl Lhr201ir*
SK-59 0.360 __.__ 0.697 1.43 1.65
carnatP~ridocit~
 Lithium in volcanic rocks 1735

depletion in lithium in granulite grade gneisses relative from sediments or altered crust in arc melts, one might
to associated amphibolite gneiss. The gneisses at Gran- expect higher Li contents in these magmas. In fact, the
ite Fails and Morton are alI migmatitic and are depleted Li contents of some primitive arc rocks are not sys-
in Rb and K, which suggests that they at some time in tematically high relative to similar oceanic basalts;
their histories experienced granulite facies pressures and samples from the Izu arc are low in lithium relative to
temperatures (GOLDICH et al., 1980; WALDEN et al., ocean ridge basalt samples of similar major element
1980). The low Li concentrations, coupled with the chemistry. Also, lithium does not always appear to
history of these rocks, suggest that lithium depletion agree with other potential “slab tracers”: for example,
in granulite facies rocks may also have occurred in samples from Bogoslov Island have high K, Ba, and
these Archean terranes. “Be contents (TERA et al., 1986) yet the Li contents
of these samples are lower than those of MORBs at
similar MgO content. However, the behavior of lithium
DISCUSSION
,relative to other trace elements in arcs is different than
for MORB and ocean islands, and suggests that there
The mantle abundance of lithium
is an additional source of Li in the sources of arc
magmas.
Our lithium data for mafic and ultramafic rocks Figure 10 is a plot of Li/Yb versus Dy/Yb ratios for
provide two different means of estimating the lithium arc volcanics and ocean island basalts (OIB). For OIBs
concentration of the upper mantle. Trace element in- Li behaves regularly relative to the REE, and as dis-
version techniques allow one to infer the Li contents cussed above, the regularities are consistent with how
of mantle sources for basahs from the FAMOUS and variable amounts of garnet as a residual phase would
Tamayo MORB suites (Table 3). Calculated relative affect Li and REE abundances. The Dy/Yb ratios of
to trace elements with source concentrations con- most arc samples range from 1.5 to 2.0, comparable
strained by cosmochemical arguments, the mantle to those of MORB. But the Li/Yb ratios observed at
content of lithium appears to be mostly in the range arcs can exceed 10, and all the arc samples have higher
1.8-2.0 ppm. The other approach to estimating the Li/Yb than oceanic rocks of similar Dy/Yb. The ver-
mantle content of lithium is to determine the Li con- tical trend of all arc data on this diagram precludes
tents of primitive ultramafic rocks. Our analyses of residual garnet as an explanation of arc Li/REE sys-
ultramafic nodules agree with the data of JAGOUTZ et tematics.
al. (1979) and suggest a mantle lithium abundance of High Ba/Ti ratios are characteristic of arc magmas,
about 1.8 ppm. However, fertile lhetzolites from the and, relative to REE, high Ba and low TiOz are char-
Ronda and Zabargad ultramafic massifs show higher acteristic of volcanics from convergent margins (e.g.
Li contents, ranging from 2.3-3.0 ppm. Though in GILL, 1981). Figure 11 shows that there is an overall
neither massif is there any clear relationship between positive correlation between Ba/Ti and Li/Yb, with
degree of alteration and lithium content, it is possible the possible exception of Bogoslov island, which is be-
that both Ronda and Zabargad have experienced hind the volcanic front in the Aleutians. This corre-
metasomatic Li enrichments. The Zabargad lhetzolites lation for lavas from the volcanic front suggests that
are associated with amphibole bearing peridotites relative enrichment of Li and Ba may occur by similar
(BONATTIet al., 1986), and the Ronda massif contains processes. Thus we conclude that absolute Li abun-
zones of LREE enrichment (REISBERGand ZINDLER, dances in arc basalts are similar to MORB, but relative
1986). The nodules analyzed in this study and those to the heavy REE, Li is enriched by factors of 1.2 to
selected by JAGOUTZ et al. ( 1979) lacked any evidence 2. These systematics clearly reflect lower Yb abun-
of metamorphic alteration and contained no hydrous dances in many arc basalts than in most MORB. The
phases. Thus, based on nodule and inverse modeling low Yb contents could have a variety of causes, but
data, a mantle lithium content of 1.9 + .2 ppm appears two obvious possibilities are that arc magmas are de-
reasonable. rived by larger extents of melting or that the arc source
is lower overall in REE abundance levels, as pointed
out by WHITE and PATCHETT (1984).
Lithium as an indicator of slab contribution at arcs Figure 11 also shows that the relative enrichment of
Ba in arcs is much greater than the relative enrichment
The data presented above show that Li contents in of Li. K also shows greater enrichment than Li, and
most oceanic rocks are low and that Dti is large relative K allows a clearer interpretation, since in MORB the
to those of other alkalis. In contrast, during seafloor behavior of K is analogous to that of La, and Li is
alteration and sedimentation Li behaves much like approximately analogous to Yb. Thus the K/Li and
potassium, and is concentrated in ocean sediments and La/Yb ratios vary coherently for any process controlled
altered oceanic crust (HOLLAND, 1980; DONNELLYet by crystal/melt equilibria in the absence of K-bearing
al., 1980). These characteristics suggest lithium may phases.
be a useful indicator of the subducted slab contribution Figure 12 compares K/Li and La/Yb variations of
to arc magmas. If there were a significant contribution arcs to those of MORB and ocean islands. In mid-
1736 J. G. Ryan and C. H. Langmuir

Yb (ppm)

50-

40-

30-
'ii
%
?
20-

IO-

IZU
0 I 1 I 1 I
0 IO 20 30 40 50
Y (ppm)

FIG. 9. L&ace element variation diagrams for arc volcanic suites. Open circlea mark andesites and
dacitcs; closed dots mark basal& A) Li versus Yb. Yb data for A&k, Okmok, and Bog&v from KAY
(1976) and ARCZULUSei 111.( 1977). Arc rocks in general show considerable Li enrichment with respect to
Yb, though each suite forms a distinct trend. B) Li VS.Y. Tholeiitic arc suites show low Li/Y correlations,
while cahxlkaline suites form almost vertical trends. C) Li VS.V.

ocean ridge and ocean island volcanics, K/Li and La/
Yb variations plot in a linear array that intersects the
origin. This array reflects a characteristic relationship
between K/Li and La/M for oceanic, mantle-derived
volcanics. Changing the source ratios of K/Li or La/
Yb independently will change the slope of the data
array, but the new correlation will still intersect the
origin, provided no K-bearing phases are residual.
Fractionation of a phase with a high partition coeffi-
cient for K will produce trends that branch off these
source arrays. For example, cq&allixation of amphi-
bole will produce trends of opposite slope, as parti-
tioning data show that amphibok qstalhmtion should
decrease K&i and increase La/Yb (NAGASAWA and
SCHNET~LER,~ 971).
Arc magmas almost without exception have high
K/Li ratios relative to La/Yb. The inverse trends of
Pelee, Bogoslov, and Adak may reflect amphibole con-
 Lithium in volcanic rocks 1737

led to decreases in the K/Li ratios relative to the La/

Yb ratios of continental magmas. Mixing of average
sediment with a depleted, MORB-type source cannot
create the K/Li-La/Yb relationships necessary to pro-
duce arc basalts. Thus, Fig. 12 shows that bulk incor-
poration of sediments into the mantle sources of arc
magmas alone will not produce the arc geochemical
signature. For sediments to be important, there would
have to be removal of K and Li from the sediments
(e.g., by a hydrothermal fluid) with the REE remaining
behind. In this way the mantle could inherit the K/Li
signature of the sediments without inheriting sedi-
mentary REE signatures. At high P and T, however,
it seems possible that both alkalis and REE may be
soluble in hydrothermal fluids. Alternatively, the upper
portions of old altered oceanic crust have appropriate
OK1.'OK
K/Li and La/Yb ratios to be the source of the added
component.

Ramifications for the ocean balance qf Li

200 300 400 One cannot determine the oceanic budget of lithium
V (ppm)
without knowing the initial Li content of newly formed
FIG. 9. (Continued) oceanic crust. This value is necessary to estimate the

trol, as amphibole has been reported in lavas from Bo-

goslov and Pelee (DUPUY et al.. 1985; ARCULUSet al.,
1977). Note that the most primitive ends ofthose arrays
are near the main arc trend. Thus Fig. 12 in combi-
nation with Figs. 10 and 11 suggests that the very high
LifYb ratios of Pelee and Adak may be produced by
amphibole fractionation, but the general increase in
the Li/Yb (and Ba/Ti) ratios in arc magmas can-
not be.
Figures lo- 12 also show that the enrichment of alkali
and alkaline earths in arcs is not uniform, as both K
and Li are enriched relative to REE, but K is enriched
relative to Li. Figure 12 further suggests that K/Li and
La/Yb behave coherently for arc basalts as a whole,
since they form an array which intersects the origin,
but on a fundamentally different slope than MORB.
This requires a change of K/Li relative to La/Yb in
the source, followed by control by mineral/melt equi-
libria in processes analogous to mid-ocean ridge vol-
canism.
It is thus necessary to find a process or component
which enriches K (Rb, Ba) and Li relative to REE and
also K (Rb, Ba) relative to Li. Addition of either high I I
2 4
temperature fluids or sediments can produce enrich-
ments in the alkalis relative to the REE (see Fig. 1 1). Dy/Yb
However, the available data (VON DAMM ef al.. 1985; FIG. 10. Li/Yb vs. Dy/Yh for arc volcanic suites. Symbols
SEYFRIEDet al., 1984) suggest that K and Li are not as in Fig. 9. The shaded field is the ocean island correlation.
fractionated by hydrothermal processes, at least at low Data for Pelee are from DUPUY el al.(1985): data for La
pressure. Also, most sediments plot on or below the Soufriere are from DOSTAL eral.(1983); Scotia’arc points are
from BAKER(I 978) and HAWKESWORTH et al. (1977). Adak,
oceanic array in Fig. 12, presumably because they are
Okmok and Bogoslov REE data sources as in Fig. 9. Arc vol-
derived from continents where fractionation of K- canics show substantial Li/Yh increases with no change in
bearing phases such as amphibole or K-feldspar has Dy/Yb, unlike ocean island suites.
1738 J. G. Ryan and C. H. Langmuir
5 IO
Li/Yb
FIG. I I. Ba/Ti VS.Li/Yb for arc suites. Symbols and data
sources as in Fig. 10. In general and in specific arc suites, Li/
Yh varies positively with Ba/Ti, due tither to amphibole frac-
tionation or to source enrichments in Li and Ba.
flux of Li from the mantle accurately, and provides an
upper constraint for calculation of the crust-to-ocean
Li flux. Using solution data from submarine hot
springs, EDMONDet al. ( 1979) calculated a lithium flux
of 6.6-I 1.0 X 10” g/yr, which STOFFYN-ECLI and
MACKENZIE( 1984) noted was probably larger than the
annual Li flux from the mantle. STOFFYN-ECLI and
MACKENZIE(1984) studied the lithium budget of the
oceans and estimated the hydrothermal Li input to be
1. l- 1.9 X 10’ ’ g/yr. Our study shows that the lithium
content of freshly formed ocean crust is not more than
3-4 ppm. Using the basalt production parameters of
STOFFYN-EGLI and MACKENZIE( 1984) and a basalt
density of 2.9 g/cm3, the total annual Li flux from
mantle to crust lies between 1.O and 2.0 X 10” g/yr.
Because much Li remains in the crust, the flux into
seawater must be substantially less than this number.
So, even the adjusted hydrothermal flux of STOFFYN-
EGLI and MACKENZIE(1984) appears to be too high.
In their study of alkali fluxes during ocean crust al-
teration, HART and STAUDIGEL(1982) concluded that
the ocean crust as a whole was a sink for K, Rb, and
Cs due to alteration-related enrichments in the upper
600 m of crust. Data for basalt samples from DSDP
holes 4 17D and 4 18A suggest that the Li content of
old, altered upper crust averages about 10 ppm (DON-
NELLYet al., 1980). Thus with alteration, the oceanic
crust will develop an upper layer of several hundred
meters thickness which may contain as much as 25
50?&of the Li flux from the mantle. If there were no
net flux of lithium from mantle to ocean, the Li content
of the lower crust would be 2-3 ppm, a value which
is not unreasonable, since Li is unlikely to be totally
stripped from the lower crustal cumulates. Without
analysis of the cumulates it is not possible to determine
how substantial a source of Li the ridges are for the
oceans, but it seems likely that most of the mantle flux
remains in the igneous ocean crust. Thus the net Li
flux from mantle to ocean may be very small indeed,
and the Li enrichments observed in marine sediments
by HOLLAND(1980) may come for the most part from
continental sources.
CONCLUSIONS
Lithium behaves as a moderately incompatible ele-
ment in magmatic systems. Its bulk solid/liquid dis-
tribution coefficient is 0.2-0.3 and is essentially inde-
pendent of the proportions of mineral phases involved
in melting and crystallization. This constancy of &,
despite changes in fractionating assemblages and melt
compositions, is supported by the thermal ditfusion
data of LESHER(1986), who found little change in Li
partitioning in liquids ranging in composition from
basalt to dacite. For MORB, Li is approximately anal-
ogous to vanadium in its melting behavior, and is sim-
ilar to Yb during low pressure cry&aGmtion. For ocean
island lavas, the influence of garnet makes Yb more
compatible than Li, and the melting behavior of Li is
approximately analogous to that of Dy. Data from pe-
ridotites as well as basalts suggest a mantle Li content
of about 1.9 ppm and show it to reside primarily in
olivine and orthopyroxene. In detail, lithium partitions
differently among mineral phases than any other well
studied element, resulting in complex relationships
between lithium and most other trace elements.
Arc basalts have Li abundances similar to those of
MORB, but have substantially higher Li/Yb ratios.
This requires both the presence of a Li-rich component
inarcsourcesandthatarcmagmasbederivedbyeither
greater extents of melting or from more depleted man-
tle than MORB. Li is enriched in arc basalts less than
are K, Rb and Ba, and arc magmas have substantially
higher K/Li than MORB. High K/U and Li/Yb ratios
require either selective removal of K and Li from sed-
iments, leaving REE behind, or a contribution from
altered oceanic crust. Bulk incorporation of sediments
into the arc source is unlikely to be the sole cause of
high alkalis in arc magmas, based on the K/Li-REE
data.
These new data on the Li contents of MORB con-
strain the amount of lithium introduced into the
oceanic crust each year, entailing reductions in most
published estimates of the hydrothermal flux of Li from
the ocean ridges. Thus, it seems that very little lithium
is added to the oceans from the ocean crust, and the
enrichments observed in sediments are probably de
rived from continental sources.
 Lithium in volcanic rocks 1739

I \
BOGOSLOV
3000

La/Yb

FIG. 12. K/Li vs. La/Yb for arc samples. Symbols and data sources as in Fig. 10. Field for altered ocean
crust from data of DONNELLY et al. (1980) and EMMERMANN and PIJCHELT(1980); field for sediments
from data of DEAN and PARDUHN (1983) and others. MORB and ocean island basalts plot as a single trend
controlled by crystal/melt fractionation. Arc basalts all plot at higher K/Li than the MORB trend, requiring
the addition of a high K/Li component to the arc source. Both marine sediments and altered ocean crust
have the appropriate K/Li; however, the La/Yb of sediments is far too high for any mixture of MORB
mantle and sediment to serve as the source for arc lavas. Either K and Li are liberated preferentially from
the sediments, or incorporation of altered ocean crust is the likely Li enrichment mechanism.

Acknowledgemenls-We would like to thank John Bender,
Enrico Bonatti, Hannes Brueckner, Bill Bryan, Mike Carr,
Fred Frey, Gil Hanson, Wes HiIdreth, Ellen Kappel, Bob Kay,
Emily Klein, Hubert Staudigel, Dave Walker, Tom Wright,
and Alan Zindler for providing samples. We also thank David
Langmuir for invaluable assistance in the early stages of this
study with atomic absorption analyses. Informal discussions
with Anne LeHuray and Chip Lesher have been invaluable
in helping to develop analytical technique and in interpreta-
tion. We thank Alan Zindler for access to his clean lab. Reviews
by Dave Christie, Jeff Rosenbaum, Youxue Zhang, Dave
Walker, Bill Leeman, and an anonymous reviewer added
much to the clarity of this manuscript. This work was sup-
ported by NSF contracts OCE84-I 1448 to Charles Langmuir
and OCEBS-I 1017 to David Walker.
Edilorial handling: F. A. Frey
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