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Combining Nd isotopes in monazite and Hf isotopes in zircon to

understand complex open-system processes in granitic magmas


Christopher M. Fisher1*, John M. Hanchar1, Calvin F. Miller2, Stacy Phillips1, Jeffrey D. Vervoort3, and
Martin J. Whitehouse4
1
Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, Newfoundland and Labrador A1B 3X5, Canada
2
Department of Earth and Environmental Sciences, Vanderbilt University, Nashville, Tennessee 37235-1805, USA
3
School of the Environment, Washington State University, Pullman, Washington 99164, USA
4
Department of Geosciences, Swedish Museum of Natural History, S-104 05 Stockholm, Sweden

ABSTRACT and relative contributions of potential sources as


Mapping the age and trace element and Sm-Nd isotope compositions of monazite grains well as subsequent processes occurring in mag-
from a peraluminous Cretaceous granite using laser ablation–split stream analysis reveals matic systems. In this paper, we examine trace
a wide range in Nd isotope and rare earth element (REE) compositions within and between element and Nd isotope variations within single
single grains. These data corroborate isotopic variability indicated by Hf isotope analysis of monazite grains. The high Nd content of mona-
zircon in the same granite sample. The REE variations indicate that monazite grew during zite allows us to “map” the surface of polished
fractional crystallization. Hf and Nd isotopes indicate that the granitic magma was generated monazite grains with multiple laser ablation–
from at least two distinct Proterozoic sources of approximately the same age: one component split stream (LASS) analyses; we present exam-
that had highly radiogenic initial 176Hf/177Hf and 143Nd/144Nd and a second component that was ples here with 37–45 spot analyses per monazite
notably less radiogenic. This study highlights the utility of in situ REE and Sm-Nd isotope grain (Table DR1 in the GSA Data Repository1).
data in monazite in magmatic systems. Further, it refines the zircon-based constraints on
magmatic processes because of sensitivity of light REEs to fractional crystallization, lower Application of Isotope “Mapping” to
probability of complications owing to inheritance, and smaller analytical volumes required. Magmatic Systems
The evolution of a magmatic system though
INTRODUCTION ever-finer spatial resolution, providing data to time is potentially recorded by the core-to-rim
The study of geochemical evolution of fel- address these questions that yield compelling composition of a growing crystal. Isotope com-
sic magmas is a fundamental focus of igneous evidence for diverse source materials of evolv- positions of growth zones can identify diverse
petrology (e.g., Bachmann et al., 2007; Villaros ing hybrid magmas. The exceptional refractory source components and incomplete homogeni-
et al., 2012; Clemens et al., 2011; Coleman et qualities of zircon have led to a revolution in zation of magma. For example, the Hf isotope
al., 2012; Walker et al., 2015). Understanding Lu-Hf isotopes studies, as this tracer isotope sys- composition of zircon—and the Nd isotope
this process involves not only constraining the tem can potentially be linked to source age and composition of monazite—record that of the
mechanism of melt generation in varied source character—and combined with elemental and melt from which the crystal grew; any core to
regions in the crust and mantle, but also how oxygen isotope composition—to better under- rim variations thus reflect changing of melts that
magmas are modified by assimilation and dif- stand the generation, emplacement, and evo- hosted that crystal during its growth.
ferentiation during their ascent through the crust. lution of granitic magmas (e.g., Hawkesworth As opposed to typical investigations where
Are such magmas products of single sources in and Kemp, 2006; Kemp et al., 2008). However, only a small number of analyses are done on
the mantle or crust, or are they hybrids with sub- determination of Hf isotope ratios by laser abla- each grain, multi-point analytical grids or tra-
stantial contributions from multiple sources? If tion–multicollector–inductively coupled plasma– verses and mapping of individual crystals pro-
from multiple sources, are these sources in the mass spectrometry (LA-MC-ICPMS) typically vides an improved view of petrogenetic process
mantle, crust, or both, and are their composi- requires a laser spot diameter of at least 40 mm to over an extended period of crystal growth. In the
tions primary or a consequence of closed-system achieve useful precision (~1 eHf unit). The typical case of monazite, LASS analyses allow Sm-Nd
fractional crystallization? If they are hybrids small size of zircon crystals (~50–200 mm)— isotope measurements to be determined simul-
derived from multiple sources, is this mixed and even smaller individual growth domains, taneously with U-Pb age and trace element con-
heritage reflected in heterogeneity in elemental as well as the common occurrence of inherited tent (Ce, Nd, Sm, Gd, and Eu) using a spot size
and isotopic compositions of whole rocks and cores—commonly preclude the detailed core- of ~20 mm (e.g., Fisher et al., 2011; Gregory et
individual crystals? Finally, if heterogeneity is to-rim traverses that are necessary to constrain al., 2009; Goudie et al., 2014).
apparent, how can it be deconvolved to constrain processes responsible for variability in Hf iso-
source materials and infer post-source process- tope composition. GEOLOGIC BACKGROUND
ing of magma? The Sm-Nd isotope system is complemen- The Sweetwater Wash pluton (SWP), in the
Advances in microanalysis now permit sub- tary to that of Lu-Hf in the study of magmatic Old Woman–Piute batholith in southeastern
mineral–scale determination of both isotope rocks (Vervoort and Patchett, 1996). Minerals
compositions and trace element contents at with high concentration of light rare earth ele- GSA Data Repository item 2017070, analytical
1 

ments (LREEs), like monazite, are common in methods, geologic map, monazite and zircon U-Pb
granites, where they control Sm-Nd isotope concordia plots, monazite elemental (X-ray) maps,
*E-mail: Current address: Department of Earth zircon and monazite data tables, whole rock data table,
and Atmospheric Sciences, The University of Alberta, systematics and REE partitioning in host mag- and monazite standards results, is available online
Edmonton, Alberta T6G 2E3, Canada; E-mail: mas. Trace element data complement the isotope at www.geosociety.org​/datarepository​/2017 or on
cmfisher@ualberta.ca. information, allowing examination of the nature request from editing@geosociety.org.

GEOLOGY, March 2017; v. 45; no. 3; p. 267–270  |  Data Repository item 2017070  | doi:10.1130/G38458.1 |  Published online 9 January 2017
GEOLOGY 
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California, USA (Fig. DR1 in the Data Reposi- Proterozoic, and in the Cretaceous composed a
A 20 depleted mant
le
tory), is part of a belt of strongly peraluminous source region for the SWP with a bimodal dis-
10
Cretaceous plutons that extends through much 0 .020 ? tribution of both radiogenic (initial positive eHf)
177 Hf =
of the length of the Cordillera in western North 0 176 Lu/ and non-radiogenic (initial eHf ~0) crust. The
range of eHf compositions observed in the mag-

ɛHf
America (Miller and Barton, 1990). The Old -10
Woman–Piute batholith intrudes mostly Protero- .00
6? matic (Cretaceous) zircon grains (-11 to -17)
=0
zoic metamorphic rocks (ca. 1.8–1.4 Ga) of the -20 17
7 Hf demonstrates isotope variability of melts dur-
Lu/
Mojave province. The LREE contents of gran- -30
176
Age (Ma) ing the crystallization of zircon in this sample.
ites and monazites of the SWP have been shown 0 500 1000 1500 2000 (Fig. 1; Table DR2).
to be controlled, in large part, by crystallization The relative REE concentrations of all
and removal of monazite from the magma (Wark B -10 monazite grains in this study are broadly con-
and Miller, 1993). The sample chosen for this sistent with growth in a fractionally crystalliz-
-12
study (SW-1) is the least differentiated of all ing magma. Feldspars have high partition coef-

ɛHf(73 Ma)
characterized samples from the pluton and has -14 ficients for Eu, and as they grow, the remaining
the largest accessory mineral content. The rela- melt is progressively depleted in Eu, which can
-16
tively well understood differentiation of LREE be assessed by Eu/Eu* (i.e., the europium anom-
in the SWP, combined with Nd and Hf isotope -18 aly) in co-crystallizing phases (Schnetzler and
diversity in its monazite and zircon populations 206
Pb/238U Age (Ma) Philpotts, 1970). Monazite has extremely high
-20
discussed below, makes it ideal for examining 65 70 75 80 partition coefficients for LREE and commonly
the Hf and Nd isotope systematics of peralumi- controls evolution of these elements in felsic per-
Figure 1. A: eHf versus age for Proterozoic and
nous granitic magma. Cretaceous zircon in sample SW-1 (Sweet- aluminous melts (e.g., Miller and Mittlefehldt,
water Wash pluton, southeastern California, 1982). As monazite grows, the concentrations of
RESULTS USA). Black diamonds represent inherited LREE are reduced in the remaining melt, result-
Proterozoic-age zircon, while gray diamonds ing in progressively lower elemental ratios of Ce/
denote magmatic (Cretaceous-age) zircon. eHf
Zircon Gd and higher Sm/Nd in monazite growth zones
is calculated at 207Pb/206Pb age for Proterozoic
Cathodoluminescence (CL) images of grains zircon and at 73 Ma for Cretaceous magmatic as crystallization progresses.
from sample SW-1 show strong evidence for zircon. Trajectories denote two apparent The Sm-Nd isotope compositions reveal
the presence of inherited zircon in a substan- trends in source Lu/Hf evident in inherited monazite growth in open and closed isotopic
tial portion of the population, consistent with zircon cores. B: eHf(73Ma) versus 206Pb/238U age. systems (Figs. 3A–3C). The Nd isotope com-
previous SIMS U-Pb investigations (Foster et positions of grains A and B (eNd calculated at
al., 1989; Miller et al., 1992). Some grains are 73 Ma) range from -12 to -20 and -11 to -15
entirely Proterozoic, many have both inherited the inherited zircon, which are similar in age to from interior to exterior, respectively, indicating
cores and younger magmatic rims, and a minor- much of the surrounding Proterozoic basement growth in an open system from an increasingly
ity are entirely Cretaceous (Fig. DR2; Table (Wooden et al., 2012). Moreover, this range is less radiogenic melt with time. In contrast, grain
DR2). U-Pb age and Hf isotopic compositions intermediate between the projected eHf(73Ma) of C has uniform eNd(73Ma) of ~-16.5 over a wide
were determined both for inherited cores and for the two end members. range of REE ratios, as would be predicted for
entirely magmatic grains and rims. The former a grain growing from fractionally crystallizing
was done to document the age and Hf isotope Monazite magma in a closed system.
composition present in the source region, and The U-Pb ages determined for the three mon- The isotopic and elemental patterns recorded
the latter to determine the Hf isotope composi- azite crystals studied (grains A, B, and C) sug- in monazite from sample SW-1 define two dis-
tions of magma. The inherited zircon cores have gest that all grew at approximately the same time tinct arrays: a horizontal array with constant
207
Pb/206Pb ages that range from 1710 to 1070 (ca. 73 Ma). With the exception of part of grains eNd(73Ma) and trace element contents suggesting
Ma, consistent with the ages of basement rocks A and C, the vast majority of ages are consistent fractional crystallization, and a vertical array
present in the region. When plotted in eHf versus to within ~2%–3%, with no evidence for Pro- with a relatively homogeneous Sm/Nd but large
time space (Fig. 1), the inherited cores define terozoic U-Pb inheritance (Fig. 2; Fig. DR3). variation in eNd(73Ma) (Fig. 3A). The bulk rock
two distinct groups at ca. 1.7 Ga; one charac- Contour maps of eNd(73Ma), Ce/Gd, Sm/Nd, eNd(73Ma) composition of -15.8 is in agreement
terized by (juvenile and) highly radiogenic Hf Eu/Eu*, and Y (Fig. 2) in monazite document with the composition defined by isotopically
isotope compositions (eHf = ~+10), and a second the evolution of the melts from which they homogeneous monazite C and the outer part
group with significantly less radiogenic Hf (eHf = grew. Monazite A has little zonation in Ce/Gd, of monazite B (Table DR3). Based on grains B
~0). Projection of this bimodal source to 73 Ma Sm/Nd, and Eu/Eu* across the analyzed section and C, this suggests that, as magma increments
gives a possible range of eHf(73Ma) of ~-4 to -27 of the crystal. Assuming that the large low-Y accumulated, mixed, and crystallized, eNd(73Ma) of
for a magma that is a mixture of these two end region in monazite B represents early growth, the initially diverse melts converged on the mean
members (Fig. 1A). The Cretaceous magmatic zoning is consistent with growth during frac- value of ~-15 to -16. Conversely, the nearly ver-
zircon grains yield a mean 206Pb/238U age of 72.6 tional crystallization, with increasing Sm/Nd tical array in eNd(73Ma) versus Sm/Nd observed in
± 1 Ma (mean square of weighted deviates = and decreasing Eu/Eu* and Ce/Gd (indicating grain A suggests that it may be an early-formed
4.9, n = 12), in agreement with previous age feldspar and monazite crystallization, respec- grain that crystallized in an open system domi-
estimates of the intrusion based on zircon and tively) (Fig. DR4). Monazite C has a wide range nated by non-radiogenic Nd isotope composition.
monazite (Kingsbury et al., 1993) and with the of REE ratios but uniform eNd(73Ma).
monazite data in the present study. Constraints on the Origin of the
Magmatic zircon yielded a large range DISCUSSION Sweetwater Wash Pluton
of eHf(73Ma) (–11 to –17) (Fig. 1B), beyond the The two groups in the eHf versus time plot Monazite and zircon analyses reveal that the
expected reproducibility of a homogeneous zir- (Fig. 1) suggest that the source rocks of the SWP magma was not isotopically homogeneous
con population but within the range predicted by inherited zircon grains crystallized in the early throughout its crystallization but rather evolved

|  Volume 45  |  Number 3  |  GEOLOGY


268 www.gsapubs.org 
through time. At least two magma sources are
evident in the generation of the pluton, one non-
radiogenic with a minimum eNd(73Ma) of ~-19 and
the other more radiogenic with a maximum of
BSE ~-11 (Fig. 3A). The less-radiogenic signature
could reflect substantial juvenile contribu-
tion from enriched lithospheric mantle, which
is known to have contributed to Mesozoic
high and Cenozoic magmatism in this region (e.g.,
Farmer et al., 1989; Gerber et al., 1995; Lee et
Y contents

al., 2001; Wooden et al., 2012).


Our zircon data, however, strongly suggest
that both components are crustal and corre-
low late with recognizable Mojave crustal sources
Grain
G
Gr i A Grain
rai
ain B
ai rain C
Grain
SW1- SW1- (Wooden et al., 2012). The more-radiogenic Nd
-10
-11 grain A grain C component revealed in monazite is most plau-
-12 sibly attributed to the radiogenic Hf source that
-13
-14
is indicated by one population of inherited zir-
ɛNd (73 Ma)

-15 con cores. This component was probably juve-


-16 nile, relatively mafic rock of Proterozoic age.
-17
-18 The non-radiogenic component deduced from
-19 SW1-
ɛNd (73 Ma)
monazite and zircon matches closely the typical,
-20 ɛNd (73 Ma) grain B ɛNd (73 Ma)

0.15 SW1- SW1-


0.14 grain A grain C
0.13
A -7 closed-system FC

mixing
0.12 monazite
monazite FC

0.11 -9 radiogenic source


0.10
-11

cor
ɛNd (73 Ma)
0.09 core

e
0.08 -13 rim
0.07 SW1- bulk
-15
0.06 Sm/144Nd grain B Sm/144Nd magma
147 147
Sm/ Nd
144 147
core
SW1- -17 rim
0.35 SW1-
grain A grain C -19 unradiogenic source
feldspar FC

rim
0.30 147
Sm/144Nd
-21
0.07 0.09 0.11 0.13 0.15
0.25

0.20
B -7 monazite grain A
-9 grain B
core grain C
0.15 -11 whole rock
SW1-
ɛNd (73 Ma)

0.10 Eu/Eu* grain B Eu/Eu* Eu/Eu* -13 rim core


core
48 SW1- SW1- bulk
grain C
-15 magma
44 grain A
WR
monazite FC

40 -17
36 rim
32 -19
28 rim Ce/Gd
-21
24 0 10 20 30 40 50
20
16 C -7 feldspar
12 core
SW1- -9
8 Ce/Gd grain B Ce/Gd Ce/Gd Eu/Eu*=0.61
-11 core
ɛNd (73 Ma)

102 SW1- SW1-


98 grain A grain C -13
U-206Pb age

94 bulk
90 -15 magma
86 core
-17 rim
82 rim
78
74 -19 rim
238

70 Eu/Eu*
66 -21
62 0.10 0.15 0.20 0.25 0.30 0.35
58 SW1-
54 UPb age grain B UPb age UPb age Figure 3. eNd(73Ma) versus Sm/ Nd (A), eNd(73Ma) 147 144

versus Ce/Gd (B), and eNd(73Ma) versus Eu/Eu*


Figure 2. Geochemical contour maps of laser ablation split-stream monazite analyses for (C) for whole rock sample and three monazite
three grains selected for detailed study (sample SW-1, Sweetwater Wash pluton, southeastern grains selected for study (Sweetwater Wash
California, USA). First row, backscattered electron (BSE) image of monazite grains showing pluton, southeastern California, USA). Thin
location of 20 mm laser ablation pits; second row, Y elemental maps; third row, eNd(73Ma); fourth arrows denote the general direction of core-
row, 147Sm/144Nd; fifth row, Eu/Eu*; sixth row, Ce/Gd; and seventh row, U-Pb age. See text for to-rim zoning, for each of the three monazite
further explanation. Arrows indicate expected evolution of a closed magmatic system under- grains: Grain A (blue); Grain B(red); Grain C
going fractional crystallization (FC). (green).

GEOLOGY  |  Volume 45  |  Number 3  | www.gsapubs.org 269


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ACKNOWLEDGEMENTS Hawkesworth, C.J., and Kemp, A.I.S., 2006, Using 1896, doi:​10​.1093​/petrology​/egv057.
Rebecca Lam, Ann Westhues, and Sarah Jantzi assisted hafnium and oxygen isotopes in zircons to unravel Wark, D.A., and Miller, C.F., 1993, Accessory mineral
in the analyses of the monazite, and their technical the record of crustal evolution: Chemical Geol- behavior during differentiation of a granite suite:
expertise is most appreciated. Sean Mulcahy and Owen ogy, v. 226, p. 144–162, doi:​10​.1016​/j​.chemgeo​ Monazite, xenotime, and zircon in the Sweet-
Neill helped with data contouring and provided valu- .2005​.09​.018. water Wash pluton: Chemical Geology, v. 110,
able discussion. We thank Lang Farmer, Andy Barth, Kemp, A.I.S., Hawkesworth, C.J., Paterson, B.A., p.  49–67, doi:​10​.1016​/0009​-2541​(93)90247​-G.
and an anonymous reviewer for constructive com- Foster, G.L., Kinny, P.D., Whitehouse, M.J., and Wooden, J.L., Barth, A.P., and Mueller, P.A., 2012,
ments that greatly improved the manuscript, and editor Maas, R., 2008, Exploring the plutonic-volcanic Crustal growth and tectonic evolution of the
Brendan Murphy for efficient editorial handling. This link: A zircon U-Pb, Lu-Hf and O isotope study of Mojave crustal province: Insights from hafnium
research was supported by an Natural Sciences and paired volcanic and granitic units from southeast- isotope systematics in zircon: Lithosphere, v. 5,
Engineering Research Council of Canada Discov- ern Australia: Transactions of the Royal Society p.  17–22, doi:​10​.1130​/L218​.1.
ery Grant to Hanchar. This is NordSIMS publication of Edinburgh: Earth Sciences, v. 97, p. 337–355,
number 485. doi:​10​.1017​/S0263593300001498. Manuscript received 9 August 2016
Kingsbury, J.A., Miller, C.F., Wooden, J.L., and Har- Revised manuscript received 1 December 2016
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Bachmann, O., Miller, C.F., and de Silva, S.L., 2007, U-Pb systematics in rocks of the eastern Mo-
The volcanic-plutonic connection as a stage for jave Desert, California, USA: Implications for Printed in USA

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