Chemical Geology 384 (2014) 47–61

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Chemical Geology
journal homepage: www.elsevier.com/locate/chemgeo

Reaction rind formation in the Catalina Schist: Deciphering a history of

mechanical mixing and metasomatic alteration
Sarah C. Penniston-Dorland a,⁎, Julia K. Gorman a, Gray E. Bebout b, Philip M. Piccoli a, Richard J. Walker a
a
Department of Geology, University of Maryland, College Park, MD 20742, USA
b
Department of Earth and Environmental Sciences, Lehigh University, Bethlehem, PA 18015-3001, USA

a r t i c l e i n f o a b s t r a c t

Article history: In the subduction-related Catalina Schist, reaction zones or ‘rinds’ developed at contacts of metamorphosed mafic
Received 23 March 2014 blocks with chemically distinct mélange matrix. These rinds exhibit complex chemical compositions that defy
Received in revised form 22 June 2014 simple, single-process explanations. A comparison of high-grade and low-grade reaction rinds, including field
Accepted 24 June 2014
observations, bulk-rock geochemistry, thin section textural observations, mineral compositional analyses, and
Available online 2 July 2014
thermodynamic modeling provides constraints on the nature and timing of the rind-forming processes.
Editor: K. Mezger Bulk-rock variations in the highly siderophile elements (HSE, including Os, Ir, Ru, Pt, Pd and Re) and MgO, Cr,
and Ni provide insight into the physical processes of mixing of ultramafic material of the mélange matrix, rich
Keywords: in these elements, with mafic material derived from the blocks. Enrichments in the concentrations of these
Subduction zone elements are found in both low-grade and high-grade reaction rinds suggesting that the processes that enrich
Mélange these elements and create the reaction rinds occur over a wide range of P–T conditions in subduction zones.
Metamorphism Differences in the chemical composition of garnets in an amphibolite-grade metamafic block, compared with gar-
Highly siderophile elements nets in the associated reaction rind, suggest that at least some of the mixing occurred before the growth of garnet
Garnet
in the blocks, perhaps at P–T conditions different from those producing the garnet. Bulk-rock variations in
elements commonly considered fluid-mobile, such as K2O, Ba and Rb, are observed in all reaction rinds. At
high-grade, enrichments of K2O, Ba and Rb are associated with replacement of garnet and amphibole by phengite
and chlorite. Because phengite is the major host for K, Ba and Rb, the addition of these elements by fluids appears
to have been a post-garnet growth phenomenon. This study highlights the significance of processes of metasomatism
and mechanical mixing in mélange zones for influencing the geochemical evolution of the slab–mantle interface. Any
“fluids” (hydrous or silicate melts) emanating from subducting slabs and entering the mantle wedge and arc lava
source regions would necessarily reflect the hybrid compositions created by these processes.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
The process of subduction juxtaposes rock types with drastically
different chemical and isotopic compositions, leading to great potential
for metasomatic alteration (Bebout, 2013). The compositional diversity
along the slab–mantle interface can be exploited to trace various
subduction zone components from sources through metamorphic
processes and ultimately into arc magmas (e.g., Gill, 1981; Hawkesworth
et al., 1993; Plank and Langmuir, 1993; Davidson, 1996; Alves et al.,
1999; Elliott, 2003; Morris and Ryan, 2003). Subduction-related metamor-
phic rocks also show evidence for a variety of processes occurring within
the “subduction channel,” the dynamic interface between the subducting
slab and the overlying mantle wedge (Shreve and Cloos, 1986; Cloos and
Shreve, 1988a,b; Bebout and Barton, 1989; Gerya et al., 2002; Angiboust
et al., 2011), that act to hybridize these disparate crustal and mantle
lithologies, including tectonic mixing and metasomatism due to
⁎ Corresponding author. Tel.: +1 301 405 6239; fax: +1 301 405 3597.
E-mail address: sarahpd@umd.edu (S.C. Penniston-Dorland).
fluid–rock interactions (e.g., Bebout and Barton, 1989; Sorensen and
Grossman, 1989; Nelson, 1995; Bebout and Barton, 2002; King et al.,
2006, 2007). Chemical and isotopic tracers can be used to elucidate
processes (e.g., mechanical mixing, melting, fluid infiltration, diffusion)
occurring within subduction zones, but careful petrologic analysis of
metamorphic rocks provides an important context for understanding
these processes (e.g., Sorensen and Barton, 1987; Bebout and Barton,
1989; Brunsmann et al., 2001; Breeding et al., 2004; Bebout, 2007;
John et al., 2008; Spandler et al., 2008; Marschall et al., 2009;
Penniston-Dorland et al., 2010; Bebout, 2014).
The tectonic mélange zones found in many subduction zone
metamorphic complexes around the world are thought to represent the
interface between the subducting slab and the overlying mantle wedge.
Reaction zones, sometimes referred to as ‘rinds’, between different lithol-
ogies, commonly at the margins of tectonic blocks, are found in mélange
zones worldwide. These reaction zones vary in mineralogy, but are
commonly composed of hydrous minerals such as amphibole, epidote,
phengite, talc, and chlorite (e.g., Evans et al., 1979; Sorensen and
Grossman, 1989; Sorensen et al., 1997; Fitzherbert et al., 2004;

http://dx.doi.org/10.1016/j.chemgeo.2014.06.024
0009-2541/© 2014 Elsevier B.V. All rights reserved.
48 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61
Marschall et al., 2009), and in some localities are nearly monomineralic
(e.g., Miller et al., 2009). Reaction zones are commonly thought to have
formed due to fluid-assisted metasomatic alteration (e.g., Sorensen and
Barton, 1987; Sorensen and Grossman, 1989; Altherr et al., 2004; Beane
and Liou, 2006; Miller et al., 2009), however, tectonic mixing has
additionally been proposed as a mechanism for creating the chemical
diversity observed in these rinds (e.g., Bebout and Barton, 2002;
Penniston-Dorland et al., 2012).
This study investigates reaction rinds of the Catalina Schist, a
subduction-related metamorphic complex in California, combining
petrology and geochemistry to unravel the mechanisms and relative
timing of the various metamorphic events experienced by these hybrid
rock types. The contrasting behaviors of different groups of more
fluid-mobile elements vs. elements that are relatively immobile in fluids
are exploited to elucidate the roles played by advective transport via
metamorphic fluids and by mechanical mixing of materials. The concen-
trations of highly siderophile elements (HSE) Os, Ir, Ru, Pt, Pd and Re
and Os isotopic composition record an ultramafic signature in reaction
rinds (Penniston-Dorland et al., 2012), providing a clearer picture of
the mechanical mixing component contributing to rind formation (see
also Bebout and Barton, 2002, which focused more on the evolution of
the mélange matrix). This study extends the earlier work on HSE to
reaction rinds from different metamorphic grades in the Catalina Schist,
and combines these data with petrologic information from high- and
low-grade rinds. Petrology and thermodynamic modeling are used to
constrain the relative timing of the various mechanisms in the overall
history of the formation of these reaction rinds. A comparison of
low-grade (lawsonite–albite and lawsonite–blueschist facies) and
high-grade (amphibolite facies) rinds is made along with field and
textural observations to construct a sequential history of reaction rind
formation, shedding light on complex metamorphic processes at
approximate depths of 15–45 km in subduction zones over temperatures
ranging from ≤200 °C to 750 °C.
2. Geologic background
Geochronology of the Catalina Schist indicates that metamorphism
occurred in the Cretaceous (K–Ar of lawsonite–blueschist facies
glaucophane, 98 ± 2 Ma and of amphibolite facies hornblende, 112 ±
3 Ma; Suppe and Armstrong, 1972, recalculated by Mattinson, 1986;
U–Pb of titanite, apatite, amphibole and garnet in amphibolite facies
metamafic blocks, 112–114 Ma; Mattinson, 1986; Lu–Hf of garnet in
an amphibolite facies metamafic block, 114.5 Ma; Anczkiewicz
et al., 2004) with 40Ar/ 39 Ar cooling ages of white mica for most
units (T between 200 and 300 °C) ranging from 90 to 100 Ma (Grove
and Bebout, 1995). Upper bounds on depositional ages based on detrital
zircons in metasedimentary rocks range from 122 Ma in amphibolite
facies to 97 Ma in lawsonite–blueschist and lawsonite–albite facies
rocks (Grove et al., 2008).
Mineralogical, thermobarometric, field, geochronological and
detrital zircon constraints have led to the conclusion that the different
metamorphic units of the Catalina Schist experienced differing prograde
P–T paths, and that the highest grade amphibolite facies rocks may
represent underthrusting along one or more major faults in the forearc,
significantly separated in space from the thrust fault along which the
lower grade units were subducted and metamorphosed (Grove et al.,
2008). Peak P–T estimates of the Catalina Schist metamorphic units
considered in this study are ~250 °C and ~0.5 GPa for lawsonite–albite
facies rocks, ~ 350 °C and ~ 1.0 GPa for lawsonite–blueschist facies
rocks, and ~ 700 °C and ~ 1.0 GPa for amphibolite facies rocks (Platt,
1975; Sorensen and Barton, 1987; Grove and Bebout, 1995). The
lower-grade units of the Catalina Schist, including the lawsonite–albite
and lawsonite–blueschist units investigated here (and by King et al.,
2006, 2007), experienced low-T prograde P–T paths similar to those
experienced by rocks subducting into modern subduction margins.
The amphibolite grade mélange rocks, investigated in detail by
Sorensen and Grossman (1989) and Bebout and Barton (1989, 2002),
provide a glimpse into the metasomatic/mixing processes operating at
higher temperatures (650–750 °C), albeit at depths at which such
temperatures would not ordinarily be experienced in modern, steady-
state subduction zones.
Major and trace-element data suggest that the protoliths for the
Catalina metamafic rocks were likely ocean-floor basalts (Sorensen,
1986), and Sm–Nd isotope data indicate depleted mantle sources
(Barton et al., 1987; data in Bebout, 1989).
The mineralogy of the metamafic blocks in these mélange zones of
the Catalina Schist varies with metamorphic grade. Lawsonite–albite
and lawsonite–blueschist facies metamafic blocks are dominantly
composed of chlorite, albite, calcic–sodic amphibole, phengite and
lawsonite. Amphibolite facies metamafic blocks are dominantly
composed of garnet, amphibole, rutile and titanite (Sorensen and
Grossman, 1989; Bebout, 1997).
Mélange matrix on Catalina consists of talc ± calcic amphibole at all
metamorphic grades with additional phases as follows: ± serpentine ±
fuchsite in lawsonite–albite facies mélange; ± fuchsite ± sodic amphibole
in lawsonite–blueschist facies mélange; and ± chlorite ± anthophyllite ±
ankerite ± enstatite in amphibolite facies mélange (Grove and Bebout,
1995; King et al., 2006). Reaction rinds surrounding metamafic blocks in
mélange have previously been described for garnet amphibolite blocks in
the Catalina Schist (Sorensen and Grossman, 1989). The mineralogy
of these rinds includes calcic amphibole, phengite, quartz, and
chlorite ± rutile ± talc. This manuscript contains the first detailed
study of the low-grade rinds in the Catalina Schist.
3. Analytical methods
Mineral assemblages were determined in thin section by optical
methods and back-scattered electron (BSE) imaging using the JEOL
8900 Electron Probe Microanalyzer (EPMA) at the University of
Maryland. Compositions of minerals were determined using
wavelength-dispersive spectrometry, natural mineral standards, and a
ZAF correction scheme (Armstrong, 1988). Mineral modes were
measured by counting N 650 points in thin section using BSE imaging.
Any uncertainty in the identification of a particular point was resolved
by obtaining an energy-dispersive X-ray spectrum (EDS).
Bulk-rock major and trace element compositions were analyzed
using X-ray fluorescence (XRF) at Franklin and Marshall College. Loss
on ignition (LOI) was determined for each sample first, followed by
XRF analysis on a fusion glass disk made from the resulting anhydrous
powder. Analysis totals for oxides should be near 100%. Repeat analyses
of whole-rock powders resulted in a relative standard deviation (RSD)
of b 0.6% for major elements and b5% for trace elements with concentra-
tions N 25 ppm (1σ) except Cr (12.7%), with elements of lower concen-
tration falling below 35% RSD. Comparison of measured whole-rock
compositions of BHVO-1 and QLO-1 standards to accepted compositions
indicates reproducibility of major element compositions within 2% RSD
(1σ) for all elements with concentrations above 0.6 wt.% and within 12%
RSD for elements with lower concentrations except for Fe2O3 and Na2O
for BHVO-1 (11.95 wt.% with 2.3% RSD and 2.41 wt.% with 6.6% RSD).
Comparison of trace element compositions for trace elements with
concentrations above 30 ppm (including Cr in BHVO-1) was within 10%
RSD and trace elements with lower concentrations varied with most
relative standard deviations falling below 35% except for Th (concentration
0.4 with 100% RSD) and Cr (concentration 1 ppm, 67% RSD).
The chemical separation and measurement techniques used in this
study for Os isotopic measurement and isotope dilution analysis of Re,
Os Ir, Ru, Pt and Pd have been published in detail elsewhere (Shirey
and Walker, 1995; Rehkämper and Halliday, 1997; Becker et al., 2006;
Schulte et al., 2009). Samples were sanded, crushed in an alumina
mortar and pestle, and ground to a fine powder using an alumina
ceramic container in a SPEX 8000M Mixer-Mill to avoid metal contam-
ination. Finely-ground sample powders were processed by inserting
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61 49

~ 0.5–2.5 g of sample powder into Pyrex™ Carius tubes along with
individual 185Re and 190Os spikes, and a separate mixed spike consisting
of 191Ir, 99Ru, 194Pt and 105Pd. Approximately 6 mL of concentrated
HNO3 and 4 mL of chilled, concentrated HCl were also added to the
tubes. The tubes were sealed, then heated at ~260 °C for at least 72 h.
Osmium was purified using a carbon tetrachloride solvent extraction
technique (Cohen and Waters, 1996) followed by microdistillation
purification (Birck et al., 1997). Rhenium, Ir, Ru, Pt, and Pd were separated
and purified from the residual acid using two successive anion exchange
columns. The Os total processing blank averaged 1.2 ± 0.9 pg with 187Os/
188
Os = 0.1517 ± 0.020 (1σ, n = 3). The blank was ≤0.5% for the two
high-Os samples and ranged up to 9% of the concentration of the
lower-Os samples. The Re, Ir, Ru, Pt, and Pd blanks for the procedure
averaged 12 ± 17, 0.5 ± 0.7, 4 ± 2, 122 ± 33, and 17 ± 13 pg respectively
(n = 3). For most samples the blanks for Ir, Pd, and Ru were b0.05%, 1%
and 1.3% respectively (except LA10-2A which were 5.4%, 12%, and 3.8%
respectively). Otherwise blanks were b 6%, except for the Pt blank for
sample LA10-2A which was 33%. The higher uncertainties are for the
samples with the lowest concentrations and do not impact the conclusions
made from these data.
Osmium was analyzed via negative thermal ionization mass spec-
trometry (Creaser et al., 1991). External reproducibility in 187Os/188Os
for Os-rich samples was about ± 0.2% based on analysis of the UB-N
standard (Puchtel et al., 2008). Rhenium, Ir, Ru, Pt and Pd analyses

Fig. 1. a) Field photo of lawsonite–blueschist facies block. Block core, block rind and mélange matrix are labeled. White box represents region of closeup photos in panels b and c. b) Closeup
photo of contact between rind and matrix. c) Interpretive sketch of photo in panel b. The interface between rind and matrix is complex and convoluted, with pieces of rind within the
matrix and pieces of matrix within the block rind. d) Drill core sample of lawsonite–albite facies block. Block rind is light colored material labeled “7d” with arrow in black ink. e) Inter-
pretive sketch of block in panel d showing complex nature of rind–matrix interface.
50 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61

Table 1
Mineral modes (volume percent).

Facies Amphibolite Lawsonite–albite Lawsonite–blueschist

Core Rind Core Rind Core Rind Core Rindb Core Rind

Mineral A10-3D A10-3A A12-A4C A12-A4R LA10-3B LA10-3F LB10-1A LB10-1B LB12-E1 LB12-E3

nc 2063 2127 2299 2129 1062 1022 659 2232 1008 1007

Amphibole 72.71 55.15 78.90 83.70 33.0 0.6 17.03 46.0

Garnet 18.57 0.28 14.83
Phengite 1.31 24.31 0.91 1.78 16.4 4.4 8.06 30.9 57.0
Chlorite 1.45 5.41 1.48 7.84 26.9 62.8 54.8 28.27 3.7 35.8
Rutile 1.99 0.56 1.48 0.23
Apatite 0.92 0.33 0.65 0.5 0.6 0.3 0.13 0.1
Pyrite 0.34 tr 0.23 tr
Quartz 0.10 13.68 2.17 7.89 0.8 1.21 0.3 0.1
Titanite 0.10 0.28 0.04 3.9 2.8 4.9 1.52 1.5 2.4
Zircon 0.10 tr 0.05 tr tr
Lawsonite 0.09 0.05 27.6 0.9 0.09 4.3
Albite 23.1 26.1 38.62 10.8 4.3
Calcite 1.3 8.0 5.06 0.9 0.3
K-feldspar 1.3 0.1
Epidote 0.19 0.2 0.2
Fe-oxide 0.1
Monazite tr
Garneta inclusions 2.28 0.34
a
Garnet inclusions are chlorite, amphibole, albite, phengite, epidote, quartz, pyrite, rutile, and titanite, bphengite and chlorite interlayered on fine-scale, EDS spectra were difficult to
interpret but results were binned based on ratio of peak heights of K vs. Mg and Mg vs. Al. cn indicates the number of points used for determination of mineral modes.

were conducted using a Nu Plasma multi-collector inductively coupled
plasma mass spectrometer coupled with a Cetac Aridus™ desolvating
nebulizer. All analyses were obtained using static, multiple multipliers.
Measured concentrations of Re, Os, Ir, Ru, Pt and Pd in the UB-N
standard were 0.210, 3.61, 3.29, 6.12, 7.30, and 7.83 ppb respectively.
Except for Pd, these values fall within the range of reported measure-
ments for this standard (Puchtel et al., 2008). The Pd concentration
measured for UB-N for this study was about 15% higher than the reported
range. Other analyses of Pd done at the same time on the same standard
powder were within the accepted range, so an anomalous concentration
in the powder aliquot analyzed is suspected.
4. Results
4.1. Field observations
Reaction rinds surrounding metamafic blocks in mélange have
previously been described for garnet amphibolite blocks in the Catalina
Schist as well as for mafic eclogite and blueschist from other localities
(e.g., Sorensen and Barton, 1987; Sorensen and Grossman, 1989;
Sorensen et al., 1997). Block and rind samples for this study were
collected mostly along beaches and in valleys where they can be
found either as bedrock exposed by waves or runoff or as large float
blocks (see Table A1 for location details). There is generally a sharp
contact between a metamafic block and its reaction rind. The rinds are
concentrically foliated with amphiboles and sheet silicates oriented
such that they wrap around the exterior of the semi-spherical
metamafic blocks. The low-grade rinds also typically have concentric
foliation, however, the nature of the interface between blocks and the
encasing matrix in lower-grade rocks is complex (see King et al.,
2006). Where observed, the boundary is convoluted and pieces of
reaction rind are observed apparently broken off from the block and
surrounded by mélange matrix. Mélange matrix appears between
pieces of broken-off rind (Fig. 1).
4.2. Mineralogy and mineral chemistry
Samples were obtained of metamafic blocks and associated reaction
rinds from the lawsonite–albite, lawsonite–blueschist, and amphibolite
facies. The mineral modes for representative block core and rind
samples are shown in Table 1.
4.2.1. Amphibolite facies metamafic blocks and reaction rinds
Amphibolite facies metamafic blocks are composed of amphibole
and garnet with phengite, chlorite and rutile and minor amounts of
apatite, pyrite, titanite, quartz and zircon. The associated rinds have
calcic amphibole, phengite, quartz, and chlorite and minor amounts of
rutile, apatite, titanite, and in rare cases garnet.
Detailed petrography of rind samples A10-3A and A10-3B revealed a
number of features. Quartz veinlets within this sample are oriented par-
allel to the concentric foliation. There are small euhedral garnets within
the quartz veins. The sample also contains resorbed garnets in the rest of
the rock that are partially pseudomorphed by phengite and chlorite
(Fig. 2a). Rind amphiboles are also pseudomorphed by chlorite and
phengite (Fig. 2b). The replacement chlorite and phengite are randomly
oriented, not aligned parallel to the concentric foliation.
Average major-element compositions of the main mineral phases in
the block core and rind of amphibolite facies samples are shown in
Table 2. The phengite in the block core contains greater concentrations
of Si compared to the phengite in the rinds, which are more Al-rich (cf.
Sorensen, 1988). The rind phengite and chlorite have an overlapping
range of Mg/(Mg + Fe) compared to phengite and chlorite from the
block core. Amphiboles in the block core and rind are dominantly
Mg-hornblende. Rind hornblendes have higher or similar average Mg/
(Mg + Fe) when compared to hornblendes from the associated
block core (0.79 compared to 0.73 for A10-5; 0.72 compared to
0.69 for A10-3).
Garnets in both the block core and rind in sample A10-3 are
generally almandine-rich (with X Fe ranging from approximately
0.50 to 0.65). Rind garnets have higher Mg and lower Ca than core
garnets (Table 2). X-ray maps reveal concentric growth zoning in
garnets in the block core (Figs. 3 and 4). Core garnets have high
concentrations of Ca and Mn in the centers, decreasing towards
rims, and low concentrations of Mg in garnet centers, increasing to-
wards rims. Rind garnets did not exhibit systematic zoning in any
of the elements analyzed. Neither Cr nor Fe displayed any systematic
variation either from garnet centers to rims, or between garnets in
block cores and rinds.
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61 51

shown normalized to estimates for primitive mantle (McDonough and

Sun, 1995) in Fig. 5. The major- and trace-element compositions of mé-
lange matrix samples are reported in Bebout and Barton (2002), King
et al. (2006), and King et al. (2007). Rinds generally have higher concen-
trations of MgO, Ni and Cr (see Figs. 5–7), compared to metamafic block
cores. These elements are also enriched in mélange matrix, since there is
a large peridotitic contribution in the mélange matrix (Bebout and
Barton, 2002). Along with these enrichments, there are depletions in
CaO, Na2O, Al2O3, and TiO2 in rinds, compared to block cores, and
these elements are relatively depleted in peridotite. Concentrations of
large ion lithophile elements (LILE) Rb, Ba, and K2O as well as SiO2 are
variable. In some rinds they are elevated relative to the associated
metamafic block cores and in some rinds they are depleted (Fig. 6).

4.4. Whole-rock highly siderophile element geochemistry

Samples of amphibolite facies blocks and rinds were previously

analyzed for concentrations of HSE as well as 187Os/188Os for two

Fig. 2. a) Photomicrograph in plane-polarized light of amphibolite facies rind sample A10-

3A. Garnet (gar) in the center of the image is surrounded by and being replaced by chlorite
(chl) and phengite (ph). b) Photomicrograph in plane polarized light of amphibolite facies
rind sample A10-3B. Chlorite (chl) and phengite (ph) pseudomorphically replace amphibole.
Dashed outline shows original amphibole crystal habit. Phengite and chlorite are randomly
oriented, not aligned with general foliation (approximately N–S on thin section).

4.2.2. Lawsonite–albite and lawsonite–blueschist facies metamafic blocks

and reaction rinds
Lawsonite–albite and lawsonite–blueschist facies metamafic blocks are
generally composed of lawsonite, albite and phengite pseudomorphing
original plagioclase phenocrysts along with chlorite and minor titanite
and apatite. The associated rinds are composed of chlorite and actinolite,
along with phengite, titanite and apatite. Both blocks and rinds contain
calcite that generally occurs in veins. One lawsonite–blueschist facies
metamafic block (LB12-E) consists of glaucophane, albite, phengite and
lawsonite along with chlorite, titanite, quartz, apatite and iron oxide and
K-feldspar and calcite in veins. The associated rind is mostly phengite and
chlorite with lawsonite, titanite, and small amounts of quartz, and calcite.
Average major-element compositions of the main mineral phases in
the block core and rind of lawsonite–albite and lawsonite–blueschist
facies samples are shown in Table 2. Amphibole in most of the
lawsonite–albite and lawsonite–blueschist facies rinds is Mg-rich
actinolite (Mg/(Mg + Fe) = 0.64 to 0.87). Phengite in the rind is also
Mg-rich with an average Mg/(Mg + Fe) of 0.80 that is higher than that
of phengite in the block core (0.62). Average Mg/(Mg + Fe) of rind
chlorite is also higher (0.60) than chlorite in the block core (0.49).

4.3. Whole-rock major- and trace-element geochemistry

Fig. 3. a) Calcium and b) manganese X-ray maps of garnet from block core sample A10-3D.
High concentrations are indicated by hot colors and low concentrations by cool colors (red
Whole-rock XRF major- and trace-element concentrations for a suite N yellow N blue). Euhedral outlines of zones within garnets suggest that original growth
of high- and low-grade block cores and rinds are reported in Table 3 and concentrations are retained.
52 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61

Table 2
Electron probe microanalyzer major-element compositions of minerals.

Phengitea Chloritea

Facies Amphibolite Lawsonite–blueschist Amphibolite Lawsonite–blueschist

Core Rind Core Rind Core Rind Core Rind

A10-3D A10-3A LB12-E1 LB12-E3 A10-3D A10-3A LB12-E1 LB12-E3

SiO2 53.73 49.28 52.07 52.33 26.39 27.70 28.89 28.26

TiO2 0.13 0.50 0.10 0.04 0.10 0.04 0.07 0.03
Al2O3 23.17 29.27 26.70 26.66 23.05 20.68 19.13 20.72
FeO 3.83 2.80 3.35 2.22 22.41 21.13 25.64 21.45
MnO 0.03 0.04 0.05 0.03 0.20 0.42 0.30 0.34
MgO 5.01 3.47 3.41 4.91 16.39 17.70 14.03 17.83
CaO 0.04 0.03 0.03 0.02 0.02 0.02 0.11 0.06
BaO 0.11 0.72 0.86 0.46 0.04 0.05 0.00 0.03
Na2O 0.03 0.26 0.18 0.03 0.01 0.02 0.24 0.01
K2O 10.25 9.87 9.78 9.76 0.01 0.01 0.03 0.02
Oxide sum 96.32 96.24 96.53 96.46 88.64 87.78 88.43 88.75

Si 3.56 3.28 3.45 3.448 2.69 2.84 3.00 2.86

Al 1.81 2.29 2.08 2.06 2.78 2.50 2.34 2.48
Ti 0.01 0.03 0.01 0.00 0.01 0.00 0.01 0.00
Feb 0.21 0.16 0.19 0.12 1.92 1.82 2.23 1.82
Mn 0.00 0.00 0.00 0.00 0.02 0.04 0.03 0.03
Mg 0.49 0.34 0.34 0.48 2.49 2.70 2.17 2.69
Ca 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01
Ba 0.00 0.02 0.02 0.01 0.00 0.00 0.00 0.00
Na 0.00 0.03 0.02 0.00 0.00 0.00 0.05 0.00
K 0.87 0.84 0.83 0.82 0.00 0.00 0.00 0.00
ne 10 18 16 14 18 10 6 14
Mg/Mg + Fe 0.70 0.69 0.62 0.80 0.56 0.60 0.49 0.60
(Range) 0.65–0.74 0.64–0.74 0.44–0.78 0.78–0.84 0.48–0.68 0.53–0.73 0.48–0.51 0.50–0.71

Amphibolea

Facies Amphibolite Lawsonite–albite Lawsonite–blueschist

Core Rind Core Rind Rind Rind Core

A10-3D A10-3A A10-5B A10-5A LA10-3F LB10-1B LB12-E1

actc hblc Na-poor Na-rich

SiO2 47.32 48.04 47.17 55.41 49.24 57.56 52.68 56.98 56.89
TiO2 0.50 0.47 0.37 0.02 0.35 0.03 1.29 0.04 0.07
Al2O3 11.70 11.62 13.35 2.04 11.06 0.10 2.92 0.66 11.75
FeO 11.54 10.65 9.76 7.66 7.81 5.66 10.49 6.77 15.21
MnO 0.06 0.27 0.06 0.08 0.08 0.16 0.25 0.16 0.13
MgO 14.35 15.07 14.66 19.53 16.55 21.73 17.94 20.34 6.55
CaO 11.14 10.64 11.27 12.79 11.28 13.45 9.34 12.57 0.40
Na2O 1.51 1.92 1.86 0.64 1.83 0.24 3.12 0.78 6.88
K2O 0.18 0.15 0.28 0.07 0.30 0.04 0.43 0.06 0.28
Oxide sum 98.29 98.83 98.78 98.25 98.49 98.96 98.47 98.38 98.19

Si 6.77 6.81 6.67 7.75 6.91 7.91 7.50 7.91 7.95

Al 1.97 1.94 2.23 0.34 1.83 0.02 0.50 0.11 1.94
Ti 0.05 0.05 0.04 0.00 0.04 0.00 0.14 0.00 0.01
Feb 1.38 1.26 1.16 0.90 0.92 0.65 1.26 0.79 1.78
Mn 0.01 0.03 0.01 0.01 0.01 0.02 0.03 0.02 0.02
Mg 3.06 3.18 3.09 4.07 3.46 4.46 3.80 4.21 1.37
Ca 1.71 1.61 1.71 1.92 1.70 1.98 1.43 1.87 0.06
Na 0.42 0.53 0.51 0.17 0.50 0.06 0.86 0.21 1.86
K 0.03 0.03 0.05 0.01 0.05 0.01 0.08 0.01 0.05
n 16 11 19 3 14 3 10 15 16
Mg/Mg + Fe 0.69 0.72 0.73 0.82 0.79 0.87 0.79 0.84 0.44
(Range) 0.67–0.72 0.69–0.77 0.68–0.78 0.81–0.83 0.77–0.81 0.87 0.64–0.84 0.82–0.86 0.35–0.55

Garneta

Facies Amphibolite

Core Rind

A10-3C A10-3D A10-3A

Garnet 8 Garnet 9 Garnet 1 Garnet 3

Center Rim Center Rim

SiO2 37.51 37.91 37.69 38.10 38.03 37.98

TiO2 0.06 0.13 0.14 0.14 0.07 0.07
Al2O3 21.34 21.51 21.16 21.43 21.26 21.28
FeO 25.94 25.92 25.17 25.07 25.21 25.44
MnO 1.58 0.71 1.15 0.42 1.70 1.97
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61 53

Table 2 (continued)
Garneta

Facies Amphibolite

Core Rind

A10-3C A10-3D A10-3A

Garnet 8 Garnet 9 Garnet 1 Garnet 3

Center Rim Center Rim

MgO 4.56 5.68 3.81 5.77 6.91 7.22

CaO 8.05 7.58 10.26 8.48 5.69 5.10
Oxide sum 99.05 99.42 99.38 99.42 98.88 99.07

Ca 0.68 0.64 0.87 0.71 0.48 0.43

Feb 1.72 1.70 1.67 1.64 1.66 1.67
Mg 0.54 0.66 0.45 0.67 0.81 0.85
Mn 0.11 0.05 0.08 0.03 0.11 0.13
Ti 0.00 0.01 0.01 0.01 0.00 0.00
Al 1.99 1.99 1.97 1.98 1.97 1.97
Si 2.98 2.98 2.98 2.98 2.99 2.98
n 4 11 5 15 10 7
Mg/Mg + Fe 0.24 0.28 0.21 0.29 0.33 0.34
(Range) 0.23–0.24 0.24–0.31 0.21 0.25–0.32 0.32–0.34 0.33–0.34
a
Number of oxygens used in calculations of mineral formulae (per formula unit) — phengite = 11, chlorite = 14, amphibole = 23, garnet = 12.
b
Calculations assume Fe+2.
c
act = actinolite, hbl = hornblende. en indicates number of analyses for each sample.

Fig. 4. Major-element compositions of garnet (in atoms per formula unit — apfu) measured by electron probe microanalyzer across traverses within garnets. Gray lines are compositions of
block core garnets, black lines are compositions of block rind garnets. X-axis on all graphs is analysis point number, a proxy for distance across garnet. The spacing between points ranged
from 30 to 100 μm for both core and rind garnets. a. Ca, b. Mg, c. Mn.
54 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61

Table 3
Whole-rock major and trace element chemistry.

Block cores Block rinds

Amphibolite Lawsonite–albite Lawsonite– Amphibolite Lawsonite–albite Lawsonite–

blueschist blueschist

A10-3D A10-5B A12-A4Ca A10-2A4 LA10-2A LA10-3B LB10-1A LB12-E1 A10-3A A10-5A A12-A4Ra A10-2A1 LA10-2C LA10-3F LB10-1B LB12-E3

(Wt.%)
SiO2 43.06 41.26 44.23 36.97 45.13 45.39 38.07 54.36 56.03 50.20 52.46 55.42 56.35 40.12 51.78 46.47
TiO2 2.87 4.71 2.49 5.10 3.48 2.14 1.41 0.65 0.99 0.61 0.89 0.09 0.03 1.77 1.03 0.88
Al2O3 13.79 14.95 14.79 17.63 17.62 24.01 17.61 18.21 10.84 10.84 11.46 5.50 2.43 12.81 14.81 21.88
Fe2O3T 16.65 15.10 15.92 17.90 13.83 11.54 11.86 10.02 10.06 8.83 11.11 7.07 7.03 13.49 7.44 9.24
MnO 0.21 0.30 0.33 0.35 0.18 0.17 0.16 0.12 0.25 0.09 0.18 0.12 0.12 0.27 0.13 0.18
MgO 11.32 11.13 10.95 5.64 9.14 4.61 9.08 5.26 11.18 16.77 13.17 20.44 25.48 25.40 12.32 13.10
CaO 10.15 10.65 9.32 12.26 3.90 6.75 16.50 3.13 7.42 10.31 8.84 10.28 7.58 5.37 6.93 2.32
Na2O 1.11 1.10 1.44 1.26 4.66 2.49 2.68 4.49 0.94 1.40 1.56 0.93 0.22 0.25 4.24 1.33
K2O 0.44 0.22 0.26 0.19 0.41 2.47 1.97 3.75 2.13 1.03 0.38 0.05 0.01 0.02 1.02 4.84
P2O5 0.34 0.79 0.27 2.76 0.57 0.33 0.27 0.15 0.16 0.01 0.02 0.01 0.01 0.29 0.20 0.04
Total 99.91 100.09 99.98 99.91 98.92 99.90 99.61 100.14 100.00 100.09 100.09 99.91 99.26 99.79 99.90 100.28
LOIb 2.27 1.50 1.77 2.07 6.26 7.21 13.08 4.74 2.98 2.07 2.15 1.37 4.13 9.17 6.52 8.55
FeO 12.12 8.54 10.10 13.56 11.49 8.67 8.56 7.04 7.92 7.05 8.65 5.42 5.42 10.22 5.89 7.05
Fe2O3 3.18 5.61 4.69 2.83 1.06 1.90 2.35 2.20 1.26 0.99 1.49 1.05 1.01 2.13 0.89 1.40

(ppm)
Rb 11.2 5.0 3.5 5.9 19.6 53.8 41.6 87.5 50.2 24.9 5.5 2.4 0.8 1.7 26.6 132.4
Sr 40 72 57 226 208 290 662 371 45 65 46 46 39 27 268 185
Y 63.2 47.3 59.5 89.9 16.2 38.5 34.2 24.9 31.8 8.8 46.2 2.4 1.0 27.2 24.4 35.4
Zr 145 195 113 738 141 150 92 51 99 81 155 12 15 31 54 53
V 574 429 495 243 264 240 319 288 232 272 230 31 51 223 220 453
Ni 115 188 96 73 137 106 95 53 348 617 335 1330 1418 769 304 162
Cr 376 155 200 73 133 225 237 75 658 1013 863 1595 2592 1381 410 101
Nb 7.1 48.7 5.2 67.8 26.0 30.4 6.4 1.3 4.4 2.9 1.8 b 0.5 b0.5 20.1 16.3 2.1
Ga 19.3 15.7 17.2 9.9 19.5 21.9 15.9 16.0 13.4 17.1 14 6.2 5.9 13.6 10.3 16.5
Cu 82 23 33 27 9 25 62 97 62 25 52 6 10 40 49 191
Zn 158 139 145 94 141 156 87 88 105 149 117 135 58 80 48 83
Co 69 62 64 39 41 43 33 36 42 57 47 52 71 89 43 49
Ba 90 81 66 112 78 827 691 1261 793 285 142 11 8 21 337 1076
La 11 20 7 28 6 20 7 10 8 3 7 4 3 3 8 11
Ce 32 97 23 162 13 50 10 14 11 5 16 5 4 12 19 27
U 1.6 2.4 b0.5 5.9 1.4 1.5 1.2 b0.5 2.5 2.4 b0.5 1.4 b0.5 0.5 1.6 b0.5
Th 2.5 10.1 3.0 11.5 1.2 5.5 1.1 2.4 2.8 0.6 b0.5 1.0 b0.5 2.0 1.4 3.4
Sc 59 40 56 29 38 30 54 31 31 25 33 9 8 22 27 21
Pb 1 2 1 1 b1 b1 1 5 b1 1 b1 b1 b1 1 b1 2
a
Concentrations are the average of 6 (A12-A4C) or 7 analyses (A12-A4R).
b
LOI = loss on ignition.

block–rind pairs and one sample of mélange matrix from the Catalina
Schist (Penniston-Dorland et al., 2012). The HSE concentrations and iso-
topic ratios for three additional block–rind pairs of lawsonite–albite
(LA10-2, LA10-3) and lawsonite–blueschist (LB10-1) facies samples
are reported in Table 4. HSE patterns are shown in Fig. 8 normalized
to primitive upper mantle values (PUM) of Becker et al. (2006).
The low-grade samples share some HSE characteristics with the
higher-grade rocks. Both high- and low-grade block cores have
HSE concentrations and 187 Os/ 188 Os consistent with basalt. Both
high- and low-grade rinds have higher concentrations of Os, Ir
and Ru, and lower initial 187Os/188Os, compared to cores (Figs. 6,
8 and 9).
5. Discussion
Reaction rinds found on the outer parts of metamafic blocks of the
Catalina Schist have distinctly different mineralogy and chemistry
when compared to both the metamafic blocks and the mélange ma-
trix. The chemical composition of the rinds can be divided into three
types of elements: those that reflect a peridotite component, those
that reflect a component of the metamafic blocks and those that do
not reflect either metamafic block or peridotite. Below we explore
these types of chemical differences and consider the possible mech-
anisms that created the chemical variations observed in the reaction
rinds.
5.1. Peridotite vs. mafic component in rinds
Reaction rinds generally have elevated concentrations of MgO,
Ni, Cr, Os, Ir and Ru compared to metamafic block cores (see
Tables 3 and 4 and Figs. 6 to 9). This suite of elements is also
enriched in rocks of the mélange matrix and has previously been
considered to reflect a peridotitic component in the matrix and
rind samples (Bebout and Barton, 2002; Penniston-Dorland et al.,
2012). Correlated with these enrichments are depletions in rinds
in elements that are found in low concentration in peridotite and
comparatively high concentration in mafic rocks, such as CaO,
Na 2 O, Al2 O 3, and TiO2 . The 187 Os/ 188 Os of rinds is lower than
metamafic block cores, consistent with the low, long-term Re/Os
that is characteristic of peridotites, compared with metamafic rocks
(Fig. 9).
The bulk rock difference in chemical composition is also reflected in
the chemical composition of the minerals in the rinds and metamafic
blocks. The Fe–Mg-bearing minerals including phengite, chlorite, and
amphibole are generally more Mg-rich in the rinds than in the
metamafic block cores.
Elevated concentrations of HSE in high-grade block rinds from the
Catalina Schist and other subduction zone mélanges have been
interpreted as the product of mechanical mixing of material derived
from metamafic blocks and peridotitic material (Penniston-Dorland
et al., 2012). Penniston-Dorland et al. (2012) reported that Os, Ir, and
Ru concentrations in high-grade rinds were only modestly lower than
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61 55

Fig. 5. Bulk rock compositions of block cores and rinds normalized to primitive mantle (McDonough and Sun, 1995). a) Major-element composition of amphibolite facies block cores (open
symbols) and rinds (filled symbols). b) Trace-element composition of amphibolite facies block cores and rinds. c) Major-element compositions of lawsonite–albite (squares) and
lawsonite–blueschist (triangles) facies block cores and rinds. d) Trace-element composition of lawsonite–albite and lawsonite–blueschist facies block cores and rinds.

normal mantle peridotite, and were little fractionated from one another,
relative to typical mantle peridotites. Similar results are observed for the
lawsonite–albite and lawsonite–blueschist facies rinds reported here
(Fig. 8). As with the high-grade blocks, the rinds are well-discriminated
from the block cores for elements enriched in peridotite such as MgO, Cr,
Ni, and the HSE, as well as Os isotopes (Fig. 9).
These characteristics are difficult to explain via fluid transport, as the
enriched elements, particularly the HSE, are not efficiently fluid
mobilized. A mechanical mixing mechanism has been suggested for
rind formation based on simple mixing calculations using Os concentra-
tions and 187Os/188Os of amphibolite-facies blocks and a typical mantle
peridotite endmember (Penniston-Dorland et al., 2012). Simple mixing
calculations were performed using the measured Os concentrations and
187
Os/188Os of two high-grade block cores as one endmember and
assuming mixing with a typical mantle peridotite bearing an Os concen-
tration of 3.9 ppb and 187Os/188Os of 0.125. The block core endmembers

Fig. 6. Bulk-rock chemical compositions of rinds relative to associated metamafic block cores. Elements are in order of decreasing average ratio. Elements with consistently higher concen-
trations in rinds compared to metamafic block cores include Ir, Ru, Os, Cr, Ni, and MgO. Elements with variable relative abundances include Ba, Rb, K2O, and SiO2. Elements with consis-
tently lower concentrations in rinds compared to metamafic block core include CaO, Na2O, Al2O3, and TiO2.
56 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61

Fig. 8. Primitive upper mantle (PUM) normalized HSE abundances for low-grade samples
of the Catalina Schist. PUM values from Becker et al. (2006). For comparison, the gray field
outlines the range of compositions reported for abyssal peridotites (Rehkämper and
Halliday, 1997; Luguet et al., 2003; Liu et al., 2009; Schulte et al., 2009) and the stippled
pattern outlines the range of compositions reported for mafic rocks (Rehkämper and
Halliday, 1997; Bézos et al., 2005; Dale et al., 2008, 2009; Schulte et al., 2009).

Complex, CA, and the Samana Metamorphic Complex, Dominican Repub-

lic (Penniston-Dorland et al., 2012). The low-grade rind compositions fall
near mixing curves defined by the high-grade block cores and peridotite.
The percentage of peridotite required ranges from b1% to 39% based on
Os concentrations (see Table 5).

5.2. Fluid-mobile element variations in rinds

Reaction rinds have variable concentrations of K2O, SiO2, Ba, and Rb

Fig. 7. Differences in bulk-rock chemical composition of high- and low-grade block cores
and rinds. a. Ni vs. Cr, b. MgO vs. Al2O3. Rinds from all three units have correlated concen-
trations of Cr, Ni, and MgO and lower Al2O3 when compared to block cores. Data for high-
grade samples from Penniston-Dorland et al. (2012).
that were chosen have the highest and lowest 187Os/188Os measured in
metamafic rocks to constrain the upper and lower bounds of mixing.
The mass percentage of each component that is required to create the
measured 187Os/188Os of rinds was calculated and the resulting mixing
curves are illustrated in Fig. 10 along with the Os concentrations and iso-
topic compositions of low-grade blocks and rinds from this study, as well
as data for high-grade blocks of the Catalina Schist, the Franciscan
compared to metamafic block cores (see Sorensen, 1988; Sorensen and
Grossman, 1989). This suite of elements is not enriched in mélange
matrix, except SiO2, and tends to be somewhat depleted in matrix
relative to high-grade rind material (see Bebout and Barton, 2002).
While the high-grade rinds are enriched in these elements, the
low-grade rinds are depleted in these elements compared to metamafic
block cores (see Fig. 6). The concentrations of these relatively
fluid-mobile elements are likely controlled by exchange between infiltrat-
ing metamorphic fluids and the rinds (Bebout and Barton, 1989; Bebout,
1997; Bebout and Barton, 2002; see also Sorensen and Grossman, 1989;
Sorensen et al., 1997). The observed high-grade rind enrichments and
low-grade rind depletions in these elements compared to metamafic
block cores suggest that there may be a difference in fluid composition
between metamorphic grades. This difference may be due to differences
in fluid source (e.g. more or less of a sedimentary component in some
fluids) or difference in element or mineral solubility under the different
P–T conditions in each metamorphic facies, suggesting a regional control
on the source and transport of these elements. The chemical differences

Table 4
Highly siderophile element concentrations, 187Os/188Os, 187Re/188Os, calculated initial 187Os/188Osi, for bulk samples. HSE concentrations are in ng/g.
187
Sample Type Os Ir Ru Pt Pd Re Os/188Os 187
Re/188Os 187
Os/188Osia

Lawsonite–albite facies
LA10-2A Core 0.017 0.010 0.057 0.145 0.073 0.066 0.2686 19 0.2374
LA10-2C Rind 1.541 2.29 3.21 1.68 1.26 0.038 0.1244 0.118 0.1242
LA10-3B Core 0.012 0.011 0.035 0.103 0.109 0.009 0.3352 3.7 0.3292
LA10-3F Rind 0.250 0.171 0.331 1.79 6.47 0.014 0.1322 0.27 0.1318

Lawsonite–blueschist facies
LB10-1A Core 0.017 0.018 0.055 0.184 0.359 0.014 0.3374 4.0 0.3309
LB10-1B Rind 0.045 0.038 0.083 0.337 0.380 0.134 0.3407 15 0.3166
a
114.5 Ma, the age of peak metamorphism of the Catalina Schist (Anczkiewicz et al., 2004), was used for calculation of initial 187Os/188Os ratios from measured 187Re/188Os.
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61
Fig. 9. Correlation between bulk-rock contents of block cores, rinds and matrix of low- (“L”)
and high-grade (“H”) samples, and mélange matrix of the Catalina Schist. a) Os, Ir, Ru with
MgO, b) Os, Ir, Ru with Ni, c) Os, Ir, Ru with Cr, and d) 187Os/188Os with MgO. Data for
high-grade samples from Penniston-Dorland et al. (2012).
57
Fig. 10. Mixing calculations (curves) compared to Os concentrations and 187Os/188Os for
low-grade samples from this study, indicated by squares, plotted along with samples
from Penniston-Dorland et al. (2012) indicated by diamonds, for amphibolite, eclogite
and blueschist blocks and rinds from the Franciscan Complex (CA) and the Samana Meta-
morphic Complex (Dominican Republic) and the Catalina Schist (larger diamonds) along
with Catalina Schist melange matrix (gray diamond).
are reflected in the modal mineralogy of the reaction rinds. There is a
greater abundance of phengite in the high-grade rinds which show overall
addition of K2O, Ba and Rb (see discussion in the next section).
5.3. Timing of chemical changes
The presence of garnets in the garnet amphibolite block cores, and
also in one of the amphibolite facies rinds, allows for the determination
of the timing of chemical changes relative to the timing of garnet
growth. As described above, the addition of K2O, Ba, and Rb to
high-grade rinds is attributed to fluid infiltration. The replacement of
both garnet and amphibole by chlorite and phengite in the amphibolite
facies indicates a late-stage alteration of garnet and amphibole in the
rinds, and since phengite is the main host of K (and likely Ba and Rb)
in these rocks, it appears that these elements were added post-garnet
growth. Therefore the fluid infiltration event that added K2O, Ba, and
Rb likely occurred after garnet growth, relatively late in the sequence
of events that affected the rinds. The fact that these elements are
enriched only in block rinds and not in the mélange matrix suggests
that there is also a mineralogical control on their distribution. The
phengite that hosts these elements is a common mineral found in
high-grade reaction rinds, but not in the amphibolite facies mélange
matrix. Fluids had to travel through the matrix in order to reach the
rinds, so it may be puzzling that the matrix is not similarly enriched in
K2O, Ba and Rb. The reason for this may be found in considering the
relative proportions of Al and Mg in mélange matrix compared to
reaction rinds (Fe contents of matrix and rinds are similar). The average
concentration of Al2O3 in mélange matrix is ~ 6 wt.% and MgO is ~ 26
wt.% (Bebout and Barton, 2002). The average Al2O3 concentration of
the rinds reported in this study is ~ 11 wt.% and MgO is ~17 wt.%. The
Al/Mg ratio of the sheet silicates increases from chlorite to biotite to
phengite. It is likely that the relatively low concentrations of Al in the
matrix stabilized chlorite, but were not high enough to stabilize
phengite or biotite. This may explain why K2O, Ba, and Rb were not
enriched in the matrix since there was not an appropriate mineral
58 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61
Table 5
Calculated percentage of peridotite component in rinds.
Os isotopic compositions
Sample 0.124 0.123 Maximum% (up to 0.129)
a
LA10-2A/C 70.9% 28.8% n/a
LA10-3B/F 7.0% 6.3% 17.5%
LB10-1A/B 0.03% 0.03% 0.03%
a
LA10-2C rind has 187Os/188Os = 0.1242 so peridotite composition involved in mixing for this sample must be less than or equal to 0.1242.
host. By contrast, the rinds have a higher Al/Mg — sufficient to stabilize
the phengite which hosted the K2O, Ba and Rb enrichments found in
some of the rinds.
In comparison, the chemical changes in elements that exhibit
variations consistent with mechanical mixing (e.g., MgO, Ni, Cr, HSE,
Al2O3, CaO, Na2O, TiO2) likely occurred earlier in the sequence of
rind-forming events. If the garnets in the block core and rind grew
before the chemical change associated with the mechanical mixing
aspect of rind formation occurred, then garnet compositions in core
and rind would be the same, however if garnets grew after the chemical
change, then the chemical composition of the garnets could potentially
be different in the core and the rind. A third possibility is that the
garnets grew during rind formation, in which case the centers of the
garnets might reflect similar compositions to those of the block core,
but the evolving whole-rock composition of the rind would be reflected
in different garnet compositions radially outward in the rind garnets
compared to the core garnets.
The concentric growth-zoning present in X-ray maps of the block
core garnets suggests that the compositions of the original garnet
growth are preserved. Rind garnets have higher Mg and Mn contents,
whereas core garnets have higher Ca contents (Fig. 4). The Fe contents
of the two types of garnets overlap. The range of concentrations of Ca,
Mg and Mn in the rind garnets does not overlap with the range of
compositions of those elements in the core garnets. Even if the rind
garnets selected for analysis were not sectioned through the true
centers of the garnets, i.e., if they represented some part of the garnets
with compositions of those observed in the cores, there would be some
overlap in composition. Here, however, there is little overlap observed.
Fig. 11. Pressure–temperature diagram showing calculated P–T conditions for garnet
stability for rind sample A10-3A. Results are from calculations using Theriak Domino and
are overlain on estimates of P–T conditions for the metamorphic facies of the Catalina Schist
(after Bebout, 2007). LA = lawsonite–albite, LBS = lawsonite–blueschist, GS = greenschist,
EBS = epidote blueschist, EA = epidote amphibolite, AM = amphibolite. Arag = aragonite,
Cal = calcite, Jd = jadeite, Qtz = quartz, Sil = sillimanite, And = andalusite.
[Os] [Ir] [Ru] [Cr] [Ni]
39.2% 65.5% 45.4% 98.6% 71.0%
6.1% 4.6% 4.2% 48.2% 35.8%
0.72% 0.57% 0.40% 7.2% 11.2%
This clear difference in garnet chemistry between core and rind,
especially MgO, suggests that the chemical changes in these elements
associated with rind formation occurred prior to the growth of garnets,
suggesting that mechanical mixing occurred in the amphibolite facies
rinds prior to the growth of garnet. Early mechanical mixing in the
history of rind formation is consistent with the evidence for mechanical
mixing (geochemical evidence and the brecciated nature of the
block–matrix contacts) in the lawsonite–albite and lawsonite–blueschist
facies rocks, which can be thought of as proxies for early stages in the rind
formation process. It is envisioned that these regions, in which pieces of
metamafic block comingle with pieces of more ultramafic-rich matrix,
could continually evolve and recrystallize as the mélange zone materials
move deeper into the subduction zone. This model is an extension of that
proposed by Bebout and Barton (2002) and King et al. (2006) in which
hydration of materials in the mélange is envisioned to result in a change
in rheology of the rind material (forming more readily deformable sheet
silicate minerals) which would have led to a focusing of deformation
along reaction zones. Subsequent breaking off of rind material created
the mélange matrix which would have been more permeable to fluid
flow thereby enhancing subsequent reaction zone formation. Deforma-
tion fabrics observed in reaction rinds (see Fig. 1 of King et al., 2006)
document the syn-tectonic nature of reaction rind formation.
If the chemical change to a more ultramafic-rich composition due to
mixing occurred prior to garnet growth in the rind, then the growth of
garnet in the rinds should be predicted by thermodynamic modeling
of the bulk composition of the rind. Thermodynamic modeling was
performed using Theriak Domino software (de Capitani and
Petrakakis, 2010) with the thermodynamic database JUN92 (Berman,
1988). Thermodynamic data for Mn-endmembers were added by
applying exchange enthalpies, entropies and molar volumes based on
Fe–Mg–Mn endmembers in the Holland and Powell (1998 updated
2002) database. The bulk rock composition used for the modeling was
that of the rind sample in which garnets were found, sample A10-3A
(with K2O reduced to reflect rind composition before reaction with
later K2O-rich fluids). The modeling predicts the growth of garnet, at
temperatures consistent with the estimated P–T conditions of the am-
phibolite facies (see Fig. 11), above 600 °C and at pressures above
0.7 GPa.
It is inferred, therefore, that the low-grade rinds represent an earlier
stage of the continuous process by which the high-grade rinds formed.
The combination of information obtained from both low-grade and
high-grade rinds, thus, may provide information about the sequence
of events that took place within the subduction channel, creating the
reaction rinds.
5.4. Overall sequence of events
Combining evidence from both high- and low-grade rinds, a general-
ized sequence of events can be inferred for the development of reaction
rinds (Fig. 12). The process is most likely not a single event occurring at
a single set of P–T conditions, but rather a continuous phenomenon that
may occur over a range of P–T conditions, if these materials are subducted
from shallow levels to greater depths within the subduction zone.
Mafic and sedimentary material from the subducting slab breaks off
and mingles with ultramafic material, possibly from the overlying
mantle wedge, beginning at relatively shallow depths. Evidence for
 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61 59

Fig. 12. Schematic sequence of events during rind formation. In the expanded sequence of stages 1 through 4, the color black is used to indicate mafic oceanic crust and gray is used to
indicate peridotitic material. The light gray hexagons indicate garnets. In stage 4 the white wavy arrows indicate fluid flow and white mineral outlines suggest mineralogical alteration
mediated by fluid flow. The relative positions of stages 1 through 4 are indicated on master subduction cross-section on the right of the figure.

the mechanical nature of the rind-forming process is found at the
lawsonite–albite and lawsonite–blueschist facies conditions of the
Catalina Schist which are thought to record P ~ 0.5 to 1.0 GPa (depths
of ~ 15–30 km). The shearing nature of the plate interface over time
creates semi-rounded blocks out of the relatively rigid basaltic rock
(and some metasedimentary and ultramafic rocks) within a matrix
derived from varying proportions of all of these lithologies, which has a
chemical composition intermediate between these lithologies (e.g.,
Bebout and Barton, 2002; King et al., 2006). At the edges of the blocks,
the outermost part of the block becomes hydrated, sheared and breaks
off, as witnessed by broken pieces of block found at the block–matrix in-
terface (see Fig. 1). Some blocks exhibit zonation in rinds with inner rinds
showing less enrichment in Mg, Cr, and Ni and outer rinds with more en-
richment (cf. Sorensen and Grossman, 1989) which possibly demonstrate
the progressive nature of this process. With time, some or all of the mixed
material may disperse into the matrix, creating the hybrid compositions
observed in mélange matrix (see Bebout and Barton, 2002; King et al.,
2006, 2007). The block pieces and matrix still at the edge of the block be-
come intermixed and this material recrystallizes to minerals stable at in-
creasing P–T conditions. This process is likely an iterative process with
new material breaking off and mixing with more matrix over time. The
concentric foliation in the rind is evidence for the dynamic nature of the
mechanical mixing processes involved in rind formation. In cases where
all of the mixed material disperses into the matrix, reaction rinds would
not form on blocks. This could explain why there are many examples in
the Catalina Schist of blocks without reaction rinds.
During subduction the metamafic block and associated rind of the
amphibolite facies sample examined in detail reach the stability field
for garnet and garnet growth occurs in both. The garnets that crystallize
in the rind are more Mg-rich and Ca-poor than the garnets that crystallize
in the block core, reflecting the difference in bulk-rock composition that
has already developed at this point, due to mixing of mafic and ultramafic
materials. These observations illustrate that mechanical mixing can
happen at relatively shallow depths and that blocks can continue to
move into the subduction zone, after this mixing process started, to
experience higher-grade metamorphic conditions.
These observations focus on the mixing of mafic and ultramafic
materials since these are the two lithologies dominant in the amphibolite
facies of the Catalina Schist, which is the location of the metamafic block
that was the focus of this detailed study. However similar concepts can
apply equally to mélange containing more sedimentary material, such
as the lower-grade rocks of the Catalina Schist.
There is likely infiltration of fluids at various points during the history
of the rind, however the only discrete evidence for this in the rinds
studied is found in the late garnet and amphibole replacement textures
(Fig. 2). Both garnets and amphiboles are replaced by randomly
oriented phengite and chlorite, suggesting that this late-stage fluid
infiltration takes place in a more static environment. The higher concen-
tration of K2O, Ba and Rb in some rinds is likely related to the late-stage
infiltration of fluids through the rind, perhaps in part during cooling
and exhumation.
6. Implications
Processes of mechanical mixing occur continuously throughout the
history of subducted material. The evidence presented here suggests
that metamafic blocks were surrounded by mélange matrix starting at
relatively low temperatures and, therefore, at shallow depths
where T ≤ 200 °C, based on the fact that lawsonite–albite facies rocks
have reaction rinds that show evidence for mechanical mixing and
where T b ~ 600 °C, based on the initial temperature at which garnet
appears in the thermodynamic models. Therefore, deformation and
mechanical mixing likely occurred over a range of P and T, throughout
the history of the subducted rocks. Such mechanical mixing of peridotitic
and basaltic materials, with or without sediment, results in an
intermediate or hybrid rock type with compositions between those
60 S.C. Penniston-Dorland et al. / Chemical Geology 384 (2014) 47–61
of the endmember materials. Measurements of HSE in arc volcanic
rocks (Alves et al., 1999, 2002) have shown ranges of concentrations
and isotopic compositions that are consistent with variable amounts
of mixing of peridotitic mantle with radiogenic Os components,
reflecting different proportions of subducted oceanic crust and
sediments in the arc lavas. The variable amounts of mixing of peridotite
suggested by the HSE concentrations and isotopic compositions in
reaction rinds of the Catalina Schist demonstrate that mechanical
mixing of disparate materials at the slab–mantle wedge interface is a
plausible mechanism to produce the HSE variability observed in arc
volcanic rocks.
Mélange mixing has been proposed as a source of other geochemical
signals observed in arc volcanic rocks (King et al., 2006, 2007; Marschall
and Schumacher, 2012). Both sets of authors demonstrated the genera-
tion of trace element and isotopic signatures overlapping with those
observed in arc volcanic rocks. Transport of mélange material through
the mantle wedge to underneath arc volcanoes by diapiric rise (in a
“cold plume”; e.g. Gerya and Yuen, 2003; Castro et al., 2010; Marschall
and Schumacher, 2012; Tumiati et al., 2013), could provide a way to
preserve the mixed signals of mélange zone materials, including the
HSE concentrations and isotopic compositions, that are then directly
melted to produce arc volcanic rocks. We suggest that, whether or not
mélange is conveyed into the mantle wedge in diapirs, it is capable of
strongly influencing the transfer of “slab signatures” into arc source
regions. Fluids (aqueous fluids or siliceous melts) infiltrating, and
produced in, such zones would bear hybridized chemical and isotopic
compositions inherited from the disparate lithologies in the subducting
oceanic lithosphere and overlying sediment.
Acknowledgments
We thank the NSF for support (grant EAR-1119111). We thank Horst
Marschall and an anonymous reviewer for their constructive reviews
and Klaus Mezger for his editorial handling of the paper. We acknowl-
edge the support of the Maryland NanoCenter and its NISPLab. We
thank Matt Kohn for assistance in thermodynamic modeling and Igor
Puchtel for assistance with the HSE analyses. The Catalina Island Conser-
vancy is acknowledged for logistics and support of sample collection of
the Catalina Schist.
Appendix A
Table A1
Sample locations.
Sample Location Latitude, longitude
A10-3A, B, C, D Ripper's Cove beach N 33°25′28.6″ W 118°25′58.7″ 46 m elev.
A12A-4C, R Valley of Ollas N 33°25′31.3″ W 118°25′58.6″ 33 m elev.
A10-2A1, 4 Mama Melt N 33°24′57.5″ W 118°26′24.0″ 265 m elev.
A10-5A, B Valley of Ollas N 33°25′28.6″ W 118°25′58.7″ 46 m elev.
LA10-2A, C Starlight Beach N 33°28′28.1″ W 118°34′52.8″ 0 m elev.
LA10-3B, F Starlight Beach N 33°28′27.6″ W 118°35′11.5″ 0 m elev.
LB10-1A, B Crab Cove, SW N 33°22′26.3″ W 118°28′56.3″ 0 m elev.
of Little Harbor
LB12-E1, 3 W of Little Harbor N 33°23′12.2″ W 118°28′32.0″ 24 m elev.
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