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Journal of South American Earth Sciences, Vol, I, No. 4. pp.

343-361, 1988
Printed in Great Britain

0895-9811/88 $3.00 + 0.00


Pergamon Press pie

Chemical mobility during low-grade metamorphism of


a Jurassic lava flow: Rio Grande Formation, Peru
L. A G U I R R E
Laboratoire de P~trologieMagmatique, U R A 721, Facult~des Sciencesde Saint-Jbr6me, U niversit~d'AixMarsoille Ill,13397 MarseilleCedex 13, France

(Received for publication January 1988)


Abstract---Chemical and mineralogicalchanges produced by very low-grade metamorphism in a 40 meter
thick,K-rich,calc-alkalineandesiteflow ofthe marine JurassicRio Grande Formation of southern coastal
Peru are discussed. This metamorphism (=spilitization)was non-deformational and generated spilitic
domains at (and near) both vesicular margins of the flow, whereas the massive central zone remained
relatively unaltered. The metadomains are characterized by mineral associationsof the zeolitefacies.
Primary minerals are Ca-plagioclase,augitic pyroxene, iron-titanitwnoxides, and (pseudomorphs aRer)
olivine. Metamorphic minerals are: albite(three generations),K-feldspar,pampellyite, chlorite,interlayered chlorite-celadonite,celadonite,various mixed-layer Si- and Fe-rich phyllosilicates,"iddingsite,"
calcite,analcime, titanite,and white mica. The effectof the metamorphism on the rock chemistry is
reflectedin changes especiallyobserved at the marginal zones ofthe flow which affectmajor, trace,and RE
elements: l)strong increaseof the ironoxidation ratio(Fe203/FeO); 2) enrichment in Na20 accompanied
by a concomitant depletionofCaO in non-amygdaloidal domains; 3 )depletionofSiO2;4) strong enrichment
in H20 and CO2; 5) marked depletionofSt and Rb; 6) enrichment in C| and S; and 7) slightdepletion in RE
elements, notably in the top zone ofthe flow. Conversely,elements such as Ti, P, Nb, and Y were fairlyimmobile, whereas Zr and K were only slightlymobilized. The effectof the metamorphism on the mineral
chemistry isexpressed by the predominance of metastabls equilibrium evidenced by the vxistencoof wide
compositional ranges in the phyllosilicates,the incomplete albitizationof the Ca-plagioclaso,and the AIrich character of the pumpollyites. The metamorphism is considered to be of hydrothermal-burial type,
which takes place at low temperature and pressure-- probably about 125-230C and lessthan 3 kb, and is
produced mainly through permeability-controlledsoawater/rockinteraction.
Resumen---Se discuten los cambios qulmicos y mineral6gicosresultantesdel metamorfismo de muy bajo
grado de una colada de andesitacalco-alcalinaricaen potasiode 40 m de espesor pertenecientea la formacibn marina Rio Grande de edad jur~sica que aflora en la costa sur del PertL El met~tmorfismo ( -o~piliti',acion) es no-deformativo y di6 lugar a la formacibn de dominios espil[ticos en los dos extremos vesic~ares de
la colada yen sus zonas contiguas. La zona central, de caracter compacto, permaneci6 re|ativamvnto fresca.
Los dominios metam6rficos se caracterizan por la presencia de asociaciones mineral6gicas pertenecientes a
la facies de zeolita. Los minerales primarios corresponden a: plagioclasa calcica, pyr(,xeno augltico, 6xidos
de hierro-titanio, y olivina, este ultimo unicamente como pseudomorfos. [~s minerales metam6rficos son:
albita (tres generaciones), feldespato potAsico, pttmpellyita, ciorita, chwita-celadonita inter-estratificados,
celedonita, ratios tipos de filosilicates inter-estratificados ricos in Fe y Si, "iddingsita," calcita, analcima,
titanita, y mica blanca. Los efectos del metamorfmmo sobre la composicibn quimica de |a roca se manifiestan en cambios observables de preferencia en las zonas extremas de la colada. Ellos at~ctan a los
elementes mayores, en trazas y Tierras Raras y consisten en: 1) un fuerte aumento de la raz6n de oxidacibn
del hierro (FesO3/FeO); 2) un enriquecimiento en Na20 que se acompafia de mm disminucibn concomitanto
del CaO en los dominios no-amigdaloideos; 3) una disminucibn del SiO.~;4) un enriquecimiento marcado en
H20 y CO2; 5) una disminucibn notoria del Sr y del Rb; 6) tm enriquecimiento en CI y Si; y 7) una ligera
disminucibn de las Tierras Raras, principalmente en la parte alta de la colada. Por el contrario, elementos
como el Ti, P, Nb, e Y fueron relativamente estables y el Zr y el K sblo levemente mbviles. E1 efecte del
metamorfismo sohre la quimica mineral se expresa pot el predominio de condiciones de equilibrio metastable evidenciadas por la existencia de amplios rangos composicionalss en los filosilicatos, la albitizaciSn
incompleta de la plagioclasa c{llcica y el caracter aluminico de las pumpellyitas. Se concluye que el metamorfmmo es del tipo hidrotermal de carga caracterizado por temperaturas y presiones bajas, probablemente
alrededor de 125-230C e inferior a 3 kb. La interacci0n entre el agua de mar y la roca, controlada por la
permeabilidad de la colada, es un factor determinante del metamorfismo.

INTRODUCTION
T H E A N D E S I T E F L O W described belongs to the Jurassic
Rio G r a n d e F o r m a t i o n of southern coastal Peru (Fig.
la). This formation w a s studied in a 4 k m long section in the Rio G r a n d e c a n y o n b e t w e e n L o m a de
M a i n s a a n d the coastline (1458'S, 7527'W; P a l p a
sheet 1:100,000, Instituto Geogr~fico Militar, I G M ,
Peru). There, the sequence observed is about 2.5 k m
thick a n d comprises m a r i n e sedimentary, volcaniclastic a n d volcanic rocks, mainly lavas of andesitic
composition (Fig. lb, c). T h e rocks are gently folded
but no trace of penetrative deformation exists. All

these rocks are affected by n o n - d e f o r m a t i o n a l , lowgrade regional metamorphism


of hydrothermalb u r i a l t y p e in t h e z e o l i t e a n d p r e h n i t e - p u m p e l l y i t e
f a c i e s ( A g u i r r e a n d O f f l e r , 1985). M o s t c o m m o n m i n eral assemblages are: 1)chlorite (+various Fe-phyllosilicates) + albite + calcite + (white mica) + (titanite); and 2 ) c h l o r i t e ( + v a r i o u s F e - p h y l l o s i l i c a t e s ) +
a l b i t e (in p a r t i a l l y a l b i t i z e d C a - p l a g i o c l a s e ) + ( K f e l d s p a r ) + p u m p e l l y i t e + ( p r e h n i t e ) + ( w h i t e mica}
+ t i t a n i t e . A n a l c i m e m a y a p p e a r in t h e f i r s t a s s e m b l a g e ; p r e h n i t e is s c a r c e a n d w a s n o t f o u n d a m o n g
t h e s e c o n d a r y m i n e r a l s o f t h e flow d e s c r i b e d in t h i s
paper.

343

~.~'-,

-~'~__
..........

SW

..,...~
..,.~::,~
.....
/ " ~ ~ ~ ,

(b)

NE

Y v

.....

r-~..~..~ ..v.. v..~..~..

...'"'.
, ,

'

(u)

Fig. 1. a) Location of the Rio Grande section in southern Peru; b) studied section along the Rio Grande canyon; c) stratigraphic column of the Rio Grande Formation between Loma de Mainsa and the
coastline. Key: Pz, Paleozoic metamorphic basement; JRG{L), Lower Unit of the Jurassic Rio Grande Formation; JRC~U), Upper Unit of the Jurassic Rio Grande Formation; TTPS, Tertiary, Pisco
Formation; 1, andesite flows; 2, Flow 51; 3, pillow lava horizon; 4, tuff; 5, ignimbrite; 6, red conglomerate; 7, brick-red sandstone; 8, limestone; 9, green phyllites; 10, unconformity; 11, fault showing
direction of movement; 12, fossil fauna.

~g

,~;-;

(a)

(c)

>

O0
4~

Chemical mobility during low-grade metamorphism of a Jurassic lava flow in Peru


The purpose of this study was to evaluate the
nature and degree of mobility of chemical elements
under the physical conditions of metamorphism
developed. The effects of chemical mobility on different types of elements (major, trace, rare earth), on
the values of the Sr initial ratio, on the K-Ar age
values, and on elements currently used in discriminant diagrams (intended to establish magma types
and geodynamic settings) were investigated.
A single lava flow 40 meters thick (Flow 51) was
chosen. Six samples representing domains with different textures and various degrees of alteration
(= metamorphism = spilitization) were taken at 1.5, 3,
8, 30, 39, and 40 meters from the base of Flow 51
(Table 1). They were analyzed for major and trace
elements (XRF, University of Nottingham), rare
earth elements (INAA, Risley, Liverpool), Sr isotopes
and K-At whole rock geochronology (BGS, London),
and mineral composition (Geoscan Mk II electron
microprobe; 15 kV, 3.5x 10-8A, normal beam width of
3p, University of Manchester). Samples analyzed
from the bottom and top zones of the flow included
amygdules.

GEOLOGIC FRAMEWORK
The Rio Grande Formation, in the studied section,
comprises two units separated by a slight angular
unconformity (Fig. lb, c). The strike varies from 300
to 360 and the dips average 30 toward the east. The
Lower Unit, ca. 500 meters thick, consists of red
agglomerates, conglomerates, conglomeratic sandstones, and fine- to medium-grained, red volcanogenic sandstones accompanied by brecciated silicic
lava flows, silicic ignimbrites, fossiliferous limestones, calcareous sandstones, and greenish turfs
(Aguirre and Offler, 1985). No basal contact was
directly observed, but this Lower Unit seems to unconformably overlie a series of green phyllites of
Paleozoic age (Ruegg, 1956) exposed along the
coastline. The Upper Unit, ca. 2000 meters thick,
largely consists of porphyritic, partly pillowed, Krich calc-alkaline andesites. Minor intercalations of
reddish conglomerates, agglomerates, and brick-red,
cross-laminated, volcanogenic sandstones are present (Aguirre and Offler, 1985). The Upper Unit is
unconformably overlain by the sedimentary Pisco
Formation of Tertiary age.
A Middle Jurassic (Dogger) age has been assigned
to the Rio Grande Formation by Ruegg (1956, 1961)
based on fossil fauna and flora representing the
Aalenian-Bajocian interval.
The position of Flow 51 is shown on Fig. lb,c. This
andesitic lava directly overlies a crossbedded, brickred volcanogenic sandstone, approximately 20
meters thick, and shows a glassy, altered, quenched
bottom rich in small amygdules (average 0.5 to 1.0
ram). In the central part of the flow, the rock is
massive and fresh to slightly altered, and the primary mineralogy is best preserved. The top is highly
vesicular (average amygdule 3 mm, maximum 10

345

ram) and strongly altered; the contact with the


overlying flow is easily recognizable by a sharp break
in texture and color. A summary of the petrographic
and mineralogical characteristics of Flow 51 is
presented in Table 1. No major vertical differences in
primary mineralogy due to physical mechanisms
e.g., differential crystal settling - - have been seen in
this flow, nor in the others belonging to the Rio
Grande Formation.

ROCK CHEMISTRY OF FLOW 51


Chemical Variations within the Flow

Flow 51 had a uniform composition before metamorphism, as strongly suggested by the virtually
constant composition of the primary minerals and
their relicts within the various zones (see Table 1).
Consequently, the chemical variations recorded
between these zones are interpreted here as essentially produced by the metamorphism affecting the
Rio Grande Formation. Chemical a n a l y s e s and
norms of the rocks r e p r e s e n t i n g the six levels
sampled are given in Table 2.
Major element variations are shown in Fig. 2
where oxide contents are plotted against height in
the flow. Main changes are observed in the Fo203/
F e e ratio, the H20-, [12Ot , CO2, Fe203, and Na20
contents - - all enhanced at both strongly altered
margins of the flow as compared with the "unaltered"
central level. The reverse behavior is observed for
the CaO and the SiO2, whereas the Tie2 and P205
are fairly immobile. Oxides with the highest correlation coefficient in relation to H20 are SiO2
(-0.921), CaO ( - 0.828), and Na20 (+0.731).
The variation in some of the trace elements is
illustrated in Fig. 3. Most remarkable are the depletions in Sr and Rb and the enrichment in S and C1
observed in the strongly altered domains, whereas
the contents of Nb, Zr, and Y remain relatively constant. Trace elements with the highest correlation
coefficients in relation to H20 are U (-0.836), Sr
(-0.717), and Rb (-0.659).
Variations in the REE pattern for the different
zones of the flow in relation to level are shown in Fig.
4. A comparison between the "unaltered" central
zone (8 m sampling point) and the top of the flow (40
m sampling point), which has the strongest alteration and the maximum concentration of amygdules,
shows that a slight general depletion in REE has
taken place in the top zone. The distribution pattern
in the altered rock is shifted in a near-parallel
fashion relative to that of the "unaltered" andesito,
implying that the REE's moved coherently (Fig. 4).
Classification and Geotectonic Setting

Several rock classification and geotectonic discrimination diagrams have been applied to Flow 51
in order to assess the degree to which metamorphism
affects their reliability. Pearce's diagrams, although

346

L. AGUIRRE

Table 1o Petrographic and mineralogic* characteristics of F l o w 51.


Phenocrysts
Ht
Zone
Above
and
Base of
Sample Flow
No.
(m)

Groundmass
Texture

Min-

Plagioclase

erals

Composition

Plagioclase
(microlites),
iron
oxide

Ano --* An5

Minerals

Included

Ferromagnesians or
Their Pseudomorphs

Mineral
Assemblages in
Amygdules

Top
61027
61026

40.0
39.0

Glassy
to
h~alopflitic

Clinopyroxene
(very scarce)

Analcime,
albite H,
Avg. An2.7
chlorite,
celadonite,
(A b I)
mixed-layer
ph yllosilicates,
white mica

Ca38 Mg42 Fe20

(rare),

1) calcite
2) mixed-layer
3)
4)
5)

c~iUmpellyite,

nopyroxene
~droplets"

6)

phyllosilicates
+ analcime
chlorite
mixed-layer
phyUosilicates
+ pumpeUyite
mixed-layer
ph yllosilicates
+ calcite
mixed-layer
phyUosilicates
+ analcime +
albite III

Amygdules very
abundant

cVpper
entral
61025

30.0

Fine,
interranuar to
intersertal

Plagioclase,
clinopyroxene,
iron
oxide,

An59 Ab37 Or4

White mica

Clinopyroxene

An4 --*An14

greenish.
brown
chlorite,
~umpellyite,

Ca38 Mg41 Fe21

(.4 b I)

(flaky),

chlorite

hematite

clinopyroxene ~iddingsite"
"droplets"

chlorite,
titanite,
K-feldspar

t pseudoolivine

1) interlayered

chloriteceladonite
2) chlorite +
interlayered
chloriteceladonite

Amygdules very
scarce

Central

61024

8.0

Medium
girained
ntergranufar

Plagioclase,
clinopyroxene,
titanomagnetite,

An58 Ab38 Or4

Clinopyroxene

Chlorite

(rare),

No amygdules

white mica
Ca38 Mg42Fe20
(flaky, very
)
scarce),
"iddingsite"
pseudotitanite (rare), (rare)
olivine ?
clinopyroxene
Titanoma~etite/hematite
sp59

titanite,
uartz,

-feldspar
Lower
Central

61023

3.0

FinePlagiograined, clase,
interiron
sertal oxide,

An59 Ab38 Or3


Ano --, A n7

chlorite,
titanite,
quartz

(Ab D

Plagioclase
(microlites),
iron
oxide,

An59 Ab38 Or3

Mixed-layer
phyllosilicates,
white mica

Clinopyroxene

1) chlorite

Ca38 Mg42Fe20

Amygdules very
scarce

chlorite
iron oxide
~iddingsite"

~ pseudo-

J olivine

Bottom

61022
61021

1.5
0.0

Glassy
to
hyalopilitic

chlorite

Ano-~ A n12
(A b I)

Chlorite,
white mica,
calcite,
pumpeUyite,
mixed-layer
phyllosilicates

Clinopyroxene

1) chlorite + cal-

Ca38 Mg43Fe19

2) calcite
3) chlorite

Titanoma~metite/hematite
uspl9

*Metamorphic minerals in italics.

cite Fe oxide

Amygdules
abundant

0.00
19.59
47.94
9.09
2.79
0.00
0.00
15.74
1.10
1.27
0.69
1.57

99.76

70.31

Total

DI

7.33

99.16

53.37

99.99

2.46
20.50
30.40
20.92
0.00
2.40
20.06
0.00
1.14
1.23
0.72
0.16

1.49

98.34

0.02

0.52

Q
Or
Ab
An
Ne
Di
Hy
Ol
Mt
I1
Ap
Ca

Fe203/FeO

Total

FeO
MnO
MgO
CaO
Na20
K20
P205
CO2
H20
H20Other
Volatiles

Fe203

54.18
0.84
16.21
4.49
3.02
0.22
4.55
5.11
3.23
3.31
0.33
0.06
2.58
0.19

61023

3.0 m

66.47

100.00

0.00
24.43
41.71
12.29
0.33
3.57
0.00
14.49
1.17
1.22
0.66
0.13

1.57

99.83

0.34

54.28
0.86
16.38
4.80
3.05
0.11
4.59
3.78
4.61
4.05
0.31
0.05
2.46
0.16

61025

30.0 m

78.25

100.00

0.00
19.52
51.29
3.59
7.44
2.98
0.00
11.07
1.07
1.18
0.63
1.23

6.02

99.33

1.44

53.94
0.82
16.04
6,38
1.06
0.09
3.10
2.41
6.87
3.20
0.29
0.47
2.76
0.46

61026

39.0 m

74.48

100.00

0.00
16.31
52.97
3.67
5.20
3.98
0.00
10.30
1.17
1.10
0.61
4.69

12.53

99.87

2.32

52.02
0.76
15.00
7.52
0.60
0.08
2.61
4.31
6.59
2.65
0.28
1.78
2.87
0.48

61027

40.0 m

the six levels

La
Ce
Pr
Nd
Sm
Eu
Tb
Dy
Ho
Yb
Lu

Zn
Zr

Ba
Cl
Co
Cr
Cu
Ga
Ni
Nb
Pb
Rb
Sr
S
Ta
Th
U
V
Y

Sample
No:

Ht A b o v e
Base:

27.6
54.3
6.6
25.0
5.5
1.2
0.7
4.9
0.8
2.7
0.4

185
208

1393
3068
33
36
265
17
14
10
18
64
290
191
0.7
15
1
232
31

61022

1.5 m

24.1
48.8
6.3
24.1
5.0
1.2
0.7
4.9
0.8
2.8
0.4

855
710
29
33
281
17
15
8
17
94
350
27
0.6
17
4
171
31
165
212

61023

3.0 m

24.6
49.4
6.8
24.5
5.2
1.2
0.7
4.9
0.7
2.9
0.4

40
38
457
17
13
8
18
110
393
<
0.6
14
4
187
30
140
217

1766

704

61024

8.0 m

61025

30.0 m

23.1
46.2
6.3
23.5
5.1
1.1
0.7
4.8
0.7
2.8
0.5

1219
1353
30
27
350
16
13
9
18
147
424
<
0.6
19
3
183
31
118
214

Table 2 Continued

Major e l e m e n t s in weight q~, trace a n d REE in ppm. N o r m s calculated on a n h y d r o u s basis.

51.77

99.91

3.04
16.50
32.13
22.26
0.00
7.87
14.86
0.00
1.22
1.25
0.68
0.10

3.85

101.59

0.26

56.12
0.89
16.90
6.58
1.71
0.11
3.68
6.87
3.54
2.78
0,32
0.04
1.38
0.41

61024

8.0 m

analyses of rocks representing


sampled in Flow 51.

52.61
0.88
16.24
6.67
0.91
0.18
4.67
2.96
5.67
3.21
0.32
0.60
3.31
0.41

61022

Sample
No:

SiO2
TiO2
A1203

1.5 m

Ht A b o v e
Base:

T a b l e 2. C h e m i c a l

23.4
49.4
5.7
21.8
4.8
1.1
0.7
5.0
0.7
2.5
0.4

959
17740
111
30
508
14
3
9
20
96
265
191
0.6
16
3
148
29
107
204

61026

39.0 m

24.2
46.5
5.3
21.8
4.5
1.0
0.6
4.3
0.6
2.3
0.4

584
8978
11
32
506
13
5
8
15
77
180
21
0.6
13
2
139
28
86
190

61027

40.0 m

-4

e..

<

[10

B
0

0'q

~,~

348

L. AGUIRRE

50

Its

qP
ur#

~
u~

~
t6"}

O0

.
I

St02

fro

c%t
I

~
U

m0

R1203

TI02

lid

m
I

F'o2O3

FeD

40

3e
28
10
O
i

50

HnO

~o

I
CaO

Noo

115

~0

4S
30
20
IS
S
lit

,,, T T T

58
I~05

C02

1420+

H20-

3O
2O
IS

Fig. 2. Content of different oxides (abscissae, percent)


where abscissae give value of the ratio.

versus

height in Flow 51 (ordinates, meters from base), except for FesO~/FeO

strictly applicable to basalts, have been utilized


because of the rather basaltic character of the andesite studied. The results obtained are presented in
Table 3.
As expected, the diagrams reflect the degree of
mobility of the elements involved. Thus, the "unaltered" sample of the central zone (8 m sampling
level) is classified as calc-alkaline andesite in the
scheme by Irvine and Baragar (1971) (Table 3),
whereas the Na-enriched rocks of the top (39 and 40
m sampling levels)and bottom (1.5 m sampling level)
zones are referred to various alkali series in the same
scheme. This dispersion clearly results from the
strong variations in N a added to the high content of
primary K in the flow.

The mobility of Sr is reflected in the Pearce and


Cann (1973) diagram of Fig. 5b: some of the points
representing the samples analyzed vacate the fieldof
calc-alkaline basalts, the set is linearly arranged
away from the Sr corner -- the points furthest away
corresponding to the Sr-depleted bottom and top
zones of the flow.
Other diagrams, based on elements here proved to
be immobile or only slightly mobile (Table 3, Figs. 6
and 7), indicate petrologic and geotectonic characteristics in agreement with those known for the
Jurassic volcanic series of southern coastal Peru to
which the Rio Grande Formation belongs (Aguirre
and Offler, 1985; Injoque, 1985).

Chemical mobility during low-grade metamorphism of a Jurassic lava flow in Peru

O1)

50

Cr

Di

Zr

q"

04

tO

---)

349

XI

t%l

t~i

4W

$r

40
30
28

10
0

Co

40
38
20
10
O

58u~'

"

Th
4O

"--7

3O

IN.
50

30

20

s.
0

In
I I E U

OD

00

Ti

Z~

28
10

I i

.
O
I

~1
I

to
I --I~

10

Fig. 3. Trace element content (abscissae,parts per million)oersu8 height in Flow 51 (ordinates,meters from base).

SAES

I/4~C

350

L. AGUIRRE

100
0
f-]
----0

3.Om
8.Om

~e.b

~t.X

1.5m

U.J
bZ
c.)

tJ

La

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

Fig. 4. R E E patterns for the six samples of Flow 51 (distancein meters from base);normalized afterHaskin et al. (1968).

MINERAL CHEMISTRY OF FLOW 51


Primary Minerals

Plagioclase appears as large phenocrysts (up to 12


m m ; Anss Ab38 Or4, on average) and in the groundmass (see Table I). Fresh, non-albitized individuals
are only found at the central zone of the flow, where
they are twinned and commonly zoned. In this level,
a tendency is observed for phenocryst rims and
groundmass laths to be slightly poorer in Ca as
compared with phenocryst cores. The orthoclase
molecular component in the primary plagoclases is
high and varies between approximately Or3.5 and
Ors.o. Elsewhere in the flow, plagioclase crystals are
partially albitized and only scattered patches of pri-

mary composition remain. Albitization is complete


in the top zone.
Clinopyroxenes are present in all the zones as
phenocrysts (up to 5 ram), intergranular individuals
in the groundmass, and "droplets" poikillitieally enclosed in plagioclase phenocrysts. Crystals are extensively altered to calcite and Fe-bearing phyllosilicates, mainly along the cleavages in such a way
that in several cases only a few relicts of fresh clinopyroxene remain. In the central zone of the flow,
however, individuals are free from alteration and
commonly twinned.
Analyzed crystals are remarkably homogeneous
augites with composition close to Ca38Mg42Fe2o.
Their Ti, Ca, Na, Cr, and Al contents plotted on the
discriminant diagrams by Leterrier et al. (1982)

Chemical

mobility d u r i n g low-grade m e t a m o r p h i s m

of a Jurassic lava flow in P e r u

351

T a b l e 3. R o c k c l a s s i f i c a t i o n and g e o t e c t o n i c s e t t i n g as inferred f r o m v a r i o u s d i s c r i m i n a n t
parameters.
Classification/Discrimination Method
SiO 2 - alkalis

Reference

Classification and/or Setting Indicated

Irvine and
Baragar (1971)

Height above base of flow:


40.0 m
39.0 m
30.0 m
8.0 m
3.0 m
1.5 m

Ne, Qtz, Ol
A1203 - normative plagioclase

Ti, Zr, Y, Sr (see Fig. 5)

Pearce and Cann


(1973)

Benmoreite
Benmoreite
Trachybasalt
Andesite
Andesite
Tristanite

Observations
Anhydrous basis

(Na-series)
(Na-series)
(K-series)
(calc-alkaline)
(calc-alkaline)
(K-series)

Field of calc-alkaline basalts

In, Zr, Ti, Y, concentration of points


Points aligned away
from the Sr corner, with
Sr-poorest values corresponding to the most
altered rocks

K20 - SiO2 (see Fig. 6)

Peccerilloand
Taylor (1976)

Basaltic andesites and andesites,


high-K calc-alkaline and shoshonite series

K20 - TiO2 - P205

T. H. Pearce
et al. (1975)

Non-oceanic basalt

Ti, Zr, Y, Nb, Ce, Ga

Winchester and
Floyd (1977)

Andesite field

La, Ce, P/La, Th/U, Zr/Y,


ZREE, La/Sm

Bailey (1981)

"Andean" type andesite

Multi-element (spider) diagram (see Fig. 7)

Pearce (1983)

Active continentalmargins

Ti/100

Compare with Central


Chile basalts, notably
with 170 Ma (high ~K,"
calc-alkaline), in Pearce
(1983)

Ti/100

\+
Zr

Zr

Y.S

Sr/2

Fig. 5. Discriminant diagrams for basalta (Pearce and Cann, 1973): a) A and B, low-K tholeiites; B, ocean-floor b asal t ; C al~d
B, calc-alkaline basalta; D, within plate basalts, b) A, low-K tholeiites; B, calc-alkaline basalta; C, ocean-floor basalts. In (b),
points in decreasing order of Sr content correspond to the following sampling levels in Flow 61 : 30 m, 8 m, 3 m, 1.5 m, 39 m, 40 m.

352

L. AGUIRRE

Fig. 6. Classification diagram by


Peccerillo and Taylor (1976). In
order of decreasing K20 content, the
points correspond to the following
sampling levels in Flow 5 1 : 3 0 m, 3
m, 1.5 m and 39 m, 40 m, 8 m.

-Y

B = Basalt
~ = Basaltic andesite
A = Andesite

Shoshonite series

~
0

Arc th;lez,ttc , t o . ~ ) t ~ ; t e s

40

45

50

55

60

65

70

;5

10eB
--O

1.5m
3.0m
0.Bm
3B.Bm
39.8m
4B.Om

[]
---'O
--,~
--'V
I

10e

==

.l
Sr

Rb
K20

Th
Ba

Nb
Ta

P205
Ce

HT
Zr

TtO2
Sm

Yb
Y

Cr
Sc

Fig. 7. Spider diagrams for the six samples of Flow 51 (distance in meters from base); normalized after Pearce (1983).

Chemical mobility during low-grade metamorphism of a Jurassic lava flow in Peru


indicate that the parental lavas are predominantly
orogenic and belong to the calc-alkaline series.
Olivine is represented as completely pseudomorphed individuals up to 4 mm across. Fe-bearing phyllosilicates, iron ore, and "iddingsite" are the main
secondary minerals. Iron ore fills microfractures and
divides the crystals in several sectors whose distribution, morphology, and alteration products closely correspond to those observed in typical altered olivines.
Iron-titanium oxides are present as predominantly
euhedral phenocrysts of up to 3 mm and are found
mainly in the bottom and central zones. They correspond to titanomagnetites with ulvospinel solid
solution values between Usp19 and Usp59. Dark reddish areas in some of these crystals suggest that
partial hematitization has occurred.

Metamorphic Minerals
Sodic plagioclase forms through widespread albitization of primary Ca-plagioclase. Based on mode of
appearance and chemical composition, three types of
albite are distinguished and named Ab I, Ab II, and
A b III.
A b I is the most abundant and results from the
ordinary "patchy" albitizationprocess accompanying
spilitization. It is characterized by a "dusty" appearance, which is commonly associated with sericitization, and compositions cluster in the range An0-Anl 0.
As a general rule, Ab I is devoid of molecular Or component (Table 4, Analysis 1).

353

Ab II (Table 4, Analysis 2) appears exclusively at


the top level as limpid veinlets cross-cutting Ab I
crystals or as transparent patches inside them. Its
composition varies from Ano to An4. 8 (36 analyses,
X=1.46, o=1.18) and no Or component is detected;
patches of Ab II are found side by side with clear
patches of analcime in the interiors of Ab I plagioclase phenocrysts.
Ab III (Table 4, Analysis 3) is only found in the top
zone (40 m sampling level) where it appears as tiny
and scarce prismatic crystals distributed in the outermost shell of composite, zoned, amygdules whose
core is occupied by analcime. The composition of
these prisms (5 analyses) corresponds to Ano, but in
this case Or varies from Or0 to Or2. 9 and significant
amounts of Fee* (0.70-1.90%) and MgO (0.30-0.60%)
- - probably representing a contamination effect on
the microprobe analyses due to a thin chlorite coating of the amygdule wall w are consistently present.
K-feldspar appears as small groundmass microlites in the central and upper central zones; their
composition is represented by Analysis 4 in Table 4.
Analcime is found in the top level as limpid
patches in Ab I plagioclase phenocrysts and in composite, zoned, amygdules where it ooccupies the central position and/or appears as a narrow and discontinuous outermost rim.
Analcime in patches (Table 4, Analysis 5) is limpid
and homogeneous in composition, with very minor
amounts of MgO (0.25%) and F e e (<0.20%) as impurities; K20 and CaO are not detected. Analcime in

Table 4. Representative microprobe analyses of metamorphic minerals, Flow 51.


8 Oxygens

Analysis
SiO2
A1203
Fee*
MnO
MgO
CaO
Na20
K20
Tie2
Total
Si
Al IV
AI VI
Fe*
Mn
Mg
Ca
Na
K
Ti

7 Oxygens

24.5 Oxygens

68.72
19.87
0.25
0.00
0.25
0.33
11.46
0.00
0.00
100.88

66.75
19.34
0.00
0.00
0.00
0.00
11.40
0.00
0.00
99.49

67.96
18.47
1.91
0.00
0.48
0.00
11,13
0.50
0,00
100.45

64.93
18.54
0.30
0.00
0.00
0.00
0.31
16.29
0.22
100.59

55.74
21.28
0.21
0.00
0.26
0.00
12.69
0.00
0.00
89,85

55.61
21.81
0.00
0.00
0.29
0.00
12.96
0.00
0.00
90.67

55.72
20.33
1.48
0.00
0.63
0.00
11.59
0.96
0.00
90.73

36.15
25.73
2.81
0.00
2.44
22.44
0.26
0.00
0.00
89.83

37.47
21.24
9.00
0.14
1.60
22.50
0.28
0.10
0.00
92.33

2.978
0.022
0.993
0.009
0.000
0.016
0,015
0.963
0.000
0.000

3,010
0.000
0.998
0,000
0,000
0,000
0.000
0.968
0.000
0.000

2.987
0.013
0.944
0.070
0.000
0.031
0.000
0.949
0.026
0.000

2.987
0.013
0.992
0.012
0.000
0.000
0.000
0.028
0.956
0.008

2.409

2.392

2.416

1.084
0.008
0.000
0.017
0.000
1.063
0.000
0.000

1.105
0.000
0.000
0.019
0.000
1.081
0.000
0.000

1.039
0.054
0.000
0.041
0.000
0.975
0.054
0.000

5.982
0.018
4.999
0.389
0.000
0.602
3.978
0.083
0.000
0.000

6.247
0.000
4.173
1.255
0.020
0.398
4.019
0.091
0.021
0.000

reel %

Ab
An
Or

98,47
1.53
0.00

100.00
0.O0
0.00

97.13
O.00
2.87

2.81
0.00
97.19

Key: I, albite ofAb I type, top zone; 2, albite ofAb H type, top zone; 3, albito ofAb m type, top zone; 4, K-feldspar,
groundmass, upper central zone; 5, analcime, limpid patch in a plagioclase phenocryst, top zone; 6, analcime, core
of amygdule, top zone; 7, analcime, rim of amygaule, top zone; 8, pumpe]lyite, patch in plagioclase phenocryst,
bottom zone; 9, pumpellyite, patch in plagioclase phenocryst, upper central zone.

354

L. AGUIRRE

the pumpellyites analyzed approach the ideal foramygdules presents contrasting compositions depenmula and cation distribution suggested by Passaglia
ding on its location. When occupying the central
and Gottardi (1973) and Coombs et aL (1976), and
position, it contains low levels of impurities and
strongly resembles analcime in patches (Table 4, they plot in the field of Al-rich pumpellyites from
Lo~che (Fig. 8; Table 4, Analyses 8 and 9). Due to the
Analysis 6). In cases where it appears at the periminute size of the pumpellyite inclusions and the
phery of amygdules (Table 4, Analysis 7), analcime
widespread alteration (albitization, chloritization,
contains significant a m o u n t s of K20 (7 analyses,
sericitization) of the plagioclase hosts, a significant
X=0.87%, 0=0.20). MgO and F e e * contents renumber of microprobe analyses show possible concorded are attributed to contamination due to the
presence of a thin chlorite coating of the amygdule
tamination effects expressed as deficiency in Cawalls.
content (13-20% as CaO), abnormally high values for
Calcite is found at the bottom and top zones and is Mg (up to 8% as MgO) and Na (up to 2% as Na20),
conspicuously absent from all other domains of the and low totals. These analyses plot toward the 1%flow. At the bottom zone, it is moderately abundant
rich area of the AFM triangle but they have not been
and is found as patches and veinlets replacing clino- used in the present study.
White mica is found in all the zones as minute
pyroxene phenocrysts and, rarely, in the cores of
small chlorite-filledamygdules (<2.0 ram). In the flakes inside albitized plagioclase phenocrysts. It is
top zone, calcite fillsamygdules which may reach 5 especially abundant in the upper central zone where
m m in diameter and may be accompanied by chlorite it confers a mottled aspect to the plagioclase crystals,
and analcime.
and is rare in the central zone where the primary CaPumpellyite is found in samples of the bottom, plagioclases are unchanged. Seven a n a l y s e s from
upper central, and top zones (see Table 1) where it individuals of the bottom and upper central zones
appears as tiny and scarce patches inside albitized show Si > 6.5 (6.5 to 7.0, mean value 6.7) calculated
on the basis of 22 oxygens in the chemical formula.
plagioclase phenocrysts; only one occurrence of pumpellyite in an amygdule was recorded. The patches The Si/AI ratio in tetrahedral sites is much higher
are fibrous aggregates showing brownish to brownish
than 3.0 (mean value 5.0). Some replacement orAl +3
by Fe 2 and Mg +2 in the octahedral sites has taken
green pleochroism. Under crossed nicols, they show
fan-like extinction,high birefringence,and abnormal
place; the celadonite content given by the ratio (Fe*
bluish-green interference colors. Compositionally,
+ Mg)/(total cations in octahedral sites) is low to

R1
.......

Vancouver islam!
California

..........

Jonestown

.........

Lo~che

. . . . .

Tai~n

vs/~
A-~,
@-. .:
,~,'-~:,

/
,./7./

50

//
//

c/) ./

Fe

25

58

7S

Mg

Fig. 8. AI-Fe*-Mgdiagram (Coombset al., 1976)showingcompositionofpumpellyite from different zones (named as in Table 1) of
Flow5 1 . K e y t o s y m b o l s : open circle, bottomzone(sample 61021);opensquare, bottomzone(sample 61022); open diamond, u p p e r
c e n t r a l z o n e ( s a m p l e 61025).

Chemical mobility during low-grade metamorphism of a Jurassic lava flow in Peru


moderate - - ranging from 5% to 13% with a mean of
11%. Therefore, the muscovites can be considered as
moderately phengitic. Replacement of K by Na in
the interlayer sites is important in some individuals.
Two representative analyses are given in Table 6
(Nos. 1 and 2).
Chlorite is abundant in Flow 51, with the exception of only the central zone. It occurs in amygdules,
as small patches in plagioclase phenocrysts, and in
the groundmass, as well as total or partial replacement of ferromagnesian minerals (olivine, in most
cases). Two compositional domains are identified on
Fig. 9 (after Hey, 1954): the first occupies the field of
the penninites and corresponds to chlorites from the
bottom zone of Flow 51; the second extends from the
boundary between pycnochlorite and diabantite into
the diabantite field and, with increasing mean Si
content, includes chlorites from the lower central,
upper central, and top zones. Some of the main characteristics of chlorites from Flow 51 are presented in
Tables 5 and 6 (Analyses 3 to 9).
Interlayered chlorite-celadonite (Table 6, Analysis
10) coexists with chlorite and calcite in amygdules of
the upper central zone. A deep emerald green characterizes the celadonitic material, which has higher

355

SiO2, MgO, and K 2 0 than known examples (e.g.,


Boles and Coombs, 1975).
Celadonite (Table 6, Analysis 11) is present in the
top zone as small, brownish, patches inside albitized
plagioclase phenocrysts. Its composition is comprised
in the celadonite range of Boles and Coomhs (1975)
and, with the exception of its low MgO content, it
closely approaches the values characterizing the AIceladonites of Wise and Eugster (1964).
Brownish Fe-phyllosilicates with significant Si,
Ca, Na, Mn, K, and AI w contents (Table 6, Analysis
12) are abundant in the bottom and top zones where
they appear in amygdules and as patches in the
groundmass. These mixed-layer phyllosilicates plot
partly in the lowermost, Si-rich, a r e a of the diabantite field (not been included in Fig. 10) and partly
out of Hey's diagram, due to their high (>4) Si
content.
A bright red "iddingsite" (Table 6, Analyses 13
and 14) appears in the lower central and central
zones as partial alteration of clinopyroxene phenocrysts, accompanying chlorite in pseudomorphs after
olivine, and associated with Fe-Ti oxides. Its composition differs, however, from commonly reported
iddingsites or saponites (e.g., Deer et al., 1964;

Fe2+Fo3

0.2

B. 5

8.8

Fe2+Fe3+M9

S~

Cl
3
Pe

Tc

Fe2+Fe3
0

R-RIPIIX3_ITE P=PYCNOCHt.0RITEB,,BRUNSVIGITED-nIRBI~4TITEC-CORUNIXbPHILIT[
Pth-PSEUD0-THURINGITES-SHERIDFINITEl]ph-lR:q4NITE CI-CLINOCHLOREPe-PENNINITE
Tc-TI~.C-CHLORITE
Fig. 9. Classificationdiagram (Hey, 1954)showing chlorites fromdifferentzones(named as in Table 1) ofFlow51. Key to symbols:
open circle, bottom zone (sample 61021); open square, bottom zone (sample 61022); open triangle pointing up, central zone (sample
61023); open diamond, upper central zone (sample 61025); open triangle pointing down, top zone (sample 61026). Cations
calculated on the basis of 14 oxygensin the chemicalformula.

Pale green

Top

95.35

10.30

94.82

CaO
Na20
K20
TiO2
Total

1.33
0.33
1.29
8.90

51.54
29.67
2.29

0.98

50.49
31.69
1.36

22oxygens

MgO

Si02
A1203
FeO*
Fe203*
MnO

Analysis

Pale green

U p p e r central

A m y g d u l e s (single m i n e r a l )

P a t c h e s in the g r o u n d m a s s
(small a n d rare)

A m y g d u l e s (+ i n t e r l a y e r e d
chlorite-celadonite + calcite)

Pseudomorphs afterolivine

crysts

P a t c h e s in plagioclase pheno-

A m y g d u l e s ( + calcite + Fe
oxides)

A m y g d u l e s (single m i n e r a l )

Metadomain

3.22-3.43

3.15-3.36

3.04-3.17

3.32-3.48

~ 1

< 1

~ 1

> 1

0.34-0.36

0.43-0.45

0.38-0.42

0.20-0.24

( N o t e 2)

(Note 1)

FeO*

XFe*

MgO
Si

1.23-1.84

1.21-1.83

1.03-1.36

1.74-2.00

AIW/AI Iv

Analyses

No. o f

.
85.00

.
86.27

.
0.83
23.29
1.37
0.90
0.20

.
0.87
21.83
0.84
0.72
0.09

34.39
14.64
10.65

32.79
15.75
12.11

.
84.83

.
0.72
21.99
0.74
0.87
0.26

34.40
14.24
11.21

0.88
18.03
0.15
2.05
87.71

29.14
15.76
21.70

14 o x y g e n s

.
85.68

.
0.39
16.65
0.23
-

29.56
14.53
24.32

85.94

0.40
16.89
0.19
__

30.29
15.63
22.54

85.77

0.63
20.84
0.16
0.63
0.15

31.61
14.52
19.34

0.03
93.18

21.68
0.34
11.77
0.17
0.11
4.90

42.53
11.65
-

10

0.55
97.45

15.95
0.85
0.78
3.51
7.89

52.78
15.14
__

11

11 o x y g e n s

Table 6. Representative microprobe analyses of phyllosilicates, Flow 51.

83.34

7.10
0.70
1.93
0.78

36.18
10.79
25.86

12

oxygens

14

Diabantite

Diabantite

Pycnochloritediabantite

Penninite

Compositional
Field
( s e e Fig. 9)

Notes: 1) cations calculated on the b a s i s of 14 o x y g e n s in the chemical formula; 2) XFe* = n F e * / ( n M g + n F e * ) .

Green

Pale green

Bottom

Lower central

Color

Zone

Table 5. Main c h a r a c t e r i s t i c s o f chlorites, F l o w 51.

85.97

16.98
0.25
0.58
-

25.50

28.19
14.47

13

87.78

19.29
0.26
0.29
0.75

18.34

35.72
13.13

14

lloxygens

7, 8

3,4,5

Chemical
Analysis
(see T a b l e 7)

C~

3.315
0.685
.
1.191
1.024
.
0.074
3.290
0.091
0.141
0.012
.

.
0.070
3.436
0.145
0.173
0.025

3.404
0.596
.
1.111
0.882

.
0.062
3.312
0.080
0.170
0.034

3.476
0.524
.
1.172
0.947

.
0.078
2.807
0.017
0.415
-

3.043
0.957
.
0.983
1.895

14 o x y g e n s

3.170
0.830
.
1.007
2.181
.
0.035
2.662
0.026
.

0.036
2.654
0.021
-

3.194
0.806
.
1.136
1.988

0.054
3.162
0.017
0.124
0.019

3.218
0.782
.
0.959
1.646

.
0.087
1.185
0.021
1.274
0.013
0.015
0.454
0.002

3.090
0.910

10

.
0.804
0.817
.
0.086
0.057
0.463
0.685
0.028

3.591
0.409

11

11 o x y g e n s

1.400
2.389
.
1.169
0.083
0.413
0.110
-

3.996
0.004

12

14
oxygens

.
2.034
0.022
0.090
-

2.265
1.370
0.365
1.177

13

2.179
0.021
0.043
0.073
-

2.707
1.173
0.120
0.926

14

11 o x y g e n s

(%)

2.374 + 1%

2.660 + 1%

3.318 + 1%

2.035 + 1%

2.659 + 1%

2.570 + 2%

40.0 m

39.0 m

30.0m

8.0 m

3.0 m

1.5 m

Height
Above Base
of Flow

T a b l e 7. S t r o n t i u m

27.9

52.3

21.5

39.8

58.8

56.0

isotopy

(nl/g)

16.61 0.8%

15.53 1%

13.62

17.93 0.9%

10.10 =l: 1%

12.33 1%

4Arrad

*Present day

159 7

149 6

164 4

134 3

95 3

129 4

(Ma)

0.70557
0.70553
0.70516
0.70546

0.3582
0.2796
0.2652

160 Ma B P

0.70610

0.70583

0.70639

0.70647

100 Ma B P

0.70716

0.70695

0.70783

0.70798

0 Ma BP*

o f F l o w 51.
87Sr/S6Sr

the six samples

0.3758

( + 0.5%)

Rb/Sratm

of rocks representing

A g e + 2o

and K.Ar geochronology

FeO* = all iron as Fe +2, Fe203* = all iron as Fe +3. Key: 1, white mica, upper central zone; 2, white mica, bottom zone; 3, chlorite, bottom zone; 4, chlorite, bottom zone;
5, chlorite, bottom zone; 6, chlorite, lower central zone; 7, chlorite, upper central zone; 8, chlorite, upper central zone; 9, chlorite, top zone; 10, interlayered chloriteceladonite, u p p e r central zone; 11, celadonite, top zone; 12, mixed-layer Fe-phyllosilicate, bottom zone; 13, "iddingsite," lower central zone; 14, "iddingsite," central zone.

0.261
0.047
0.331
1.498

.
0.193
1.740
.

3.416
0.253

6.801
1.199

3.629
0.151

6.685
1.315

Si
AlIV
Fe IV
A1VI
Fe 2.
Fe +3.
Mn
Mg
Ca
Na
K
Ti

Analysis

22 o x y g e n s

Table 6 (continued)

"1

~o

u~

,
e-

oP'S

fD

o~

f~

('3

358

L. AGUIRRE

Laverne, 1987) - - especially concerning lower FeO*


and higher A1203 and MgO contents in the "iddingsites" from Flow 51.
Titanite is scarce m present as small grains in the
groundmass and, very rarely, as inclusions in plagioclase phenocrysts.

Effect of Spilitization on Rock Chemistry


Comparisons between the different zones analyzed
led to the following conclusions regarding the effects
of spilitization on rock chemistry, notably about element mobility:
1) P, Ti, and Y were essentially immobile.

I S O T O P E C H E M I S T R Y O F FLOW 51
Samples from the six points indicated in Table 1
were analyzed to determine the S7Sr/S6Sr ratio and KAr whole rock age. Strontium ratios at 160 Ma and
100 Ma were calculated (Beckinsale, written comm.;
Brook, written comm.); the results are shown in
Table 7. The values obtained are considerably scattered, notably in the case of the K-Ar ages. It can be
observed that the oldest age and the lowest value for
the 87Sr/SeSr correspond to the "unaltered," central
zone of the flow (sample at 8 m above base of flow),
while the youngest age together with the highest
S7Sr/SeSr value were obtained from the strongly altered top. The oldest K-Ar age, 164+4 Ma, calculated
for the "unaltered" level of Flow 51 corresponds to
the latest Middle Jurassic (latest Callovian); this is
younger than the Aalenian-Bajocian age interval
assigned by Ruegg (1956, 1961) to the Rio Grande
Formation based on paleontological evidence (187176 Ma, according to the GSA's 1983 Geologic Time
Scale).
It is important to note that, according to our field
record and stratigraphic framework, Flow 51 and
Ruegg's fossiliferous strata belong to the Upper and
Lower Units of the Rio Grande Formation, respectively, and are separated by an unconformity (Fig.
lb,c). Considering the ages involved (and provided
the date obtained for the "unaltered" central zone of
the flow is taken as crystallization age), a MiddleJurassic tectonic event is suggested. This event
could be related to the one marked by a Bathonian
regional unconformity known in n o r t h e r n Chile
(Mufioz Cristi, 1973; Zentilli, 1974).

DISCUSSION AND CONCLUSIONS


Alteration in Flow 51 is evidenced by various
chemical and mineralogical changes (=spilitization)
taking place with differing intensity at different
levels of this lava unit. This uneven alteration pattern is charcterized by pervasive mineral transformations at the two margins of the flow (bottom
and top zones) and by almost complete preservation
of the primary mineralogy at the central part. The
main control for the p a t t e r n is attributed to permeability - - a close relationship existing between
changes in proportion and composition of secondary
minerals and the a b u n d a n c e of a m y g d u l e s and
veinlets representing former voids (see Table 1).
Similar alteration has been described in detail by
Levi et al. (1982) from a lava flow in central Chile.

2) Zr was partly mobile, showing slight depletion at


the bottom and top zones.
3) Ca is depleted toward the bottom and top zones in
amygdule-poor domains, but increases at the topmost level where amygdules are larger and abundant. This complementary behavior of Ca has
been pointed out for similar cases by Thompson
(1971) and Levi et al. (1982).
4) Na content increases at both margins, mainly at
the top zone. A rough chemical budget from the
available data would suggest addition of Na from
an external source, most probably seawater.
5) Si is depleted at both margins.
6) H20 and CO2, as well as the oxidation ratio Fe203/
FeO, are strongly enriched at the bottom and top
zones.
7) Sr is lost, concomitantly with Ca, at both spilitized
margins of the flow - - a situation attributed to the
process of plagioclase albitization. A similar pattern of depletion is shown by the Rb.
8) K is not significantly affected by spilitization.
The leading role of H 2 0 in the alteration process is
made clear by the calculation of c o r r e l a t i o n coefficients of the different major and trace elements
with respect to water. Si, Ca, Na, Sr, and Rb show
the highest correlation values, permitting the conclusion that their mobility has been accomplished by
permeability-controlled fluid transport.
REE have been mobile during alteration but the
shifting of their patterns (see Fig. 4) takes place in a
near-parallel fashion, resulting in general depletion
in the case of the most altered sample. Similar behavior has been established in other cases of spilitization (Hellman et al., 1977; Nystr6m, 1984). The
effects of alteration on the Sr isotopes and on the KAr geochronology have been shown to consist in an
increase of the 87Sr/~eSr ratio coupled with a decrease
in the K-Ar age in the most altered top zone of the
flow. The variations recorded here in some elements
currently regarded as "immobiles" indicate that caution should be used when applying certain discriminant diagrams and classification systems - - e.g., see
in Table 3 how Irvine and Baragar's (1971) classification works for the spilitization zones of Flow 51.
The same conclusion is valid in the case of Sr isotope

Chemical mobility during low-grade metamorphism of a Jurassic lava flow in Peru


ratios and K-Ar ages, especially when results are
used for stratigraphic purposes.

Effects of Spilitization on Mineral Chemistry


Mineralogically, the alteration is characterized by
assemblages where albite, chlorite, mixed-layer
phyllosilicates, and calcite largely predominate (accompanied by minor pumpellyite and analcime) and
from which epidote, prehnite, and actinolite are conspicously absent. The effects of spilitization on mineral chemistry are shown by a generalized disequilibrium resulting from the lack of pervasiveness of the
alteration process. This disequilibrium is reflected
by the following:
15 The incomplete replacement of Ca-plagioclase by
Na-plagioclase evidenced by the common presence
of patchy feldspars with the exception of the top
and bottom zones.
2) The wide range of compositions established for the
phyllosilicates. The presence of significant K, Na,
and Ca content in several of them, added to their
large Alan/A1rv ratio, suggests that a considerable
degree of interlayering has occurred which resulted in the formation of chlorite-celadonite
mixtures and other Fe-rich, mixed-layer types.
35 The Al-rich composition of the pumpellyite (see
Fig. 8). This feature, which might be taken as indicative of intermediate-high pressure metamorphic conditions (points plotting in the pumpellyiteactinolite facies, Lo~che zone), is interpreted here,
however, as the result of low-scale rock chemical
control under disequilibrium crystallization. It
has been pointed out (Coombs et al., 1976; Schiffman and Liou, 1980; Cortesogno et al., 1984; Cho et
al., 1986) that pumpellyites replacing large plagioclase crystals, and those crystallized in metabasites in which the primary augitic pyroxene has
largely or partly survived, are characterized by
higher Al contents than pumpellyites in other
metadomains. This is precisely the case with Flow
51.
Spread in composition toward the Fe-rich area of
the AI-Fe*-Mg triangle is shown by a large number of
Ca-poor, low-total, pumpellyite analyses discarded as
being suspected of contamination. If independent of
contamination, this compositional trend might be
interpreted as corresponding to the disperse pattern
characteristic of pumpellyites formed in incompletely
equilibrated domains (Offler et al., 1981; Nystr6m,
1983; Cortesogno et al., 19845.
The metamorphic minerals closely follow changes
in rock composition, and element mobility is reflected
in various features of particular mineral phases as,
for instance:
1) The strong changes in Fe and Si observed in
chlorites (Fig. 9). Chlorites richest in Fe* are

359

found in the lower central and upper central zones


where the rock is highest in FeO and lowest in
Fe203 (see Fig. 2). Conversely, chlorites poorest in
Fe* appear in the FeO-poor, Fe203-rich bottom
zone. Chlorites richest in Si belong to amygdules
and veinlets of the bottom and top zones where
rocks are lowest in SiO2 content and had a maximum permeability at the time of alteration. These
characteristics suggest that low SiO2 in these two
zones could have resulted from leaching and that
at least part of the Si removed from the rocks was
trapped in the available spaces. The recurrent
presence in composite amygdules of a narrow chloritic rim enriched in K, Mg, and Na seems to indicate that seawater was the main fluid involved.
2) The high Si content and the presence of abundant
Ca, Na, Mn, and K in the interlayer sites of Fephyllosilicates of mixed-layer type, notably in the
top zone, confirming the mobility of those elements and the role of seawater.
3) The progressive loss of Ca in the plagioclases from
the massive central zone toward both vesicular
margins of the flow where total albitization is recorded. This loss of Ca in the feldspars is coupled
with widespread generation of calcite, which fills
most of the amygdules in the top zone.
4) The late concentration of Na in the fluids producing the formation ofAb II, Ab Ill, and analcime.

Physical Conditions and Type of Metamorphism


As stated earlier, metastable equilibrium prevails
in Flow 51 - - a situation that complicates analysis of
the physical conditions of metamorphism. Following
generally accepted criteria, the mineral assemblages
contained in amygdules are considered here as representing equilibrium domains. In the present case,
these assemblages indicate that the metamorphism
is of very low grade (low temperature and pressure5
and corresponds to a subgreenschist facies. Few index minerals or associations are available to circumscribe the boundaries of such facies. The presence of
either pumpellyite or analcime (in separate assemblages} is insufficient for that purpose. Conversely,
the absence of some minerals c h a r a c t e r i s t i c a l l y
found in low-grade metabasalts - - e.g., epidote, prehnite, and Ca-zeolites - - is a more significant feature.
Compared to other low-grade metamorphic terrains,
the mineral asssociations in this flow share some
important characteristics with the zeolite facies
metamorphic assemblages present in the Del Puerto
Ophiolite described by Evarts and Schiffman (19835
and in the Taiwan Ophiolite studied by Liou (1979).
As in the case of Flow 51, epidote and prehnite are
absent in these two terrains, whereas pumpellyite
and minor analcime appear, ltowever, a major difference is the presence of Ca-zeolites (laumontite,
heulandite, thompsonite) in the Del Puerto and Taiwan rocks u minerals absent from the Rio Grande

360

L. A G U I R R E

flow. A possible e x p l a n a t i o n for this difference could


be found in the high pCO2 a c c o m p a n y i n g m e t a m o r p h i s m of the P e r u v i a n lava, as s u g g e s t e d by a b u n d a n t c a l c i t e in a m y g d u l e s in the b o t t o m a n d top
zones. Calcite coexists t h e r e with o t h e r m e t a m o r p h i c
m i n e r a l s , n o t a b l y phyllosilicates, in conditions supposed to r e p r e s e n t e q u i l i b r i u m . It is well e s t a b l i s h e d
(Zen, 1961; Boles a n d Coombs, 1975, a m o n g others)
t h a t , a t a h i g h v a l u e oflJC02, Ca-zeolite a s s e m b l a g e s
a r e i n h i b i t e d in f a v o r of c l a y - c a r b o n a t e facies.
T h e c r i t e r i a p r e s e n t e d above strongly suggest t h a t
F l o w 51 u n d e r w e n t m e t a m o r p h i s m u n d e r zeolite
facies conditions. A r o u g h q u a n t i t a t i v e a p p r o a c h can
be i n t e n d e d on the s a m e c o m p a r a t i v e bases as above:
1) T h e e n t r a n c e of epidote in the Del P u e r t o m e t a m o r p h i c a s s e m b l a g e s occurs a t 225C, according to
E v a r t s a n d S c h i f f m a n (1983). T h e s e s a m e a u t h o r s
indicated the v a l u e s 125C a n d 225C as corresp e n d i n g to the p u m p e l l y i t e - i n and p u m p e l l y i t e - o u t
t e m p e r a t u r e s , respectively.
2) F o r m a t i o n of a n a l c i m e in the Icelandic g e o t h e r m a l
fields covers a wide i n t e r v a l of t e m p e r a t u r e s (70300C) a n d is not confined to a n y of the different
zeolite zones e s t a b l i s h e d for these fields ( K r i s t m a n n s d o t t i r a n d T o m a s s o n , 1978). H o w e v e r , laum o n t i t e in t h a t s a m e region d i s a p p e a r s a t 230C,
i n d i c a t i n g a possible regional u p p e r b o u n d a r y for
the zeolite facies.
3) T h e b o u n d a r y b e t w e e n t h e z e o l i t e a n d t h e
p r e h n i t e - p u m p e l l y i t e facies h a s been calculated as
T = 1 9 0 + 3 0 C a n d P = l . l + 0 . 5 kb for t h e K a r m u t s e n m e t a b a s i t e s of British C o l u m b i a by Cho et
al. (1986).
4) Z e o l i t e f a c i e s m e t a m o r p h i s m in t h e T a i w a n
O p h i o l i t e w o u l d c o v e r t h e i n t e r v a l 150-250C
u n d e r Pf less t h a n 2 kb (Lieu, 1979).
In conclusion, a comparison with quantitative
d a t a c o n c e r n i n g b r o a d l y s i m i l a r t e r r a i n s s e e m s to
indicate t h a t m e t a m o r p h i s m of Flow 51 took place a t
t e m p e r a t u r e s in t h e i n t e r v a l 125-230 C a n d a t
p r e s s u r e s below 3 kb (and p r o b a b l y m u c h lower), as
indicated by the a b s e n c e of lawsonite. T h e s e physical
conditions c o r r e s p o n d to the zeolite facies of regional
m e t a m o r p h i s m . Moreover, in the highly p e r m e a b l e
m a r g i n s of the flow, n o t a b l y in its top zone w h e r e
pCO2 was p r o b a b l y high d u r i n g m e t a m o r p h i s m as
a l r e a d y shown, the v a l u e of p H 2 0 ( = P f - p C O 2 ) was
low a n d the r a t i o P f / P 1 less t h a n 1.0 T h e s e conditions w o u l d p e r m i t h y d r a t i o n r e a c t i o n s to t a k e
place at temperatures lower than those corresp o n d i n g to the r e l a t i o n Pf =P1 (see Fyfe el al., 1958;
C o o m b s et al., 1959; a n d Fig. 9 in Boles and Coombs,
1977). T h u s , it is possible t h a t some m e t a m o r p h i c
r e a c t i o n s in the case of Flow 51 m i g h t h a v e occurred
a t t e m p e r a t u r e s close to the lower b o u n d a r y of the Ti n t e r v a l s u g g e s t e d above.

S t r o n g evidence for s e a w a t e r / r o c k i n t e r a c t i o n is
p r e s e n t e d by the m i n e r a l c h e m i s t r y . T h e m e t a m o r p h i s m a f f e c t i n g t h e Rio G r a n d e l a v a s c o u l d be
correctly described as o f h y d r o t h e r m a l - b u r i a l type.
Acknowledgements--Field work was possible thanks to a

Guggenheim Foundation Fellowship awarded to the author. I am


grateful to L. Silva and G. Ostermann for their invaluable help
during the campaign in Peru; to P. Harvey and B. Atkin for the
XRF analyses of Flow 51; to R. D. Beckinsale and M. Brook for the
isotopic and geochronological analyses; to M. Brotherten tbr his
help in REE determinations; to D. Hermitte for his persevering
help with computer programs, calculations and diagrams; to R.
Dassulle who prepared one of the figures; and to N. Issa for her
patient and skillful typing. I thank Drs. R. J. Merriman and B.
Roberts for their constructive criticism and suggestions, which
greatly improved a previous manuscript.

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