Vol. 45 No.

4 SCIENCE IN CHINA (Series D) Apnl2002

Redox state of amphibole-bearing mantle peridotite

from Niishan, Anhui Province in eastern China and its
implications

Ll Jianping (��4-)1·2 & ZHANG Sheng (5� 1..)1

1. Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Gu�ngzl1ou 510640, cr.·�:'\,
2. State Key Laboratory of Department of Earth Sciences, Nanjint; Llniversity, Nanjinc <! 'CJO��\ c-,;na
Correspondence should be addressed to Li Jianping (email: jpli@gib.aL.:.;n ant' jpingliQ,��•ina con')

Received October 11, 2001

Abstract Using secor�::..�v sp;r,91 stand�rd rr.1;Uwrj, ·.ve have measured precisely the composi­
tions of snir.::,;.;; ,1f e: n�p ·1ibo;9 -t:.e.:l.l ing :nant1e peridotite xenoliths from NOshan in eastern China,
anLI c,::�lc·.uat•:'d tt;e rm:-11t1e oxygen fugacities recorded by the xenoliths. Results indicate that the
mantle me:::�>omati3m for forming amphiboles in NOshan region of Anhui has resulted in the de­
crease of mantle redox, which is in contrast with theoretical estimation and previous research re­
sults from other areas around the world. Combining with related studies on the mantle of eastern
China, we give a reasonable explanation to the 'new finding' and further elucidate the composi­
tions and nature of mantle fluids in eastern China.

Keywords: Niishan of Anhui in eastern China, mantle metasomatism, mantle amphibole, mantle C-D-H fluids, mantle

redox state.

Mantle amphibole is the result of the metasomatism of mantle C-0-H fluids. Its forming
mechanism can be expressed as
Px + 01 + Sp + (melt) + fluid = Amphi, (1)
where Px, 01 and Sp represent pyroxene, olivine and spinel, respectively, while fluid represents
mantle C-0-H fluids with water, and melt represents silicate- or carbonate-rich melt. During
11
this process, participation of H 20-rich mantle fluids is necessary. DJ et al.1 , through the studies
on amphibole-bearing mantle peridotite xenoliths, reconfirmed the above process, and directed out
that the mantle metasomatism is characteristic of alkalic nature. The previous studies indicate that
the mantle redox state and the compositions of mantle C-H-0 fluids, mainly consisting of CH4,
Hz, COz, CO and H zO, can interact and affect each other under certain temperature and pressure.
As H zO has the strongest oxidizing ability in mantle C-H-0 meta.wmatic fluids, its metasoma­
tism to mantle leading to the formation of amphibole will raise the mantle redox state. Amphi­
bole-bearing mantle peridotite rocks or xenoliths from other regions in the world have testified
12 5
this conclusion - 1.
But the studies on amphibole-bearing mantle xenoliths from .1\ iishan of Anhui Province in
eastern China show that the recorded mantle redox state is in contrm.t with the above conclusion.
That means that the genetic mechanism of this kind of mantle amphiboles was different from that

© 1994-2006 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
 No.4 REDOX STATE OF AMPHIBOL E-BEARING PERIDOTITE IN E-CHIN A 349

of the common ones and it involved of a special process of mantle fluid. This paper tries to eluci­
date the forming process of this kind of amphiboles and discuss the compositions and evolution of
mantle metasomatic fluids.

1 Calculation of oxygen fugacity

1.1 Calculating methods

For spinel lherzolite or harzburgite, from the 01-0px-Sp mineral assemblage, the following
reaction equilibrium can be established.
6FezSi04(0l) + Oz = 3Fe2Siz06(Cpx) + Li<'e304(Sp \ (2)
where FezSi04, FezSiz06 and Fe 04 are the Fa, Fs and Mt compom�nt in o;, Oj:.x, ::tnfl. Sp, respec­
3 6
tively. Using the thermodynamic data obtai;;c,j icr the re;at_;c>ti mil'.en:t�s ty Mattioli and Wood1 1,
the following formula can h� jtdl>ce:l to ca:oilatf: til•� CL�J;5,cn fugacity recorded by rocks.

l�'g�fc,2 hT = !<,_e �!6;'10 )pT + 0.35 + 220 1T + 0.35- 0.0369P IT -12 log X �1

where T and P represent temperature (K) and pressure (bar), respectively, f ��Q the equilibrium
oxygen fugacity of buffer reaction [3 FezSi04(Fa) + Oz = 2 Fe 04 (Mt) + 3Si0z(Qz)], XFe the Fa
3
mole fraction in 01 or the Fs mole fraction at Ml and M2 positions in Opx, and a Fe3o4 the activity
of Mt in Spinel. aFqo4 can be calculated according to the following formula obtained by Wood17 1:
log a Fe3o4 = log[(Fe2+)(Fe3+)14]+[406(Al)2+653(Mg)(Al)+299(Cd+199(Al)(Cr)

+346(Mg)(Cr)]IT. (4)
3
M represents Fe2+, Mg, AI, Cr, Fe + cation numbers in spinel structural formula on the basis of 4
oxygens.

1.2 Precise measurement of Fe3+I I: Fe in spinel and other mineral compositions

The uncertainties in the oxygen fugacity calculation mainly derive from the analytical errors
of mineral compositions. Among them the error caused by Fe3+ content in spinel is most severe.
The Fe3+1I: Fe errors in spinel obtained from common electron probe analyses can usually attain
±0.025 (1 standard deviation), which leads to the calculation errors of .6logfo2(FMQ) [= logfo2

- log f (;�MQ ], nearly 30%-40%. Therefore, precisely measuring Fe3+ in spinel is the key to esti­
mate mantle oxygen fugacity.
Both Mossbauer spectroscopy and single mineral chemical analysis can precisely measure
the Fe3+/.I: Fe in spinel, but the approaches are too complex to be used when the amount of sam­
ples is not enough to separate enough spinels, besides, magnetic separating of spinel has ruled out
the heterogeneity to some extent, and further homogenizes the compositions in measuring process,
which are not what we wanted sometimes (for example, for the compositional and geochemical
study in mm-cm scale). Although conventional electron microprobe analysis could quantitatively

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 350 SCIENCE IN CHINA (Series D) Vol.45

3+
determine mineral compositions in situ, the Fe in spinel can only be acquired by stoichiometry.
In such case, the minor error in MgO and Ab03 of spinel will lead to the evident inaccuracy of
Fe203 content obtained by stoichiometry. Thus, based on the secondary spinel standard, this study
3
has determined the Fe +(L Fe in spinel by electron microprobe analysis. The related principles and
methods are as follows:
3 3
As the determined Fe +I L Fe ratio (Fe + I L Fe)Moss by Mossbauer spectroscopy can basically
3+ : 3
represent the true values (Fe IL Fe)true. the difference between (Fe ·+I L Fe)true and the ratio (Fe +I

L Fe)probe acquired by conventional electron microprobe analy._;is can be expres�:;l! cy tlie follow­
81
ing linear relationships1 :
(5)
3+
where (Fe 1l::Fe)probe repref':i:ts lhe de:t:rmired va.1t.P� sy electron microprobe analysis, A, B
represent t}l� •:adat.�i� c:ons�a�r.s c:!:angii,g wiih different analytical conditions of electron micro­
3
proi:-t- S0, t;J.king t!·,e winels whose (Fe +I L Fe)1rue is known as secondary spinel standards, con­
ductiniS t.he electron microprobe analysis together with the unknown spinels under the same condi­
tions, and after acquiring A and B values in eq. (5) through detemtining more than 3 secondary
3+
spinel standards with different AV(Al+Cr) ratios, the (Fe /l::Fe)1rue ratios of unknown spinels can
finally be obtained through formula (5), with an uncertainty less than 0.01 (two standard devia­
181
tions) .
This study chose the samples (KLB8305, KLB8311, KLB8315, KLB8316) recommended by
8 3+
Wood and Virgo1 1 as secondary spinel standards with (Fe 1l::Fe)uue values of 0.20, 0.21, 0.15,
51
and 0.25, respectively. Woodland et al. 1 , using Mossbauer spectroscopy, has testified a series of
3+
spinels (Fe I L Fe range from 0.09 to 0.28) calibrated by the sam{: secondary spinel standards.
Their results have reconfirmed that the secondary spinel standard method is reliable, revealing that
3
though Fe + /l::F e of these standard spinels ranges only from 0.15 to 0.32, eq. (5) based on them
3+
also suits for calibrating spinels with Fe /l::Fe lower than 0.15.
0.20 0.20
Fe3-/l:Fe"'"- rot>c=O.l 08 · AI/(AI+Cr)-0.0486 Fe3+1rFe,ruc- obc=0.1543 · AI/(AI+Cr)-0.0715
p p
0.15 R2=0 9623 0.15
R2=0.9467

Jl .l! 0.10
� 010 �

~
� �
0
{..:.. 0.05
"'
u..
- 0.05
� �
r�
-u.."' OJ
0 u.. 0

-0.05 -0.05

(a) (b)
-010 -0. 1 0
0.4 0.5 0. 6 07 0.8 09 1.0 04 0.5 O.tS 0.7 0.8 0.9 1.0
Al/(AI+Cr) Al/(AI+Cr)

3
Fig. I. The relations of (Fe •/E Fe),rue-proo. vs AI/(Al+Cr) of secondary spinel standard measured m random 2 days.

:J © 1994-2006 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
 No.4 REDOX S T ATE OF AMPHIBOLE-BEARING PERIDOTITE IN E-CHINA 351

The electron probe analysis was conducted at Department of Earth Sciences, Nanjing Uni­
versity, and employed the analytical conditions, voltage 15 kv, beam current 20 nA, counting time
20 s and beam diameter <1 )..lm . The measurement of second spinel standard was conducted daily,
and the measurement of 5-7 spinel samples was conducted under the same condition with 6-9
analytical data for each spinel. Fig. 1 illustrates the results of second spinel sandard measured in
random 2 days. The good linear relationship has reconfirmed the existence of relation exhibited by
eq. (5), which changes with the measurement conditions.
The compositions of other minerals (01, Opx, Cpx) by electron microprobe we:-� d.�lermined
under the same condition and 5-7 analytical data were C'!J,cained for each !l,Lntr.ll.

1.3 Estimation of equilibrium temperature ancl. pr::.• -:ure

Equilibrium T and P can al�0 1csult ir evident ca1culat�0e error of oxygen fugacity. But, as

log f ;�o is al�� a fm�ctin of' T a11<.! P, ;n cak-..dating 6log f02 (FMQ) ( = log fo2- log f;�o ],
the infl,lt:n•.t: l':1 it cJusecl by T and P will decrease because of their mutual offset. For example,
the 6logf0/fMQ) caused by lOO'C temperature error is just 0.15 unit of log, while the uncer-

tainty of 6log fo2(FMQ) caused by 0.6 GPa pressure error is about 0.18 unit of log, thus in the

stable range of mantle spinel facies (0.8-2.0 GPa), the calculating error of 6log foiFMQ)

caused by pressure is negligible.

In order to compare with other research results, this paper also uses pyroxene-thermometry of
191
Wells to calculate the equilibrium temperature of rocks to avoid the systematic error caused by
different geothermometries. As the compositions of pyroxenes in amphibole-bearing mantle xeno­
liths from Niishan exhibit a certain degree of heterogeneity from core to rim while those of olivine
and spinel are homogeneous, the temperature estimated from rim composition is more approach­
ing the latest equilibrated temperature. As lacking appropriate geobarometry for mantle spinel
peridotite, the estimation of equilibrium pressure is obtained according to mantle geother­
101
mal-barometric curves acquired by Xu et al.1 , and the results indicate that the equilibrium pres­
sures of amphibole-bearing and amphibole-absent mantle peridotites from Niishan of Anhui Prov­
ince are about 1.2 GPa and 1.5 GPa, respectively.

2 Oxygen fugacity recorded by mantle xenoliths from Niishan

The values of 6logf02 (FMQ) recorded by mantle xenoliths in basalts from Niishan, Anhui

Province can be found in table 1 and fig. 2. The results indicate that although the general range of
6logfoiFMQ) is within that of lithospheric mantle (6log folFMQ) = -2 . 5-+ 1.5), the amphi­

bole-bearing mantle peridotite xenoliths have recorded lower oxygen fugacity compared with an­
hydrous mantle peridotite xenoliths, contrary to the research results from other areas in the world,
13 4 lll 151
such as Eifel , , in Germany and Pyrenees in France. Fig. 2 shows that the range of variation
in 6logfoiFMQ) for amphibole-bearing xenoliths is larger than that of amphibole-absent xeno-

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 352 SCIENCE IN CHINA (Series D) Vol. 45

Table I P rincipal chemical compositions of spinels and Silicates. and the relative oxygen fugacities of mantle xenoliths of
Nlishan, Anhui Province in eastern China

Amphibole-bearing mantle spinel peridotite

Sample
N-11 N-24 N-26 N-32 N-37 N-22 N- 13 N-17
----�·--

Spinel
AI/(A1+Cr) 0.84 0.87 0.90 0 87 0.85 0.8 1 0.85 0.90
F e3' /1:Fe(probe) 0.027 0.048 0.019 0.098 0.051 0.117 0.114 0.071
Fe1'11:Fe(true) 0.085 0.118 0.093 0 143 0.118 0.178 0.181 0.120
loga.,, -3.059 -2.498 -2.802 -2.521 -2.468 -2 .20 1 -2. 181 -2.523
Olivine
X Mg 0.896 0.900 0.892 0 897 0.900 e.:�::v :).ii96 0.889
XF, 0.098 0.095 0.103 0.098 J.Cci� 0.1\)5 G.� �J � 0.105
Orthopyroxene
XF, (M2 ) 0.090 0.0!!6 o.n4 'l.Ol\7 !\C05 0.095 0.092 0.092
X F,(MI) f\.'l8u o.�n O.L'76 f\.J'/6 0.076 0.092 0.087 0.086
{IE, ( 'i21 C.130 G.624 0.682 0.700 0.729 0.732 0.721
h.'(l'e+I,'!J) c'.09� 0.087 0.097 0.090 0.088 0.099 0.095 0.095
Clinoi'yiOxe�'�

liEn 0.063 0.051 0.057 0.065 0.027 0.056 0.057 0.051

T(K) 1232 1178 1227 1238 1074 1192 1196 1179
.0.1og /02 (FMQ) -1.96 -0.88 -1.73 -0.99 - 1.09 -0.38 -0.3 1 -1.19

Anhydrous mantle spinel peridotite

Sample
N-10 N-2 1 N-28 N-34 N-35 N-42-6 N-7
Spinel
AI/(AI+Cr) 0.77 0.77 0.91 0.90 0.87 0.90 0.85
3
Fe ' /1:Fe(probe) 0.208 0. 17 1 0.197 0. 11 7 0.200 0.324 0.132
3
Fe '/1:Fe(true) 0.264 0.227 0.247 0.190 0.268 0.407 0.205
loga�" -2.042 -2.389 -2.136 -2.284 -2.100 -1.637 -2.473
Olivme

XMg 0.888 0.901 0.886 0.888 0.888 0.887 0.895

X F, 0.106 0.093 0.108 0.105 0.106 0.108 0.099
Orthopyroxene
XF,(M2 ) 0.088 0.087 0.102 0.096 0.093 0.100 O.Oll7
XFe(M J) 0.080 0.076 0.089 0.082 0.082 0.094 0.080
aE, 0.678 0.636 0.613 0.633 0.629 0.662 0.661
Fei(Fe+Mg) 0.093 0.092 0.109 0 100 0.099 0.107 0.093
Clinopyroxene

aa:n 0.109 0.130 0.118 0.082 0.116 0.100 0.136

T(K) 1357 1419 1394 1300 1388 1333 1422
.0.1og /02 (FMQ) -0.26 -0.33 -0.17 -0.61 -0.24 0.80 -0.7 1

liths, and some .6log foiFMQ) recorded by the former is similar to that by the latter. These im-

ply that the original oxidation state of the amphibole-bearing xenoliths should be the same as that
of the anhydrous mantle peridotite, and decrease to different extent as a function of variable de-
gree of metasomatism. In addition, it is noted that one .6log foiFMQ) recorded by amphi-

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 No. 4 REDOX STATE OF AMPHIBOLE-BEARING PERIDOTITE IN E -CHINA 353

bole-absent xenolith is much higher than the 2 00

others, and this heteogeneity might be the result I 50 o Amphibole-absent

1.00 e Amphibole-bearing
of local influence by late oxidizing C-0-H
0

fluid in a small scale, as the oxygen fugacity 0 0 50

::;:
buffer capacity of mantle is not strong because � 0.00
.o 0
'-.,0 <o
3 81 •
of low Fe + content in mantle1 . OIJ
0
-0.50
0
0
<i •
•
Mantle redox states recorded by the same -] 00 •
•
-150
mantle rock or xenolith can also be compared '/,
3+ -2.0(11- ..
with each other by Fe fL.Fe in spinel. This can
-2.50 l_-- __]______ -____]___ -----'- - --L.___J
avoid to some extent calculating error of oxygen o:,-o o. 75 no t'.<�5 :; 90 o. 95 1 oo
r'..i/(AI+Cr)
fugacity caused by chemical disequil!brium by
p;t;. 2. L:ilogfo (FMQ) recorded by mantle peridotites
metasomtism and in�<::('m,�..:y of �stimating of 2
from NUshan of Anhui Province in eastern China.
equilibri!:L< rempe1atu:c <lild prt:SSu!e. flg. 3
J+
illustrates ti1a� :he Fe I L. Fe ratios in spinels of amphibole-bearing mantle peridotites from
Ntishan of Anhui in eastern China are relatively low, which is just in contrast with that of other
3+
regions in the world, e.g. the Fe /L.Fe ratios in spinels of amphibole-bearing mantle peridotites
from Pyrenean of France are relatively high (fig. 3(b)).

0.50 ,-------· -,

0 Amphibole-absent 0.4 r------,

0 o Amphibole-absent
0.40 • Amphibole-beanng
• Amphibole-beanng

Fig. 3. Variatrons of Fe3+/L:Fe in spinels of mantle peridotite from Pyrenean of France and Niishan of Anhui Province in east­
ern China. (a) NUshan, Anhur Provmce m eastern China; (b) Pyrenean. France.

The above results suggest that the amphibole-forming mantle metasomtism involved a reduc­
tion process, which seems to be in contradiction to the metasomatic theory on the formation of
mantle amphibole, thus in the following this paper will conduct a detailed discussion on this new
discovery and its geological implications.

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 354 SCIENCE lN CHINA (Senes D) Vol. 45

3 Discussions

3.1 Implications for oxidation state of amphibole-bearing mantle xenoliths from Ni.ishan
In a closed system if mantle amphibole is the result of metasomatism of asthenospheric man­
tle fluids, the mantle redox state will be raised. As the C-H-0 flJid from asthenospheric mantle

would be rich in C02-H20 and poor in CH4, the reaction of the H20-rich fluids with either shal­
low lithosperic mantle or asthenospheric mantle at relatively low T and P conditions during man­
tle diapir for reaching a new equilibrium will lead to the rise of mantle redox state, The above
situations were usually found on amphibole-bearing contine�1lal mantle. �uch as ;h� regions of
Eifel in Germany and Pyrenean in France. Besides, ll'. an o:-e'"• sy:\terr,, if 1he weta�'om:::'jc fluids
orginate from dehydration of subducting cn1st a•:J &re ric..h in 0'):,-H/', •l1e metasomatism oc­
curring at overlying mantle "�iiSt:<:[ by tltllSe flu:c.'s ca'1PO� Gilly result in partial melting and mag­
matism but al�c. li:il�e tile m:m: cle redoA. state, which usually are found at continent-ocean subduc­
3
tioD .?.:ore.>, :;ud, �·: H&waii a:1d Tahitti1 1. The closed and opening systems could be identified by
4 11
oxyger; isdope compositions of amphibole1 " 1. The lower redox Hate properties showed by am­
phibole-bearing mantle peridotites from Ni.ishan of Anhui in eastern China (fig. 2) has ruled out
the possibilities of crustal fluids, as the crustal fluids are rich in H 20-C02. It cannot be the result
of the thermodynamatic non-equilibrium, otherwise the redox state of the amphibole-bearing man­
tle peridotite should be the same as that of anhydrous mantle peridotite. The fact that spinels of the
amphibole-bearing and amphibole-absent peridotite xenoliths have the same Cr/(Cr+Al) ratio
range (figs. 2 and 3) implies that the variations of oxygen fugacity are not the results of different
degrees of partial melting of mantle peridotite. Thus, the only explanation for this is that the am­
phibole-forming process had involved a process of relatively redJced mantle C-H-0 fluids,
:•+
which had decreased the mantle redox states and reduced part of Fe in spinel.

3.2 Forming mechanism of Ni.ishan mantle amphibole

The equilibrium temperature recorded by amphibole-bearing mantle peridotite xenoliths from
Ni.ishan of Anhui is lower than that of amphibole-absent mantle peridotites (table 1), which repre­
sents the second cooling history before being caught by host basaltic magma, corresponding with
12
mantle uprise events in neogene and paleogene, respectively1 1. The existence of veined par­
tial-melting areas and glasses in amphibole-bearing peridotite implies that the in situ partial melt­
ing ever occurred in the rocks. Microscopic investigations and geochemical evidences also proved
113 14
that melts had participated in the formation of Ni.ishan amphiboles ' 1 . According to the local
2
excessively high geothermal gradient (80 mW/m ), we can infer that the mantle uplift may result
3
from the uplift of asthenospheric mantle. Xu et al.11 1, from the fact that the highest temperature
recorded by exsolved pyroxenes approached asthenospheric potential temperature (1280"C ) esti­
1151
mated by McKenzie and Bickle , revealed that the original materials of mantle xenoliths in this
area derived from asthenospheric mantle.

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 No.4 REDOX STATE OF AMPHIBOLE-BEARING PERIDOTITE IN E-CHINA 355

Combining the above petrological and geochemical characteristics, the following explana­
tions about the genesis of mantle amphibole in this area could be obtained. At Niishan of Anhui in
eastern China, two upheavals of asthenospheric mantle occurred. The first had brought some as­
thenospheric materials to lithospheric mantle, which had been re-equilibrated during the first
cooling stage, and the second made the CO-CH4-rich asthenospheric mantle fluids enter into
lithospheric mantle, which finally concentrated at the upper section of the uplifted mantle through
percolating and infiltrating. If P, T and redox state are in a new circumstance, the·,e CO­
CH4-rich fluids develop the following reaction with rocks:
CH4 + 2CO + 6Fe20
= 2H20.,. 3CO? + l�FeO. (6)
3 2
This process has made the mantle fluids rich in CO;�- !-i.'O ?.ttd pmt of Fe"+r�r<.!l-.,ed to Fe +. The
H20-bearing mantle fluids may furtt..-,r lea(. to the 1'1 situ 1xutc?..! htelting of rocks, and then the
formed melts togeti-J.;:.. wi1.tl C02·· -f-hO-r!.-:h tiu!Js dtsplaced original mantle minerals, forming
amphitK.. les <.!m:ng �t1<; s��c·Jnd cooling stage. This is consistent with the fact that the equilibrium
temperatut;: oi ·he amphibole-bearing peridotite is lower than that of the amphibole-absent one at
Ni.ishan (table 1).
In fact, high temperature and high pressure experiments conducted by Taylor and Green1161
have already shown that mantle peridotite may react with CH4-rich C-0-H fluid at subsolidus
P, T andfo2 conditions of normal anhydrous mantle, thus making the fluids rich in C02-H20 by

the oxidization of CH4 and then resulting in partial melting of peridotite called redox melting. This
experimental result supports strongly the above inference about the genesis of mantle amphibole
of Ni.ishan in Anhui Province.
The interface between lithosphere and asthenosphere is about 60 km in eastern China1101. It
means that the garnet lherzolite xenoliths from eastern China derived from asthenospheric man­
tle1171 , which can also be proved by their rheology and deformation characteristics118'191. Xia et
2
al.1 01 , from the studies on fluid inclusions of mantle xenoliths from eastern China, proved that
CH4 in fluid compositions in garnet lherzolites is generally richer than that of spinel lherzolites,
e.g., the CH4 content in fluid inclusion in pyroxene of garnet lherzolites from Xilong area has at­
tained 12.1 mol%. This result implies that C-0-H fluid derived from asthenospheric mantle
(garnet peridotite) is probably richer in CH4. The deep-derived hypogenic CH4-rich fluid may also
be preserved because of being trapped in minerals when ascending to a relatively shallow position
e.g., the CH4 content in certain fluid inclusion in spinel lherzolites from some areas (Damaping in
2
Zhangjiakou, Huinan, Wangqing and Jiaohe in Jilin) measured by Du et al.1 1l has attained
12.1- 17.5 mol%. Owing to the decompression and heating during the ascending of mantle xeno­
liths associated with hot host magma, the inclusions trapped in deeper place with higher pressure
may lose their closing, and the measured fluid inclusions represent just the ones trapped at rela­
tively shallower position. These hypogenic fluids might have been partly oxidized for the rising of
oxygen fugacity before being trapped at a shallower place, and its original compositions should

© 1994-2006 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
 356 SCIENCE IN CHINA (Series D) Vol. 45

consist of more reduced composition CH4. From this, we can confirm that the CH4 content in as­
thenospheric mantle C-0-H fluids in eastern China is definitely richer than that of lithospheric
mantle. This fact supports the above genetic explanation of amphibole from another aspect.

3.3 Redox state of asthenospheric and lithospheric mantle

Apparently, the above inference is contrary to the viewpoint that continental asthenospheric
mantle is being more oxidized than lithospheric mantle. In fact, thi� idea is based on the following
evidences: (i) Asthenospheric mantle-derived basaltic magma has a higher oxidizatio·.t state than
that of lithospheric mantle; (ii) Amphibole-bearing mantle pe:-idotite having f('corded relatively
high oxidization state is the result of metasomtism of <sthenos�Leric mantle fb:ds. Hov'�Ner, the
oxidation state recorded by asthenospheric mar.11:;-ueriv?·i magma can1ot , .�;::resent the state of
source region, as the oxidation stz!e has eviden f rehti o.'ls witi1 the degrees of partial melting,
crystallization cliff�i.'JnL:cih'Xl ch:i1·.g the ��L.:;r,d�11g of the magma, exchange with the oxygen at
22
shc.�liJW t:lac�s, �:tci d�?.gassit.?/ '. Moreover, even in a closed system, in the lithospheric region,
the me�:Jsch'atic amphtoole-fom1ing fluids may not originate from asthenospheric mantle and they
may be derived from lithospheric mantle itself totally or partly. The known oxygen isotope evi­
dences show that some amphibole-bearing mantle periditites originally taken as formed in a closed
system may also exhibit certain opening state to oxygen, e.g., the amphibole-bearing mantle peri­
111 1
dotite xenoliths from Eifel, Germany • Therefore the view that continental asthenospheric man­
tle is more oxidized than lithospheric mantle based on above evidences are worth further consid­
eration.
Contrary to this, asthenospheric mantle may be more reduced than lithospheric mantle be­
1231
cause of the material addition of lower or transitional mantle with high degree of reduction state .
Furthermore, since the solubility of H 20 in magma is greatly higher than that of CH4, the mag­
matic activities in asthenspheric mantle could also lead to the enrichment of CH4 in residual t1uid.
The properties of the mantle C-0-H fluids in eastern China have reconfirmed this conclusion.

4 Conclusions

From the above discussions, the following conclusions could be obtained:

(1) The mantle metasomatism occurring in Ni.ishan, Anhui of eastern China, leading to the
formation of amphibole, has reduced the oxidation state and resulted from the effect of co­

CH4-rich asthenospheric mantle fluids. When CH4-rich mantle C-0-H t1uids ascended to
3+
lithosperic mantle, part of CH4 was oxidized and part of Fe in spinel was reduced at new P, T
and fo2 conditions. This process had made the fluid rich in COz-H20 further resulting in the in

situ partial melting of the rocks. This melt, together with C02-H;O-rich mantle fluids, reacted
with rocks fom1ing mantle amphibole.
(2) The fact found at Ni.ishan in Anhui Province suggests that asthenospheric mantle may be
more reduced than that of lithospheric one. The rise of mantle oxidation state caused by amphi-

© 1994-2006 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
 No. 4 REDOX STATE OF AMPHIBOLE-BEARING PERIDOTITE IN E-CHINA 357

bole-forming metasomatism occurring in continental lithospheric mantle may not be the direct
result of asthenospheric mantle fluid, but may be related to lithosphere and even crustal fluids.

Acknowledgements This work was supported by the National Natural Science Foundatton of Chma (Grant No.
49673 I85). the Ministry of Science and Technology of China (Grant No. 95-Pre-39) and the Key Laboratory of the Department
of Earth Sciences. Nanjing Umversity. The authors are mdehted to Dr Xu Yigang for supplying samples and Wang Rucheng for
mvaluable assistance in the electron microprobe analysis.

References

I. Du LetJan, Yong Jiashu, Cheochemistry of alcali metals in mantle fluids, in Geochemistry of Mantle Fluids "n·" Astheno­
sphere (Asthenohths) lin Chinese) (ed. Du Letian), Beijing: Geological Puhlish:n•J House, 199f;, 154---22'1
2. Dawson, J B., Smith, J. V., Metasomatized and vemed upper mar.cle xenoliths from P�,:o J-lil', Tamania: E·•Ide'lce for
anomalously-light mantle beneath the Tanzanian sector of the East Aln.;an roft \'a. ley, Con'r .. M n�ra' 1-'e!r'Jl., 19�8. 100:
510-527.
3. Mattioli. G. S., Baker, M. B., Rutter, M. J. I Tpper n-,,_ntlt dX) g�n t\tpci'y a,;<];,� r·;!;;uon to metasomatism, J. Geol., 1989,
97:521-536.
4. Bryndzia. L. T.. T):n is, A. ·,1., Nco(', l'l. fhe 1:;�1tovr ''Jmpositlon of ( q D) water m amphiboles and the redox state of
am!'h:�·oie-b( 1rin0 •'Pf'=' •'1Lntle s1,ird peridotites, Feol. Soc. Am. Prog., 1990,22: A254.
5. Wc'O,ilallc\, P .. , Kor,,probs:. J .• Wood, B., Oxygen thermobarometry of orogenic lherzolite massifs, J Petrol, 1992, 33:
203--2.'-0.
6. Matt1ot., G. S., Wood, B .. Magnetite act1v111es across the MgAl204-Fe304 spinel join, with application to thermobaromet­
ric estimates of upper mantle oxygen fugacity, Contri. Mineral Petrol., 1988,98:148� 162.
7. Wood, B. J., An experimental test of the spmel peridotite oxygen barometer, J. Geophys. Res., 1990, 95(Bl0):
15845�15852.
8. Wood, B., Virgo, D., Upper mantle oxidation state· Ferric iron contents of lherzolite spinels by 57 Fe Mossbauer spectros­
copy and resultant oxygen fugacities, Geochim. Cosmochim. Acta, 1989,53· 1277-1291.
9. Wells, P. R., Pyroxene thermometry in simple and complex systems, Contn. Mmeral Petrol., 1977,62:129-139.
10. Xu Yigang, Lin Chuanyong, Sht lanbm et a!., Upper mantle geotherm for eastern China and its geological implications,
Science in China (in Chinese), Ser. B, 1995,38: 1482-1492.
II. Witt, G. E., Seck, H A., Origin of amphibole in recrystallized and porphyrocla,stic mantle xenoliths from the Rhentsh
Massif: Implications for the nature of mantle metasomatism, Earth Planet Sci. Lett., 1989,91: 327-340.
12. Kempton, P. D., Harmon, R. S , Stosch, H. G. et al., Open-system 0-1sotope behaviour and trace element ennchment in the
sub-Eifel mantle, Earth Planet Sc1. Lett., I 988,89:273�287.
13. Xu Yigang, Mercier, J. C., Lm, Chuanyong, Amphibole-bearing pendotite xenoliths from Ntishan, Anhui Province: Evi­
dence for melt percolation process in the upper mantle and lithospheric uplift, Chinese J. Geochem., 1997,16:213-229.
14. Xia, L. Q., Xia, Z. C., Zhang, C. et a!., On the relationship between mantle metasomatism and partial meltmg-ev1dence
from mantle-derived lherzolite xenoliths from Ntishan, China, Chinese Journal of Geochemistry, 1993, 12:289�307.
15. McKenzie, M.A., Bickle, M. J., The volume and composition of melt generated by extension of the lithosphere, J. Petrol.,
1988,29:625�679.
16. Taylor, W. R., Green, D. H., Measurement of reduced peridotite-C-0-H solidus and implicatiOns for redox meltmg of the
mantle, �ature, 1988, 332: 349�352.
17. Fan Qicheng, Liu Ruoxin, Xie Hongsheng et a!., Expenmental study of spmel-garnet phase transition in upper mantle and
its significance, Science in China (in Chinese), Ser. D, 1997. 40:383-389.
18. Lm Chuanyong, Xu Yigang, Zhang Xiaoou et al., Pnmary study on deformation characteristics, tluids effect and astheno­
sphere of upper mantle m eastern China, in Geochemistry of Mantle Fluids and Asthenosphere (Asthenohths) (in Chinese)
(ed. Du Letian), Beijing· Geological Publishing House, 1996,312-340
19. Lin Chuanyong, Shi Lanbin, Han Xiuling et a!., Thermal structure and rehology of upper mantle beneath Zhejian Province,
Chma, Science in Chma (in Chmese) Ser. D, 1998, 41:171-178.
20. Xta lmq1, Cao Ronglong, Study on the nature of fluids in upper mantle from Xilong area of Zhejian Provmce of Chma,
Chmese SCience Bulletin, 1991,36: 395�399.
21. Du Lehan, Wang Ju, Huang Shutao, Degassing of Earth, Bulletin of Mineralogy, Petrology and geochemistry (in Chinese),
1995,1:45--47.
22. Ballhaus, C., Redox states of lithospheric and asthenosphenc upper mantle, Contri. Mineral Petrol., 1993,114:331-348.
23. Green, D. H., Falloon, T. J., Taylor, W. R., Mantle-derived magmas- roles of variable source peridotite and vanable C-H-0
fltlid compositions, in Magmatic Processes: Physicochemical Principles (ed. Mysen, B. 0.), Geochem. Soc., Penn State
Umv., 1987,139�154.

© 1994-2006 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net