Study of the composition of amphiboles in the

tremolite-actinolite series by micro-Raman

and SEM-EDXS
Danilo Bersani , Sergio And , Paolo Gentile , Laura Scrocco and Pier Paolo Lottici
1

University of Parma, Department of Physics and Earth Sciences , Parco Area delle Scienze 7/a, 43124 Parma (Italy)

University of Milano-Bicocca, Department of Geological Sciences and Geotechnologies, Piazzale della Scienza 4, 20126 Milano (Italy)

1. The aim of the work is to find a non-destructive

Table 1:
analyzed samples, position of the main Raman
peak and X=Mg/(Mg+ +Fe2+) ratio obtained by
SEM-EDXS.

method for the identification of the composition

of nephritic jades Ca2(Mg2+,Fe2+)5Si8O22(OH)2
based on Raman spectroscopy.
We started from the fundamental work on the
cation distribution on amphiboles of Wang et
al. [3] and from the application of Raman
micro-spectroscopy on the study of jades
proposed by Chen et al. [2] to develop a quick
method for the identification of nephrite using
both low-wavenumber and high wavenumber
parts of the spectrum.
In this work we analyzed by micro-Raman
spectroscopy twenty samples of minerals in
the tremolite-actinolite series, coming from
different localities in the Alps, to study the
relationship between the Raman spectra and
the composition, obtained by SEM-EDXS, and
the influence of different cations (Table 1).
The ratio X= Mg /(Mg +Fe ) discriminates
the members of the series:
2+

2+

2+

X0.9
= tremolite
0.5<X<0.9 = actinolite
X<0.5
= ferro-actinolite.

Wavenumber
(cm-1)

Mg /(Mg +Fe )
(from EDXS)

#1

671,41

0,81

#2

672,94

0,88

#3

672,95

0,87

#4

672,47

0,83

#5

669,30

0,76

#6

671,41

0,76

#7

672,76

0,85

#8

673,85

0,94

#9

674,05

0,96

#10

671,60

0,89

#11

673,50

0,94

#12

673,04

0,92

#13

673,87

0,95

#14

672,68

0,87

#16

674,75

1,00

#17

665,64

0,44

#18

672,54

0,85

#19

669,50

0,67

#20

671,94

0,85

#21

674,23

0,99

2+

2+

1-7

8-15

16-21

a single peak (A) ~ 3674 cm-1 for substitution MgMgMg,

a second peak (B) ~ 3657 cm-1 for substotution MgMgFe or MgFeMg,
a third peak (C) ~ 3646 cm-1 for substitution FeFeMg or FeMgFe
a fourth peak (D) ~3620 cm-1 for substitution FeFeFe.
This behavior is due to the fact that in nephrites the OH group vibrations are
influenced by the population of 3 metal sites where Fe 2+ or Mg2+ could be
present [2].

1
O
H

2
3

From a simple statistical model based on the population of the 3 sites, we

obtain another relation useful to estimate the X value from the Raman
spectrum: X=(A12)/(1/3+A12), where A12 is the ratio between the areas of A
and B Raman bands, often the most visible ones.
In this way we obtained 2 simple and independent methods to evaluate the
composition of nephritic minerals from their Raman spectrum.

X ratio (from SEM-EDXS)

Raman spectra were then measured on the

same spots used for SEM-EDS analysis and a
correlation between the X ratio with the
Raman peak positions was obtained.
The
increase of
X = Mg2+/(Mg2++Fe2+)
corresponds to a linear increase of the
main peak wavenumber.

N.

2+

2. Raman spectra at high wavenumbers (symmetric OH stretching) show:

X ratio (from Raman OH bands)

Wavenumber (cm-1)
600
674.4

Correlation between X= Mg2+ /(Mg2+ +Fe2+) and the

wavenumber of the main Raman peak.

500

X ratio (from SEM-EDXS)

Comparison between the values of X= Mg2+ /(Mg2+
+Fe2+) measured by SEM-EDXS and estimated by
Raman.

3.
1061.3
1071.5

1030.2

931.9

751.1

416.4

333.0
351.4

0.0

100

394.5

223.8
233.5
251.3

200

370.1

300

179.2

Intensity(cnt)

400

0
200

300

400

500

600
700
1
RamanShift(cm )

800

900

800

900

1000

We verified the shift at low wavenumbers of the main peak with the increase of iron, performing a micrometric Raman
map on a zoned needle-shaped actinolite crystal coming from Alpe Rosso (Vigezzo Valley, Italy).
Micro-photo of a zoned actinolite crystal: the green
colour, increasing from left to right, is due to Fe ions.

Map of the position of the Peak 1:

light = higher wavenumber (Fe-poor)
dark = lower wavenumber (Fe-rich)

Campolongo, Switzerland
671.8

700

600

947.5

742.1

514.7

349.1
371.1
391.5
413.3
436.1

100

156.9
174.7

200

929.6

300
223.5

Intensity(cnt)

400

105
69
0.8
.0

1028.4

500

0
200

300

400

500

600
700
RamanShift(cm1 )

1000

1100

Malenco Valley, Italy

References
1.Rong Wang and Wei-Shan Zhang, Application of Raman spectroscopy in the nondestructive analyses of ancient Chinese jades, J. Raman Spectrosc. 42, 1324 (2011)
2.T.-H. Chen, T. Calligaro, S. Pags-Camagna, M. Menu, Investigation of Chinese archaic jade by PIXE and -Raman spectrometry, Appl. Phys. A 79, 177 (2004)
3.A. Wang, P. Dhamelincourt, G. Turrell, Raman Microspectroscopic Study of the Cation Distribution in Amphiboles, Appl. Spectrosc. 42, 1441 (1988)