Radiation Measurements, Vol. 24, No. 4, pp.

485-491, 1995 Copyright 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved

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LUMINESCENCE SPECTROSCOPY OF THE EARTH

BORIS S. GOROBETS, ALEXANDER M. PORTNOV and ALEXANDER A. ROGOZHIN Ecodetector-VIMS Ltd, Staromonetny per., 31, Moscow 109017, Russia (Received 27 September 1994; revised 24 November 1994; in final form 28 November 1994) AbstractThe first attempt to consider global radiation luminescence fields (spheres) of the Earth has been undertaken. In general four types of luminescent fields characterize the superficial geospheres. (1) Luminescence of organic and bioorganic substances comprising the atmosphere, the hydrosphere, the lithosphere and the technosphere, being a unique distinguishing property of our planet in the Universe. (2) Recombination luminescence of key rock-forming minerals (feldspar, quartz, carbonates) that is characteristic of the granite and sedimentary layers occupying some 30% of the Earth's crust. (3) Photoluminescence of dozens of ironless minerals in so-called fluorescence anomalies formed with the help of fluids ascending along fractures and faults to the surface of the Earth. While ascending they accumulate many rare metal elements including transition ones. Entering crystal lattices of ironless mineral-dielectrics these metals form centres of luminescence. (4) Artificial luminescent materials created in the technosphere in the 20th century. The main types have origins in natural luminophors. So, in every field of application of photo-, thermo, cathodo-, electro-, X-ray-luminophors and laser crystals they have many analogues among the luminescent minerals.

1. INTRODUCTION The emission of light, excited in substances by incidental light (photoluminescence PL) or stimulated by ionizing radiations (recombination luminescence RL including thermoluminescence TL) or by chemical reactions etc. represents induced (secondary) geophysical fields of the Earth. But, on a global scale these fields have not been considered so far. Here, we undertake the first attempt of their general consideration based upon experimental data obtained in previous research into natural substances. The data treated in this paper have been obtained by well-known methods of luminescence spectroscopy for nearly 160 minerals (some 2500 samples) in the Luminescence Research Laboratory of the Institute of Mineral Resources (VIMS) since 1967 (Gorobets, 1981; Bakhtin and Gorobets, 1992). Thousands of spectra of emission and excitation, and PL lifetimes were measured and interpreted for samples taken from all the geospheres and from almost all the types of rocks and ore deposits. In addition, the data for some 90 minerals obtained by other authors have been included in the discussion (Tarashchan, 1978; Marfunin, 1979; Walker, 1985; Waychunas, 1988; Votyakov et ai, 1993). 2. DISCUSSION Four global fields of luminescence radiation of different nature can be revealed in the different geospheres: luminescence of organic substances existing in all the geospheres; recombination luminescence

of key minerals in granite and sedimentary layers of the lithosphere; photoluminescent anomalies in peculiar parts of the lithosphere; luminescence of artificial compounds in the technosphere (Fig. 1). 2.1. Organic photoluminescence field This encompasses all the geospheres: the atmosphere, the hydrosphere and lithosphere. Bioorganic luminescence is evidently a unique property distinguishing the Earth from other planets in the Universe. As an example, the fluorescence spectra of living vegetation are given in Fig. 2(a). Traces of inanimate organic substances were observed in hundreds of samples from all the key types of rocks (Fig. 2(b)). The signals are less intense the darker the rocks. The well-known fluorescence properties of bitumens and oils are studied by so-called luminescence bitumenology, and they also have to be included in the organic luminescence field. 2.2. Mineral recombination luminescence field This is basically formed by five key rock-forming minerals: plagioclase, potassium feldspar, quartz, calcite and dolomite. In granite layers occupying some 20% of the lithosphere, RL is due mainly to feldspar and quartz. In rocks of the sedimentary layer accounting for some 10% of the lithosphere, RL is due mainly either to quartz in sands (2%) or to calcite and more rarely dolomite in limestones (2.8%) and metamorphic carbonate rocks (marbles) accounting for 0.7% of the lithosphere.

485

486

B. S. GOROBETS et al.

[Ml* 5Bf-"ES' ! [2
Fig. 1. Schematic section of the geospheres showing the presence of four key types of luminescent fields: I. organic luminescence field (1.. .9); II. recombination luminescence field (3,4, 5); III. photoluminescence field (6', 6"); IV. artificial luminescent materials (9). Designations: (1) atmosphere; (2) hydrosphere; (3) limestones; (4) sands; (5) granite layer; (6') alteration geological body, including a zone of weathering (oxidation); (6") vein body; (7) abyssal fluids; (8) basalt layer; (9) technosphere.

vm

The general systematization of minerals according to their luminescent properties is given in Fig. 3. Non-luminescent compounds are non-transparent metals, (metallides) as well as 'semitransparent' dielectrics and semiconductors with an abundance of quenching centres. RL is observed in the rest of the dielectrics due to recombinations on oxygen or halide centres. It is this 'through' component of RL to which wide bands in the high energy part of emission spectra usually correspond (Fig. 4). Apart from these, the RL spectra of feldspar, quartz and carbonates contain bands corresponding to the main impurity centres of recombination (Fe3+, Mn2+ and Tl + ). TL of quartz, feldspar and calcite is applied to estimate total radiation dose accumulated from the moment of crystallization in country rocks due to radiation background, e.g. for dating Quaternary sediments. It is also used to measure radiation exposures for monitoring nuclear contamination (Hiitt and Jaek, 1989; Stoneham et al., 1993; Wintle, 1993). Spectra of X-ray luminescence of feldspar, quartz, calcite and dolomite are used in geology to correlate granite or carbonate series (Tarashchan, 1978). X-ray luminescence is also used in mineral processing to distinguish dead and pay rocks in electronic sorters, removing lean stuff and recovering ore minerals, e.g. diamonds, scheelite, fluorite, etc. (Gorobets and Novikov, 1991). Basalt layer, containing dark and almost non-transparent minerals, accounting for 50% of the

lithosphere takes almost no part in forming the RL field of the Earth. It contains no key minerals capable of luminescence because of the high content of iron (Fe2+) entering silicates and quenching the luminescence. Of course, one can find in basalt samples some grains of luminescent minerals (apatite and zircon), but these minerals are only accessories and form no macroscopic luminescent anomalies. One can also obtain weak TL signals from some samples of minerals of the basalt layer. However, their intensity is several orders of magnitude less than the TL in granite and sedimentary layers. So, this layer can be treated practically non-luminescent as a whole. Naturally, the RL field of the Earth is inhomo-geneous. It has anomalies related to ionization and emission levels, quenching and fading effects forming the general structure of the RL field, and this is to be researched in more detail. 2.3. Mineral photoluminescence field This accounts only for < 0.1 % of the volume of the lithosphere. The PL field is distributed in the Earth's crust extremely inhomogeneously, forming photolu-minescent (or fluorescent, which is less correct but a more convenient attribute), anomalies (Gorobets and Portnov, 1992). Resonance PL of minerals is due, as a rule, to the centres formed by metal elements or metal-ligand complexes, having energetic intervals between electron levels in the optical range. These

LUMINESCENCE SPECTROSCOPY OF THE EARTH elements are: Eu2+, Sm2+, Yb2+, Ce3+ (4f-configur-ation; 4f-5d-transition); Nd3+, Pr3+, Sm3+, Eu3+, Gd3 + , Tb3+, Dy3+, Er3+, Yb3+ (4f-4f); Cr3+, Mn2+, Fe3+, Ti3 + , V3+ (3d-3d); Ag+ (4d-4s); Sn2+ (5s-5p), Tl+(6s-6p); Ti4+, Mo6+, W6+ forming polyhedra with oxygen (O(p)-d-transitions); U6+ forming uranyl UO2^ (0(p)-5f). The typical PL spectra of 10 minerals are given in the Fig. 5. The rest of the PL and RL spectra of some 250 minerals are in the monographs (Tarashchan, 1978; Gorobets, 1981; Bakhtin and Gorobets, 1992). In rare cases these elements form the host crystal lattice of manganese and uranyl minerals, scheelite (CaW04), powellite (CaMo04) and cholorargyrite (AgCl). Much more often the listed luminescent elements are present as impurities substituting intrinsic cations if their radii and charges are close enough. Thus, Mn2+ substitutes Mg2+ and Ca2+ in many magnesium and calcium minerals. Tl+ substitutes big alkali cations: K+ in feldspars and Cs+ in pollucite. TR3+ and TR2+ substitute Ca2+ in many calcium minerals. Cr3+ substitutes Al3+ in oxygen octahedra (e.g. in ruby and spinel). Fe3+ substitutes Al3+ and

487

Si4+ in tetrahedra in aluminosilicates and so on (Fig. 3). For a mineral to become fluorescent the following three conditions must be satisfied at once: (1) a suitable type of crystal lattice favourable to form emission centres; (2) sufficient content of PL centres (usually >0.01%); and (3) a small amount of iron being the principal quenching element in nature (less than 0.5-1%). Unlike the considered transition elements, rare enough in the lithosphere (with the exception of iron), the petrogenic cations of Si, Al, Ca, Mg, K and Na accounting for most of the Earth's crust, have closed outer electron shells. They do not form levels for resonance transitions in crystal lattices of the key rock-forming minerals: feldspar, feldspatoides, quartz, carbonates, to say nothing of pyroxenes, amphiboles, micas and clays abundant with iron. At the same time, average amounts of the majority of lumi-nogenous elements in these minerals are 10 3-10~6%, that is much lower than their limiting sensitivities ~ 10 '-10 '%. So, they are not fluorescent in background rocks, basalt, granite or sedimentary layers. The situation changes radically in some uncommon

(a)

(b)

X(100nm)

\(100nm)

Fig. 2. (a) PL spectra of vegetation: (1) grass; (2) green foliage; (3) whortleberries; (4) green needle; (5) moss Sphagnum; (6) algae; (7) lichen Umblicaria sp. I. Trans-beta-carotene; II. Vitamin K,; III. Chlorophill-a; IV. Riboflavin (Interpretation of the spectral bands after). Chappele et al. (1984). (b) PL spectra of organic substances diffused in background rocks: amagmatic rocks: (1) pyroxenite; (2) gabbro; (3) andesite; (4) gneissodiorite; (5) gneissogranite: bmetamorphic rocks: (1) shale (actinolite-chlorite); (2) shale (quartz-sericite); (3) shale (quartz-mica); (4) marble (dark coloured); (5) horn with wollastonite (fresh split); (5') horn (weathered): csedimentary rocks: (1) salt; (2) limestone; (3) carbonate soils; (4) snow; (5) clay, gravel, sand, non-carbonate soils having almost no fluorescence. (X"c = 337 mm, T ~ 10-50 ns.) The given spectra are after Vassiliev et al. (1990).

Mineral compounds Luminescent Dielectrics Eg>5eV Semiconductors KEg<5eV I. Partition into four types of chemical Halides bonding: Oxygen compounds 1. S n
2 +

Homo-atomic minerals RL,PL of donor- acceptor Sulfides pairs, clusters

21.

D A

N- centres III. Electron an sublattice

20. Zn -S +
+ 2+ 2+ 2

I
Anion wide bands in RL Spectra: O" +e->(02")* +hv ; F"2 +e-F2*>2F+hv II. Partition into groups of mineral-forming metals:
2+

M i n e r a l s w

22. CI

23.

cu -cr
2+ 3+

S"2 02 IV. Absorbed i

25. Gels of Si0

Ag^
TS+

Tl Minerals
6+ 6+

Mn TR ,TR
4+

with
6+

intrinsic metal centres

6+

Mn

u
Sn 8.

3.Cr
Ti.
4 +

i t Ag h i m

5.

6.
W

Mo T
2+

T-

MniT

VO4"

CrO2"

TiO*"

M0O2" WO2," M0O2

U02+

purity metal centres 11. 10. Na

2+
r

Mg 7^

2+

c 12. Alpct 13. Altetr ,

.3+

.4+

14. K* ,Cs
+

15. Ca
T

2+

d+

3+

2+

ZnI+ 16.
Mn2+

Ti Cr Mn 2+ 241 17. Sr ,Ba

Fe 18. Zr4+

Mn 19. (Y,La)3^ Mineral-forming metals .3+/, 3+ TR (Sm,Gd,Dy) <centres UO

2+

TR3+ TR2+ Pb2+ TR3+

Ti4+

Fig. 3. Schematic partition of minerals into groups with various luminescent properties due to the different types of chemical b (1) rhodonite; (2) vanadinite; (3) crocoite; (4) ramsayite; (5) powellite; (6) scheelite; (7) otunite; (8) cassiterite; (9) chlorargyrite; ( (13) feldspars; (14) microcline, pollucite; (15) calcite, apatite, fluorite; (16) willemite; (17) strontianite, barite; (18) zircon; (19) gaga moissanite; (22) sodalite, pyromorphite; (23) calcite, dolomite, hydrozincite; (24) forsterite; (25) halcedony

LUMINESCENCE SPECTROSCOPY OF THE EARTH

489

2.4. Luminescence of artificial compounds formed in the technosphere of the Earth The eldest and most powerful laboratory of lu-minophors on the Earth is, as we have seen, the Earth itself. Up to the 20th century all the scientific data on luminescent materials were supplied by research into natural substances. The brightly luminescent minerals that could be prepared with comparative ease became the first artificial luminophors. The majority of activators of crystallophosphors were previously discovered in minerals: Cr3 + , Mn2f, U6;, Mo6', W6+, TR2+ and TR3 + . However, some activators were established first in phosphors and only later discovered in minerals: Tl + , Pb21, Ag4, Ti4+ and V11. The most important luminophors in each of the following groups are, as a rule, analogues of natural minerals. Photoluminophors: Halophosphates, analogues of apatite (accounting for 90% of the world production), wallastonite, enstatite. Cathodolu-minophors: the main examples of which are ZnS, CdS (sphalerite, greenokite), ZnO (zincite), Zn2Si04-Mn (willemite), CaMgSi206-Ti (diopside); CaAlF>Mn (gearksutite), CaW04 (scheelite). X-ray luminophors: the main compounds are BaS04-Pb (barite), ZnS-CdS (sphalerite-greenokite), CaW04 (scheelite). Elec-troluminophors: almost all of which are made on the basis of ZnS, or ZnS CdS. Scintillators: the inorganic scintillators were synthesized on the basis of investigations of alkali-halide phosphors NaCl and KC1 activated by various impurities. These fundamental studies resulted in synthesizing the key scintillators Nal-Tl and Csl-Tl. Besides them, some other mineral bases are used: CaF: pure and CaF2-Eu, CaW04, PbW04 (stolzite), ZnS. (All of these are direct analogues of minerals.) TL dosimeters: the well-known dosimeters are CaS04-Mn. CaS04-Dy (anhydrite), CaF2-Mn (fluorite). Laser materials: the first solid material where laser generation was obtained was Al20,-Cr34 (ruby). Subsequently, laser effects were investigated in detail in CaF; doped with TR, U. Nowadays many mineral laser matrices are known and used: garnets, alexandrite, f'orsterite. diamond and some others. Synthetic organic luminophors: since organic compounds include enormous numbers of individual species, the correspondence is best seen between large classes of artificial and natural inanimate organic substances and not between the individual substances: bitums. oils, hydrocarbons and their numerous derivatives. Evidently, there are no artificial analogues of bioor-ganic substances anywhere in the observed Universe. Perhaps all the material discussed above shows that spectroscopists who work with minerals have the advantage of studying, in parallel, vast sets of objects with quite various composition and structure. As a result they sometimes manage to observe fine effects clarifying some fundamental processes in solids. Let us cite three examples.

\ (lOOnm) Fig. 4. Recombination luminescence spectra of the key rock-forming minerals: (1) calcite; (2) dolomite; (3) plagioclase; (4) microcline; (5) quartz. parts of the lithosphere, where strong processes of the interacting of rocks with abyssal fluids took place (Fig. 1). The fluids leached rare elements including the polyvalent transition metals out from country rocks and accumulated them. Two main factors are supposed to rule this process: basicity-acidity and redox potential of fluids soaking upwards through the rocks. Unlike rocks, fluids are very unsteady systems easy to alter their physico-chemical parameters while ascending from depth to the surface. The temperature and pressure of fluids decreased along with their basicity-acidity and redox potential. So, on the way from the mantle to the Earth's surface, the polyvalent luminogenous elements reached the peaks of their activity in the fluids roughly in the following sequence: N (which enters diamonds), Cr3+, Ce3+, Eu2+, Yb2+, Mn2+, Fe3+, Dy3+, W6+, Mo6+, U6+ and Ag+. Ascending through fractures and faults of the Earth's crust, fluids deposited rare elements in zones of lower temperature and pressure forming ore bodies of known types: kimberlites, carbonatites, nepheline sienites, pegmatites, skarns, greisens, hydrothermal veins and their derivatives. Probably all the fracture zones of the lithosphere passed through by fluids become fluorescent anomalies which can trace ore deposits. Just near the Earth's surface the environment is strongly acidic and oxidizing, due to nitrogen and oxygen of the atmosphere. Hence, fluorescent minerals composed of U6+, Ag+, Mo6+, V5+ and Cr6+ ions in the highest valencies appeared in the sedimentary layer. Also, carbonyl and carboxyl took an active part in forming PL centres in calcite, dolomite and rare carbonates cerrusite (PbC03) and hydrozincite (Zn5(C03)2(0H)6).

B. S. GOROBETS et al. (a)

(0
4 3 ^ ^ H -=: / \ Mn
z+

S<
exc^ (g)

/
\
T~

\
1.5-103

\A
A
T

/em.
T

/*\

I\
K'b
/ x "*

~ 4.103 /\ 7

Fe3+

/s H

exc.
i

/ <" / ^1 /em. * 1 1
[U02]2+

ko kj k2

^VT~300

/ knsko-n.Aks
5.5

\ (lOOnra) Fig. 5. Emission (em) and excitation (exc) spectra of photoluminescence of minerals with transition metal centres: (a) halite; (b) pollucite; (c), (f) apatite; (d) datolite; (e) strontianite (Gd, Ce) and scheelite (Pr, Nd, Sm, Eu, Tb, Dy); (g) eucryptite; (h) ramsayite; (i) halcedony. PL decay time z is given in 10"6 s.

Mn2+ minerals: rhodonite, rhodochrosite, triplite etc. (12 species) show dark red PL and RL uncommon to Mn2+. The excitation centre proved to be regular Mn 2+, unlike the emission centre with Mn2+ situated near some lattice defect. Energy transfer takes place between them. The PL decay time (~ 10'4s) depends on the distance between Mn2+-0-Mn2+ in different types of lattice that is usual for systems with energy transfer. However, in some Mn

minerals there is no energy transfer because the links in the lattice are Mn2+-0-0-Mn2+ (e.g. in carpholite giving yellow emission with large decay time ~ 10-3 s). The emitting Mn2+ centre is in an anomalous strong field (Z>q ~ 1000 cm"1, whereas its normal value is about 700 cm"1). Therefore, a great Stokes shift takes place and perhaps Mn2+ emission level changes from 4T,(G) to 4 T,(I). The latter falls off steeply in the diagram of Tanabe-Sugano. It could

LUMINESCENCE SPECTROSCOPY OF THE EARTH explain the dark red emission unusual for the impurity Mn2+ ion (Gorobets et ai, 1978). U6+ minerals show similar effects. In carbonates there is no energy transfer between UO2^. They, therefore, give bright blue-green PL at 298 K with maximal PL lifetime (T ~ 6 x 10" s), narrow spectral lines and a large vibration constant (Ak = 820-840 cm1). In sulphates, phosphates and arsenates, uranyls are bound more strongly and their PL is green with emission lifetimes, vibration constants and temperature of quenching a little lower. In silicates, vanadates, molybdates and hydroxides of uranyl strong exchange interaction and energy transfer takes place. In this case, PL lifetime falls to 1 x 10" s and Ak decreases to 750-680cm". Yellow, orange and even red (which is quite unexpected) PL of these minerals can be observed at low temperature (Sidorenko et ai, 1986). An example of a seemingly simple but actually difficult system to explain is the main tin mineral cassiterite Sn02. As a rule it gives yellow PL with UV lamp excitation at 77 K. The detailed investigation resulted in an unobvious hypothesis: Sn2+ centres luminesce in the Sn02 matrix (Gaft et ai, 1988). Thus, it is reasonable to anticipate that general luminescence spectroscopy could pick up some ideas and fine effects from the kingdom of minerals as well as adopt more useful luminophors.
AcknowledgementThe authors thank the Russian Foundation of Fundamental Research for financial support.

491

REFERENCES Bakhtin A. I. and Gorobets B. S. (1992) Optical Spectroscopy of Minerals and Rocks and its Application for Prospecting of Ores. Kazan University, Kazan, Russia (in Russian). Chappele E. W., Wood F. M., McMurtrey J. E. and Newcomb W. W. (1984) Laser-induced fluorescence of green plants. 1: a technique for the remote detection of

plant stress and species differentiation. Appl. Optics 23, 134-138. Gaft M. L., Gorobets B. S Marshukova N. K Pavlovski A. B., Rassulov V. A. and Rogozhin A. A. (1988) Detection of cassiterite ore in situ by means of laser-induced luminescence. Dokladi Akademii Nauk SSSR 299, 176-178 (in Russian). Gorobets B. S., Gaft M. L. and Laverova V. L. (1978) Fluorescence of manganese minerals. J. Appl. Spectr. 28, 750-752. Gorobets B. S. (1981) Spectra of Luminescence of Minerals. VIMS, Moscow (in Russian). Gorobets B. S. and Portnov A. M. (1992) Luminescent anomalies in the Earth crust used for remote-sensing searches of ores. Geology geophys. 2, 45-52 (in Russian). Gorobets B. S. and Novikov V. V. (1991) Luminescence sorting of ores. Priroda, 3, 44-49 (in Russian). Hiitt G. and Jaek I. (1989) Dating accuracy of laboratory reconstruction of palaeodose. Appl. Radial. Isot. 40, 1057-1063. Marfunin A. S. (1979) Spectroscopy, Luminescence and Radiation Centres in Minerals. Springer, Berlin. Sidorenko G. A., Gorobets B. S. and Dubinchuk V. T. (1986) Modern Methods of Mineralogical Analysis of Uranium Ores. Energoatomizdat, Moscow (in Russian). Stoneham D., Bailiff I., Hiitt G, Brodski L., Goksu Y., Haskell E. and Jungner H. (1993) TL accident dosimetry measurements on samples from the town of Pripyat. Nucl. Tracks Radial. Meas. 21, 195-200. Tarashchan A. N. (1978) Luminescence of Minerals. Naukova Dumka, Kiev (in Russian). Vassiliev N. A., Bessmertnyi A. K., Shmitko S. L., Volkov K. A. and Voievoda V. M. (1990) Experimental methodical studies of the possibilities of ore prospecting with the help of airborne lidar. Report of the Prospecting geological association 'Aero-geologia', Soyuzgeolfond, Moscow. Votyakov S. L., Krasnobaev A. A. and Krokhalev V. Ya. (1993) Problems of Applied Spectroscopy of Minerals. UIF Nauka, Ekaterinburg. Walker G. (1985) Mineralogical application of luminescence technique. In Chemical Bonding and Spectroscopy in Mineral Chemistry. Chapman and Hall, London. Waychunas G. A. (1988) Luminescence, X-ray emission and new spectroscopies. Rev. Mineralogy 18, 639-696. Wintle A. G. (1993) Recent development in optical dating of sediments. Radial. Prot. Dosim. 47, 627-635.

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