2. Materials and Methods
A set of fifty representative samples were collected in the areas shown in
Figure 2,
Figure 3 and
Figure 6. Thirty of these samples, labeled CHP-1–15 (Chapesvara-I) and CHP-16–30 (Chapesvara-II), were studied in detail mineralogically and geochemically. The Chapesvara-II samples were taken along the traverse
a–b (
Figure 6) and across the following units (bottom to top; this study): amphibole-olivine zone (IV), central dunite zone (II), olivine-bearing orthopyroxenite zone (III), and the upper contact facies (I) (
Figure 7). These lithologies represent a comagmatic series that likely formed in the order from I to IV under closed-system conditions during crystallization of the komatiitic magma. A representative example of the outcrops sampled is shown in
Figure 8.
All the analyses were conducted at the Analytical Center for Multi-Elemental and Isotope Studies, Institute of Geology and Mineralogy, SB RAS, in Novosibirsk, Russia. The minerals were analyzed using a JEOL JXA-8100 instrument in wavelength-dispersion spectrometry mode (WDS). An accelerating voltage of 20 kV and a probe current of 20–50 nA were used. We employed
Kα analytical lines for all elements except for Cr, where the
Kβ1 line was used because of peak overlap. Periods of measurements at the peaks were 20 or 10 s. The superposition of the Ti
Kβ1 line on the V
Kα line and of the V
Kβ line on the Cr
Kα line was accommodated using the
overlap correction software. The beam diameter was ~1 μm. Natural specimens of olivine (Mg, Si, Fe and Ni) and chromiferous or manganiferous garnet (Ca, Cr and Mn) were used as standards for olivine. A natural specimen of magnesian chromite (for Cr, Fe, Mg, and Al), manganiferous garnet (Mn), ilmenite (Ti), and synthetic oxides NiFe
2O
4 (Ni), ZnFe
2O
4 (Zn), and V
2O
5 (V) were used as standards for the chromian spinel. Grains of orthopyroxene and amphiboles were analyzed using pyrope (Si, Al, Fe), a glass Ti standard (GL-6), chromiferous garnet (Cr), diopside and pyrope (Mg, Ca), manganiferous garnet (Mn), albite (Na), and orthoclase (K). Clinopyroxene was analyzed with essentially the same set of standards, and diopside was used for Si, Ca, and Mg. The following standards were applied in the analysis of plagioclase: orthoclase (Si, Al, K), diopside (Ca), pyrope (Fe), and albite (Na). All the data were processed with the ZAF method of corrections. The calculated values of detection limit (for 1σ criteria) are: ≤0.01 wt. % for Ti, Cr, Fe, Ni, Ca, Zn, Mn, and K, and 0.02 wt. % (Na and Al). Special tests [
16,
17] were done to evaluate the accuracy and reproducibility of the analytical procedures.
The whole-rock abundances of trace elements, including the rare-earth elements (REE), were established at the same center by inductively coupled plasma–mass spectrometry (ICP–MS) using a high-resolution Finnigan MAT mass spectrometer (the model ELEMENT; Finnigan MAT, San Jose, CA, USA). The analytical procedures used were described in [
18,
19]. Contents of major oxides in the rocks were established at the same center by X-ray fluorescence (XRF) using procedures [
20] based on the use of an ARL 9900XP spectrometer Thermo Fisher Scientific, Waltham, MA, USA) equipped with a Lifumat 2.0-Ox high-frequency induction furnace (Linn High Therm GmbH, Eschenfelden, Germany) and a HERZOG hydraulic HTP 40 pellet press (HERZOG Maschinenfabrik GmbH & Co. KG, Osnabrück, Germany). A special set of state-approved standards was used to evaluate the precision of the XRF analyses.
4. Discussion
The successions of dunite–harzburgite–olivine-bearing orthopyroxenite in the Chapesvara-I and Chapesvara-II subvolcanic intrusive complexes are notably magnesian. The mean Mg# values are 86.6 (Chapesvara-I) and 86.5 (Chapesvara-II). A UCF rock (upper contact facies) displays a slightly lower value, 81.6. This unit occurs near the upper contact, presumably part of a chilled margin, and was likely produced by the rapid crystallization of the intruding melt in its almost unfractionated state. The whole-rock Al
2O
3/TiO
2 values are 23.9 (Chapesvara-I) and 21.0 (Chapesvara-II), giving a mean of 22.45, close to 22.9 (UCF), all very close to the primitive mantle value of ~22 [
26]. The depleted mantle has a notably higher Al
2O
3/TiO
2 value of ~32 [
27], consistent with the greater compatibility of Al with respect to Ti.
We thus believe that primitive ultramafic magma rose from a deep level in the Chapesvara area of the Serpentinite Belt as a consequence of an unusual tectonic setting. Indeed, the Chapesvara sill-like bodies are located within a major shear zone accompanied by an abundant collisional mélange, part of the Tanaelv high-grade ductile thrust belt. This belt is closely associated with the Lapland Granulite Terrane, LGT (or Lapland Granulite Belt), forming part of the Paleoproterozoic Lapland–Kola Collisional Orogen (LKCO). The Chapesvara intrusive bodies are thus positioned at the boundary of the two large terranes of the Baltic Shield: the Paleoproterozoic LGT and the Belomorian Composite Terrane (BCT) of the Archean age. Deep channels controlling the migration of ultramafic magma thus appeared because of the presence of major faults marking this juxtaposition. Note that the LKCO structure is an essential component of Paleoproterozoic orogenies affecting the entire North Atlantic region and resulting in the formation of a considerable portion of the Nuna supercontinent; the Baltic (Fennoscandian) Shield is considered to be one of surviving fragments of the Nuna supercontinent [
28].
On the basis of geochemical characteristics and their highly magnesian nature, the Chapesvara rocks resemble some picrites [
29,
30]. In spite of the absence of spinifex textures, they closely resemble some examples of the most highly magnesian komatiites, such as those of the Barberton Belt in South Africa, for which magmas with up to 34.8% MgO (and 30.9% MgO in a chilled margin sample) were postulated on the basis of whole-rock chemistry and olivine compositions ([
31,
32,
33,
34,
35,
36,
37,
38,
39], and references therein). The chilled margin sample of the Alexo komatiite flow in Ontario, Canada contains 28% MgO [
32], and ~26% MgO is found in a komatiitic sequence at Inyala in Zimbabwe [
39]. In addition, a Hawaiian picrite at Mauna Loa was reported with olivine having a Mg# up to ~92, corresponding to a calculated value 21.2% MgO in a parental melt [
30]. The level of ~28% MgO is considered to be realistic for the parental magma of the Munro komatiites in the Abitibi Greenstone Belt, Ontario, Canada. The Munro-type komatiites are Al-undepleted, also having close to a primitive-mantle Al
2O
3/TiO
2 ratio of about 22 [
31]. Note that Al-depleted komatiites are considered to have been produced in unusually hot mantle plumes by extremely deep (~400 km), high-degree and equilibrium melting at a depth where garnet was a stable residual phase. In contrast, Al-undepleted and Al-enriched komatiites are produced in mantle plumes as a result of shallower melting associated with a garnet-free residue ([
37] and references therein).
According to calculations [
37], the estimated parental magma of the Al-undepleted komatiite at Komati contains ~30 wt. % MgO and ~12 wt. % FeO, leading to the initial crystallization of Fo
94. The analyzed UCF sample at Chapesvara-II gave 37.04% MgO, 14.88% FeO
total (or 16.54% Fe
2O
3 total), and the olivine phase is Fo
92. This sample (CHP-30) yields a very low value of the molar MgO/SiO
2 ratio, close to that of dunitic rocks located at the center (
Figure 16f,
Table 9). Thus, this sample is unlikely to have been subjected to any extent of magmatic contamination by the host rock. Besides, this sample seems to be undifferentiated. Indeed, it is the most primitive of the suite, as indicated by the lowest value of (Gd/Yb)
N, 0.52, and the lowest abundances of middle to heavy REE in the chondrite-normalized spectrum (
Figure 20). Thus, we contend that this sample reflects fairly well the basic characteristics of a primary melt. The Cr content of sample CHP-30 is anomalously high (10.03 wt. % Cr
2O
3;
Table 9). This enrichment is related to the occurrence of a contact-style mineralization in disseminated chromite.
We thus infer that the UCF rock, which contains the most magnesian olivine (Fo
92), was the first to crystallize close to the upper contact. Similarly, Arndt [
32] documented the occurrence of most magnesian composition of olivine (Fo
94) in the upper chilled margin of the Alexo komatiite flow in Ontario, Canada. After the UCF zone, the inferred area of further crystallization shifted to a central portion of the Chapesvara-II body, where the olivine phase, Fo
89.5, crystallized as the second most magnesian composition (
Figure 12a). The documented trend of chromian spinel variations is consistent with the inference that crystallization continued at the center (
Figure 12d). The zone of high-MgO dunitic rocks (
Figure 7 and
Figure 16c) crystallized in situ in the central portion at this stage of crystallization.
As noted, at low stratigraphic levels, orthopyroxene was entirely transformed to a tremolite-dominant assemblage as a result of an increase in H
2O in the system; i.e., in the late-crystallized portions. In addition, the extent of deuteric alteration and the development of hydrous silicates increase toward the bottom. The inferred crystallization of a primary amphibole at a late magmatic stage presumably reflects the buildup in levels of H
2O in the magma. Synthetic tremolite is in its field of stability at 840 °C and 6 kbar [
24], whereas the association enstatite + quartz is converted to anthophyllite in the presence of H
2O over a range of 670–800 °C at 2 kbar [
25]. These conditions are consistent with deposition of the calcic amphibole from a hydrous fluid.
Two trends of evolution are recognized at Chapesvara-II. The first trend displays a relative maximum or minimum close to the center, which then splits into two linear subtrends. These are divergent and directed upward or downward. This pattern is manifested in the variations documented of Mg# in olivine and chromian spinel, the whole-rock contents of Al and Ca, and in levels of incompatible elements: Ti, V, Zr, Y, and Hf (
Figure 12a,d,
Figure 15d,e,
Figure 16d,
Figure 17a,
Figure 18b,d,e). The second type of element distribution is represented by a single line and shows a decrease or increase from top to bottom; such a pattern applies to the variations in incorporation of Ni in olivine, the Fe
3+# index in chromian spinel, and in values of Mg# in bulk-rock compositions. In addition, the total amounts of REE, Nb, and Th, which gradually increase downward, are related to the type-2 trend (
Figure 12b,f,
Figure 15b, and
Figure 18a,c,f).
The contrasting development and possible interference of the two types of evolutionary trends reveal a complex history of crystallization in the Chapesvara-II body. It began with the formation of the UCF zone and continued with the crystallization and accumulation of olivine in the dunite zone close to the center. There were two fronts of crystallization, one moving upward and one progressing downward. The upward subtrend appears to be of subordinate importance, as relevant ranges of values are at least two times smaller than those displayed by the downward subtrend (
Figure 12a,d,
Figure 15d,e,
Figure 16d,
Figure 17a,
Figure 18b,d,e). Along the downward trend, the extent of progressive fractional crystallization was much greater (
Figure 12b,f,
Figure 15b,
Figure 18a,c,f). These observations indicate that the general crystallization of the Chapesvara-II sill-like body proceeded from the top to the bottom in response to the preferential heat loss through the roof. At the same time, the lithological units observed in the comagmatic series likely formed in the order from I to IV (
Figure 7) under closed-system conditions during crystallization of the komatiitic magma.
The oxidation state of iron in spinel-type phases is a well-established monitor of magmatic oxygen fugacity [
40,
41]. Our results based on compositions of chromian spinel (
Figure 12f) imply that the general level of
fO
2 likely increased downward with progressive crystallization of the Chapesvara-II body. In addition, a relative increase in
fO
2 at the UCF level, associated with the deposition of accessory chromite, points to the intruding melt itself as the likely agent of oxidation. The inferred trend of increasing
fO
2 downward (
Figure 12f) and close to the chilled margin was likely caused by a relative enrichment in oxygen content of the evolving magma due to the escape of hydrogen once bubbles of H
2O appeared [
42].
As noted, tremolite-dominant assemblages formed at the expense of Ca-poor pyroxene in the late-crystallized portions at Chapesvara-II. This feature implies the influx of Ca via a late hydrous fluid at a stage of deuteric alteration. What we found, thus, differs from a normal process of “uralitization” [
43,
44], which represents an autometasomatic alteration of primary clinopyroxene to form “uralite” (i.e., Ca-amphiboles of the actinolite–tremolite series). The same phenomenon is evident in the Pados-Tundra intrusion, where orthopyroxene oikocrysts are entirely replaced by a deuteric assemblage of talc + tremolite [
21]. The relative Ca-enrichment, thus, occurred under closed-system conditions at Chapesvara, in contrast to other systems (e.g., [
45]).
A puzzling aspect of the Chapesvara–II zoned sill is the presence of the Central Dunite Zone (
Figure 7,
Figure 15a, and
Figure 16c). This zone contrasts with the olivine-enriched cumulates in the more voluminous Pados-Tundra complex [
6] and other layered intrusions, which are located at a lower structural level [
46,
47]. The buildup of olivine in the core of concentrically zoned complexes of alkaline ultramafic rocks like Kondyor [
48] seems unrelated in view of the important petrogenetic differences. A zonal arrangement of the same type as that at Chapesvara-II seems present in a large ultramafic complex (possibly up to ~15 km
2 in size) investigated previously in the upper reaches of the River Terma in the Serpentinite Belt. As noted [
49], there is a reported dominance in central portions of dunite, grading to peridotite (harzburgite) towards the periphery in this body.
We presume that three events (
Figure 21a,b) could be crucial in the crystallization history of the Chapesvara-II sill: (I) the formation of a complementary system of convection subcells around a zone of very hot melt present in the center of magmatic reservoir during cooling; (II) an intensive accumulation of crystallizing olivine crystals in the area between the functioning subcell-I and subcell-II; and (III) the double-front crystallization of the bulk volume of remaining melt. The inferred subcells generated around the zone of thermal maximum (
Figure 21a) are elliptical and subvertically elongate in the cross-section, as expected in case of sheet-like or similar geometries (cf. [
50]). In addition, komatiite flows are expected to convect vigorously during cooling [
32]. In our case, these subcells of convection may have played a twofold role: (1) to transport and accumulate the olivine crystals suspended and clumped together close to the center to form the central dunite zone, and (2) to cause the split of the magmatic reservoir into two subsystems in the upper and bottom half of the sill, which evolved more or less independently, thus showing the contrasting fronts and fractionation trends. The phase Fo
89.5 presumably crystallized close to the thermal maximum area in the center, and the opposite trends of cryptic variations involve progressively less forsteritic olivine (
Figure 12a).
The conditions of crystallization could differ in important ways in other portions of the chamber, in which olivine-rich cumulate likely formed as a result of olivine settling to the bottom. Thus, there might be areas showing the development of rhythmic cycles of dunite–(harzburgite)-olivine-bearing orthopyroxenite, as was reported by the previous investigators (
Figure 5) [
11]. On the other hand, our observations may stimulate a re-examination of the presently known structure of the Chapesvara complex.
5. Conclusions
(1) The Chapesvara-I and Chapesvara-II bodies are comagmatic. They belong to one and the same ultramafic subvolcanic complex, which forms part of the Serpentinite Belt in the Kola Peninsula.
(2) The Chapesvara complex is a well-documented example of a highly magnesian Al-undepleted komatiite related to a primitive mantle source, which is associated with northeastern-striking shear zones related with the Tanaelv high-grade ductile thrust belt in the northeastern Fennoscandian Shield.
(3) The Chapesvara complex crystallized from a primitive komatiitic melt that displays an unusual combination of a highly magnesian and Cr-enriched composition with a relative enrichment in Fe, as follows from our observations made on the rock of the upper contact facies at Chapesvara-II. The latter rock is the most primitive in the series, as it contains the most forsteritic olivine (Fo92), has the lowest value of (Gd/Yb)N, 0.52, and the lowest abundances of middle to heavy REE in the chondrite-normalized spectrum. It likely is representative of the basic characteristics of primary melt inferred not only for Chapesvara, but also for the Pados-Tundra layered complex and other subvolcanic suites of the Serpentinite Belt.
(4) We documented a double-front type of crystallization for the first time in a subvolcanic ultramafic complex.
(5) The Chapesvara-II body displays a progressive build-up in fO2 during crystallization. The parental komatiitic melt itself was likely the source of oxidation. We attribute the enrichment in intrinsic oxygen fugacity of the evolving magma to the escape of hydrogen upon degassing in a subvolcanic setting upon vesiculation and dissociation of H2O.
(6) The characteristics of the Chapesvara-II sill-like body are indicative of vigorous convection of the komatiitic magma with the inferred existence of a complementary system of convection subcells functioning around a zone of very hot melt (present in the center of magmatic reservoir). These circumstances were important (a) to cause the split of the magmatic reservoir into two subsystems, evolving independently, and (b) to transport and accumulate the olivine crystals suspended and clumped together close to the center to form dunitic cumulate of the central dunite zone.