Cecilia Pérez-Soba

Microbial weathering of Fe-rich phyllosilicates and formation of pyrite in the dolomite precipitating environment of a Miocene lacustrine system

Sedimentary sequences composed of selenite gypsum, mudstone, and dolomite microbialites cropping out in the eastern part of the Madrid Basin were deposited in a mudflat – saline-lake system during the Miocene. In some dolomite beds enriched in detrital grains, dolomite crystals occur intergrown with framboidal pyrite clusters that in many cases are arranged along the associated phyllosilicate cleavages, which accounts for the mineral disaggregation, and eventually for the mineral replacement. High-resolution FE-SEM investigations across the interface between the pyrite and the phyllosilicate show that a single phyllosilicate is replaced by iron sulphides in different microsites, with retention of some aspects of the parent structure. Pyrite formed in the sediment as texturally complex framboids, coexisting with amorphous to poorly crystalline iron-rich sulphide phases, and include carbonaceous filaments with biogenic isotopic signatures (δ13C = −22.95‰). Microprobe analytical data indicate the weathered phyllosilicates to be significantly depleted in Fe relative to Si and Al. The selective release of Fe has not involved the mineral transformation to secondary phyllosilicates, which suggests a preferential microbial colonization of the Fe-bearing minerals rather than a thermodynamically driven degradation of those minerals. Depleted δ34S values in pyrite further suggest that sulphate microbial reduction to sulphide was active within the sediment during the alteration of the silicates. This paper gives new insight into the microbial weathering of phyllosilicates and the subsequent formation of pyrite through a sequence of intermediate products enriched in iron. These processes were coeval with the microbially-mediated precipitation of dolomite, which further reinforces the role of the microbes in the formation of the sulphides.

Metaluminous pyroxene-bearing granulite xenoliths from the lower continental crust in central Spain: their role in the genesis of Hercynian I-type granites

Basic and intermediate meta-igneous xenoliths are very scarce within the granulite population transported by the Permian alkaline lamprophyric dyke swarmof the Spanish Central System(SCS). These xenoliths aremetaluminous pyroxene-bearing charnockites (sensu lato). They show LREE-poor plagioclase and orthopyroxene-clinopyroxene. Crystallization conditions were estimated at about 850 to 1000 ◦C and 9 to 11 kbar, a slightly higher range than that estimated for the associated peraluminous granulites, but indicating derivation from the lowermost crust. Whole-rock geochemistry suggests that the charnockite samples are not a cogenetic suite. The more basic varieties have affinities with cumulates from previous calc-alkaline underplated protoliths, whereas intermediate charnockites have a restitic origin. The similarity in Sr-Nd-Pb isotopic signatures between these restitic charnockites and some SCS I-type granites suggests a genetic relationship. This study, including Pb isotopic data from the whole granulite xenolith suite, reinforces the lower-crustal derivation of the SCS Hercynian granitic batholith.

Magmatic graphite inclusions in Mn-Fe-rich fluorapatite of perphosphorus granites (the Belvís pluton, Variscan Iberian Belt)

Abstract Three Mn-Fe-rich fluorapatite types have been found in the highly evolved peraluminous and perphosphorous granites of the Belvís pluton. One of these apatite types includes abundant graphite microinclusions, suggestive of a magmatic origin for the graphite. The Belvís pluton is a reversely zoned massif composed by four highly fractionated granite units, showing a varied accessory phosphate phases: U-rich monazite, U-rich xenotime, U-rich fluorapatite, and late eosphorite-childrenite. The strong peraluminous character of the granites determines an earlier monazite and xenotime crystallization, so the three types of fluorapatite record late stages of phosphate crystallization. The earlier type 1 apatite is mostly euhedral, small and clear; type 2 apatite is dusty, large (<2800 μm) and mostly anhedral, with strong interlobates interfaces with the main granite minerals, more abundant in the less fractionated units and absent in the most evolved unit; type 3 is subeuhedral to anhedral, shows feathery aggregate texture, and only appears in the most evolved unit. Apatite composition was acquired by electron microprobe analyses, laser ablation inductively coupled plasma-mass spectrometry and electron energy loss spectroscopy. Type 1 and type 2 apatite display similar broad compositional ranges showing high MnO (up to 4.30 wt%) and FeO (up to 2.88 wt%) contents, without traces of carbon in apatite structure. Type 2 differs from type 1 by having slightly higher LREE and Sr contents. REE spectra also differ, with type 1 displaying both variable LREE slope and negative Eu anomaly, whereas type 2 shows constant LREE slope and higher negative Eu anomaly, although both display similar HREE slope. Type 3 apatite displays higher FeO contents (up to 5.09 wt%), positively correlated with higher Cl-Na-Li-Be-B-Zn contents and extremely low Y-REE contents when compared to the other apatite types. Cation substitution indicates that part of the Fe content is as Fe3+. Graphite has been found exclusively as abundant microinclusions in type 2 apatite, parallel or randomly distributed, and heterogeneously grouped in clusters within the crystals. High-resolution electronic images show that graphite occurs with unusual habits: filaments of stacked hexagonal flakes up to 15 μm length and up to 0.5 μm width. Textural and chemical features suggest a highly crystallized melt, which favor compartmentalizing in compositional microdomains where the apatite types would have crystallized. The cocrystallization of type 2 apatite and graphite suggests a C-F-P-rich melt, sufficiently saturated to acquire an immiscible character with the highly evolved silicate melt in late-magmatic stages. As type 2 differs from type 1 apatite by higher LREE and Sr contents, we interpret that fluxing components were favorably concentrated in those residual less-depleted LREE-Sr fraction melts, once monazite and zircon (and xenotime) would have crystallized. Type 3 apatite records a change in the ultimate melt stage: an increase of the oxygen fugacity coupled with high undercooling by volatile lost of highly fractionated residual Cl-richer melts. The presence of biogenic carbon in granite peraluminous melts derived from metasedimentary sources and its later crystallization as graphite filaments opens a discussion on the carbon behavior during magma evolution, especially in highly polymerized melt framework.