Multicoloured tourmalines from Elba Island, commonly display dark-coloured terminations due to incorporation of Fe, and also occasionally Mn. The mechanisms which led to the availability of these elements in the late-stage residual fluids are not yet completely understood. For this purpose, we investigated a representative tourmaline crystal found naturally in two fragments within a wide miarolitic cavity in the Rosina pegmatite (San Piero in Campo, Elba Island, Italy), and characterised by late-stage dark-coloured overgrowths. Microstructural and paragenetic observations, together with compositional and spectroscopic data (electron microprobe and optical absorption spectroscopy), provide evidence which shows that the formation of the dark-coloured Mn-rich overgrowths are the result of a pocket rupture. This event caused alteration of the cavity-coating spessartine garnet by highly-reactive late-stage cavity fluids by leaching processes, with the subsequent release of Mn to the residual fluids. We argue that the two fragments were originally a single crystal, which underwent natural breakage followed by the simultaneous growth of Mn-rich dark terminations at both breakage surfaces. This conclusion supports the evidence for a pocket rupture event, responsible for both the shattering of the tourmaline crystal and the compositional variation of the cavity-fluids related to the availability of Mn, which was incorporated by the tourmaline crystals. Additionally, a comparison of the dark overgrowths formed at the analogous and the antilogous poles, provides information on tourmaline crystallisation at the two different poles. The antilogous pole is characterised by a higher affinity for Ca, F and Ti, and a selective uptake of Mn2+, even in the presence of a considerable amount of Mn3+ in the system. This uneven uptake of Mn ions resulted in the yellow–orange colouration of the antilogous overgrowth (Mn2+ dependent) rather than the purple-reddish colour of the analogous overgrowths (Mn3+ dependent).

Microlite-group minerals occur as common replacement products after primary and secondary columbite-group minerals (CGM) in albitised blocky K-feldspar and in coarse-grained, muscovite-rich units of the Schinderhübel I, Scheibengraben and Bienergraben beryl–columbite pegmatites in the Maršíkov District (Silesian Unit, Bohemian Massif, Czech Republic). Textural and compositional variations of microlite-group minerals were examined using electron probe micro-analyses and microRaman spectroscopy (μRS). A complex post-magmatic evolution of the pegmatites and the following microlite populations (Mic) and related processes were found: (1) precipitation of U, Na-rich and F-poor Mic I on cracks in CGM; (2) alteration of Mic I to U-rich together with Na- and F-poor Mic II; and (3) partial replacement of Mic I and II by Mic III with a distinct Na, U and Ti loss and Ca and F gain. Stage (2) includes an extensive leaching of Na, without U loss. The final stage (3) produced euhedral-to-subhedral oscillatory zoned Ca and F enriched Mic III with distinctly different composition to the previous F-poor and A-site vacant Mic II. Aggregates of fersmite are associated commonly with Mic III. Distal Mic IIId occurs locally on cracks in K-feldspar or quartz, with compositions analogous to Mic III. Compositional variations and textural features of microlite-group minerals during dissolution–reprecipitation processes serve as sensitive tracers of post-magmatic evolution in granitic pegmatites recording complex interactions between magmatic pegmatite units and externally derived, hydrothermal metamorphic fluids.

In the Fregeneda area different pegmatitic types can be distinguished on the basis of their mineralogy, internal structure and field relationships. The most common type corresponds with simple pegmatites with a homogeneous internal structure, but Li and Sn-bearing pegmatites are also relatively widespread, besides a minority group of Fe-Mn phosphate-bearing pegmatites that has recently been characterized. These pegmatites are located in an intermediate zone, between the barren pegmatites and the most evolved Li and Sn-bearing bodies, and they carry a complex association of phosphate minerals. The study of these phosphates has allowed the identification of the primary phases as wyllieite, graftonite, sarcopside, triplite-zwieselite and ferrisicklerite; the secondary phosphates are rosemaryite, heterosite-purpurite, alluaudite and väyrynenite. In this study, the main characteristics of these phosphate minerals are reported, including their chemical composition, analysed by electron microprobe, and their unit-cell parameters, calculated using X-ray powder diffraction techniques.

A common transformation mechanism in this phosphate association is the oxidation of the transition metal cations at the same time as Na-leaching in wyllieite to generate rosemaryite, and Li-leaching in ferrisicklerite to generate heterosite. The occurrence of sarcopside lamellae in ferrisicklerite and heterosite is evidence of the replacement processes of the former by the latter. A Na-metasomatic replacement of the early phosphates as ferrisicklerite and graftonite, producing alluaudite, is also a well developed process.

Phosphate minerals occur in pegmatites with an intermediate degree of fractionation, appearing between the barren and the more evolved pegmatites with Li and Sn, which is in agreement with the pegmatite field zonation established in the literature.

Quartz from different zones within five granitic pegmatites of the rare-element class from the Borborema Pegmatite Province in northeast Brazil were analysed for fourteen trace elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The concentrations of Li (6—150 ppm), B (1—9 ppm) and Ge (1—23 ppm) in quartz show a positive correlation with Al (30—770 ppm). The concentrations of these elements increase from the border zone to the quartz core of pegmatites of the spodumene or lepidolite subtypes. The Ge concentrations in the quartz core are the highest so far reported in igneous quartz. In the less evolved pegmatites of the beryl-columbite subtype, the Al, Li, B, and Ge concentrations in quartz from all zones remain at the same level as the border and wall zones. The Ti concentrations in quartz from the core of the more evolved pegmatites are below 3 ppm (with Al >250 ppm), contrasting with 7—25 ppm (with Al <280 ppm) in samples from the border and wall zones of the less evolved and more evolved pegmatites. The concentrations of Al. Li, B, Ge, and Ti in quartz are therefore confirmed as good indicators of the degree of magma fractionation and analyses of pegmatite quartz cores can be used for exploration purposes to distinguish pegmatites with high metallogenic potential. Atoms of Li and Al are incorporated into quartz such that Li/Al ranges between 0.75 and 1.0. This suggests a coupled substitution of the form Si4+ ↔ (Li+ + Al3+). The other elements analysed either showed an erratic distribution (e.g. Be and P) or were below the respective limits of detection (Na, K, Rb, Ca, Sr, Mn, Fe) in most samples.

Pegmatites of the Fregeneda area, Salamanca, Spain, show a zonal distribution, from barren to enrichment in Li, Sn, Rb, Nb>Ta, B and P. They intrude pre-Ordovician metasediments which were metamorphosed to sillimanite-zone conditions near the Lumbrales granite. Field, mineralogical and petrographic data show the following zonal sequence from the granite outward: (1) barren pegmatites (pegmatites T1, T2, T3 and T4) with quartz, K-feldspar > albite, muscovite, tourmaline ± andalusite ± garnet; (2) intermediate pegmatites (types T5 and T6), characterized by the occurrence of beryl and Fe-Mn-Li phosphates; and (3) fertile pegmatites (dykes T7 and T8), with lepidolite, cassiterite, columbite, albite > K-feldspar, montebrasite and spodumene.

Tourmaline from different pegmatites shows significant compositional variations. Trace element variations in mica and K-feldspar suggest that the origin of the different pegmatitic bodies may be explained by three different paths of fractional crystallization of melts generated by partial melting of quartzo-feldspathic rocks.

Micas of the muscovite–lepidolite series are main constituents of the evolved pegmatites from the Okatjimukuju-Kaliombo portion of the Karibib belt, Namibia. The compositional variations shown by the micas from the intermediate zones are mainly controlled by the Li3Al-1□-2 and SiLi2Al-2□-1 substitution schemes, whereas for the micas from the core margins and the replacement bodies, only the first of these two exchange vectors seems to operate. The chemical composition of the micas not only depends on the degree of pegmatite evolution, but also on the position in the internal zonation of the pegmatite. Micas from the core margins and the replacement units are generally richer in F, Li, Rb, Cs and Zn than those from the intermediate zones. In general, the contents of these elements increase with decreasing K/Rb ratio. However, some data departing from this general trend are also observed, which could be related to subsolidus processes. Some pegmatite bodies show a complete internal evolution, developed from the margins to the core zone, which is reflected in the chemical composition of the micas. The regional distribution of pegmatites does not define a zonation, because an overlapping of pegmatites with different degrees of evolution occurs. This could be due to the high level of evolution attained by most of the rare-element pegmatites, and to their topography with respect to a dome structure of the basement.

The crystal chemistry of tapiolite is more complicated than previously recognized. Perusal and synthesis of relatively recent publications reveals a ‘hidden’ story about tapiolite, one that: (1) permits quantification of the effects of Mn, Fe3+, Ti (and Sn) upon the unit-cell parameters of maximally ordered tapiolite; (2) shows that the effect of Nb = Ta substitution upon unit-cell parameters is insignificant; (3) casts doubt on the usefulness of heating experiments for accurately evaluating cation order in tapiolite; (4) suggests that rutile exsolves from tapiolite upon heating in air at lower temperatures than previously established; (5) shows that the maximum solubility of TiO2 in FeTa2O6 tapiolite during the later stages of crystallization of granitic pegmatites is ∼1 mol.%; (6) shows that the heating paths for at least some natural tapiolite samples are not necessarily linear, consisting of two sequential steps; (7) sheds doubt on the usefulness of unit-cell parameters as quantitative measures of long-range cation order, Q, in tapiolite; but (8) does show that the intensity ratio I011/I110 can provide an accurate and reasonably precise measure of cation order in tapiolite.

The primary focus of this review is on P-T conditions, mineralogical indicators of melt or fluid composition and textural evolution; lesser treatment is given to pegmatite sources or to pegmatite-wallrock interactions. Investigations of stable and radiogenic isotopes have revealed that the source materials for pegmatites are likely to be more heterogeneous or varied than previously thought, especially for peraluminous pegmatites, but that overall pegmatites bear a clear intrusive relationship with their hosts, as opposed to an origin in situ. The P-T conditions of crystallisation of some lithium-rich pegmatites have been constrained by lithium aluminosilicate stability relations in combination with stable isotope or fluid inclusion methods. Experimental studies have elucidated the effects of components such as Li, B, P and F, which are common in some classes of pegmatites, to liquidus relations in the hydrous haplogranite system. Experimentation has also provided corroboration of an old concept of pegmatite crystallisation—that pegmatites owe their distinctive textures and mineral/chemical zonation to relatively rapid crystallisation of melt from the margins inwards at conditions far from the equilibrium (i.e. from supercooled liquids). The origin of aplites, whether alone, layered, or paired with pegmatites, remains an active area of research. Studies of fluid inclusions, crystal-vapour equilibria and wallrock alteration have helped to define the timing and compositions of vapour phases in pegmatites and to aid in the economic evaluation of deposits.