Gem Elbaite as a Recorder of Pegmatite Evolution: In Situ Major, Trace Elements and Boron Isotope Analysis of a Colour-Zoning Tourmaline Crystal

Few studies have focused on gem-quality tourmaline acting as a petrogenetic recorder, and the colour genesis of pink elbaite is still controversial. We carry out in situ major, trace element and boron isotope composition analyses on a single tourmaline crystal. This crystal is characterized by sudden transformation from colourless to pink, which can represent full pegmatite magma evolution. According to the analysis results, all spots are divided into alkali groups according to X-site occupancy and subdivided into elbaite series. The pink part accommodates higher concentrations of volatile and incompatible elements. The result is most consistent with successive pegmatite evolution in which the colourless part crystallized from the early stage, while the pink part crystallized from the late stage. The relatively consistent δ11B value between the colourless and the pink part suggests no fluid exsolution occurred during pegmatite evolution. The slight increase of δ11B values within the pink part and the colourless part may be due to mica crystallization. The combination of (Li++Mn2+) (Al3++Xvac)-1 and the exclusive positive linear relationship of Mn2+ vs. Ti4+ indicate that Mn2+ is the main cause of pink, while Mn2+-Ti4+ intervalence charge transfer also plays an important role.

Boron isotope evidence for devolatilized and rehydrated recycled materials in the Icelandic mantle source

Enriched mantle heterogeneities are widely considered to be generated through subduction, but the connections between specific subducted materials and the chemical signatures of mantle heterogeneities are not clearly defined. Boron is strongly isotopically fractionated at the surface and traces slab devolatilization, making it a potent tracer of previously subducted and recycled materials. Here, we present high-precision SIMS boron concentrations and isotope ratios on a comprehensive suite of quenched basaltic glasses from all neovolcanic zones in Iceland, two rhyolite glasses, and a set of primitive melt inclusions from central Iceland. Boron isotope ratios (δ11B) in Icelandic basalts and melt inclusions range from -11.6‰ to -1.0‰, averaging -4.9‰, which is higher than mid-ocean ridge basalt (MORB; δ11B = -7.1‰). Because the δ11B value of the Icelandic crust is low, the high δ11B compositions of the Icelandic lavas are not easily explained through crustal assimilation processes. Icelandic basalt glass and melt inclusion B/Ce and δ11B values correlate with trace element ratio indicators of the degree of mantle partial melting and mantle heterogeneity (e.g. Nb/Zr, La/Yb, Sm/Yb), which indicate that the boron systematics of basalts are controlled by mantle heterogeneity. Additionally, basalts with low B/Ce have high 206Pb/204Pb, further indicating mantle source control. These correlations can be used to deduce the boron systematics of the individual Icelandic mantle components. The enriched endmember within the Iceland mantle source has a high δ11B value and low B/Ce, consistent with the composition of “rehydrated” recycled oceanic crust. The depleted endmember comprises multiple distinct components with variable B/Ce, likely consisting of depleted MORB mantle and/or high 3He/4He mantle and two more minor depleted components that are consistent with recycled metasomatized mantle wedge and recycled slab gabbro.The compositions of these components place constraints on the devolatilization history of recycled oceanic crust. The high δ11B value and low B/Ce composition of the enriched component within the Iceland mantle source is inconsistent with a simple devolatilization process and suggests that the recycled oceanic crust component may have been isotopically overprinted by B-rich fluids derived from the underlying hydrated slab lithospheric mantle (i.e. “rehydration”). Further, the B/Ce and δ11B systematics of other OIBs can be used to constrain the devolatilization histories of recycled components on a global scale. Globally, most OIB B/Ce compositions suggest that recycled components have lost >99% of their boron, and their δ11B values suggest that rehydration may be a sporadic process, and not ubiquitous.

Magmatic-Hydrothermal Mineralization Processes at the Yidong Tin Deposit, South China: Insights from In Situ Chemical and Boron Isotope Changes of Tourmaline

Owing to the superimposition of water-rock interaction and external fluids, magmatic source signatures of ore-forming fluids for vein-type tin deposits are commonly overprinted. Hence, there is uncertainty regarding the involvement of magmatic fluids in mineralization processes within these deposits. Tourmaline is a common gangue mineral in Sn deposits and can crystallize from both the magmas and the hydrothermal fluids. We have therefore undertaken an in situ major, trace element, and B isotope study of tourmaline from the Yidong Sn deposit in South China to study the transition from late magmatic to hydrothermal mineralization. Six tourmaline types were identified: (1) early tourmaline (Tur-OE) and (2) late tourmaline (Tur-OL) in tourmaline-quartz orbicules from the Pingying granite, (3) early tourmaline (Tur-DE) and (4) late tourmaline (Tur-DL) in tourmaline-quartz dikelets in the granite, and (5 and 6) core (Tur-OC) and rim (Tur-OR), respectively of hydrothermal tourmaline from the Sn ores. Most of the tourmaline types belong to the alkali group and the schorl-dravite solid-solution series, but the different generations of magmatic and hydrothermal tourmaline are geochemically distinct. Key differences include the hundredfold enrichment of Sn in hydrothermal tourmaline compared to magmatic tourmaline, which indicates that hydrothermal fluids exsolving from the magma were highly enriched in Sn. Tourmaline from the Sn ores is enriched in Fe3+ compared to the hydrothermal tourmaline from the granite and displays trends of decreasing Al and increasing Fe content from core to rim, relating to the exchange vector Fe3+Al–1. This reflects oxidation of fluids during the interaction between hydrothermal fluids and the mafic-ultramafic wall rocks, which led to precipitation of cassiterite. The hydrothermal tourmaline has slightly higher δ11B values than the magmatic tourmaline (which reflects the metasedimentary source for the granite), but overall, the tourmaline from the ores has δ11B values similar to those from the granite, implying a magmatic origin for the ore-forming fluids. We identify five stages in the magmatic-hydrothermal evolution of the system that led to formation of the Sn ores in the Yidong deposit based on chemical and boron isotope changes of tourmaline: (1) emplacement of a B-rich, S-type granitic magma, (2) separation of an immiscible B-rich melt, (3) exsolution of an Sn-rich, reduced hydrothermal fluid, (4) migration of fluid into the country rocks, and (5) acid-consuming reactions with the surrounding mafic-ultramafic rocks and oxidation of the fluid, leading to cassiterite precipitation.