Search

Secondary fluorescence (SF) is known to be a potential source of error in electron probe microanalysis (EPMA) when analyzing for a trace or minor element near a phase boundary. This often overlooked effect leads to a concentration enhancement whenever the neighboring phase contains a high concentration of the analyzed element. Here we show that SF may also lead to a concentration decrease, which can be mistakenly interpreted as a depletion. To examine this issue, we compare Ni profiles measured on well-characterized, homogeneous olivine [(Mg,Fe)2SiO4] grains embedded in basaltic glass, with semi-analytical calculations and numerical simulations of SF across phase boundaries. We find that the Ni content consistently decreases with decreasing distance to the interface or grain radius, deviating from the expected concentration by ∼2-5% at 10 μm from the interface. This decrease is explained by the lower bremsstrahlung fluorescence emitted from the sample as compared to that emitted from the standard. The analytical error due to boundary fluorescence affecting other elements of petrologic importance in olivine is discussed., Competing Interests: Conflict of Interest The authors declare that they have no competing interest., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Microscopy Society of America.)

Water strongly influences the physical properties of the mantle and enhances its ability to melt or convect. Its presence can also be used to trace recycling of surface reservoirs down to the deep mantle 1 , which makes knowledge of the water content in the Earth's interior and its evolution crucial for understanding global geodynamics. Komatiites (MgO-rich ultramafic magmas) result from a high degree of mantle melting at high pressures 2 and thus are excellent probes of the chemical composition and water contents of the deep mantle. An excess of water over elements that show similar geochemical behaviour during mantle melting (for example, cerium) was recently found in melt inclusions in the most magnesium-rich olivine in 2.7-billion-year-old komatiites from Canada 3 and Zimbabwe 4 . These data were taken as evidence for a deep hydrated mantle reservoir, probably the transition zone, in the Neoarchaean era (2.8 to 2.5 billion years ago). Here we confirm the mantle source of this water by measuring deuterium-to-hydrogen ratios in these melt inclusions and present similar data for 3.3-billion-year-old komatiites from the Barberton greenstone belt. From the hydrogen isotope ratios, we show that the mantle sources of these melts contained excess water, which implies that a deep hydrous mantle reservoir has been present in the Earth's interior since at least the Palaeoarchaean era (3.6 to 3.2 billion years ago). The reconstructed initial hydrogen isotope composition of komatiites is more depleted in deuterium than surface reservoirs or typical mantle but resembles that of oceanic crust that was initially altered by seawater and then dehydrated during subduction. Together with an excess of chlorine and depletion of lead in the mantle sources of komatiites, these results indicate that seawater-altered lithosphere recycling into the deep mantle, arguably by subduction, started before 3.3 billion years ago.

Pyrite (cubic FeS 2 ) is the most abundant metal sulfide in nature and also the main host mineral of toxic mercury (Hg). Release of mercury in acid mine drainage resulting from the oxidative dissolution of pyrite in coal and ore and rock resulting from mining, processing, waste management, reclamation, and large construction activities is an ongoing environmental challenge. The fate of mercury depends on its chemical forms at the point source, which in turn depends on how it occurs in pyrite. Here, we show that pyrite in coal, sedimentary rocks, and hydrothermal ore deposits can host varying structural forms of Hg which can be identified with high energy-resolution XANES (HR-XANES) spectroscopy. Nominally divalent Hg is incorporated at the Fe site in pyrite from coal and at a marcasite-type Fe site in pyrite from sedimentary rocks. Distinction of the two Hg bonding environments offers a mean to detect microscopic marcasite inclusions (orthorhombic FeS 2 ) in bulk pyrite. In epigenetic pyrite from Carlin-type Au deposit, up to 55 ± 6 at. % of the total Hg occurs as metacinnabar nanoparticles (β-HgS NP ), with the remainder being substitutional at the Fe site. Pyritic mercury from Idrija-type Hg deposit (α-HgS ore) is partly divalent and substitutional and partly reduced into elemental form (liquid). Divalent mercury ions, mercury sulfide nanoparticles, and elemental mercury released by the oxidation of pyrite in acid mine drainage settings would have different environmental pathways. Our results could find important applications for designing control strategies of mercury released to land and water in mine-impacted watersheds.

Archaean komatiites (ultramafic lavas) result from melting under extreme conditions of the Earth's mantle. Their chemical compositions evoke very high eruption temperatures, up to 1,600 degrees Celsius, which suggests even higher temperatures in their mantle source. This message is clouded, however, by uncertainty about the water content in komatiite magmas. One school of thought holds that komatiites were essentially dry and originated in mantle plumes while another argues that these magmas contained several per cent water, which drastically reduced their eruption temperature and links them to subduction processes. Here we report measurements of the content of water and other volatile components, and of major and trace elements in melt inclusions in exceptionally magnesian olivine (up to 94.5 mole per cent forsterite). This information provides direct estimates of the composition and crystallization temperature of the parental melts of Archaean komatiites. We show that the parental melt for 2.7-billion-year-old komatiites from the Abitibi greenstone belt in Canada contained 30 per cent magnesium oxide and 0.6 per cent water by weight, and was depleted in highly incompatible elements. This melt began to crystallize at around 1,530 degrees Celsius at shallow depth and under reducing conditions, and it evolved via fractional crystallization of olivine, accompanied by minor crustal assimilation. As its major- and trace-element composition and low oxygen fugacities are inconsistent with a subduction setting, we propose that its high H2O/Ce ratio (over 6,000) resulted from entrainment into the komatiite source of hydrous material from the mantle transition zone. These results confirm a plume origin for komatiites and high Archaean mantle temperatures, and evoke a hydrous reservoir in the deep mantle early in Earth's history.

Recycled subducted ocean crust has been traced by elevated 187Os/188Os in some studies and by high nickel and low manganese contents in others. Here, we show that these tracers are linked for Quaternary lavas of Iceland, strengthening the recycling model. An estimate of the osmium isotopic composition of both the recycled crust and the mantle peridotite implies that Icelandic Quaternary lavas are derived in part from an ancient crustal component with model ages between 1.1 _ 109 and 1.8 _ 109 years and from a peridotitic end-member close to present-day oceanic mantle.