Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps.

Alteration of ultramafic rocks plays a major role in the production of hydrocarbons and organic compounds via abiotic processes on Earth and beyond and contributes to the redistribution of C between solid and fluid reservoirs over geological cycles. Abiotic methanogenesis in ultramafic rocks is well documented at shallow conditions, whereas natural evidence at greater depths is scarce. Here we provide evidence for intense high-pressure abiotic methanogenesis by reduction of subducted ophicarbonates. Protracted (≥0.5-1 Ma), probably episodic infiltration of reduced fluids in the ophicarbonates and methanogenesis occurred from at least ∼40 km depth to ∼15-20 km depth. Textural, petrological and isotopic data indicate that methane reached saturation triggering the precipitation of graphitic C accompanied by dissolution of the precursor antigorite. Continuous infiltration of external reducing fluids caused additional methane production by interaction with the newly formed graphite. Alteration of high-pressure carbonate-bearing ultramafic rocks may represent an important source of abiotic methane, with strong implications for the mobility of deep C reservoirs.

Polysomatic apatites.

Certain complex structures are logically regarded as intergrowths of chemically or topologically discrete modules. When the proportions of these components vary systematically a polysomatic series is created, whose construction provides a basis for understanding defects, symmetry alternation and trends in physical properties. Here, we describe the polysomatic family A(5N)B(3N)O(9N + 6)X(Ndelta) (2 < or = N < or = infinity) that is built by condensing N apatite modules (A(5)B(3)O(18)X(delta)) in configurations to create B(n)O(3n + 1) (1 < or = n < or = infinity) tetrahedral chains. Hydroxyapatite [Ca(10)(PO(4))(6)(OH)(2)] typifies a widely studied polysome where N = 2 and the tetrahedra are isolated in A(10)(BO(4))(6)X(2) compounds, but N = 3 A(15)(B(2)O(7))(3)(BO(4))(3)X(3) (ganomalite) and N = 4 A(20)(B(2)O(7))(6)X(4) (nasonite) are also known, with the X site untenanted or partially occupied as required for charge balance. The apatite modules, while topologically identical, are often compositionally or symmetrically distinct, and an infinite number of polysomes is feasible, generally with the restriction being that an A:B = 5:3 cation ratio be maintained. The end-members are the N = 2 polysome with all tetrahedra separated, and N = infinity, in which the hypothetical compound A(5)B(3)O(9)X contains infinite, corner-connected tetrahedral strings. The principal characteristics of a polysome are summarized using the nomenclature apatite-(A B X)-NS, where A/B/X are the most abundant species in these sites, N is the number of modules in the crystallographic repeat, and S is the symmetry symbol (usually H, T, M or A). This article examines the state-of-the-art in polysomatic apatite synthesis and crystallochemical design. It also presents X-ray and neutron powder diffraction investigations for several polysome chemical series and examines the prevalence of stacking disorder by electron microscopy. These insights into the structure-building principles of apatite polysomes will guide their development as functional materials.

Pseudomorphic 2A--> 2M--> 2H phase transitions in lanthanum strontium germanate electrolyte apatites.

Apatite-like materials are of considerable interest as potential solid oxide fuel cell electrolytes, although their structural vagaries continue to attract significant discussion. Understanding these features is crucial both to explain the oxide ion conduction process and to optimise it. As the composition of putative P6(3)/m apatites with ideal formula [A(I)(4)][A(II)(6)][(BO(4))(6)][X](2) is varied the [A(I)(4)(BO(4))(6)] framework will flex to better accommodate the [A(II)(6)X(2)] tunnel component through adjustment of the A(I)O(6) metaprism twist angle (varphi). The space group theory prescribes that framework adaptation during phase changes must lead to one of the maximal non-isomorphic subgroups of P6(3)/m (P2(1), P2(1)/m, P1[combining macron]). These adaptations correlate with oxygen ion conduction, and become crucial especially when the tunnels are filled by relatively small ions and/or partially occupied, and if interstitial oxygens are located in the framework. Detecting and completely describing these lower symmetry structures can be challenging, as it is difficult to precisely control apatite stoichiometry and small departures from the hexagonal metric may be near the limits of detection. Using a combination of diffraction and spectroscopic techniques it is shown that lanthanum strontium germanate oxide electrolytes crystallise as triclinic (A), monoclinic (M) and hexagonal (H) bi-layer pseudomorphs with the composition ranges: [La(10-x)Sr(x)][(GeO(4))(5+x/2)(GeO(5))(1-x/2)][O(2)] (0

Crystal chemistry of mimetite, Pb10(AsO4)6Cl1.48O0.26, and finnemanite, Pb10(AsO3)6Cl2.

The crystal chemistries of synthetic mimetite, Pb(10)(As(5+)O(4))(6)(Cl(2 - x)O(x/2)), a neutral apatite, and finnemanite, Pb(10)(As(3+)O(3))(6)Cl(2), a reduced apatite, were characterized using a combination of X-ray powder diffraction, neutron diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Both phases conform to hexagonal P6(3)/m symmetry; however, the temperature-driven transformation of clinomimetite to mimetite described earlier was not confirmed. The average mimetite structure is best described through the introduction of partially occupied oxygen sites. A better understanding of the mixed arsenic speciation in apatites can guide the formulation of waste form ceramics and improve models of long-term durability after landfill disposal.

Cadmium and lead ion capture with Three dimensionally ordered macroporous hydroxyapatite.

The capability of three dimensionally ordered macroporous (3DOM) hydroxyapatite, Ca10(PO4)6(OH)2 (HAp), to capture cadmium and lead ions from their respective salt solutions was studied as a function of temperature. Synthesis of 3DOM material was achieved by colloidal crystal templating of polystyrene spheres (1 microm diameter) using calcium nitrate (Ca(NO3)2) and orthophosphoric acid (H3PO4) as precursors. The macroporous product consisted primarily of HAp (>80% depending on the sintering temperature) together with amorphous calcium phosphate. The sorption ability of 3DOM material to Cd/Pb ion was benchmarked against HAp powder prepared via the same route without the template. On the basis of quantitative X-ray diffraction (XRD) and analytical transmission electron microscopy(ATEM) 3DOM HAp demonstrated a higher uptake of cadmium, viz. x = 0.71 in Ca10-xCdx(PO4)6(OH)2 than nonporous HAp (x = 0.42). The incorporation of Cd was homogeneous in the 3DOM HAp crystals (as compared to the powder) leading to a decrease in lattice parameters as Cd2+ has a smaller ionic radius compared to Ca2+. A preference for Cd to enter the Ca" tunnel site of HAp was consistent with this being the readily exchangeable site. The lead-bearing solution acted to collapse the macropores through the rapid crystallization of pyromorphite (Pb10(P04)6(OH)2) via a dissolution-precipitation mechanism, possibly promoted by the amorphous component, that overwhelmed HAp ion exchange. The rapid crystallochemical incorporation of Cd and fixation of Pb by 3DOM HAp demonstrates the potential of thin-walled porous structures for the treatment of contaminated waters.