Geochemical and tectonic uplift controls on rock nitrogen inputs across terrestrial ecosystems

Rock contains > 99% of Earth's reactive nitrogen (N), but questions remain over the direct importance of rock N weathering inputs to terrestrial biogeochemical cycling. Here we investigate the factors that regulate rock N abundance and develop a new model for quantifying rock N mobilization fluxes across desert to temperate rainforest ecosystems in California, USA. We analyzed the N content of 968 rock samples from 531 locations and compiled 178 cosmogenically derived denudation estimates from across the region to identify landscapes and ecosystems where rocks account for a significant fraction of terrestrial N inputs. Strong coherence between rock N content and geophysical factors, such as protolith, (i.e. parent rock), grain size, and thermal history, are observed. A spatial model that combines rock geochemistry with lithology and topography demonstrates that average rock N reservoirs range from 0.18 to 1.2 kg N m-3 (80 to 534 mg N kg-1) across the nine geomorphic provinces of California and estimates a rock N denudation flux of 20-92 Gg yr-1 across the entire study area (natural atmospheric inputs ~ 140 Gg yr-1). The model highlights regional differences in rock N mobilization and points to the Coast Ranges, Transverse Ranges, and the Klamath Mountains as regions where rock N could contribute meaningfully to ecosystem N cycling. Contrasting these data to global compilations suggests that our findings are broadly applicable beyond California and that the N abundance and variability in rock are well constrained across most of the Earth system

Reaction mechanism for the replacement of calcite by dolomite and siderite: Implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation

Carbonate reactions are common in mineral deposits due to CO2-rich mineralising fluids. This study presents the first in-depth, integrated analysis of microstructure and microchemistry of fluid-mediated carbonate reaction textures at hydrothermal conditions. In doing so, we describe the mechanisms by which carbonate phases replace one another, and the implications for the evolution of geochemistry, rock microstructures and porosity. The sample from the 1.95 Moz Junction gold deposit, Western Australia, contains calcite derived from carbonation of a metamorphic amphibole—plagioclase assemblage that has further altered to siderite and dolomite. The calcite is porous and contains iron-rich calcite blebs interpreted to have resulted from fluid-mediated replacement of compositionally heterogeneous amphiboles. The siderite is polycrystalline but nucleates topotactically on the calcite. As a result, the boundaries between adjacent grains are low-angle boundaries (<10°), which are geometrically similar to those formed by crystal–plastic deformation and recovery. Growth zoning within individual siderite grains shows that the low-angle boundaries are growth features and not due to deformation. Low-angle boundaries develop due to the propagation of defects at grain faces and zone boundaries and by impingement of grains that nucleated with small misorientations relative to each other during grain growth.The cores of siderite grains are aligned with the twin planes in the parent calcite crystal showing that the reactant Fe entered the crystal along the twin boundaries. Dolomite grains, many of which appear to in-fill space generated by the siderite replacement, also show alignment of cores along the calcite twin planes, suggesting that they did not grow into space but replaced the calcite. Where dolomite is seen directly replacing calcite, it nucleates on the Fe-rich calcite due to the increased compatibility of the Fe-bearing calcite lattice relative to the pure calcite. Both reactions are interpreted as fluid-mediated replacement reactions which use the crystallography and elemental chemistry of the calcite. Experiments of fluid-mediated replacement reactions show that they proceed much faster than diffusion-based reactions. This is important when considering the rates of reactions relative to fluid flow in mineralising systems

Intracontinental Eocene-Oligocene Porphyry Cu Mineral Systems of Yunnan, Western Yangtze Craton, China: Compositional Characteristics, Sources, and Implications for Continental Collision Metallogeny

The Yao’an porphyry Au system, Machangqing porphyry Cu-Mo system, and Beiya porphyry-skarn Au system, are spatially and temporally associated with potassic felsic intrusions emplaced during the Eocene to Oligocene epochs at 37 to 33 Ma in a postcollisional intracontinental setting in western Yunnan, western Yangtze craton, China. The Yao’an monzonite and quartz monzonite porphyry intrusions are alkaline and potassic with high K2O/Na2O ratios (1.1–1.5). They have Sr-Nd-Pb isotopes similar to coeval lamprophyres and are characterized by uniform zircon eHf (–6.4 to –8.7) and d18O values (6.6–7.0‰). They are interpreted as products of fractional crystallization of lamprophyre-like potassic mafic magma derived from ancient metasomatized lithospheric mantle, a scenario similar to the mid-Cretaceous postcollisonal Scheelite Dome gold system in Yukon, Canada. The Machangqing granitic intrusions are high K calc-alkaline and show high Sr, Sr/Y, and La/Yb, but low Y and Yb geochemical signatures. They have Sr-Nd-Pb isotope compositions similar to amphibolite xenoliths hosted by potassic felsic intrusions in western Yunnan. The zircon eHf values of the Machangqing granitic intrusions are positive (0.3–4.7), and the zircon-depleted Hf mantle model ages are 1.1 to 0.8 Ga. They also have mantle-like zircon d18O values (5.5–6.4‰). The Machangqing granites were most likely derived from partial melting of Neoproterozoic lower crust. The Beiya granitic intrusions are alkaline, with high K2O/Na2O (1.9–2.7), Sr/Y and La/Yb ratios, high Sr contents, and low Y and Yb contents. They contain abundant zircon inheritance and have variable magmatic zircon eHf (–4 to +4) and the highest magmatic zircon d18O values (6.6–7.8‰). The Beiya felsic intrusions are interpreted to be derived from partial melting of a K-rich mafic source mixed with a metasedimentary component. The Eocene-Oligocene intracontinental potassic intrusions and associated mineralization in western Yunnan are located proximal to the Mesozoic Jinsha suture, suggesting that this Mesozoic lithospheric boundary may have provided a first-order control on localization of Cenozoic mineral systems. These potassic felsic intrusions are coeval with regional potassic mafic magmatism in western Yunnan and were emplaced between 37 to 33 Ma, after the collision between India and Asia at ca. 60 to 55 Ma. It is therefore postulated that continental collision may have preferentially thickened the continental lithospheric mantle (CLM) adjacent to the Jinsha suture, in which overthickened lower continental lithospheric mantle was subsequently removed during 37 to 33 Ma, inducing melting of residual metasomatized lithospheric mantle as well as lower crust. The gold-rich Yao’an and Beiya intrusions are alkaline and potassic, characterized by high zircon d18O values (&gt;6.5‰), which is consistent with supracrustal contributions. In contrast, the Cu-Mo-rich Machangqing intrusions are high K calc-alkaline with mantle-like zircon d18O values (&lt;6.5‰) and juvenile eHf signatures, indicating negligible supracrustal recycling. Empirically, source compositions played an important role in determing the metal endowment among intrusions formed under the same tectonic setting with similar ages in western Yunnan. In western Yunnan, gold tends to be associated with alkaline and potassic melts with a supracrustal contribution, whereas Cu-Mo mineralization seems to be more related with juvenile crustal sources with little supracrustal influence