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Abstract Much controversy has occurred in the past few decades regarding the nature of the sources, the petrogenetic processes, and the tectonic regime(s) of the Jurassic magmatism within the Southeast China magmatic belt. This study aims to contribute to the discussion with mineral chemistry, and whole-rock element and Sr-Nd-Hf-Pb isotopic geochemical data from granitic rocks and microgranular mafic enclaves from Macao, where two discrete groups of I-type biotite granites have been identified (referred to as Macao Group I [MGI] and Macao Group II [MGII]). It is proposed that the granitic magmas were generated by partial melting of infracrustal medium- to high-K, basaltic Paleoproterozoic to Mesoproterozoic protoliths (Nd depleted mantle model age [TDM2] = 1.7–1.6 Ga and Hf TDM2 = 1.8–1.6 Ga), triggered by underplating of hot mantle-derived magmas in an extensional setting related to the foundering of a previously flat slab (paleo–Pacific plate) beneath the SE China continent. The main differences between the two groups of Macao granites are attributed to assimilation and fractional crystallization processes, during which upper-crustal Paleozoic metasediments were variably assimilated by MGI magmas. This is evidenced by an increase in initial 87Sr/86Sr ratios with degree of evolution, presence of metasedimentary enclaves, and high percentage of zircon xenocrysts with Paleozoic ages. In addition, other processes like late-stage fluid/melt interaction and magma mixing also left some imprints on granite compositions (rare earth element tetrad effect plus non–charge-and-radius-controlled behavior of trace elements and decoupling between different isotope systems, respectively). The distribution of isotopically distinct granites in SE China reflects the nature of the two Cathaysia crustal blocks juxtaposed along the Zhenghe-Dapu fault.

Hydrothermal activities on ultraslow-spreading ridges exhibit diverse characteristics, long histories with multiple participants, and might form large-scale, high-grade sulfide deposits. The Duanqiao hydrothermal field (DHF) is located at the segment with the thickest oceanic crust and a large axial magma chamber on the Southwest Indian Ridge, providing unique perspective of sulfide metallogenesis on ultraslow-spreading ridges. Previous studies revealed that DHF sulfide exhibits distinct features of enrichment of ore-forming elements in comparison with those of hydrothermal fields on sediment-starved mid-ocean ridges. However, the genesis and processes responsible for such differences remain poorly constrained. In this study, mineralogical, geochemical and S and Pb isotopic analyses were performed on relict sulfide mound samples to characterize DHF formation. The samples show clear concentric mineral zonation from the interior to the exterior wall. Assemblages of chalcopyrite, sphalerite, and pyrite are distributed mainly in the interior wall, whereas pyrite and marcasite are distributed mainly in the exterior wall. The low Cu content and Pb isotopic composition of the sulfide indicate that the metals are derived mainly from basement basalts. The δ34S values exhibit positive values distributed over a reasonably narrow range (2.42‰–7.97‰), which suggests approximately 62.1%–88.5% of S with basaltic origin. Compared with most hydrothermal fields along the sediment starved mid-ocean ridges, the DHF sulfide shows particularly high contents of Pb (263–2630 ppm), As (234–726 ppm), Sb (7.32–44.3 ppm), and Ag (35.2 to >100 ppm). The δ34S values exhibit an increasing tendency from the sample exterior to the interior. We propose that these features probably reflect the existence of a subsurface zone refining process. Our results provide new insight into the sulfide formation process and contribute to understanding the metallogenic mechanism of hydrothermal sulfides on ultraslow-spreading ridges.

A 1:12,000 geological map of the Macao Special Administrative Region has been produced through detailed field work supported by petrographic, mineralogical, geochronological and geochemical data obtained in previous studies. This map aims to represent a reliable tool to understand the geological evolution of the region and for management of the territory. The geology of Macao is dominated by two groups of Jurassic granitic rocks belonging to an intrusive suite located along the coast of Southeast China: Macao Group I (MGI: 164.5 ± 0.6 to 162.9 ± 0.7 Ma) and Macao Group II (MGII: 156.6 ± 0.2 to 155.5 ± 0.8 Ma), including the associated microgranite, aplite and pegmatite dikes and quartz veins. Remnants of the metasedimentary wall-rock are present as Devonian xenoliths enclosed within the granites. Younger Jurassic to Cretaceous andesite to dacite dikes (150.6 ± 0.6 to <120 Ma) intrude the granitic rocks. Additionally, Quaternary sedimentary deposits cover the older lithologies.

Hydrothermal activity on mid-ocean ridges is an important mechanism for the delivery of Zn from the mantle to the surface environment. Zinc isotopic fractionation during hydrothermal activity is mainly controlled by the precipitation of Zn-bearing sulfide minerals, in which isotopically light Zn is preferentially retained in solid phases rather than in solution during mineral precipitation. Thus, seafloor hydrothermal activity is expected to supply isotopically heavy Zn to the ocean. Here, we studied sulfide-rich samples from the Duanqiao-1 hydrothermal field, located on the Southwest Indian Ridge. We report that, at the hand-specimen scale, late-stage conduit sulfide material has lower δ66Zn values (−0.05 ± 0.15 ‰; n = 19) than early-stage material (+0.13 ± 0.15 ‰; n = 10). These lower values correlate with enrichments in Pb, As, Cd, and Ag, and elevated δ34S values. We attribute the low δ66Zn values to the remobilization of earlier sub-seafloor Zn-rich mineralization. Based on endmember mass balance calculations, and an assumption of a fractionation factor (αZnS-Sol.) of about 0.9997 between sphalerite and its parent solution, the remobilized Zn was found consist of about 1/3 to 2/3 of the total Zn in the fluid that formed the conduit samples. Our study suggests that late-stage subsurface hydrothermal remobilization may release isotopically-light Zn to the ocean, and that this process may be common along mid-ocean ridges, thus increasing the size of the previously identified isotopically light Zn sink in the ocean.

The widespread W-(Mo)-Sn-Nb-Ta polymetallic mineralization in Southeast (SE) China is genetically associated with Mesozoic highly fractionated granitic rocks. Such rocks have enigmatic mineralogical and geochemical features, making its petrogenesis an intensely debated topic. To better understand the underlying magma evolution processes, petrography, garnet chemistry and whole-rock major and trace element data are reported for Jurassic highly fractionated granitic rocks and associated microgranite and aplitepegmatite dikes from Macao and compared with coeval similar granitic rocks from nearby areas in SE China. Despite the fact that the most evolved rocks in Macao are garnet-bearing aplite-pegmatite dikes, the existence of coeval two-mica and garnet-bearing biotite and muscovite granites displaying more evolved compositions (e.g, lower Zr/Hf ratios) indicates that the differentiation sequence reached higher degrees of fractionation at a regional scale. Although crystal fractionation played an important role, late-stage fluid/melt interactions, involving F-rich fluids, imparted specific geochemical characteristics to Macao and SE China highly fractionated granitic rocks such as the non-CHARAC (CHArge-and-RAdius-Controlled) behavior of trace elements, leading, for example, to non-chondritic Zr/Hf ratios, Rare Earth Elements (REE) tetrad effects and Nb-Ta enrichment and fractionation. Such process contributed to the late-stage crystallization of accessory phases only found in these highly evolved facies. Among the latter, two populations of garnet were identified in MGI (Macao Group I) highly fractionated granitic rocks: small grossular-poor euhedral grains and large grossular-rich skeletal garnet grains with quartz inclusions. The first group was mainly formed through precipitation from highly evolved Mn-rich slightly peraluminous melts under low-pressure and relatively low temperature (∼700 °C) conditions. Assimilation of upper crust metasedimentary materials may have contributed as a source of Mn and Al to the formation of garnet. The second group has a metasomatic origin related to the interaction of magmatic fluids with previously crystallized mineral phases and, possibly, with assimilated metasedimentary enclaves or surrounding metasedimentary strata. The highly fractionated granitic rocks in Macao represent the first stage in the development of granite-related W-(Mo)-Sn-Nb-Ta mineralization associated with coeval more evolved lithotypes in SE China.

The geochemistry and mineralogy of sediments provide relevant information for the understanding of the origin and metallogenic mechanism of ferromanganese nodules and crusts. At present, there are still few studies on the sediment origin of the Clarion–Clipperton Zone (CCZ) of the east Pacific, particularly on the systematic origin of sediments with a longer history/length. Here, bulk sediment geochemistry and clay mineral compositions were analyzed on a 5.7 m gravity core (GC04) obtained at the CCZ, an area rich in polymetallic nodules. The results indicate that the average total content of rare earth elements (REE), including yttrium (REY), in sediments is 454.7 ppm and the REEs distribution patterns normalized by the North American Shale Composite of samples are highly consistent, with all showing negative Ce anomalies and more obvious enrichment in heavy REE (HREE) than that of light REE (LREE). Montmorillonite/illite ratio, discriminant functions and smear slide identification indicate multiple origins for the material, and are strongly influenced by contributions from marine biomass, while terrestrial materials, seamount basalts and their alteration products and authigenic source also make certain contributions. The REY characteristics of the sediments in the study area are different from those of marginal oceanic and back-arc basins, and more similar to pelagic deep-sea sediments. Based on LREE/HREE-1/δCe and LREE/HREE-Y/Ho diagrams, we conclude that samples from the study area had pelagic sedimentary properties which suffered from a strong “seawater effect”.

Macao ( 30 Km2) is a territory characterized by small granitic intrusions, located along the coastal region of Southeast China (Cathaysia Block). Granitoids occur as different facies, including microgranite dykes, with distinct textural, mineralogical and geochemical features, for which a middle-upper Jurassic age ( 164 Ma) has been proposed. New data suggest that these granitoids are mostly high-K calc-alkaline metaluminous (A/CNK = 0.8 - 1.1) biotite granites, consistent with total absence of primary muscovite. They show variable amounts of SiO2 (67-77%), reflecting different degrees of magmatic evolution. There is also variability in terms of trace elements, particularly Rare Earth Elements (REEs), evidenced by decreasing (La/Sm)N, (Gd/Lu)N, (Ce/Yb)N and (Eu/Eu*)N towards the more evolved samples, which can be partly attributed to fractional crystallization processes. Most of the granitoids are characterized by (La/Yb)N = 3 - 10.8, showing negative Ba, Nb, Sr, Zr, P, Ti and Eu anomalies. On the other hand, microgranite dykes, along with a few more evolved granites, show an opposite tendency, being usually enriched in HREEs relatively to LREEs with (La/Yb)N = 0.4 - 1.1. Our data suggests intermediate genetic affinities between I-type and A-type granites. Although these granitoids are mostly metaluminous (characteristic of I-types), Ga/Al ratios, usually used to identify A-types, are close to the accepted boundary between A-type and other granite types. The affinities with A-type granites are more marked for the more evolved facies, which depict higher values of FeOt/MgO (14 - 60) and K2O/MgO (60 - 250). Their trace element characteristics are also transitional between WPG (Within-plate granites) and Syn-COLG (Collision Granites). We interpret those transitional characteristics (A/I and WPG/Syn-COLG) of Macao granitoids as reflecting an origin by melting of infracrustal sources over a period of high heat transfer from mantle to crust during an extensional tectonic setting probably contemporaneous with the subduction of the paleo-Pacific plate beneath the Eurasia, whose paleo-suture is thought to be located in the east flank of the Central Range, Taiwan.