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The on-board identification of ore minerals during a cruise is often postponed until long after the cruise is over. During the M127 cruise, 21 cores with deep-seafloor sediments were recovered in the Trans-Atlantic Geotraverse (TAG) field along the Mid Atlantic Ridge (MAR). Sediments were analyzed on-board for physicochemical properties such as lightness (L*), pH and Eh. Selected samples were studied for mineral composition by X-ray powder diffraction (XRD). Based on XRD data, sediment samples were separated into high-, low- and non-carbonated. Removal of carbonates is a common technique in mineralogical studies in which HCl is used as the extraction agent. In the present study, sequential extraction was performed with sodium acetate buffer (pH 5.0) to remove carbonates. The ratio between the highest calcite XRD reflection in the original samples (Iorig) vs its XRD-reflection in samples after their treatment with the buffer (Itreat) was used as a quantitative parameter of calcite removal, as well as to identify minor minerals in carbonated samples (when Iorig/Itreat > 24). It was found that the lightness parameter (L*) showed a positive correlation with calcite XRD reflection in selected TAG samples, and this could be applied to the preliminary on-board determination of extraction steps with acetate buffer (pH 5.0) in carbonated sediment samples. The most abundant minerals detected in carbonated samples were quartz and Al- and Fe-rich clays. Other silicates were also detected (e.g., calcic plagioclase, montmorillonite, nontronite). In non-carbonated samples, Fe oxides and hydroxides (goethite and hematite, respectively) were detected. Pyrite was the dominant hydrothermal mineral and Cu sulfides (chalcopyrite, covellite) and hydrothermal Mn oxides (birnessite and todorokite) were mineral phases identified in few samples, whereas paratacamite was detected in the top 20 cm of the core. The present study demonstrates that portable XRD analysis makes it possible to characterize mineralogy at cored sites, in particular in both low- and high-carbonated samples, before the end of most cruises, thus enabling the quick modification of exploration strategies in light of new information as it becomes available in near-real time.
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Limited special education and related services are available for children with autism spectrum disorder (ASD) in Macau, especially those who are educated in general education classrooms. No intervention study has been conducted on these children. This study was conducted to explore the relationship between a board game play intervention and board game play behaviors and social communication of children with ASD educated in general education classrooms in Macau. A repeated measures design was used and the results of this study showed the mean occurrence of unprompted board game play behaviors per session during intervention was not significantly different from that during pre- or post-intervention. The mean occurrence of social communication per session during intervention was significantly higher than that during pre- and post-intervention. These findings suggest a positive relationship existed between the board game intervention used in this study and social communication of children with ASD.
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The recently explored inactive Tianzuo hydrothermal field, in the amagmatic segment of the ultraslow-spreading Southwest Indian Ridge (SWIR), is closely associated with detachment faults. In this site, sulfide minerals are hosted by serpentine-bearing ultramafic rocks and include high-temperature (isocubanite, sphalerite, and minor pyrrhotite) and low-temperature (pyrite I, marcasite, pyrite II, and covellite) phases. In this study, trace-element concentrations of isocubanite and pyrite II were used to elucidate mineralization processes in ultramafic rocks hosting sulfides. Results show that isocubanite is enriched in metals such as Cu, Co, Sn, Te, Zn, Se, Pb, Bi, Cd, Ag, In, and Mn, and pyrite II is enriched in Mo and Tl. The marked enrichment in Te, Cu, Co, and In in isocubanite (compared with Se, Zn, Ni, and Sn, respectively) is most likely due to the contribution of magmatic fluids from gabbroic intrusions beneath the hydrothermal field. The intrusion of gabbroic magmas would have enhanced serpentinization reactions and provided a relatively oxidizing environment through the dissolution of anhydrite precipitated previously in the reaction zone, within high temperature and low pH conditions. This might have facilitated the extraction of metals by initial hydrothermal fluids, leading to the general enrichment of most metals in isocubanite. Metals in pyrite II have compositions similar to those of isocubanite, except for strong depletion in magmatically derived Te, Cu, Co, and In. This means that serpentinization processes had a dominating role in pyrite II precipitation as well. The enrichment of pyrite II in Mo and Tl is also indicative of seawater contribution in its composition. The study concludes that serpentinization reactions contribute effectively both to high- and low-temperature sulfide mineralization at Tianzuo hydrothermal field, with gabbroic intrusions further promoting high-temperature sulfide mineralization, providing additional metals, fluids and heat. In contrast, low-temperature sulfide mineralization occurred during the cooling of gabbroic intrusions, with decreasing rates of serpentinization reactions and a significant influence of seawater.
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Reaction of ultramafic rocks with seawater and subsequent serpentinization has been considered one of the most important factors controlling the formation of ultramafic-hosted seafloor massive sulfide (UM-SMS) deposits. However, the mineralization processes responsible for these deposits remain poorly understood, in particular because they are less abundant as compared with their basaltic counterparts. In this work, serpentinites with different alteration grades collected at the Tianzuo hydrothermal field (THF), Southwest Indian Ridge, were studied. Mineralogical and chemical analyses were performed in the secondary opaque minerals resulting from serpentinization to understand the role of this process during the formation of UM-SMS deposits. Our results show that these opaque minerals mainly consist of magnetite, hematite, pentlandite, and minor pyrite, suggestive of high but varying oxygen and sulfur fugacities. The hematite is characterized by an enrichment in Mg, Si, Ni, and Co as compared with magnetite. Pentlandite associated with hematite has elevated and consistent Ni contents as compared with that associated with magnetite. These results indicate that breakdown and decomposition of primary silicate and sulfide minerals during serpentinization has controlled the sources of ore-forming materials. Concentrations of Te are variable and show a positive correlation with Ni in pentlandite associated with magnetite or hematite, suggesting that gabbroic intrusions provided additional material to the hydrothermal system. Oxidation and sulfidation conditions are ideal for the formation of trisulfur ion S3− in THF, which can significantly improve the capability of hydrothermal fluids for leaching ore-forming metals from the wall rocks, promoting the formation of THF. In addition of reduced systems, hydrothermal fluids with high oxygen and sulfur fugacities triggered by extensive seawater infiltration can most likely also develop in ultramafic-hosted systems. These results suggest that the areas with well-developed fractures are promising candidates for further exploration of UM-SMS deposits along mid-oceanic ridges.
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Seafloor massive sulfide (SMS) deposits are important deep-sea mineral resources expected to occur predominantly on slow- and ultraslow-spreading mid-ocean ridges. Resource estimates are already available for some of the largest SMS deposits on slow-spreading ridges but not on ultraslow-spreading ridges. Based on geological mapping and sampling, this study investigates the distribution and content of sulfide-rich deposits in the Yuhuang-1 hydrothermal field (YHF), located on the ultraslow-spreading Southwest Indian Ridge. The sulfide-rich deposits in the YHF are composed of two areas ∼500 m apart: the southwest sulfide area (SWS) and the northeast sulfide area (NES). We calculated the volume of sulfide-rich mounds in the YHF and arrived at a total accumulation of ∼10.6 × 106 tons, including at least ∼7.5 × 105 tons of copper and zinc and ∼18 tons of gold. Furthermore, considering the coverage of layered hydrothermal sediment mixed with sulfide-rich breccias, which may have underlying massive sulfide deposits, the maximum total mass was estimated at ∼45.1 × 106 tons. This suggests that the YHF is one of the largest SMS deposits worldwide and confirm that ultraslow-spreading ridges have the greatest potential to form large-scale SMS deposits.
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The territory of Macao is composed of several granitic intrusions belonging to one of the biggest granite provinces in the world, the Southeast China Magmatic Belt (SCMB), located in the southeast (SE) area of the Cathaysia Block. The SCMB is known by the occurrence of large volumes of Mesozoic magmatic rocks (over 90% are granitic rocks and equivalent volcanic rocks with minor basalts), occupying a total outcrop area of nearly 200.000 km2. The geology of Macao (~30 Km2) is dominated by granitic rocks displaying a wide range of textural, mineralogical and chemical features, making it an ideal region to study these rocks and the petrogenetic processes responsible for their diversity. This study employed a wide range of research methodologies, namely field studies, petrography, zircon geochronology, mineral chemistry, whole-rock elemental and isotopic geochemistry to determine the nature of the source, the petrogenetic processes and the tectonic regimes of the Mesozoic magmatism in this region. Thus, the data collected along this study aims to provide new knowledge on the tectono-magmatic evolution of Macao, in particular, and of SE China, in general. The results obtained from the high-precision U–Pb zircon geochronology, acquired through isotope dilution thermal ionization mass spectrometry (ID-TIMS) and in-situ laser ablation multi-collector inductively coupled mass spectrometry (LA-MC-ICPMS), revealed different ages for Macao granites. Despite its relatively small area, the determined ages tightly constrain the Macao granitic magmatism to two periods, ranging from 164.5 ± 0.6 to 162.9 ± 0.7 Ma (MGI – Macao Group I granites) and 156.6 ± 0.2 to 155.5 ± 0.8 Ma (MGII – Macao Group II granites). In addition, younger dacitic rocks were dated at 150.6 ± 0.6 Ma and <120 Ma. The existence of two proximal but distinct granitic pulses, spanning for a time of about 9 Ma and separated by ca. 6 Ma, in the Macao granitic suite suggests that it was incrementally assembled. This hypothesis is also extendable to the neighbouring Hong Kong region, where the magmatic activity occurred in four major pulses spanning for about 24 Ma. However, the MGII granites indicate the occurrence, on the Pearl River Delta region, of a magmatic pulse between those defined in Hong Kong at the origin of Lamma Suite (165–160 Ma) and the Kwai Chung Suite (148–146 Ma). In addition, Rare Element Earth (REE) ratios suggest that this pulse may only occur in Macao area, while MGI granites show evolving trends of REE ratios similar to those of Jurassic granites outcropping in vast areas of the Cathaysia Block (SE China). Inheritance patterns in the zircon U–Pb data indicate the presence of a population of antecrysts (165–180 Ma) crystallized from earlier magmatic pulses and a population of inherited zircons, from Precambrian to Phanerozoic sources, incorporated into the magmas during melting and/or ascent/emplacement at crustal levels. The oldest inherited ages (2.4 Ga and possibly 2.9 Ga) suggest contribution of Proterozoic and possibly of late Archaean crustal sources for the Macao magmatism. The granitic rocks of Macao are mainly high-K calc-alkaline metaluminous to weakly peraluminous I-type granites with variable degrees of fractionation. Fractional crystallization played an important role in the evolution of these granites, though the fractionation paths differ for the highly fractionated facies of both groups mainly due to distinct accessory fractionating phases. Such difference is evident by distinct REE evolution trends: while MGI magmas seem to have evolved by gradual enrichment in heavy REE relatively to light REE, originating progressively flatter REE patterns, magmas from MGII are marked by depletion of middle REE, leading to progressively concave upward REE patterns. However, while most of the geochemical variation of the MGII granites can be explained by fractional crystallization, the same is not true for MGI granites. The MGI highly fractionated granites show evidence for the REE tetrad effect and are characterized by non-CHArge-and-RAdius-Controlled (non-CHARAC) behaviour of trace elements, suggesting late-stage melt/fluid interactions involving F-rich fluids. The stage of evolution represented by the MGI highly fractionated granites corresponds to the onset of fluid/melt interaction in a highly evolved granitic system, which may have led to enhanced hydrothermal activity in more evolved stages, as those represented in neighbouring areas in SE China. Significant differences in isotopic composition were also observed, with the MGII being characterized by a much narrow range of initial 87Sr/86Sr ratios and εNd(t) and εHf(t) values than MGI. Based on these differences, the MGII granites are considered to be part of a comagmatic suite that has evolved in closed system, contrasting with what can be inferred for MGI. The increase in initial 87Sr/86Sr ratios with degree of evolution, the presence of metasedimentary enclaves and the high percentage of inherited zircon with Paleozoic ages in MGI, suggest the occurrence of an assimilation fractionation crystallization (AFC) process. The AFC processes were a major cause for the I-S transitional characteristics of the MGI highly fractionated granites and possibly of the other similar Jurassic biotite granites in SE China. The observed decoupling of Sr, Nd and Hf isotope systems might have resulted from magma mixing between the granitic and more mafic magmas, which caused the homogenization of Sr isotope ratios but not of the Nd and Hf ones. Such process is also supported by the occurrence of Microgranular Mafic Enclaves (MME) hosted by the granites. Isotope and major element compositions together with model ages strongly suggest that Macao granitic magmas were generated by partial melting of infracrustal medium-to-high K basaltic Paleo-Proterozoic to Mesoproterozoic protoliths heated by, and mixed to some degree with mantle-derived magmas. The temporal and spatial association of Macao and SE China Jurassic I-type granites with basaltic/gabbroic rocks, syenites and A-type granites, displaying typical intraplate chemical features, indicates an extensional regime rather than an active margin for the origin of these rocks. It also points to an important role of mantle-derived magmas in the production of SE China Jurassic granites. Adiabatic decompression melting of the asthenospheric mantle produced mafic magmas, which underplated at the base of the crust (Moho), subsequently triggering partial melting of the lower crust to generate the granitic magmas. The Jurassic Macao granites are interpreted as being produced in an intraplate extensional setting related to the break-off and foundering of a previously flat-slab (Paleo-Pacific plate) beneath the Eurasian plate. The boundary between east and west Cathaysia blocks is roughly along the Zhenghe-Dapu Fault (ZDF), which intersects the SE China coast near Hong Kong and is thought to have played a major role for the Mesozoic magmatic activity in this region. The stronger isotopic affinities of Macao granites with the other granitic rocks and lower crustal xenoliths from the western Cathaysia Block suggest that the ZDF is likely to pass south of Macao, a fact that has not been mentioned before. In addition to the Early Yanshanian (Jurassic) granitic magmatism in Macao, the younger ages obtained for the dacite dykes indicate that the territory was also affected, to a lesser degree, by Late Yanshanian (Cretaceous) magmatism. The transition from granitic to dacitic magmatism most likely corresponds to a change in the regional tectonic regime, which induced a significant change in the magma genesis processes. In contrast with the intraplate features of Macao and SE China Jurassic granites and coeval mafic rocks, the geochemical features of the Macao dacite dykes (e.g. high LILE/HFSE ratios and negative anomalies of Nb, Ta and Ti) are identical to those characterizing arc-like subduction-related magmas. These dacites are most likely evolved products of arc-like magmatism and may testify the reestablishment of a normal subduction system in this area of SE China.
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