Trace Element Contents in Sphalerite from the Nayongzhi Zn-Pb Deposit, Northwestern Guizhou, China: Insights into Incorporation Mechanisms, Metallogenic Temperature and Ore Genesis

The Nayongzhi Zn-Pb deposit, located in the southeastern margin of the Sichuan-Yunnan-Guizhou (S-Y-G) Zn-Pb metallogenic province, China, has been recently discovered in this region and has an estimated resource of 1.52 Mt of metal at average grades of 4.82 wt % Zn and 0.57 wt % Pb. The ore bodies are hosted in the Lower Cambrian Qingxudong Formation dolostone and occur as stratiform, stratoid and steeply dipping veins. The predominant minerals are sphalerite, galena, dolomite, calcite with minor pyrite, and barite. In this paper, the inductively coupled plasma mass spectrometry (ICP-MS) technique has been used to investigate the concentrations of Fe, Cd, Ge, Ga, Cu, Pb, Ag, In, Sn, Sb, Co and Mn in bulk grain sphalerite from the Nayongzhi deposit, in an effort to provide significant insights into the element substitution mechanisms, ore-forming temperature and genesis of the deposit. This study shows that those trace elements (i.e., Cd, In, Sn, Sb, Fe, Mn, Cu, Ga, Ge, Ag, and Co) are present in the form of isomorphism in sphalerite, and strong binary correlation among some elements suggests direct substitution as Zn2+Fe2+ and coupled substitutions as Zn2+Ga3+ + (Cu, Ag)(+) and Zn2+In3+ + Sn3+ + (vacancy), despite there being no clear evidence for the presence of Sn3+. Sphalerite from the Nayongzhi deposit is enriched in Cd, Ge and Ga and depleted in Fe, Mn, In and Co, which is similar to that of the Mississippi Valley-type (MVT) deposit and significantly different from that of the Volcanogenic Massive Sulfide (VMS) deposit, Sedimentary-exhalative (Sedex) deposit, skarn, and epithermal hydrothermal deposit. Moreover, the ore-forming temperature is relatively low, ranging from 100.5 to 164.4 degrees C, as calculated by the GGIMFis geothermometer. Geological characteristics, mineralogy and trace element contents of sphalerite suggest that the Nayongzhi deposit is a MVT deposit. In addition, according to the geological characteristics, Ag content in sphalerite, and Pb isotope evidence, the Nayongzhi deposit is distinct from the deposits associated with the Indosinian Orogeny in S-Y-G Zn-Pb metallogenic province (e.g., Huize, Daliangzi, Tianbaoshan and Tianqiao deposits), thus, suggesting that multi-stage Zn-Pb mineralization may have occurred in this region

U-Pb zircon age, geochemical and isotopic characteristics of carbonatite and syenite complexes from the Shaxiongdong, China

The Qinling is an important orogenic belt, which formed by the joining of the North China and South China blocks. The Shaxiongdong carbonatite–syenite complexes were emplaced at the southern margin of South Qinling and border the South China block. LA-ICPMS (Laser Ablation Inductively Coupled Plasma Mass Spectrometry) zircon U–Pb geochronology constrains the syenite emplacement age to be 441.8 ± 2.2 Ma, which is significantly earlier than the collision of the South China block and South Qinling along the Mianlue suture (200–240 Ma) near where the complexes reside. Trace-element abundances and C–O–Sr–Nd–Pb isotopes for the carbonatites and calcite separates indicate an igneous origin. They and associated syenites show overlaps of initial 87Sr/86Sr ratios (0.7029–0.7033, 0.7030–0.7032) and εNd (2.8 to 4, 2.5 to 6 for syenites and carbonatites, respectively), which implies that the carbonatites may derive from a carbonated alkali silicate melt. However, the rocks are composed dominantly of calcite. They have markedly lower Th, Nb, Zr and P contents compared to average calciocarbonatites worldwide. Calcites from the carbonatites are also characterized by low REE contents and relatively flat REE patterns. This indicates that the carbonatites are calcite-rich cumulates, which were produced from a residual liquid derived from an intensively fractioned carbonatite magma. In addition, the syenites are characterized by negative Pb and no Nb anomalies. They show lower Sr isotopes and higher εNd than syn/post-orogen related granites emplaced in the Qinling. This indicates that the complexes formed in a rifting environment. It is noted that Sr and Nd isotopic compositions from the carbonatites and syenites are close to HIMU mantle source values. Variations in 207Pb/206Pb (0.785–0.842) and 208Pb/206Pb (1.954–2.110) ratios from the calcites best fit a model involving mixing HIMU and EM1 components. Therefore, plume activity may play an important role in the complex generation and tectonic evolution of the South China block. Geological support for this deduction is the presence of numbers of Silurian dyke swarms. We hypothesize that the upwelling plume metasomatizing the continental lithosphere resulted in the South Qinling separating from South China block along the Mianlue suture during the early Paleozoic period

U-Pb zircon age, geochemical and isotopic characteristics of carbonatite and syenite complexes from the Shaxiongdong, China

The Qinling is an important orogenic belt, which formed by the joining of the North China and South China blocks. The Shaxiongdong carbonatite-syenite complexes were emplaced at the southern margin of South Qinling and border the South China block. LA-ICPMS (Laser Ablation Inductively Coupled Plasma Mass Spectrometry) zircon U-Pb geochronology constrains the syenite emplacement age to be 441.8 ± 2.2 Ma, which is significantly earlier than the collision of the South China block and South Qinling along the Mianlue suture (200-240 Ma) near where the complexes reside. Trace-element abundances and C-O-Sr-Nd-Pb isotopes for the carbonatites and calcite separates indicate an igneous origin. They and associated syenites show overlaps of initial 87Sr/86Sr ratios (0.7029-0.7033, 0.7030-0.7032) and εNd (2.8 to 4, 2.5 to 6 for syenites and carbonatites, respectively), which implies that the carbonatites may derive from a carbonated alkali silicate melt. However, the rocks are composed dominantly of calcite. They have markedly lower Th, Nb, Zr and P contents compared to average calciocarbonatites worldwide. Calcites from the carbonatites are also characterized by low REE contents and relatively flat REE patterns. This indicates that the carbonatites are calcite-rich cumulates, which were produced from a residual liquid derived from an intensively fractioned carbonatite magma. In addition, the syenites are characterized by negative Pb and no Nb anomalies. They show lower Sr isotopes and higher εNd than syn/post-orogen related granites emplaced in the Qinling. This indicates that the complexes formed in a rifting environment. It is noted that Sr and Nd isotopic compositions from the carbonatites and syenites are close to HIMU mantle source values. Variations in 207Pb/206Pb (0.785-0.842) and 208Pb/206Pb (1.954-2.110) ratios from the calcites best fit a model involving mixing HIMU and EM1 components. Therefore, plume activity may play an important role in the complex generation and tectonic evolution of the South China block. Geological support for this deduction is the presence of numbers of Silurian dyke swarms. We hypothesize that the upwelling plume metasomatizing the continental lithosphere resulted in the South Qinling separating from South China block along the Mianlue suture during the early Paleozoic period

Design Rules of the Mixing Phase and Impacts on Device Performance in High-Efficiency Organic Photovoltaics

In nonfullerene acceptor- (NFA-) based solar cells, the exciton splitting takes place at both domain interface and donor/acceptor mixture, which brings in the state of mixing phase into focus. The energetics and morphology are key parameters dictating the charge generation, diffusion, and recombination. It is revealed that tailoringthe electronic properties of the mixing region by doping with larger-bandgap components could reduce the density of state but elevate the filling state level, leading to improved open-circuit voltage (VOC) and reduced recombination. The monomolecular and bimolecular recombinations are shown to be intercorrelated, which show a Gaussian-like relationship with VOC and linear relationship with short-circuit current density (JSC) and fill factor (FF). The kinetics of hole transfer and exciton diffusion scale with JSC similarly, indicating the carrier generation in mixing region and crystalline domain are equally important. From the morphology perspective, the crystalline order could contribute to VOC improvement, and the fibrillar structure strongly affects the FF. These observations highlight the importance of the mixing region and its connection with crystalline domains and point out the design rules to optimize the mixing phase structure, which is an effective approach to further improve device performance