Sic and associated ultra-reduced minerals were reported in various geological settings, however, their genesis and preservation mechanism are poorly understood. Here, we reported a Sic-dominated ultra-reduced mineral assemblage, including Sic, Tic, native metals (Si, Fe, and Ni) and iron silicide, from carbonatitic xenoliths in Dalihu, Inner Mongolia. All minerals were identified in situ in polished/thin sections. Sic is 20–50 μm in size, blue to colorless in color, and usually identified in the micro-cavities within the carbonatitic xenolith. Four types of Sic polytypes were identified, which are dominated by β-SiC (3C polytype) and 4H polytype followed by 15R and 6H. These Sic are featured by 13C-depleted isotopic compositions (δ13C = –13.2 to –22.8‰, average = –17.7‰) with obvious spatial variation.
The volatile components CO2 and H2O induce mantle melting and thus exert major controls on mantle heterogeneity. Primitive intraplate alkaline magmatic rocks are the closest analogues for incipient mantle melts and provide the most direct method to assess such mantle heterogeneity. Given the considerable Ca isotope differences among carbonate, clinopyroxene, garnet, and orthopyroxene in the mantle (up to 1 ‰ for δ44/40Ca), δ44/40Ca of alkaline rocks is a promising tracer of lithological heterogeneity. We present stable Ca isotope data for ca. 1.4 Ga lamproites, 590–555 Ma ultramafic lamprophyres and carbonatites, and 142 Ma nephelinites from Aillik Bay in Labrador, eastern Canada. These primitive alkaline rock suites are the products of three stages of magmatism that accompanied lithospheric thinning and rifting of the North Atlantic craton. The three discrete magmatic events formed by melting of different lithologies in a metasomatized lithospheric mantle column at various depths: (1) MARID-like components (mica-amphibole-rutile-ilmenite-diopside) in the source of the lamproites; (2) phlogopite-carbonate veins were an additional source component for ultramafic lamprophyres during the second event; and (3) wehrlites at shallower depths were an important source component for nephelinites during the final event. The Mesoproterozoic lamproites show lower δ44/40Ca values (0.58 to 0.66 ‰) than MORBs (0.84 ± 0.03 ‰, 2se). This cannot be explained by fractional crystallization or melting of the clinopyroxene-dominated source but can be attributed to a source enriched in the alkali amphibole K-richterite, which has characteristically low δ44/40Ca. The δ44/40Ca values of the ultramafic lamprophyre suite during the second rifting stage are remarkably uniform, with overlapping ranges for primary carbonated silicate melts (aillikite: 0.67 to 0.75 ‰), conjugate carbonatitic liquids (0.71 to 0.82 ‰) and silicate-dominated damtjernite liquid (primary damtjernite: 0.68 to 0.72 ‰). This suggests negligible Ca isotope fractionation during liquid immiscibility of carbonate-bearing magmas. Combined with previously reported δ44/40Ca values for carbonatites and kimberlites, our data suggest that carbonated silicate melts in Earth's mantle have δ44/40Ca compositions resolvably lower than those for MORBs (0.74 ± 0.02 ‰ versus 0.84 ± 0.03 ‰, 2se). The δ44/40Ca values of the Cretaceous nephelinites (0.72 to 0.78 ‰) are homogenous and similar to those of the 590–555 Ma ultramafic lamprophyres, suggesting that the wehrlitic source component for the nephelinites formed by mantle metasomatism during interaction with rising aillikite magmas during the second rifting stage. Our results highlight that both K-richterite and carbonate components in mantle sources can result in the systematically low δ44/40Ca values of alkaline magmas, which may explain previously reported low δ44/40Ca values of alkaline rocks and some carbonatites. Our study indicates that Ca isotopes are a robust tracer of lithological variation caused by volatiles in the Earth's upper mantle.
La/Fe/TiO2 composite photocatalysts were synthesized by Sol-Gel method and well characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen-physical adsorption, and UV-Vis diffuse reflectance spectra (UV-Vis DRS). It is interesting that the doped catalysts were in anatase phase while the pure TiO2 was in rutile phase. In addition, the composites possessed better physical chemical properties in photocatalytic activity than pure TiO2: stronger visible-light-response ability, larger specific surface area, and more regular shape in morphology. The photodegradation results of ammonia nitrogen indicate that: the La/Fe/TiO2 had higher catalytic activity to ammonia nitrogen waste water compared pure TiO2 and the other single metal-doped TiO2. pH 10 and 2 mmol/L H2O2 were all beneficial to the removal of ammonia nitrogen by La/Fe/TiO2. However, the common inorganic ions of Cl−, NO3−, SO42−, HCO3−/CO32−, Na+, K+, Ca2+ and Mg2+ in water all inhibited the degradation of ammonia nitrogen. By balance calculation, at least 20% of ammonia nitrogen was converted to N2 during the 64.6% removal efficiency of ammonia nitrogen.
Human are widely exposed to multiple metals, some of which have suspected reproductive toxicity, but no human studies have investigated the developmental effects of prenatal metal exposure. We aimed to evaluate the associations between prenatal multiple metal exposure and reproductive development in boys at 2–3 years using multi-pollutant approach. This prospective study used data of 564 mother–child pairs recruited from the Guangxi Birth Cohort Study. Twenty serum metal concentrations were measured. Least absolute shrinkage and selection operator (LASSO) penalized regression was used to identify independent associations between prenatal multiple metal exposure and testicular volume (TV), and anogenital distance (AGD). Adjusted estimates were then obtained using multiple linear regression analysis, and the regression tree method was used to explore the interactions. Boys in the highest quartile of prenatal lead exposure had a 0.064 mL (95% CI: −0.124, −0.004) smaller ln-transformed TV, 0.060 cm (95% CI: −0.110, −0.011) shorter ln-transformed anopenile distance (AGDap), and 0.115 cm (95% CI: −0.190, −0.039) shorter ln-transformed anoscrotal distance (AGDas) than boys in the lowest quartile (all Ptrend < 0.05). Chromium was inversely with ln-transformed AGDap (β = −0.078, 95% CI: −0.127, −0.030) and ln-transformed AGDas (β = −0.113, 95% CI: −0.188, −0.038), while stibium was positivity associated with ln-transformed AGDap (β = 0.091, 95% CI: 0.046, 0.136) and strontium was positivity associated with ln-transformed AGDas (β = 0.120, 95% CI: 0.051, 0.189) (all Ptrend < 0.05). And the critical window of vulnerability may be the late pregnancy (the second and third trimester). Moreover, we detected interaction effects between lead, chromium and stibium on AGDap; lead, chromium and strontium on AGDas. The results suggest that prenatal exposure to lead, chromium, stibium and strontium may affect TV and/or AGD in infant boys. Potential mechanisms for the complex metal interactive effects during vulnerable periods are worthy of further investigation.
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