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• Granitoids of Singhbhum Craton. • Two generation of TTGs at 3.42 and 3.32 Ga formed by melting of juvenile mafic crust. • Later K-rich, silicic granites at 3.28 and 3.25 Ga formed by melting of tonalites. • Recurring crustal melting in a gradually thickening oceanic plateau. • Final cratonisation of the Singhbhum Craton at 3.25 Ga. A significant part of many Archean cratons formed during Paleoarchean. Yet, the mechanism and tectonic setting of formation of Paleoarchean continental crust remain highly debated. In this contribution, we present field, petrographic, geochemical, zircon U-Pb age and Hf isotope data on Paleoarchean granitoids from west-central part of the Singhbhum Craton (Champua-Hat Gamharia corridor), India. The whole process starting from nucleation of a juvenile continent to its evolution and final stabilization is documented. The core of the craton nucleated with formation of 3.45–3.40 Ga TTGs showing juvenile character (zircon ɛHf t = +0.6 to +7.1). These rocks show slightly depleted HREE and Y, negligible Eu-anomaly (Eu/Eu* = 0.90 to 1.00) and moderate Sr/Y (25–64), consistent with derivation from a low-K mafic crust at a pressure near the lower end of the garnet stability field, causing subordinate garnet retention in the residue and negligible role of plagioclase. A second generation of TTG formation took place at 3.32 Ga in the area by deeper melting of a juvenile mafic crust (zircon ɛHf t = +1.3 to +5.7) as suggested by strongly depleted HREE and Y, and high Sr/Y (52–155) implying significant amount of garnet retention in the residue. Subsequently, the area witnessed intracrustal melting at 3.28 and 3.25 Ga which tapped moderately old to juvenile (zircon ɛHf t = −1.9 to +4.5), mostly TTG sources at variable depths generating potassic, LILE-enriched, high-silica granites. Intrusion of these potassic granites marks the final cratonization of the Singhbhum Craton. The sequence of events is interpreted in terms of repeated crustal melting and granitoid generation in a gradually thickening oceanic plateau with a progressive change in granitoid source from mafic to felsic in composition. A synthesis of rock assemblage, regional geological setting and structural pattern also supports intraplate nature of the magmatism in Singhbhum Craton, which might have been a significant mechanism of crustal growth worldwide during Paleoarchean. Further, a comparison of juvenile crustal growth and crustal reworking events of the Singhbhum and other Indian cratons show that these cratons record distinct evolutionary histories and were probably nucleated at different sites. [ABSTRACT FROM AUTHOR]

Variations of the stable Ca isotopic compositions (noted as δ44/40Ca relative to the SRM915a standard) of basalts are interpreted as effects of mantle sources. Mantle pyroxenites are a minor but integral part of the mantle and, as fusible components, they are important source rocks to understand chemical and isotopic heterogeneity in mantle-derived magmas. However, the effect of pyroxenites on the Ca isotopic composition of the mantle has been poorly constrained. To which extent mantle pyroxenites and their formation processes such as melt-peridotite reaction, particularly involving recycled crustal materials, lead to heterogeneity in δ44/40Ca of the mantle is unknown. Here, we report δ44/40Ca of different types of pyroxenites (spinel pyroxenites, garnet pyroxenites, and phlogopite-bearing spinel clinopyroxenites) and minerals separates, along with surrounding peridotites from Hannuoba xenoliths, North China Craton to address the issue. Initial 87Sr/86Sr ratio indicates that recycled crustal materials were incorporated into parental magmas of garnet pyroxenites (0.70391–0.70715) and phlogopite-bearing clinopyroxenites (0.7142–0.7149), consistent with previous conclusions from Sr-Nd isotopes. Overall, the δ44/40Ca of garnet pyroxenites ranges from 0.86‰ to 0.98‰ (average 0.90 ± 0.05‰, n = 10) and the host peridotites affected by the infiltrating melts from 0.87‰ to 0.93‰ (0.89 ± 0.04‰, n = 8). Each pair (n = 8) of garnet pyroxenite and host peridotite displays no measurable difference in δ44/40Ca. The spinel pyroxenites and phlogopite-bearing spinel clinopyroxenites also show similar δ44/40Ca (0.94 ± 0.06‰ and 0.98 ± 0.05‰, respectively). The indistinguishable δ44/40Ca among these different types of pyroxenites and surrounding peridotites suggest no obvious Ca isotope variations during silicate melt-peridotite interaction and fractional crystallization, even if recycled silicate materials were involved. These results indicate that the mantle source with variable proportions of pyroxenites in equilibrium conditions overall would show uniform δ44/40Ca. It implies that the basic magmas derived from such peridotite-pyroxenite source would display limited variations in δ44/40Ca, even if their radiogenic isotopes show strong heterogeneity. The conclusion is consistent with no systematic variations in the available δ44/40Ca of different basalt types such as DMM, EM1 and HIMU. However, garnets in mantle rocks of recent work and this study generally display heavier δ44/40Ca than co-existing clinopyroxenes, implying that melts generated by partial melting of mantle sources with abundant residual garnets may show lighter δ44/40Ca values than MORBs. [ABSTRACT FROM AUTHOR]

The deep carbon cycle requires tracers to understand carbon sequestration and mobility in the deep Earth. Recently, the use of metal stable isotopes has emerged as a promising and innovative approach to address element cycles, such as the use of magnesium and zinc isotopes to trace the magnesium carbonate cycle. However, despite the prevalence of calcium carbonate as the dominant sedimentary carbonate during the Phanerozoic era, its tracking through the use of metal stable isotopes has proven challenging. Here we show that deep subduction of Phanerozoic calcium carbonates can significantly decrease the δ44/40Ca value, while simultaneously increasing the δ66Zn value and 87Sr/86Sr ratio of the mantle. The Neogene Dalihu basalts in Inner Mongolia have high 87Sr/86Sr ratios, ranging from 0.7058 to 0.7063, which are positively correlated with Sr/Nd ratio, indicating the presence of sedimentary carbonate within their mantle source. The Dalihu basalts exhibit significantly lower δ44/40Ca values (0.51 to 0.70‰) but higher δ66Zn values (0.35 to 0.45 ‰) than the mantle. These low δ44/40Ca values cannot be attributed to partial melting, even when considering the jadeite effect. Our calculations indicate that adding 5–10% recycled calcium carbonate into the mantle source explains the high 87Sr/86Sr ratio and δ66Zn values but low δ44/40Ca values of the Dalihu basalt. Therefore, recycled calcium carbonate directly influences correlated Ca-Zn-Sr isotope variation, thereby providing compelling evidence for its role in the deep carbon cycle. Our findings suggest that combining metal stable isotopes with radiogenic Sr isotope is a powerful tracer of the deep carbon cycle. [ABSTRACT FROM AUTHOR]

Substantial quantities of sediments are known to enter the deep lithosphere at subduction zones, but the extent to which sediments melt and the process involved in sediment contribution to the deep lithosphere are inadequately understood. Vigorous debate continues about whether the subducted sediment component is terrigenous or pelagic and transported as a hydrous melt, an aqueous fluid, or bulk sediment. In this contribution, we conduct an integrated study on a variety of deep-seated xenoliths in the Neogene Hannuoba basalts from the northern margin of the North China Craton. Among these xenoliths, clinopyroxenite xenoliths are compositionally and isotopically distinct. Mineral chemistry shows that the clinopyroxenite xenoliths come from a depth near the MOHO, rather than from the mantle as suggested previously. The clinopyroxenite xenoliths have extremely evolved Sr-Nd-Hf isotopic compositions and are interpreted to have a late Archean protolith age. The extremely low contents of Cr and Ni for the clinopyroxenite xenoliths preclude a magmatic origin. Instead, a metasomatic origin is suggested, which is strongly supported for the clinopyroxenites by the occurrence of hydrous minerals and high contents of large-ion-lithophile elements (K, Rb, Ba, Th and Sr) and light rare earth elements, as well as elevated δ18O (9.9–11.3‰) and light δ26Mg (−1.04‰ to −1.42‰) isotopic compositions. Furthermore, their high high-field-strength element (Nb, Ta, Zr and Hf) contents indicate that the metasomatic agent is a hydrous melt, rather than an aqueous fluid. The metasomatic melts are considered to be derived from a mixed source of sedimentary carbonates and ancient, felsic continental materials. A combination of zircon ages and oxygen isotope data for the clinopyroxenite xenoliths further restricts the timing of metasomatism to the late Paleozoic. Considering the regional tectonic setting, the sediments most likely came from the subducted Paleo-Asian oceanic slab. Thus the Hannuoba clinopyroxenite xenoliths provide direct evidence for melting of the subducted Paleo-Asian oceanic slab sediment and its interaction with the deep lithosphere. The data show that melting of subducted sediments can take place at a much shallower depth than commonly thought and place an independent constraint on future models of slab geotherms. [ABSTRACT FROM AUTHOR]

Abstract Mechanisms of lithospheric transformation beneath the North China Craton (NCC) were widely discussed, but the northern NCC was less studied compare to the eastern part. In this research, In-situ major and trace element and Sr isotopic compositions of spinel peridotite and pyroxenite xenoliths carried by the Yangyuan Tertiary basalt were analyzed to constrain subduction style of the Paleo-Asian oceanic plate (PAOP) and its influence on the northern NCC. These xenoliths were classified into dunite, pyroxenite, and two groups of lherzolites according to their petrography and chemical features. The petrography and mineral chemistry suggest that the dunite, pyroxenite, and Group 1 lherzolites are residues of partial melting which experienced subsequent hydrous metasomatism. Correlations between 87Sr/86Sr with the Zr/La and Zr/Nb ratios in clinopyroxenes from these xenoliths suggest that the metasomatic agents should be fluids derived from the subducted PAOP. Mineral Rb Sr isochron of the pyroxenite show that the minimum age of the metasomatism event should be 295 ± 38 Ma. Major element compositions of minerals in the Group 2 lherzolites are more fertile compare to the dunite and Group 1 lherzolites. Clinopyroxenes in these xenoliths exhibit LREE-depleted REE patterns with relatively high HREE contents and 87Sr/86Sr ratios (0.70403–0.70482). Chemical zonations are preserved in several clinopyroxenes with incompatible elements depleted from core to rim, which should be the results of melt depletion after metasomatism. Patches of silica-rich glasses were present along the grain boundaries. These glasses have sediment-like Pb isotopic compositions and trace elements distribution patterns and thus are supposed to represent the melt from recycled sediments. Combined with geophysical and tectonic evidences, we propose that roll-back of the southward low-angle subducted PAOP in the late stage of subduction contributed to remelting of the PAOP subduction-modified mantle wedge beneath the northern NCC. Highlights • The Yangyuan basalt-borne xenoliths record subduction related metasomatism • Rb Sr isochron gives the minimum age of 295 ± 38 Ma for the metasomatism event. • Slab roll-back resulted in remelting of the subduction-modified mantle wedge. • Patches of silica-rich glass were derived from the subducted sediment diapirs. [ABSTRACT FROM AUTHOR]

The processes responsible for the origin and evolution of Early Archean continental crust are not properly understood. Questions regarding the pattern of crustal growth (episodic vs. continuous) and the role of crust-mantle interaction in the temporal change of crustal composition and thickness are still being widely debated. In order to address the above issues, we present whole-rock geochemistry and detrital zircon U-Pb-Hf isotopes, and trace-element data from Mesoarchean clastic rocks of two selected greenstone belts of western Dharwar Craton. The mineralogically mature character of the sampled sandstones along with their high K 2 O/Na 2 O, Rb/Sr and CIA values, relatively enriched concentrations of La and Th over Cr and Sc, variably negative Eu-anomaly, and high U/Yb values of detrital zircons are indicative of their derivation from strongly weathered stable continental provenance dominated by low-HREE TTGs and K-rich granites of shallow crustal origin. Detrital zircon U-Pb ages indicate the maximum age of deposition for these sandstones is ∼3.1 Ga. The detrital zircon U-Pb and Lu-Hf data suggest two major crust formation events at 3.54–3.33 Ga and 3.27–3.12, mainly via juvenile crustal addition and subsequent rapid reworking. Besides, ∼3.6 Ga detrital zircons with negative εHft values suggest that the antiquity of the western Dharwar Craton can be traced back at least up to 3.8 Ga. Reworking of the older continental crust occurred during ∼ 3.25 Ga and ∼ 3.15–3.07 Ga, the last one represented by emplacement of K-rich granites. Zircon trace element ratios indicate a maximum increase in crustal thickness at ∼3.2 Ga followed by a crustal thinning at around ∼3.15 Ga. The detrital record in combination with geological setting suggests an episodic crustal growth and reworking in the western Dharwar Craton during Paleoarchean to early Mesoarchean period which was possibly related to intraplate processes. • Juvenile crust in Western Dharwar Craton formed at 3.54–3.33 Ga. • The juvenile crust reworked during 3.27–3.12 Ga. • Reworking of older crust occurred at ∼3.25 Ga, ∼3.15–3.07 Ga and ∼ 3.02 Ga. • Maximum crustal thickness attained at ∼3.2 Ga followed by thinning up to ∼3.1 Ga. • Link between crustal thickening and partial convective overturn is suggested. [ABSTRACT FROM AUTHOR]

Although Mesozoic granites are widely distributed in the Gan-Hang Belt in Southeast China, their petrogenesis and geodynamic settings are still matters of dispute. Here, the major and trace elements, Sr-Nd isotopic compositions, zircon U‐Pb dating and Hf isotopes of three late Mesozoic granite plutons from Machebu, Shenzhongwu and Daixi in northern Zhejiang Province were analyzed to investigate their petrogenesis. These granite plutons are featured by an A2-type granite geochemical signature (e.g., high SiO 2 (71 to 78 wt.%), total alkalis (Na 2 O + K 2 O = 7.57 to 9.12 wt.%), rare earth elements (total REE = 174 to 519 ppm) and HFSE contents, with mostly high FeO T /(FeO T + MgO) (0.82 to 0.93) and Ga/Al ratios (2.49 to 5.07) and low Ce 4 + /Ce 3 + ratios in zircons (1 to 90)), suggesting they were formed in an extensional tectonic setting. Combining whole rock Zr contents, mineral assemblages and the An content of plagioclase, it was suggested that these granites could have formed at a high temperature (> 850 °C) with a low H 2 O content (~ 2.5 wt.%). Assuming the granite with the lowest SiO 2 and high CaO contents as the “primary granite melt”, the melting pressure was estimated to be 2.5 kbar based on model calculations using MELTs. Taking into account the effect of plagioclase fractional crystallization during the granite emplacement into shallow crustal levels, the initial melting pressure could be > 2.5 kbar at the stable field of plagioclase. This agrees well with the very low and variable Sr and Eu contents of these granite plutons. Zircon U–Pb dating yields a weighted mean 206 Pb/ 238 U age of 130.9 ± 1.0 Ma for the Machebu granite, 134.4 ± 2.1 Ma for the Shenzhongwu granite and 131.9 ± 1.2 Ma for the Daixi granite. The ε Hf (t) values of the zircons in these plutons gradually increase from southwest to northeast, i.e., from − 14.5 ~ − 3.5 for the Machebu granite to − 1.5 ~ − 0.2 for the Shenzhongwu granite and from 5.1 ~ 8.6 for the Daixi granite, suggesting the origin of different parent rocks. These granites have two-stage Nd model (T DM2 (Nd)) ages of 1099 Ma–838 Ma, and zircons from these granites and the Neoproterozoic basement in the Gan-Hang Belt plot on the same evolutionary trend in the ε Hf (t)-age diagram. It is interesting to note that the collection of literature data shows a positive correlation between SiO 2 and ε Nd (t) for the late Mesozoic A-granites in the Gan-Hang Belt, and the Neoproterozoic A-granites in the Gan-Hang Belt cluster in two groups of the high-SiO 2 -ε Nd (t) group and low-ε Nd (t) group. The positive correlation of SiO 2 -ε Nd (t) demonstrated by the late Mesozoic A-granites can be well explained by a high-degree of melting of mixtures between the two groups of Neoproterozoic A-granites. We thus suggest that the late Mesozoic A-type granites in the Gan-Hang Belt could have been derived from the rejuvenated Neoproterozoic rocks rather than directly from the Mesoproterozoic metamorphic basement as a result of subduction. [ABSTRACT FROM AUTHOR]

Palaeoarchaean granitoids are exposed over wide area in the Singhbhum craton whose origin and role in crustal evolution are not well constrained. This study presents whole-rock and mineral chemical data coupled with zircon U-Pb dating and Hf isotope results on such granitoids from the central part of the craton to understand their petrogenesis, tectonic setting and role in continental crustal evolution. The first phase of granitoid magmatism in this area is represented by a 3.47 Ga Na-rich, gneissic tonalite belonging to the Archaean TTG (tonalite-trondhjemite-granodiorite) suite. This rock is characterized by high-HREE (heavy rare earth elements), negative Eu anomaly, low Sr/Y ratio and positive zircon Hf isotope signature (εHf t = +2.1 to +4.8). It is interpreted to be formed by shallow melting of a juvenile mafic source. At 3.35 Ga a silicic, ferroan porphyritic biotite granite formed. It shows variable K/Na, low Y and high Sr/Y, moderately fractionated HREE and positive zircon εHf t (+1.8 to +4.0), and is explained as a product of high-temperature melting of a heterogeneous, juvenile source consisting of tonalites and mafic rocks at lower crustal depth. The final phase of granitoid magmatism is marked by a 3.30 Ga non-porphyritic ferroan, silica-rich biotite granite. Geochemical characteristics like moderately high K, moderately fractionated HREE, low Ca and Sr/Y, and zircon εHf t (+0.8 to +3.7) suggest that the granite was formed by high-pressure melting of a tonalite-dominated source with short crustal residence. All the three granitoid phases display low Mg, Ni and Cr contents and magnesium number (Mg#) precluding direct involvement of mantle in their origin. Rather, crustal reworking caused by episodic plume-related mafic-ultramafic magma underplating and intraplating in an oceanic plateau setting is suggested as the possible mechanism for formation of the granitoids. Successive crustal reworking events involved progressively greater amount of previously formed felsic crust generating more evolved, K-rich granitoids. It appears to be a globally important process which led to effective crustal differentiation and maturing of the cratons during Palaeoarchaean. [ABSTRACT FROM AUTHOR]

Subduction and collision are the key processes triggering geochemical refertilization of the lithospheric mantle beneath cratons. However, the way that the subducted plate influences the cratonic lithospheric mantle remains unclear. Here, in-situ major and trace-element and Sr isotopic compositions of peridotite and pyroxenite xenoliths carried by the Dongbahao Cenozoic basalts, located close to the northern margin of North China Craton (NCC), were examined to investigate the effects of the subducted Paleo-Asian oceanic plate on the lithospheric mantle of the NCC. Based on petrographic and geochemical features, peridotites were subdivided into two types recording two-stage metasomatism. Clinopyroxene (Cpx) in both types of peridotites show chemical zoning. In those peridotites we refer to as Type 1 peridotites, Cpx exhibit uniform convex-upward rare earth element (REE) patterns but core-rim variations in 87 Sr/ 86 Sr ratios (0.7065–0.7082 in the cores and 0.7043–0.7059 in the spongy rims), and have high (La/Yb) N ratios (> 1.12) (N means normalized to chondrite), relatively low Ti/Eu ratios (< 3756) and negative high field strength element (HFSE) (Nb, Ta, Zr, Hf and Ti) anomalies in the cores, indicating early-stage metasomatism by carbonatitic melts derived from the subducted sedimentary carbonate rocks. Cpx in the Type 2 peridotites have highly variable REE patterns (from light rare earth element (LREE)-depleted to LREE-enriched) and feature zoned Sr isotopic compositions contrasting to those in Type 1, i.e., increasing 87 Sr/ 86 Sr ratios from the cores (0.7020–0.7031) to the spongy rims (0.7035–0.7041). Accompanying variations of 87 Sr/ 86 Sr ratios, Cpx in both types of peridotites display increasing Nb/La ratios from the cores to the spongy rims. In addition, Cpx in the Type 2 peridotites show remarkably increased (La/Yb) N , Ca/Al, Sm/Hf and Zr/Hf ratios but decreased Ti/Eu and Ti/Nb ratios from the cores to the spongy rims. These features imply a later-stage metasomatism by CO 2 -rich silicate melts derived from carbonated eclogites. Pyroxenites were also classified into two types. Both types of pyroxenites show higher Ni content in Cpx and orthopyroxene than peridotites at the same Mg# (= 100 ∗ Mg/(Mg + Fe), atomic number) level. Their Cpx show high Ti/Eu, Ti/Sr ratios and similar 87 Sr/ 86 Sr ratios (0.7039–0.7055) to the Cpx spongy rims in peridotites, suggesting that pyroxenites originated from silicate melt-peridotite reactions in the later-stage metasomatism. These observations collectively indicate that the lithospheric mantle beneath the northern NCC presents evidence for two distinct mantle metasomatic events. We propose that both were caused by the subduction of the Paleo-Asian oceanic plate, which could have contributed significantly to the transformation of the lithospheric mantle beneath the northern NCC. [ABSTRACT FROM AUTHOR]

An integrated study of zircon U–Pb ages and Hf–O isotopic compositions, whole rock elemental and Sr–Nd isotope geochemistry was conducted on three lithologically diverse middle Jurassic plutons from the Eastern Hebei area of the North China Craton (NCC), in order to reveal both their petrogenesis and possible tectonic affinity. The three plutons have consistent magmatic zircon U–Pb ages from 167 ± 1 Ma to 173 ± 1 Ma. The Nianziyu pluton has typical characteristics of appinite with low SiO 2 (43.7–52.6%), high Ca, Mg, Fe and H 2 O contents. It possesses subduction-related trace element patterns, enriched Nd–Hf isotopic signatures as well as elevated zircon δ 18 O values (6.2–7.2‰), arguing for an enriched mantle source metasomatized by fluids related to subduction. The Shuihutong monzogranites have high silica (SiO 2 = 75.4–75.9%) and alkali contents, low Ca contents and striking negative Ba, Sr and Eu anomalies. Samples from the pluton have more evolved Nd–Hf isotopic values and are considered to be most likely derived from anatexis of ancient lower continental crust. Hybridization between mantle- and ancient lower crust-derived magmas is proposed for the mafic microgranular enclave-bearing Baijiadian granitoids, which are characterized by variable ε Nd (t) and ε Hf (t) values. Integrated with the regional geologic history, we suggest that the formation of the three middle Jurassic plutons were related to the subduction of the Paleo-Pacific ocean plate beneath the NCC. Their petrogenetic differences reflect complex magmatic processes in subduction settings involving melting of multiple sources, possible partly facilitated by fluid metasomatism and water-rich magma injection, accompanied with various degrees of magma mixing. The appearance of middle Jurassic appinitic rocks leads us to propose that the NCC destruction and lithosphere thinning were facilitated and controlled by the weakening of the lithospheric mantle after hydration because of the subduction of the paleo-Pacific ocean plate. The lower crust of the craton was also reactivated at the same time due to the subduction. [ABSTRACT FROM AUTHOR]

It has been advocated that the stagnant Pacific slab within the mantle transition zone played a critical role in the genesis of the Cenozoic basalts in the eastern part of the North China Craton (NCC); however, it is not clear whether this recycled oceanic crust contributed to the chemical makeup of the Cenozoic basalts in the Trans-North China Orogen (TNCO, the central zone of the NCC). Here, we show that Cenozoic basalts from the TNCO are featured by low CaO contents, high TiO 2 and FeO T contents and high Fe/Mn and Zn/Fe ratios, indicating a mantle source of pyroxenite. Temporally, these basalts evolved from alkali basalts of Late Eocene–Oligocene age to coexisting alkali and tholeiitic basalts of Late Miocene–Quaternary age. Spatially, their isotopic and chemical compositions vary symmetrically from the center to both the north and the south sides along the TNCO, i.e., SiO 2 contents and 87 Sr/ 86 Sr ratios increase, FeO T contents and 143 Nd/ 144 Nd, Sm/Yb and Ce/Pb ratios decrease. The estimated average melting pressure of the TNCO tholeiitic basalts (~ 3 GPa) agrees well with the present lithosphere thickness beneath the north region of the TNCO (~ 90–120 km). The temporal and spatial chemical variations of Cenozoic basalts in the TNCO suggest that the recycled oceanic crust in the mantle of the TNCO is mainly related to the southward subduction of the Paleo-Asian oceanic plate and the northward subduction of the Tethyan ocean plate. The westward subduction of Pacific slab may not have contributed much than previously thought. [ABSTRACT FROM AUTHOR]

In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of 204 Hg on 204 Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for 20x Pb/ 204 Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for 20x Pb/ 206 Pb and <0.06% (RSD, k = 2) for 20x Pb/ 204 Pb with the exception of 20x Pb/ 204 Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g −1 ) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g −1 ). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol. [ABSTRACT FROM AUTHOR]

Archean cratons display spatial and temporal changes in the composition and thickness of the crust, which has important implications for intracrustal differentiation, attainment of long-term stability, and operation or absence of plate tectonics. The geodynamic reason(s) for these changes, though, is a controversial subject. To address this issue, the present contribution investigates the spatial and temporal changes in granitoid compositions of the well-exposed Singhbhum Craton. It reports new zircon U-Pb and Lu-Hf, and whole-rock geochemical data on Paleoarchean granitoids from some of the less-studied parts of the Singhbhum Craton. The new information is then collated with previously reported data from the central part (cratonic core) of the Singhbhum Craton to illustrate the spatial and temporal changes in granitoid chemistry, using selected major oxide and pressure-sensitive elemental ratios. Temporal changes in the characteristics of the granitoids suggest that the crust building in Singhbhum Craton possibly started in a relatively thin oceanic plateau with the emplacement of low-pressure TTGs and diorites during ∼3.53–3.47 Ga. The ∼3.47–3.42 Ga period marks a gradual increase in crustal thickness, inferred from progressively increasing Al 2 O 3 and pressure-sensitive trace element ratios of the TTGs. Subsequently, as a result of protracted mantle upwelling and consequent juvenile TTG addition, the composition of the bulk continental crust differentiated into a more evolved felsic composition by ∼3.35 Ga, when the first potassic granite was emplaced. Spatial distribution of the granitoids suggests partial convective overturn (contemporaneous sinking of greenstones and diapiric rise of shallow- to mid-crustal granitoid domes) played a role in bringing the older as well as juvenile TTGs to a melting depth, generating ∼3.35–3.25 Ga spatially restricted high-silica, high-potassic, low-pressure K-rich granite and transitional granitoid domes. TTG magmatism also continued contemporaneously during this period. During ∼3.33–3.32 Ga, continental crust in Singhbhum Craton reached the maximum thickness, inferred from the formation of high-pressure (or low-HREE) TTGs. Afterward, possibly delamination of dense lower crustal residue caused the crust to become thinner, as recorded by progressively low-pressure K-rich granite and transitional granitoid emplacement until ∼3.28 Ga. Near the end of Paleoarchean (∼3.26–3.25 Ga), the crust became thicker again, further yielding high-pressure TTGs and K-rich granites. We suggest an oceanic plateau-like setting (characterized by relatively inefficient heat extraction compared to a modern-day subduction zone) where plume magmatism and delamination of anatectic residues of crustal melting caused the time-transgressive thickening and thinning of the continental crust, respectively. This process resulted in change in melting depth and, in turn, in the granitoid chemistry. Therefore, the Paleoarchean crustal architecture and the bulk crustal composition of the Singhbhum Craton controlled the temporal change in granitoid chemistry in an ongoing tectonic regime (partial convective overturn-dominated setting) without any distinct tectonic shift. [ABSTRACT FROM AUTHOR]

[Display omitted] • Linglong and Guojialing granitoids were strongly depleted in S and Au. • Mafic magmas underplated in Jiaodong before 130 Ma were also poor in S and Au. • Magma underplating had not enriched the Jiaodong lower crust in sulfides and Au. • The crust was unlikely to be the primary Au source of the Jiaodong gold deposits. Mantle-derived magmas widely underplated the lower crust of eastern North China Craton (NCC) during the large-scale extension in the Mesozoic. The giant Jiaodong gold deposits formed at 120 ± 5 Ma, slightly later than the extensive magma underplating. It remains poorly constrained whether the magma underplating had pre-enriched the crust in significant sulfides and gold (Au) via sulfide accumulation, facilitating subsequent regional Au mineralization in the Jiaodong. In this study, we applied high-precision methods to determine the concentrations of S, Cu, Ag, and Au in the Mesozoic mafic and felsic igneous rocks related to the Jiaodong gold deposits. The studied samples include Guojialing granodiorites (n = 7) and their coeval mafic microgranular enclaves (MMEs, n = 13), as well as two Linglong granites. The Linglong and Guojialing granitoids display no sulfides and extremely low Au concentrations, so they are unlikely to be the major Au source. The MMEs resulted from Mesozoic magma underplating and related magma mixing at ∼130 Ma. The MMEs are also free of sulfides and show remarkably low concentrations of S, Cu, Ag, and Au. The S concentrations of MMEs are far lower than those required for sulfide saturation. This indicates that the S- and Au-depleted nature of MMEs was unlikely caused by sulfide segregation of sulfide-saturated magmas but inherited from the S- and Au-poor parental magmas. Therefore, the mantle-derived mafic magmas in the Jiaodong Peninsula, which had underplated the lower crust before 130 Ma, probably have not led to the extensive sulfide accumulation and gold pre-enrichment in the deep crust. [ABSTRACT FROM AUTHOR]

Lunar mare basalts provide a probe to study the magmatic and thermal evolution of the Moon. The Chang'e-5 (CE-5) mission returned samples from a young and hitherto unsampled mare terrain, providing fresh opportunities to understand lunar volcanic history. A detailed petrologic survey was conducted in this study on basalt fragments and glasses from the returned CE-5 soil samples. Relatively large-sized (100–400 μm) basaltic fragments were hand-picked and examined for texture, mineral assemblage and mineral chemistries. Basaltic fragments exhibit dominantly subophitic textures and are phenocryst-free, with low to intermediate-Ti (2.1–5.5 wt%) and low Mg# (Mg/(Mg + Fe) × 100, 19–47, with an average whole-rock Mg# of 33) consistent with olivine-melt equilibrium calculation (Mg# = 34). A range of highly evolved basaltic materials have been identified, in which abundant fayalitic olivine, symplectitic intergrowths, and Si + K-rich mesostasis co-exist were found resulting from late-stage silicate liquid immiscibility. Basaltic glass compositions largely overlap with basaltic fragment compositions suggesting they are locally derived. The CE-5 basalts have a relatively limited range of eruption temperatures of 1150–1230 °C. Based on their petrographic and geochemical characteristics, some CE-5 mare basalts are highly evolved and some of the resultant basaltic melt products underwent high crystallization. Thermodynamic modeling using MELTS suggests highly evolved basaltic magma was produced by a low-pressure and simple fractional crystallization under reduced conditions. This may have occurred at the surface in the inflated Em4/P58 flow with a thickness of ~50 m. The low degree of partial melting mantle source of the parental melts is the late-stage lunar magma ocean cumulates in a similar manner to some evolved low-Ti mare basalt meteorites, although the source of CE-5 basalts may have been slightly more Ti-rich. • Young low to intermediate-Ti basaltic lavas of the Chang'e-5 site are highly evolved, with average Mg# = 33 • Some basalts show silicate liquid immiscibility (SLI) textures underwent significant fractional crystallization • Relatively low-pressure (1 bar to 5 kbar) simple fractional crystallization under reduced conditions could produce the highly evolved magma • The crystallization of the CE-5 basalts leading to the compositions and the SLI textures are likely to have occurred in the 50 m thick Em4/P58 flow that CE-5 sampled [ABSTRACT FROM AUTHOR]

Complete dissolution is essential for achieving accurate analytical results for geological samples. Hydrofluoric acid is the most effective mineral acid for breaking up strong Si–O bonds to form SiF6 −2 ions in acidic solution. However, HF is rather inefficient in the open-vessel acid digestion of refractory minerals such as zircon due to its low boiling point (boiling point of 38.3% HF=112°C). In this study, a decomposition technique using the solid compound NH4F in an open vessel (Savillex Teflon vial) has been investigated for the multi-element analysis of various rock reference materials. The higher boiling point (260°C) of NH4F allows for an elevated digestion temperature in open vessels, which enables the decomposition of refractory phases. Using this method, Zr was completely recovered from the granodiorite GSP-2 reference material in 1–1.5h at 250°C, which is ~12 times faster than using conventional closed-vessel acid digestion at 190°C (high-pressure PTFE digestion bomb). There is a positive correlation between the test sample mass and the amount of NH4F required for complete recovery of Zr, Hf, Nb, Ta, and heavy rare earth elements in GSP-2, which is due to the resistance of zircon (which is a major reservoir for heavy rare earth elements) to decomposition at lower reagent to sample ratios. The recommended proportion of NH4F, relative to the amount of sample powder required for complete element recovery, is 6:1. Unlike in NH4F-assisted high-pressure acid digestion, our results clearly indicate that adding HNO3 severely inhibited the digestion capabilities of NH4F for refractory minerals such as zircon in open vessels. The most outstanding advantage of the new method is that the digestion can be performed in a conventional Savillex Teflon vial instead of a high-pressure PTFE digestion bomb. Moreover, NH4F−open-vessel acid digestion is not hampered by the formation of insoluble fluorides, which represents another important advantage of this new sample decomposition method. Similar to HF and HNO3, ultra-pure NH4F can be produced using a conventional PFA sub-boiling purification system, and it does not induce new interference species in ICP-MS analysis. Additionally, this reagent is removed by taking the sample to dryness, which is important to keep the total dissolved solid of the final solution presented to the instrument low. NH4F has many of the same safety handling requirements of HF, especially when being heated to dryness to remove the Si as SiF4, and excess reagent as HF, so safety issues are still a concern. The developed NH4F−open-vessel acid digestion method has been successfully applied to the digestion of a series of international geological reference materials. This simple, effective, and comparatively safe dissolution method shows great potential for the digestion of geological samples. [ABSTRACT FROM AUTHOR]

Alkaline magmas play a key in understanding crust-mantle interaction and deep carbon recycling. Here, petrography and in situ mineral analyses of evolved alkaline rocks from the North China Craton are reported to decipher mantle metasomatism by recycled carbonated sediments via reconstruction of primary magma composition. The alkaline rocks are nepheline syenites for which new, consistent zircon and titanite U Pb ages of ~235 Ma are presented. The rocks are highly evolved (SiO 2 = 58.1–60.0 wt%) with negative anomalies for Sr, Ba, Ti, P and Eu, and relative depletion of MREE, indicating fractional crystallization of feldspar, apatite, titanite and amphibole. Core-rim variation of 87Sr/86Sr (0.7052–0.7092) of late-crystallized low Mg# clinopyroxene and feldspar are attributed to crustal assimilation. The origin of primary alkaline magma is recorded in early high Mg# (70–84) clinopyroxenes with weak Eu anomalies (Eu/Eu* = 0.94–1.29), suggesting that they crystallized from a little-differentiated mantle-derived magma (Mg# > 60). Their variable 87Sr/86Sr ratios (0.7031–0.7060) correlate positively with Sr/Y and (La/Yb) N and negatively with Ti/Eu ratios, but are not correlated with Mg# or Eu/Eu*. Moreover, the REE patterns of melt equilibrated with high 87Sr/86Sr clinopyroxene is similar to coeval alkaline rocks from adjacent areas. These features indicate that the primary alkaline magma was derived from the mixing of depleted mantle and enriched mantle metasomatized by carbonatite melts from subducted crustal materials. Low zircon ε Hf (t) values (−1.4 to −2.8) imply that the subducted crustal material was carbonated sediments. Calcite and CO 2 inclusions occur in early-crystallized olivine, clinopyroxene and zircon, and amphibole and fluorapatite both reveal a volatile-rich (H 2 O, F and CO 2) alkaline magma derived from mantle enriched by carbonate metasomatism. The mineral archives of alkaline rocks not only record mantle metasomatism by recycled carbonated sediments, but also fractional crystallization and assimilation during magma evolution. [ABSTRACT FROM AUTHOR]

The oxygen fugacity of a magma controlling element distribution and mobility is influenced by multiple factors including source composition and magmatic processes (e.g., assimilation and degassing). Here, whole-rock and in situ mineral analyses of the alkaline complex from the northern North China Craton are reported to investigate the influence of source composition and magmatic processes on the evolution of the melt oxidation state. The alkaline complex comprises orthoclase pyroxenites, pyroxene syenites, and syenites with similar mineral assemblages and trace element patterns. Consistent zircon and titanite U-Pb age of ~234 Ma is presented for the alkaline rocks. Their high large ion lithophile elements content, negative high field strength element anomalies, and high 87Sr/86Sr ratio suggest a metasomatized mantle origin by recycled crustal material. Magnetite and hematite inclusions were found in the early-crystallized minerals including clinopyroxene and apatite. Fluorapatites are characterized by high S (SO 3 up to 0.64 wt%) and low Mn contents, with estimated ΔFMQ higher than +3. These features together indicate a primary oxidized magma inherited from the metasomatized mantle. However, inclusion-rich fluorapatites with decreasing S and increasing Mn content from the core to the rim were found in some pyroxene syenites. Moreover, the S content of inclusion-rich fluorapatite from these pyroxene syenites is lower than that of other rock types in the complex, which may correspond to a decrease in oxygen fugacity of ~2.5 log units. These features suggest that the oxidized magma was later transformed into reduced magma. Oriented Cu-rich sulfide in inclusion-rich fluorapatite formed during the reducing event. δ65Cu of the pyroxene syenite with inclusion-rich fluorapatite (−0.06 to −0.24‰) and sulfides in fluorapatite (−0.26‰) are lighter than those of other rock types (+0.30 to +0.43‰), suggesting that the sulfides were derived from extraneous materials via magma assimilation. Variable and high 87Sr/86Sr ratios (0.7071–0.7085) in titanites and high-207Pb/206Pb rims of zoned K-feldspar in the pyroxene syenite imply that the reduced extraneous materials were derived from ancient crust. Overall, in situ mineral analyses and Cu isotopes indicate a direct link between the transformation of alkaline magma from an oxidized to a reduced state with source composition and magmatic processes, and improve our understanding of element mobility and distribution. • Oxidized alkaline magma derived from metasomatized mantle by carbonated melts. • Varied S and Mn in apatite imply the transformation of oxidized magma to reduced. • Sr–Pb–Cu isotopes suggest the redox changes induced by magma hybridization. • Redox state of alkaline magma control element mobility and mineralization. [ABSTRACT FROM AUTHOR]

• Crustal xenoliths trapped by Guojialing granodiorites display rather low Au contents. • The Precambrian metamorphic outcrop rocks also show low Au contents. • The metal contents are consistent with the metamorphic devolatilization model. • The Precambrian basement was not the main Au source for Jiaodong giant gold deposits. The Jiaodong gold deposits, eastern China define a giant gold province in the Precambrian high-grade metamorphic crustal basement. Given the early metamorphism, the crustal basement would have been so depleted in gold that cannot be the main source for the later Mesozoic gold deposits. However, previously reported gold contents from crustal rocks were variably high (e.g., >5–10 ppb) and often interpreted to reflect the contribution of crustal basement. In this study, after careful field sampling, we obtained high-precision Au and S contents (with Cu and Ag for many samples) to solve the controversial issue. The Au contents were determined by internal standardization to platinum which was obtained from isotope dilution via high-sensitivity Element XR, and/or another independent method by GFAAS after polyurethane foam pretreatment. These methods achieved low procedural blanks (<0.02 ppb) and reliable analyses of low-Au samples. The analyzed metamorphic crustal rocks are from surface outcrops (n = 30) and crustal xenoliths (n = 10) in the Jiaobei terrane, where hosts the predominant Jiaodong gold resources (>85% of 5000 t). The Archean and Paleoproterozoic metamorphic outcrop rocks were sampled far from gold deposits and faults with the minimum effect of ore-forming fluids, and they display overall low Au contents (0.20 ± 0.18 ppb and 0.47 ± 0.29 ppb, respectively). More importantly, the crustal xenoliths trapped in pre-mineralization Guojialing granodiorites were not affected by hydrothermal overprint and better reflect the pristine features of the metamorphic basement. Although the crustal xenoliths contain variable sulfides with a wide range of Cu, Ag and S contents, they show rather low Au contents (0.18 ± 0.15 ppb). These results indicate the strong depletion of Au contents in the Precambrian crustal basement, consistent with the metamorphic devolatilization model. The Precambrian metamorphic crustal basement thus was rather difficult as the main gold source for the Jiaodong gold deposits, suggesting alternative sources. [ABSTRACT FROM AUTHOR]

Carbonates in subducting oceanic slabs can survive beyond slab dehydration and be transferred into the deep mantle. Such deep carbon cycling plays a critical role in generating carbonatitic to alkaline melts. However, whether and how this process has influenced the lithospheric mantle still remains enigmatic. To address these issues, here we provide a detailed petrographic, in-situ chemical and Sr isotopic study on two mantle xenoliths (a wehrlite and a melt pocket-bearing peridotite) entrained by the Changle Miocene basalts from the eastern China. The Changle wehrlite contains carbonate melt inclusions and apatites and is merely enriched in clinopyroxene relative to the Changle lherzolites. The clinopyroxenes are characterized by high (La/Yb) N (4.7–41) and low Ti/Eu (873–2292) ratios and equilibrated with carbonated silicate melt-like compositions. These petrographic and chemical features indicate that the wehrlite was formed by reaction between peridotite and carbonated silicate melts. On the other hand, the Changle melt pocket-bearing peridotite is suggested to have been produced by in-situ melting/breakdown of amphiboles of an amphibole-rich dunite. Low olivine Fo (~89), presence of amphiboles with high (La/Yb) N (~50) and low Ti/Eu (~1070) ratios suggest that such amphibole-rich dunite would have been formed by reaction of peridotite with hydrous alkaline basaltic melts from a carbonated mantle. Our data, combined with previously reported data of the Changle lherzolite xenoliths, unravel a series of mantle metasomatisms by carbonatitic to alkaline melts from carbonated mantle sources. The consistently high 87Sr/86Sr ratios (up to 0.7036) of the clinopyroxenes in both the wehrlites and lherzolites indicate the carbonate components in the mantle sources were derived from the stagnant Pacific slab within the Mantle Transition Zone. This study provides a fresh perspective on the role of deep carbon cycling from subducted oceanic slabs in chemical modification of intracontinental lithospheric mantle through reaction with different types of melts. • In-situ chemistry and Sr isotopes of two Changle peridotite xenoliths are studied • The wehrlite was formed by carbonated silicate melt-peridotite reaction • The melt-pocket bearing peridotite recorded alkaline melt-peridotite reaction • Recycling of carbonate-rich components from the stagnant Pacific slab in the MTZ • Significance of deep carbon cycle on chemical modification of lithospheric mantle [ABSTRACT FROM AUTHOR]

• The Fe speciation data help bridge the global data gap of Fe species gap during 1500–1400 Ma. • The global Fe speciation data suggest underestimated oxic depositional conditions during the Mesoproterozoic. • Oxic environment could have provided suitable habitats for complex eukaryotes and their subsequent evolution. The Mesoproterozoic (1600–1000 million years ago, Ma) is thought to have experienced important changes in ocean chemistry and eukaryote evolution. Our understanding of global redox conditions remains in its infancy, and redox data derived from the Mesoproterozoic thus far indicate heterogeneity and complexity in the realm of ocean redox, which hampers our understanding of the potential significance of variations in ocean redox on eukaryote evolution. In this study, we report analyses of Fe species and redox-sensitive trace metals of U and Mo from the Jixian Group, including the Wumishan, Hongshuizhuang and Tieling formations, as well as the Xiamaling Formation, in the Yanshan Basin in North China. The Fe speciation data from the Wumishan, Hongshuizhuang, and Tieling formations first reported in this study help bridge the global data gap of Fe species data during 1500–1400 Ma. Our data suggest likely oxic bottom water conditions for the Wumishan Formation and ferruginous bottom water conditions for the Tieling Formation. The Fe species data can distinguish ferruginous conditions for the upper Hongshuizhuang from sulfidic depositional conditions for the lower-middle Hongshuizhuang Formation. Based on Fe species and trace metal data, redox conditions likely varied from anoxic conditions with transient euxinia in the lower-middle Xiamaling Formation to oxic conditions in the upper Xiamaling Formation. The new Fe speciation data from the Yanshan Basin, when combined with previously published data, show a surprisingly high proportion of middle Proterozoic samples with very low highly reactive to total iron ratios. This suggests either a relatively large extent of oxic seafloor, or non-uniformitarian iron cycling. Resolving this discrepancy will be key to understanding the extent of suitable habitats for complex eukaryotes. [ABSTRACT FROM AUTHOR]

• Rutile xenocrysts were captured from the basement by the Yangyuan carbonatites. • The Zr-in-rutile thermometer records formation of the rutiles at 743–932 °C. • Cr and Nb contents and Hf isotopes in rutiles support pelitic granulite protoliths. • U-Pb rutile cooling ages peak at 1810 ± 4 Ma, 1735 ± 5 Ma, and 1673 ± 8 Ma. • In combination with dating results from other systems yields episodic cooling path. The amalgamation of the North China Craton along the Trans-North China Orogen at ~1.85 Ga has been widely discussed, but its thermal evolution after amalgamation is relatively poorly constrained. This study presents U-Pb ages, trace element compositions, and Hf isotopes of rutile xenocrysts carried by the Yangyuan Cenozoic carbonatites, revealing an episodic cooling history of the Trans-North China Orogen. The Zr-in-rutile thermometer records formation of the rutiles under granulite facies at 743–932 °C. Cr and Nb concentrations in rutiles support a pelitic protolith, which is consistent with 176Hf/177Hf ratios that are close to zircons from pelitic granulites in the orogen. U-Pb ages of the rutiles are cooling ages, for which three populations can be clearly delineated. In combination with dating results from other systems, three episodes of cooling can be identified: [1] active cooling after the ~1.85 Ga peak metamorphism, with a cooling rate increasing from 7.9 °C/Ma in the period 1850–1810 Ma to 15.3 °C/Ma at 1810–1792 Ma; [2] active cooling after mantle upwelling at ~1.78 Ga, with cooling rate increasing from 8.7 °C/Ma at 1780–1735 Ma to 17.2 °C/Ma between 1735 and 1719 Ma; [3] passive cooling after a rifting event at ~1.68 Ga, with cooling rate decreasing from 20.6 °C/Ma at 1680–1673 Ma to 6.9 °C/Ma in the period 1673–1633 Ma. The first two episodes correspond to exhumation-related cooling, while the last episode resulted from the rift-to-drift transition of the North China Craton due to increasing distance from the heat source during break-up of the Columbia supercontinent. [ABSTRACT FROM AUTHOR]

Competing Interests: Conflict of interest The authors declare that they have no conflict of interest.

Using boron as a test analyte, laser ablation (LA) solution sampling multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is proposed and validated as a fast method for isotopic analysis in natural liquids and digested samples without any prior purification process. We demonstrated that the solution reference standard can be used as a bracketing standard for in situ δ 11 B analysis in solids. Based on a sensitivity enhancement of 8- to 9-fold, all testing solutions were diluted in a 5% (v/v) NH 3 ·H 2 O instead of classical 2% (v/v) HNO 3 . With a discrete and minimal sample solvent loading by the LA sampling strategy, it produces nearly "dry" plasma conditions that tolerate the sample matrix remarkably. The memory effect, one of the most difficult challenges in boron analysis, was dramatically eliminated with only 15 s wash time; thus, each analysis took less than 100 s. No significant matrix effects were observed for varying 50-100% boron concentrations in the samples and varying 20-60% NH 3 ·H 2 O matrix used for the dilution, as well as for samples doped with a 1/100 synthetic seawater matrix. The external precision of δ 11 B measurements in NIST 951a was ± 0.30‰ (2SD). Good agreement with the values described in literature studies was achieved for δ 11 B measurements in eight geological reference materials, with precisions between 0.4 and 0.7‰ (2SD), confirming the accuracy of the proposed method. The proposed method offers advantages of simple sample preparation, fast analysis, and little use of chemical reagents.

A novel "wave" signal-smoothing and mercury-removing device has been developed for laser ablation quadrupole and multiple collector ICPMS analysis. With the wave stabilizer that has been developed, the signal stability was improved by a factor of 6.6-10 and no oscillation of the signal intensity was observed at a repetition rate of 1 Hz. Another advantage of the wave stabilizer is that the signal decay time is similar to that without the signal-smoothing device (increased by only 1-2 s for a signal decay of approximately 4 orders of magnitude). Most of the normalized elemental signals (relative to those without the stabilizer) lie within the range of 0.95-1.0 with the wave stabilizer. Thus, the wave stabilizer device does not significantly affect the aerosol transport efficiency. These findings indicate that this device is well-suited for routine optimization of ICPMS, as well as low repetition rate laser ablation analysis, which provides smaller elemental fractionation and better spatial resolution. With the wave signal-smoothing and mercury-removing device, the mercury gas background is reduced by 1 order of magnitude. More importantly, the (202)Hg signal intensity produced in the sulfide standard MASS-1 by laser ablation is reduced from 256 to 0.7 mV by the use of the wave signal-smoothing and mercury-removing device. This result suggests that the mercury is almost completely removed from the sample aerosol particles produced by laser ablation with the operation of the wave mercury-removing device. The wave mercury-removing device that we have designed is very important for Pb isotope ratio and accessory mineral U-Pb dating analysis, where removal of the mercury from the background gas and sample aerosol particles is highly desired. The wave signal-smoothing and mercury-removing device was applied successfully to the determination of the (206)Pb/(204)Pb isotope ratio in samples with low Pb content and/or high Hg content.