In situ Pb and bulk Sr isotope analysis of the Yinchanggou Pb-Zn deposit in Sichuan Province (SW China): Constraints on the origin and evolution of hydrothermal fluids

The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11 wt% Pb + Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: ²⁰⁶Pb/²⁰⁴Pb = 18.17–18.24, ²⁰⁷Pb/²⁰⁴Pb = 15.69–15.71, ²⁰⁸Pb/²⁰⁴Pb = 38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.11–18.40, ²⁰⁷Pb/²⁰⁴Pb = 15.66–15.76, ²⁰⁸Pb/²⁰⁴Pb = 38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher ²⁰⁶Pb/²⁰⁴Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (²⁰⁶Pb/²⁰⁴Pb = 18.17–18.19), whereas the latter has higher ²⁰⁸Pb/²⁰⁴Pb ratios (38.59–38.63) than the former (²⁰⁸Pb/²⁰⁴Pb = 38.51–38.59). However, both types of galena have the same ²⁰⁷Pb/²⁰⁴Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected ⁸⁷Sr/⁸⁶Sr ratios of country sedimentary rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit as a strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.     

Genesis of the Huangshaping W–Mo–Cu–Pb–Zn polymetallic deposit in Southeastern Hunan Province,China: Constraints from fluid inclusions,trace elements,and isotopes

The Huangshaping polymetallic deposit is located in southeastern Hunan Province, China. It is a world-class W–Mo–Pb–Zn–Cu skarn deposit in the Nanling Range Metallogenic Belt, with estimated reserves of 74.31 Mt of W–Mo ore at 0.28% WO₃ and 0.07% Mo, 22.43 Mt of Pb–Zn ore at 3.6% Pb and 8.00% Zn, and 20.35 Mt of Cu ore at 1.12% Cu. The ore district is predominantly underlained by carbonate formations of the Lower Carboniferous period, with stocks of quartz porphyry, granite porphyry, and granophyre. Skarns occurred in contact zones between stocks and their carbonate wall rocks, which are spatially associated with the above-mentioned three types of ores (i.e., W–Mo, Pb–Zn, and Cu ores).Three types of fluid inclusions have been identified in the ores of the Huangshaping deposit: aqueous liquid–vapor inclusions (Type I), daughter-mineral-bearing aqueous inclusions (Type II), and H₂O–CO₂ inclusions (Type III). Systematic microthermometrical, laser Raman spectroscopic, and salinity analyses indicate that high-temperature and high-salinity immiscible magmatic fluid is responsible for the W–Mo mineralization, whereas low-temperature and low-salinity magmatic-meteoric mixed fluid is responsible for the subsequent Pb–Zn mineralization. Another magmatic fluid derived from deep-rooted magma is responsible for Cu mineralization.Chondrite-normalized rare earth element patterns and trace element features of calcites from W–Mo, Pb–Zn, and Cu ores are different from one another. Calcite from Cu ores is rich in heavy rare earth elements (187.4–190.5 ppm), Na (0.17%–0.19%), Bi (1.96–64.60 ppm), Y (113–135 ppm), and As (9.1–29.7 ppm), whereas calcite from W–Mo and Pb–Zn ores is rich in Mn (> 10.000 ppm) and Sr (178–248 ppm) with higher Sr/Y ratios (53.94–72.94). δ¹⁸O values also differ between W–Mo/Pb–Zn ores (δ¹⁸O = 8.10‰–8.41‰) and Cu ores (δ¹⁸O = 4.34‰–4.96‰), indicating that two sources of fluids were, respectively, involved in the W–Mo, Pb–Zn, and Cu mineralization.Sulfur isotopes from sulfides also reveal that the large variation (4‰–19‰) within the Huangshaping deposit is likely due to a magmatic sulfur source with a contribution of reduced sulfate sulfur host in the Carboniferous limestone/dolomite and more magmatic sulfur involved in the Cu mineralization than that in W–Mo and Pb–Zn mineralization. The lead isotopic data for sulfide (galena: ²⁰⁶Pb/²⁰⁴Pb = 18.48–19.19, ²⁰⁷/²⁰⁴Pb = 15.45–15.91, ²⁰⁸/²⁰⁴Pb = 38.95–39.78; sphalerite: ²⁰⁶Pb/²⁰⁴Pb = 18.54–19.03, ²⁰⁷/²⁰⁴Pb = 15.60–16.28, ²⁰⁸/²⁰⁴Pb = 38.62–40.27; molybdenite: ²⁰⁶Pb/²⁰⁴Pb = 18.45–19.21, ²⁰⁷/²⁰⁴Pb = 15.53–15.95, ²⁰⁸/²⁰⁴Pb = 38.77–39.58 chalcopyrite: ²⁰⁶Pb/²⁰⁴Pb = 18.67–19.38, ²⁰⁷/²⁰⁴Pb = 15.76–19.90, and ²⁰⁸/²⁰⁴Pb = 39.13–39.56) and oxide (scheelite: ²⁰⁶Pb/²⁰⁴Pb = 18.57–19.46, ²⁰⁷/²⁰⁴Pb = 15.71–15.77, ²⁰⁸/²⁰⁴Pb = 38.95–39.13) are different from those of the wall rock limestone (²⁰⁶Pb/²⁰⁴Pb = 18.34–18.60, ²⁰⁷/²⁰⁴Pb = 15.49–15.69, ²⁰⁸/²⁰⁴Pb = 38.57–38.88) and porphyries (²⁰⁶Pb/²⁰⁴Pb = 17.88–18.66, ²⁰⁷/²⁰⁴Pb = 15.59–15.69, ²⁰⁸/²⁰⁴Pb = 38.22–38.83), suggesting Pb²⁰⁶-, U²³⁸-, and Th ²³²-rich material are involved in the mineralization. The Sm–Nd isotopes of scheelite (ε_Nd(t) = − 6.1 to − 2.9), garnet (ε_Nd(t) = − 6.8 to − 6.1), and calcite (ε_Nd(t) = − 6.3) from W–Mo ores as well as calcite (ε_Nd(t) = − 5.4 to − 5.3) and scheelite (ε_Nd(t) = − 2.9) from the Cu ores demonstrate suggest more mantle-derived materials involved in the Cu mineralization.In the present study we conclude that two sources of ore-forming fluids were involved in production of the Huangshaping W–Mo–Pb–Zn–Cu deposit. One is associated with the granite porphyry magmas responsible for the W–Mo and then Pb–Zn mineralization during which its fluid evolved from magmatic immiscible to a magmatic–meteoritic mixing, and the other is derived from deep-rooted magma, which is related to Cu-related mineralization.     

Assessment of geochemical anomalies for gold exploration using lead isotopes in west Hainan, China

Lead isotopic ratios and Pb contents have been measured along typical profiles across orebodies of the Baoban and Tuwaishan gold deposits on Hainan Island, China. These deposits are hosted by the middle to upper Proterozoic Baoban Group, which is composed of migmatite and extends for about 51 km on the hanging-wall side of the Gezhen Fault. The deposits have a common initial Pb isotopic ratio of ²⁰⁶Pb/²⁰⁴Pb = 18.683, but show distinctive variations within each deposit.The Pb isotopic ratios are more homogeneous in the orebodies and altered auriferous rocks than in the migmatite wall rocks. The richest orebody in the study area is known as the V1 orebody of the Baoban deposit; it has the lowest and most homogeneous ²⁰⁶Pb/²⁰⁴Pb ratio. This feature suggests that in this migmatitic area, it is possible to distinguish ores from barren wall rocks, and rich ore shoots from non-commercial mineralization, by their distinctive Pb isotopic ratios.A lower initial Pb isotopic ratio (²⁰⁶Pb/²⁰⁴Pb= 18.538) was measured in two other deposits, Beiniu and Erjia, which occur in the same migmatite and are controlled by the same fault as the Baoban and Tuwaishan deposits. Therefore, two metallogenic phases may have taken place, one at 85 Ma and the other at 170 Ma; these ages can be calculated using the Pb growth model of Cumming and Richards.The feasibility of evaluating geochemical anomalies through their Pb isotopic signatures was investigated by comparing the Pb isotopic ratios of B horizon soils from significant and non-significant anomalies with those obtained from the ores and alteration zone rocks. The results show that the Pb isotopic ratios in significant anomalies are consistent with those of the ores, whereas the signatures of non-significant anomalies are heterogeneous and rather different from those of the ores.Six unexplored anomalies have been evaluated using this criteria; five of them were found to be non-significant. One anomaly, however, presents the same signature as the Beiniu deposit, suggesting that it may be related to undiscovered ore close to the Gezhen Fault. Plans have been made to drill this target.     

Pb isotope evidence for contaminant-metal dispersal in an international river system: The lower Danube catchment,Eastern Europe

Lead isotope signatures (²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb), determined by magnetic sector ICP-MS in river channel sediment, metal ores and mine waste, have been used as geochemical tracers to quantify the delivery and dispersal of sediment-associated metals in the lower Danube River catchment. Due to a diverse geology and range of ore-body ages, Pb isotope signatures in ore-bodies within the lower Danube River catchment show considerable variation, even within individual metallogenic zones. It is also possible to discriminate between the Pb isotopic signatures in mine waste and river sediment within river systems draining individual ore bodies. Lead isotopic data, along with multi-element data; were used to establish the provenance of river sediments and quantify sedimentary contributions to mining-affected tributaries and to the Danube River. Data indicate that mining-affected tributaries in Serbia and Bulgaria contribute up to 30% of the river channel sediment load of the lower Danube River. Quantifying relative sediment contributions from mining-affected tributaries enables spatial patterns in sediment-associated metal and As concentrations to be interpreted in terms of key contaminant sources. Combining geochemical survey data with that regarding the provenance of contaminated sediments can therefore be used to identify foci for remediation and environmental management strategies.     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Geology,geochronology and geochemistry of granitic intrusions and the related ores at the Hongshan Cu-polymetallic deposit: Insights into the Late Cretaceous post-collisional porphyry-related mineralization systems in the southern Yidun arc,SW China

The Hongshan Cu-polymetallic deposit is located in the southern Yidun arc in southwestern China, where both subduction-related (Late Triassic) and post-collisional (Late Cretaceous) porphyry–skarn–epithermal mineralization systems have been previously recognized. In this study, two distinct magmatic events, represented by diorite porphyry and quartz monzonite porphyry, have been revealed in the Hongshan deposit, with zircon SHRIMP U–Pb ages of 214 ± 2 Ma and 73.4 ± 0.7 Ma, respectively. The 73 Ma age is comparable to the Re–Os ages of 77 to 80 Ma of ore minerals from the Hongshan deposit, indicating that the mineralization is related to the Late Cretaceous quartz monzonite porphyries rather than Late Triassic diorite porphyries. The Late Triassic diorite porphyries belong to the high-K calc-alkaline series and show arc magmatic geochemical characteristics such as enrichment in Rb, Ba, Th and U and depletion in HFSEs, indicating that they were formed during the westward subduction of the Garzê–Litang Ocean. In contrast, the Late Cretaceous quartz monzonite porphyries show shoshonitic I-type geochemical characteristics, with high SiO₂, K₂O, LILE, low HREE, Y and Yb contents, and high LREE/HREE and La/Yb ratios. These geochemical characteristics, together with the Sr–Nd–Pb isotopic compositions (average (⁸⁷Sr/⁸⁶Sr)_i = 0.7085; ε_Nd(t) = − 6.0; ²⁰⁶Pb/²⁰⁴Pb = 19.064, ²⁰⁷Pb/²⁰⁴Pb = 15.738, ²⁰⁸Pb/²⁰⁴Pb = 39.733) suggest that the quartz monzonite porphyries originated from the partial melting of the ancient lower crust in response to underplating of mafic magma from subduction metasomatized mantle lithosphere, possibly triggered by regional extension in the post-collisional tectonic stage. The S isotopic compositions (δ³⁴S_V-CDT = 3.81‰ to 5.80‰) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.014 to 18.809, ²⁰⁷Pb/²⁰⁴Pb = 15.550 to 15.785, and ²⁰⁸Pb/²⁰⁴Pb = 38.057 to 39.468) of ore sulfides indicate that the sulfur and metals were derived from mixed mantle and crustal sources. It is proposed that although the Late Triassic magmatic event is not directly related to mineralization, it contributed to the Late Cretaceous mineralization system through the storage of large amounts of sulfur and metals as well as water in the cumulate zone in the mantle lithosphere through subduction metasomatism. Re-melting of the mantle lithosphere including the hydrous cumulate zone and ancient lower crust during the post-collisional stage produced fertile magmas, which ascended to shallow depths to form quartz monzonite porphyries. Hydrothermal fluids released from the intrusions resulted in porphyry-type Mo–Cu ores in and near the intrusions, skarn-type Cu–Mo ores in the country rocks above the intrusions, and hydrothermal Pb–Zn ores in the periphery.     

Genesis of the South Zhuguang Uranium Ore Field,South China: Pb Isotopic Compositions and Mineralization Ages

U–Pb isotopic analyses indicate that ores from the South Zhuguang uranium ore field, south China, have high common (non‐radiogenic) Pb contents, with variable and relatively radiogenic initial Pb contents. The U–Pb isochron method was used to date these ores, with plots of ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb being used to identify sample suites with similar initial Pb isotopic ratios and to normalize variable initial Pb isotopic ratios. The resulting U–Pb isochrons indicate two substages of uranium mineralization at ~57 and 52 Ma, with a later hydrothermal reformation at ~49 Ma, which homogenized Pb isotopic compositions. Initial Pb isotopic systematics indicate that the ore‐forming fluid was characterized by high ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios and low ²⁰⁸Pb/²⁰⁴Pb ratios, suggesting that the ore‐forming fluid was sourced from Cretaceous–Paleogene red‐bed basins, rather than from magma or the mantle, with consideration of mineralization ages.     

Lead isotopic signatures of wine and vineyard soils—tracers of lead origin

The Pb contents and ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb isotopic ratios were studied in the soils and wines (2004 harvest) of three vineyard areas of the Czech Republic. The areas differ in their geological basements and anthropogenic loading. The isotopic compositions of wine in areas with intensive industry (Most, North Bohemia ²⁰⁶Pb/²⁰⁷Pb_wine = 1.178 ± 0.004) and the agricultural areas of Central Bohemia (Roudnice nad Labem ²⁰⁶Pb/²⁰⁷Pb_wine = 1.176 ± 0.007) are similar to the Pb isotopic composition of airborne particulate material typical of polluted and industrial environments (²⁰⁶Pb/²⁰⁷Pb = 1.17–1.19). The isotopic composition of wine from Prague (²⁰⁶Pb/²⁰⁷Pb_wine = 1.174 ± 0.003) is different from that of the soil, which was severely contaminated in the past by vehicular Pb (²⁰⁶Pb/²⁰⁷Pb_soil = 1.147–1.168). This fact shows that interception of airborne Pb by plants is greater than its uptake by the root system.     

Nd,Sr and Pb isotopic and REE geochemical study of some Miocene submarine hydrothermal deposits (Kuroko deposits) in Japan

Neodymium, Sr and Pb isotopic compositions, along with rare earth element (REE) concentrations were determined for twelve black ores and one yellow ore from twelve localities of the Kuroko deposits, Japan. The ores were generated by submarine hydrothermal activity during the Miocene age. Neodymium isotopic compositions of the ores (_Nd: –4.9 to +6.5) mostly overlap with spatially associated igneous rocks. On a Nd versus Sr isotopic correlation diagram, however, ⁸⁷Sr/⁸⁶Sr ratios are shifted from the associated igneous rocks towards the higher contemporaneous seawater ratio. REE patterns are highly variable, ranging from light REE enriched to depleted, and show no Ce anomalies, as would be expected if they were derived from seawater. These results suggest that the REEs contained in ores were mainly derived from the associated igneous rocks, but that the ore Sr is a mixture derived from both seawater and the igneous rocks. Most Pb isotopic compositions fall within the range defined by the associated igneous rocks (²⁰⁶Pb/²⁰⁴Pb=18.35–18.84, ²⁰⁷Pb/²⁰⁴Pb=15.59–15.97 and ²⁰⁸Pb/²⁰⁴Pb=38.53–39.90), although several samples have very radiogenic compositions that were most likely derived from basement rocks. Our new Pb isotopic results display greater variation, and have a larger range of more radiogenic compositions than has been noted previously for these ores. In addition, the black ore with the most radiogenic Pb isotopic composition also has the least radiogenic Nd isotopic composition. This suggests that at least some of the Pb contained in the ores was derived mainly from older basement rocks. The large positive Eu anomalies for some black ores are consistent with a high-temperature origin for the parental fluids, irrespective of the source rock. The single yellow ore examined, however, has a small negative Eu anomaly, which may indicate derivation from a lower temperature fluid. Previous studies suggested that the Kuroko ores were formed in the presence of organic materials in an anoxic basin. Combined Nd, Sr, Pb and Os isotopic and REE abundance data indicate that multiple sources were involved in the genesis of Kuroko ores.     

The sources of ore-forming material in the low-sulfidation epithermal Wulaga gold deposit,NE China: Constraints from S,Pb isotopes and REE pattern

The Wulaga gold deposit, located in Heilongjiang province, NE China, is a subvolcanic rock-hosted, low-sulfidation epithermal gold deposit, and has an Au reserve of about 84 tons. The gold mineralization occurs in a crypto-explosive breccia, and is spatially and temporally associated with an Early Cretaceous granodioritic porphyry. Three individual stages of mineralization have been identified in the Wulaga gold deposit: an early white quartz-euhedral vein stage, a fine-grained pyrite–marcasite–stibnite–chalcedony stage, and a late calcite–pyrite stage. The sulfur isotopic values of sulfide minerals vary in a wide range from − 4 to 4.9‰, but are concentrated in the range of − 3 to 0‰, implying that sulfur in the hydrothermal fluids was derived from magmatic volatiles. Lead isotopic results of the granodioritic porphyry (²⁰⁶Pb/²⁰⁴Pb = 18.341–18.395, ²⁰⁷Pb/²⁰⁴Pb = 15.507–15.523, ²⁰⁸Pb/²⁰⁴Pb = 38.174–38.251) and sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.172–18.378, ²⁰⁷Pb/²⁰⁴Pb = 15.536–15.600, ²⁰⁸Pb/²⁰⁴Pb = 38.172–38.339) are comparatively consistent and clustered together between the orogenic and upper mantle lines, indicating the lead in the ores is closely related to the parent magma of the granodioritic porphyry. The REE patterns of fluid inclusions trapped in sulfides are similar to those of the granodioritic porphyry, which confirms the magmatic origin of the REE in the hydrothermal fluids. The characteristics of S and Pb isotopes and REE suggest that the ore-forming materials of the Wulaga gold deposit are partly magmatic in origin, and related to a high-level hydrous granodioritic magma.     

Ore genesis and hydrothermal evolution of the Huanggang skarn iron–tin polymetallic deposit,southern Great Xing'an Range: Evidence from fluid inclusions and isotope analyses

The southern Great Xing'an Range is one of the most important metallogenic belts in northern China, and contains numerous Pb–Zn–Ag–Cu–Sn–Fe–Mo deposits. The Huanggang iron–tin polymetallic skarn deposit is located in the Sn-polymetallic metallogenic sub-belt. Skarns and iron orebodies occur as lenses along the contact between granite plutons and the Lower Permian Huanggangliang Formation marble or Dashizhai Formation andesite. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity, i.e., skarn, oxide and sulfide stages, all contributed to the formation of the Huanggang deposit.The skarn stage is characterized by the formation of garnet and pyroxene, and high-temperature, hypersaline hydrothermal fluids with isotopic compositions that are similar to those of typical magmatic fluids. These fluids most likely were generated by the separation of brine from a silicate melt instead of being a product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by amphibole, chlorite, quartz and magnetite. The hydrothermal fluids of this stage are represented by L-type fluid inclusions that coexist with V-type inclusions with anomalously low δD values (approximately − 100 to − 116‰). The decrease in ore fluid δ¹⁸O_H2O values with time coincides with marked decreases in the fluid salinity and temperature. Based on the fluid inclusion and stable isotopic data, the ore fluid evolved by boiling of the magmatic brine. The sulfide stage is characterized by the development of sphalerite, chalcopyrite, fluorite, and calcite veins, and these veins cut across the skarns and orebodies. The fluids during this stage are represented by inclusions with a variable but continuous sequence of salinities, mainly low-salinity inclusions. These fluids yield the lowest δ¹⁸O_H2O values and moderate δD values ( − 1.6 to − 2.8‰ and − 101 to − 104‰, respectively). The data indicate that the sulfide stage fluids originated from the mixing of residual oxide-stage fluids with various amounts of meteoric water. Boiling occurred during this stage at low temperatures.The sulfur isotope (δ³⁴S) values of the sulfides are in a narrow range of − 6.70 to 4.50‰ (mean = − 1.01‰), and the oxygen isotope (δ¹⁸O) values of the magnetite are in a narrow range of 0.1 to 3.4‰. Both of these sets of values suggest that the ore-forming fluid is of magmatic origin. The lead isotope compositions of the ore (²⁰⁶Pb/²⁰⁴Pb = 18.252–18.345, ²⁰⁷Pb/²⁰⁴Pb = 15.511–15.607, and ²⁰⁸Pb/²⁰⁴Pb = 38.071–38.388) are consistent with those of K-feldspar granites (²⁰⁶Pb/²⁰⁴Pb = 18.183–18.495, ²⁰⁷Pb/²⁰⁴Pb = 15.448–15.602, ²⁰⁸Pb/²⁰⁴Pb = 37.877–38.325), but significantly differ from those of Permian marble (²⁰⁶Pb/²⁰⁴Pb = 18.367–18.449, ²⁰⁷Pb/²⁰⁴Pb = 15.676–15.695, ²⁰⁸Pb/²⁰⁴Pb = 38.469–38.465), which also suggests that the ore-forming fluid is of magmatic origin.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Geology,geochemistry, and geochronology of the Wangjiazhuang porphyry–breccia Cu(–Mo) deposit in the Zouping volcanic basin,eastern North China Block

The Wangjiazhuang porphyry–breccia Cu(–Mo) deposit is located in the Zouping volcanic basin, western Shandong Province. Seven molybdenite samples yield a Re–Os weighted mean age of 127.8 ± 0.7 Ma (2σ), which is identical within error to the zircon weighted mean ²⁰⁶Pb/²³⁸U age of 128.3 ± 1.3 Ma (2σ) determined for quartz monzonite samples. The host rock is characterized by high concentrations of K₂O (4.26–4.53 wt.%), Na₂O (4.97–5.76 wt.%), LILEs and LREEs, and high Mg# (> 40), and low concentrations of HFSEs and HREEs, with K₂O/Na₂O ratios of 0.76–0.88. The quartz monzonite also has high Sr/Y (69.9–112.5) and (La/Yb)_N (22.0–30.0) ratios, similar to adakitic rocks worldwide. Relatively low initial ⁸⁷Sr/⁸⁶Sr ratios (0.70549–0.70556), high ε_Nd(t) values (2.58–3.06), high radiogenic Pb [(²⁰⁶Pb/²⁰⁴Pb)i = 18.3424–18.4606, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.5692–15.5985, (²⁰⁸Pb/²⁰⁴Pb)_i = 38.1714–38.2734] and high zircon ε_Hf(t) values (− 2.1 to + 4.3) indicate that the magma was likely derived from the partial melting of subducted oceanic crust which then reacted with the peridotitic mantle wedge. Both the breccia and porphyry ores have a narrow range of δ³⁴S (− 4.8 to + 2.1‰) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.295–18.402, ²⁰⁷Pb/²⁰⁴Pb = 15.551–15.573, and ²⁰⁸Pb/²⁰⁴Pb = 38.215–38.331), suggesting that the ore metals were extracted primarily from the quartz monzonite or similar source. Subduction of the Paleo-Pacific slab during the Early Cretaceous resulted in the formation of the Wangjiazhuang quartz monzonite and associated Cu(–Mo) deposit in western Shandong Province.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

U-Th-Pb isotope systematics related to igneous rocks and ore Pb,Mount Isa,Queensland

This study is a search for a genetic relationship between Pb sulphide ore and igneous rocks in the region of Mount Isa, Queensland. The approach involves derivation of Pb isotope initial ratios by the whole-rock isochron method, and comparison of the initial ratios (Pb²⁰⁶/Pb²⁰⁴, Pb²⁰⁷/Pb²⁰⁴ and Pb²⁰⁸/Pb²⁰⁴) with the isotopic composition of the ore Pb. Data are reported for four igneous units; Kalkadoon granodiorite, Kalkadoon adamellite, Sybella granite and Eastern Creek volcanics. The results display considerable scatter for each of the units, and reveal the effects of recent surficial loss of U. The positioning of isochrons is aided by previous Rb-Sr geochronological data wherever possible. Comparison of initial ratios and ore Pb suggests that none of the igneous rock units is co-genetic with the ore deposit. Both phases of the Sybella Granite are more radiogenic and are apparently younger than the ore Pb. The Kalkadoon Granite is possibly related to the ore through some post-emplacement process of extraction and transport of Pb (e.g. by erosion or by anatectic magma generation) to the present site of the orebodies.     

Shallow impact: Isotopic insights into crustal contributions to the Sudbury impact melt sheet

The largest known terrestrial impact melt sheet occurs within the 1850 Ma Sudbury Structure, Ontario. In order to evaluate the relative contributions of different target lithologies to the melt sheet, we have investigated the Pb isotope compositions of feldspar separates from early-formed quartz diorite magmas within Offset Dykes from around the impact structure. The samples define a linear array on plots of age-corrected ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb. Samples from Offset Dykes hosted by the Huronian Supergroup (South Range) have a range of ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ from 15.424 to 17.255 and ²⁰⁷Pb/²⁰⁴Pb₁₈₅₀ from 15.390 to 15.801, whilst those hosted by Archean gneisses of the Superior Province (North Range) cluster around ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ ≈ 14.8 and ²⁰⁶Pb/²⁰⁴Pb₁₈₅₀ ≈ 15.1. These values can be approximated by binary mixing between the two major groups of target lithologies. A mix of 60-70% of Superior Province gneisses with 30-40% of Huronian metasedimentary material closely matches the Pb isotope compositions of North Range Offset Dyke samples, whereas in the South Range the required Huronian component is up to ca. 80%.These mixing proportions are consistent with Sr, Nd and Os isotope and trace element constraints. A third minor component, either locally-exposed Paleoproterozoic mafic rocks or the lower crust is also required. However, the isotopic, trace element and Ni-Cu-platinum group element characteristics of the melt sheet can be accommodated without the involvement of an average lower crustal or meteoritic component.A major contribution of Huronian supracrustal material, which had a pre-impact thickness of up to 12 km, is required to explain the chemical characteristics of the impact melts, which also have a strong upper crustal affinity (e.g. Eu/Sm = 0.22, Rb/Sr = 0.2-0.35). As such, a shallower level of melting is apparent than that predicted by many previous impact models for the Sudbury event. This can be accommodated by considering approach trajectories for the impactor oblique to the Earth’s surface. In addition, the isotopic and trace element variability identified indicates that the melt sheet was heterogeneous at an early stage, and may not have been completely homogenised during crater formation. Our findings have significant implications for the nature of the Sudbury impact event, the evolution of the melt sheet and the crustal sources of metals contained in Sudbury’s world class Ni-Cu-PGE sulphide ores.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Sulphur and Lead Isotope Compositions of the Dajiangp—ing Deposit in Western Guangdong Province1

Abstract The Dajiangping pyrite deposit located in the middle sector of the Yunkai uplift in western Guangdong is a stratiform sulphide deposit occurring in Sinian marine clastic and fine clastic rocks. The formation of the deposit was related to submarine exhalation and hot brine deposition. A part of it was reformed by late-stage hydro thermal solution. The δ³⁴S values of pyrite vary from — 25.55‰ to + 21.07‰, which are inversely proportional to the content of organic carbon in ore and pyrite. Passing from striped fine-grained pyrite ore to massive coarse-grained pyrite ore, i.e. from south to north, the sulphur isotopic composition changes from the light sulphur-enriched one to the heavy sulphur-enriched one. The lead isotopic composition of striped ore is consistent with that of the country locks of orebodies and the lead is radiogenic lead derived from the upper crust. The lead isotopic composition of massive ore is relatively homogeneous and its ²⁰⁶/Pb²⁰⁴Pb, ²⁰⁷/Pb²⁰⁴Pb and ²⁰⁸/Pb²⁰⁴Pb ratios are a bit lower than those of striped ore; the lead result from mixing of synsedimentary ore lead with that derived from basement migmatite brought by late-stage hydrothermal solutions.     

An Isotopic (Sr, Nd and Pb) Tracer Study on the Xiaoxinancha Gold-rich Copper Deposit in Yanbian, China: Implication for the Geodynamic Model of Diagenesis and Metallogenesis

An isotopic study was systemically carried out on the granitic complex, diorite-porphyrite, ores and ore minerals of the 103 Ma Xiaoxinancha gold-rich copper deposit in Jilin province to determine the geodynamic model of diagenesis and metallogenesis. Results show that the initial Nd and Sr isotopic compositions of the granitic complex are in the range of 0.70425–0.70505 for (87Sr/86Sr)i , 0.51243–0.51264 for INd, and –1.31 to +2.64 for εNd(t); those of the diorite-porphyrite are in the range from 0.70438–0.70448 for (87Sr/86Sr)i, 0.51259–0.51261 for INd, and +1.56 to +2.09 for εNd(t). For ores and sulfides, the (87Sr/86Sr)i , INd, and εNd(t) values are in the range from 0.70440–0.70805, 0.51259–0.51279 and +1.72 to +5.56, respectively. The Pb isotopic ratios of the granitic complex range from 18.2992–18.6636 for 206Pb/204Pb, from 15.5343–15.5660 for 207Pb/204Pb, and from 38.1640–38.5657 for 208Pb/204Pb. For diorite-porphyrite, the isotopic ratios of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb are 18.3919, 15.5794 and 38.3566, respectively, whereas those of the ores and ore sulfides vary from 18.2275–18.3770 for 206Pb/204Pb, from 15.5555–15.5934 for 207Pb/204Pb and from 38.1318–38.3131 for 208Pb/204Pb. The results indicate that the mineralization was correlated to the formation and evolution of the granitic complex and the diorite-porphyrite. Combining with the reported data in petrologic characteristics, elemental geochemistry and chronology, conclusions can be drawn that the geodynamic settings of diagenesis and metallogenesis of this deposit were consistent with the subduction of the Izanagi oceanic plate during the Early Cretaceous. The diorite-porphyrite was formed by the emplacement of the adakitic magma triggered by partial melting of the enriched mantle, which originated from the derivative continental lithospheric mantle metasomatized by dehydration fluids from the subducting oceanic crust. The granitic complex was produced by fractional crystallization of the mixture between the adakitic magma and the high-K calc-alkaline acidic magma, which were generated by the remelting of the lower crust in the course of intraplate upwelling of the adakitic magma. The ore-bearing fluid reservoir convened in a late stage of the evolution of the mixed magma chamber.     

Certification of ERM‐EB400, the First Matrix Reference Material for Lead Isotope Amount Ratios,and ERM‐AE142, a Lead Solution Providing a Lead Isotopic Composition at the Edge of Natural Variation

Lead isotope amount ratios are commonly used in diverse fields such as archaeometry, geochemistry and forensic science. Currently, five reference materials with certified lead isotope amount ratios are available, namely NIST SRM 981, 982 and 983, GBW‐04442 and NMIJ 3681‐a. Only NIST SRM 981 and NMIJ 3681‐a have approximately natural isotopic compositions, and NIST SRM 981 is predominantly used for correcting mass discrimination/mass fractionation in the applied mass spectrometric procedures. Consequently, there is no other certified reference material available to be used for validation and/or quality control of the analytical procedures applied to lead isotope amount ratio measurements. To fill this gap, two new reference materials have been produced and certified for their lead isotope amount ratios. For both certified reference materials, complete uncertainty budgets have been calculated and SI traceability has been established. This provides the users with independent means for validating and verifying their analytical procedures and for conducting quality control measures. ERM‐EB400 is a bronze material with a nominal lead mass fraction of 45 mg kg^?1 and certified lead isotope amount ratios of n(²⁰⁶Pb)/n(²⁰⁴Pb) = 18.072(17) mol mol^?1, n(²⁰⁷Pb)/n(²⁰⁴Pb) = 15.578(18) mol mol^?1 and n(²⁰⁸Pb)/n(²⁰⁴Pb) = 38.075(46) mol mol^?1 with the associated expanded uncertainties (k = 2) given in brackets. ERM‐AE142 is a high‐purity solution of lead in 2% nitric acid with a nominal mass fraction of 100 mg kg^?1 and certified Pb isotope amount ratios of n(²⁰⁶Pb)/n(²⁰⁴Pb) = 21.114(17) mol mol^?1, n(²⁰⁷Pb)/n(²⁰⁴Pb) = 15.944(17) mol mol^?1 and n(²⁰⁸Pb)/n(²⁰⁴Pb) = 39.850(44) mol mol^?1 with the associated expanded uncertainties (k = 2) given in brackets. Both materials are specifically designed to fall within the natural lead isotopic variation and to assist users with the validation and verification of their analytical procedures. Note that while one of these reference materials requires the chemical separation of Pb from its matrix (ERM‐EB400), the other does not (ERM‐AE142). As additional information, δ^208/206Pb_{NIST SRM981} values are provided for both materials. For ERM‐AE142, a delta value of δ^208/206Pb_{NIST SRM981} = ?28.21(30)‰ was obtained, and for ERM‐EB400, a delta value of δ^208/206Pb_NIST SRM981= ?129.47(38)‰ was obtained, with the associated expanded uncertainties (k = 2) given in brackets.