Possible Carbonate Origin of Ore Sulfur from Geumseong Mo Deposit, South Korea

Abstract: In order to know the cause of the high δ³⁴S values of the Korean ore deposits (Ishihara et al., 2000), Geumseong molybdenum skarn deposit and related Jurassic granitoids and Cambro-Ordovician carbonates were selected for the δ³⁴S analyses. Two sulfide samples occurring in hydrothermal veins in fresh granitoids quarry at Songhaksan yielded δ³⁴S values of +6.9 and +8.8 permil. These are slightly higher than +5.3 permil δ³⁴S of the averaged rock sulfides for the Jurassic Daebo granitoids. Pyrite and molybdenite from the Geumseong deposit vary from +8.6 to +11.5 permil (average + 10.7 permil). The intruded carbonates contain very low amount of SSS (structurally substituted sulfate) as 2.9 to 8.1 ppm with high δ³⁴S values between +28.8 and + 40.0 permil, and sulfides sulfur of 52 to 779 ppm with variable δ³⁴S values between +3.2 and +22.5 per–mil. It is concluded that sulfur of the host carbonates was extracted and migrated into the skarn deposit at the time of the granitoid intrusion and the related hydrothermal convection, on the basis of the location of the skarn deposit occurring between the carbonates and Jurassic granitoids, and of very low contents of SSS sulfur in the carbonates. A part of SSS possibly contaminated into the Jurassic granite.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.     

Sulfur Content and Isotopic Ratio of Cambro-Ordovician Carbonate Rocks from South Korea: A Possible Source for Mesozoic Magmatic-hydrothermal Ore Sulfur

Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ³⁴S values. The δ³⁴S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ³⁴S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ³⁴S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ³⁴S value of +12.8 permil (n=24). The estimated δ³⁴S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ³⁴S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ³⁴S values of the Korean ore deposits might be caused to some extent by ³⁴S enrichment from the host carbonates, resulting in the low SSS contents observed.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

δ30Si and δ29Si Determinations on USGS BHVO-1 and BHVO-2 Reference Materials with a New Configuration on a Nu Plasma Multi-Collector ICP-MS

We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the ¹⁴N¹⁶O and ¹⁴N₂ interferences overlying the ³⁰Si and the ²⁸Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ³⁰Si and δ²⁹Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ³⁰Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ³⁰Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.     

Dating cleavage formation in slates and phyllites with the 40Ar/39Ar laser microprobe: an example from the western New England Appalachians, USA

Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution ⁴⁰Ar/³⁹Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S₂, S₃, and S₄) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S₃ and S₄ are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative ⁴⁰Ar/³⁹Ar geochronology. Mean ⁴⁰Ar/³⁹Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S₃ and 345.5 ± 1.7 Myr for S₄. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S₃ and S₄, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.     

Plio–Pleistocene Hydrothermal Activity Related to Gold Mineralization in the Seta Area, Northeastern Hokkaido, Japan

Abstract: Plio–Pleistocene hydrothermal activity resulted in high grade low sulfidation epithermal gold mineralization in the Seta area, the southern end of the Monbetsu-Kamishihoro Graben of northeastern Hokkaido, Japan. Hydrothermal activity and accompanying hydrothermal eruptions began at approximately 2 Ma along NNW-SSE trending faults, the Tohbu-ko fault I and II. This activity resulted in two main zones of gold mineralization, the west quartz-adularia veins(QAV) and east stock-work zone(STZ), formed between 1. 8 and 1. 2 Ma. A smectite-chlorite alteration zone is observed at deeper levels, while kaolinite and kaolinite-smectite zones occur at shallower levels with an acid-leached zone present near the surface. The kaoli-nite and kaolinite-smectite zones are also distributed along faults and the STZ, to depths of several hundred meters. δ³⁴S values of pyrite and alunite from the kaolinite and silicified zones indicate alunite formed by the oxidation of sulfide, either H₂S(vapor) or mineral.
Formation of the STZ and the southern part of the QAV took place during lacustrine sedimentation, while formation of the northern part of the QAV took place after eruption of andesitic lava; the latter being associated with widespread alteration formed under neutral-pH conditions. δ¹⁸O values of quartz veins and silicified rocks indicate that the paleo-hydrothermal waters have a large meteoric component, increasing with decreasing depth in the STZ. Acid hydrothermal waters, resulting from near surface oxidation of H₂S were responsible for acid-leaching and kaolinization of surrounding rocks. Between 1. 4 and 0. 3 Ma, the acid hot waters drained back along the STZ to depths of at least 500m, as a result of a fall in the paleo-water table level.     

K-Ar Ages of Tin-Polymetallic Mineralization in the Oruro Mining District, Central Bolivian Tin Belt

Abstract. K-Ar age determinations were carried out on vein- and rock-forming minerals from five vein-type tin-polymetallic ore deposits of the Oruro mining district in the central part of the Bolivian tin belt. The sericite from vein selvedges and an altered host rock provides good estimates of the ages of hypogene mineralization, and supergene alunite and jarosite provide ages for erosional and weathering episodes. It is concluded that hypogene mineralization in the Oruro mining district took place during the early to middle Miocene: 15.8±0.8 Ma at San José, 20.1±l.l Ma at Morococala, 20.5±1.0 Ma at Avicaya, and 19.6±1.0 Ma at Llallagua. Fine grained supergene alunite (δ³⁴S = -10.1 960) and jarosite yield K-Ar ages of 6.7±0.7 Ma at Avicaya and 3.9±0.7 Ma at Bolivar, respectively, suggesting that erosion and chemical weathering were active at those times.     

40Ar/39 mineral ages from the Scituate Granite, Rhode Island: implications for Late Palaeozoic tectonothermal activity in New England

The alkalic Scituate Granite was emplaced into crystalline sequences within the New England Esmond–Dedham terrane in the Late Devonian ( c. 370 Ma). Variably recrystallized amphibole (iron-rich, hastingsite–hastingsitic hornblende) from four variably deformed samples of the pluton record south-westerly younging ⁴⁰Ar/³⁹Ar plateau ages ranging between 276 and 263 Ma. These are interpreted to date diachronous cooling through temperatures appropriate for intracrystalline retention of argon following late Palaeozoic orogenic activity. Iron-rich biotite concentrates from the samples record only slightly younger ages, and therefore suggest relatively rapid post-metamorphic cooling. The ⁴⁰Ar/³⁹Ar ages indicate that the late Palaeozoic tectonothermal overprint was much more regionally pervasive than was previously considered. The apparent timing of this activity is similar to previous estimates for the chronology of high-grade metamorphism throughout the adjacent Hope Valley terrane and for phases of ductile movement on the intervening Lake Char–Honey Hill fault system.     

New Constraints on Ages of Glasses Proposed as Reference Materials for Fission-Track Dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated ⁴⁰Ar/³⁹Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 ± 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the ⁴⁰Ar/³⁹Ar age of 15.21 ± 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 ± 0.06 to 5.72 ± 0.12 Ma have been published previously. New ⁴⁰Ar/³⁹Ar ages gave an average of 5.12 ± 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new ⁴⁰Ar/³⁹Ar ages than the previously published ages. Roccastrada glass (Italy) - a new ⁴⁰Ar/³⁹Ar age, 2.45 ± 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm^-2). Defects that might produce "spurious" tracks are virtually absent. An independent ⁴⁰Ar/³⁹Ar age of 8.77 ± 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.     

40Ar/ 39Ar dating of Penninic Front tectonic displacement (W Alps) during the Lower Oligocene (31–34 Ma)

Direct absolute dating of the Penninic Frontal Thrust tectonic motion is achieved using the ⁴⁰Ar/³⁹Ar technique in the Pelvoux Crystalline Massif (Western Alps). The dated phengites were formed syn-kinematically in shear zones. They underline the brittle-ductile stretching lineation, pressure-shadow fibres and slickensides consistent with underthrusting of the European continental slab below the propagating Penninic Thrust. Chlorite–phengite thermobarometry yields 10–15 km and T ∼280 °C, while ⁴⁰Ar/³⁹Ar phengite ages mainly range between 34 and 30 Ma, with one younger age at 27 Ma. This Early Oligocene age range matches a major tectonic rearrangement of the Alpine chain. Preservation of prograde ⁴⁰Ar/³⁹Ar ages is ascribed to passive exhumation of the Pelvoux shear zone network, sandwiched between more external thrusts and the Penninic Front reactivated as an E-dipping detachment fault. Partial resetting in the Low Temperature part of argon spectra below 24 Ma is ascribed to brittle deformation and alteration of phengites.     

Mesozoic tectonothermal development of the Sambagawa, Mikabu and Chichibu belts, south-west Japan: evidence from 40Ar/39Ar whole-rock phyllite ages

Abstract Five whole-rock ⁴⁰Ar/³⁹Ar plateau ages from low-grade sectors of the Sambagawa belt (Besshi nappe complex) range between 87 and 97 Ma. Two whole-rock phyllite samples from the Mikabu greenstone belt record well-defined ⁴⁰Ar/³⁹Ar plateau ages of 96 and 98 Ma. Together these ages suggest that a high-pressure metamorphism occurred in both the Sambagawa and Mikabu belts at c. 90–100 Ma. The northern Chichibu sub-belt may consist of several distinct geochronological units because metamorphic ages increase systematically from north ( c. 110 Ma) to south ( c. 215 Ma). The northern Chichibu sub-belt is correlated with the Kuma nappe complex (Sambagawa belt). Two whole-rock phyllite samples from the Kurosegawa terrane display markedly older metamorphic ages than either the Sambagawa or the Chichibu belts.
Accretion of Sambagawa-Chichibu protoliths began prior to the middle Jurrasic. Depositional ages decrease from middle Jurassic (Kuma-Chichibu nappe complex) to c. 100 Ma (Oboke nappe complex) toward lower tectonostratigraphic units. The ages of metamorphic culmination also decrease from upper to lower tectonostratigraphic units. The Kurosegawa belt and the geological units to the south belong to distinctly different terrances than the Sambagawa-Chichibu belts. These have been juxtaposed as a result of transcurrent faulting during the Cretaceous.     

Anthropogenic CO2 in Southern Ocean surface waters: evidence from stable organic carbon isotopes

We present an approach for tracing the fate of anthropogenic CO₂, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ¹³C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO₂ (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO₂ concentrations in Atlantic surface waters, estimated from the δ¹³C_org of surface sediments, are compared to recently measured surface water [CO₂ (aq)] values taken from literature. We obtain only a slight increase in [CO₂ (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO₂ released by human activities has been stored in Southern Ocean surface waters.     

40Ar/39Ar Constraints on the tectonic history and architecture of the ultrahigh-pressure Sulu orogen

New ⁴⁰Ar/³⁹Ar ages are presented from the giant Sulu ultrahigh-pressure (UHP) terrane and surrounding areas. Combined with U-Pb ages, Sm-Nd ages, Rb-Sr ages, inclusion relationships, and geological relationships, they help define the orogenic events before, during and after the Triassic collision between the Sino–Korean and Yangtze Cratons. In the Qinling microcontinent, tectonism occurred between 2.0 and 1.4 Ga. The UHP metamorphism occurred in the Yangtze Craton between 240 and 222 Ma; its thermal effect on the Qinling microcontinent was limited to partial resetting of K-feldspar ⁴⁰Ar/³⁹Ar ages. Subsequent unroofing at rates of 5–25 km Myr⁻¹ brought the UHP terrane to crustal levels where it underwent a relatively short amphibolite facies metamorphism. The end of that metamorphism is marked by ⁴⁰Ar/³⁹Ar ages in the 219–210 Ma range, implying cooling at crustal depths at rates of 50–200 °C Myr⁻¹. Ages in the 210–170 Ma range may reflect protracted cooling or partial resetting by Jurassic or Cretaceous magmatism. Jurassic 166–149 Ma plutonism was followed by cooling at rates of c. 15 °C Myr⁻¹, suggesting relatively deep crustal conditions, whereas Cretaceous 129–118 Ma plutonism was succeeded by cooling at rates of c. 50 C Myr⁻¹, suggesting relatively shallow crustal depths.     

Very high 18o enrichment in Archean cherts from South India: implications for Archean ocean temperature

Stable carbon and oxygen isotopic compositions of essentially unmetamorphosed Archean (> 2.6 Gyr old) cherts and carbonates of the Dharwar Sequence of southern India, from the northernmost part of the Dharwar-Shimoga supracrustal belt (Kalche and Nagargali), have been determined. The cherts from the Nagargali area, which preserve oolitic texture and cryptocrystalline silica, show highly enriched δ¹⁸O values ranging from 28 to 31.4%o relative to SMOW. Such values are the highest yet reported from Archean nondetrital sediments, but are similar to those of modern marine cherts. On the assumption of a seawater δ¹⁸O of 0%₀, calculation of temperature based on the maximum δ¹⁸O value of 31.4%₀ yields a value of 40°C. This is significantly less than 70–80°C reported for the Archean oceans based on cherts and chert-phosphate pairs. Diagenetically recrystallized microcrystalline chert-dolomite pairs of Kalche area exhibit a range of oxygen isotopic ratios similar to those reported for Archean cherts and carbonates from other parts of the world. The temperature of diagenesis is estimated to be about 68°C.     

Reconsideration of the age of blueschist facies metamorphism on the Seward Peninsula, Alaska, based on phengite 40Ar/39Ar results

Abstract ⁴⁰Ar/³⁹Ar step-heating and single-grain laser fusion ages from phengites from the polydeformed and polymetamorphosed blueschist-greenschist facies Nome Group fall into two groups. Samples from the upper part of the structural section that have experienced a relatively weak metamorphic and deformational post-blueschist facies overprint and one sample from the Cape Nome orthogneiss yield plateau ages of 116-125 Ma. More intensely overprinted samples yield hump-shaped spectra with minimum ages of 123 Ma and maximum ages of 334 Ma. Samples with hump-shaped spectra are derived from a greater structural depth than most samples with plateau ages. Unreasonably old maximum ages from some of the disturbed spectra suggest that the hump-shaped spectra result from the incorporation of excess ⁴⁰Ar. This interpretation conflicts with previous interpretations of similarly disturbed spectra from the Brooks Range, which have been argued to provide minimum ages for blueschist facies metamorphism. Since the maximum temperatures achieved by all samples were probably above the blocking temperature of Ar in phengite, the 116-125 Ma plateau ages are a minimum age for blueschist facies metamorphism on the Seward Peninsula, Alaska.     

Sr-Nd-Pb isotope ratios, geochemical compositions, and 40Ar/39Ar data of lavas from San Felix Island (Southeast Pacific): Implications for magma genesis and sources

We present the first trace element and age data combined with new Sr, Nd, and Pb isotope ratios on lavas from San Felix Island in the Southeast Pacific. A ⁴⁰Ar/³⁹Ar plateau age of 421 ± 18 ka implies young intraplate volcanic activity in this region relative to the ∼22 Ma old volcanism on the neighbouring Easter seamount chain (ESC). The incompatible element compositions of the San Felix magmas are similar to those of EM1-type basalts from Gough, although the isotopic compositions differ. San Felix formed some 20 Ma after the ESC plume affected the plate in this region but no chemical signature of the ESC material is observed in the young volcanic rocks. The composition of the San Felix basalts indicates a mantle source containing old continental lithospheric material from either metasomatized mantle or recycled sediments, which ascends in a weak mantle plume.     

Tectonothermal evolution of high-alumina rocks within the Protogine Zone, southern Sweden

Abstract The Protogine Zone comprises a system of anastomosing deformation zones which approximately parallel the eastern boundary of the Sveconorwegian (1200–900 Ma) province in south-west Sweden. Ages of granulite facies metamorphism in the Sveconorwegian province require exhumation from c . 30 to 35 km crustal depths after 920–880 Ma. ⁴⁰Ar/³⁹ Ar cooling ages are presented for muscovite from high-alumina rocks formed by hydrothermal leaching associated with the Protogine Zone. Growth of fabric-defining minerals was associated with a ductile deformational event; muscovite from these rocks cooled below argon retention temperatures ( c . 375 ± 25° C) at c . 965–955 Ma. Muscovite from granofels in zones of intense alteration indicates that temperatures > 375 ± 25° C were maintained until c . 940 Ma. Textural relations of Al₂SiO₅ polymorphs and chloritoid suggest that dated fabrics formed during exhumation. The process of exhumation, brittle overprint on ductile structures and hydrothermal activity along faults within the Protogine Zone tentatively are interpreted as the peripheral effects of initial Neoproterozoic exhumation of the granulite region of south-western Sweden.
Muscovite in phyllonites associated with the 'Sveconorwegian thrust system'cooled below argon retention temperatures at c . 927 Ma. Exhumation associated with this cooling could have been related to extension and onset of brittle-ductile deformation superimposed on Sveconorwegian contraction.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

Three Secondary Reference Materials for Lithium Isotope Measurements: Li7-N, Li6-N and LiCl-N Solutions

The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing ⁷Li or ⁶Li spikes and either L-SVEC or IRMM-016 certified reference materials to produce solutions having a known Li concentration and isotopic composition. The Li7-N and Li6-N solution samples (1.5 mol l⁻¹ HNO₃) have nominal δ⁷Li isotopic compositions of 30.1‰ and -9.7‰ respectively relative to L-SVEC and concentrations of 100 mg l⁻¹. Repeated measurement of these samples using the QUAD-ICP-MS at the CRPG yielded δ⁷Li of 30.4 ± 1.1‰ (n = 13) and -8.9 ± 0.9‰ (n = 9) at the 2s level of confidence. An additional LiCl-N solution was measured and yielded a delta value of 9.5 ± 0.6‰ (n = 3). Identical results were obtained at the BRGM (Orléans, France) from determinations performed with a Neptune MC-ICP-MS (30.2 ± 0.3‰, n = 89 for the Li7-N, -8.0 ± 0.3‰, n = 38 for the Li6-N and 10.1 ± 0.2‰, n = 46 for LiCl-N at the 2s level of confidence). The deviation of measured composition relative to the nominal value for the Li6-N solution might be explained by either contamination during preparation or an error during sample weighing. These secondary reference materials, previously passed through ion exchange resin or directly analysed, may be used for checking the accuracy of Li isotopic measurements over a range of almost 40‰ and will be available to the scientific community upon request to J. Carignan or N. Vigier, CRPG.