Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ⁶⁵Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ⁶⁵Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ⁶⁵Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ⁶⁵Cu. Additionally, four reference materials (with published δ⁶⁵Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g^?1 to 497 µg g^?1 and δ⁶⁵Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

Sub‐Permil Interlaboratory Consistency for Solution‐Based Boron Isotope Analyses on Marine Carbonates

Boron isotopes in marine carbonates are increasingly used to reconstruct seawater pH and atmospheric pCO₂ through Earth’s history. While isotope ratio measurements from individual laboratories are often of high quality, it is important that records generated in different laboratories can equally be compared. Within this Boron Isotope Intercomparison Project (BIIP), we characterised the boron isotopic composition (commonly expressed in δ¹¹B) of two marine carbonates: Geological Survey of Japan carbonate reference materials JCp‐1 (coral Porites) and JCt‐1 (giant clam Tridacna gigas). Our study has three foci: (a) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ¹¹B; (b) to determine to what degree the chosen analytical approach may affect the resultant δ¹¹B; and (c) to provide well‐constrained consensus δ¹¹B values for JCp‐1 and JCt‐1. The resultant robust mean and associated robust standard deviation (s*) for un‐oxidised JCp‐1 is 24.36 ± 0.45‰ (2s*), compared with 24.25 ± 0.22‰ (2s*) for the same oxidised material. For un‐oxidised JCt‐1, respective compositions are 16.39 ± 0.60‰ (2s*; un‐oxidised) and 16.24 ± 0.38‰ (2s*; oxidised). The consistency between laboratories is generally better if carbonate powders were oxidatively cleaned prior to purification and measurement.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Genesis of the Changba–Lijiagou Giant Pb-Zn Deposit, West Qinling, Central China: Constraints from S-Pb-C-O isotopes

The extensive Changba-Lijiagou Pb-Zn deposit is located in the north of the Xihe–Chengxian ore cluster in West Qinling. The ore bodies are mainly hosted in the marble, dolomitic marble and biotite-calcite-quartz schist of the Middle Devonian Anjiacha Formation, and are structurally controlled by the fault and anticline. The ore-forming process can be divided into three main stages, based on field geological features and mineral assemblages. The mineral assemblages of hydrothermal stage I are pale-yellow coarse grain, low Fe sphalerite, pyrite with pits, barite and biotite. The mineral assemblages of hydrothermal stage II are black-brown cryptocrystalline, high Fe shalerite, pyrite without pits, marcasite or arsenopyrite replace the pyrite with pits, K-feldspar. The features of hydrothermal stage III are calcite-quartz-sulfide vein cutting the laminated, banded ore body. Forty-two sulfur isotope analyses, twenty-five lead isotope analyses and nineteen carbon and oxygen isotope analyses were determined on sphalerite, pyrite, galena and calcite. The δ34 S values of stage I(20.3 to 29.0‰) are consistent with the δ34 S of sulfate(barite) in the stratum. Combined with geological feature, inclusion characteristics and EPMA data, we propose that TSR has played a key role in the formation of the sulfides in stage I. The δ34 S values of stage II sphalerite and pyrite(15.1 to 23.0‰) are between sulfides in the host rock, magmatic sulfur and the sulfate(barite) in the stratum. This result suggests that multiple S reservoirs were the sources for S2-in stage II. The δ34 S values of stage III(13.1 to 22‰) combined with the structure of the geological and mineral features suggest a magmatic hydrothermal origin of the mineralization. The lead isotope compositions of the sulfides have 206 Pb/204 Pb ranging from 17.9480 to 17.9782, 207 Pb/204 Pb ranging from 15.611 to 15.622, and 208 Pb/204 Pb ranging from 38.1368 to 38.1691 in the three ore-forming stages. The narrow and symmetric distributions of the lead isotope values reflect homogenization of granite and mantle sources before the Pb-Zn mineralization. The δ13 CPDB and δ18 OSMOW values of stage I range from-0.1 to 2.4‰ and from 18.8 to 21.7‰. The values and inclusion data indicate that the source of fluids in stage I was the dissolution of marine carbonate. The δ13 CPDB and δ18 OSMOW values of stage II range from-4 to 1‰ and from 12.3 to 20.3‰, suggesting multiple C-O reservoirs in the Changba deposit and the addition of mantle-source fluid to the system. The values in stage III are-3.1‰ and 19.7‰, respectively. We infer that the process of mineralization involved evaporitic salt and sedimentary organic-bearing units interacting through thermochemical sulfate reduction through the isotopic, mineralogy and inclusion evidences. Subsequently, the geology feature, mineral assemblages, EPMA data and isotopic values support the conclusion that the ore-forming hydrothermal fluids were mixed with magmatic hydrothermal fluids and forming the massive dark sphalerite, then yielding the calcite-quartz-sulfide vein ore type at the last stage. The genesis of this ore deposit was epigenetic rather than the previously-proposed sedimentary-exhalative(SEDEX) type.     

Silicification of sulphate evaporites and their carbonate replacements in Eocene marine sediments, Tunisia: two diagenetic trends

Samples of chert nodules, diagenetic carbonates and evaporites (gypsum/anhydrite) collected from the gypsiferous limestones of the Kef Eddour Member (Ypressian‐Priabonian) near Metlaoui and Sehib (Tunisia) show selective silicification with great variety in the silicified by‐products. Based on δ¹³C values, which support an organic origin for the carbon, carbonates replaced evaporites microbially through bacterial sulphate reduction. Observations and results suggest two scenarios for chert formation that are related to the rate and timing of diagenetic carbonate replacement of the evaporites (anhydrite/gypsum). In the absence of early diagenetic carbonate phases, silica with δ¹⁸O values from +25 to +28·6‰ [standard mean ocean water (SMOW)] replaced the outer parts of anhydrite nodules at pH < 9. In contrast, pore‐fluid pH values > 9 in the innermost parts of the anhydrite nodules prevented silica precipitation. The record of this chemical barrier is preserved in the microquartz rims and geode features that formed in the inner parts of the nodules after dissolution of the anhydrite nucleus. The microbial diagenetic replacement of evaporites (bacterial sulphate reduction) by carbonates (calcite, aragonite and dolomite) favoured silica replacement of carbonates rather than evaporites. Silica, with δ¹⁸O signature of +21 to +26‰ (SMOW), replaced carbonates on a volume‐for‐volume basis, yielding a more siliceous groundmass, and accounting for 90–95% of the nodules. The relatively higher δ¹⁸O values of quartz replacing anhydrite can be explained by a diagenetic fluid in equilibrium with mixed (meteoric/marine) to marine water. The lower δ¹⁸O values of the quartz that replaced the diagenetic carbonates are ascribed to flushing by meteoric water in a later diagenetic stage. The silica supply for chert formation could be derived from the reworked bio‐siliceous deposits (diatomites) to the west of the basin [vestiges of an opal‐CT precursor undetectable by X‐ray diffraction (XRD) were revealed by δ²⁹Si magic‐angle‐spinning nuclear magnetic resonance investigations], diagenesis of the extraformational and overlying clay‐rich beds (the host limestones are clay‐poor as shown by XRD measurements), and minor volcanogenic and hydrothermal contributions during early diagenetic stages.     

Effect of pedogenesis on the stable isotopic composition of calcretes and n‐alkanes: Implications for palaeoenvironmental reconstruction

In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ¹³C_PC and δ¹⁸O_PC) showed more variation compared with non‐pedogenic pond calcretes (δ¹³C_SPC and δ¹⁸O_SPC) in profile‐B. The δ¹³C_PC and δ¹³C_SPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ¹⁸O_PC and δ¹⁸O_SPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ¹³C_OM) and n‐alkanes (δ¹³C_n‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ¹³C_OM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ¹³C_OM values is a result of the difference in the sources and preservation of organic matter. However, the δ¹³C_n‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ¹³C_n‐alk values are unaffected by the pedogenic modifications.     

MC‐ICP‐MS Isotope Measurements with Direct Injection Nebulisation (d‐DIHEN): Optimisation and Application to Boron in Seawater and Carbonate Samples

We report here an optimisation of the demountable direct injection high efficiency nebuliser (d‐DIHEN) for isotopic measurements with a Neptune (ThermoFisher Scientific, Bremen, Germany) multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS) and describe a method for boron isotopic ratio determination. With direct injection nebulisation 100% of the analyte was introduced into the ICP‐MS plasma and wash times were drastically reduced for elements such as boron and thorium. Compared to the classical stable introduction system (SIS: double Scott/cyclonic spray chamber), sensitivity for boron was 2–5 times higher with d‐DIHEN and wash times up to ten times shorter. Repeatability of ¹¹B/¹⁰B sample‐calibrator bracketing measurements reached 0.25‰ (2s) for seawater and coral samples. Method accuracy and reproducibility were tested on mixed reference solutions having δ¹¹B values in the ranges ?90 to +40‰ and ?2 to +2.5‰, demonstrating our ability to distinguish δ¹¹B values with differences of only 0.25‰. The international seawater reference material NRCC NASS‐5 (National Research Council, Ottawa, Canada), analysed in different sessions over a 10‐month period, yielded an average δ¹¹B value of +39.89 ± 0.25‰, in the upper range of previously published seawater values. A comparison between δ¹¹B determined by d‐DIHEN MC‐ICP‐MS and positive‐TIMS (P‐TIMS) for four modern corals showed an excellent agreement (with bias of less than 0.4‰).     

Geochemical constraint on origin and evolution of solutes in geothermal springs in western Yunnan,China

Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO₃, Na–HCO₃, and Na (Ca)–SO₄ type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ¹¹B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ¹¹B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ¹⁸O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ¹¹B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ¹¹B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.     

Geochemical and boron,oxygen and hydrogen isotopic constraints on the origin of salinity in groundwaters from the crystalline basement of the Alpine Foreland

The B isotopic composition, in combination with O and H isotopes and hydrochemical tracers, is utilized to constrain the evolution of basement-hosted groundwaters via water–rock interactions and fluid infiltration from external (sedimentary) reservoirs. Two distinct groundwater types have been identified in the Central European crystalline basement (N Switzerland–SW Germany): (1) fresh groundwaters characterized by low values of δ¹¹B (−3.5 to −0.6‰), δ¹⁸O (−12.0 to −10.0‰), and δD (−86.8 to −71.9‰), and (2) brackish groundwaters with distinctly heavier B, O, and H isotopic compositions (δ¹¹B=+6.4 to +17.6‰, δ¹⁸O=−9.4 to −5.6‰, δD=−67.6 to −60.8‰). Fresh groundwaters show a systematic decrease in δ¹¹B, related to an increase in B concentrations (and degree of total mineralization), along the pathway of groundwater migration which can only be interpreted in terms of leaching of crystalline host rocks. A δ¹¹B value of −3.3‰ is inferred for the crustal B source (mainly Hercynian granites) involved in the leaching process, in agreement with the known δ¹¹B range of granitic rocks. The evolution of brackish groundwaters, derived from crystalline basement reservoirs with little water circulation, is more complex. As indicated by B–O–H stable isotope and hydrochemical (e.g. B/Cl, Na/Cl, and Br/Cl) constraints, brackish groundwaters from the study area are influenced by admixture of sediment-derived fluids which infiltrated from Late Paleozoic (Permo-Carboniferous) and Early Mesozoic (Lower Triassic) sedimentary strata. The data presented show that B isotopes are sensitive to mixing processes of fluids derived from different crustal reservoirs and, hence, may be utilized as a tracer for constraining the internal (autochthonous) vs external (allochthonous) origin of salinity in basement-hosted groundwaters.     

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemical Evidence of 13C,18O and 87Sr/86Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and 87Sr/86Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than ?5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate-derived, with the δ13C generally more than ?2.0‰PDB, δ18O less than ?10.0‰PDB, Z value more than 120 and 87Sr/86Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid (including possibly a little mantle-derived fluid or meteoric water), with the δ13C generally ranging from ?2.0‰ to ?8.0‰PDB, δ18O from ?10.0‰ to ?18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to ?10.0‰PDB, δ18O less than ?8.0‰PDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

NIST RM 8301 Boron Isotopes in Marine Carbonate (Simulated Coral and Foraminifera Solutions): Inter‐laboratory δ11B and Trace Element Ratio Value Assignment

The boron isotopic ratio of ¹¹B/¹⁰B (δ¹¹B_SRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ¹¹B_SRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ¹¹B_SRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.     

Change of Organic δ13C in Ornithogenic Sediments of the Xisha Archipelago, South China Sea and its Implication for Ecological Development

Organic carbon isotopes in sediments have been frequently used to identify the source of organic matter.Here we present a study of organic δ~(13)C on two sediment profiles influenced by guano from Guangjin and Jinqing islands in the Xisha Archipelago,South China Sea.Organic matter from ornithogenic coral sand sediments has two main sources,guano pellets and plant residues,and their organic δ~(13)C(δ~(13)C_(OM)) are significantly different.Organic carbon δ~(13)C_(guano) is much higher thanδ~(13)C_(plants),and δ~(13)C_(OM)of bulk samples is intermediate.Based on a two-end-member mixing model,the proportions of guano-and plant-derived organic matter in the bulk samples were reconstructed quantitatively.The results showed that seabirds began to inhabit the islands around approximately1200-1400 AD,and that guano pellets have been an important source of soil organic matter since then.With the accumulation of guano-derived nutrients,plants began to develop prosperously on the islands in the last 200 years,which is reflected by the significant increase of plant-derived organic matter in the upper sediment layer.However,guano-derived organic matter decreased greatly in recent decades,indicating a rapid decrease in seabird population.Our results show that organic δ~(13)C can be effectively used to quantitatively determine different source contributions of OM to bulk ornithogenic coral sand sediments.     

Primary and diagenetic isotopic signals in fossils and hemipelagic carbonates: the Lower Jurassic of northern Spain

Stable isotope and trace element analyses of 230 Jurassic (Pliensbachian–Toarcian) samples from northern Spain have been performed to test the use of geochemical variations in fossils (belemnites and brachiopods) and whole‐rock hemipelagic carbonates as palaeoceanographic indicators. Although the succession analysed (Reinosa area, westernmost Basque–Cantabrian Basin) has been subject to severe thermal alteration during burial diagenesis, the samples appear to be well preserved. The degree of diagenetic alteration of the samples has been assessed through the application of integrated petrographic, chemical and cathodoluminescence analyses. It is demonstrated that brachiopods and whole‐rock carbonates, although widely used for palaeoceanic studies, do not retain their primary marine geochemical composition after burial diagenesis. In contrast, there is strong evidence that belemnite rostra preserve original isotopic values despite pervasive diagenesis of the host rock. Well‐preserved belemnite shells (non‐luminescent to slightly luminescent) typically show stable isotope values of +4·3‰ to –0·7‰δ¹³C, +0·7‰ to –3·2‰δ¹⁸O, and trace element contents of <32 μg g^–1 Mn, <250 μg g^–1 Fe, >950 μg g^–1 Sr and Sr/Mn ratios >80. This study suggests that the degree to which diagenesis has affected the preservation of an original isotopic composition may differ for different low‐Mg calcite fossil shells and hemipelagic bulk carbonates, behaviour that should be considered when marine isotopic signatures from other ancient carbonate rocks are investigated. Multiple non‐luminescent contemporaneous belemnite samples passed the petrographic and geochemical tests to be considered as palaeoceanic recorders, yet their δ¹³C and δ¹⁸O values exhibited moderate scatter. Such variability is likely to be related to the palaeoecological behaviour of belemnites and/or high‐frequency secular variations in sea‐water chemistry superimposed on the long‐term isotopic trend. A pronounced positive carbon‐isotope excursion (up to +4·3‰) is documented in the early Toarcian serpentinus biozone, which correlates with the Toarcian δ¹³C maximum reported in other European and Tethyan regions.     

The δ60/58Ni Values of Twenty‐Six Selected Geological Reference Materials

The high‐precision δ^60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ^60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ^60/58Ni _{NIST SRM 986} values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ^60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.     

Palaeoenvironmental and diagenetic reconstruction of a closed‐lacustrine carbonate system – the challenging marginal setting of the Miocene Ries Crater Lake (Germany)

Chemostratigraphic studies on lacustrine sedimentary sequences provide essential insights on past cyclic climatic events, on their repetition and prediction through time. Diagenetic overprint of primary features often hinders the use of such studies for palaeoenvironmental reconstruction. Here the potential of integrated geochemical and petrographic methods is evaluated to record freshwater to saline oscillations within the ancient marginal lacustrine carbonates of the Miocene Ries Crater Lake (Germany). This area is critical because it represents the transition from shoreline to proximal domains of a hydrologically closed system, affected by recurrent emergent events, representing the boundaries of successive sedimentary cycles. Chemostratigraphy targets shifts related to subaerial exposure and/or climatic fluctuations. Methods combine facies changes with δ ¹³C–δ ¹⁸O chemostratigraphy from matrix carbonates across five closely spaced, temporally equivalent stratigraphic sections. Isotope composition of ostracod shells, gastropods and cements is provided for comparison. Cathodoluminescence and back‐scatter electron microscopy were performed to discriminate primary (syn‐)depositional, from secondary diagenetic features. Meteoric diagenesis is expressed by substantial early dissolution and dark blue luminescent sparry cements carrying negative δ ¹³C and δ ¹⁸O. Sedimentary cycles are not correlated by isotope chemostratigraphy. Both matrix δ ¹³C and δ ¹⁸O range from ca −7·5 to +4·0‰ and show clear positive covariance (R  = 0·97) whose nature differs from that of previous basin‐oriented studies on the lake: negative values are here unconnected to original freshwater lacustrine conditions but reflect extensive meteoric diagenesis, while positive values probably represent primary saline lake water chemistry. Noisy geochemical curves relate to heterogeneities in (primary) porosity, resulting in selective carbonate diagenesis. This study exemplifies that ancient lacustrine carbonates, despite extensive meteoric weathering, are able to retain key information for both palaeoenvironmental reconstruction and the understanding of diagenetic processes in relation to those primary conditions. Also, it emphasizes the limitation of chemostratigraphy in fossil carbonates, and specifically in settings that are sensitive for the preservation of primary environmental signals, such as lake margins prone to meteoric diagenesis.     

Barium Isotopic Compositions in Thirty‐Four Geological Reference Materials Analysed by MC‐ICP‐MS

Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g^?1, SiO₂ from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ^138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ^138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ^138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.     

A Rapid Method for Determining Boron Concentration (ID‐ICP‐MS) and δ11B (MC‐ICP‐MS) in Vegetation Samples after Microwave Digestion and Cation Exchange Chemical Purification

We present in this article a rapid method for B extraction, purification and accurate B concentration and δ¹¹B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ¹¹B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g^?1 of total salts or 25 μg g^?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ¹¹B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).     

Sedimentological and marine eogenetic control on porosity distribution in Upper Cretaceous carbonate turbidites (central Albania)

Results of a detailed petrographic and stable isotope study illustrate that sedimentological differences and eogenetic dissolution/precipitation processes controlled porosity distribution within carbonate turbidites of the Ionian basin (central Albania). Based on lithology characteristics and porosity distribution observed in outcrop, individual turbidite beds can be subdivided into four distinct intervals, i.e. from base to top: (A) a non‐porous wackestone/floatstone or packstone followed by (B) porous packstone–grainstone that grades into (C) wackestone and (D) non‐porous mudstone with pelagic foraminifera. Wackestone interval C is characterized by an alternation of porous and non‐porous laminae. Changes in turbidity current flow regime controlled the initial presence of matrix micrite giving rise to both matrix‐ and grain‐supported lithologies within turbidite sequences. These are non‐porous and porous, respectively. Four eogenetic diagenetic processes (dissolution, cementation, neomorphism and compaction) acted shortly after deposition and modified primary porosity characteristics and distribution. Alteration by meteoric water is excluded based on the continuous burial until the Oligocene of the studied deep marine carbonates. Moreover, the stable isotope data with values between −2·1‰ and +0·7‰ for δ¹⁸O_V‐PDB and between +1‰ and +3‰ for δ¹³C_V‐PDB, favour alteration by marine‐derived pore‐waters. Compaction and aggrading neomorphism occurred dominantly in intervals characterized by higher matrix micrite content, i.e. the floatstone base and the wackestone–mudstone upper turbidite part. Framework‐stabilizing cementation occurred dominantly in the packstone–grainstone middle part of the turbidite beds. In the latter porous lithologies, matrix micrite was not compacted because of the grain fabric and the framework‐stabilizing cements. Here, neomorphism of micrite into microrhombic euhedral calcite occurred and microporosity was preserved.