Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia

The well-studied Paleozoic Cooma metamorphic complex in southeastern Australia is characterized by a uniform siliciclastic protolith, of uniform age, with a continuous range of metamorphic grade from subgreenschist- to upper amphibolite-facies, and migmatite-grade in an annular pattern around the Cooma granodiorite. Those conditions are optimal for investigating variations of N concentrations and δ¹⁵N values during progressive metamorphism. Nitrogen concentrations decrease and δ¹⁵N increases with increasing metamorphic grade (sub-chlorite zone: 120 ppm N, δ¹⁵N = 2.3‰; chlorite zone: 110 ppm N, δ¹⁵N = 3.0‰; biotite and andalusite zone: 85 ppm N, δ¹⁵N = 3.8 ‰; sillimanite and migmatite zones: 40 ppm N, δ¹⁵N = 10.7‰). Covariation of K and N contents is consistent with N substituting for K as NH₄⁺ in micas. Observed trends of increasing δ¹⁵N values with decreasing nitrogen concentrations can be explained by a continuous release of nitrogen depleted in ¹⁵N with progressive metamorphism, which causes an enrichment of ¹⁵N in the residual nitrogen of the rock. Equilibrium models for Rayleigh distillation and batch volatilisation for data of the greenschist and amphibolite facies metasedimentary rocks can be explained by N₂-NH₄⁺ exchange at temperatures of 300-600 °C, whereas observed large fractionations for the upper amphibolite-facies and melt products in the migmatite-grade samples may be interpreted as NH₃-NH₄⁺ exchanges at temperature of 650-730 °C. Lower values in the highest grade zones may also stem in part from input of ¹⁵N-depleted fluids from the granodiorite.The magnitude of isotope fractionation of nitrogen is about 1-2‰ during progressive metamorphism of metasedimentary rocks from sub-chlorite zone to biotite-andalusite zone, which is consistent with previous studies. Consequently, the large spread of δ¹⁵N values in Archean greenschist-facies metasedimentary rocks of −6‰ to 30‰ can be accounted for by variable mixtures of mantle plume-dominated volatiles with a δ¹⁵N of −5‰, and a ¹⁵N-enriched marine sedimentary kerogen component inherited from a CI chondrite veneer having δ¹⁵N of 30‰ to 42‰.     

Assessment of grain-scale homogeneity and equilibration of carbon and oxygen isotope compositions of minerals in carbonate-bearing metamorphic rocks by ion microprobe

Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ¹⁸O and ±0.71‰ for δ¹³C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ¹⁸O and 0.10-0.29‰ for δ¹³C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ¹³C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ¹³C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ¹⁸O (up to 9.4‰), intercrystalline inhomogeneity in δ¹⁸O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ¹⁸O and δ¹³C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ¹⁸O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ¹⁸O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.     

Ammonium loss and nitrogen isotopic fractionation in biotite as a function of metamorphic grade in metapelites from western Maine, USA

Ammonium fixed in micas of metamorphic rocks is a sensitive indicator both of organic-inorganic interactions during diagenesis as well as of the devolatilization history and fluid/rock interaction during metamorphism. In this study, a collection of geochemically well-characterized biotite separates from a series of graphite-bearing Paleozoic greenschist- to upper amphibolite-facies metapelites, western Maine, USA, were analyzed for ammonium nitrogen () contents and isotopic composition (δ¹⁵N_NH4) using the HF-digestion distillation technique followed by the EA-IRMS technique. Biotite separates, sampled from 9 individual metamorphic zones, contain 3000 to 100 ppm with a wide range in δ¹⁵N from +1.6‰ to +9.1‰. Average contents in biotite show a distinct decrease from about 2750 ppm for the lowest metamorphic grade (∼500 °C) down to 218 ppm for the highest metamorphic grade (∼685 °C). Decreasing abundances in are inversely correlated in a linear fashion with increasing K⁺ in biotite as a function of metamorphic grade and are interpreted as a devolatilization effect. Despite expected increasing δ¹⁵N_NH4 values in biotite with nitrogen loss, a significant decrease from the Garnet Zones to the Staurolite Zones was found, followed by an increase to the Sillimanite Zones. This pattern for δ¹⁵N_NH4 values in biotite inversely correlates with Mg/(Mg + Fe) ratios in biotite and is discussed in the framework of isotopic fractionation due to different exchange processes between or , reflecting devolatilization history and redox conditions during metamorphism.     

On the possibility of a kinetic fractionation of nitrogen stable isotopes during natural diamond growth

In a diamond from New South Wales (Australia), cubic and octahedral growth sectors, as identified by cathodoluminescence (CL), show slight differences in N-contents of 29 and 42 ppm respectively but no significant differences in either δ¹³C, δ¹⁵N and nitrogen aggregation state with values at +1.96‰, +19.4‰, and 25% Type IaAB aggregation, respectively.Two gem cubes from the Orapa kimberlite (Botswana) were studied by CL revealing a nonfaceted cubic growth. Accordingly, nine other gem cubes were combusted and yielded δ¹³C-values from -5.33‰ to -6.63‰, δ¹⁵N from -1.0‰ to -5.5‰, and nitrogen contents from 914 to 1168 ppm, with nitrogen aggregation state being only Type IaA (zero % B). The gem cubes show striking similarities to fibrous/coated diamonds, not only in both δ¹³C ranges (less than 3‰ from -5 to -8‰), but also in the high levels of nitrogen (≈ 1000 ppm), suggesting that the two diamond types are related. Additionally, no δ¹⁵N variation was detected between the cube and octahedral growth sectors of the Australian diamond, in the cube sectors of the nine gem cubes from Botswana, nor in fibrous/coated diamonds previously studied. These analyses contrast with an earlier study on a synthetic diamond, which reported a strong kinetic fractionation of N-isotopes of about 40‰ between cube and octahedral growth. The present evidence, therefore, suggests that kinetic fractionation of N-isotopes does not operate during natural diamond formation.     

Nitrogen components in ureilites

Abundances and isotopic compositions of nitrogen and argon have been investigated in bulk samples as well as in acid-resistant C-rich residues of a suite of ureilites consisting of six monomict (Haverö, Kenna, Lahrauli, ALH81101, ALH82130, LEW85328), three polymict (Nilpena, EET87720, EET83309), and the diamond-free ureilite ALH78019. Nitrogen in bulk ureilites varies from 6.3 ppm (in ALH 78019) to ∼55 ppm (in ALH82130), whereas C-rich acid residues have ∼65 to ∼530 ppm N, showing approximately an order of magnitude enrichment, compared with the bulk ureilites, somewhat less than trapped noble gases. Unlike trapped noble gases that show uniform isotopic composition, nitrogen shows a wide variation in δ¹⁵N values within a given ureilite as well as among different ureilites. The variations observed in δ¹⁵N among the ureilites studied here suggest the presence of at least five nitrogen components. The characteristics of these five N components and their carrier phases have been identified through their release temperature during pyrolysis and combustion, their association with trapped noble gases, and their carbon (monitored as CO + CO₂ generated during combustion). Carrier phases are as follows: 1) Amorphous C, as found in diamond-free ureilite ALH78019, combusting at ≤500°C, with δ¹⁵N = -21‰ and accompanied by trapped noble gases. Amorphous C in all diamond-bearing ureilites has evolved from this primary component through almost complete loss of noble gases, but only partial N loss, leading to variable enrichments in ¹⁵N. 2) Amorphous C as found in EET83309, with similar release characteristics as component 1, δ¹⁵N ≥ 50‰ and associated with trapped noble gases. 3) Graphite, as clearly seen in ALH78019, combusting at ≥700°C, δ¹⁵N ≥ 19‰ and devoid of noble gases. 4) Diamond, combusting at 600-800°C, δ¹⁵N ≤ -100‰ and accompanied by trapped noble gases. 5) Acid-soluble phases (silicates and metal) as inferred from mass balance are expected to contain a large proportion of nitrogen (18 to 75%) with δ¹⁵N in the range -25‰ to 600‰. Each of the ureilites contains at least three N components carried by acid-resistant C phases (amorphous C of type 1 or 2, graphite, and diamond) and one acid-soluble phase in different proportions, resulting in the observed heterogeneity in δ¹⁵N. In addition to these five widespread components, EET83309 needs an additional sixth N component carried by a C phase, combusting at <700°C, with δ¹⁵N ≥ 153‰ and accompanied by noble gases. It could be either noble gas-bearing graphite or more likely cohenite. Some excursions in the δ¹⁵N release patterns of polymict ureilites are suggestive of contributions from foreign clasts that might be present in them.Nitrogen isotopic systematics of EET83309 clearly confirm the absence of diamond in this polymict ureilite, whereas the presence of diamond is clearly indicated for ALH82130. Amorphous C in ALH78019 exhibits close similarities to phase Q of chondrites.The uniform δ¹⁵N value of −113 ± 13 ‰ for diamond from both monomict and polymict ureilites and its independence from bulk ureilite δ¹⁵N, Δ¹⁷O, and %Fo clearly suggest that the occurrence of diamond in ureilites is not a consequence of parent body-related process. The large differences between the δ¹⁵N of diamond and other C phases among ureilites do not favor in situ shock conversion of graphite or amorphous C into diamond. A nebular origin for diamond as well as the other C phases is most favored by these data. Also the preservation of the nitrogen isotopic heterogeneity among the carbon phases and the silicates will be more consistent with ureilite formation models akin to “nebular sedimentation” than to “magmatic” type.     

Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation

Dissolved inorganic nitrogen, largely in reduced form (), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH₄(T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH₄(T) concentration and δ¹⁸O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH₄(T) and other solutes in some areas. The isotopic composition of dissolved NH₄(T) is highly variable (δ¹⁵N = −6‰ to +30‰) and is positively correlated with pH values. In comparison to likely δ¹⁵N values of nitrogen source materials (+1‰ to +7‰), high δ¹⁵N values in hot springs with pH >5 are attributed to isotope fractionation associated with loss by volatilization. NH₄(T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative δ¹⁵N values that are attributed to condensation. NH₄(T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH₄(T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.     

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because ³⁴S/³²S ratios of vent fluid H₂S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ³³S (≡δ³³S-0.515 δ³⁴S) values of up to 0.04‰ even if δ³⁴S values are identical. Detection of such small Δ³³S differences is technically feasible by using the SF₆ dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H₂S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ³³S values ranging from −0.002 to 0.033 and δ³⁴S from −0.5‰ to 5.3‰. The combined δ³⁴S and Δ³³S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ³⁴S but also in Δ³³S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ³³S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that ³³S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.     

The isotopic composition of nitrate produced from nitrification in a hardwood forest floor

Dual isotopic analysis of nitrate (¹⁵N/¹⁴N and ¹⁸O/¹⁶O) is increasingly used to investigate the environmental impacts of human-induced elevated atmospheric nitrate deposition. In forested ecosystems, the nitrate found in surface water and groundwater can originate from two sources: (1) atmospheric deposition, and (2) nitrate produced from nitrification in forest soils (microbial nitrate). Application of the dual nitrate isotope technique for determining the relative importance of nitrate sources in forested catchments requires knowledge of the isotopic composition of microbial nitrate. We excluded precipitation inputs to three zero-tension lysimeters installed below the F-horizon (Oe) at the Turkey Lakes Watershed (TLW) in order to measure the isotopic composition of microbial nitrate produced in situ. To our knowledge, this is the first in situ study of the isotopic composition of microbial nitrate in forest soils. Over a 2-week period, nitrate produced by nitrification was periodically flushed to the lysimeters by watering the area with a nitrogen-free solution. Nitrate produced in the forest floor had δ¹⁸O values ranging from +3.1‰ to +10.1‰ with a mean of +5.2‰. These values were only slightly higher than from the expected value of +1.0‰ calculated for chemolithoautotrophic nitrification, which depends on the δ¹⁸O of available O₂ and H₂O. In addition to nitrate, we also collected soil gas to determine if soil respiration and O₂ diffusion affected soil gas δ¹⁸O-O₂, which is typically assumed to be identical to atmospheric O₂ (+23.5‰) when calculating microbial nitrate δ¹⁸O values. No significant difference in δ¹⁸O-O₂ from atmospheric O₂ was found in forest soils to a depth of 55 cm, and therefore ¹⁸O-enrichment of soil gas O₂ could not explain the modest enrichment of nitrate ¹⁸O. Evaporative ¹⁸O-enrichment of soil water available to nitrifiers in the forest floor is a plausible mechanism for slightly elevated nitrate δ¹⁸O values. However, the observed nitrate δ¹⁸O values could also be explained by a minor contribution of nitrate from heterotrophic nitrifiers. The δ¹⁵N of nitrate produced ranged from −10.4 to −7.3‰ and, as expected, was depleted in ¹⁵N relative to soil organic nitrogen. Microbial nitrate produced in the forest floor was also significantly depleted in ¹⁵N relative to microbial nitrate exported in groundwater and headwater streams at the TLW. We hypothesize that ¹⁵N-depleted forest floor nitrate is not detected in groundwaters largely because of: (1) the immobilization of forest floor nitrate in the mineral soil and (2) the mixing of the remaining forest floor nitrate with nitrate generated in the mineral soil, which is expected to have higher δ¹⁵N values. This study demonstrates that current methods of calculating a priori the δ¹⁸O of microbial nitrate provide a reasonable value for nitrate produced by nitrification at the TLW.     

Extraordinary C enrichment of diether lipids at the Lost City Hydrothermal Field indicates a carbon-limited ecosystem

Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ¹³C values of total organic carbon range from −21.5‰ vs. VPDB at an extinct carbonate chimney to −2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ¹³C > −15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in ¹³C lacked or contained lower amounts of these diethers.Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ¹³C values ranging from −2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ¹³C values between −11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in ¹³C, with δ¹³C as low as −28.7‰ in chimneys and −45‰ in fissures.The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of ¹³C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to ¹³C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ¹³C values typical of abiotic carbon.     

Cl,N, C isotopic analysis of common agro-chemicals for identifying non-point source agricultural contaminants

The isotopic compositions of commercially available herbicides were analyzed to determine their respective ¹⁵N, ¹³C and ³⁷Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ³⁷Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ¹⁵N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ¹³C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.     

Stable nitrogen and carbon isotope (δN and δC) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ¹⁵N and δ¹³C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ¹⁵N and δ¹³C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ¹⁵N and δ¹³C values between sites was present. Skeletal δ¹⁵N values significantly increased and δ¹³C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of −0.013‰ m⁻¹ and +0.023‰ m⁻¹ are recommended for δ¹⁵N and δ¹³C, respectively. Average depth-corrected δ¹⁵N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ¹³C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ¹³C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ¹⁵N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ¹⁵N record, and suggests that these corals may be useful for δ¹⁵N-based paleoceanographic reconstructions. Variability in δ¹³C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ¹⁵N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ¹³C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.     

Metamorphic growth and recrystallization of zircons in extremely O-depleted rocks during eclogite-facies metamorphism: Evidence from U-Pb ages, trace elements, and O-Hf isotopes

A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ¹⁸O values of 0.1-10.1‰, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ¹⁸O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ¹⁸O values of −10.0‰ to −2.2‰, low Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ¹⁸O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ¹⁸O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ¹⁸O magmatic core and the negative δ¹⁸O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ¹⁸O fluids. The zircons recrystallized in solid-state maintained positive δ¹⁸O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ¹⁸O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ¹⁸O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.     

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of N-depleted nitrogen

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for ¹⁵N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu^* anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ¹³C vs. δ¹⁵N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in ¹⁵N and ¹³C from a pristine source having δ¹³C ? −36‰ and δ¹⁵N ? −4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH₄⁺_(rock) and N_2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large ¹³C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ¹⁵N value (+11‰), while C (up to 120 ppm and δ¹³C −38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The ¹⁵N-¹³C-depleted pristine source has δ ¹⁵N values from −7‰ to −4‰ and ⁴⁰Ar/³⁶Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and ⁴⁰Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.     

Ion microprobe analysis of graphite from ca. 3.8 Ga metasediments, Isua supracrustal belt, West Greenland: Relationship between metamorphism and carbon isotopic composition

In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ¹³C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ¹³C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ¹³C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ¹³C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively ¹³C-depleted graphite indicates that the regional metamorphism increased the δ¹³C values of the Isua graphite. This is consistent with the regional trend of ¹³C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused ¹³C-enrichment of Isua graphite. The δ¹³C values of graphite reported here (δ¹³C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ¹³C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the ¹³C-enrichment of Isua graphite, previously reported large ¹³C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).     

Nitrogen in peridotite xenoliths: Lithophile behavior and magmatic isotope fractionation

In order to document the origin and speciation of nitrogen in mantle-derived rocks and minerals, the N and Ar contents and isotopic compositions were investigated for hydrous and anhydrous peridotite xenoliths from Ataq, Yemen, from Eifel, Germany, and from Massif Central, France. Nitrogen and Ar were extracted by stepwise combustion with a fine temperature resolution, followed by fusion in a platinum crucible. A large isotopic disequilibrium of up to 25.4‰ is observed within single peridotite xenoliths, with δ¹⁵N values as low as −17.3‰ in phlogopite whereas clinopyroxene and olivine show positive δ¹⁵N values. Identical Sr isotopic ratios of phlogopite, clinopyroxene and whole rock in this wehrlite sample are consistent with crystallization from a common reservoir, suggesting that the light N signature of phlogopite might be the result of isotopic fractionation during N uptake from the host magma. The nitrogen concentration is systematically high in phlogopite, (7.6-25.7 ppm), whereas that of bulk peridotite xenoliths is between 0.1 and 0.8 ppm. The high N content of phlogopite is at least partly due to host magma-mineral interaction, and may also suggest the occurrence of N as that substituted for K⁺ during mineral growth in mafic magmas. Such speciation is consistent with the fact that N and Rb contents correlate well for a set of samples from mantle regions that were affected by subduction-related metasomatism and magmatism. The N/Rb ratios of these samples are comparable with values estimated for subduction zone magmas, but are one order of magnitude lower than the N/Rb ratios characterizing subducting slabs. This difference suggests preferential release of N relative to alkalis in the forearc region. N/⁴⁰Ar^∗ ratios of minerals from analyzed mantle xenoliths are much higher than those of vesicles in MORBs and OIBs, requiring either the occurrence of nitrogen speciation in the mantle more compatible than Ar, significant loss of fluid phase during entrainment, or long residence time of volatile elements in the mantle source(s) of fluids to increase drastically the ⁴⁰Ar^∗ budget of the latter.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

This study investigates the application of sulphur isotope ratios (δ³⁴S) in combination with carbon (δ¹³C) and nitrogen (δ¹⁵N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ³⁴S values were found. The δ³⁴S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ³⁴S values of the fish were clustered and ³⁴S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly ³⁴S-depleted sulphur influenced the soil. The humans show the largest range of δ³⁴S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ³⁴S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R² = 0.71; p < 0.0001) between their δ¹⁵N and δ³⁴S compositions. These δ³⁴S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ³⁴S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.     

Temporal variations in the concentration and isotopic signature of ammonium- and nitrate–nitrogen in soils under a breeding colony of Black-tailed Gulls (Larus crassirostris) on Kabushima Island,northeastern Japan

Temporal variations in the concentration and N isotopic ratios of inorganic N (NH₄– and NO₃–N) as affected by the soil temperature regime together with the input of bird excreta were analyzed in a sedentary soil under a dense colony (1.6 nests/m²) of breeding Black-tailed Gulls (Laruscrassirostris: a ground-nesting seabird). Surface soil samples were taken monthly from mid-March to late July 2005 from Kabushima Island, Hachinohe, northeastern Japan. The spatial concentration of inorganic N in the soils varied considerably on all sampling dates. There may be a statistically significant trend, showing increased NH₄–N content from settlement up to early June when the input of fecal N attains its maximum, and then decreases towards the end of breeding activity (early August). Abundant NO₃–N was observed in all soils, particularly in the later stage of breeding (up to 3800 mg-N/kg dry soil), refuting earlier claims that nitrification is unimportant in the soils. δ¹⁵N values of NH₄ in the soils showed unusually high values up to +51‰, reflecting N isotope fractionation due to volatilization of NH₃ during the mineralization. Mean δ¹⁵N values of the monthly collected totals of NH₄ and NO₃ were not significantly different at the 5% level based on ANOVA and significant differences were observed only among the three means of NO₃–N collected in mid-March (settlement of colony: δ¹⁵N = −0.2 ± 3.5‰) and late July (later stages of breeding: δ¹⁵N = +22.1 ± 7.0‰, +23.3 ± 7.8‰) at the 1% and 5% levels by t-test, respectively. Such an observation of significantly increased δ¹⁵N values for NO₃–N in soils from the fledgling stage indicates the integration of denitrification coupled with nitrification under a limited supply of fecal N.     

Kinetic nitrogen isotope fractionation associated with thermal decomposition of NH3: Experimental results and potential applications to trace the origin of N2 in natural gas and hydrothermal systems

Ammonia (NH₃) is the major intermediate phase in the pathway of nitrogen (N) transfer from the fixed N phases (e.g., in crustal material) to free N₂ (e.g., in natural gas reservoirs and volcanic gases). Yet the N isotopic behavior during these N-cycling processes remains poorly known. In an attempt to contribute to the understanding of N cycling using N isotopes, we carried out laboratory experiments to investigate the N isotopic effect associated with thermal decomposition of ammonia (2NH₃ → N₂ + 3H₂). Pure NH₃ (with initial δ¹⁵N_NH3 of ∼ −2‰, relative to air standard) was sealed into quartz tubes and thermally decomposed at 600, 700 or 800 °C from 2 hours to 500 days. With the progress of the reaction, the δ¹⁵N of the remaining NH₃ and the accumulated N₂ increased from −2 to +35‰ and from −20 to −2‰, respectively. The differences of the N-isotope fractionations at the three temperatures are not significant. Modeling using the Rayleigh distillation model yielded similar kinetic N-isotope fractionation factors (α_N2-NH3) of 0.983 ± 0.002 for 600, 700 and 800 °C. Applied to geological settings, this significant isotope discrimination (∼17‰) associated with partial decomposition of NH₃/NH₄⁺ from crustal sources (δ¹⁵N_average ∼ +6.3‰) can produce mantle-like (i.e. ∼ −5‰) or even lower δ¹⁵N values of N₂. This may explain the large variation of δ¹⁵N (−20 to +30‰) of N₂ in natural gas reservoirs. It can also possibly explain the extreme ¹⁵N-depletion of N₂ in some volcanic gases. This possibility has to be carefully considered when using N isotopes to trace geological N cycling across subduction zones by analysis of volcanic N₂.     

Complex trajectories of aquatic and terrestrial ecosystem shifts caused by multiple human-induced environmental stresses

Large shifts in the isotopic compositions of organic matter (OM) in lake sediments, over the last few hundred years, are commonly interpreted as representing changes in photosynthetic productivity corresponding to eutrophication or in the input of terrestrial OM due to human disturbances. Based on multiple-proxy data (C:N ratio, δ¹³C and δ¹⁵N of OM, δ¹³C of calcite, lithology and fossil pollen) from a 700-year sediment core at White Lake, New Jersey (USA), we propose a new explanation that relates these large shifts in OM δ¹³C and δ¹⁵N to human-induced changes in aquatic OM producers. Combined records of geochronology, fossil pollen and lithology from White Lake reveal that the upland forest was cleared by European settlers for farmland beginning around 1745 A.D. and has gradually reforested since 1930 after the abandonment of the farmlands. For the pre-agricultural period, OM had relatively constant but extremely low δ¹³C_VPDB (−35.8 to −34.5‰) and δ¹⁵N_Air (−3.5 to −2.5‰) and high atomic C:N ratios (13.7 to 16.7), indicating a stable anoxic lake environment with prominent microbial producers. Following the human disturbance (since 1745), high OM mass accumulation rates and abundances of the green alga Pediastrum indicate an increase in aquatic photosynthetic productivity due to enhanced nutrient input from disturbed uplands. However, carbonate δ¹³C remains constant or even decreases during this period, implying that increasing productivity did not elevate the δ¹³C of dissolved inorganic carbon and thus cannot explain the observed large increase in OM δ¹³C (7.4‰) and δ¹⁵N (5.8‰) over this period. Instead, δ¹³C, δ¹⁵N and C:N ratios of OM and differences in δ¹³C between calcite and OM suggest that the large increase in OM δ¹³C and δ¹⁵N can be attributed to a human-induced ecological shift in the predominant organic source from anaerobic bacteria to autotrophic phytoplankton. During the post-agricultural period, mass accumulation rates of OM, carbonate and silicate, and the δ¹³C of OM and calcite all decreased significantly, corresponding to stabilization of the uplands. However, over the last 70 years, an intensifying aquatic stress from the deposition of ¹⁵N-enriched industrial pollutants has resulted in a steady increase of 1.9‰ in δ¹⁵N. Proxy records for lake (δ¹³C and δ¹⁵N of OM) and upland conditions (pollen and silicates) at White Lake show complex trajectories of the aquatic and terrestrial ecosystems in response to past human disturbances.