Holocene lake development and glacial-isostatic uplift at Lake Skallen and Lake Oyako,Lützow-Holm Bay,East Antarctica: Based on biogeochemical facies and molecular signatures

The paleolimnology of two lakes which were isolated as a result of the crustal uplift during the late Holocene along the Soya Coast, Lützow-Holm Bay, East Antarctica were studied. The focus was on temporal variations in the biogeochemical composition of sediment cores recovered from Lake Skallen at Skallen and Lake Oyako at Skarvsnes. Both sets of lake sediments record environmental changes associated with a transition from marine to lacustrine settings, as indicated by analyses of C and N contents, nitrogen isotopic compositions (δ¹⁵N), and major element concentrations. Changes in the dominant primary producers during the marine–lacustrine transition (marine diatom to cyanobacteria) at L. Skallen was clearly revealed by biogenic opal-A, diatom assemblages, and molecular signature from denaturing gradient gel electrophoresis (DGGE) with 16S ribosomal RNA (rRNA) gene analysis. Radiocarbon dating of acid-insoluble organic C suggested that the environmental transition from marine to fresh water occurred at 2940 ± 100 cal yr BP at L. Skallen and 1060 ± 90 cal yr BP at L. Oyako. Based on these data, a mean crustal uplift rate of 3.2 mm yr⁻¹ is inferred for the history of marine–lacustrine transition via brackish conditions. The geological setting causing glacio-isostatic uplift was the primary factor in controlling the transition event in sedimentary and biological facies.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Carbon and hydrogen isotope variation of plant biomarkers in a plant-soil system

Stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of n-alkanes, anteiso-alkanes, n-alkanoic acids, n-alkanols, phytol and sterols in raw leaves of Acer argutum and Acer carpinifolium, their fallen leaves, mold and soils from a natural Acer forest were measured in order to: (1) understand isotopic variation of the plant biomarkers in a plant-soil system and (2) evaluate which biomarker is the most effective recorder of soil vegetation. Long-chain (> C₂₄) n-alkanes, n-alkanoic acids and n-alkanols are gradually enriched in ¹³C up to 12.9‰ (average of 4.3‰) and depleted in D up to 94‰ (average of 55‰) from raw leaves to soils. However, anteiso-alkanes, phytol and sterols show little variation in both δ¹³C (< ± 1‰) and δD (< ± 2‰) from raw leaves to soils. These isotope signatures in a plant-soil system indicate that isoprenoid plant biomarkers such as sterols in soils faithfully preserve the isotopic compositions of dominant higher plants growing on the soils without a diagenetic effect upon the isotopic compositions. In contrast, long-chain n-alkyl molecules in soils undergo specific isotopic modification during biodegradation associated with early diagenesis and/or a significant contribution from heterotrophic reworking.     

Abundance of mass 47 CO2 in urban air, car exhaust, and human breath

Atmospheric carbon dioxide is widely studied using records of CO₂ mixing ratio, δ¹³C and δ¹⁸O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally ¹³C¹⁸O¹⁶O) provides an additional constraint. In particular, the mass 47 anomaly (Δ₄₇) can distinguish between CO₂ produced by high temperature combustion processes vs. low temperature respiratory processes. Δ₄₇ is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured ¹³C and ¹⁸O values. In this study, we estimate the δ¹³C (vs. VPDB), δ¹⁸O (vs. VSMOW), δ47, and Δ₄₇ values of CO₂ from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO₂ from these sources. δ47 is defined as , where is the R⁴⁷ value for a hypothetical CO₂ whose δ¹³C_VPDB = 0, δ¹⁸O_VSMOW = 0, and Δ₄₇ = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO₂] from 383 to 404 μmol mol⁻¹, in δ¹³C and δ¹⁸O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ₄₇ from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ¹³C (similar to the δ¹³C of local gasoline), δ¹⁸O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ₄₇ of 0.41 ± 0.03‰. Both δ¹⁸O and Δ₄₇ values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO₂ and water generated by combustion of gasoline-air mixtures. Samples of CO₂ from human breath were found to have δ¹³C and δ¹⁸O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ₄₇ in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.     

Fatty acid and stable isotope (δC, δN) signatures of particulate organic matter in the lower Amazon River: Seasonal contrasts and connectivity between floodplain lakes and the mainstem

Fatty acid (FA) composition and stable isotope (δ¹³C, δ¹⁵N) signatures of four aquatic plants, plankton, sediment, soil and suspended particulate organic matter (SPOM) collected from open floodplain lakes (Várzea) and rivers of the central Brazilian Amazon basin were gathered during high and low water stages in 2009. SPOM from Várzea had a major contribution of autochthonous material from phytoplankton and C₃ aquatic plants. As shown from stable isotope composition of SPOM (δ¹³C −31.3 ± 3.2‰; δ¹⁵N 3.6 ± 1.5‰), the C₄ aquatic phanerogam (δ¹³C −13.1 ± 0.5‰; δ¹⁵N 4.1 ± 1.7‰) contribution appeared to be weak, although these plants were the most abundant macrophyte in the Várzea. During low water season, increasing concentration of 18:3ω3 was recorded in the SPOM of lakes. This FA, abundant mainly in the Várzea plants (up to 49% of total FAs), was due to the accumulation of their detritus in the ecosystem. This dry season, when connectivity with the river mainstem was restricted, was also characterized by a high concentration in the SPOM of the cyanobacteria marker 16:1ω7 (up to 21% of total FAs). The FA compositions of SPOM from the Amazon River also exhibited significant seasonal differences, in particular a higher concentration of 16:1ω7 and 18:3ω3 during the dry season. This suggests a seasonal contribution of autochthonous material produced in Várzea to the Amazon River SPOM.     

K–Ar dating and δO–δD tracing of illitization within and outside the Shea Creek uranium prospect,Athabasca Basin,Canada

Isotope analyses (K–Ar, δ¹⁸O and δD) were performed on illite from both the sandstone cover and the underlying basement, close to and distant from Shea Creek, an unconformity-type U deposit (Athabasca Basin, Canada); the illite had previously been characterized crystallographically. In the barren areas away from deposit, illite is mainly of the cis-vacant 1M polytype occurring as relatively coarse-grained lath-shaped particles, while it occurs as fine-grained particles of the trans-vacant 1M type next to and in the U mineralized strata. The tectonic-induced hydrothermal system that favored illite crystallization was multi-episodic 1453 ± 2, 1330 ± 20 and probably about 1235 Ma ago. These illite-forming episodes appear to have occurred contemporaneously to those favoring the concentration of the associated U oxides, which were dated independently by the U–Pb method in the Shea Creek deposits and elsewhere in the Athabasca Basin.     

Stable carbon and oxygen isotope fractionation in bivalve (Placopecten magellanicus) larval aragonite

The relationship between stable isotope composition (δ¹³C and δ¹⁸O) in seawater and in larval shell aragonite of the sea scallop, Placopecten magellanicus, was investigated in a controlled experiment to determine whether isotopes in larval shell aragonite can be used as a reliable proxy for environmental conditions. The linear relationship between δ¹³C_DIC and δ¹³C_aragonite (r² = 0.97, p < 0.0001, RMSE = 0.18) was:

δ¹³C_DIC=1.15(±0.05)∗δ¹³C_aragonite-0.85(±0.04)     

Tissue N content and N natural abundance in epilithic mosses for indicating atmospheric N deposition in the Guiyang area,SW China

Tissue N contents and δ¹⁵N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ¹⁵N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ¹⁵N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH₃ released from excretory wastes and sewage, while the less negative δ¹⁵N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH₃. With more negative values in the urban area than in the rural area, the pattern of moss δ¹⁵N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NO_x–N. Therefore, NH_x–N is the dominant N form deposited in the Guiyang area, which is supported by higher NH_x–N than NO_x–N in local atmospheric deposition. From the data showing that moss is responding to NH_x–N/NO_x–N in deposition it can be further demonstrated that the variation of moss δ¹⁵N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NH_x/agriculture-NH_x than the ratio of NH_x–N/NO_x–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.     

The origins and behaviour of carbon in a major semi-arid river,the Murray River,Australia, as constrained by carbon isotopes and hydrochemistry

δ¹³C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ¹⁸O and δ²H values of water, δ³⁴S values of dissolved SO₄, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ¹³C_DIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ¹³C_DIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO₂; this interpretation is consistent with pCO₂ values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ¹³C_DIC values are similar to those that would be produced by the weathering of marine limestone (δ¹³C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ¹³C_DIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO₂ values and δ¹³C_DIC values are best explained by a combination of mineralisation of low δ¹³C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ¹³C values.     

Oxygen isotope compositions of phosphate from arvicoline teeth and Quaternary climatic changes, Gigny, French Jura

Oxygen isotope compositions of biogenic phosphates from mammals are widely used as proxies of the isotopic compositions of meteoric waters that are roughly linearly related to the air temperature at high- and mid-latitudes. An oxygen isotope fractionation equation was determined by using present-day European arvicoline (rodents) tooth phosphate: δ¹⁸O_p = 20.98(±0.59) + 0.572(±0.065) δ¹⁸O_w. This fractionation equation was applied to the Late Pleistocene karstic sequence of Gigny, French Jura. Comparison between the oxygen isotope compositions of arvicoline tooth phosphate and Greenland ice core records suggests to reconsider the previously established hypothetical chronology of the sequence. According to the δ¹⁸O value of meteoric water-mean air temperature relationships, the δ¹⁸O value of arvicoline teeth records variations in mean air temperatures that range from 0° to 15°C.     

In situ U-Pb, O and Hf isotopic compositions of zircon and olivine from Eoarchaean rocks, West Greenland: New insights to making old crust

The sources and petrogenetic processes that generated some of the Earth’s oldest continental crust have been more tightly constrained via an integrated, in situ (U-Pb, O and Hf) isotopic approach. The minerals analysed were representative zircon from four Eoarchaean TTG tonalites and two felsic volcanic rocks, and olivine from one harzburgite/dunite of the Itsaq Gneiss Complex (IGC), southern West Greenland. The samples were carefully chosen from localities with least migmatisation, metasomatism and strain. Zircon was thoroughly characterized prior to analysis using cathodoluminescence, scanning electron, reflected and transmitted light imaging. The zircon from all but one sample showed only minor post-magmatic recrystallisation. ²⁰⁷Pb/²⁰⁶Pb dating of oscillatory-zoned zircon using SHRIMP RG (n = 142) indicates derivation of the felsic igneous rocks from different batches of magma at 3.88, 3.85, 3.81, 3.80 and 3.69 Ga.Analyses of ¹⁸O/¹⁶O compositions of olivine from a harzburgite/dunite (n = 8) using SHRIMP II in multi-collector mode, indicate that the oxygen isotopic composition of this sample of Eoarchaean mantle (δ¹⁸O_Ol = 6.0 ± 0.4‰) was slightly enriched in ¹⁸O, but not significantly different from that of the modern mantle. Zircon δ¹⁸O measurements from the six felsic rocks (n = 93) record mean or weighted mean compositions ranging from 4.9 ± 0.7‰ to 5.1 ± 0.4‰, with recrystallised domains showing no indication of oxygen isotopic exchange during younger tectonothermal events. δ¹⁸O_Zr compositions indicate that the primary magmas were largely in equilibrium with the mantle or mantle-derived melts generated at similar high temperatures, while calculated tonalite δ¹⁸O_WR compositions (6.7-6.9‰) resemble those of modern adakites.LA-MC-ICPMS zircon ¹⁷⁶Hf/¹⁷⁷Hf analyses were obtained from six samples (n = 122). Five samples record weighted mean initial ε_Hf compositions ranging from to 0.5 ± 0.6 to −0.1 ± 0.7 (calculated using λ¹⁷⁶Lu = 1.867 × 10⁻¹¹ yr⁻¹), while one sample records a composition of 1.3 ± 0.7, indicating the magmas were generated from a reservoir with a time averaged, near chondritic Lu/Hf. The derivation of TTG magmas from a chondritic Lu/Hf source implies either that there was not voluminous continental crustal growth nor major mantle differentiation leading to Lu/Hf fractionation during the Hadean or Eoarchaean, or alternatively that rapid recycling of an early formed crust allowed the early mantle to maintain a chondritic Lu/Hf.Previous studies have demonstrated that ancient TTG rocks were mostly produced by dehydration melting of mafic rocks within the stability field of garnet, probably in flatly-subducted or buried oceanic crust. The oxygen isotopic signatures measured here at high spatial resolution allow the source materials to be better defined. Melting of a mixed mafic source consisting of ∼80% unaltered gabbro (δ¹⁸O_WR = 5.5‰) with ∼20% hydrothermally altered gabbro/basalt (δ¹⁸O_WR = 4.0‰) would produce tonalite magmas within the average compositional range observed. ¹⁸O-enriched components such as altered shallow basaltic oceanic crust and pelagic or continental sediments were not present in the sources of these TTG melts. The absence of high ¹⁸O signatures may indicate either the rarity of low temperature altered sediments, or their effective removal from the down-going slab.     

Carbon and oxygen stable isotope compositions of late Pleistocene mammal teeth from dolines of Ajoie (Northwestern Switzerland)

Fossils of megaherbivores from eight late Pleistocene ¹⁴C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ¹³C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C₃ plant-dominated environment. Enamel δ¹⁸O_PO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ¹⁸O_PO4–δ¹⁸O_H2O-calibrations for modern mammals and a present-day precipitation δ¹⁸O_H2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.     

Mo isotope composition in Mo-rich high- and low-T hydrothermal systems from the Swiss Alps

We analyzed the molybdenum (Mo) isotope compositions (IC) of 59 samples from two molybdenite mineralizations (Alpjahorn and Grimsel) and from a Mo-rich hydrothermal breccia (Grimsel) from the Aar Massif, Switzerland. The formation temperature of the Late Paleozoic Mo mineralizations (300-600 °C) is much higher than that of the Pliocene breccia (100-160 °C). The Mo IC of the molybdenites varies over 1.35‰. Even in a single hand specimen it spans 0.45‰, indicating that fractionation processes during molybdenite precipitation can vary on a cm scale. The Mo IC of most molybdenites analyzed here are significantly heavier than that of the host rock (δ^98/95Mo = (0.05 ± 0.1)‰) and show a bimodal distribution centered around δ^98/95Mo ≈ 1.1‰ and 0.2‰. This result rules out single stage Rayleigh fractionation as the relevant formation mechanism and instead, redox variations are suggested to be a main factor controlling the Mo IC of the studied high-temperature Mo deposits. The range of the Mo IC in one single deposit, the Alpjahorn, overlaps with the variation range of almost all other published values for Mo IC in Mo deposits. Compared to the molybdenites, the breccia shows an even wider variation of 3.0‰ (δ^98/95Mo between −1.6‰ and +1.4‰). In contrast to the high-T molybdenite deposits, here the Mo was transported via oxidized surface waters into the breccia system, where it was reduced and precipitated. This indicates that oxidation and reduction of Mo complexes may lead to highly variable Mo IC in hydrothermal systems.     

Variations in composition and abundance of white mica in the hydrothermal alteration system at Hellyer,Tasmania, as revealed by infrared reflectance spectroscopy

Short-wave infrared (SWIR) spectral reflectance of hydrothermally altered volcanic rocks in the footwall of the Hellyer massive sulfide deposit was measured with a portable PIMA-II infrared spectrometer. The Al–OH band was used to derive information on the octahedral Al content and the abundance of white mica (sericite) in the hydrothermal alteration and mineralization system. The range of the Al–OH band wavelength from 2192 nm to 2222 nm corresponds to the number of octahedral Al (Al^vi) in white mica approximately from 3.9 to 3.0 (based on 4 octahedral cations per formula). This Al^vi range represents a significant compositional variation, covering most of the compositional region between muscovite (Al^vi = 4.0) and phengite (Al^vi = 3.0). Furthermore, the spectral reflectance data show that the compositional variation of white mica is spatially related to hydrothermal alteration zoning, such that phengitic white mica tends to occur in 1) main upflow fluid channel, 2) intensely altered volcanic rocks, and 3) Pb–Zn mineralization, whereas muscovitic white mica was formed preferentially distal to massive sulfide mineralization on the margin of the footwall alteration system. The results suggest that the Al–OH band wavelength, and therefore the octahedral Al content, of white mica can be used as vectors to mineralization to map the hydrothermal system at Hellyer.     

Sulfur and carbon isotope records from 1700 to 800 Ma carbonates of the Jixian section, northern China: Implications for secular isotope variations in Proterozoic seawater and relationships to global supercontinental events

This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ³⁴S_CAS using the same samples analyzed for δ¹³C_carbonate. This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ¹³C_carbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ³⁴S_CAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300-1100 Ma, and 1000-900 Ma. In the Changcheng Group, δ³⁴S_CAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰.In the late Paleoproterozoic (1700-1600 Ma), a >10‰ decrease in δ³⁴S_CAS and ∼3‰ increase in δ¹³C_carbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ³⁴S_CAS and >3‰ for the δ¹³C_carbonate at ca. 1450-1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300-1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ¹³C and δ³⁴S of seawater increased gradually with increasing variability. Most impressive areδ³⁴S_CAS values that exceed +30‰ in two intervals at ca. 1300-1100 Ma and ca. 1000-900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

The record of temperature, wind velocity and air humidity in the δD and δO of water inclusions in synthetic and Messinian halites

Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L⁻¹) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ¹⁸O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s⁻¹, slopes of the δD-δ¹⁸O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ¹⁸O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ¹⁸O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.     

Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols

We present analyses of stable isotopic ratios ¹⁷O/¹⁶O, ¹⁸O/¹⁶O, ³⁴S/³²S, and ³³S/³²S, ³⁶S/³²S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ∼1 km³), Mt. Spurr (Alaska, 1953, <1 km³), Gjalp (Iceland, 1996, 1998, <1 km³), Pinatubo (Phillipines, 1991, 10 km³), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km³), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km³), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km³ and 2.04 Ma 2500 km³, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage.This global dataset spans a significant range in δ³⁴S, δ¹⁸O, and Δ¹⁷O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent (Δ¹⁷O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of‘ these isotopic ranges. Sulfate with Δ¹⁷O > 0.2‰ is present as 1-10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ¹⁷O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin.Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO₂, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ³⁴S range and exhibit fractionation relationships that do not follow the expected equilibrium slopes of 0.515 and 1.90 for ³³S/³²S vs. ³⁴S/³²S and ³⁶S/³²S vs. ³⁴S/³²S, respectively. The data presented here are consistent with modification of a chemical mass-dependent fractionation of sulfur isotopes in the volcanic plume by either a kinetic gas phase reaction of volcanic SO₂ with OH and/or a Rayleigh processes involving a residual Rayleigh reactant—volcanic SO₂ gas, rather than a Rayleigh product. These results may also imply at least two removal pathways for SO₂ in volcanic plumes.Above-zero Δ¹⁷O values and their positive correlation with δ¹⁸O in sulfate can be explained by oxidation by high-δ¹⁸O and high-Δ¹⁷O compounds such as ozone and radicals such as OH that result from ozone break down. Large caldera-forming eruptions have the highest Δ¹⁷O values, and the largest range of δ¹⁸O, which can be explained by stratospheric reaction with ozone-derived OH radicals. These results suggest that massive eruptions are capable of causing a temporary depletion of the ozone layer. Such depletion may be many times that of the measured 3-8% depletion following 1991 Pinatubo eruption, if the amount of sulfur dioxide released scales with the amount of ozone depletion.     

Chemostratigraphy of the Tamengo Formation (Corumbá Group,Brazil): A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumbá Group, cropping out in the southern Paraguay Belt in Brazil, is one of the most complete Ediacaran sedimentary archives of palaeogeographic, climatic, biogeochemical and biotic evolution in southwestern Gondwana. The unit hosts a rich fossil record, including acritarchs, vendotaenids (Vendotaenia, Eoholynia), soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina, Titanotheca). The Tamengo Formation, made up mainly of limestones and marls, provides a rich bio- and chemostratigraphic record. Several outcrops, formerly assigned to the Cuiabá Group, are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria. High-resolution carbon isotopic analyses are reported for the Tamengo Formation, showing (from base to top): (1) a positive δ¹³C excursion to +4‰ PDB above post-glacial negative values, (2) a negative excursion to −3.5‰ associated with a marked regression and subsequent transgression, (3) a positive excursion to +5.5‰, and (4) a plateau characterized by δ¹³C around +3‰. A U-Pb SHRIMP zircon age of an ash bed interbedded in the upper part of the δ¹³C positive plateau yielded 543 ± 3 Ma, which is considered as the depositional age ( Babinski et al., 2008a). The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide, including the Nama Group (Namibia), the Dengying Formation (South China) and the Nafun and Ara groups (Oman). This plateau is constrained between 542 and 551 Ma, thus consistent with the age of the upper Tamengo Formation. The negative excursion of the lower Tamengo Formation may be correlated to the Shuram–Wonoka negative anomaly, although δ¹³C values do not fall beyond −3.5‰ in the Brazilian sections. Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation. One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall, but a tectonic interpretation cannot be completely ruled out.     

Diffuse gas emissions at the Ukinrek Maars,Alaska: Implications for magmatic degassing and volcanic monitoring

Diffuse CO₂ efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO₂ efflux, in many places exceeding 1000 g m⁻² d⁻¹, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m² in area. Total diffuse CO₂ emission was estimated at 21–44 t d⁻¹. Gas vents 3-km away at The Gas Rocks produce 0.5 t d⁻¹ of CO₂ that probably derives from the Ukinrek Maars basalt based on similar δ¹³C values (∼−6‰), ³He/⁴He ratios (5.9–7.2 R_A), and CO₂/³He ratios (1–2 × 10⁹) in the two areas. A lower ³He/⁴He ratio (2.7 R_A) and much higher CO₂/³He ratio (9 × 10¹⁰) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO₂ emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.