Heterogeneity and incorporation of chromium isotopes in recent marine molluscs (Mytilus)

The mollusc genus Mytilus is abundant in various modern marine environments and is an important substrate for palaeo‐proxy work. The redox‐sensitive chromium (Cr) isotope system is emerging as a proxy for changes in the oxidation state of the Earth's atmosphere and oceans. However, potential isotopic offsets between ambient sea water and modern biogenic carbonates have yet to be constrained. We measured Cr concentrations ([Cr]) and isotope variations (δ⁵³Cr) in recent mollusc shells (Mytilus) from open and restricted marine environments and compared these to ambient sea water δ⁵³Cr values. We found a large range in mollusc [Cr] (12–309 ppb) and δ⁵³Cr values (?0.30 to +1.25‰) and in the offset between δ⁵³Cr values of mollusc shells and ambient sea water (, ?0.17 to ?0.91‰). Step digestions of cultivated Mytilus edulis specimens indicate that Cr is mainly concentrated in organic components of the shell (periostracum: 407 ppb, n = 2), whereas the mollusc carbonate minerals contain ≤3 ppb Cr. Analyses of individual Cr‐hosting phases (i.e., carbonate minerals and organic matrix) did not reveal significant differences in δ⁵³Cr values, and thus, we suggest that Cr isotope fractionation may likely take place prior to rather than during biomineralisation of Mytilus shells. Heterogeneity of δ⁵³Cr values in mollusc shells depends on sea water chemistry (e.g., salinity, food availability, faeces). The main control for δ⁵³Cr values incorporated into shells, however, is likely vital effects (in particular shell valve closure time) since Cr can be partially or quantitatively reduced in sea water trapped between closed shell valves. The δ⁵³Cr values recorded in Mytilus shells may thus be de‐coupled from the redox conditions of ambient sea water, introducing additional heterogeneity that needs to be better constrained before using δ⁵³Cr values in mollusc shells for palaeo‐reconstructions.     

Chromium isotopic composition of core‐top planktonic foraminifera

The chromium isotope system (⁵³Cr/⁵²Cr expressed as δ⁵³Cr relative to NIST SRM 979) is potentially a powerful proxy for the redox state of the ocean–atmosphere system, but a lack of temporally continuous, well‐calibrated archives has limited its application to date. Marine carbonates could potentially serve as a common and continuous Cr isotope archive. Here, we present the first evaluation of planktonic foraminiferal calcite as an archive of seawater δ⁵³Cr. We show that single foraminiferal species from globally distributed core tops yielded variable δ⁵³Cr, ranging from 0.1‰ to 2.5‰. These values do not match with the existing measurements of seawater δ⁵³Cr. Further, within a single core‐top, species with similar water column distributions (i.e., depth habitats) yielded variable δ⁵³Cr values. In addition, mixed layer and thermocline species do not consistently exhibit decreasing trends in δ⁵³Cr as expected based on current understanding of Cr cycling in the ocean. These observations suggest that either seawater δ⁵³Cr is more heterogeneous than previously thought or that there is significant and species‐dependent Cr isotope fractionation during foraminiferal calcification. Given that the δ⁵³Cr variability is comparable to that observed in geological samples throughout Earth's history, interpreting planktonic foraminiferal δ⁵³Cr without calibrating modern foraminifera further, and without additional seawater measurements, would lead to erroneous conclusions. Our core‐top survey clearly indicates that planktonic foraminifera are not a straightforward δ⁵³Cr archive and should not be used to study marine redox evolution without additional study. It likewise cautions against the use of δ⁵³Cr in bulk carbonate or other biogenic archives pending further work on vital effects and the geographic heterogeneity of the Cr isotope composition of seawater.     

Pigment production and isotopic fractionations in continuous culture: okenone producing purple sulfur bacteria Part II

Okenone is a carotenoid pigment unique to certain members of Chromatiaceae, the dominant family of purple sulfur bacteria (PSB) found in euxinic photic zones. Diagenetic alteration of okenone produces okenane, the only recognized molecular fossil unique to PSB. The in vivo concentrations of okenone and bacteriochlorophyll a (Bchl a) on a per cell basis were monitored and quantified as a function of light intensity in continuous cultures of the purple sulfur bacterium Marichromatium purpuratum (Mpurp1591). We show that okenone‐producing PSB have constant bacteriochlorophyll to carotenoid ratios in light‐harvesting antenna complexes. The in vivo concentrations of Bchl a, 0.151 ± 0.012 fmol cell^?1, and okenone, 0.103 ± 0.012 fmol cell^?1, were not dependent on average light intensity (10–225 Lux) at both steady and non‐steady states. This observation revealed that in autotrophic continuous cultures of Mpurp1591, there was a constant ratio for okenone to Bchl a of 1:1.5. Okenone was therefore constitutively produced in planktonic cultures of PSB, regardless of light intensity. This confirms the legitimacy of okenone as a signature for autotrophic planktonic PSB and by extrapolation water column euxinia. We measured the δ¹³C, δ¹⁵N, and δ³⁴S bulk biomass values from cells collected daily and determined the isotopic fractionations of Mpurp1591. There was no statistical relationship in the bulk isotope measurements or stable isotope fractionations to light intensity or cell density under steady and non‐steady‐state conditions. The carbon isotope fractionation between okenone and Bchl a with respect to overall bulk biomass (¹³ε_{pigment – biomass}) was 2.2 ± 0.4‰ and ?4.1 ± 0.9‰, respectively. The carbon isotopic fractionation () for the production of pigments in PSB is more variable than previously thought with our reported values for okenone at ?15.5 ± 1.2‰ and ?21.8 ± 1.7‰ for Bchl a.     

Local paleoenvironmental controls on the carbon‐isotope record defining the Bitter Springs Anomaly

Large magnitude (>10‰) carbon‐isotope (δ¹³C) excursions recorded in carbonate‐bearing sediments are increasingly used to monitor environmental change and constrain the chronology of the critical interval in the Neoproterozoic stratigraphic record that is timed with the first appearance and radiation of metazoan life. The ~10‰ Bitter Springs Anomaly preserved in Tonian‐aged (1000–720 Ma) carbonate rocks in the Amadeus Basin of central Australia has been offered as one of the best preserved examples of a primary marine δ¹³C excursion because it is regionally reproducible and δ¹³C values covary in organic and carbonate carbon arguing against diagenetic exchange. However, here we show that δ¹³C values defining the excursion coincide with abrupt lithofacies changes between regularly cyclic grainstone and microbial carbonates, and desiccated red bed mudstones with interbedded evaporite and dolomite deposits, recording local environmental shifts from restricted marine conditions to alkaline lacustrine and playa settings that preserve negative (?4‰) and positive (+6‰) δ¹³C values, respectively. The stratigraphic δ¹³C pattern in both organic and carbonate carbon recurs within the basin in a similar way to associated sedimentary facies, reflecting the linkage of local paleoenvironmental conditions and δ¹³C values. These local excursions may be time transgressive or record a relative sea‐level influence manifest through exposure of sub‐basins isolated by sea‐level fall below shallow sills, but are independent of secular seawater variation. As the shallow intracratonic setting of the Bitter Springs Formation is typical of other Neoproterozoic carbonate successions used to construct the present δ¹³C seawater record, it identifies the potential for local influences on δ¹³C excursions that are neither diagenetic nor representative of the global exogenic cycle.     

Sulphur cycling in a Neoarchaean microbial mat

Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass‐independent fractionation (S‐MIF) signal in rocks <~2.4 Ga has been used to date a dramatic rise in atmospheric oxygen levels. However, intricacies of the S‐cycle before the Great Oxidation Event remain poorly understood. For example, the isotope composition of coeval atmospherically derived sulphur species is still debated. Furthermore, variation in Archaean pyrite δ³⁴S values has been widely attributed to microbial sulphate reduction (MSR). While petrographic evidence for Archaean early‐diagenetic pyrite formation is common, textural evidence for the presence and distribution of MSR remains enigmatic. We combined detailed petrographic and in situ, high‐resolution multiple S‐isotope studies (δ³⁴S and Δ³³S) using secondary ion mass spectrometry (SIMS) to document the S‐isotope signatures of exceptionally well‐preserved, pyritised microbialites in shales from the ~2.65‐Ga Lokammona Formation, Ghaap Group, South Africa. The presence of MSR in this Neoarchaean microbial mat is supported by typical biogenic textures including wavy crinkled laminae, and early‐diagenetic pyrite containing <26‰ μm‐scale variations in δ³⁴S and Δ³³S = ?0.21 ± 0.65‰ (±1σ). These large variations in δ³⁴S values suggest Rayleigh distillation of a limited sulphate pool during high rates of MSR. Furthermore, we identified a second, morphologically distinct pyrite phase that precipitated after lithification, with δ³⁴S = 8.36 ± 1.16‰ and Δ³³S = 5.54 ± 1.53‰ (±1σ). We propose that the S‐MIF signature of this secondary pyrite does not reflect contemporaneous atmospheric processes at the time of deposition; instead, it formed by the influx of later‐stage sulphur‐bearing fluids containing an inherited atmospheric S‐MIF signal and/or from magnetic isotope effects during thermochemical sulphate reduction. These insights highlight the complementary nature of petrography and SIMS studies to resolve multigenerational pyrite formation pathways in the geological record.     

Stable isotope enrichment in laboratory ant colonies: effects of colony age,metamorphosis, diet,and fat storage

Ecologists use stable isotopes to infer diets and trophic levels of animals in food webs, yet some assumptions underlying these inferences have not been thoroughly tested. We used laboratory‐reared colonies of Solenopsis invicta Buren (Hymenoptera: Formicidae: Solenopsidini) to test the effects of metamorphosis, diet, and lipid storage on carbon and nitrogen stable isotope ratios. Effects of metamorphosis were examined in ant colonies maintained on a control diet of domestic crickets and sucrose solution. Effects of a diet shift were evaluated by adding a tuna supplement to select colonies. Effects of lipid content on stable isotopes were tested by treating worker ants with polar and non‐polar solvents. δ¹³C and δ¹⁵N values of larvae, pupae, and workers were measured by mass spectrometry on whole‐animal preparations. We found a significant effect of colony age on δ¹³C, but not δ¹⁵N; larvae, pupae, and workers collected at 75 days were slightly depleted in ¹³C relative to collections at 15 days (Δδ¹³C = ?0.27‰). Metamorphosis had a significant effect on δ¹⁵N, but not δ¹³C; tissues of each successive developmental stage were increasingly enriched in ¹⁵N (pupae, +0.5‰; workers, +1.4‰). Availability of tuna resulted in further shifts of about +0.6‰ in isotope ratios for all developmental stages. Removing fat with organic solvents had no effect on δ¹³C, but treatment with a non‐polar solvent resulted in enriched δ¹⁵N values of +0.37‰. Identifying regular patterns of isotopic enrichment as described here should improve the utility of stable isotopes in diet studies of insects. Our study suggests that researchers using ¹⁵N enrichment to assess trophic levels of an organism at different sites need to take care not to standardize with immature insect herbivores or predators at one site and mature ones at another. Similar problems may also exist when standardizing with holometabolous insects at one site and spiders or hemimetabolous insects at another site.     

Records of palaeo‐seawater condition from oxygen‐isotope profiles of early Pleistocene fossil molluscs from the Seoguipo Formation (Korea)

Kim, J.K., Khim, B.‐K., Woo, K.S., & Yoon, S.H. 2009: Records of palaeo‐seawater condition from oxygen‐isotope profiles of early Pleistocene fossil molluscs from the Seoguipo Formation (Korea). Lethaia, Vol. 43, pp. 170–181. High‐resolution δ¹⁸O profiles of early Pleistocene fossil molluscs (Mizuhopecten tokyoensis hokurikuensis) from the shallow‐marine sedimentary Seoguipo Formation (Korea) were found to exhibit distinct annual cycles identified by their unique seasonality (δ¹⁸O amplitude). A direct comparison of fossil δ¹⁸O profiles with that of living shells (Amusium japonicum japonicumi) indicated that the palaeoseawater conditions differed from present‐day seawater. Specifically, the positive δ¹⁸O shift in the isotope profile of the fossil specimens relative to that of the living mollusc shell reflected that palaeotemperature was lower than that today. However, a comparison of the coldest palaeotemperatures (determined from the heaviest δ¹⁸O values of fossil shells), with the present‐day winter temperatures indicates that temperature variation alone cannot account for the entire positive δ¹⁸O offset. These findings indicate that variation in the seawater δ¹⁸O_w values plays a dominant role in the biogenic carbonate precipitation of fossils. Thus, the fossil shells obtained from stratigraphic units suggest different palaeoenvironmental conditions, including lower temperatures and ¹⁸O‐enriched glacial seawater, when compared with the present‐day conditions. The Seoguipo Formation records at least five cycles of relative sea‐level fluctuations, with changes in fossil δ¹⁸O amplitudes separated by sequence boundaries likely to reflect variations of unique palaeoseawater condition, although the oxygen‐isotope profile of fossil molluscs appears to provide a snap‐shot of the palaeoclimatic signature. □Early Pleistocene, mollusc fossils, oxygen isotope, palaeoenvironment, seawater temperature.     

Chromium geochemistry of the ca. 1.85 Ga Flin Flon paleosol

Fractionation of stable Cr isotopes has been measured in Archaean paleosols and marine sedimentary rocks and interpreted to record the terrestrial oxidation of Cr(III) to Cr(VI), providing possible indirect evidence for the emergence of oxygenic photosynthesis. However, these fractionations occur amidst evidence from other geochemical proxies for a pervasively anoxic atmosphere. This study examined the Cr geochemistry of the ca. 1.85 Ga Flin Flon paleosol, which developed under an atmosphere unambiguously oxidising enough to quantitatively convert Fe(II) to Fe(III) during pedogenesis. The paleosol shows an extreme range in Cr isotope composition of 2.76 ‰ δ^53/52Cr. The protolith greenstone (δ^53/52Cr: ?0.23 ‰), the deepest weathering horizon (δ^53/52Cr: ?0.15 to ?0.23 ‰) and a residual corestone in the upper paleosol (δ^53/52Cr: ?0.01 ‰) all exhibit Cr isotopic compositions comparable to unaltered igneous rocks. The most significant isotopic fractionation is preserved in the areas influenced by oxidative subaerial weathering (i.e. increase in Fe(III)/Fe(II)) and the greatest loss of mobile elements. The uppermost paleosol horizon is both Cr and Mn depleted and offset to significantly ⁵³Cr‐enriched compositions (δ^53/52Cr values between +1.50 and +2.38 ‰), which is not easily modelled with the oxidation of Cr(III) and loss of isotopically heavy Cr(VI). Instead, the currently preferred model for these data invokes the open‐system removal of isotopically light aqueous Cr(III) during either pedogenesis or subsequent hydrothermal/metamorphic alteration. The ⁵³Cr enrichment would then represent the preferential dissolution or complexation of isotopically light aqueous Cr(III) species (enhanced by lower pH conditions and possibly the presence of complexing ligands) and/or the residual signature from preferential adsorption of isotopically heavy Cr(III). Both scenarios would contradict the widely held assumption that only redox reactions of Cr can generate large magnitude isotopic fractionations and, if substantiated, non‐redox isotope effects would complicate the conclusive fingerprinting of ancient atmospheric O₂ from Cr isotope data alone.     

Biogeochemical probing of microbial communities in a basalt‐hosted hot spring at Kverkfjöll volcano,Iceland

We investigated bacterial and archaeal communities along an ice‐fed surficial hot spring at Kverkfjöll volcano—a partially ice‐covered basaltic volcano at Vatnajökull glacier, Iceland, using biomolecular (16S rRNA, apsA, mcrA, amoA, nifH genes) and stable isotope techniques. The hot spring environment is characterized by high temperatures and low dissolved oxygen concentrations at the source (68°C and <1 mg/L (±0.1%)) changing to lower temperatures and higher dissolved oxygen downstream (34.7°C and 5.9 mg/L), with sulfate the dominant anion (225 mg/L at the source). Sediments are comprised of detrital basalt, low‐temperature alteration phases and pyrite, with <0.4 wt. % total organic carbon (TOC). 16S rRNA gene profiles reveal that organisms affiliated with Hydrogenobaculum (54%–87% bacterial population) and Thermoproteales (35%–63% archaeal population) dominate the micro‐oxic hot spring source, while sulfur‐oxidizing archaea (Sulfolobales, 57%–82%), and putative sulfur‐oxidizing and heterotrophic bacterial groups dominate oxic downstream environments. The δ¹³C_org (‰ V‐PDB) values for sediment TOC and microbial biomass range from ?9.4‰ at the spring's source decreasing to ?12.6‰ downstream. A reverse effect isotope fractionation of ~3‰ between sediment sulfide (δ³⁴S ~0‰) and dissolved water sulfate (δ³⁴S +3.2‰), and δ¹⁸O values of ~ ?5.3‰ suggest pyrite forms abiogenically from volcanic sulfide, followed by abiogenic and microbial oxidation. These environments represent an unexplored surficial geothermal environment analogous to transient volcanogenic habitats during putative “snowball Earth” scenarios and volcano–ice geothermal environments on Mars.     

Stable isotopic (δ13C and δ18O) signatures of biogenic calcretes marking discontinuity surfaces: a case study from Upper Cretaceous carbonates of central Dalmatia and eastern Istria,Croatia

Biogenic calcretes associated with a regional Cretaceous to Paleogene subaerial unconformity and an intraformational composite (polygenic) surface in Upper Cretaceous intra-platform peritidal successions in central Dalmatia and eastern Istria, Croatia (Adriatic-Dinaridic Carbonate Platform), were analyzed for their δ¹³C and δ¹⁸O signatures in order to provide insight into the conditions of subaerial exposure and calcrete development. The distinctly negative δ¹³C signatures of biogenic calcretes marking the regional subaerial unconformity differ considerably from the δ¹³C values of the host marine limestones. This indicates carbon isotope exchange of primary marine CaCO₃ with CO₂ released by root and rhizomicrobial respiration and subsequent precipitation of pedogenic calcrete. The range of δ¹³C (from ?13.1 to ?8.2 ‰ Vienna PeeDee Belemnite standard, VPDB) and δ¹⁸O (from ?10.1 to ?6.1 ‰ VPDB) values of calcretes are similar to those reported from calcretes elsewhere, and the δ¹³C values of biogenic calcretes with typical Microcodium aggregates (?13.1 to ?12.3 ‰ VPDB) at the ?ibenik locality are very close to, or at the lower limit of, values for soil carbonates formed in isotopic equilibrium with soil CO₂. These values are expected for authigenic pedogenic carbonates formed under the influence of C₃ plant communities, without influence from heavier carbon from pre-existing carbonate and lack of input of atmospheric CO₂. Such low δ¹³C values support the interpretation of Microcodium aggregates as being precipitated under a direct biological control within the soil, although the relationship between formation mechanisms and stable isotope signatures of Microcodium needs further investigation. The δ¹³C values (?4.4 to ?3.6 ‰ VPDB) of rhizogenic calcretes formed inside firmground Thalassinoides burrows of the composite surface at the ?ibenik locality are more negative than the δ¹³C values of the host marine limestones, which confirms that the composite surface went through a phase of meteoric pedo(dia)genesis. However, the overall δ¹³C values of calcretes are less negative than expected, which might reflect contamination from associated primary marine carbonate. This study represents the first detailed stable isotope investigation of calcretes from carbonate successions of the External Dinarides, and the results may be applied to discontinuities present in other shallow-water carbonate rock successions.     

Tracing dietary origins of aphids and the predatory beetle Propylea japonica in agricultural systems using stable isotope analyses

Tracing dietary origins of the predatory beetle Propylea japonica (Thunberg) (Coleoptera: Coccinellidae) aids understanding their roles in the food web and provides information to develop strategies for effective conservation in agroecosystems comprised of wheat [Triticum aestivum L. (Poaceae)], cotton [Hirsutum spp. (Malvaceae)], and maize [Zea mays L. (Poaceae)]. Intrinsic markers of carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) in P. japonica need to be developed to ascertain the source(s) of diet. Experiments were carried out to examine the changes of δ¹³C and δ¹⁵N among the three crops, pests (wheat, cotton, and maize aphids; all Hemiptera: Aphididae), and P. japonica fed on aphids of each of the three crops. Results indicated that δ¹³C values in P. japonica fed on wheat, cotton, and maize aphids were ?27.2 to ?26.5‰, ?24.2 to ?23.9‰, and ?11.0 to ?10.7‰, respectively, whereas their δ¹⁵N values were 1.1 to 2.9‰, 6.0 to 7.4‰, and ?0.6 to 0.1‰, respectively. δ¹³C and δ¹⁵N plots clearly identify the three crops, the dietary origins of the aphids, and the host origins of the aphid prey consumed by the ladybird beetles, as each pathway displays a non‐overlapping pattern. Based on the values of δ¹³C and δ¹⁵N of the three food webs, dietary origins can be traced in the predatory beetle P. japonica derived from wheat, cotton, and maize crops.     

Isotopic biosignatures in carbonate‐rich,cyanobacteria‐dominated microbial mats of the Cariboo Plateau,B.C.

Photosynthetic activity in carbonate‐rich benthic microbial mats located in saline, alkaline lakes on the Cariboo Plateau, B.C. resulted in pCO₂ below equilibrium and δ¹³C_DIC values up to +6.0‰ above predicted carbon dioxide (CO₂) equilibrium values, representing a biosignature of photosynthesis. Mat‐associated δ¹³C_carb values ranged from ~4 to 8‰ within any individual lake, with observations of both enrichments (up to 3.8‰) and depletions (up to 11.6‰) relative to the concurrent dissolved inorganic carbon (DIC). Seasonal and annual variations in δ¹³C values reflected the balance between photosynthetic ¹³C‐enrichment and heterotrophic inputs of ¹³C‐depleted DIC. Mat microelectrode profiles identified oxic zones where δ¹³C_carb was within 0.2‰ of surface DIC overlying anoxic zones associated with sulphate reduction where δ¹³C_carb was depleted by up to 5‰ relative to surface DIC reflecting inputs of ¹³C‐depleted DIC. δ¹³C values of sulphate reducing bacteria biomarker phospholipid fatty acids (PLFA) were depleted relative to the bulk organic matter by ~4‰, consistent with heterotrophic synthesis, while the majority of PLFA had larger offsets consistent with autotrophy. Mean δ¹³C_org values ranged from ?18.7 ± 0.1 to ?25.3 ± 1.0‰ with mean Δ¹³C_inorg‐org values ranging from 21.1 to 24.2‰, consistent with non‐CO₂‐limited photosynthesis, suggesting that Precambrian δ¹³C_org values of ~?26‰ do not necessitate higher atmospheric CO₂ concentrations. Rather, it is likely that the high DIC and carbonate content of these systems provide a non‐limiting carbon source allowing for expression of large photosynthetic offsets, in contrast to the smaller offsets observed in saline, organic‐rich and hot spring microbial mats.     

Biogenic methane contributes to the food web of a large,shallow lake

相似文献   

Unprecedented 34S‐enrichment of pyrite formed following microbial sulfate reduction in fractured crystalline rocks

In the deep biosphere, microbial sulfate reduction (MSR) is exploited for energy. Here, we show that, in fractured continental crystalline bedrock in three areas in Sweden, this process produced sulfide that reacted with iron to form pyrite extremely enriched in ³⁴S relative to ³²S. As documented by secondary ion mass spectrometry (SIMS) microanalyses, the δ³⁴S_pyrite values are up to +132‰V‐CDT and with a total range of 186‰. The lightest δ³⁴S_pyrite values (?54‰) suggest very large fractionation during MSR from an initial sulfate with δ³⁴S values (δ³⁴S_sulfate,0) of +14 to +28‰. Fractionation of this magnitude requires a slow MSR rate, a feature we attribute to nutrient and electron donor shortage as well as initial sulfate abundance. The superheavy δ³⁴S_pyrite values were produced by Rayleigh fractionation effects in a diminishing sulfate pool. Large volumes of pyrite with superheavy values (+120 ± 15‰) within single fracture intercepts in the boreholes, associated heavy average values up to +75‰ and heavy minimum δ³⁴S_pyrite values, suggest isolation of significant amounts of isotopically light sulfide in other parts of the fracture system. Large fracture‐specific δ³⁴S_pyrite variability and overall average δ³⁴S_pyrite values (+11 to +16‰) lower than the anticipated δ³⁴S_sulfate,0 support this hypothesis. The superheavy pyrite found locally in the borehole intercepts thus represents a late stage in a much larger fracture system undergoing Rayleigh fractionation. Microscale Rb–Sr dating and U/Th–He dating of cogenetic minerals reveal that most pyrite formed in the early Paleozoic era, but crystal overgrowths may be significantly younger. The δ¹³C values in cogenetic calcite suggest that the superheavy δ³⁴S_pyrite values are related to organotrophic MSR, in contrast to findings from marine sediments where superheavy pyrite has been proposed to be linked to anaerobic oxidation of methane. The findings provide new insights into MSR‐related S‐isotope systematics, particularly regarding formation of large fractions of ³⁴S‐rich pyrite.     

Environmental insights from high‐resolution (SIMS) sulfur isotope analyses of sulfides in Proterozoic microbialites with diverse mat textures

In modern microbial mats, hydrogen sulfide shows pronounced sulfur isotope (δ³⁴S) variability over small spatial scales (~50‰ over <4 mm), providing information about microbial sulfur cycling within different ecological niches in the mat. In the geological record, the location of pyrite formation, overprinting from mat accretion, and post‐depositional alteration also affect both fine‐scale δ³⁴S patterns and bulk δ³⁴S_pyrite values. We report μm‐scale δ³⁴S patterns in Proterozoic samples with well‐preserved microbial mat textures. We show a well‐defined relationship between δ³⁴S values and sulfide mineral grain size and type. Small pyrite grains (<25 μm) span a large range, tending toward high δ³⁴S values (?54.5‰ to 11.7‰, mean: ?14.4‰). Larger pyrite grains (>25 μm) have low but equally variable δ³⁴S values (?61.0‰ to ?10.5‰, mean: ?44.4‰). In one sample, larger sphalerite grains (>35 μm) have intermediate and essentially invariant δ³⁴S values (?22.6‰ to ?15.6‰, mean: ?19.4‰). We suggest that different sulfide mineral populations reflect separate stages of formation. In the first stage, small pyrite grains form near the mat surface along a redox boundary where high rates of sulfate reduction, partial closed‐system sulfate consumption in microenvironments, and/or sulfide oxidation lead to high δ³⁴S values. In another stage, large sphalerite grains with low δ³⁴S values grow along the edges of pore spaces formed from desiccation of the mat. Large pyrite grains form deeper in the mat at slower sulfate reduction rates, leading to low δ³⁴S_sulfide values. We do not see evidence for significant ³⁴S‐enrichment in bulk pore water sulfide at depth in the mat due to closed‐system Rayleigh fractionation effects. On a local scale, Rayleigh fractionation influences the range of δ³⁴S values measured for individual pyrite grains. Fine‐scale analyses of δ³⁴S_pyrite patterns can thus be used to extract environmental information from ancient microbial mats and aid in the interpretation of bulk δ³⁴S_pyrite records.     

Isotopic discrimination and kinetic parameters of RubisCO from the marine bloom‐forming diatom,Skeletonema costatum

The cosmopolitan, bloom‐forming diatom, Skeletonema costatum, is a prominent primary producer in coastal oceans, fixing CO₂ with ribulose 1,5‐bisphosphate carboxylase/oxygenase (RubisCO) that is phylogenetically distinct from terrestrial plant RubisCO. RubisCOs are subdivided into groups based on sequence similarity of their large subunits (IA–ID, II, and III). ID is present in several major oceanic primary producers, including diatoms such as S. costatum, coccolithophores, and some dinoflagellates, and differs substantially in amino acid sequence from the well‐studied IB enzymes present in most cyanobacteria and in green algae and plants. Despite this sequence divergence, and differences in isotopic discrimination apparent in other RubisCO enzymes, stable carbon isotope compositions of diatoms and other marine phytoplankton are generally interpreted assuming enzymatic isotopic discrimination similar to spinach RubisCO (IB). To interpret phytoplankton δ¹³C values, S. costatum RubisCO was characterized via sequence analysis, and measurement of its K_CO2 and V_max, and degree of isotopic discrimination. The sequence of this enzyme placed it among other diatom ID RubisCOs. Michaelis‐Menten parameters were similar to other ID enzymes (K_CO2 = 48.9 ± 2.8 μm ; V_max = 165.1 ± 6.3 nmol min^?1 mg^?1). However, isotopic discrimination (ε = [¹²k/¹³k ? 1] × 1000) was low (18.5‰; 17.0–19.9, 95% CI) when compared to IA and IB RubisCOs (22–29‰), though not as low as ID from coccolithophore, Emiliania huxleyi (11.1‰). Variability in ε‐values among RubisCOs from primary producers is likely reflected in δ¹³C values of oceanic biomass. Currently, δ¹³C variability is ascribed to physical or chemical factors (e.g. illumination, nutrient availability) and physiological responses to these factors (e.g. carbon‐concentrating mechanisms). Estimating the importance of these factors from δ¹³C measurements requires an accurate ε‐value, and a mass‐balance model using the ε‐value for S. costatum RubisCO is presented. Clearly, appropriate ε‐values must be included in interpreting δ¹³C values of environmental samples.     

Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates

An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three‐ and four‐isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of δ¹³C, δ³⁴S, Δ³³S, and Δ³⁶S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS δ¹³C measurement of organic matter is identified. Small (2–3 μm) organic domains in carbonate matrices are analyzed with sub‐permil accuracy and precision. Separate 20‐ to 50‐μm domains of kerogen in a single ~0.5 cm³ sample of the ~2.7 Ga Tumbiana Formation have δ¹³C = ?52.3 ± 0.1‰ and ?34.4 ± 0.1‰, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the ~2.6 Ga Jeerinah Formation and the ~2.5 Ga Mount McRae Shale is systematically ¹³C‐enriched relative to co‐occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Δ³³S and more extreme spatial gradients in Δ³³S and Δ³⁶S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of δ³⁴S, Δ³³S, and Δ³⁶S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass‐independent sulfur isotope fractionation (S‐MIF) associated with the Mesoarchean continued into the early Neoarchean, and that the connections between methane and sulfur metabolism affected the production and preservation of S‐MIF during the first half of the planet's history.     

Declining coral calcification in massive Porites in two nearshore regions of the northern Great Barrier Reef

Temporal and spatial variation in the growth parameters skeletal density, linear extension and calcification rate in massive Porites from two nearshore regions of the northern Great Barrier Reef (GBR) were examined over a 16‐year study period. Calcification rates in massive Porites have declined by approximately 21% in two regions on the GBR ～450 km apart. This is a function primarily of a decrease in linear extension (～16%) with a smaller decline in skeletal density (～6%) and contrasts with previous studies on the environmental controls on growth of massive Porites on the GBR. Changes in the growth parameters were linear over time. Averaged across colonies, skeletal density declined over time from 1.32 g cm^?3 (SE = 0.017) in 1988 to 1.25 g cm^?3 (0.013) in 2003, equivalent to 0.36% yr^?1 (0.13). Annual extension declined from 1.52 cm yr^?1 (0.035) to 1.28 cm yr^?1 (0.026), equivalent to 1.02% yr^?1 (0.39). Calcification rates (the product of skeletal density and annual extension) declined from 1.96 g cm^?2 yr^?1 (0.049) to 1.59 g cm^?2 yr^?1 (0.041), equivalent to 1.29% yr^?1 (0.30). Mean annual seawater temperatures had no effect on skeletal density, but a modal effect on annual extension and calcification with maxima at ～26.7 °C. There were minor differences in the growth parameters between regions. A decline in coral calcification of this magnitude with increasing seawater temperatures is unprecedented in recent centuries based on analysis of growth records from long cores of massive Porites. We discuss the decline in calcification within the context of known environmental controls on coral growth. Although our findings are consistent with studies of the synergistic effect of elevated seawater temperatures and pCO₂ on coral calcification, we conclude that further data on seawater chemistry of the GBR are required to better understand the links between environmental change and effects on coral growth.     

Tracking a century of change in trophic structure and dynamics in a floodplain wetland: integrating palaeoecological and palaeoisotopic evidence

相似文献   

Altitudinal gradients of grassland carbon and nitrogen isotope composition are recorded in the hair of grazers

Aim The hair of grazers provides an isotopic record of environmental and nutritional signals. Here, we assess the effect of altitude on the carbon and nitrogen isotope composition of the hair of ruminant grazers and its relation to grassland vegetation, to evaluate the use of hair isotope data for ecosystem reconstruction, animal nutritional ecology and biogeochemical studies in montane environments. Location European Alps. Methods We sampled grassland vegetation (pure C₃) and the hair of ruminants along an altitudinal gradient (400–2500 m), and analysed their isotope composition (δ¹³C and δ¹⁵N). Results were compared with published effects of altitude on ¹³C in C₃ plants at the species level and on ¹⁵N at the community level. The study was complemented with a comparison of diet and hair isotope composition in ruminants held in confinement. Results δ¹³C of hair increased (c. 1.1‰ km⁻¹) and δ¹⁵N decreased (c. 1.1‰ km⁻¹) with altitude. The same changes occurred in local grassland vegetation, and in regional to global grassland data sets. Offsets between hair and vegetation ¹³C or ¹⁵N (‘diet–hair shift’) were independent of altitude. Sheep (Ovis aries) and cattle (Bos taurus) exhibited a ¹³C shift near +3‰, but that of goats (Capra hircus) was larger (+4.2‰) in alpine environments and in confinement. The diet–hair shift for ¹⁵N was more variable (+2.1 to +3.6‰). Main conclusions Grazer hair provides a faithful spatially and temporally integrated record of grassland isotope composition, useful for ecosystem and environment reconstruction. The effect of altitude on hair ¹⁵N is important for studies of trophic relationships: an altitude shift of 2000 m produced the same effect in hair ¹⁵N as would a shift from an animal tissue‐based to a plant‐based diet. The similarity of altitude effects on δ¹³C of individual plant species, vegetation and hair indicates that the effect of altitude on species‐level ‘intrinsic water use efficiency’ scales up linearly to the community and landscape level.