Inorganic δ13C Research Articles

Devonian-Carboniferous boundary beds in the Kuz-Yama section (Northern Cis-Urals) - Conodonts, ostracods, and carbon isotope record

The Devonian-Carboniferous boundary interval is characterized by biotic crisis, global transgressive-regressive sequences and carbon cycle change, probably caused by climatic changes and volcanic activity. This interval attracts the attention of researchers worldwide in relation to selecting a new Devonian-Carboniferous boundary level. However the Northern Cis-Urals region remains poorly studied in this respect. This study focuses on the Kuz-Yama key section (Northern Cis-Urals) and contributes to our knowledge of the regional expression of the Devonian-Carboniferous boundary in northeastern Europe. The study of the Kuz-Yama section (Verkhnyaya Pechora Trough) involved an examination of the calciturbidites, hemipelagic shales and carbonates that constitute the poorly constrained uppermost Famennian to lower Tournaisian deep-water succession. The conodont and ostracod associations are poorly diversified. The presence of Polygnathus zikmundovae, in association with a positive δ13Ccarb excursion (up to 3.9 ‰), marks the base of the Late praesulcata conodont Zone (=base of the Protognathodus kockeli conodont Zone) in the lower part of the succession. The Devonian-Carboniferous boundary is indicated by the appearance of Siphonodella sulcata, that coincides with a positive shift in the decoupling of δ13Ccarb and δ13Ccon values, probably caused by a global decrease in CO2 associated with the regional crisis within pelagic ecosystems. The sulcata conodont Zone, bounded by the first occurrence of Siphonodella sulcata at the bottom and Siphonodella bransoni at the top of the section, contains Tournaisian ostracods. The ostracods compose mixed associations of the shallow-water Pseudoleperditia venulosa-Coryellina alba-Cribroconcha primaris ostracod Zone and the deep-water Armilla uralica ostracode Zone. The co-occurrence of shallow-water and deep-water conodont and ostracod taxa in the Tournaisian part of the section enhances the correlation of the shallow-water and deep-water conodont and ostracod zonations. The base of the shallow-water Siphonodella ludmilae conodont Zone roughly correlates with the base of the deep-water bransoni Zone. The base of Armilla uralica deep-water ostracod Zone in the Kuz-Yama section lies within the Pseudoleperditia venulosa-Coryellina alba-Cribroconcha primaris shallow-water ostracod Zone. The following sequence of events can be recognised in the Kuz-Yama section: first occurrence of Polygnathus zikmundovae Zhuravlev (approximately corresponding to the base of the Protognathodus kockeli Zone), positive shift in the inorganic δ13C (= Hangenberg carbon isotope excursion), latest Famennian regression, negative shift in the δ13C of conodont elements just below the base of the sulcata Zone, entry of the Tournaisian transgression, positive shift in decoupled inorganic and conodont δ13C near the base of sulcata Zone, positive shift in inorganic δ13C in the sulcata Zone, appearance of the Tournaisian ostracods, first occurrences of the conodonts Siphonodella bransoni Ji and S. ludmilae Zhuravlev & Plotitsyn (= base of the bransoni Zone). In general, this sequence corresponds to that identified around the Devonian-Carboniferous boundary in other regions.

LAGOA SALGADA: AN OVERVIEW OF A BRAZILIAN HYPERSALINE LAGOON ENVIRONMENTAL STUDIES OVER THE LAST 5000 YEARS USING RADIOCARBON DATE CORRECTIONS

ABSTRACTThe Lagoa Salgada is located in the Paraíba do Sul river delta plain on the coast of Rio de Janeiro state, Brazil, and is one of the few lagoons in the world that have well-developed recent stromatolites. Lagoa Salgada is a hypersaline lagoon formed in a very complex environmental system subjected to terrestrial and oceanic influences under different sea level regimes and climate variations. In addition, sediment and stromatolites are characterized by unusually positive inorganic δ13C VPDB values. For this reason, it has been the target of several geological and paleoenvironmental studies, which, in their great majority, require a geochronological technique in order to determine the changes in the environment over time. When radiocarbon (14C) dating is used, it is necessary to consider some details as the source of 14C in the environment and perform 14C ages calibration accordingly. In the present paper, a bibliographic survey was carried out in order to review the data treatment and improve the environmental evolution discussion based on accurate calibration. Using the Marine20 curve and an undetermined ΔR, we generated growth and depositional models to establish an overview of the formation of this lagoon.

No biological effect on magnesium isotope fractionation during stromatolite growth

The growth and morphology of stromatolites have been previously linked to diverse microbial activities. However, the role of microbial metabolisms on carbonate formation during stromatolite growth remains controversial. Magnesium isotopes have been proposed to serve as a tracer of microbial carbonate formation, implying a potential biological isotope fractionation. To further elucidate whether Mg isotope fractionation is modified during microbial carbonate formation, this study reports Mg isotope compositions of Holocene stromatolites and pore waters from Lagoa Salgada, a coastal ephemeral lake in Brazil. The stromatolitic carbonates are composed of high-Mg calcites characterized by extremely positive inorganic δ13C values, up to +20‰, and variable δ26Mg values, ranging from −2.98‰ to −0.68‰. Multiple pieces of evidence consistently demonstrate changes in microbial metabolism resulting from ecosystem fluid chemistry evolution. However, the direction of Mg isotope fractionation associated with carbonate precipitation remained invariable despite the changes in microbial activity. Mineralogical features indicate that the stromatolitic carbonates formed via 2-D nucleation. An isotopic mass balance calculation based on the observed variations in δ26Mg values and Mg concentrations of associated pore waters argues for an Mg isotopic equilibrium fractionation factor of −2.60‰ associating with the carbonate formation at Lagoa Salgada, well-matching experimental values for abiotic calcite precipitation. Thus, the observed δ26Mg variability of stromatolitic carbonates is primarily controlled by the changes of physicochemical conditions in the ambient fluid. We infer that during the formation of stromatolites, a consortium of different microbial communities produces extracellular polymeric substances, which serve as a substrate for carbonate nucleation from ambient fluid without significantly affecting the fractionation of Mg-isotopes. Our findings shed light on the effects of microbial processes on carbonate formation during stromatolite growth and improve the current understanding of the Mg isotope record in microbial carbonates.

Ontogenetic resource utilization and migration reconstruction with δ13C values of essential amino acids in the Cynoscion acoupa otolith.

With the increasing anthropogenic impacts on fish habitats, it has become more important to understand which primary resources sustain fish populations. This resource utilization can differ between fish life stages, and individuals can migrate between habitats in search of resources. Such lifetime information is difficult to obtain due to the large spatial and temporal scales of fish behavior. The otolith organic matrix has the potential to indicate this resource utilization and migration with δ13C values of essential amino acids (EAAs), which are a direct indication of the primary producers. In a proof‐of‐concept study, we selected the Acoupa weakfish, Cynoscion acoupa, as a model fish species with distinct ontogenetic migration patterns. While it inhabits the Brazilian mangrove estuaries during juvenile stages, it moves to the coastal shelf as an adult. Thus, we expected that lifetime resource utilization and migration would be reflected in δ13CEAA patterns and baseline values in C. acoupa otoliths. By analyzing the C. acoupa otolith edges across a size range of 12–119 cm, we found that baseline δ13CEAA values increased with size, which indicated an estuarine to coastal shelf distribution. This trend is highly correlated with inorganic δ13C values. The δ13CEAA patterns showed that estuarine algae rather than mangrove‐derived resources supported the juvenile C. acoupa populations. Around the juvenile size of 40 cm, resource utilization overlapped with those of adults and mean baseline δ13CEAA values increased. This trend was confirmed by comparing otolith core and edges, although with some individuals potentially migrating over longer distances than others. Hence, δ13CEAA patterns and baseline values in otoliths have great potential to reconstruct ontogenetic shifts in resource use and habitats. The insight could aid in predictions on how environmental changes affect fish populations by identifying the controlling factors at the base of the food web.

Soil Inorganic Carbon Sequestration Following Afforestation Is Probably Induced by Pedogenic Carbonate Formation in Northwest China.

In arid and semiarid areas, the effects of afforestation on soil organic carbon (SOC) have received considerable attention. In these areas, in fact, soil inorganic carbon (SIC), rather than SOC, is the dominant form of carbon, with a reservoir approximately 2–10 times larger than that of SOC. A subtle fluctuation of SIC pool can strongly alter the regional carbon budget. However, few studies have focused on the variations in SIC, or have used stable soil carbon isotopes to analyze the reason for SIC variations following afforestation in degraded semiarid lands. In the Mu Us Desert, northwest China, we selected a shifting sand land (SL) and three nearby forestlands (Populus alba) with ages of 8 (P-8), 20 (P-20) and 30 (P-30) years, and measured SIC, SOC, soil organic and inorganic δ13C values (δ13C-SOC and δ13C-SIC) and other soil properties. The results showed that SIC stock at 0–100 cm in SL was 34.2 Mg ha-1, and it increased significantly to 42.5, 49.2, and 68.3 Mg ha-1 in P-8, P-20, and P-30 lands, respectively. Both δ13C-SIC and δ13C-SOC within the 0–100 cm soil layer in the three forestlands were more negative than those in SL, and gradually decreased with plantation age. Afforestation elevated soil fine particles only at a depth of 0–40 cm. The entire dataset (260 soil samples) exhibited a negative correlation between δ13C-SIC and SIC content (R2 = 0.71, P < 0.01), whereas it showed positive correlation between SOC content and SIC content (R2 = 0.52, P < 0.01) and between δ13C-SOC and δ13C-SIC (R2 = 0.63, P < 0.01). However, no correlation was observed between SIC content and soil fine particles. The results indicated that afforestation on shifting SL has a high potential to sequester SIC in degraded semiarid regions. The contribution of soil fine particle deposition by canopy to SIC sequestration is limited. The SIC sequestration following afforestation is very probably caused by pedogenic carbonate formation, which is closely related to SOC accumulation. Our findings suggest that SIC plays an important role in the carbon cycle in semiarid areas and that overlooking this carbon pool may substantially lead to underestimating carbon sequestration capacity following vegetation rehabilitation.

Do fish remains provide reliable palaeoenvironmental records? An examination of the effects of cooking on the morphology and chemistry of fish otoliths, vertebrae and scales

The morphological and chemical properties of fish calcified structures provide excellent environmental and anthropogenic proxies; however, pre-depositional handling may alter these properties, confounding interpretations. This study examines the effects of some traditional processing and cooking methods on the morphological and chemical properties of modern fish otoliths (ear bones), vertebrae, and scales using an experimental approach. Whole mulloway (Argyrosomus japonicus) were treated using a range of techniques, including boiled in freshwater and saltwater; roasted directly on a fire and wrapped in clay; salted; and completely burnt. Samples were also obtained from untreated fish as controls for comparison. Otoliths, vertebrae and scales from the samples were subjected to morphological, trace element (7Li, 23Na, 24Mg, 55Mn, 86Sr, 138Ba, 208Pb, and 65Zn all ratioed to 43Ca) and stable isotope analyses (otoliths and vertebrae – inorganic δ13C and δ18O; scales – organic δ13C and δ15N). Results reveal disparities in the chemistry and morphology of otoliths and vertebrae processed in different ways. The otolith and vertebrae carbonate δ18O values were lower in samples that experienced heating; burnt samples differed significantly from the control samples. Otolith and vertebrae trace elements were largely unaffected by the treatments relative to the controls; however, some individual elements within the burning and salting groups varied significantly. The impacts observed in the fish scales were less substantial. Results provide a basis for evaluating the suitability of archaeological samples for analysis. We recommend avoiding the use of heated samples. Findings highlight the need to conduct palaeoenvironmental reconstructions based on chemistry and stable isotope data of archaeological remains with caution.

The stable carbon isotopic composition of organic material in platform derived sediments: implications for reconstructing the global carbon cycle

AbstractIn pelagic carbonate sediments, the degree to which the δ13C values of inorganic and organic fractions co‐vary has been used to interpret rates of production, burial and decomposition of organic carbon. This relationship is relatively consistent through time, permitting estimates of organic carbon production and preservation. However, as the majority of pelagic sediments older than 200 Myr have been subducted, carbonate sediments deposited in epeiric seas and platforms are often substituted for pelagic carbonates in analyses of ancient global carbon cycling. There are well‐known pitfalls to using shallow marine carbonate materials, including diagenesis, semi‐isolation of depositional environments and input of different types of sediments with varying inorganic δ13C (δ13Cinorganic) values, which can obscure any global signatures. One method used to assess whether global changes in δ13C are accurately represented by δ13Cinorganic records is to examine variations in the δ13C of co‐occurring organic material (δ13Corganic). If a δ13Corganic record co‐varies with a co‐occurring δ13Cinorganic record, it is argued that the signals must be related to variations in the global carbon cycle. This assumption has been investigated by analysing the isotopic composition of the organic carbon preserved in the uppermost 150 m of periplatform sediments recovered during ODP Leg 166 from the western margin of Great Bahama Bank. The δ13Corganic values measured in this study were compared to previously published δ13Cinorganic records measured on identical samples, thus allowing a study of the correlation between the two records through time. These analyses showed that the correlation coefficient between δ13Cinorganic and δ13Corganic increased from the proximal location (Site 1005, r2 = 0·1), to the distal site (Site 1006, r2 = 0·63). The importance of platform‐derived carbonate and organic material at the proximal location, Site 1005, is reflected in the absence of a co‐variation between inorganic and organic δ13C records, which exhibit no correlation on the platform itself. In contrast, the co‐variance in δ13C values at the basinal location, Site 1006, is explained by a two‐point mixing model, which demonstrates the importance of both pelagic and platform‐derived carbonate and organic carbon in generating the positive correlation between the organic and inorganic δ13C values; this results in a correlation between δ13Cinorganic and δ13Corganic records at Site 1006 that is unrelated to global carbon cycling. Such data question the applicability of using δ13Corganic values to support the ability of δ13Cinorganic values to record global carbon cycling in carbonates recovered from environments where multiple sources of carbonate and organic carbon contribute to the bulk δ13C signal.

The need to correct for the Suess effect in the application of δ13C in sediment of autotrophic Lake Tanganyika, as a productivity proxy in the Anthropocene

The change in dissolved inorganic δ13C in the ocean resulting from the change in δ13C in atmospheric CO2 owing to anthropogenic activities (the Suess effect) is well known. The need to correct for the Suess effect when applying δ13C in organic matter in lacustrine sediment deposited during the anthropocene as a productivity proxy, is widely although not universally acknowledged. This paper reviews conceptions about the Suess effect in lacustrine δ13Corg and methods to adjust for the Suess effect when δ13Corg is used to infer recent changes in aquatic productivity. Lake Tanganyika is used as an example to illustrate the necessity of the correction. When the Suess effect is not considered, interpretations of sediment core data can result that are opposite to those achieved with the correction applied, as is here shown in Lake Tanganyika and in other lakes. A new method to correct for the Suess effect is provided which has the advantage of being applicable to data for a larger period (1700–2000) than methods currently available. In addition, Lake Tanganyika is shown to be a net sink for CO2.

Monitoring food web changes in tide-restored salt marshes: A carbon stable isotope approach

Primary producer (angiosperms, macroalgae, submerged aquatic vegetation), suspended particulate matter, andFundulus heteroclitus isotope values (δ13C, δ15N, δ34S) were examined to assess their use as indicators for changes in food web support functions in tidally-restored salt marshes. Study sites, located throughout the southern New England region (USA), ranged fromSpartina alterniflora-dominated reference marshes, marshes under various regimes and histories of tide restoration, and a severely tide-restrictedPhragmites australis marsh.Fundulus δ13C values were greater for fish from referenceSpartina marshes than for fish from adjacent tide-restricted or tide-restored marshes where higher percent cover of C3 plants, lower water column salinities, and more negative dissolved inorganic δ13C values were observed. The difference inFundulus δ13C values between a tide-restrictedPhragmites marsh and an adjacent referenceSpartina marsh was great compared to the difference between marshes at various stages of tide restoration and their respective reference marshes, suggesting that food web support functions are restored as the degree of tidal restriction is lessened. While a multiple isotopic approach can provide valuable information for determining specific food sources to consumers, this study demonstrates that monitoringFundulus δ13C values alone may be useful to evaluate the trajectory of ecological change for marshes undergoing tidal restoration.

Global carbon isotopic events associated with mass extinction and glaciation in the late Ordovician

Mass extinctions and glacioeustatic sea-level changes in the lower part of the Hirnantian (final stage of the Ashgill) are accompanied by shifts in marine stable-isotope compositions. Previously published stable-isotope changes have been used to identify the onset and demise of the Gondwana glaciation and to suggest relationships between biotic changes and carbon cycling within the oceans. However, the existing isotopic data set had limitations because it was derived from Ordovician low-latitude settings and from carbonates or organic carbon in separate areas. We report new data from Ordovician high-latitude carbonates and demonstrate parallel shifts in organic and carbonate δ13C from Baltica. Brachiopod shells from a high-palaeolatitude, periglacial setting in Argentina have elevated δ13C values similar to those described previously from low-latitude sites. The new data demonstrate that the positive Hirnantian δ13C excursion, previously only recognised from low-palaeolatitude areas, was widespread and probably global in extent. The poor preservation state of the brachiopods unfortunately prevented the determination of a reliable oxygen isotopic value from the same material. Preliminary carbon isotopic data from thermally immature organic matter from Estonia provide the first indication of a synchronous shift in organic and inorganic δ13C in sediments from the same basin. This work provides new data of critical importance for constraining models of end-Ordovician palaeoceanography and climate change.