Organic Matter Redox State Driven by Specific Sources in Mangrove Sediments: A Case Study from Peruvian Ecosystems

In order to determine the organic matter redox state in relation to specific sources in mangrove sediments, two 60 cm-long sediment cores were collected from mangrove-covered and mudflat zones within a mangrove forest in Peru. Sediment subsamples from these cores were analyzed to determine δ13C values and C:N ratios, whereas two redox indices, namely, electrochemical (fEAOM) and spectroscopical (A1650/A3400) indices, were taken from a previous study and correlated with the geochemical indices obtained from this work. These indices may provide accurate information on sedimentary organic matter diagenesis by oxidative processes through its redox state. The results show that the electrochemical index (fEAOM) and the spectroscopical index (A1650/A3400) for mangrove-covered sediments exhibited a positive correlation with δ13C values and a negative correlation with C:N molar ratios. These correlations suggest that the more labile sedimentary organic matter derived from non-terrestrial sources is in a more oxidized state than that derived from mangrove vegetation. However, this was not valid for mudflat zones, where non-significant correlations between geochemical indices were observed. Furthermore, the results suggest that the redox state of the organic matter deposited over time is dependent on source mixing influences, being better preserved in the presence of mangrove-derived organic matter.

Origin of the Coloured Karst Fills in the Neogene Extensional System of NE Iberia (Spain)

Karst fills from the onshore Penedès Basin and offshore València Trough display red, pink, orange and ochre colours. Their Mössbauer spectra indicate that Fe3+ contained in goethite is the dominant species in reddish-pink fills, whereas Fe2+ contained in dolomite and clays is more dominant in the orange and ochre ones. The lower δ13C values and higher 87Sr/86Sr ratios of the karst fills with respect to their host carbonates can reflect the input of soil-derived CO2 and an external radiogenic source into the karst system. This geochemical composition, together with the non-carbonate fraction of the fills, consists of authigenic and transported illite, illite-smectite interlayers, as well as kaolinite, chlorite, pyrite, quartz, ilmenite, magnetite, apatite and feldspar, account for a mixed residual-detrital origin of fills. This polygenic origin agrees with that of the terra rossa sediments described worldwide. The different colours of karst fills are attributed to fluctuations in the water table, which control the Eh/pH conditions in the karst system. Thus, reddish colours reflect low water table levels and oxidising episodes, and orange and ochre ones reflect high water table levels and more reducing episodes. The greenish colours of fills could be related to fluctuations in the Fe3+/Fe2+ ratio.

Climatic variations during the Holocene inferred from radiocarbon and stable carbon isotopes in speleothems from a high-alpine cave

Rapid and continuous analysis of radiocarbon (14C) concentration in carbonate samples at spatial resolution down to 100 µm has been made possible with the new LA-AMS (laser ablation accelerator mass spectrometry) technique. This novel approach can provide radiocarbon data at a spatial resolution similar to that of stable carbon (C) isotope measurements by isotope ratio mass spectrometry of micromilled samples and, thus, can help to interpret δ13C signatures, which otherwise are difficult to understand due to numerous processes contributing to changes in the C-isotope ratio. In this work, we analyzed δ13C and 14C on the Holocene stalagmite SPA 127 from the high-alpine Spannagel Cave (Austria). Both proxies respond in a complex manner to climate variability. Combined stable carbon and radiocarbon profiles allow three growth periods characterized by different δ13C signatures to be identified: (i) the period 8.5 to 8.0 ka is characterized by relatively low δ13C values with small variability combined with a comparably high radiocarbon reservoir effect (expressed as dead carbon fraction, dcf) of around 60 %. This points towards C contributions of host rock dissolution and/or from an “old” organic matter (OM) reservoir in the karst potentially mobilized due to the warm climatic conditions of the early Holocene. (ii) Between 8 and 3.8 ka there was a strong variability in δ13C with values ranging from −8 ‰ to +1 ‰ and a generally lower dcf. The δ13C variability is most likely caused by changes in C exchange between cave air CO2 and dissolved inorganic carbon in drip water in the cave, which are induced by reduced drip rates as derived from reduced stalagmite growth rates. Additionally, the lower dcf indicates that the OM reservoir contributed less to stalagmite growth in this period possibly as a result of reduced meteoric precipitation or because it was exhausted. (iii) In the youngest section between 3.8 and 2.4 ka, comparably stable and low δ13C values, combined with an increasing dcf reaching up to 50 % again, hint towards a contribution of an aged OM reservoir in the karst. This study reveals the potential of combining high-resolution 14C profiles in speleothems with δ13C records in order to disentangle climate-related C dynamics in karst systems.

The paleoecology of Pleistocene giant megatheriid sloths: stable isotopes (δ13C, δ18O) of co-occurring Megatherium and Eremotherium from southern Brazil

The Pampa in subtropical Brazil (State of Rio Grande do Sul) is the only area of South America known so far where fossils of the Pleistocene giant megatheriid sloths Megatherium americanum, characteristic of subtropical-temperate areas, and Eremotherium laurillardi, widespread in the tropical zone, were discovered in the same deposits (Pessegueiro Creek and Chuí Creek), but it is not clear whether this co-occurrence is a product of taphonomic mixture, or co-existence, which would imply niche partitioning. In order to understand their paleoecology and reconstruct the associated paleoenvironments, dentin samples of both megatheriids from the two sites were analyzed for their carbon (δ13C) and oxygen (δ18O) isotope ratios. The δ13C values of Megatherium indicate mixed diet of C3-C4 plants with higher content of the latter in Pessegueiro Creek, whereas the δ13C values of Eremotherium indicate C3-dominated diets, the more negative value in Pessegueiro Creek possibly related to the canopy effect. The δ18O of Eremotherium points to 18O-depleted water sources, possibly also influenced by the diet, whereas Megatherium ingested 18O-enriched water. The results show that co-existence of both megatheriids would have been ecologically possible, and that the Pampa was occupied by open grasslands/woodlands, with closed forests in Pessegueiro Creek. The δ13C of Eremotherium from intertropical Brazil indicate a more generalist habit than Megatherium from subtropical Brazil and Argentina, which probably facilitated its dispersion from the tropics up to subtropical areas along two different routes, one along the coastal plain, and the other along the Paraná River Basin across central South America, following the southward expansion of riparian forests during warmer stages. The reduction of those forests during intervening cold stages possibly led to its disappearance in southern Brazil. Keywords: Quaternary, paleobiogeography, stable isotopes, Pampa, coastal plain, megafauna.

Beachrock as a Paleoshoreline Indicator: Example from Wadi Al-Hamd, South Al-Wajh, Saudi Arabia

The present study concerns the Holocene inland beachrocks that are exposed in the Red Sea coastal plain at the mouth of Wadi Al-Hamd, South Al-Wajh City, Saudi Arabia, and their utility as an indicator for Holocene climate and sea level changes. In addition, the framework composition, and carbon and oxygen isotopic data, are employed to interpret the origin of their cement. The beachrock consists mainly of gravel and coarse-grained terrigenous sediments dominated by lithic fragments of volcanic rocks, cherts and rare limestones along with quartz, feldspars and traces of amphiboles and heavy minerals. In addition, rare skeletal remains dominated by coralline algae, benthic foraminifera and mollusca remains are recognized. The allochems are cemented by high Mg-calcite (HMC) formed mainly in the intertidal zone under active marine phreatic conditions. The cement takes the form of isopachous to anisopachous rinds of bladed crystals, micritic rim non-selectively surrounding siliciclastic and skeletal remains, and pore-filling micrite. Pore-filling micrite cement occasionally displays a meniscus fabric, suggesting a vadose environment. The δ18O and δ13C values of carbonate cement range from −0.35‰ to 1‰ (mean 0.25‰) and −0.09‰ to 3.03‰ (mean 1.85‰), respectively, which are compatible with precipitation from marine waters. The slight depletion in δ18O and δ13C values in the proximal sample may suggest a slight meteoric contribution.

Carbon and nitrogen dynamics in the coastal Japan Sea inferred from 15 years of measurements of stable isotope ratios of Calanus sinicus

Human activities have caused sometimes dramatic changes to the marine environment globally and locally during the last half century. We hypothesized that the carbon and nitrogen stable isotope ratios (δ13C and δ15N) of the copepod Calanus sinicus, one of the dominant secondary producers of North Pacific coastal waters, would record anthropogenic impacts on the coastal environment of the Japan Sea. We monitored these isotope ratios during the spring at four stations in the Japan Sea from 2006 to 2020. The δ13C values ranged from −24.7 ‰ to −15.0 ‰ and decreased from the spring bloom (February/March) to the post-bloom (June/July). This monthly variation was attributed to changes in both the physiology of C. sinicus and phytoplankton δ13C. The negative correlation between the δ13C values of C. sinicus and their carbon:nitrogen ratios reflected lipid accumulation by the copepods; high δ13C values were associated with high sea surface chlorophyll a concentrations. The δ15N values ranged from 2.8 ‰ to 8.8 ‰. The tendency of the δ15N values to increase from the bloom to post-bloom was attributable to an increase of the δ15N of the phytoplankton associated with nitrate depletion and Rayleigh fractionation. These monthly changes were synchronized among the four stations, but δ13C and δ15N differed significantly between stations. Interannual variations were statistically significant, but there were no significant monotonic trends. Interannual variations differed between δ13C and δ15N as well as among stations. These results suggest that local conditions rather than global-scale trends were the primary determinants of elemental cycles in this coastal ecosystem.

Spektrometria masowa i analiza izotopowa biomarkerów frakcji nasyconej

GC-IRMS analysis extends and confirms (or not) the interpretation based on the results of GC-MS analyses. For example, it is very useful in determining the sedimentation environment of organic matter. GC-MS analysis of biomarkers and the results are reliable, but only GC-IRMS studies can confirm it. In this study, the origin of BNH (28,30-bisnorhopane from chemoautotrophic bacteria) and origin of higher carotenoids and their derivatives from Chlorobiaceae or Chromotiaceae bacteria were confirmed through isotopic analyzes. Biomarkers were analyzed using the GC-IRMS and EA-IRMS apparatus. The obtained chromatograms from the IRMS analyses were compared with the archival GC-MS analyses for the same samples in order to identify individual chemical compounds. In addition to the existing methodology of sample preparation for analyses, a non-standard method was also used, consisting in the separation of n-alkanes from branched hydrocarbons. The repeatability of the method was determined on the GC-IRMS and the values of δ13C for selected biomarkers from the saturated fraction were determined. It was found that samples with low biomarker content are not suitable for analysis. On the other hand, too high concentration of the analyte causes an increase of the chromatogram baseline and worse separation of the peaks, which is also a problem. For the crude oils the δ13C values were initially determined for the biomarkers of the saturated fraction from the hopanes group: bisnorhopane (BNH), oleanane, C29 norhopane, C30 hopane, moretane and the C31-C35 homohopane series. Relatively small differences in δ13C values were found between BNH/hopanes and BNH/crude oils, which suggests the same source of origin for all biomarkers (including BNH). Determining biomarkers in the aromatic fraction using the GC-IRMS method was not successful. In the future, a special methodology for preparing samples for carbon isotopic analyses of aromatic fraction will be required.

Differentiating early from later diagenesis in a Cretaceous sandstone and petroleum reservoir of the Cedar Mountain Formation, Utah

ABSTRACT Previously published anomalous whole-rock stable isotopic values from the Poison Strip Sandstone Member of the Cretaceous Cedar Mountain Formation (CMF) of eastern Utah are of uncertain origins. This study investigated the diagenetic history and the processes responsible for these anomalous data. Accordingly, we integrated photomicroscopic techniques including polarized light microscopy, epifluorescence and cathodoluminescence (CL) imaging, micromilling of stable isotope samples, and fluid-inclusion heating and freezing measurements to this end. The key observations involved the microscopic mapping of calcite cement stratigraphy using CL imaging to permit the analysis of stable isotopes of calcite cements that crystallized during early and late diagenesis. The mapping of calcite cement zones of sufficient submillimeter size to mill out and isolate microgram-sized stable isotope samples enabled this discrimination. Early diagenetic calcite cements have the most positive δ18O values (-10 to -8.5‰ Vienna Pee Dee Belemnite [VPDB]) of all components. The pattern of δ13C and δ18O variation in this early diagenetic cement indicates affinities with early meteoric diagenesis previously documented in published literature on the CFM. The late diagenetic calcite cements yield the most negative δ18O values (-18 to -16‰ VPDB). We interpret the late diagenetic cements to be responsible for the anomalously low whole-rock δ18O values previously reported from the Poison Strip Sandstone Member. Our discoveries of bitumen in late-stage pore fillings and liquid petroleum in the fluid inclusions of late diagenetic calcite cements of the Poison Strip Sandstone Member explain the lower whole-rock organic matter δ13C values and anomalous Δ13C values reported from the unit. Comparatively lower carbonate δ18O and organic δ13C values originally derived from whole-rock analyses of samples from the Poison Strip Sandstone Member resulted from high-temperature basinal diagenesis (hydrothermal circulation and/or petroleum migration), rather than the alternative interpretation of early diagenesis related to a Cretaceous paleoclimatic perturbation. Our results are illustrative of methods to resolve the long-standing geologic problem of discriminating and characterizing products of early vs. late diagenesis in terrigenous clastic sedimentary strata.