Low δ13C Values Research Articles

Peruvian Fur Seals as Archivists of El Niño Southern Oscillation Effects

Peru’s coastal waters are characterized by significant environmental fluctuation due to periodic El Niño- La Niña- Southern Oscillation (ENSO) events. This variability results in ecosystem-wide food web changes which are reflected in the tissues of the Peruvian fur seal (Arctocephalus australis). Stable isotope ratios (δ13C and δ15N) in Peruvian fur seal vibrissae (whiskers) are used to infer temporal primary production and dietary variations in individuals. Sea surface temperature anomaly (SSTA) recordings from the Niño 1+2 Index region captured corresponding ENSO conditions. Fluctuations in δ15N values were correlated to SSTA records, indicating that ENSO conditions likely impact the diet of these apex predators over time. Anomalous warm phase temperatures corresponded to decreased δ15N values, whereas cold phase anomalous conditions corresponded to increased δ15N values, potentially from upwelled, nutrient-rich water. Vibrissae δ13C values revealed general stability from 2004 to 2012, a moderate decline during 2013 (La Niña conditions) followed by a period of increased values concurrent with the 2014–2016 El Niño event. Both δ13C and δ15N values were inversely correlated to each other during the strongest El Niño Southern Oscillation event on record (2014–2016), possibly indicating a decline in production leading to an increase in food web complexity. Lower δ13C and δ15N values were exhibited in female compared to male fur seal vibrissae. Findings suggest ENSO conditions influence resource availability, possibly eliciting changes in pinniped foraging behavior as well as food web of the endangered Peruvian fur seal.

Genesis of interlayer oxidation zone-type uranium deposit in the channel conglomerates, Beisantai area, Junggar Basin: An insight into uranium mineralization

The Beisantai deposit is a newly discovered typical interlayer oxidation zone-type uranium deposit mainly hosted in distributary channel conglomerates of the Neogene Shawan Formation in East Junggar Basin, northwest China. This study aims to reveal the genetic process of the Beisantai deposit and constrain the mineralization characteristics conducted through petrographic observation, Rock-Eval pyrolysis, high-resolution microscopic mineralogical observation based on BSE, C-O isotopes of calcite cement, and in-situ measurements on pyrite of trace elements and S isotope. There are two types of calcite cements, including diagenetic microcrystalline calcite and epigenetic sparry calcite, dominantly occurring in the redox transition zone and the oxidation zone, respectively. The broad heterogeneity of δ13C values, ranging from −29.2‰ to −6.52‰, indicates the mixed sources of carbon. Given the poor organic content in sediments (0.05% in sandstone and from 0.11% to 0.26% in mudstones), the large amount of organic carbon in the transition zone conglomerates, revealed by the super low δ13C values, is attributed to extrinsic hydrocarbons. Besides, the widespread dissolution of microcrystalline calcite also indicates a weakly acidic environment in the formation. The heavy carbon isotopes are sourced from surface freshwater and the dissolved CO2, which causes the epigenetic metasomatism of early-stage calcite. Thus, the infiltrated groundwater is characterized as alkaline with carbonate dissolved. Pyrites are highly enriched in ore-bearing rocks, with complex morphologies. The extremely negative sulfur isotopic signatures (δ34S values from −48.38‰ to −35.65‰) indicate that these pyrites precipitate through bacterial sulfate reduction (BSR). Combined with the morphology features, distribution patterns, and the decrease in light sulfur isotope and several trace elements, including As, Se, Ni, and Co between individual pyrites and ore-related pyrites, a successive process of pyritization can be revealed. Ore-related pyrites are formed at the late stage. The pervasive coffinite replacement of pyrite suggests that uranium mineralization should occur after the cessation of pyritization, resulting from the consumption of organic matter. Distinctive bio-oxidation features of pyrite can also be observed, characterized as deep and oriented holes. Thus the role of microbes such as Acidithiobacillus thiooxidans is non-negligible, which enhances the dissolution rate of pyrite and the reduction of U(Ⅵ). Overall, as the major reducing material during the ore stage, the large amount of pyrite has played the predominant role in the precipitation of coffinite, with the catalysis and acceleration of microbes.

Exploring the paleoceanographic changes registered by planktonic foraminifera across the Cenomanian-Turonian boundary interval and Oceanic Anoxic Event 2 at southern high latitudes in the Mentelle Basin (SE Indian Ocean)

Planktonic foraminiferal population dynamics and benthic foraminiferal and radiolaria distributions combined with δ13C and δ18O measurements of both bulk carbonate and foraminifera provide clues concerning the paleoceanographic changes across the Cenomanian-Turonian boundary interval and the Oceanic Anoxic Event 2 (OAE 2) at southern high latitudes. Samples analyzed are from Integrated Ocean Discovery Program (IODP) Expedition 369 Site U1516 in the Mentelle Basin (eastern flank of the Naturaliste Plateau, Indian Ocean, SW Australia). Site U1516 was located at 60°–62°S paleolatitude during the mid-Cretaceous, and it is the first high latitude locality in the Southern Hemisphere where planktonic foraminifera are consistently recorded across the OAE 2 interval and its associated positive δ13C excursion. The sedimentary record at Site U1516 consists of a sequence of alternating black, dark greenish gray, and light greenish gray claystone in the Cenomanian that grade to white and light gray calcareous chalk interbedded with chert in the Turonian. The correlation between the δ13C and δ18O profiles at Site U1516 and the European reference section at Eastbourne (England) coupled with the integrated calcareous plankton biostratigraphy and stable isotopic data at Site U1516, indicate that a complete record of OAE 2 at Site U1516 was recovered. Below and in the lower part of OAE 2, the planktonic foraminiferal assemblages are dominated by small-sized (125–38 μm) opportunistic species of Microhedbergella and radiolaria indicating a dominantly eutrophic regime. Above the onset of OAE 2, a trough in the δ13C profile (Plenus Carbon Isotope Event: P-CIE) coinciding with a δ18O increase may correspond to the Plenus Cold Event as observed at low latitudes, although no evidence of cooling is registered in the microfossil assemblages. At Site U1516, the middle part of OAE 2 at the initiation of the plateau phase of the δ13C profile is masked by absence of carbonate, by the highest TOC values, and high biogenic silica (dominance of radiolaria) indicating this interval corresponded to a time of highly stressed eutrophic conditions with possible shoaling of the Carbonate Compensation Depth (CCD). Above this interval, bulk isotopic results yield lower δ13C values, and the CaCO3 increases are associated with the presence of even smaller-sized Microhedbergella showing cyclic fluctuations in absolute abundances with benthic foraminifera indicating dominantly eutrophic conditions likely affected by upwelling of nutrient-rich and δ13C-depleted intermediate water masses. Toward the top of OAE 2 and across the Cenomanian-Turonian boundary interval, the planktonic foraminiferal assemblages show changes in composition (e.g., Microhedbergella is replaced by Muricohedbergella), species occupying relatively deep ecological niches appear and an overall increase in diversity is observed. These features coupled with the foraminiferal species-specific δ13C and δ18O patterns reveal that Site U1516 occupied a paleoceanographic setting still affected by eutrophy likely related to enhanced input of nutrients but with episodes of stability with ecological/thermal separation in the surface waters. This interval also records the highest sea surface water paleotemperatures values estimated as 20°–23°C based on δ18O values of foraminiferal test and assuming seawater δ18O values of −1‰V-SMOW. Mesotrophic to oligotrophic conditions persisted after the OAE 2 and throughout the Turonian as evidenced by a diverse planktonic foraminiferal assemblage with different species occupying separate ecological niches in the mixed layer and thermocline.

Diet of a threatened endemic fox reveals variation in sandy beach resource use on California Channel Islands.

The coastal zone provides foraging opportunities for insular populations of terrestrial mammals, allowing for expanded habitat use, increased dietary breadth, and locally higher population densities. We examined the use of sandy beach resources by the threatened island fox (Urocyon littoralis) on the California Channel Islands using scat analysis, surveys of potential prey, beach habitat attributes, and stable isotope analysis. Consumption of beach invertebrates, primarily intertidal talitrid amphipods (Megalorchestia spp.) by island fox varied with abundance of these prey across sites. Distance-based linear modeling revealed that abundance of giant kelp (Macrocystis pyrifera) wrack, rather than beach physical attributes, explained the largest amount of variation in talitrid amphipod abundance and biomass across beaches. δ13C and δ15N values of fox whisker (vibrissae) segments suggested individualism in diet, with generally low δ13C and δ15N values of some foxes consistent with specializing on primarily terrestrial foods, contrasting with the higher isotope values of other individuals that suggested a sustained use of sandy beach resources, the importance of which varied over time. Abundant allochthonous marine resources on beaches, including inputs of giant kelp, may expand habitat use and diet breadth of the island fox, increasing population resilience during declines in terrestrial resources associated with climate variability and long-term climate change.

Carbonate cementation in the Tithonian Jeanne d’Arc sandstone, Terra Nova Field, Newfoundland: Implications for reservoir quality evolution

AbstractPetrographic and in situ geochemical analyses were carried out on cores of the fluvial sandstone (<50 to >4 mm; sublithic quartz arenite) dominated Tithonian Jeanne d’Arc Formation interval from wells C‐09 and E‐79 of the Terra Nova oilfield to understand diagenetic control on reservoir quality of the formation. Lithic clasts are dominantly carbonates and shales. Successively, early near‐surface dolomite cementation, eogenetic dolomite dissolution, burial calcite cementation and its subsequent dissolution are the major diagenetic events that controlled the reservoir quality of the sandstone. Dolomite cement grades from mostly Fe‐rich (FeCO3 ca 12 ± 2 normalized mol.%) in the upper part of the formation to Fe‐poor (<0.07 normalized mol.%) in the lower part of the formation in both wells. The dolomite and calcite cements generally have low Sr and Na; enriched Y and low δ18O and δ13C values relative to typical marine carbonates. Strontium is enriched in the Fe‐poor (higher Mg) dolomite relative to the Fe‐rich phase. Mineral liberation analyses of shale samples reveal common Fe‐chlorite and minor glauconite. Furthermore, considerable amounts of solutes in the early diagenetic pore fluid were likely derived from water—rock interaction with underlying Oxfordian Rankin Formation marine carbonate that was also exposed in the watershed of the study area at the time. Together, these suggest that the dolomites were formed from an early diagenetic bicarbonate‐rich pore fluid of mixed meteoric and seawater origin. The origin and distribution of early dolomite cementation and other successive diagenetic events have a depositional cycle control. Episodic post‐deposition transgression of seawater and/or compactional fluid expulsion from shales into overlying sandstones led to formation of dolomite cement. Subsequent infiltration of organic acid‐charged meteoric‐water into underlying dolomite‐cemented sandstones resulted in early dissolution. This porosity was mostly occluded by re‐precipitation of calcite. Increase in the abundance of relic corroded dolomite crystals with depth in each cycle indicates that early dissolution was most effective at the top of the cycles. Iron depletion in the calcite cement with depth through the formation points to a local derivation of reactants from in situ dolomite species; implying a stratigraphic control. Calcite cementation was succeeded by continuous mesogenetic dissolution concomitant mechanical compaction. The responsible low‐pH pore fluid attained its composition via enhanced H+ contribution from silicate burial diagenesis. The control of depositional settings on the major diagenetic processes makes it a key contribution to region‐wide reservoir quality prediction for the formation.

Turning eastward: New radiocarbon and stable isotopic data for Middle Holocene hunter-gatherers from Fofanovo, Trans-Baikal, Siberia

A considerable amount of bioarchaeological research – including AMS 14C dating and stable carbon and nitrogen isotope analyses (δ13C and δ15N) – has been undertaken on the hunter-gatherers from the area west of Lake Baikal, known as Cis-Baikal. No such work has previously been reported for the east side of the lake, Trans-Baikal. Here, we present new radiocarbon dates and isotopic results for twenty individuals from the Fofanovo cemetery, located along the Selenga River on the southeast coast of Lake Baikal.Once corrected for an old carbon effect using regression equations developed for Cis-Baikal, the radiocarbon results form 4 chronological clusters: 1) Late Mesolithic (LM), around 7950 cal BP (n = 3); 2) Late Neolithic (LN), between ca. 6000 and 5500 cal BP (n = 5); 3) LN to Early Bronze Age (EBA), between ca. 4900 and 4500 cal BP (n = 2); and the largest cluster 4) later EBA, around 3700 cal BP (n = 10). The LM Cluster 1 dates indicate that formal cemetery use in Trans-Baikal may have begun earlier than in Cis-Baikal. Clusters 2 and 3 reveal a previously unidentified LN component to the cemetery. Additionally, the EBA Cluster 4 appears to be largely synchronous with the EBA in Cis-Baikal.As a group, the Fofanovo individuals are isotopically distinct from the Middle-Holocene hunter–gatherers in the microregions of Cis-Baikal, exhibiting a combination of low δ13C values (−19.4 ± 0.9‰) but high δ15N values (15.2 ± 0.8‰). This likely reflects the distinctive isotopic ecology of the lower Selenga River, combined with use of aquatic resources from Lake Baikal itself. While further sampling is needed to test its robustness, a statistically significant difference between the LN (n = 6) and EBA (n = 11) was found, suggesting a greater reliance on the seasonal resources of the Selenga River during the EBA.Further analyses on these and other individuals from the cemetery are planned and will undoubtably provide additional insights into hunter-gatherer subsistence adaptations and dietary variation in Trans-Baikal, highlighting both differences and similarities with those of Cis-Baikal.

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

Abstract. 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.

Bedding-parallel calcite veins indicate hydrocarbon–water–rock interactions in the over-mature Longmaxi shales, Sichuan Basin

Bedding-parallel calcite veins in shales archive hydrocarbon–water–rock interactions, but such processes in highly–over mature shales are poorly understood in terms of their geological and geochemical significance. To fill the knowledge gap, we conducted a combined petrographic, geochemical, isotopic, and fluid inclusion study of the Silurian Longmaxi Formation in the Sichuan Basin, China, to investigate these processes. Our results show that bedding-parallel calcite veins grow nearly vertically along the median plane, and exhibit antitaxial and two stages of growth. The early calcite veins have high δ13C values (0.08‰–4.75‰) and the diagenetic fluids were relatively low-temperature (120–150 °C) and high-salinity (11.2%), and formed during primary migration of hydrocarbon-bearing fluids in the oil window. The late calcite veins have relatively low δ13C values (−7.01‰ to −0.08‰) and the diagenetic fluids were high-temperature (180–210 °C) and low-salinity (8.9%), and formed in the gas window. The similar 87Sr/86Sr and δ13C values of the calcite veins and surrounding host rocks, combined with the relatively uniform fluid δ18OV-SMOW values, indicate that the calcite-precipitating fluids were derived mainly from the surrounding host-rocks and organic fluids. The formation of bedding-parallel calcite veins records the two-stage, fluid-overpressured evolution of organic matter in the oil and gas generation stages.

Stable Isotopic Evidence for Nutrient Rejuvenation and Long-Term Resilience on Tikopia Island (Southeast Solomon Islands)

Tikopia Island, a small and relatively isolated Polynesian Outlier in the Southeast Solomon Islands, supports a remarkably dense human population with minimal external support. Examining long-term trends in human land use on Tikopia through archaeological datasets spanning nearly 3000 years presents an opportunity to investigate pathways to long-term sustainability in a tropical island setting. Here, we trace nutrient dynamics across Tikopia’s three pre-European contact phases (Kiki, Sinapupu, Tuakamali) via stable carbon and nitrogen isotope analysis of commensal Pacific rat (Rattus exulans) and domestic pig (Sus scrofa) bone and tooth dentine collagen. Our results show a decline in δ15N values from the Kiki (c. 800 BC-AD 100) to Sinapupu (c. AD 100–1200) phases, consistent with long-term commensal isotope trends observed on other Polynesian islands. However, increased δ15N coupled with lower δ13C values in the Tuakamali Phase (c. AD 1200–1800) point to a later nutrient rejuvenation, likely tied to dramatic transformations in agriculture and land use at the Sinapupu-Tuakamali transition. This study offers new, quantifiable evidence for deep-time land and resource management decisions on Tikopia and subsequent impacts on island nutrient status and long-term sustainability.

Distinct macroinvertebrate soil food webs at one-meter scale in a Mediterranean agroecosystem

Soil macroinvertebrates play a central role in ecosystem processes such as decomposition and nutrient cycling, but the extent to which macroinvertebrate food web structure varies within ecosystems is basically unknown. Here, we examined changes in plant and macroinvertebrate community composition at increasing distances from trees within a citrus grove, following a gradient in organic matter and water availability created by the localized fertilization and irrigation of citrus trees. In addition, we analysed stable isotope signatures (δ13C and δ15N) of soil, plants, and macroinvertebrates to investigate changes in trophic structure within the grove. The macroinvertebrate community near the tree trunks had a higher number of detritivores and predators than the community located farther away. After correcting the isotope values of macroinvertebrates by their isotopic baseline, a spatial shift in trophic structure emerged: macroinvertebrates near the trunks had lower δ13C-values than those located farther away (i.e., they apparently relied more on plant- based resources). This pattern is attributable to species only found near the trunks. In contrast, species distributed across the studied area showed no differences in their isotopic signatures across space, suggesting that they are connecting otherwise two compartmentalized food webs. A reduction in organic matter and water availability at increasing distances from trees is the most parsimonious explanation of the observed isotopic gradient in soil and plants, and this may, in turn, be responsible for the observed changes in food web composition and structure. This study shows that spatial variability in macroinvertebrate soil food webs can be present at scales as small as one meter if spatial variability in environmental factors is high enough.

Contrasting life-history traits of black spruce and jack pine influence their physiological response to drought and growth recovery in northeastern boreal Canada

An increase in frequency, intensity and duration of drought events affects forested ecosystems. Trees react to these changes by adjusting stomatal conductance to maximize the trade-off between carbon gains and water losses. A better understanding of the consequences of these drought-induced physiological adjustments for tree growth could help inferring future productivity potentials of boreal forests. Here, we used samples from a forest inventory network in Canada where a decline in growth rates of black spruce (Picea mariana (Mill.) B.S.P.) and jack pine (Pinus banksiana Lamb.) occurred in 1988–1992, an exceptionally dry period, to verify if this growth decline resulted from physiological adjustments of trees to drought. We measured carbon and oxygen isotope ratios in growth rings of 95 spruces and 49 pines spanning 1985–1993. We used 13C discrimination (Δ13C) and 18O enrichment (Δ18O) as proxies for intrinsic water use efficiency and stomatal conductance, respectively. We studied how inter-annual variability in isotopic signals was linked to climate moisture index, vapor pressure deficit and annual snowfall amount. We found significantly lower Δ13C values over 1988–1990, and significantly higher Δ18O values in 1988–1989 and 1991 compared to the 1985–1993 averages. We also observed that a low climatic water balance and a high vapor pressure deficit were linked with low Δ13C and high Δ18O in the two study species, in parallel with low growth rates. The latter effect persisted into the year following drought for black spruce, but not for jack pine. These findings highlight that small differences in physiological parameters between species could translate into large differences in post-drought recovery. The stronger and longer lasting impact on black spruce compared to jack pine suggests a less efficient carbon use and a lower acclimation potential to future warmer and drier climate conditions.

Separate Feeding Between the Pelagic Stage of the Squat Lobster Munida gregaria and the Larger Sized Zooplankton Crustacean Groups in the Beagle Channel as Revealed by Stable Isotopes

In southern Patagonia, the Beagle Channel shows very low production during winter but simultaneously sustains very dense aggregations of the pelagic stage of squat lobster (Munida gregaria), a benthic decapod whose pelagic juveniles have the largest body size within the chitinous pelagic community. To assess the coexistence of the mesozooplankton community and the pelagic M. gregaria stage under the harsh feeding winter conditions, we conducted a research cruise at two locations connected to the Beagle Channel, Yendegaia Bay (land terminating-glacier) and Pia Fjord (marine-terminating glacier). Our results showed that the zooplankton communities were similar in these two fjords, that a single pelagic group dominated in terms of biomass (pelagic Munida gregaria), and that differences in vertical distribution existed between most of the principal crustacean zooplankton and pelagic M. gregaria. All groups showed consumption of terrestrially derived organic matter, as revealed by their δ13C values. However, the isotopic composition, trophic positions (TP), and isotopic niche areas of the groups separated pelagic M. gregaria, presenting some of the lowest δ15N and the highest δ13C values, and the narrowest isotopic niche width. Pelagic M. gregaria was dominated by a single body size class along the 0–100 m water column, with no diel changes in vertical distribution, remained mostly in the upper layers (0–50 m), and benefited from the slightly higher phytoplankton concentrations at shallower depths as revealed by their higher δ13C values and low trophic position. In contrast, the other groups, including zoea M. gregaria stages, developed changes in distribution between day and night or remained deeper in the water column. These groups showed higher δ15N values, higher TP, and lower δ13C values, most of which probably fed on a nanoheterotrophs and terrestrial particulate organic matter mixture at deeper layers. Thus, the different vertical distributions, different trophic level food sources, and slightly different organic carbon sources apparently reduced any potential competence for food resources and form part of the feeding strategy that may facilitate the coexistence of the different large pelagic crustaceans under harsh feeding winter conditions in this high latitude austral region.

14C DATES AND STABLE ISOTOPE ECOLOGY OF MARINE VERTEBRATES IN THE LATE PLEISTOCENE-EARLY HOLOCENE CHAMPLAIN SEA

ABSTRACTThe late Pleistocene to early Holocene Champlain Sea provides a unique opportunity to study the development of marine ecosystems in a context of global climatic change. This study presents radiocarbon (14C) dates and stable isotope analyses on 15 vertebrate specimens from Champlain Sea sediments, including the Charlotte Whale, which is Vermont’s State marine fossil. Data are used in an attempt to investigate the timing of colonization and ecological dynamics in this newly formed sea. Using the average marine correction,14C dates on four specimens likely calibrate prior to or possibly synchronous with the accepted origination date for the Champlain Sea, implying larger marine reservoir effects than the average marine correction in the vertebrate tissues. Without knowing the specific marine reservoir offsets, it is not possible to calculate the timing of colonization or its relation to concurrent climatic change. Observed lower δ13C and δ15N values in walruses, a fin whale, and a right whale support consumption of prey from lower trophic levels such as bivalve mollusks, krill, and copepods. Higher isotopic values in beluga whales and a bird, the thick-billed murre, support consuming fish, such as cod and capelin. These isotopic data show comparable values and relationships as observed in modern arctic marine ecosystems.

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.

Influence of ball milling with PTFE plastic tube on carbon isotope ratio measurement of C4 plants.

Before the measurement of stable carbon isotope signatures (δ13C), plant samples should be well homogenized. Using a ball-mill fitted with poly tetra fluoroethylene (PTFE) plastic tubes is one of the most efficient and convenient methods. However, sample-tube plastic might contaminate plant samples during milling. In this study, a two-factor experiment was carried out using four growth chambers, with different relative humidity of the air (50% and 80%) and δ13C of the air (13C depleted and enriched). Leaf samples of Cleistogenes squarrosa (C4) were milled and homogenized using a ball-mill fitted with PTFE tubes and measured for δ13C, and the results were compared with that of leaf samples milled using metal tubes. Due to plastic contamination, 13C discrimination (Δ13C) of the two groups of plants, which were grown in CO2 with different δ13C and could be assumed as replicates, were significantly different (with an offset of 4.8‰ on average). The contamination led to errors in δ13C of individual leaves up to 8‰. Given the lower Δ13C value of C4 plants (normally about 1‰-8‰) compared with that of C3 plants, such an error caused by plastic contamination far exceeded the acceptable error range. By using a two-member mixing model that was similar to the 'Keeling plot', such errors could be effectively eliminated, and the δ13C of plant samples and pollutants were accurately estimated. Our results showed that the widely applied method of using PTFE tubes for ball-mill homogenization is not suitable for examining Δ13C of C4 plants, as it might lead to large errors. For studies with high precision requirements, samples should be milled in stainless-steel tubes.

Carbon isotope trends in north-west European mosasaurs (Squamata; Late Cretaceous)

The carbon stable isotope composition (δ13C) of tooth enamel in mosasaurid squa-mates reflects aspects of their diet and diving behaviour. Here we present new δ13C data for such marine squamates from the Maastrichtian of Denmark and compare these with results obtained in previous studies from the lower-latitude type area of the Maastrichtian Stage (latest Cretaceous; 72.1–66.0 Ma) in the south-east Nether-lands and north-east Belgium. For the Danish samples, there is a weak correlation between mosasaur body size and δ13C values, with larger-sized taxa having lower δ13C values, comparable to what has previously been observed for mosasaurs from the Maastrichtian type area.

Isotopic Tracers Suggest Limited Trans-Oceanic Movements and Regional Residency in North Pacific Blue Sharks (Prionace glauca)

Blue sharks (Prionace glauca) are globally distributed, large-bodied pelagic sharks that make extensive migrations throughout their range. In the North Pacific, mark-recapture studies have showntrans-Pacific migrations, but knowledge gaps in migration frequency hinder understanding of regional connectivity and assessments of regional demography for stock assessments. Here, we use oceanographic gradients of stable isotope ratios (i.e., regional isoscapes) to determine exchange rates of blue sharks between the East and West North Pacific Ocean (EPO and WPO). We generated regional δ13C and δ15N distributions for blue sharks from published values in the North Pacific (n= 180; both sexes, juveniles and adults combined). Discriminant analysis suggested lowtrans-Pacific exchange, categorizing all western (100%) and most eastern (95.3%) blue sharks as resident to their sampling region, with isotopic niche overlap of WPO and EPO highly distinct (0.01–5.6% overlap). Limitedtrans-Pacific movements suggest that other mechanisms maintain genetic mixing of the North Pacific blue shark population. Potential finer scale movement structure was indicated by isotopic differences in sub-regions of the eastern and western Pacific, though application of mixing models are currently limited by aberrantly low blue shark δ13C values across studies. Our results suggest that blue shark population dynamics may be effectively assessed on a regional basis (i.e., WPO and EPO). We recommend further studies to provide size- and sex-specific movement patterns based on empirical isotopic values with large sample sizes from targeted regions. Strategically applied stable isotope approaches can continue to elucidate migration dynamics of mobile marine predators, complementing traditional approaches to fisheries biology and ecology.

Molybdenum isotope composition of seep carbonates – Constraints on sediment biogeochemistry in seepage environments

Methane seepage causes significant changes in the local diagenetic environment and impacts the marine sedimentary cycles of sulfur, carbon, and molybdenum (Mo), which are intimately linked to each other. Molybdenum isotopic compositions were determined for authigenic carbonate nodules and bulk sediments of a 230-m long sediment core collected at a methane seep site in the South China Sea. Authigenic carbonate nodules occur at different sediment depths and display low δ13C values around −50‰ revealing that carbon predominantly derived from biogenic methane. Moreover, seep carbonate nodules are substantially enriched in Mo (Al-normalized enrichment factors MoEF between 27 and 70), and display nearly constant δ98Mo values around an average of +1.9‰ (relative to NIST3134 = +0.25‰), close to the Mo isotopic composition of modern seawater (+2.3‰). Linear positive correlations between δ98Mo values and pyrite sulfur contents and Mo contents were identified for seep carbonate samples. This implies that Mo scavenging into pyrite is likely controlled by hydrogen sulfide availability derived from sulfate-driven anaerobic oxidation of methane (SD-AOM). The essentially constant and high δ98Mo values suggest that Mo species were nearly quantitatively incorporated into the authigenic carbonates under highly sulfidic conditions, probably at times when the sulfate-methane transition zones (SMTZ) was situated at shallow sediment depth at times of high seepage activity. In contrast, bulk sediments that exhibit typical marine δ13C values close to 0‰ (versus VPDB), hence devoid of methane-derived seep carbonates, are characterized by low Mo contents (MoEF = ~0.9). Their lower δ98Mo values mostly ranging from +0.2 to +0.8‰, in accord with low Mo contents, likely reflect input of detrital Mo. Bulk sediments bearing seep carbonate nodules display variable δ13C values lower than −5‰ and are characterized by a wide range in Mo contents (MoEF from 1.5 to 45.3) and δ98Mo values (+0.7 to +3.0‰). The high δ98Mo values of some sediment samples, relative to the seep carbonate signature, might indicate an additional accumulation of a 98Mo enriched pool of molybdenum during later SD-AOM at a deeper SMTZ postdating initial seep carbonate formation; such 98Mo enrichment was probably caused by preceding preferential removal of lighter Mo isotopes from pore fluids. Our results indicate that Mo isotope systematics of seep deposits can provide constraints on the dynamics of the biogeochemical cycling of carbon, sulfur, and trace elements in methane seep environments. A potential for authigenic carbonates to archive the Mo isotopic composition of seawater is indicated, but will have to be assessed in future studies.

Redox geochemistry of the red ‘orthoceratite limestone’ of Baltoscandia: Possible linkage to mid-Ordovician palaeoceanographic changes

The orthoceratite limestone of the Ordovician epicontinental sea of Baltoscandia is one of the oldest Phanerozoic examples of pelagic marine red beds (MRBs). Being enriched in authigenic haematite, MRBs are considered to be sensitive palaeoceanographic redox indicators. In this paper, the origin of the reddening of the Ordovician MRBs and its timing and redox conditions were addressed at two sections, and in a drill core in the Kinnekulle area, Sweden, through the application of diffuse reflectance spectroscopy, sedimentary petrology (microfacies and electron microprobe), bulk-rock and in-situ element geochemistry (laser-ablation ICP-MS) and molybdenum stable isotope systematics. Enrichment in haematite (up to ~0.05 wt%) occurred during very early diagenesis under low sedimentation rates (~5 mm/kyr), which is comparable to several examples of Phanerozoic MRBs. The reddening was associated with the mm-scale, in-situ mobility of Fe, Mn, As, Mo and U, due to Fe–Mn redox cycling between primary and secondary minerals and pore water under oxic and suboxic to anoxic conditions; it was not related to significant changes in seawater chemistry. Stratigraphic red-to-grey transitions likely coincided with two mid-Darriwilian global regressions (the so-called Täljsten and at the base of the Gullhögen Formation), likely due to the effects of changing sedimentation rates and sub-bottom redox potentials. The Ordovician MRBs coincided with a positive δ13C excursion during the middle Darriwilian, which is different to MRB examples cited from the Devonian to the Cretaceous age, which frequently coincide with shifts to lower values of δ13C. Although MRBs are believed to show a time-specific occurrence in greenhouse or transitional greenhouse-to-icehouse climatic modes by several authors, our study suggests that causal links between MRBs and global carbon cycle remain unclear.

Storage of soil carbon as particulate and mineral associated organic matter in irrigated woody perennial crops

Agricultural practices such as annual crop production, land use change and grazing on marginal lands lead to a loss of soil carbon (C) stock. But soil C losses are not universal in agricultural systems and modest soil C gains can occur when constraints such as a lack of water are removed. To characterize this we used a meta-analysis of published data focused on semi-arid regions, where irrigation is required for crop production. We showed that soil C stocks declined under cereals, cotton, maize and non-woody horticultural crops when compared to native unirrigated adjacent grassland or shrubland. By contrast, cultivation of irrigated, woody perennial crops generally leads to an accumulation of soil C. Identifying the mechanisms by which C is retained in the soils beneath woody perennial crops, and any limits to C accumulation, was the main goal of this study. A mechanistic understanding of soil organic C content accumulation, upon land use change, can be gained by dividing soil into particulate organic matter (POM) and mineral associated organic matter (MAOM). Here, we analyzed the C and natural abundance 13C concentrations in POM and MAOM fractions in soils from eight apple orchards and eight vineyards irrigated using a dripline, and eight apple and eight cherry orchards irrigated with micro-spray. Samples were also taken from eight native grassland areas adjacent to the agricultural sites for comparison. Several decades of woody crop production doubled the average soil C concentration in comparison to the native sites, from to 10.1 ± 1.48 g C kg−1 to 20.1 ± 0.96 g C kg−1 over a depth of 0–15 cm. Most of the C was associated with POM, which increased in concentration from 7.9 ± 1.19 g C kg−1 to 14.2 ± 0.79 g C kg−1 in 0–15 cm soils, an increase of 80%. This was crop dependent, being highest in the cherry orchards and lowest in the vineyard soils. Although holding less C, the MAOM concentration increased by 166%, changing from 2.22 ± 0.33 to 5.91 ± 0.62 g C kg−1; no differences existed between crops but the MAOM C concentration appeared to be constrained to a maximum value of ~ 12 g C kg−1. MAOM and POM had markedly different δ13C values: MAOM was more enriched, indicative of greater microbial processing, whereas POM had a lower δ13C value consistent with the dominant standing vegetation. δ13C values were more depleted in both fractions at the agricultural sites compared to the native sites, indicating the accumulation of greater amounts of less processed C at the agricultural sites, due to higher C inputs. We conclude the soils in this region respond to irrigated perennial woody crop production by retaining C within both POM and MAOM fractions. Accumulation of C as MAOM is constrained by the minerology of the soils in this region, but is unconstrained for POM which dominates the soil C content, and is potentially vulnerable to changes in management practices and land use.