Estimating stable carbon isotope values of microphytobenthos in the Arctic for application to food web studies

Most studies on Arctic food webs have neglected microphytobenthos as a potential food source because we currently lack robust measurements of δ¹³C values for microphytobenthos from this environment. As a result, the role of microphytobenthos in high latitude marine food webs is not well understood. We combined field measurements of the concentration of aqueous carbon dioxide and the stable carbon isotopic composition of dissolved inorganic carbon (δ¹³C_DIC) from bottom water in the Beaufort and Chukchi seas with a set of stable carbon isotopic fractionation factors reflecting differences in algal taxonomy and physiology to estimate the stable carbon isotope composition of microphytobenthos-derived total organic carbon (δ¹³C_p). The δ¹³C_p for Phaeodactylum tricornutum, a pennate diatom likely to be a dominant microphytobenthos taxon, was estimated to be ?23.9 ± 0.4 ‰ as compared to a centric diatom (Porosira glacialis, δ¹³C_p = ?20.0 ± 1.6 ‰) and a marine haptophyte (Emiliana huxleyi, δ¹³C_p = ?22.7 ± 0.5 ‰) at a growth rate (µ) of 0.1 divisions per day (d^?1). δ¹³C_p values increased by ~2.5 ‰ when µ increased from 0.1 to a maximum growth rate of 1.4 d^?1. We compared our estimates of δ¹³C_p values for microphytobenthos with published measurements for other carbon sources in the Arctic and sub-Arctic. We found that microphytobenthos values overlapped with pelagic sources, yet differed from riverine and ice-derived carbon sources. These model results provide valuable insight into the range of possible isotopic values for microphytobenthos from this region, but we remain cautious in regard to the conclusiveness of these findings given the paucity of field measurements currently available for model validation.     

Contrasting δ<Superscript>15</Superscript>N Values of Atmospheric Deposition and <Emphasis Type="Italic">Sphagnum</Emphasis> Peat Bogs: N Fixation as a Possible Cause

Nitrogen (N) isotope systematics were investigated at two high-elevation ombrotrophic peat bogs polluted by farming and heavy industry. Our objective was to identify N sources and sinks for isotope mass balance considerations. For the first time, we present a time-series of δ¹⁵Ν values of atmospheric input at the same locations as δ¹⁵Ν values of living Sphagnum and peat. The mean δ¹⁵Ν values systematically increased in the order: input NH₄ ⁺ (?10.0‰) < input NO₃ ^? (?7.9‰) < peat porewater (?5.6‰) < Sphagnum (?5.0‰) < shallow peat (?4.2‰) < deep peat (?2.2‰) < runoff (?1.4‰) < porewater N₂O (1.4‰). Surprisingly, N of Sphagnum was isotopically heavier than N of the atmospheric input (P < 0.001). If partial incorporation of reactive N from the atmosphere into Sphagnum was isotopically selective, the residual N would have to be isotopically extremely light. Such N, however, was not identified anywhere in the ecosystem. Alternatively, Sphagnum may have contained an admixture of isotopically heavier N. Ambient air contains such N in the form of N₂ (δ¹⁵Ν_N2 = 0‰). Because high energy is required to break the triple bond, microbial N fixation is likely to proceed only under limited availability of pollutant N. Also for the first time, a δ¹⁵Ν comparison is presented between anoxic deeper peat and porewater N₂O. Isotopically light N is removed from anoxic substrate by denitrification, whose final product, N₂, escapes into the atmosphere. Porewater N₂O is an isotopically heavy residuum following partial N₂O reduction to N₂.     

Stromatolite records of environmental change in perennially ice-covered Lake Joyce,McMurdo Dry Valleys,Antarctica

Calcite-rich columnar stromatolites grew in perennially ice-covered Lake Joyce in the McMurdo Dry Valleys, Antarctica, during a period of environmental change associated with rising lake level. Stromatolite calcite contains carbon and oxygen isotope records of changes to microbial activity in response to variable light environments and water chemistry through time. The stromatolites grew synchronously with correlative calcite zones. The innermost (oldest) calcite zone has a wide range of δ¹³C_calcite values consistent with variable photosynthetic effects on local DIC ¹³C/¹²C. Subsequent calcite zones preserve a progressive enrichment in δ¹³C_calcite values of approximately + 2.6‰ through time, with δ¹³C_calcite values becoming less variable. This enrichment likely records the removal of ¹²C by photosynthesis from the DIC reservoir over decades, with photosynthetic effects decreasing as light levels became lower and more consistent through time. Mean δ¹⁸O_calcite values of the innermost calcified zone were at least 1‰ lower than those of the other calcified zones (t test p-level < 0.001). The significant difference in δ¹⁸O_calcite values between the innermost and other calcified zones could be a product of mixing source waters with different isotopic values associated with the initiation of lake stratification associated with rising lake level. Overall, Lake Joyce stromatolites record significant lateral variability in relative photosynthetic rate and long-lived lake water stratification with microbial modification of the DIC pool. Such processes provide criteria for interpreting microbial activity within polar paleolake deposits and may shed light on variability in lake environments associated with changing climate in the McMurdo Dry Valleys.     

Morphological and geochemical variations of <Emphasis Type="Italic">Cyprideis</Emphasis> (Ostracoda) from modern waters of the northern Neotropics

The variability of modern Cyprideis salebrosa and Cyprideis americana (Ostracoda) from the northern Neotropics were investigated in order to understand site specific influences on the isotopic composition of their valves (δ¹⁸O, δ¹³C) in comparison to their host water and to connect this to morphological features of their valves (valve size, nodosity). C. salebrosa was found in a stream (Shell Creek, Florida) and a slightly brackish lake (Laguna del Rincon, Dominican Republic; salinity <0.7 psu) while C. americana occurred in a coastal lake with polyhaline waters (Parrotee Pond, Jamaica; salinity: >20 psu). Valve size and position of nodes differed between the two species. A reverse temperature dependency have been considered to influence Shell length (seasonally in Shell Creek, summer: 1076 µm; winter: 1092 µm, supposedly permanently in Laguna del Rincon, 1035 µm). But, regarding the small dataset other factors could not be excluded to influence ostracod valve size. A decline of node frequency of C. salebrosa is mainly related to an increase in salinity. Isotopic values of ostracod valves reflect the trend in stable isotopes of their host water. Variations in Cyprideis salebrosa δ¹⁸O and δ¹³C values signify differences in their host water. Offsets of ostracod valves to a theoretical calcite precipitated in their host water with an uncertain time lag (+0.015 to +2.63 ‰) needs to be clarified. This study presents a contribution to the understanding of environmental influences on modern ostracod shell characters as basis for paleontological applications.     

Kangaroo tooth enamel oxygen and carbon isotope variation on a latitudinal transect in southern Australia: implications for palaeoenvironmental reconstruction

Tooth enamel apatite carbonate carbon and oxygen isotope ratios of modern kangaroos (Macropus spp.) collected on a 900-km latitudinal transect spanning a C₃–C₄ transition zone were analysed to create a reference set for palaeoenvironmental reconstruction in southern Australia. The carbon isotope composition of enamel carbonate reflects the proportional intake of C₃ and C₄ vegetation, and its oxygen isotope composition reflects that of ingested water. Tooth enamel forms incrementally, recording dietary and environmental changes during mineralisation. Analyses show only weak correlations between climate records and latitudinal changes in δ¹³C and δ¹⁸O. No species achieved the δ¹³C values (~?1.0 ‰) expected for 100 % C₄ grazing diets; kangaroos at low latitudes that are classified as feeding primarily on C₄ grasses (grazers) have δ¹³C of up to ?3.5 ‰. In these areas, δ¹³C below ?12 ‰ suggests a 100 % C₃ grass and/or leafy plant (browse) diet while animals from higher latitude have lower δ¹³C. Animals from semi-arid areas have δ¹⁸O of 34–40 ‰, while grazers from temperate areas have lower values (~28–30 ‰). Three patterns with implications for palaeoenvironmental reconstruction emerge: (1) all species in semi-arid areas regularly browse to supplement limited grass resources; (2) all species within an environmental zone have similar carbon and oxygen isotope compositions, meaning data from different kangaroo species can be pooled for palaeoenvironmental investigations; (3) relatively small regional environmental differences can be distinguished when δ¹³C and δ¹⁸O data are used together. These data demonstrate that diet–isotope and climate–isotope relationships should be evaluated in modern ecosystems before application to the regional fossil record.     

A δ<Superscript>15</Superscript>N assessment of nitrogen deposition for the endangered epiphytic orchid <Emphasis Type="Italic">Laelia speciosa</Emphasis> from a city and an oak forest in Mexico

Atmospheric nitrogen deposition poses a major threat to global biodiversity. Tropical epiphytic plants are especially at risk given their reliance on atmospheric sources of nutrients. The leaf, pseudobulb, and root carbon and nitrogen content, C:N ratio, as well as the nitrogen isotopic composition were studied for individuals of Laelia speciosa from a city and from an oak forest in Mexico. The nitrogen content of leaves was similar between the city and the oak forest, reaching 1.3 ± 0.2 % (dry mass). The δ¹⁵N of leaves, pseudobulbs, and roots reached 5.6 ± 0.2 ‰ in the city, values found in sites exposed to industrial and vehicular activities. The δ¹⁵N for plant from the oak forest amounted to –3.1 ± 0.3 ‰, which is similar to values measured from sites with low industrial activities. Some orchids such as Laelia speciosa produce a single pseudobulb per year, i.e., a water and nutrient storage organ, so the interannual nitrogen deposition was studied by considering the ten most recent pseudobulbs for plants from either site formed between 2003 and 2012. The C:N ratio of the ten most recent pseudobulbs from the oak forest, as well as that of the pseudobulbs formed before 2010 for plants in the city were indistinguishable from each other, averaging 132.4 ± 6.5, while it was lower for the two most recent pseudobulbs in the city. The δ¹⁵N values of pseudobulbs from the oak forest averaged ?4.4 ± 0.1 ‰ for the entire series. The δ¹⁵N ranged from 0.1 ± 1.6 ‰ for the oldest pseudobulb to 4.7 ± 0.2 ‰ for the pseudobulb formed in the city from 2008 onwards. Isotopic analysis and the C:N ratio for L. speciosa revealed that rates of nitrogen deposition were higher in the city than in the forest. The δ¹⁵N values of series of pseudobulbs showed that it is possible to track nitrogen deposition over multiple years.     

Inter- and intra-annual tree-ring cellulose oxygen isotope variability in response to precipitation in Southeast China

Key message

Compared with annual tree-ring cellulose δ ¹⁸ O, intra-annual cellulose δ ¹⁸ O has potential to reconstruct precipitation with higher resolution and stronger signal intensity.

Abstract

Annual tree-ring cellulose oxygen isotope values (δ¹⁸O) of Fokienia hodginsii provide a promising proxy of monsoon-season precipitation in Southeast China. Measuring intra-annual cellulose δ¹⁸O values may reveal the seasonal variability of precipitation and the associated climate influences. Here, we examine intra-annual variation of cellulose δ¹⁸O values in Fokienia hodginsii and Cryptomeria fortune from Fujian Province, Southeast China. Both species exhibited considerable intra-annual variations in cellulose δ¹⁸O (range ~6 ‰) with a consistent pattern of enriched values near the annual ring boundary and depleted values in the central portion of the ring. Seasonal patterns in the tree-ring δ¹⁸O values generally followed changes in precipitation δ¹⁸O values. Compared with annual tree-ring cellulose δ¹⁸O, intra-annual cellulose δ¹⁸O has potential to reconstruct precipitation with higher resolution and stronger signal intensity. July tree-ring cellulose δ¹⁸O is significantly correlated (r = ?0.58, p < 0.05) with July precipitation, and June–August tree-ring cellulose δ¹⁸O and annual tree-ring cellulose δ¹⁸O, respectively, explain 52 and 41 % of the actual variance of April–August precipitation. In addition, May–October cellulose δ¹⁸O values during El Niño years are higher than in La Niña years, and April to October rainfall is lower in El Niño years than in La Niña years. Combining the significant correlations between inter-annual cellulose δ¹⁸O values and sea surface temperatures in the central tropical Pacific, our results support the hypothesis that El Niño–Southern Oscillation affects tree-ring cellulose δ¹⁸O in Southeast China by modulating seasonal precipitation.

     

Use of stable isotopes to understand food webs in Macao wetlands

In this study, components of the food-web in Macao wetlands were quantified using stable isotope ratio techniques based on carbon and nitrogen values. The δ¹³C and δ¹⁵N values of particulate organic matter (δ¹³C_POM and δ¹⁵N_POM, respectively) ranged from ?30.64 ± 1.0 to ?28.1 ± 0.7 ‰, and from ?1.11 ± 0.8 to 3.98 ± 0.7 ‰, respectively. The δ¹³C values of consumer species ranged from ?33.94 to ?16.92 ‰, showing a wide range from lower values in a freshwater lake and inner bay to higher values in a mangrove forest. The distinct dietary habits of consumer species and the location-specific food source composition were the main factors affecting the δ¹³C values. The consumer ¹⁵N-isotope enrichment values suggested that there were three trophic levels; primary, secondary, and tertiary. The primary consumer trophic level was represented by freshwater herbivorous gastropods, filter-feeding bivalves, and plankton-feeding fish, with a mean δ¹⁵N value of 5.052 ‰. The secondary consumer level included four deposit-feeding fish species distributed in Fai Chi Kei Bay and deposit-feeding gastropods in the Lotus Flower Bridge flat, with a mean δ¹⁵N value of 6.794 ‰. The tertiary consumers group consisted of four crab species, one shrimp species, and four fish species in the Lotus Flower Bridge Flat, with a mean δ¹⁵N value of 13.473 ‰. Their diet mainly comprised organic debris, bottom fauna, and rotten animal tissues. This study confirms the applicability of the isotopic approach in food web studies.     

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.     

Characteristics of stable isotope signature of diet in tissues of captive Japanese macaques as revealed by controlled feeding

We determined the magnitude of isotopic fractionation of carbon and nitrogen stable isotope ratios (as enrichment factors, Δδ¹³C and Δδ¹⁵N, respectively) between the tissues and diets of captive Japanese macaques (Macaca fuscata) using a controlled feeding experiment, to provide basic data for reconstructing their feeding habits. The Δδ¹³C and Δδ¹⁵N values, respectively, were 0.9 ± 0.2 ‰ (mean ± standard deviation, SD) and 3.0 ± 0.3 ‰ for whole blood, 1.3 ± 0.2 ‰ and 4.3 ± 0.3 ‰ for plasma, and 0.8 ± 0.2 ‰ and 3.0 ± 0.2 ‰ for red blood cells. However, the Δδ¹³C and Δδ¹⁵N values for hair were 2.8 ± 0.3 ‰ and 3.4 ± 0.2 ‰, respectively. No difference was detected in the δ¹³C and δ¹⁵N values of hair sampled from different parts of the body. We investigated the effects of diet on δ¹³C in growing hair by alternating the diet of the macaques each month between two diets that differed markedly in δ¹³C. Hair regrown after shaving repeatedly recorded the δ¹³C of the diet consumed during the time of hair growth. On the other hand, hair naturally grown during the diet-change experiment did not show a clear pattern. One possible reason is that the hair had grown abnormally under unnatural indoor conditions and showed complicated isotope signatures. To reconstruct the long-term feeding history of Japanese macaques, we need to further clarify the relationships between the stable isotope signature of diet and various body tissues.     

Trophic plasticity among spring vs. cave populations of <Emphasis Type="Italic">Gammarus minus:</Emphasis> examining functional niches using stable isotopes and C/N ratios

In some environments, species may exhibit trophic plasticity, which allows them to extend beyond their assigned functional group. For Gammarus minus, a freshwater amphipod classified as a shredder or detritivore, cave populations have been observed consuming heterotrophs as well as shredding leaves, and therefore may be exhibiting trophic plasticity. To test this possibility, we examined the C and N stable isotope and C/N ratios for cave and spring populations of G. minus. A 15-day feeding experiment using leaves and G. minus from a spring population established that the diet-tissue discrimination factor was 3.2 ‰ for δ¹⁵N. Cave G. minus were 8 ‰ higher in δ¹⁵N relative to cave leaves, indicating they did not derive nitrogen from leaves, whereas field collected spring populations were 2–3 ‰ higher than spring leaves, indicating that they did. Cave G. minus were 2.6 ‰ higher in δ¹⁵N than the cave isopod, Caecidotea holsingeri. Relative to spring populations, Organ Cave G. minus were ¹⁵N enriched by 6 ‰, suggesting they occupied a different trophic level, or incorporated an isotopically distinct N source. While stable isotopes cannot tell what the cave G. minus are eating, the isotopes certainly show that G. minus are not eating leaves and are trophically distinct form the surface populations. Differences in C/N ratios were observed, but reflect the size of the G. minus examined and not feeding group or habitat. The isotope data strongly support the hypothesis that cave populations of G. minus have become generalist or omnivorous by including animal protein in their diet.     

Complex agriculture during the second millennium <Emphasis Type="SmallCaps">bc</Emphasis>: isotope composition of carbon studies (δ<Superscript>13</Superscript>C) in archaeological plants of the settlement Cerro del Castillo de Alange (SW Iberian Peninsula,Spain)

The isotope composition of fruits and seeds of Hordeum vulgare L. (barley), Triticum aestivum/durum (wheat) and Vicia faba var. minor (faba bean) from three chronological phases between 2200 and 1321 cal bc of the settlement Cerro del Castillo de Alange (SW Iberian Peninsula) have been studied. The δ¹³C values for cereals were between ?24.40 and ?20.39‰ (V-PDB), with a mean of ?22.01‰, the discrimination (Δ) being 15.96‰. The legumes registered similar values, between ?26.25 and ?20.49‰ (mean = ?22.59‰), with a differential for the period of 16.51‰. In both cases, a change was noted from the first phase, where water availability is clearly a limiting factor for plant development. In subsequent phases the growing conditions appear be wetter. By comparison, we measured samples of Quercus ilex-coccifera (oak) charcoal, which shows similar values throughout the series. This suggests that there was no significant climate shift to moister conditions that could explain the above results, but rather they were the consequence of a change in crop management. In addition, we measured samples of a current rainfed Triticum sp. (year 2014), which averaged Δ¹³C 15.56‰. The changes between the three phases could indicate the development of mixed models of exploitation that combine strategies based on the use of rainfed and potentially irrigated areas during the 2nd millennium bc. The implementation of such a cropping technique, taking advantage of the river banks, could be a response to the processes of climatic degradation that begin in the Middle Holocene. The situation of the Cerro del Castillo reservoir between the rivers of the Guadiana and Matachel rivers is consistent with the development of this type of practice indicated by the isotopic and archaeobotanical data.     

Hypoxia within macrophyte vegetation limits the use of methane-derived carbon by larval chironomids in a shallow temperate eutrophic lake

Methane-derived carbon (MDC) can subsidize lake food webs. However, the trophic transfer of MDC to consumers within macrophyte vegetation is largely unknown. We investigated the seasonality of δ¹³C in larval chironomids within Nelumbo nucifera (Gaertn.) and Trapa natans var. Japonica (Nakai) vegetation in the shallow, eutrophic Lake Izunuma in Japan. Over the past several years, N. nucifera has rapidly expanded across more than 80% of the lake surface. Prior to the expansion of N. nucifera (2007–2008), a previous study reported extremely low larval δ¹³C levels with peak sediment methane concentrations in August or September. After the expansion of N. nucifera (2014–2015), we observed extreme hypoxia as low as or lower than 1 mg l^?1 among the macrophyte coverage during June and August. During August and September, no larvae could be found among N. nucifera, and larvae in T. natans showed relatively high δ¹³C levels (>???40‰). In contrast, larvae were markedly ¹³C–depleted (down to ??60‰) during October and November. The renewed supply of oxygen to the lake bottom may stimulate MOB activity, leading to an increase in larval assimilation of MDC. Our results suggest that macrophyte vegetation can affect the seasonality of MDC transfer to benthic consumers under hypoxic conditions in summer.     

Aerial decay influence on the stable oxygen and carbon isotope ratios in tree ring cellulose

Sub-fossil wood is often affected by the decaying process that introduces uncertainties in the measurement of oxygen and carbon stable isotope composition in cellulose. Although the cellulose stable isotopes are widely used as climatic proxies, our understanding of processes controlling their behavior is very limited. We present here a comparative study of stable oxygen and carbon isotope ratios in tree ring cellulose in decayed and non-decayed wood samples of Swiss stone pine (Pinus cembra) trees. The intra-ring stable isotope variability (around the circumference of a single ring) was between 0.1 and 0.5‰ for δ¹⁸O values and between 0.5 and 1.6‰ for δ¹³C values for both decayed and non-decayed wood. Observed intra-tree δ¹⁸O variability is less than that reported in the literature (0.5–1.5‰), however, for δ¹³C it is larger than the reported values (0.7–1.2‰). The inter-tree variability for non-decayed wood ranges between 1.1 and 2.3‰ for δ¹⁸O values, and between 2 and 4.7‰ for δ¹³C values. The inter-tree differences for δ¹⁸O values are similar to those reported in the literature (1–2‰ for oxygen and 1–3‰ for carbon) but are larger for δ¹³C values. We have found that the differences for δ¹⁸O and δ¹³C values between decayed and non-decayed wood are smaller than the variation among different trees from the same site, suggesting that the decayed wood can be used for isotopic paleoclimate research.     

Facies development and sequence stratigraphy of the Ludfordian (Upper Silurian) deposits in the Zbruch River Valley, Podolia, western Ukraine: local facies overprint on the δ13Ccarb record of a global stable carbon isotope excursion

The Ludfordian (Upper Silurian) succession in Podolia, western Ukraine, represents a Silurian carbonate platform developed in an epicontinental sea on the shelf of the paleocontinent of Baltica. Coeval deposits throughout this basin record a positive stable carbon isotope excursion known as the Lau excursion. The record of this excursion in Podolia exhibits an unusual amplitude from highly positive (+6.9 ‰) to highly negative (?5.0 ‰) δ¹³C_carb values. In order to link δ¹³C_carb development with facies, five sections in the Zbruch River Valley were examined, providing microfacies characterization and revised definitions of the Isakivtsy, Prygorodok, and Varnytsya Formations. The Isakivtsy Fm. is developed as dolosparite replacing originally bioclastic limestone. The Prygorodok Fm., recording strongly depleted (down to ?10.53 ‰) to near zero (0.12 ‰) δ¹³C_carb values is developed as laminated, organic-rich dolomicrite with metabentonite and quartz siltstone beds. The Varnytsya Fm. is characterized by peritidal deposition with consistent, slightly negative δ¹³C_carb values (?0.57 to ?3.20 ‰). It is proposed that dolomitization of the Isakivtsy Fm. is associated with a sequence boundary and erosional surface. The overlying Prygorodok Fm. represents the proximal part of a TST deposited in restricted and laterally extremely variable environments dominated by microbial carbonate production. The transition to the overlying Varnytsya Fm. facies is marked by a maximum flooding surface. The SB and MFS are potentially correlative within the basin and support a global rapid sea-level fall previously proposed for this interval. The interpretation of the Prygorodok Fm. as coastal lake deposits may explain the unusual δ¹³C_carb values and constitute one of the few records of this type of environment identified in the early Paleozoic.     

Annual variability in dentin δ15N and δ13C reveal sex differences in weaning age and feeding habits in Risso's dolphins (Grampus griseus)

Teeth of odontocetes accumulate annual dentinal growth layer groups (GLGs) that record isotope ratios, which reflect the time of their synthesis. Collectively, they provide lifetime records of individual feeding patterns from which life history traits can be inferred. We subsampled the prenatal dentin and postnatal GLGs in Risso's dolphins (Grampus griseus) (n = 65) that stranded or were collected as bycatch in Taiwan (1994–2014) and analyzed them for δ¹⁵N and δ¹³C. Age‐specific δ¹⁵N and δ¹³C values were corrected for effects of calendar year, stranding site, C/N, and sex. δ¹⁵N values were higher in prenatal layers (14.94‰ ± 0.74‰) than in adult female GLGs (12.58‰ ± 0.20‰), suggesting fetal enrichment during gestation. Decreasing δ¹⁵N values in early GLGs suggested changes in dietary protein sources during transition to complete weaning. Weaning age was earlier in males (1.09 yr) than in females (1.81 yr). Significant differences in δ¹⁵N values between weaned males and females suggest potential sexual segregation in feeding habits. δ¹³C values increased from the prenatal to the 4th GLG by ~1.0‰, indicative of a diet shift from ¹³C‐depleted milk to prey items. Our results provide novel insights into the sex‐specific ontogenetic changes in feeding patterns and some life history traits of Risso's dolphins.     

The prominent role of bacterial sulfate reduction in the formation of glendonite: a case study from Paleogene marine strata of western Washington State

Ikaite (CaCO₃·6H₂O) forms at near-freezing temperatures and its precipitation is favored by high alkalinity and high concentrations of dissolved phosphate. With increasing temperatures during early burial, ikaite transforms into its calcite pseudomorph referred to as glendonite. To further constrain the biogeochemical processes that impact the transformation of ikaite to glendonite, glendonites from Cenozoic strata of western Washington State, USA, were analyzed for their petrographic characteristics, stable isotope (C, O, S) patterns, and lipid biomarker inventories. Glendonites from the Humptulips, Pysht, Lincoln Creek, and Astoria Formations occur in strata that enclose abundant methane-seep deposits. Despite robust evidence for the anaerobic oxidation of methane (AOM) at these ancient seep sites, molecular signatures of this biogeochemical process were not found within glendonite. Glendonite was found to contain abundant, moderately ¹³C-depleted iso- and anteiso-fatty acids, compounds interpreted as biomarkers of sulfate-reducing bacteria in marine settings. The ³⁴S-enrichment in carbonate-associated sulfate (δ³⁴S_CAS = 54.1 ‰) and the ³⁴S-depletion of pyrite (δ³⁴S_CRS = 6.8–12.5 ‰) in glendonite samples confirm that bacterial sulfate reduction was a prominent process in the sedimentary environment during the transformation of ikaite to glendonite. Low δ¹³C_glendonite values, such as those of the Washington State glendonites (as low as ?21‰), have previously been interpreted as signatures of methane-derived carbon; however, the admittedly small data set obtained from the Washington State glendonites is best explained with organoclastic sulfate reduction as the alkalinity engine driving carbonate precipitation. This surprising finding reveals that more comprehensive work is needed to decipher the biogeochemical processes that governed the transformation of ikaite to glendonite in ancient marine settings, including the relative contribution of organoclastic sulfate reduction and AOM.     

Production of δ-decalactone from linoleic acid via 13-hydroxy-9(Z)-octadecenoic acid intermediate by one-pot reaction using linoleate 13-hydratase and whole <Emphasis Type="Italic">Yarrowia lipolytica</Emphasis> cells

Objective

To produce δ-decalactone from linoleic acid by one-pot reaction using linoleate 13-hydratase with supplementation with whole Yarrowia lipolytica cells.

Results

Whole Y. lipolytica cells at 25 g l^?1 produced1.9 g l^?1 δ-decalactone from 7.5 g 13-hydroxy-9(Z)-octadecenoic acid l^?1 at pH 7.5 and 30 °C for 21 h. Linoleate 13-hydratase from Lactobacillus acidophilus at 3.5 g l^?1 with supplementation with 25 g Y. lipolytica cells l^?1 in one pot at 3 h produced 1.9 g l^?1 δ-decalactone from 10 g linoleic acid l^?1 via 13-hydroxy-9(Z)-octadecenoic acid intermediate at pH 7.5 and 30°C after 18 h, with a molar conversion yield of 31 % and productivity of 106 mg l^?1 h^?1.

Conclusion

To the best of our knowledge, this is the first production of δ-decalactone using unsaturated fatty acid.

     

Comparison of the exploitation of methane-derived carbon by tubicolous and non-tubicolous chironomid larvae in a temperate eutrophic lake

Carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) in three sympatric species of larval chironomids were analyzed in a temperate eutrophic shallow lake in Japan. Markedly lower δ¹³C values were reported in Chironomus plumosus (?51.2 ‰) and Tanypus sp. (?43.5 ‰) than those in photoautotrophic carbon sources [particulate organic matter (POM) and sediment]. There were positive correlations between δ¹³C and δ¹⁵N in the two chironomid species. These results indicated that they assimilated carbon derived from biogenic methane by exploiting methane-oxidizing bacteria (MOB). In contrast, Propsilocerus akamusi exhibited similar δ¹³C values to those of POM or sediment. A δ¹³C-based isotope mixing model was used to estimate the dietary contributions of MOB to each chironomid species. The mean contributions ranged from 11 to 15 % in C. plumosus, 13 to 19 % in Tanypus sp., but only up to 5 % in P. akamusi. In an aquarium, we observed that individuals of C. plumosus and Tanypus sp., which exhibited low δ¹³C values, built U-shaped larval tubes in the sediment, and an oxidized layer developed around these tubes. Propsilocerus akamusi did not exhibit this behavior. These results suggest that tube building may provide larval chironomids with greater access to methane-derived carbon through increased opportunities to feed on MOB.     

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.