Growth history and ecology of the Atlantic surf clam,Spisula solidissima (Dillwyn), as revealed by stable isotopes and annual shell increments

The shells of the Atlantic surf clam, Spisula solidissima (Dillwyn), contain a record of both life history and environmental changes. These shell records were investigated using oxygen and carbon stable isotopic analyses (δ¹⁸O, δ¹³C) and shell growth increment analyses. δ¹⁸O variations across annual shell increments reflect the yearly cycle of sea-water temperatures off the New Jersey coast, further documenting the proposed annual periodicity of the major shell increments. The 11-yr shell record analyzed here confirms that shell growth is most rapid in spring-early summer, slow in late summer-fall, and extremely slow or non-existent in winter. Shell growth appears to occur in isotopic equilibrium with sea water and measured δ¹⁸O values are used to refine the aragonite-water temperature scale. Variations in the timing of annual growth increment formation are noted as well as ontogenetic effects upon the range of isotopic values recorded in shell carbonate. Both the δ¹⁸O and δ¹³C profiles are influenced by changes in the sea-water temperature regime over the 11-yr period studied (1965–1976) and record these effects in the shell. The combination of stable isotope and growth increment analyses provides a powerful tool for interpreting the shell records of both modern and fossil molluscs.     

Biologically driven isotopic fractionations in bivalves: from palaeoenvironmental problem to palaeophysiological proxy

Traditional bulk stable isotope (δ¹⁸O and δ¹³C) and clumped isotope (Δ₄₇) records from bivalve shells provide invaluable histories of Earth's local and global climate change. However, biologically driven isotopic fractionations (BioDIFs) can overprint primary environmental signals in the shell. Here, we explore how conventional measurements of δ¹⁸O, δ¹³C, and Δ₄₇ in bivalve shells can be re-interpreted to investigate these physiological processes deliberately. Using intrashell Δ₄₇ and δ¹⁸O alignment as a proxy for equilibrium state, we separately examine fractionations and/or disequilibrium occurring in the two major stages of the biomineralisation process: the secretion of the extrapallial fluid (EPF) and the precipitation of shell material from the EPF. We measured δ¹⁸O, δ¹³C, and Δ₄₇ in fossil shells representing five genera (Lahillia, Dozyia, Eselaevitrigonia, Nordenskjoldia, and Cucullaea) from the Maastrichtian age [66–69 million years ago (Ma)] López de Bertodano Formation on Seymour Island, Antarctica. Material was sampled from both the outer and inner shell layers (OSL and ISL, respectively), which precipitate from separate EPF reservoirs. We find consistent δ¹⁸O values across the five taxa, indicating that the composition of the OSL can be a reliable palaeoclimate proxy. However, relative to the OSL baseline, ISLs of all taxa show BioDIFs in one or more isotopic parameters. We discuss/hypothesise potential origins of these BioDIFs by synthesising isotope systematics with the physiological processes underlying shell biomineralisation. We propose a generalised analytical and interpretive framework that maximises the amount of palaeoenvironmental and palaeobiological information that can be derived from the isotopic composition of fossil shell material, even in the presence of previously confounding ‘vital effects’. Applying this framework in deep time can expand the utility of δ¹⁸O, δ¹³C, and Δ₄₇ measurements from proxies of past environments to proxies for certain biomineralisation strategies across space, time, and phylogeny among Bivalvia and other calcifying organisms.     

Ligamental increments of the mid-Holocene Pacific oyster Crassostrea gigas are reliable independent proxies for seasonality in the western Bohai Sea,China

Modern living and mid-Holocene shells of Crassostrea gigas from the western Bohai Sea in China were subjected to sclerochronological analysis with the aim of determining whether their concave bottoms and growth breaks on resilifer surfaces, as well as corresponding translucent growth bands visible in cross-section, have seasonal significance. An additional aim was to obtain ontogenetic information from mid-Holocene fossil shells. We compared δ¹⁸O and δ¹³C profiles compiled with high and low sampling resolution for the same shell in order to test the consistency of the results and identify a suitable sampling strategy for future sclerochronological studies. The results show that concave bottoms on the resilifer surface and corresponding translucent growth bands in cross-section formed during the cold season. These features are appropriate indicators of annual growth increments in fossil C. gigas shells. Moreover, growth breaks located near convex tops indicate annual growth increments for that part of the shell which grew when the organism was sexually mature. Therefore, spawning-related growth breaks and alternating winter freeze shocks (concave bottoms) are excellent morphological features in determining annual growth increments. Consequently, the life span, growth rate, and timing of spawning and death can be determined from the increments of ligament growth of these fossil oyster shells. For future sclerochronological studies, an adaptive micro-sampling strategy could be used for different increments of ligament growth that represent different seasons. Such a strategy would be more efficient in providing reliable insights into growth history of shells with variable growth rates of annual increments.     

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

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

Investigating the potential for Southern Hemisphere climate reconstruction using stable isotopes in Tasmanian tree rings

Few annually dated stable isotope records exist across Oceania. Stable carbon and oxygen isotope ratios have the potential to enhance climate reconstructions currently reliant on tree ring width chronologies. The purpose of this study is to explore the sources of variability in a stable oxygen isotope chronology derived from A. selaginoides from Mount Read, Tasmania. This high elevation site receives abundant rainfall throughout the year and is ∼130 km from the Global Network of Isotopes in Precipitation (GNIP) site at Cape Grim. We crossdated 10 new tree core samples against an existing ring width chronology (954–2011 CE) and analyzed the δ¹⁸O from the individual rings for the period 1960–2018. Using high resolution (0.25 degrees) climate data and ECMWF ERA5 reanalysis data, we disentangled the effects of local climate and source region on the isotopic signatures recorded in the annual rings. In addition, we used HYSPLIT backward trajectory analysis to characterize the source region of precipitation to Mount Read and whether the source region has influence over the δ¹⁸O_TR series. Median δ¹⁸O_TR (n = 10) is correlated with local temperature and vapor pressure deficit in the early growing season. In addition, spatial correlations reveal that median δ¹⁸O_TR is positively correlated with temperature and negatively correlated with precipitation in the source region. However, measurements of δ¹⁸O_TR exhibit high inter-tree variation, particularly between 1960 and 1990. Our results indicate that this δ¹⁸O_TR proxy may provide additional information about past moisture conditions during the growing season, potentially contributing to more robust reconstructions of the Southern Hemisphere climate dynamics; however, additional sampling may be necessary to resolve inter-tree variation in δ¹⁸O_TR.     

Unthinned slow-growing ponderosa pine (Pinus ponderosa) trees contain muted isotopic signals in tree rings as compared to thinned trees

Key message

The muted wood isotopic signal in slow-growing trees of unthinned stands indicates lower responsiveness to changing environmental conditions compared to fast-growing trees in thinned stands.

Abstract

To examine the physiological processes associated with higher growth rates after thinning, we analyzed the oxygen isotopic values in wood (δ¹⁸O_w) of 12 ponderosa pine (Pinus ponderosa) trees from control, moderately, and heavily thinned stands and compared them with wood-based estimates of carbon isotope discrimination (?¹³C), basal area increment (BAI), and gas exchange. We found that (heavy) thinning led to shifts and increased inter-annual variability of both stable carbon and oxygen isotope ratios relative to the control throughout the first post-thinning decade. Results of a sensitivity analysis suggested that both an increase in stomatal conductance (g _s) and differences in source water among treatments are equally probable causes of the δ¹⁸O_w shift in heavily thinned stands. We modeled inter-annual changes in δ¹⁸O_w of trees from all treatments using environmental and physiological data and found that the significant increase in δ¹⁸O_w inter-annual variance was related to greater δ¹⁸O_w responsiveness to changing environmental conditions for trees in thinned stands when compared to control stands. Based on model results, the more muted climatic response of wood isotopes in slow-growing control trees is likely to be the consequence of reduced carbon sink strength causing a higher degree of mixing of previously stored and fresh assimilates when compared to faster-growing trees in thinned stands. Alternatively, the muted response of δ¹⁸O_w to climatic variation of trees in the control stand may result from little variation in the control stand in physiological processes (photosynthesis, transpiration) that are known to affect δ¹⁸O_w.     

Oxygen and carbon isotope variations in Chamelea gallina shells: Environmental influences and vital effects

Stable isotopes in mollusc shells, together with variable growth rates and other geochemical properties, can register different environmental clues, including seawater temperature, salinity and primary productivity. However, the strict biological control over the construction of biominerals exerted by many calcifying organisms can constrain the use of these organisms for paleoenvironmental reconstructions. Biologically controlled calcification is responsible for the so called vital effects that cause a departure from isotopic equilibrium during shell formation, resulting in lower shell oxygen and carbon compared to the equilibrium value. We investigated shell oxygen and carbon isotopic composition of the bivalve Chamelea gallina in six sites along with a latitudinal gradient on the Adriatic Sea (NE Mediterranean Sea). Seawater δ¹⁸O and δ¹³C_DIC varied from North to South, reflecting variations in seawater temperature, salinity, and chlorophyll concentration among sites. Shell δ¹⁸O and δ¹³C differed among sites and exhibited a wide range of values along with the ~400 km latitudinal gradient, away from isotopic equilibrium for both isotopes. These results hampered the utilization of this bivalve as a proxy for environmental reconstructions, in spite of C. gallina showing promise as a warm temperature proxy. Rigorous calibration studies with a precise insight of environment and shell growth are crucial prior to considering this bivalve as a reliable paleoclimatic archive.     

Isotopic signatures (δO and δC) of bivalve shells from cold seeps and hydrothermal vents

The oxygen and carbon isotopic compositions of 108 modern shells of various bivalve species collected from cold seeps and hydrothermal vents were investigated in order to evaluate whether these parameters can provide information on environmental geochemical variability as well as on bivalve species and on the type of symbiotic bacteria present in their gills. The results show that the carbonate of bivalve shells from hydrothermal vents is characterized by abnormal positive δ¹³C values due to kinetic isotope effects, whereas the carbonate of bivalve shells from cold seeps exhibits positive as well as negative δ¹³C values suggesting that oxidized methane emitted by the seeping fluids may be incorporated in the shell. Comparison of the δ¹⁸O and δ¹³C values of bivalve shells hosting different chemosymbiotic bacteria suggests that each type of symbiosis is associated with a specific environment and bivalve species, indicating that there is a strong physiological/metabolic control on the incorporation of stable isotopes during the biomineralization process.     

Seasonal stable isotope variations of the modern Amazonian freshwater bivalve Anodontites trapesialis

In a floodplain lake of the Amazon River near the city of Iquitos, northeastern Peru, a one-year monitoring experiment was conducted during which water samples and living bivalves (Anodontites trapesialis) were collected with the aim to investigate seasonal δ¹⁸O variation in and fractionation between bivalve aragonite and host water. Both host water and molluscan growth increments show more than 8‰ seasonal variation in δ¹⁸O. In the floodplain lake under study the δ¹⁸O variation of the water is controlled by contrasting dry and wet season evaporation-precipitation regimes. Molluscan δ¹⁸O appears to be in equilibrium with the host water. Although an approximately 4.0‰ offset occurs, δ¹³C records of water and bivalves are in good agreement, suggesting that both δ¹⁸O and δ¹³C of the shells of freshwater bivalve A. trapesialis are good recorders of (palaeo-)environmental conditions. The δ¹³C of Dissolved Inorganic Carbon (DIC) is governed by plant growth and/or by changes in aquatic chemistry, affecting the DIC pool.     

Reconstruction of source water using the δ18O of tree ring phenylglucosazone: A potential tool in paleoclimate studies

The oxygen isotope ratios of tree ring cellulose have a great potential as proxy for the oxygen isotope ratios of source water, which is related to climate. However, source water isotopic signatures can be masked by plant physiological and biochemical processes during cellulose synthesis. To minimize biochemical effects in the recording of source water, we modified the cellulose molecule to phenylglucosazone, which only has oxygen attached to carbon 3–6 (O_C3–6) of the cellulose glucose moieties, thus eliminating the oxygen attached to carbon 2 of the cellulose glucose moieties (O_C-2). Here we developed a method to use small amounts of inter and intra-annual tree ring cellulose for phenylglucosazone synthesis. Using this new method we tested if the oxygen isotope ratios of source water reconstructed from tree ring phenylglucosazone (δ¹⁸O_sw^PG) and the observed source water (δ¹⁸O_sw^obs) would have a better agreement than those reconstructed from the tree ring cellulose molecule. Annual tree ring samples were obtained from Pinus sylvestris (1997–2003) (Finland) and Picea abies (1971–1992) (Switzerland) and intra-annual tree ring samples were obtained from Pinus radiata (October 2004–March 2006) (New Zealand), each near a meteorological station where precipitation and relative humidity (RH) were measured periodically. The δ¹⁸O of tree ring cellulose and tree ring phenylglucosazone for each of the three species were then used to back calculate the δ¹⁸O of source water according to a previous published empirical equation. As expected, the δ¹⁸O of tree ring phenylglucosazone was superior than cellulose in the reconstruction of source water available to the plant. Deviation between δ¹⁸O_sw^PG and δ¹⁸O_sw^obs was in part correlated with variation in atmospheric relative humidity (RH) which was not observed for the cellulose molecule. We conclude that this new method can be applicable to inter and intra-annual tree ring studies and that the use of the tree ring phenylglucosazone will significantly improve the quality of paleoclimate studies.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

Recent and historical discharge of a large European river system - oxygen isotopic composition of river water and skeletal aragonite of Unionidae in the Rhine

Seasonal variations in the oxygen isotopic composition of Rhine River water were analyzed in detail and compared with the oxygen isotopic record from recent and historical specimens of freshwater bivalves (Unionidae). The purpose of this study was to investigate the potential use of these aragonitic bivalves as proxy recorders for varying amounts and sources of discharge, and thereby infer climate change. Seasonal variations in the river water δ¹⁸O are on the order of 1-2‰. During summer, Alpine melt-water contributes significantly to the total discharge, resulting in average values of −10 to −10.5‰, whereas the non-Alpine contribution is higher during winter, as indicated by mean δ¹⁸O values of −8.5 to −9‰. The basic pattern of the modern seasonal variation of δ¹⁸O of river water can be described by a numerical mass balance approximation of the various contributions from the Alpine and non-Alpine catchments with their average δ¹⁸O composition. The δ¹⁸O of growth increments in the prismatic shell layer of Anodonta corresponds perfectly to what is predicted by known fractionation of ¹⁸O between water and aragonite. Shell growth is restricted to water temperatures above 8-10°C, so variations in δ¹⁸O and the river water temperature are faithfully recorded by relatively large growth increments during summer. The distinctive isotopic signatures of individual flood events during summer and autumn are also recorded in the shells.     

Records of upwelling, seasonality and growth in stable-isotope profiles of Pliocene mollusk shells from Florida

Oxygen and carbon isotopic profiles across the shells of well-preserved bivalves and gastropods from the Pliocene Pinecrest Beds near Sarasota, Florida, provide detailed records of the paleoen-vironmental and paleoclimatic conditions under which these high-density shell beds accumulated, as well as offer insight into shell-growth rates and longevity. Eight turritellid gastropods were analyzed from within and surrounding two Turritella-rich beds, an upper bed within unit 2(2.5-2.0 Ma) and a lower bed situated near the top of the main shell bed, unit 6/7(3.5-2.5 Ma). Three bivalves plus another turritellid specimen from a lower horizon (middle of unit 6/7), considered to represent offshore, normal-marine conditions, were also analyzed. The isotopic profiles of all shells reflect year-round shell growth in a seasonal, subtropical to warm-temperate paleoenvironment. Cyclical patterns in δ¹⁸O reflect annual variations in water temperature which on average ranged from 15 to 24d?C; minimum paleoseasonality contrasts varied from 7 to 9d?C. Summer paleo-temperatures compare favorably with those detemined from ostracodes, whereas winter temperatures appear slightly cooler. Except for one pectinid specimen, temperature differences between horizons and specimens are small. Annual δ¹⁸O cycles indicate: Turritella apicalis lived longer and grew slightly faster than Turritella gladeensis; and, shell growth rates and increment formation in Mercenaria campechiensis are comparable to modern Florida populations. Coincident episodes of heavy δ¹⁸O and light δ¹⁸C in both turritellids and bivalves suggest a pattern of seasonal upwelling. This cool, nutrient-rich, upwelled water may be partially responsible for the great abundance of Pinecrest fossils. □Stable isotopes, Pliocene, Pinecrest Beds, Florida, upwelling, paleotemperature, mollusk, Turritella.      

The influence of seawater carbonate ion concentration [CO32−] on the stable carbon isotope composition of the planktic foraminifera species Globorotalia inflata

We sampled the upper water column for living planktic foraminifera along the SW-African continental margin. The species Globorotalia inflata strongly dominates the foraminiferal assemblages with an overall relative abundance of 70–90%. The shell δ¹⁸O and δ¹³C values of G. inflata were measured and compared to the predicted oxygen isotope equilibrium values (δ¹⁸O_eq) and to the carbon isotope composition of the total dissolved inorganic carbon (δ¹³C_DIC) of seawater. The δ¹⁸O of G. inflata reflects the general gradient observed in the predicted δ¹⁸O_eq profile, while the δ¹³C of G. inflata shows almost no variation with depth and the reflection of the δ¹³C_DIC in the foraminiferal shell seems to be covered by other effects. We found that offsets between δ¹⁸O_shell and predicted δ¹⁸O_eq in the surface mixed layer do not correlate to changes in seawater [CO₃²⁻].To calculate an isotopic mass balance of depth integrated growth, we used the oxygen isotope composition of G. inflata to estimate the fraction of the total shell mass that is grown within each plankton tow depth interval of the upper 500 m of the water column. This approach allows us to calculate the Δδ¹³C_{interval added-DIC}; i.e. the isotopic composition of calcite that was grown within a given depth interval. Our results consistently show that the Δδ¹³C_IA-DIC correlates negatively with in situ measured [CO₃²⁻] of the ambient water. Using this approach, we found Δδ¹³C_IA-DIC/[CO₃²⁻] slopes for G. inflata in the large size fraction (250–355 μm) of − 0.013‰ to 0.015‰ (μmol kg^− 1)^− 1 and of − 0.013‰ to 0.017‰ (μmol kg^− 1)^− 1 for the smaller specimens (150–250 μm). These slopes are in the range of those found for other non-symbiotic species, such as Globigerina bulloides, from laboratory culture experiments. Since the Δδ¹³C_IA-DIC/[CO₃²⁻] slopes from our field data are nearly identical to the slopes established from laboratory culture experiments we assume that the influence of other effects, such as temperature, are negligibly small. If we correct the δ¹³C values of G. inflata for a carbonate ion effect, the δ¹³C_shell and δ¹³C_DIC are correlated with an average offset of 2.11.     

Sclerochronological study of the gigantic inoceramids Sphenoceramus schmidti and S. sachalinensis from Hokkaido,northern Japan

Here, we present the first sclerochronological investigation of shells of the gigantic inoceramids Sphenoceramus schmidti and S. sachalinensis from the middle Campanian cold seep carbonate‐bearing strata of the Yezo Basin in Hokkaido (northern Japan). Stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope values were measured in the aragonitic and calcitic shell layers of both species and compared to those of other co‐occurring benthic (mainly bivalves and gastropods) and demersal molluscs (ammonites). Sedimentological and stable isotope data suggest that these bivalves lived near cold seeps and were exposed to high H₂S level in the seawater. The inoceramid shells exhibited higher δ¹³C and lower δ¹⁸O values than the coeval non‐cold seep molluscs. We ascribed the anomalous isotopic pattern to a combination of vital and environmental effects determined by the hosting of chemosymbionts and the exposure to warm interstitial waters. Inoceramid δ¹³C minima coincided with growth lines and likely reflect changes in nutrient supply by the chemosymbionts. Absolute temperatures estimated from δ¹⁸O values of Sphenoceramus schmidti and S. sachalinensis were, on average, ca. 4–5°C warmer than those reconstructed for the non‐seepage environment (19.3 ± 0.7°C). Short‐term δ¹⁸O fluctuations of the inoceramid material indicate local temperature ranges of up to 5.2°C, that is four times larger than those reconstructed from the benthic and demersal fauna (1.3°C). In general, our data suggest that the stable carbon and oxygen isotope values of the studied Sphenoceramus spp. were strongly affected by short‐term fluctuations in seepage activity and do not reflect seasonal fluctuations.     

The role of <Emphasis Type="Italic">Salvelinus</Emphasis> in contemporary studies of evolution,trophic ecology and anthropogenic change

The aim of this study was to better understand the relations between carbon and oxygen stable isotope values of ambient water, mollusc shells, macrophytes and their carbonate encrustations, commonly used in palaeolimnological studies. Water, molluscs and macrophytes were sampled from the littoral zone in Lake Lednica, NW Poland. The influence of carbon species assimilated during photosynthesis and the net intensity of photosynthesis resulting from the size of charophyte species and the density of their stands were postulated to be the most important factors causing the species-specific δ¹³C values of charophyte thalli and encrustations. It was suggested that photosynthetic activity of charophytes affected not only the δ¹³C values of charophyte encrustations but also mollusc shells by changing δ¹³C values of DIC within charophyte stands. In addition, incorporation of metabolic carbon into the shell was proposed as the main cause of both the ¹³C depletion of mollusc shells relative to δ¹³C values of DIC and the species-specific δ¹³C values of shells. Mollusc shells were precipitated at the isotope equilibrium or close to the equilibrium with δ¹⁸O values of lake water. Charophyte encrustations were found to be ¹⁸O depleted due to the kinetic isotope effects during intense photosynthesis and thus fast precipitation of the calcite.     

Oxygen isotopic composition of sulfate in deep sea pore fluid: evidence for rapid sulfur cycling

We present new data of oxygen isotopes in marine sulfate (δ¹⁸O_SO4) in pore fluid profiles through organic‐rich deep‐sea sediments from 11 ODP sites around the world. In almost all sites studied sulfate is depleted with depth, through both organic matter oxidation and anaerobic methane oxidation. The δ¹⁸O_SO4 increases rapidly near the top of the sediments, from seawater values of 9 to maxima between 22 and 25, and remains isotopically heavy and constant at these values with depth. The δ¹⁸O_SO4 in these pore fluid profiles is decoupled from variations in sulfur isotopes measured on the same sulfate samples (δ³⁴S_SO4); the δ³⁴S_SO4 increases continuously with depth and exhibits a shallower isotopic increase. This isotopic decoupling between the δ³⁴S_SO4 and the δ¹⁸O_SO4 is hard to reconcile with the traditional understanding of bacterial sulfate reduction in sediments. Our data support the idea that sulfate or sulfite and water isotopically exchange during sulfate reduction and that some of the isotopically altered sulfur pool returns to the environment. We calculate that the rapid increase in the δ¹⁸O_SO4 in the upper part of these sediments requires rates of this oxygen isotope exchange that are several orders of magnitude higher than the rates of net sulfate reduction calculated from the sulfate concentration profiles and supported by the δ³⁴S_SO4. We suggest several mechanisms by which this may occur, including ‘net‐zero’ sulfur cycling, as well as further experiments through which we can test and resolve these processes.     

Paleosalinity in a brackish lake during the Holocene based on stable oxygen and carbon isotopes of shell carbonate in Nakaumi Lagoon, southwest Japan

Based on the relationship between salinity and δ¹⁸O and δ¹³C of modern shells in the Lake Nakaumi-Shinji lagoon system (southwestern Japan), where the salinity changes regularly from ca. 1 PSU to 34 PSU, a paleosalinity record for Nakaumi Lagoon during the Holocene has been derived from bulk mollusk shell δ¹⁸O and δ¹³C data. The robust relationships between the salinity and modern shell δ¹⁸O_ar and δ¹³C_ar (aragonite) were used to calibrate the paleosalinity reconstruction. The salinity relationships are expressed by the regressions:

Salinity (PSU)=3.86 δ¹⁸O_ar(‰ VPDB)+33.9 (n=18, r=0.978)     

Assessing between-colony oxygen isotope variability in the coral Porites lobata at Clipperton Atoll

The eastern Pacific warm tongue is a region of stable and elevated sea surface temperature (SST) located just north of the equator in the eastern Pacific. This warm water mass is thought to influence the position of the Intertropical Convergence Zone (ITCZ) in the eastern Pacific and to directly influence climate in Central America. To assess the use of corals in the development of paleoclimatic reconstructions in this region, we have developed oxygen isotope (δ¹⁸O) time-series from multiple specimens of the massive coral Porites lobata collected at Clipperton Atoll (10°18′N, 109°13′ W). Six near-monthly δ¹⁸O records from different sized (age) colonies where produced for the interval 1986–1994, and three of these were extended back to 1969. All corals sampled were found to contain numerous fish-grazing skeletal scars (～0.5?mm deep scallop shaped hiatuses). Samples collected at 1?mm intervals showed anomalous ¹⁸O/¹⁶O in the area of a bite scar, with 2 to 2.5?mm sampling intervals (10–12/year) minimizing these effects. Our results show that the average δ¹⁸O disequilibrium offset (vital effect) from equilibrium seawater composition for individual corals can vary by up to 0.4‰. However all δ¹⁸O results suggest that the vital effect offset is constant over time. Similar “offsets” are observed in the tops of old (age=～100?y) and young (age=～10?y) colonies, further suggesting that the biologically mediated vital effect offset does not change as a Porites colony ages. A 6-coral average composite δ¹⁸O record was constructed from 1985–1994 and a 3-coral average δ¹⁸O_anomaly record was constructed from 1969–1994. Regression analysis between monthly SST and the 6 coral average δ¹⁸O records yields an r ² correlation of 0.54 (individual r ²-values ranged from 0.27–0.55). The 3 coral δ¹⁸O_anomaly average record has an even lower correlation to SST, with an r ² of 0.40. Potential causes of the only moderate correlation to SST are explored and we find that inferred salinity effects, fish grazing scars, and slight chronology imperfections have all contributed to a reduced correlation to SST. Nevertheless, all El Niño events in this time period appear to be recorded by coral skeletal δ¹⁸O.     

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.