Late Carboniferous hydrocarbon-seep carbonates from the glaciomarine Dwyka Group,southern Namibia

Limestone deposits with columnar to lenticular geometry (max. 3.2 m in height and 1.5 m in diameter) occur within the uppermost part of the Ganigobis Shale Member, a marine mudstone unit capping the second deglaciation sequence of the glaciomarine Dwyka Group in southern Namibia. The limestones mainly consist of four authigenic carbonate phases (microspar, banded/botryoidal cement, yellow calcite, spheroidal calcite). Extremely negative δ¹³C values (as low as ? 51‰ VPDB) indicate a hydrocarbon-derived origin of the carbonates with biogenic methane being the most likely carbon source. The limestones contain a low-diversity but high-abundance faunal assemblage of tubular fossils. These fossils closely resemble the tubes of modern and fossil seep-dwelling vestimentiferan tube worms in terms of size, shape, arrangement, and taphonomical patterns.     

Magnesium and strontium compositions of recent symbiont-bearing benthic foraminifera

Minor and trace elements in foraminiferal carbonates are potential paleo-proxies of climate, nutrient and seawater composition. There are very few reports of trace element composition of symbiont-bearing, larger foraminifera that are known to be important constituents of shallow-marine, modern and ancient carbonates. In this paper we examine the range of variation in Mg and Sr content of Recent species of these foraminifera from a lagoon of Lakshadweep Atoll (Indian Ocean) and Akajima Islands, Japan. Two hyaline species, Amphistegina lessonii and Neorotalia calcar,and two porcellaneous species, Amphisorus hemprichii and Marginopora vertebralis were collected live from Lakshadweep islands. Mg / Ca in these foraminifera is of an order of magnitude higher than the values reported for planktonic and symbiont-free benthic foraminifera. The Sr / Ca values are, however, comparable with the reported values in other foraminiferal taxa and they are found to vary within a narrow range. Electron-probe micro-analysis of three symbiont-bearing benthic species indicates spatial heterogeneity of high orders in Mg / Ca composition in all the species. The annual variation in temperature and pH of the lagoon water cannot explain the observed amplitude of the compositional variation. The photosynthesis and respiration of the symbionts and host foraminifera are possibly the major cause of compositional heterogeneity in individual tests, as has also been recently postulated for symbiont-bearing planktonic foraminiferal species. It highlights the need to isolate biological factors and necessitates species-specific paleotemperature scale in paleoclimatic analysis. We also analyzed δ¹⁸O, δ¹³C, Ca, Mg and Sr in carefully dissected chambers of a reef-dwelling, porcellaneous benthic foraminifer, Marginopora kudakajimaensis, collected live in four seasons. A moderate positive correlation is observed between Mg / Ca and temperature. However, large inter- and intra-test variation in Mg limits the precision of Mg / Ca as palaeotemperature proxy. The Sr / Ca of the test calcite is unrelated to temperature of the sea water. The δ¹³C of M. kudakajimaensis does not correlate with δ¹⁸O, Mg / Ca or Sr / Ca.     

A negative carbon isotope excursion defines the boundary from Cambrian Series 2 to Cambrian Series 3 on the Yangtze Platform,South China

A globally recorded negative carbon isotope excursion characterizes the transition from Cambrian Series 2 to Cambrian Series 3. This transition is also well exposed in sedimentary successions on the Yangtze Platform, and the Wuliu–Zengjiayan section, Guizhou Province, South China has been proposed as a potential Global Stratotype Section and Point (GSSP) for this boundary. Here, we report δ¹³C_carb values for the Jianshan and the Wuliu–Zengjiayan sections. Both sections display a progressive decrease in δ¹³C from values around + 3‰ upwards in stratigraphy to a pronounced δ¹³C minimum with values as low as ? 6.9‰ at the proposed boundary level, and a return to δ¹³C values between 0 and + 1‰ in the upper part of the sections. The δ¹³C minimum is thought to be caused by a transgressive event, flooding the shelf area with ¹³C depleted basinal anoxic bottom water. Our δ¹³C data are in good agreement with carbon isotope profiles recorded elsewhere. These define the so called ROECE event (Redlichiid–Oleneliid Extinction Carbon Isotope Excursion, cf. Zhu et al., 2006, 2007) and may reflect the perturbation of the global carbon cycle during the Cambrian Series 2 to Cambrian Series 3 transition.     

Stable oxygen and carbon isotopes of live benthic foraminifera from the Bay of Biscay: Microhabitat impact and seasonal variability

We determined the stable oxygen and carbon isotopic composition of live (Rose Bengal stained) benthic foraminifera (> 150 μm size fraction) of seven taxa sampled along a downslope transect between 140 to 2000 m water depth in the Bay of Biscay. At the five stations, Hoeglundina elegans, Cibicidoides pachydermus, Uvigerina peregrina, Uvigerina mediterranea preferentially occupy shallow infaunal niches, whereas Melonis barleeanus and Uvigerina elongatastriata occupy an intermediate infaunal microhabitat, and Globobulimina spp. live in a deep infaunal niche close to the zero oxygen boundary.When compared with δ¹⁸O values of calcite formed in equilibrium with bottom waters, U. peregrina forms its test in close equilibrium with bottom water δ¹⁸O. All other foraminiferal taxa calcify with a constant offset to calculated equilibrium calcite. There is no systematic relationship between the foraminiferal microhabitat depth and the Δδ¹⁸O between foraminiferal and equilibrium calcite. We calculated correcting factors for the various taxa, which are needed for constructing multispecies-based oxygen isotope records in paleoceanographic studies of the study area.The δ¹³C values of foraminiferal taxa investigated in this study do neither record bottom water δ¹³C_DIC in a 1 : 1 relationship nor with a constant offset, but appear to be mainly controlled by microhabitat effects. The increase of δ¹³C values of shallow infaunal taxa with increasing water depth reflects the decrease of the exported flux of organic carbon along the bathymetric transect and early diagenetic processes in the surface sediment. This is particularly the case for the shallow infaunal U. peregrina. The δ¹³C values of deep infaunal Globobulimina spp. are much less dependent on the exported organic matter flux. We suggest that the Δδ¹³C between U. peregrina and Globobulimina spp. can shed light on the various pathways of past degradation of organic detritus in the benthic environments.At a station in 550 m water depth, where periodic eutrophication of sediment surface niches was demonstrated previously, we performed a two-year seasonal survey of the isotopic composition of foraminiferal faunas. No marked seasonal changes of the stable carbon isotopic composition of shallow, intermediate and deep infaunal foraminiferal taxa were observed. Thus, the δ¹³C values of foraminiferal individuals belonging to the > 150 μm fraction may result from rather long-term calcification processes lasting for several weeks or months, which limit the impact of ephemeral ¹²C enrichment of shallow infaunal niches on the isotope chemistry of adult individuals during eutrophic periods. Only highly opportunistic taxa reproducing or calcifying during phytoplankton bloom periods and the subsequent deposits of phytoplankton remains in the benthic environment may exhibit a particularly low δ¹³C, indicative of such short productive periods.     

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.     

δ15N and δ13C diet–tissue discrimination factors for large sharks under semi-controlled conditions

Stable isotopes (δ¹⁵N and δ¹³C) are being widely applied in ecological research but there has been a call for ecologists to determine species- and tissue-specific diet discrimination factors (?¹³C and ?¹⁵N) for their study animals. For large sharks stable isotopes may provide an important tool to elucidate aspects of their ecological roles in marine systems, but laboratory based controlled feeding experiments are impractical. By utilizing commercial aquaria, we estimated ?¹⁵N and ?¹³C of muscle, liver, vertebral cartilage and a number of organs of three large sand tiger (Carcharias taurus) and one large lemon shark (Negaprion brevirostris) under a controlled feeding regime. For all sharks mean ± SD for ?¹⁵N and ?¹³C in lipid extracted muscle using lipid extracted prey data were 2.29‰ ± 0.22 and 0.90‰ ± 0.33, respectively. The use of non-lipid extracted muscle and prey resulted in very similar ?¹⁵N and ?¹³C values but mixing of lipid and non-lipid extracted data produced variable estimates. Values of ?¹⁵N and ?¹³C in lipid extracted liver and prey were 1.50‰ ± 0.54 and 0.22‰ ± 1.18, respectively. Non-lipid extracted diet discrimination factors in liver were highly influenced by lipid content and studies that examine stable isotopes in shark liver, and likely any high lipid tissue, should strive to remove lipid effects through standardising C:N ratios, prior to isotope analysis. Mean vertebral cartilage ?¹⁵N and ?¹³C values were 1.45‰ ± 0.61 and 3.75‰ ± 0.44, respectively. Organ ?¹⁵N and ?¹³C values were more variable among individual sharks but heart tissue was consistently enriched by ~ 1–2.5‰. Minimal variability in muscle and liver δ¹⁵N and δ¹³C sampled at different intervals along the length of individual sharks and between liver lobes suggests that stable isotope values are consistent within tissues of individual animals. To our knowledge, these are the first reported diet–tissue discrimination factors for large sharks under semi-controlled conditions, and are lower than those reported for teleost fish.     

δ13C and stomatal number variability in the Cretaceous conifer Frenelopsis

The ¹³C/¹²C ratios of leaves of the conifer morphotype Frenelopsis were measured to decipher the influences of water and salt stress on stomatal density (SD), epidermal cell density (ECD) and stomatal index (SI). Three morphospecies were analyzed: F. ugnaensis from freshwater fluvio-lacustrine deposits (Upper Barremian), F. turolensis and alata from coastal deposits (Lower-Middle Albian and Upper Albian respectively). The cuticle δ¹³C values show a large variation from ? 28‰ to ? 21‰. Comparison with previously published marine carbonate δ¹³C records indicate that the difference in cuticle δ¹³C between the different deposits are mainly due to difference in CO₂-plant isotope fractionation rather than to change in isotopic composition of inorganic carbon in the atmosphere and ocean. The less negative δ¹³C and wide range in δ¹³C of F. turolensis and alata (? 27.5 to ? 21‰), compared to F. ugnaensis, (? 28 to ? 25‰) are interpreted as a result of salt and/or water stress. The data as a whole yield a good relationship between the ¹³C/¹²C ratio and SD (r = 0.67, n = 42, p < 0.001), SI (r = 0.53, n = 41, p < 0.001), hence suggesting that the differences in SD and SI between the three morphospecies are related to freshwater/saline environment. Looking at single morphospecies, the SD of F. ugnaensis decreases with increasing δ¹³C value (r = ? 0.57, n = 15, p = 0.026) as well as a decrease of SI (r = ? 0.62, n = 15, p = 0.013), possibly reflecting warmer and drier conditions. Average SI of F. alata does not significantly change with δ¹³C and inferred soil salinity in contrast to SD (p < 0.01).     

Discriminating the endogenous and exogenous urinary estrogens in human by isotopic ratio mass spectrometry and its potential clinical value

Estrogens were prohibited in the food producing animals by European Union (96/22/EC directive) and added to the Report on Carcinogens in United States since 2002. Due to very low concentration in serum or urine (～pg/mL), the method of control its abuse had not been fully developed.The endogenous estrogens were separated from urines of 18 adult men and women. The exogenous estrogens were chemical reference standards and over the counter preparations. Two patients of dysfunctional uterine bleeding (DUB) administered exogenous estradiol and the urines were collected for 72 h. The urinary estrogens were separated by high-performance liquid chromatography (HPLC) and confirmed. The exogenous and exogenous estrogens were analyzed by gas chromatography combustion isotope ratio mass spectrometry (GC–C–IRMS) to determine the ¹³C/¹²C ratio (δ¹³C‰).The δ¹³C‰ values of reference standard of E1, E2, and E3 were ?29.36 ± 0.72, ?27.98 ± 0.35, ?27.62 ± 0.51, respectively. The δ¹³C‰ values of the endogenous E1, E2, and E3 were ?21.62 ± 1.07, ?22.14 ± 0.98, and ?21.88 ± 1.16, with P < 0.01 (t-test). Two DUB patients’ urinary estradiol δ¹³C‰ values was depleted to ?28.02 ± 0.33 after the administration. The progesterone, 17α-hydroxyprogesterone, pregnanediol, as well as desogestrel and ethinylestradiol from contraceptives were also determined.Stable carbon isotope analysis can distinguish the endogenous and exogenous urinary estrogen in human.     

Effect of salinity and seawater calcite saturation state on Mg and Sr incorporation in cultured planktonic foraminifera

Trace elements incorporated in planktonic foraminiferal test carbonate are commonly used as paleoproxies. For instance, Mg/Ca ratios are frequently used for reconstructing sea surface temperature and, together with the foraminiferal stable oxygen isotope ratios, are also used as paleosalinity proxy. Foraminiferal Sr/Ca ratios constitute another example of the application of trace elements in paleostudies since they may reflect the Sr/Ca values of seawater. However, over the past few decades it has been proven that the incorporation of trace elements in foraminiferal calcite is controlled by more than one environmental parameter. To quantify the effect of salinity on Mg and Sr incorporation planktonic foraminifera Globigerinoides sacculifer (sensu stricto) were grown in the laboratory under different environmental conditions. Laboratory experiments allowed us to separate a direct salinity effect from a possible independent impact through differences in the calcite saturation state of the seawater (Ω). Although the temperature effect is more important than the salinity effect, a change of 4 salinity units is equivalent to a 1 °C bias on Mg/Ca-based temperatures. This effect of salinity on Mg incorporation is minor. However, when using Mg/Ca-based temperatures in combination with foraminiferal δ¹⁸O to calculate salinity, it cannot be neglected. The present study shows salinity as the overriding control on Mg incorporation within the range of Ω studied (Ω between 5.25 and 6.50; [CO₃²⁻] between 218 and 270 μmol/kg) at a constant temperature of 26 °C. In contrast, Ω appears to be the main control on foraminiferal Sr incorporation (0.10 mmol/mol per 100 µmol/kg rise in [CO₃²⁻]), whereas salinity has a non significant influence on Sr/Ca.     

Ecology and physiology of White River mammals based on stable isotope ratios of teeth

To characterize the ecology and physiology of common late Eocene–early Oligocene White River mammals, we analyzed the carbon and oxygen isotope composition of tooth enamel carbonate for six of the most abundant taxa: the perissodactyls Brontops (brontothere), Mesohippus (equid) and Subhyracodon (rhino); and the artiodactyls Merycoidodon (oreodont), Leptomeryx (leptomerycid) and Poebrotherium (camelid).δ¹³C values of middle and rear molars (M2s and M3s) and premolars range from ? 13.1‰ to ? 7.7‰ (V-PDB), consistent with pure C3 diets. In the late Eocene, Mesohippus, Merycoidodon, and Leptomeryx show indistinguishable average δ¹³C values (～ ? 10‰). In contrast, Brontops and Subhyracodon exhibit lower (? 11.2‰) and higher (? 8.7‰) values, respectively. Early Oligocene values for Mesohippus and Merycoidodon remain indistinguishable from each other and lower than the value of Leptomeryx, Poebrotherium, and Subhyracodon (～ ? 8.5‰). These results likely indicate niche separation in terms of habitat preference between the investigated sympatric taxa. More specifically, assuming a δ¹³C value of atmospheric CO₂ of ? 5.5‰, our data suggest a preference of Brontops for mesic forested areas, of Mesohippus and Merycoidodon for woodlands, and of Subhyracodon and Poebrotherium for more open habitats (e.g., grasslands). The higher Oligocene versus Eocene average δ¹³C exhibited by Leptomeryx possibly reflects a preference of the new Oligocene species L. evansi for more open and/or xeric habitats relative to the Eocene species L. speciosus.Late Eocene and early Oligocene average δ¹⁸O of Mesohippus, Merycoidodon, Leptomeryx, and Subhyracodon are similar (～ 25‰, V-SMOW), possibly indicating comparable water dependency for these taxa. In contrast, the higher δ¹⁸O of Poebrotherium (26.6‰) suggests lower water dependency whereas the lower δ¹⁸O of Brontops (23.0‰) may result from a high water dependency or, more likely, from its preference for humid habitats. Because hind-gut fermentation in perissodactyls requires high water intake, whereas fore-gut fermentation does not, our results might indicate the presence of fore-gut fermentation in early Oligocene camelids but its absence or incomplete development in late Eocene–early Oligocene oreodonts and leptomerycids.     

Foraminiferal oxygen and carbon isotopes during the last 34 kyr off northern Japan,northwestern Pacific

Oxygen and carbon isotopes of foraminifera were analyzed in core PC4, water depth 1366 m, off northern Japan, near the east side of the Tsugaru Strait (130 m depth) between the open northwestern Pacific Ocean and the Japan Sea. At present, the site is at the confluence of the Tsugaru Warm Current which flows eastwards out of the Sea of Japan through the Tsugaru Strait, the subarctic Oyashio Current and the subtropic Kuroshio Current. During the Last Glacial Maximum (LGM), the Oyashio Current penetrated further to the South and outflow from the Japan Sea was restricted by glacio-eustatic sea level lowering.The isotopic values of the planktic foraminifer Neogloboquadrina pachyderma (sinistral) and the benthic foraminifer Uvigerina akitaensis reflect rapid millennial-scale paleoceanographic changes between 34 and 6 ka. Hydrographic changes during deglaciation were related to events at high northern latitudes, but Holocene hydrographic changes were dominated by local effects, such as the development of the outflow of the Tsugaru Warm Current. High values of planktic δ¹⁸O during the LGM reflect the southward advance of the Oyashio Current. These values decreased by 0.3‰ from 19.4 to 18.9 ka, then increased by 0.5‰ at 18 ka, with highest values between 17.5 and 15 ka. The δ¹⁸O oscillations between 19.4 and 15 ka may reflect millennial-scale warm–cold oscillations during Heinrich event 1. Planktic microfossil data indicate that cold Oyashio waters flowed from the northwestern Pacific into the Japan Sea via the Tsugaru Strait between 17 and 16 ka, consistent with the occurrence of the highest planktic δ¹⁸O values in core PC4. Planktic δ¹⁸O values rapidly decreased by 0.9‰ at 15 ka, possibly reflecting the effects of both a rapid increase in fresh water flux and rising temperatures in the subarctic North Pacific. During the Younger Dryas, cold event planktic δ¹⁸O values increased by 0.5‰, followed by a gradual decrease by 1‰ from the early to middle Holocene, reflecting a gradual increase in eastward outflow via the Tsugaru Strait with sea level rise. Both planktic and benthic foraminiferal δ¹³C values oscillated between 34 and 10 ka, at relatively large amplitudes (about 0.5‰), then remained relatively stable during the last 10 kyr. Several negative planktic and benthic (∼ − 0.7‰) δ¹³C excursions were present in sediment dated between the precipitation of secondary carbonates during episodic methane release possibly associated with methane release from continental margin sediments.     

Seasonal climatic fluctuations in the Late Triassic tropics—High-resolution oxygen isotope records from aragonitic bivalve shells (Cassian Formation,Northern Italy)

Three megalodontoid bivalves from the Upper Triassic Cassian Formation (N Italy, Dolomites) were sampled for δ¹³C and δ¹⁸O sclerochronology (n = 270). With more than 1000 described invertebrate species, the Cassian Formation has one of the best records of an Early Mesozoic tropical fauna. In addition, the Cassian Formation is one of the very few Triassic occurrences with original aragonite preservation, with all studied shells consisting of pristine aragonite. The presence of aragonite and crossed lamellar as well as fibrous prismatic shell microstructures shown for the first time for Triassic megalodontoids suggests absence or minimal impact of diagenetic alteration. The δ¹³C values range from 3.6 to 5.8‰ and show a distinct cyclicity in two studied shells whereas a third shell shows no obvious cyclicity. In one bivalve specimen, the cycles are somewhat offset from δ¹⁸O cycles and in the other specimen δ¹⁸O and δ¹³C curves are inversely correlated. Seasonal variation in freshwater runoff including nutrient input and subsequent changes in plankton productivity during dry and wet seasons may explain δ¹³C cyclicity. δ¹⁸O values show a pronounced cyclicity within each of the studied shells varying from ? 3.6 to ? 1.4‰. The variations in δ¹⁸O suggest a pronounced seasonality in Late Triassic tropical shallow waters of the western Tethys, with inferred seasonal temperature changes ranging from 24 to 32 °C. Influx of fresh water during the rainy seasons (mega-monsoon) or upwelling might also explain part of the variation in δ¹⁸O. The presented data suggest that the diverse Cassian fauna lived under conditions characterized by warm sea-surface waters with a pronounced seasonality. Similar conditions are reported for some modern tropical settings.     

Carbon and oxygen isotope evidence for high-frequency (104–105 yr) and My-scale glacio-eustasy in Middle Pennsylvanian cyclic carbonates (Gray Mesa Formation), central New Mexico

We combine cyclo- and sequence stratigraphy along with whole rock δ¹³C and conodont apatite δ¹⁸O analysis to document high-frequency (10⁴–10⁵ yr) and My-scale sea-level changes for the Middle Pennsylvanian (Desmoinesian or Moscovian) Gray Mesa Formation of central New Mexico. Approximately 75 subtidal cycles (1–8 m) are grouped into 4 1/2 My-scale depositional sequences (40–80 m). About 50% of the cycles show evidence of prolonged subaerial exposure at cycle tops with the development of calcretes, diagenetic mottling, and regolith intraclasts. High-resolution δ¹³C analysis of whole rock limestones across nine of the cycles indicates that the cycle tops were diagenetically altered by isotopically light, meteoric fluids during sea-level fall and lowstand. These δ¹³C trends support the interpretation that high-frequency sea-level changes were responsible for cycle development.Conodont apatite δ¹⁸O values from sampled cycles indicate that the high-frequency sea-level changes were driven by glacio-eustasy combined with changes in surface seawater temperature (SST). δ¹⁸O values from conodont apatite, spanning parts of three depositional sequences indicate that My-scale glacio-eustasy and/or SST changes controlled sequence development. δ¹⁸O shifts indicate that the magnitudes of 10⁴–10⁵ yr glacio-eustasy were between ～ 55 and 170⁺ m combined with tropical SST changes of ～ 1.5°–6 °C. Calculated My-scale glacio-eustatic oscillations were between ～ 60 and 140 m with SST changes of < 3.5 °C. The most plausible driver for the My-scale paleoclimate changes is long-period obliquity (～ 1.2 My) variations. These calculated high-frequency, glacio-eustatic values are similar or greater than Pleistocene values, and lie within the range estimated for other Middle Pennsylvanian successions using a variety of independent eustatic proxies. The similarity in range of magnitudes between high-frequency and My-scale sea-level changes combined with the large differences in magnitudes between individual high-frequency sea-level oscillations helps explain the lack of systematic cycle-stacking patterns within these Pennsylvanian icehouse sequences.     

Soil and tree ring chemistry of Pinus banksiana and Populus tremuloides stands as indicators of changes in atmospheric environments in the oil sands region of Alberta,Canada

The impact of chronic air pollution such as increased CO₂ and NO_x emissions on forest ecosystems in the Athabasca oil sands region in Alberta, Canada, was investigated in Pinus banksiana (jack pine) and Populus tremuloides (trembling aspen, aspen) stands in two watersheds (NE7 and SM8) located at different distances from the main emission sources of oil sands mining and upgrading facilities, using δ¹³C, δ¹⁵N, and Ca/Al of soil and tree ring samples as indicators. Watershed NE7 was exposed to greater amounts of acid deposition due to its closeness to the mining and upgrading area. The δ¹⁵N in the forest floor was lower (p < 0.05) in NE7 (ranged from −1.42 to −0.87‰) than in SM8 (−0.54 to 1.43‰), implying a greater amount of recent deposition of ¹⁵N-depleted N in NE7. Tree ring δ¹³C gradually decreased over time for both tree species/watersheds, indicating the influence of ¹³C-depleted CO₂ emitted from industrial sources. Tree ring N concentration and δ¹⁵N were not different between watersheds and did not significantly change with time. Interestingly, however, the difference between watersheds (NE7–SM8) that is expressed as Diff_N (for N) increased with concomitant decreases in Diff_δ¹⁵N over time, implying greater increases in ¹⁵N-depleted N input in NE7 than in SM8. Such trends were stronger in aspen stands (R² = 0.64 and p < 0.001 for Diff_N and R² = 0.44 and p < 0.01 for Diff_δ¹⁵N between 1964 and 2009) than in jack pine stands. We conclude that δ¹⁵N in the forest floor and differences in N and δ¹⁵N of tree rings between watersheds are useful indicators reflecting the impact of spatial variations of air pollution on forest stands in the Athabasca oil sands region in western Canada.     

Surface-water cooling and salinity decrease during the Middle Miocene climate transition at Southern Ocean ODP Site 747 (Kerguelen Plateau)

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal δ¹⁸O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high δ¹⁸O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloides δ¹⁸O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal δ¹⁸O shift during the MMCT at ~ 13.9 Ma. This divergence in δ¹⁸O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water δ¹⁸O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in δ¹⁸O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~ 13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal δ¹⁸O records spanning the MMCT correspond with changes in the vertical δ¹³C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.     

Freeze tolerance and accumulation of cryoprotectants in the enchytraeid Enchytraeus albidus (Oligochaeta) from Greenland and Europe

The freeze tolerance and accumulation of cryoprotectants was investigated in three geographically different populations of the enchytraeid Enchytraeus albidus (Oligochaeta). E. albidus is widely distributed from the high Arctic to temperate Western Europe. Our results show that E. albidus is freeze tolerant, with freeze tolerance varying extensively between Greenlandic and European populations. Two populations from sub Arctic (Nuuk) and high Arctic Greenland (Zackenberg) survived freezing at −15 °C, whereas only 30% of a German population survived this temperature. When frozen, E. albidus responded by catabolising glycogen to glucose, which likely acted as a cryoprotectant. The average glucose concentrations were similar in the three populations when worms were frozen at −2 °C, approximately 50 μg glucose mg⁻¹ tissue dry weight (DW). At −14 °C the glucose concentrations increased to between 110 and 170 μg mg⁻¹ DW in worms from Greenland. The average glycogen content of worms from Zackenberg and Nuuk were about 300 μg mg⁻¹ DW, but only 230 μg mg⁻¹ DW in worms from Germany showing that not all glycogen was catabolised during the experiment. Nuclear magnetic resonance spectrometry (NMR) was used to screen for other putative cryoprotectants. Proline, glutamine and alanine were up regulated in frozen worms at −2 °C but only in relatively small concentrations suggesting that they were of little significance for freeze survival. The present study confirms earlier reports that freeze tolerant enchytraeids, like other freeze tolerant oligochaete earthworms, accumulate high concentrations of glucose as a primary cryoprotectant.     

Tarbellastraea (Scleractinia): A new stable isotope archive for Late Miocene paleoenvironments in the Mediterranean

Geochemical proxy records of sea surface temperature (SST) or sea surface salinity (SSS) variability on intra- and interannual time-scales in corals from geological periods older than Pleistocene are extremely rare due to pervasive diagenetic alteration of coralline aragonite. Very recently, however, stable isotope data (δ¹⁸O, δ¹³C) from specimens of Porites of Late Miocene age (10 Ma) have been shown to preserve original environmental signatures. In this paper we describe new finds of the zooxanthellate corals Porites and Tarbellastraea in exceptional aragonite preservation from the island of Crete in sediments of Tortonian (～ 9 Ma) and Early Messinian (～ 7 Ma) age. Systematic, comparative stable isotope analysis of massive Tarbellastraea and Porites sampled from the same beds and localities reveal identical stable isotope fractionation patterns in both genera. Therefore, extinct Tarbellastraea represents an additional environmental archive fully compatible and mutually exchangeable with Porites. Provided that seasonal variations in δ¹⁸O reflect SST changes only, seasonal SST contrasts of 7.3 °C for the Tortonian and 4.8 °C for the Early Messinian are inferred, implying warmer summer and cooler winter SSTs during the Tortonian than during the Messinian. However, reduced δ¹⁸O seasonality (1.1‰ in the Tortonian and 0.7‰ in the Messinian) and slightly less negative mean δ¹⁸O in Messinian corals (? 2.4‰) compared to Tortonian specimens (? 2.7‰) may not necessarily indicate a long-term fall in SSTs, but changes in surface water δ¹⁸O, i.e. global ice build-up or enhanced evaporation during summer or increased precipitation/river discharge during winter and changes in insolation. On the other hand, coral communities of Tortonian and Messinian age in central Crete are identical, and compatible annual extension rates indicate similar average SSTs during the two investigated time periods. In addition, lithological and paleobotanical data from Central Crete document a change from humid to dry climatic conditions during the Late Miocene. Therefore, a likely explanation for the observed shift in coral mean δ¹⁸O and reduced δ¹⁸O seasonality from the Tortonian to the Early Messinian is a change in ambient seawater δ¹⁸O caused by a change in the hydrological balance towards high evaporation/high salinity during summer.     

Effect of tertiary sewage effluent additions on Prymnesium parvum cell toxicity and stable isotope ratios

We investigated the ability of the ichthyotoxic haptophyte Prymnesium parvum to use sewage-originated nutrients applying stable carbon (C) and nitrogen (N) isotope techniques. P. parvum was cultured under N and phosphorus (P) sufficient and deficient conditions in either sewage effluent-based medium or in a nitrate- and phosphate-based control. Cell densities and toxicities were monitored and stable carbon N isotopes signatures (δ¹³C and δ¹⁵N) of P. parvum and the sewage effluent analysed. Nitrogen and P sufficient cultures achieved the highest biomass followed by P and N deficient cultures, regardless of sewage effluent additions. The P deficient cultures with sewage effluent had higher toxicity, estimated as haemolytic activity (9.4 ± 0 × 10^?5 mg Saponin equiv. cell^?1) compared to the P deficient control and to all N deficient and NP sufficient cultures. Nutrient deficient conditions had no effect on the cell δ¹⁵N, but a decreasing effect on δ¹³C in the inorganic N deficient treatment. Growth in sewage-based media was followed by a substantial increase in the cell δ¹⁵N (10.4–16.1‰) compared to the control treatments (2.4–4.9‰), showing that P. parvum is capable of direct use of sewage-originated N, inorganic as well as organic. Uptake of terrestrial derived C in the sewage treatments was confirmed by a decrease in cell δ¹³C, implying that P. parvum is able to utilize organic nutrients in sewage effluent.     

The environmental water of the middle Eocene Arctic: Evidence from δD, δ18O and δ13C within specific compounds

The extensive vertical exposure (> 150 m) of terrestrial sediments on Axel Heiberg Island, which contain thick fossiliferous lignites, presents an exceptional opportunity to follow the establishment and re-establishment of Arctic Metasequoia forests during the middle Eocene. We compared δD values in n-alkanes of chain length 23, 25, 27 and 29 with δ¹⁸O values in phenylglucosazone (P-G) derived from α-cellulose; we also analyzed %-abundance of ferns, gymnosperms and angiosperms using pollen and spores isolated from each lignite. Our results showed that forest composition was altered upon uplift, as gymnosperms became more abundant within the relatively well-drained upland sediments. This was also reflected in the small (1‰), but significant, increase in the δ¹³C value of TOM from lowland to upland environments. However, neither the δD values of n-alkanes nor the δ¹⁸O in P-G were statistically different in the upland sediments, as compared to the lowland sediments; from this we inferred that the oxygen isotope signature of environmental water available to the forests for plant growth was relatively uniform throughout the time of the fossil forests. The δD value of environmental water implied by both n-alkanes and P-G ranged from ? 168 to ? 131% and was considerably enriched compared to all environmental water samples available from the modern Arctic region (< ? 180%). In addition to indicating a warmer Eocene Arctic, subject to meteoric transport patterns different from today's, these results argue against the presence of an Eocene polar ice cap.     

Facies-dependent δ13C variation from a Cryogenian platform margin,South Australia: Evidence for stratified Neoproterozoic oceans?

Analysis of a Cryogenian interglacial platform margin in the Adelaide Geosyncline reveals a strong carbonate δ¹³C-facies relationship. Detailed chronostratigraphic correlation between sections ranging from shallow platform facies to deep basinal facies indicates the presence of a carbon isotopic gradient of between 8 and 11‰ in time-equivalent strata. Shallow-water back-reef facies have δ¹³C values up to 8.2‰, while equivalent basinal sediments have δ¹³C values between ? 3 and 0‰. Allochthonous blocks that have been transported from the platform margin into basinal environments retain their heavy δ¹³C values (4–9‰) and are surrounded by basinal calcareous shales with light δ¹³C values (ave. 0.8‰). The regional and stratigraphic consistency of these δ¹³C trends suggests a primary marine origin.We interpret this δ¹³C-facies correlation to be the result of ocean stratification/stagnation that significantly reduced the rate of deep-ocean ventilation and produced a large deep-water, organically derived carbon reservoir. We suggest that stratification may have been a persistent feature of the global ocean throughout much of Neoproterozoic time. Ocean stratification may explain many of the unusual features that characterise the sedimentary record of this era, including large-scale δ¹³C variation, extreme climatic fluctuations, and the presence of cap carbonates. A highly variable climatic regime would be expected with the development of a large deep-water carbon reservoir. Small changes in ocean circulation could rapidly transfer or remove large volumes of carbon to and from the surface-ocean and atmospheric reservoirs, leading to intense greenhouse or icehouse conditions respectively.