Plio-Pleistocene vegetation changes in the North China Plain: Magnetostratigraphy, oxygen and carbon isotopic composition of pedogenic carbonates

The Plio-Pleistocene history of C₄ plant biomass in northwestern China has been documented from the loess-soil sequences of the Loess Plateau region. However, how C₄ plants evolved in the warmer and low-elevation eastern China monsoon zone is still poorly known mainly because of the unavailability of well-dated geological records. In this study, a 203.6-m core of floodplain deposits was recovered from the North China Plain near Tianjin and dated magnetostratigraphically. The results define a chronosequence for the last 3.3 Ma. The late Quaternary portion of the core consists of fluvio-marine sediments while the rest of the section (3.3-0.6 Ma) contains abundant paleosols formed on the floodplain, as confirmed by soil micromorphological evidence. The stable carbon and oxygen isotopic composition of pedogenic carbonates was measured to document vegetation and climate changes. The results reveal mixed C₃ and C₄ vegetation with an estimated C₄ abundance of ~ 40-60% from ~ 3.1 to ~ 2.2 Ma, and a subsequent gradual decline to ~ 25% until ~ 0.6 Ma. This trend is consistent with the data from the loess-soil sequences further west on the Loess Plateau, suggesting they are regionally significant changes. The lowering of growing-season temperature and/or drier conditions induced by global cooling would explain this overall decline.     

Hominid environments at Hadar from paleosol studies in a framework of Ethiopian climate change

The amount and seasonal distribution of paleo-rainfall is a major concern of paleoanthropology because they determine the nature of the vegetation and the structure of the ecosystem, particularly in eastern Africa. The δ¹⁸O and δ¹³C of paleosol carbonates are quantitative proxies of these critical features of the paleoenvironment. The Afar region of Ethiopia lies between the African and Indian summer monsoons, and is prone to profound climate change. In the western Afar, the dominant paleoenvironment of the Hadar Formation during the late Pliocene was a major meandering river's distal low, flat floodplain, on which muds accreted that were continuously transformed into vegetated soils with Bk horizons rich in CaCO₃. The mean δ¹³C of paleosols throughout the Hadar Formation translates to an average vegetative cover across the extensive floodplain of about 30% of the C₄ grasses and 70% of unspecified C₃ plants. The character of the paleosols, such as the one at Locality 333, and their δ¹⁸O_Carbonate argue for a highly seasonal rainfall of about twice today's amount, implying that the C₃ plants were mostly sizeable trees and that the biome for Australopithecus afarensis was a grassy woodland. The amount of grasses abruptly increased in the lower Busidima Formation with its early Homo and artifacts to a more open grassy woodland of ca. 50% grasses. However, this transition in δ¹³C is not mirrored in the δ¹⁸O, which persists at a quite negative average value of −6.4‰ over the entire >2-Myr duration of both formations. This value for the carbonate means that the paleosoil water was a quite negative −4.1‰, a significant 5‰ more negative than our estimate of modern rain at Hadar. We put the negative δ¹⁸O of paleo-Hadar's rainfall into an isotopic framework of the dynamic history of climate change in sub-Saharan northern Africa. There have been two end-member climate regimes: (1) an earlier persistently pluvial Pliocene regime, with its strong summer monsoon, as registered in the Hadar Formation; and (2) the modern cyclical, mostly arid regime that began ca. 1 Myr ago, which has been punctuated by about ten cyclically predictable brief millennia-long pluvial episodes. The best known pluvial of the latter regime is the latest one, the African Humid Period (AHP), just 9.0-6.5 kyr ago, whose δ¹⁸O_Rainfall matches that for paleo-Hadar. The known climatological factors that brought on the AHP are probably the same ones that were persistently present for the Afar of the Pliocene. This dynamic rainfall history undoubtedly has influenced hominid occupation of the keystone Afar area at the gateway out of, and into, Africa.     

Stable isotope ecology of Miocene bovids from northern Greece and the ape/monkey turnover in the Balkans

Eurasia was home to a great radiation of hominoid primates during the Miocene. All were extinct by the end of the Miocene in Western Eurasia. Here, we investigate the hypothesis of climate and vegetation changes at a local scale when the cercopithecoid Mesopithecus replaced the hominoid Ouranopithecus along the Axios River, Greece. Because they are herbivorous and were much more abundant than primates, bovids are preferred to primates to study climate change in the Balkans as a cause of hominoid extinction. By measuring carbon stable isotope ratios of bovid enamel, we conclude that Ouranopithecus and Mesopithecus both evolved in pure C₃ environments. However, the large range of δ¹³C values of apatite carbonate from bovids combined with their molar microwear and mesowear patterns preclude the presence of dense forested landscapes in northern Greece. Instead, these bovids evolved in rather open landscapes with abundant grasses in the herbaceous layer. Coldest monthly estimated temperatures were below 10 °C and warmest monthly temperatures rose close to or above 20 °C for the two time intervals. Oxygen isotope compositions of phosphate from bulk samples did not show significant differences between sites but did show between-species variation within each site. Different factors influence oxygen isotope composition in this context, including water provenience, feeding ecology, body mass, and rate of amelogenesis. We discuss this latter factor in regard to the high intra-tooth variations in δ¹⁸O_p reflecting important amplitudes of seasonal variations in temperature. These estimations fit with paleobotanical data and differ slightly from estimations based on climate models. This study found no significant change in climate before and after the extinction of Ouranopithecus along the Axios River. However, strong seasonal variations with relatively cold winters were indicated, conditions quite usual for extant monkeys but unusual for great apes distributed today in inter-tropical regions.     

Oxygen and carbon isotope compositions of middle Cretaceous vertebrates from North Africa and Brazil: Ecological and environmental significance

In order to investigate mid-Cretaceous terrestrial climates of low paleolatitudes, Moroccan, Tunisian and Brazilian vertebrate apatites have been analyzed for their oxygen and carbon isotope compositions of phosphates (δ¹⁸O_p) and carbonates (δ¹⁸O_c, δ¹³C_c). At each site, coexisting theropod dinosaurs, titanosaurid sauropods, pterosaurs, crocodilians, turtles and fish have distinct δ¹⁸O_p and δ¹³C_c values reflecting their ecologies, diets and foraging environments. Oxygen isotope compositions of surface waters (δ¹⁸O_w) estimated from turtle and crocodile δ¹⁸O_p values range from − 5.0 ± 1.0‰ to − 2.4 ± 1.0‰, which do not differ from mean annual rainwater values occurring today under inter-tropical sub-arid to arid climates. High water temperatures ranging from 21 ± 6 °C to 34 ± 2 °C deduced from fish δ¹⁸O_p values are in agreement with those published for mid-Cretaceous low latitudes. Temporary or seasonal droughts are inferred from high δ¹⁸O_p values of lungfish teeth, even though lower reptile δ¹⁸O_p values suggest the use of distinct and most likely larger or regularly renewed bodies of water. Environmental conditions of the studied low latitude regions during the Aptian-Cenomanian interval were somewhat similar to those experienced today under semi-arid to arid tropical or equatorial climates, but with higher mean surface temperatures than present-day ones.     

Astronomical dating of the Xiantai, Donggutuo and Maliang Paleolithic sites in the Nihewan Basin (North China) and implications for early human evolution in East Asia

Magnetostratigraphic studies have established a first-order chronological framework for the Paleolithic sites in the Nihewan Basin (North China), which enabled tracking early human evolution in East Asia. However, to fully understand how well early humans were adapted to climate change, a truly precise dating of the Paleolithic sites is required. Here, we established a high-resolution astronomical timescale for the Xiantai and Donggutuo fluvio-lacustrine successions at the eastern margin of the Nihewan Basin employing low-field magnetic susceptibility (χ) as a climatic indicator, aiming to further refine the ages of the Xiantai, Donggutuo and Maliang Paleolithic sites. Starting from an initial age model constrained by geomagnetic reversals, larger-scale χ cycles were firstly tuned to orbital obliquity using an automatic orbital tuning method. This first-order tuning was followed by simultaneously tuning χ to both obliquity and precession. The finally tuned χ records can be correlated almost cycle-by-cycle with the quartz grain-size record of the Chinese loess sequence and the marine δ¹⁸O record. The astronomically estimated age of the Xiantai Paleolithic site is ca. 1.48 Ma, corresponding to paleosol layer S₂₀ of the Chinese loess sequences or marine oxygen isotope stage (MIS) 49, an interglacial period. The astronomical estimate for the Donggutuo Paleolithic site ranges from ~ 1.06 Ma to 1.12 Ma, corresponding to paleosol/loess layers S₁₁-S₁₂ or MIS 31-33, spanning both interglacial and glacial periods. The astronomically estimated age of the Maliang Paleolithic site is ~ 0.79 Ma, corresponding to loess layer L₈ or MIS 20, a glacial period. This astronomical finding further implies that early humans may have permanently occupied China as far north as 40^oN since at least 1.1 Ma, and before this time the occupation may be intermittent.     

Winter-spring precipitation as the principal control on predominance of C3 plants in Central Asia over the past 1.77 Myr: Evidence from δC of loess organic matter in Tajikistan

Although changes in atmospheric CO₂ levels are thought to be the major factor driving long-term C₃/C₄ vegetation evolution, recent studies tend to emphasize the effect of regional climate conditions on C₃/C₄ variations. The middle latitudes (30-45°), in which C₃/C₄ plants are highly sensitive to environmental changes, provide an optimal basis for the investigation of the relative impacts of climate and pCO₂ on shifts in C₃/C₄ cover. In order to assess the factors controlling these shifts as well as the complex interactions between environmental factors, the carbon isotopic composition of bulk organic matter from the Chashmanigar loess section (southern Tajikistan) was measured for the past 1.77 Myr. In general, the δ¹³C record shows mostly negative values throughout the sequence, almost all δ¹³C values falling between − 23‰ and − 26‰, indicating a predominance of C₃ plants in Central Asia over this time period, despite the presence of numerous glacial-interglacial cycles. From 0.85 Myr to the present, the δ¹³C values become increasingly positive, reflecting a growing C₄ signal. However, this C₄ component is not detectable prior to 0.25 Myr, after which minor peaks are evident at ∼ 228, ∼ 171 and ∼ 18 kyr. The δ¹³C record from Chashmanigar indicates that winter-spring precipitation, i.e., Mediterranean climatic conditions, have characterized Central Asia throughout the past 1.77 Myr, leading to the predominance of C₃ vegetation. In the context of glacial-interglacial-scale changes in atmospheric CO₂, therefore, it is climate rather than pCO₂ that controls C₃/C₄ variations in Asia’s middle latitudes. The gradual increase in the C₄ component since 0.85 Myr, especially the notable peaks after 0.25 Myr, may have been caused by an increase in summer precipitation due to an enhanced southward shift of the climate zones.     

Variation in bulk tissue, fatty acid and monosaccharide δ13C values between autotrophic and heterotrophic plant organs

The flowers of 23 species of grass and herb plants were collected from a mesotrophic grassland to assess natural variability in bulk, monosaccharide and fatty acid δ¹³C values from one plant community and were compared with previous analyses of leaves from the same species. The total mean bulk δ¹³C value of flower tissues was −28.1‰, and there was no significant difference between the mean δ¹³C_flower values for grass (−27.8‰) and herb (−28.2‰) species. On average bulk δ¹³C_flower values were 1.1‰ higher than bulk δ¹³C_leaf values, however, the δ¹³C_flower and δ¹³C_leaf values of grasses did not differ between organs suggesting that carbon isotope discrimination is different in grass and herb species. The abundance of different monosaccharides abundance varied between plant types, i.e. xylose concentrations in the grass flowers were as high as 40%, compared with up to 15% in the herb species, but the general relationship δ¹³C_arabinose > δ¹³C_xylose > δ¹³C_glucose > δ¹³C_galactose which had been observed in leaves was similar in flowers (total mean δ¹³C values = −25.9‰, −27.2‰, −28.8‰ and −28.1‰, respectively). However, the average 5.4‰ depletion in the δ¹³C values of the C_16:0, C_18:2 and C_18:3 fatty acids in flowers compared to bulk tissue was significantly greater than observed for leaves. The trend C_16:0 < C_18:2 < C_18:3 previously observed in leaves was also observed in grass flowers (δ¹³C_C16:0 = −33.8‰; δ¹³C_C18:2 = −33.1‰; δ¹³C_C18:3 = −34.2‰) but not herb flowers (δ¹³C_C16:0 = −34.1‰; δ¹³C_C18:2 = −32.4‰; δ¹³C_C18:3 = −34.5‰). We conclude: (i) that the biological processes influencing carbon isotope discrimination in grass flowers are different from herbs flowers; and, (ii) that a range of post-photosynthetic fractionation effects caused the observed differences between flower and leaf δ¹³C values, especially the significant ¹³C-depletion in flower fatty acid δ¹³C values.     

Seasonal variations in bulk tissue, fatty acid and monosaccharide δC values of leaves from mesotrophic grassland plant communities under different grazing managements

Leaves of 26 grass, herb, shrub and tree species were collected from mesotrophic grasslands to assess natural variability in bulk, fatty acid and monosaccharide δ¹³C values under different grazing management (cattle- or deer-grazed) on three sample dates (May, July and October) such that interspecific and spatiotemporal variations in whole leaf tissues and compound-specific δ¹³C values could be determined. The total mean leaf bulk δ¹³C value for plants was −28.9‰ with a range of values spanning 7.5‰. Significant interspecific variation between bulk leaf δ¹³C values was only determined in October (P = <0.001) when δ¹³C values of the leaf tissues from both sites was on average 1.5‰ depleted compared to during July and May. Samples from May were significantly different between fields (P = 0.03) indicating an effect from deer- or cattle-grazing in young leaves. The average individual monosaccharide δ¹³C value was 0.8‰ higher compared with whole leaf tissues. Monosaccharides were the most abundant components of leaf biomass, i.e. arabinose, xylose, mannose, galactose and glucose, and therefore, fluctuations in their individual δ¹³C values had a major influence on bulk δ¹³C values. An average depletion of ca. 1‰ in the bulk δ¹³C values of leaves from the deer-grazed field compared to the cattle-grazed field could be explained by a general depletion of 1.1‰ in glucose δ¹³C values, as glucose constituted >50% total leaf monosaccharides. In October, δ¹³C values of all monosaccharides varied between species, with significant variation in δ¹³C values of mannose and glucose in July, and mannose in May. This provided an explanation for the noted variability in the tissue bulk δ¹³C values observed in October 1999. The fatty acids C_16:0, C_18:2 and C_18:3 were highly abundant in all plant species. Fatty acid δ¹³C values were lower than those of bulk leaf tissues; average values of −37.4‰ (C_16:0), −37.0‰ (C_18:2) and −36.5‰ (C_18:3) were determined. There was significant interspecific variation in the δ¹³C values of all individual fatty acids during October and July, but only for C_18:2 in May (P = <0.05). This indicated that seasonal trends observed in the δ¹³C values of individual fatty acids were inherited from the isotopic composition of primary photosynthate. However, although wide diversity in δ¹³C values of grassland plants ascribed to grazing management, interspecific and spatiotemporal influences was revealed, significant trends (P = <0.0001) for fatty acid and monosaccharide δ¹³C values: δ¹³C_16:0 < δ¹³C_18:2 < δ¹³C_18:3 and δ¹³C_arabinose > δ¹³C_xylose > δ¹³C_glucose > δ¹³C_galactose, respectively, previously described, appear consistent across a wide range of species at different times of the year in fields under different grazing regimes.     

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.     

Differentiation of benthic marine primary producers using stable isotopes and fatty acids: Implications to food web studies

A two-dimensional biomarker approach, using stable isotopes (δ¹³C, δ¹⁵N) and fatty acids, was used to evaluate differences both amongst and within benthic primary producer types (seagrass, fleshy red algae, calcareous red algae, brown algae, and seagrass periphyton) that are typical of the nearshore, temperate Australian region. The primary source of variance (as examined by permutational ANOVA) for all biomarkers examined was amongst primary producer types, as opposed to amongst species within type. δ¹³C showed a clear separation (Monte Carlo p < 0.05) between seagrass (range of means = −10.1 to −14.0‰) and macroalgae (−14.6 to −25.2‰), but could not differentiate amongst the algal types examined. Similarly, distinct δ¹⁵N signatures (p < 0.05) were found only for seagrass (range of means = 3.6-4.1‰) versus calcareous red algae (4.6-5.5‰), with all other types overlapping in their mean δ¹⁵N values. In contrast, multivariate analysis of fatty acid data (using Canonical Analysis of Principal coordinates; CAP) distinguished not only between seagrass and macroalgae, but also between red and brown algae (and to a limited extent between the calcareous and fleshy red algal types). The principal unsaturated fatty acids in the samples were C₂₀ polyunsaturates (found primarily in the macroalgae and periphyton), and C₁₈ mono- and polyunsaturates, with high proportions of 18:2n-6 and 18:3n-3 typical of the seagrasses. The C₁₈ monounsaturate 18:1n-7 was one of the most diagnostic compounds for the red algae examined, being present in very low amounts in seagrass and virtually absent in the brown algae. Conversely, brown algae were high in 18:4n-3, with 20:4n-3 particularly diagnostic of the kelp Ecklonia radiata. In contrast to stable isotopes, fatty acids helped distinguish different algal groups, thereby providing support that a two-dimensional approach using stable isotopes and fatty acids is likely to provide the most useful tool to distinguish primary producers in food web structure.     

Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat

We studied C stable isotopic composition (δ¹³C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C₃ photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in ¹³C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue δ¹³C differed by species and by forest type, with values from open-canopied wetlands more enriched in ¹³C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C₃ pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C₃ pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis.     

The evolution of ecological specialization in southern African ungulates: competition‐ or physical environmental turnover?

Using long‐term diet reconstructions spanning the past one million years, we contrast hypotheses that biotic interactions versus physical environmental changes are primary drivers of evolutionary turnover in mammals. We use stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope ratios in tooth enamel carbonate to trace herbivore niche shifts through the Late Quaternary Land Mammal Ages (LMAs) of grassland savannas in the South African interior (Cornelian‐1.0 to 0.6 Ma; Florisian‐500 to 10 ka; and Holocene/modern). Data reveal niche separation amongst closely related coeval taxa, and dispersals through time into empty niche spaces following extinctions. This suggests a primary role of competitive exclusion and niche displacement for speciation and extinctions in these early grassland environments. However, niche changes through time show a similar trend in many taxa, entailing increased δ¹³C (elevated C₄ grass consumption) from the Cornelian to the Florisian, and from the Florisian to the Holocene/modern, and elevated δ¹⁸O in Holocene/modern taxa that reflect global aridification around the terminal Pleistocene. Commonality in isotopic trends implies universal environmental forcing of ecological, and ultimately macroevolutionary, turnover. Yet some taxa shift from a mixed C₃/C₄ diet in the Florisian to a near‐pure C₃ diet today. Indeed, we find that while δ¹³C data are normally distributed for Cornelian fossils, non‐normal distributions characterize more recent time intervals. Such distributions are in line with the bimodal distribution of δ¹³C and diet in contemporary African ungulates. Thus, while environmental forcing did not, by necessity, lead to increases in C₄ intake, the results show changes from mixed to more specialized diets. We propose that this niche specialization was a function of long‐term exposure to C₄ grasslands, consistent with predictions that relatively high metabolic demands of C₄ grazing in subtropical environments forced the differentiation of herbivores into one of two highly specialized feeding niches, i.e. C₃ browsing or C₄ grazing.     

Paleoclimate during Neandertal and anatomically modern human occupation at Amud and Qafzeh, Israel: the stable isotope data

The δ¹³C(en) and δ¹⁸O(en) values of goat and gazelle enamel carbonate indicate that Neandertals at Amud Cave, Israel (53-70 ka) lived under different ecological conditions than did anatomically modern humans at Qafzeh Cave, Israel (approximately 92 ka). During the Last Glacial Period, Neandertals at Amud Cave lived under wetter conditions than those in the region today. Neither faunal species ate arid-adapted C₄ plants or drought-stressed C₃ plants. The variation in gazelle δ¹⁸O(en) values suggests multiple birth seasons, which today occur under wetter than normal conditions. The magnitude and pattern of intra-tooth variation in goat δ¹⁸O(en) values indicate that rain fell throughout the year unlike today.Anatomically modern humans encountered a Qafzeh Cave region that was more open and arid than Glacial Period Amud Cave, and more open than today's Upper Galilee region. Goat δ¹³C(en) values indicate feeding on varying amounts of C₄ plants throughout the year. The climate apparently ameliorated higher in the sequence; but habitats remained more open than at Amud Cave. Both gazelles and goats fed on C₃ plants in brushy habitats without any inclusion of C₄ plants. The magnitude of intra-tooth variation in goat δ¹⁸O(en) values, however, suggest that some rain fell throughout the year, and the relative representation of woodland dwelling species indicates the occurrence of woodlands in the region.Climate differences affecting the distribution of plants and animals appear to be the significant factor contributing to behavioral differences previously documented between Neandertals and anatomically modern humans in the region. Climate forcing probably affected the early appearances of anatomically modern humans, although not the disappearance of Neandertals from the Levant.     

Tracing the pathway of compositional changes in bone mineral with age: Preliminary study of bioapatite aging in hypermineralized dolphin's bulla

Background

Studies of mineral compositional effects during bone aging are complicated by the presence of collagen.

Methods

Hypermineralized bullae of Atlantic bottlenose dolphins of < 3 months, 2.5 years, and 20 years underwent micrometer-scale point analysis by Raman spectroscopy and electron microprobe in addition to bulk analysis for carbon.

Results

Bulla central areas have a mineral content of ~ 96 wt.% and 9–10 wt.% carbonate in their bioapatite, which is ~ 2 wt.% more than edge areas. Ca/P atomic ratios (~ 1.8) and concentrations of Mg, S, and other minor/trace elements are almost constant in central areas over time. Maturity brings greater over-all homogeneity in mineral content, stoichiometry, and morphology throughout the central and edge areas of the bullae. During aging, edge areas become less porous, whereas the concentration of organics in the edge is reduced. Enhancement of coupled substitutions of CO₃^2 − for PO₄^3 − and Na for Ca during aging increases carbonate content up to ~ 10 wt.% in the adult bulla.

Conclusions

1) Changes in physical properties during aging did not occur simultaneously with changes in chemical properties of the bone mineral. 2) Compositional changes in bone mineral were minor during the neonatal to sub-adult stage, but significant during later maturity. 3) Na and CO₃ concentrations co-vary in a 1:1 molar proportion during aging. 4) The mineral's crystallinity did not decrease as CO₃ concentration increased during aging.

General significance

Hypermineralized dolphin's bulla, due to extreme depletion in collagen, is an ideal material for investigating mineralogical changes in bioapatite during bone aging.     

Middle Eocene–late Oligocene climate variability: Calcareous nannofossil response at Kerguelen Plateau,Site 748

A major deterioration in global climate occurred through the Eocene–Oligocene time interval, characterized by long-term cooling in both terrestrial and marine environments. During this long-term cooling trend, however, recent studies have documented several short-lived warming and cooling phases. In order to further investigate high-latitude climate during these events, we developed a high-resolution calcareous nannofossil record from ODP Site 748 Hole B for the interval spanning the late middle Eocene to the late Oligocene (~ 42 to 26 Ma). The primary goals of this study were to construct a detailed biostratigraphic record and to use nannofossil assemblage variations to interpret short-term changes in surface-water temperature and nutrient conditions. The principal nannofossil assemblage variations are identified using a temperate-warm-water taxa index (Twwt), from which three warming and five cooling events are identified within the middle Eocene to the earliest Oligocene interval. Among these climatic trends, the cooling event at ~ 39 Ma (Cooling Event B) is recorded here for the first time. Variations in fine-fraction δ¹⁸O values at Site 748 are associated with changes in the Twwt index, supporting the idea that significant short-term variability in surface-water conditions occurred in the Kerguelen Plateau area during the middle and late Eocene. Furthermore, ODP Site 748 calcareous nannofossil paleoecology confirms the utility of these microfossils for biostratigraphic, paleoclimatic, and paleoceanographic reconstructions at Southern Ocean sites during the Paleogene.     

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.     

Foliar and litter needle carbon and oxygen isotope compositions relate to tree growth of an exotic pine plantation under different residue management regimes in subtropical Australia

Background and aim

Significant differences in tree growth were observed in an exotic pine plantation under different harvest residue management regimes at ages 2–10 years. However, the variations in tree growth between residue management treatments could not be explained by soil and foliar nutrient analyses, except by potassium (K) concentration. Therefore, this study determined the carbon isotope composition (δ¹³C) and oxygen isotope composition (δ¹⁸O) of current and archived foliar samples from the exotic pine plantation to establish relationships with foliar K concentration and tree growth indices as a means to determine changes in stomatal conductance (g_s) and photosynthetic rate (A_max) or water use efficiency (WUE), and therefore understand the variations in tree growth across treatments.

Methods

The harvest residue treatments were: (1) residue removal, RR₀; (2) single level residue retention, RR₁; and (3) double level residue retention, RR₂. Foliar δ¹³C and δ¹⁸O were determined for samples at ages 2, 4, 6 and 10 years, and the atmospheric ¹³C discrimination (Δ¹³C), intercellular CO₂ concentration (C_i) and WUE were determined from the δ¹³C data. Litter needle δ¹³C and δ¹⁸O were also determined over 15 months between ages 9 and 10 years. These parameters or variables where correlated to each other as well as to the periodic mean annual increment of basal area (PAIB) and the periodic mean annual increment of tree diameter at breast height (PAID) across the treatments and over time. Foliar δ¹³C and δ¹⁸O were also related to published data of foliar K concentrations of the same trees.

Results

Significant variations of foliar δ¹³C, and therefore WUE and Δ¹³C, across treatments were only observed at ages 4 and 10 years old, and foliar δ¹⁸O at age 4 years old only. The results showed increasing foliar δ¹³C, δ¹⁸O and WUE, and decreasing Δ¹³C and Ci, from RR₀ to RR₂ treatments. However, while the WUE was positively related to the PAID and PAIB at age 4 years, it was negatively related to PAID and PAIB at age 10 years old. Litter needle δ¹³C, indicative of WUE, was also negatively related to the PAID at age 10 years old. . At age 4 years, foliar δ¹³C and δ¹⁸O were positively related with a steep slope of 7.70 ‰ across treatments, and that both isotopes were positively related to foliar K concentrations. Similarly, δ¹⁸O was negatively related to the Δ¹³C. No significant relationship can be determined between foliar δ¹³C, or Δ¹³C, and δ¹⁸O at age 10 years old. In addition, WUE was increasing (p?<?0.001) and Δ¹³C and C_i decreasing (p?<?0.001) with decreasing PAID over time.

Conclusions

The variations at age 4 years in foliar δ¹³C or Δ¹³C and δ¹⁸O and increasing WUE with increasing growth rate suggest growth induced water-stress with increasing residue-loading rate as a result of the nutritional effect of the harvest residues on tree growth. At age 10 years, the negative relationships between WUE and PAID indicate nutrient limitation has an over-riding effect on δ¹³C variations rather than g_s. This was due to the lack of a significant relationship between foliar Δ¹³C and δ¹⁸O at this age, as well as over time.     

Ancient forests and grasslands in the desert: Diet and habitat of Late Pleistocene mammals from Northcentral Sonora, Mexico

Despite high taxonomic diversity elsewhere in North America during the Pleistocene, vertebrate faunas are exceedingly rare in the region of northern Mexico. Térapa, a unique fossil site located in the present-day desert of Northcentral Sonora, Mexico (29°41′N, 109°39′W, 605 m elevation), contributes to our understanding of the paleoecology and paleoclimate of the region during the Late Pleistocene, ca. 43,000-40,000 cal. yr BP. At least 60 vertebrate taxa, including amphibians, turtles, a crocodilian, snakes, birds and many mammals, have been recovered from an 11-m thick sequence of fossiliferous sediments. The diversity and tropical affinity of these taxa suggest a more-forested environment than the thornscrub desert habitat present in this region today.Isotopic analyses of tooth enamel carbonate from ancient mammalian herbivores suggest that the Sonoran desert has undergone considerable climate change since the Late Pleistocene. Bulk carbon (δ¹³C) and oxygen (δ¹⁸O) isotopes from nine mammalian fossils indicate a habitat mosaic with variations in diet that include browsers, mixed feeders and C4 hyper-grazers (δ¹³C range of − 10‰ to 2‰). Unique to this site are δ¹³C tooth enamel values of − 6.1 and − 5.6 ‰ for the deer Odocoileus, which suggest a more variable diet than strict browsing, including possibly feeding on CAM and/or C4 plants. Serial sampling of carbon (δ¹³C) and oxygen (δ¹⁸O) isotopes for ancient mammal teeth with hypsodont dentitions (fossil Equus and Bison,) as well as δ¹⁸O meteroric water estimates from well-supported climatic models suggest a cooler and more equable environment at Térapa during the Late Pleistocene. These results also support previous habitat reconstructions inferred from the macrobotanical and packrat midden records of northern Sonora (Mexico). High-resolution stable isotope geochemistry indicates that: 1) ancient Térapa was covered with forest and grassland habitats that extended northward into Mexico by about 350 km relative to their present-day northern limits during the Late Pleistocene; and 2) an Amount Effect (AE) is demonstrated in the fossil record at Térapa even though the climate was less seasonal compared to the modern desert habitat.     

Stepwise and large-magnitude negative shift in δ13Ccarb preceded the main marine mass extinction of the Permian–Triassic crisis interval

Large perturbations to the global carbon cycle occurred during the Permian–Triassic boundary mass extinction, the largest extinction event of the Phanerozoic Eon (542 Ma to present). Controversy concerning the pattern and mechanism of variations in the marine carbonate carbon isotope record of the Permian–Triassic crisis interval (PTCI) and their relationship to the marine mass extinction has not been resolved to date. Herein, high-resolution carbonate carbon isotope profiles (δ¹³C_carb), accompanied by lithofacies, were generated for four sections with microbialite (Taiping, Zuodeng, Cili, and Chongyang) in South China to better constrain patterns and controls on δ¹³C_carb variation in the PTCI and to test hypotheses about the temporal relationship between perturbations to the global carbon cycle and the marine mass extinction event. All four study sections exhibit a stepwise negative shift in δ¹³C_carb during the Late Permian–Early Triassic, with the shift preceding the end-Permian crisis being larger (> 3‰) than that following it (1–2‰). The pre-crisis shifts in δ¹³C_carb are widely correlatable and, hence, represent perturbations to the global carbon cycle. The comparatively smaller shifts following the crisis demonstrate that the marine mass extinction event itself had at most limited influence on the global carbon cycle, and that both Late Permian δ¹³C_carb shifts and the mass extinction must be attributed to some other cause. Their origin cannot be uniquely determined from C-isotopic data alone but appears to be most compatible with a mechanism based on episodic volcanism in combination with collapse of terrestrial ecosystems and soil erosion.     

Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species

Almost no δ¹⁸O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ¹⁸O relationship between leaf water and cellulose. We measured δ¹⁸O values of bulk leaf water (δ¹⁸O_LW) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ¹⁸O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally ¹⁸O‐enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε_bio) of more than 27‰ relative to δ¹⁸O_LW, which might be explained by isotopic leaf water and sucrose synthesis gradients. δ¹⁸O_LW and δ¹⁸O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε_bio = 25.1‰). Interestingly, damping factor p_exp_x, which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ¹⁸O_LW but not if modelled directly from δ¹⁸O of individual carbohydrates. We conclude that δ¹⁸O_LW is not always a good substitute for δ¹⁸O of synthesis water due to isotopic leaf water gradients. Thus, compound‐specific δ¹⁸O analyses of individual carbohydrates are helpful to better constrain (post‐)photosynthetic isotope fractionation processes in plants.