Isotopic evidence for temporal variation in proportion of seasonal precipitation since the last glacial time in the inland Pacific Northwest of the USA

Large-scale atmospheric circulation patterns determine the quantity and seasonality of precipitation, the major source of water in most terrestrial ecosystems. Oxygen isotope (δ¹⁸O) dynamics of the present-day hydrologic system in the Palouse region of the northwestern U.S.A. indicate a seasonal correlation between the δ¹⁸O values of precipitation and temperature, but no seasonal trends of δ¹⁸O records in soil water and shallow groundwater. Their isotope values are close to those of winter precipitation because the Palouse receives  75% of its precipitation during winter. Palouse Loess deposits contain late Pleistocene pedogenic carbonate having ca. 2 to 3‰ higher δ¹⁸O values and up to 5‰ higher carbon isotope (δ¹³C) values than Holocene and modern carbonates. The late Pleistocene δ¹⁸O values are best explained by a decrease in isotopically light winter precipitation relative to the modern winter-dominated infiltration. The δ¹³C values are attributed to a proportional increase of atmospheric CO₂ in soil CO₂ due to a decrease in soil respiration rate and ¹³C discrimination in plants under much drier paleoclimate conditions than today. The regional climate difference was likely related to anticyclonic circulation over the Pleistocene Laurentide and Ice Sheet.     

Climatic and non-climatic effects on the δO and δC compositions of Lake Awassa, Ethiopia, during the last 6.5 ka

A comparison of a 6450 ¹⁴C yr δ¹⁸O and δ¹³C record of authigenic calcite from Lake Awassa, Ethiopia, with other proxy climate records in the area suggests that the lake records long-term regional climate changes. Co-varying and increasing δ¹⁸O and δ¹³C values from 4800 BP suggest an aridification of climate after the early Holocene insolation maximum. After 4000 BP, humid conditions return until after 2800 BP when δ¹⁸O increases again, reflecting more arid conditions recorded elsewhere in Ethiopia. In addition to these long-term changes, there are abrupt decreases in both δ¹⁸O_calcite and δ¹³C_calcite immediately after tephra layers. The likeliest explanation for these abrupt decreases in isotopes is the effect of tephra on the lake's catchment vegetation. δ¹⁸O, δ¹³C and lake-level measurements from Lake Awassa since the 1970s suggest that the lake is currently isotopically sensitive to short-term (annual–decadal) climate change. However, during this period, the catchment has undergone progressive deforestation that may have caused an increase in runoff. Caution is therefore required when reconstructing palaeoclimates as a contemporary lake may not always be a good analogue for lake hydrology in the past.     

Satellite prediction of soil δC distributions in a southern African savanna

Stable carbon isotopes have been frequently used to indicate carbon pools and processes in soils, plants, and the atmosphere. Carbon isotope compositions are particularly useful in partitioning soil carbon sources between C₃ and C₄ vegetation because of the distinct δ¹³C distributions for C₃ and C₄ vegetation. Remote sensing is a powerful tool used to identify ecosystem patterns and processes at larger scales. A union of these two approaches would hold promise for spatially continuous estimates of carbon isotope compositions. In the current study, a framework is presented for using high spatial resolution remote sensing to predict soil δ¹³C distributions across a southern Africa savanna ecosystem. The results suggest that if the vegetation–soil δ¹³C relationship can be established, soil δ¹³C distributions can be estimated by high-resolution satellite images (e.g., IKONOS, Quickbird). Despite limitations remote sensing is a promising tool to expand estimates of terrestrial δ¹³C spatial patterns and dynamics.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.     

Stable isotopes of pedogenic carbonates from the Somma–Vesuvius area,southern Italy,over the past 18 kyr: palaeoclimatic implications

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ¹⁸O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ¹⁸O of pedogenic carbonate recorded after this eruption. The δ¹³C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO₂, and the pedogenic carbonate. Carbon isotopes suggest prevailing C₃ vegetation and negligible mixing with volcanogenic or atmospheric CO₂. Copyright © 2000 John Wiley & Sons, Ltd.     

Carbon isotope and C/N ratios of suspended matter in rivers: an indicator of seasonal change in C4/C3 vegetation

A combination of δ ¹³C values with C/N ratios in suspended matter has been used to examine the seasonal relationship between C₄ and C₃ vegetation along the Loess Plateau, NW China. The C isotopic composition of suspended organic matter in rivers, together with C/N ratios can differentiate between soil and plant material, and can be used to estimate the relative contributions of soil organic C and plant litter to the suspended matter. The relationship between C isotopic composition and C/N ratios indicates that the samples are a mixture of two end members: (1) modern soils with relatively constant δ ¹³C values, low C content and low C/N ratios; (2) plant litter with varying δ ¹³C values, high C content and high C/N ratios. The results reflect the seasonal distribution of C₄/C₃ vegetation within the area studied, as part of the Loess Plateau. The abundance of C₄ grasses is about 20% for the current summer vegetation ecosystem in the eastern part of the Loess Plateau. Hence, the use of δ ¹³C values and C/N ratios of suspended matter in rivers and modern soil may be useful for reflecting seasonal distribution of C₄/C₃ vegetation in catchments. This could be a useful tool for distinguishing between catchments for GIS studies, and long term planning for ecological management of catchment areas.     

Transition from arid to hyper-arid environment in the southern Levant deserts as recorded by early Pleistocene cummulic Aridisols

The time at which deserts established their current arid or hyper-arid conditions remains a fundamental question regarding the history of Earth. Cosmogenic isotope exposure ages of desert pavement and welded, calcic–gypsic–salic Reg soils that developed on relatively flat alluvial surfaces ～2 Ma ago in the Negev Desert indicate long geomorphic stability under extremely dry conditions. Over a short interval during their initial stage of development between 1–2 Ma, these cumulative soils are characterized by calcic soils reaching maximum stage III of carbonate morphology. This interval is the only period when calcic soil horizons formed on stable abandoned alluvial surfaces in the southern Negev Desert. Since ～1 Ma pedogenesis changed toward more arid soil environment and the formation of gypsic–salic soil horizons that were later followed by dust accumulation. The dichotomy of only moderately-developed calcic soil (stages II–III) during a relatively long time interval (10⁵–10⁶ years) indicates an arid environment that does not support continuous development but only occasional calcic soil formation. The very low δ¹⁸O and relatively high δ¹³C values of these early pedogenic carbonates support soil formation under arid climatic conditions. Such an environment was probably characterized by rare and relatively longer duration rainstorms which occasionally allowed deeper infiltration of rainwater and longer retention of soil moisture. This, in turn enabled the growth of sparse vegetation that enhanced deposition of pedogenic carbonate. At ～1 Ma these rare events of slightly wetter conditions ceased and less atmospheric moisture reached the southern Negev Desert leading to deposition of soluble salts and dust deposited in the soils. The combination of long-term hyperaridity, scarcity of vegetation and lack of bioturbation, salts cementation, dust accumulation and tight desert pavement cover, has protected the surfaces from erosion forming one of the most remarkably stable landscapes on Earth, a landscape that essentially has not eroded, but accumulated salt and dust for more than 10⁶ yr.     

Long-term biogeochemical cycling in agroecosystems inferred from C, C and N

We investigated C and N cycling in long-term agroecological experiments initiated over 50 years ago at a cool, semi-arid site on the North American Great Plains. We used isotopes at natural abundance to trace C and N exchange between soils and plants in contrasting cropping systems. Both ¹³C and ¹⁴C indicated that the soil organic matter was isotopically distinct from current plant inputs, suggesting that recently added plant C was cycling independently of much of the soil C pool. For tracing recent C flows, bomb-¹⁴C was more sensitive than ¹³C, and increased more in high – than in low – yielding systems. Analysis of ¹⁵N in plant tissues, as an index of ¹⁵N in actively cycling soil N, suggested that biological and industrial N fixation both tended to decrease plant ¹⁵N, whereas livestock manure addition increased ¹⁵N abundance. Collectively, the data suggest that soil organic matter is kinetically heterogeneous, so that a majority of soil C and N inputs and outputs exchange with only the small pool of soil organic matter that is actively cycling. Consequently, recently photosynthesized C and deposited N may not readily enter the old, stable fractions of soil organic matter. Practices to retain CO₂ from the atmosphere and prevent leakage of reactive N to non-agricultural systems should therefore focus on management of this active pool.     

Do Stable Isotope Data from Calcrete Record Late Pleistocene Monsoonal Climate Variation in the Thar Desert of India?

Late Pleistocene terrestrial climate records in India may be preserved in oxygen and carbon stable isotopes in pedogenic calcrete. Petrography shows that calcrete nodules in Quaternary sediments of the Thar Desert in Rajasthan are pedogenic, with little evidence for postpedogenic alteration. The calcrete occurs in four laterally persistent and one nonpersistent eolian units, separated by colluvial gravel. Thermoluminescence and infrared- and green-light-stimulated luminescence of host quartz and feldspar grains gave age brackets for persistent eolian units I–IV of ca. 70,000–60,000, ca. 60,000–55,000, ca. 55,000–43,000, and ca. 43,000–25,000 yr, respectively. The youngest eolian unit (V) is <10,000 yr old and contains no calcrete. Stable oxygen isotope compositions of calcretes in most of eolian unit I, in the upper part of eolian unit IV, and in the nonpersistent eolian unit, range between −4.6 and −2.1‰ PDB. These values, up to 4.4‰ greater than values from eolian units II and III, are interpreted as representing nonmonsoonal¹⁸O-enriched “normal continental” waters during climatic phases when the monsoon weakened or failed. Conversely, 25,000–60,000-yr-old calcretes (eolian units II and III) probably formed under monsoonal conditions. The two periods of weakened monsoon are consistent with other paleoclimatic data from India and may represent widespread aridity on the Indian subcontinent during isotope stages 2 and 4. The total variation in δ¹³C is 1.7‰ (0.0–1.7‰), and δ¹³C covaries positively and linearly with δ¹⁸O. δ¹³C values are highest when δ¹⁸O values indicate the most arid climatic conditions. This is best explained by expansion of C₄grasses at the expense of C₃plants at low latitudes during glacial periods when atmosphericpCO₂was lowered. C₄dominance was overridingly influenced by global change in atmosphericpCO₂despite the lowered summer rainfall.     

A map of autumn precipitation for the third millennium BP in the Eastern Iberian Peninsula from charcoal carbon isotopes

Carbon isotope composition (δ¹³C) in tree-rings has become routinely used in palaeoclimatic research for the assessment of changes in plant water availability in seasonally dry climates. However, the distribution of long tree-ring records around the world is very limited. Alternatively, the original climate signal of wood δ¹³C is well preserved in fossil charcoal and, accordingly, charcoal δ¹³C can be used to quantify past changes in water availability (e.g. precipitation). We report a case study on spatial palaeoclimate reconstruction which aims to characterize the transition between Bronze and Iron Ages, the so-called Iron Age Cold Epoch (ca. 900–300 BCE), using charcoals of Quercus ilex/coccifera from a set of 11 contemporary archaeological sites of eastern Spain. Climatic inferences were obtained after calibrating a linear model predicting seasonal precipitation from δ¹³C of Q. ilex wood samples obtained across a rainfall gradient. The best regression model corresponded to September–December (autumn) precipitation (P_aut), in agreement with the fact that Q. ilex is able to exploit previous-year water reserves thanks to very effective water uptake. Subsequently, we estimated P_aut from the δ¹³C of fossil charcoal to infer spatial patterns in water availability. Overall, estimated past P_aut was about 19% higher (296 mm) than present-time values averaged across archaeological sites (249 mm). However, a clear geographic pattern of differences in precipitation could be observed in which the inner continental regions of eastern Spain were characterized by more humid conditions in the past, whereas the coastal strip of the Mediterranean Sea barely differed in past and present P_aut values. The quite uniform distribution of archaeological sites over eastern Spain allowed development of contour maps of absolute and relative (to present) past P_aut using gridded interpolation methods implemented in a GIS, highlighting the potential of this approach for reconstructing high-resolution spatial patterns of past climate.     

Human impacts, climate change, and aquatic ecosystem response during the past 2000 yr at Lake Wandakara, Uganda

Analyses of carbon and hydrogen isotope ratios of terrestrial leaf waxes and the carbon and nitrogen abundance, ratio, and isotopic composition of bulk sediments from Lake Wandakara, a crater lake in western Uganda, East Africa, document human and climatic controls on the aquatic system and on the surrounding terrestrial vegetation during the past two millennia. Our data indicate that Wandakara was a relatively stable, productive lake surrounded by C₃ vegetation from AD 70 to 1000. Abrupt changes in the δ¹³C of terrestrial leaf waxes indicate a series of abrupt shifts in the relative abundance of C₃ and C₄ vegetation caused by a combination of climate change and human activities around Wandakara beginning at AD 1000. Abrupt shifts in bulk sediment organic geochemistry, particularly C/N ratios and δ¹⁵N, indicate that human activities at this time caused permanent changes in the limnology of Lake Wandakara, including eutrophication. Our results suggest that the biogeochemistry of Lake Wandakara was more sensitive to shifting human impacts than to climate variations during the past millennium, highlighting the importance of understanding the intensity of pre-colonial human impacts on Africa's aquatic ecosystems.     

12,000-Year, preliminary results of the stable nitrogen and carbon isotope record from the Empakai Crater lake sediments, Northern Tanzania

The stable isotope compositions of organic carbon and nitrogen, the contents of organic carbon and nitrogen and C/N ratios for two cores recovered from the Empakai Crater at water depths of 11 and 20 m are used to document climatic changes in northern Tanzania. Eight ¹⁴C AMS dates determined on total organic matter (OM) indicate that the sedimentation rate in this lake is about 30 cm/ka for the late Pleistocene to early Holocene period. There are differences in the δ¹³C values of organic carbon between the two cores, which may be a result of differences in location from the present shoreline and of different water depths. In the deeper-water core the δ¹³C values show a general downcore decrease to the base of the core with a sharp change to lower values of about 4‰ at a depth of 100 cm (8.7 ka). The general trend of downcore decrease in ¹³C values can be attributed either to a systematic decrease in the relative proportion of C₄ type of OM, owing to an increase in precipitation and change in vegetation cover from grassland to forest, or to utilization of isotopically enriched carbon during photosynthesis. The δ¹⁵N values show a general downcore increase with again a sharp change of about 5‰ to lower values at about 8.7 ka. A sharp change of about 5‰ and 4‰ to more depleted values at a depth of 100 cm of both ¹⁵N and ¹³C, respectively, suggests either hiatus or abrupt change in climatic condition from wetter conditions to drier conditions. There is enhanced preservation of OM in the lake as depicted by high mean values of organic carbon and nitrogen at both sites.     

Stable carbon and oxygen isotope investigation in historical lime mortar and plaster – Results from field and experimental study

Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ¹³C_matrix and δ¹⁸O_matrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ¹⁸O_matrix = 0.61 · δ¹³C_matrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO₂ into alkaline Ca(OH)₂ solutions shows a similar relationship, δ¹⁸O_calcite = 0.67 · δ¹³C_calcite − 6.4 (VPDB). Both relationships indicate that the ¹³C/¹²C and ¹⁸O/¹⁶O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO₂ from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO₂ (δ¹³C_matrix ≈  −25‰ and δ¹⁸O_matrix ≈ −20‰). As calcite formation continued the remaining gaseous CO₂ is subsequently enriched in ¹³C and ¹⁸O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H₂O, e.g. evaporation, the source of CO₂, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for ¹⁴C dating.     

The formation of caliche in soils of the Mojave Desert,California

Radiocarbon and ²³⁰Th-²³⁴U dates of calcic horizons from calciorthid soil profiles in the Mojave Desert were used to calculate the rate of deposition of pedogenic CaCO₃. A major period of CaCO₃ deposition appears to have occurred about 20000 yBP forming calcic horizons below 100-cm depth during a climatic regime with greater effective rainfall than in the present. The overall rate of deposition has been 1.0 to 3.5 g CaCO₃/m²/yr during soil formation. This rate is consistent with present-day rates, assuming that the atmospheric deposition of Ca limits the process. Stable isotope ratios in calcic horizons indicate that CaCO₃ precipitated from a soil environment with CO₂ of ? 15.5%. ${}^{13}\text{C}{}^{12}\text{C}$ (vs. PDB) and H₂O of + 2.0%. ${}^{18}\text{O}{}^{16}\text{O}$ (vs. SMOW). These values suggest that CaCO₃ precipitates when seasonal drought simultaneously lowers soil pore pCO₂ and enriches soil water ¹⁸O by evaporation. The role of soil calcic horizons in the global geochemical cycle of carbon is discussed.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

Fe(CO3)OH in goethite from a mid-latitude North American Oxisol: estimate of atmospheric CO2 concentration in the Early Eocene “climatic optimum”

Measured mole fractions (X) and δ¹³C values of the Fe(CO₃)OH component in pedogenic goethite from a mid-latitude Oxisol of Early Eocene age (≈52 Ma B.P.) range from 0.0014 to 0.0064 and −20.1 to −15.4‰, respectively. These values of X imply that concentrations of CO₂ gas in the paleosol were ≈7400 to ≈34,000 ppm. δ¹³C and 1/X are correlated and define a linear, soil-CO₂ diffusive mixing line with a positive slope. Such positive slopes are characteristic of mixing of two isotopically distinct CO₂ endmembers (atmospheric CO₂ and CO₂ from oxidation of soil organic matter). From the intercept of the mixing line, it is calculated that the δ ¹³C value of organic matter in the ancient soil was ≈−28.0‰. The magnitude of the slope implies an Early Eocene atmospheric CO₂ concentration of ≈2700 ppm.A simple model for forest soils suggests that a “canopy effect” may cause atmospheric CO₂ concentrations deduced from pedogenic minerals to underestimate the actual concentrations of atmospheric CO₂. If a significant forest canopy were present at the time of formation of pedogenic goethite in the Ione Fm, the concentration of 2700 ppm calculated for atmospheric CO₂ could be slightly low, but the underestimate is expected to be < ≈300 ppm (i.e., less than the analytical uncertainty). The relatively high concentration of 2700 ppm inferred for atmospheric CO₂ at ≈52 Ma B.P. would have been coincident with the Early Eocene climatic optimum. This result seems to support the case for an important role for variations of atmospheric CO₂ in the modification of global paleoclimate.     

Stable carbon isotope characteristics of different plant species and surface soil in arid regions

The stable carbon isotope composition in surface soil organic matter (δ¹³Csoil) contains integrative information on the carbon isotope composition of the standing terrestrial plants (δ¹³Cleaf). In order to obtain valuable vegetation information from the δ¹³C of terrestrial sediment, it is necessary to understand the relationship between the δ¹³C value in modern surface soil and the standing vegetation. In this paper, we studied the δ¹³C value in modern surface soil organic matter and standing vegetation in arid areas in China, Australia and the United States. The isotopic discrepancy between δ¹³Csoil and δ¹³Cleaf of the standing dominant vegetation was examined in those different arid regions. The results show that the δ¹³Csoil values were consistently enriched compared to the δ¹³Cleaf. The δ¹³Cleaf values were positively correlated with δ¹³Csoil, which suggests that the interference of microorganisms and hydrophytes on the isotopic composition of surface soil organic matter during soil organic matter formation could be ignored in arid regions. The averaged discrepancy between δ¹³Csoil and δ¹³Cleaf is about 1.71%in Tamarix L. in the Tarim Basin in China, 1.50% in Eucalytus near Orange in Australia and 1.22% in Artemisia in Saratoga in the United States, which are different from the results of other studies. The results indicate that the discrepancies in the δ¹³C value between surface soil organic matter and standing vegetation were highly influenced by the differences in geophysical location and the dominant species of the studied ecosystems. We suggest that caution should be taken when organic matter δ¹³C in terrestrial sediment is used to extract paleovegetation information (C₃/C₄ vegetation composition), as the δ¹³C in soil organic matter is not only determined by the ratio of C₃/C₄ species, but also profoundly affected by climate change induced variation in the δ¹³C in dominant species.     

Evidence for Holocene environmental changes in the northern Fertile Crescent provided by pedogenic carbonate coatings

Holocene environmental changes in the northern Fertile Crescent remain poorly understood because of the scarcity of local proxy records in the region. In this study we investigated pedogenic (soil-formed) carbonate coatings on stones at the Pre-Pottery Neolithic site Göbekli Tepe as an indicator of local early-mid Holocene environmental changes. The ¹⁴C ages and stable isotopic composition of carbon and oxygen in thin (0.2–0.3 mm thick) pedogenic carbonate lamina indicate two main periods of coating formation: the early-Holocene (ca. 10000–6000 cal yr BP) and the mid-Holocene (ca. 6000–4000 cal yr BP). During the first period, there was an inverse relationship between δ¹³C and δ¹⁸O curves: a decrease in δ¹³C values coincide with an increase in δ¹⁸O values. For this period a trend towards higher temperatures is suggested. In the mid-Holocene, the mean rate of coating growth was 2–3 times higher than in the early Holocene. Both δ¹³C and δ¹⁸O reached their maximum values during this time and the direction of changes of the δ¹³C and δ¹⁸O curves became similar. The combination of data suggests that this period was the most humid in the Holocene and on average warmer than the early Holocene. At ca. 4000 cal yr BP secondary accumulation of carbonate ceased, presumably reflecting a shift to a more arid climate.     

Physico-chemical environment of pedogenic carbonate formation in Devonian vertic palaeosols, central Appalachians, USA

The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn²⁺ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe²⁺ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in ¹³C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO₂. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO₂; the use of nodule compositions may result in overestimation of P_CO2 by as much as 30%.     

Higher plant vegetation changes during Pliocene sapropel formation

The δ¹³C values of higher plant wax C_27–33 n-alkanes were determined in three, time-equivalent Pliocene (2.943 Ma) sapropels and homogeneous calcareous ooze from three different sites forming an east-west transect in the eastern Mediterranean Basin in order to study the composition of the vegetation on the continents surrounding the Mediterranean Sea. A two-end member mixing model transformed the measured δ¹³C values into the contribution of C₄ plants to the terrestrial vegetation. These calculations indicated a high C₄ plant contribution (i.e. 40–50%) in the periods just before and just after sapropel formation. During sapropel deposition the C₄ plant contribution increased by up to 20% at all sites. This is interpreted to record the increased overall plant coverage of the Mediterranean borderlands resulting from the change in formerly barren desert areas into C₄ grass-dominated savannahs as a response to the wetter climate during sapropel deposition. Enhanced accumulation rates (ARs) of long-chain n-alkanes (C_27–33) and n-alkan-1-ols (C_26–30) towards the middle of the sapropel in concert with a decrease in the Ti/Al ratio confirm an increased delivery of terrigenous organic matter at all sites. These biomarkers were probably predominantly fluvially transported to the Mediterranean Sea, not only by the Nile but by fossil wadi river systems on the northern African continent.