A 53 year seasonally resolved oxygen and carbon isotope record from a modern Gibraltar speleothem: Reconstructed drip water and relationship to local precipitation

The response of a climate proxy against measured temperature, rainfall and atmospheric circulation patterns at sub-annual resolution is the ultimate test of proxy fidelity but very few data exist showing the level of correspondence between speleothem climate proxies and the instrumental climate record. Cave sites on the Gibraltar peninsula provide a unique opportunity to calibrate speleothem climate proxies with the longest known available precipitation isotopes and instrumental records. An actively growing speleothem sampled from New St. Michaels Cave in 2004 is composed of paired laminae consisting of light columnar calcite and a darker microsparitic calcite. Stable isotope analysis of samples micromilled in 100 μm steps at the equivalent of bi-monthly intervals reveals fabric-correlated annual cycles in carbon isotopes, oxygen isotopes and trace elements responding to seasonal changes in cave microclimate, hydrology and ventilation patterns. Calcite δ¹³C values reach a minimum in the light columnar fabric and evidence from trace element behaviour and cave monitoring indicates that this grows under cave ‘winter’ conditions of highest pCO₂, whereas the dark microsparitic calcite, characterised by elevated δ¹³C and δ¹⁸O values grows under low ‘summer’ pCO₂ conditions. Drip water δ¹³C_DIC reaches a minimum in March–April, at which time the attenuated δ¹⁸O signal becomes most representative of winter precipitation. An age model based on cycle counting and the position of the ¹⁴C bomb carbon spike yields a precisely dated winter oxygen isotope proxy of cave seepage water for comparison with the GNIP and instrumental climate record for Gibraltar. The δ¹⁸O characteristics of calcite deposited from drip water representing winter precipitation for each year can be derived from the seasonally resolved record and allows reconstruction of the δ¹⁸O drip water representing winter precipitation for each year from 1951–2004. These data show an encouraging level of correspondence (r² = 0.47) with the δ¹⁸O of rainfall falling each year between October and March and on a decadal scale the δ¹⁸O of reconstructed winter drip water mirrors secular change in mean winter temperatures.     

Can biomass burning produce a globally significant carbon-isotope excursion in the sedimentary record?

Negative carbon-isotope excursions have been comprehensively studied in the stratigraphic record but the discussion of causal mechanisms has largely overlooked the potential role of biomass burning. The carbon-isotopic ratios (δ¹³C) of vegetation, soil organic matter and peat are significantly lower than atmospheric carbon dioxide (CO₂), and thereby provide a source of low ¹³C CO₂ when combusted. In this study, the potential role of biomass burning to generate negative carbon isotope excursions associated with greenhouse climates is modeled. Results indicate that major peat combustion sustained for 1000 yr increases atmospheric CO₂ from 2.5× present atmospheric levels (PAL) to 4.6× PAL, and yields a pronounced negative δ¹³C excursion in the atmosphere ( 2.4‰), vegetation ( 2.4‰) and the surface ocean ( 1.2‰), but not for the deep ocean ( 0.9‰). Release of CO₂ initiates a short-term warming of the atmosphere (up to 14.4 °C, with a duration of 1628 yr), which is consistent with the magnitude and length of an observed Toarcian excursion event. These results indicate that peat combustion is a plausible mechanism for driving negative δ¹³C excursions in the rock record, even during times of elevated pCO₂.     

Late Pleistocene to Holocene composite speleothem O and C chronologies from South Island, New Zealand—did a global Younger Dryas really exist?

Oxygen and carbon data from eight stalagmites from northwest South Island are combined to produce composite records of δ¹⁸O and δ¹³C from 23.4 ka to the present. The chronology is anchored by 43 thermal ionization mass spectrometry (TIMS) uranium series ages. Delta ¹⁸O values are interpreted as having a first order positive relationship to temperature, but also to be influenced by precipitation in a complex manner. Delta ¹³C is interpreted as responding negatively to increases in atmospheric CO₂ concentration, biological activity and precipitation amount.

Six climatic phases are recognized. After adjustment of 1.2‰ for the ice volume effect, the δ¹⁸O record between 23 and 18 ka varies around −3.72‰ compared to the Holocene average of −3.17‰. Late-glacial warming commenced between 18.2 and 17.8 ka and accelerated after 16.7 ka, culminating in a positive excursion between 14.70 and 13.53 ka. This was followed by a significant negative excursion between 13.53 and 11.14 ka of up to 0.55‰ depth that overlapped the Antarctic Cold Reversal (ACR) and spanned the Younger Dryas (YD). Positive δ¹⁸O excursions at 11.14 ka and 6.91–6.47 ka represent the warmest parts of the Holocene. The mid-Holocene from 6 to 2 ka was marked by negative excursions that coincide with increased glacial activity in the South Island. A short positive excursion from 0.71 to 0.57 ka was slightly later than the Medieval Warm Period of Europe.

Delta ¹³C values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in δ-values after 17.79 ka probably corresponds to an increase in atmospheric CO₂ concentration, biological activity and wetness at the end of the Last Glaciation, but the reversal identified in the δ¹⁸O record from 13.53 to 11.14 ka was not reflected in δ¹³C changes. The lowest δ¹³C values coincided with the early Holocene climatic suboptimum when conditions were relatively wet as well as mild.

Major trends in the δ¹⁸O_c record are similar to the Northern Hemisphere, but second order detail is often distinctly different. Consequently, at the millennial scale, a more convincing case can be made for asymmetric climatic response between the two hemispheres rather than synchronicity.     

Ages and composition of gas trapped in Allan Hills and Byrd core ice

Gas is extracted from large (6–31 kg) Antarctic ice samples to obtain sufficient CO₂ for¹⁴C measurements with small low-level proportional counters. The¹⁴C ages of Byrd core ice are in accord with glaciological estimates ranging from (2.2_−1.1^+1.4)×10³ yr at 271 m depth to more than 8 × 10³ yr at 1071 m depth. The CO₂ abundances in gas extracted from Byrd core ice range from 0.0216 to 0.051%, with below present-day atmosphere CO₂ abundances for ice from 1068 and 1469 m depths. The CO₂ abundance in gas from Allan Hills surface ice samples ranges between four and six times the atmospheric value and the CO₂ had a specific activity three times that of contemporary carbon. A possible explanation for the anomalously high specific activity is surface melting with the incorporation into CO₂ of¹⁴C produced by cosmic ray spallation of oxygen in ice. The CO₂ abundance in gas extracted from subsurface Allan Hills ice ranged from 0.030 to 0.065%, and the specific activities are below contemporary carbon, indicating ages greater than 5×10³ yr. The¹⁸O/¹⁶O ratio of oxygen in the trapped gas is the same as that of atmospheric oxygen and differs markedly from the¹⁸O/¹⁶O ratio in the ice. The O₂, N₂, and Ar abundances and isotopic compositions are similar to those in contemporary air, except for positive¹⁵N/¹⁴N ratios in a few samples.     

Carbon isotopes in submarine basalts

High-sensitivity stepped extraction reveals two isotopically distinct forms of carbon in submarine basalt glasses: an isotopically light carbon component released by combustion from 200 to 600°C and an isotopically heavy CO₂ liberated from vesicles (magmatic carbon) from 600 to 1200°C. The δ¹³C_PDB of the low release temperature carbon varies from −24 to −30‰ and is believed to be surficial organic contamination. A survey of various types of oceanic glasses demonstrates that the δ¹³C of magmatic CO₂ varies from −4.2 to −7.5‰ in mid-ocean ridge basalt (MORB), from −2.8 to −6.7‰ in glasses from Hawaii and Explorer Seamount and from −7.7 to −16.3‰ in glasses from the Scotia Sea and Mariana Trough. Magmatic CO₂ in back-arc basin basalts (BABB) is on average 5‰ lighter than equivalent CO₂ in MORB and can be explained by the mixing in the source regions for BABB magmas of juvenile (MORB-like) CO₂ with an organic carbon component from subducted pelagic sediments. It is inferred that significant amounts of pelagic carbonate carbon (δ¹³C 0‰) must be recycled into the mantle.     

Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO₂–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (100°C) aquifer of mixed marine–meteoric water. The measured ³He/⁴He ratios and δ¹³C of both the free gases (4.5–7.3 R_a and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 R_a and −7.1 to −0.9‰), together with their covariation with the He/CO₂ ratio, constrain a ³He/⁴He ratio of 7.3±0.1 R_a and a δ¹³C of ca. −4‰ for the magmatic end-member. These latter are best preserved in fluids emanating inside the active caldera of Pantelleria, in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir. Outside the caldera, the magmatic component is more affected by air dilution and, at a few sites, by mixing with either organic carbon and/or radiogenic ⁴He leached from the U–Th-rich trachytic host rocks of the aquifer. Pantelleria magmatic end-member is richer in ³He and has a lower (closer to MORB) δ¹³C than all fluids yet analyzed in volcanic regions of Italy and southern Europe, including Mt. Etna in Sicily (6.9±0.2 R_a, δ¹³C=−3±1‰). This observation is consistent with a south to north increasing imprint of subducted crustal material in the products of Italian volcanoes, whose He and C (but also O and Sr) isotopic ratios gradually evolve towards crustal values northward of the African–Eurasian plate collision boundary. Our results for Pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or ‘less contaminated’, ³He-richer mantle source beneath the Sicily Channel rift zone. The lower than MORB ³He/⁴He ratio but higher than MORB CO₂/³He ratio of Pantelleria volatile end-member are compatible with petro-geochemical evidence that this mantle source includes an upwelling HIMU–EM1-type asthenospheric plume component whose origin, according to recent seismic data, may be in the lower mantle.     

Production of selected cosmogenic radionuclides by muons: 2. Capture of negative muons

We have determined the production yields for radionuclides in Al₂O₃, SiO₂, S, Ar, K₂SO₄, CaCO₃, Fe, Ni and Cu targets, which were irradiated with slow negative muons at the Paul Scherrer Institute in Villigen (Switzerland). The fluences of the stopped negative muons were determined by measuring the muonic X-rays. The concentrations of the long-lived and short-lived radionuclides were measured with accelerator mass spectrometry (AMS) and γ-spectroscopy, respectively. Special emphasis was put on the radionuclides ¹⁰Be, ¹⁴C and ²⁶Al produced in quartz targets, ²⁶Al in Al₂O₃ and S targets, ³⁶Cl in K₂SO₄ and CaCO₃ targets, and ⁵³Mn in Fe₂O₃ targets. These targets were selected because they are also the naturally occurring target minerals for cosmic ray interactions in typical rocks. We also present results of calculations for depth-dependent production rates of radionuclides produced after cosmic ray μ⁻ capture, as well as cosmic ray-induced production rates of geologically relevant radionuclides produced by the nucleonic component, by μ⁻ capture, by fast muons and by neutron capture.     

Compound-specific radiocarbon dating of Ross Sea sediments: A prospect for constructing chronologies in high-latitude oceanic sediments

We present an overview of the problems relating to the development of sedimentary chronologies for Antarctic margin sediments, and review the recent application of compound-specific radiocarbon dating methods for resolving them. Radiocarbon dating of solvent-extractable, short-chain (C₁₄, C₁₆, and C₁₈) fatty acids isolated from surface sediments of the Ross Sea, Antarctica, revealed their ages to be consistent with that of the modern dissolved inorganic carbon (DIC) reservoir age (pre-bomb, Δ¹⁴C≈−150‰; post-bomb, Δ¹⁴C≈−100‰) in this region. This contrasts sharply with the radiocarbon ages of bulk organic matter in the corresponding sediments are substantially older (Δ¹⁴C=−298‰ to −712‰). Furthermore, the radiocarbon ages of these fatty acids progressively increase with the core depth. These results clearly show a utility of the compound-specific radiocarbon dating for developing sediment chronologies in the Antarctic margin sediments. This approach is potentially applicable to Arctic Ocean, as well as other areas of Southern Ocean where similar interferences by fossil or pre-aged carbon inputs have hindered the progress in the development of late Quaternary paleoceanographic records.     

Solar modulation of cosmogenic nuclide production over the last millennium: comparison between C and Be records

For about the last 30 years it has been recognized that the high frequency component of the tree rings ¹⁴C/¹²C record is dominated by the modulation of the cosmic ray flux by the solar wind. In particular, it has been demonstrated that the three most recent periods of low sunspot occurrence were characterized by high values of atmospheric ¹⁴C/¹²C. During the last millennium other periods of high ¹⁴C/¹²C values were observed but their solar origin is still debatable. In the present work we compare these fluctuations with an independent record of cosmogenic ¹⁰Be measured in ice from the South Pole to check the solar origin of the observed ¹⁴C/¹²C variations. In order to compare quantitatively the results obtained on ¹⁰Be and ¹⁴C, it is necessary to take into account the different behaviour of these two cosmogenic isotopes, and especially the damping effect of the carbon cycle in the case of ¹⁴C. As an input to a 12-box numerical model we used the relative fluctuations of the ¹⁰Be concentrations record measured in South Pole ice and converted it into a synthetic ¹⁴C record. We took into account the fact that ¹⁰Be modulation is enhanced in polar regions due to the orientation of the geomagnetic field. As expected, the fluctuations of the modelled ¹⁴C record are much smaller (a factor of 20) than those observed for the raw ¹⁰Be record. In addition, the variations are smoother and shifted in time by a few decades. The ¹⁰Be-based ¹⁴C variations closely resemble the ¹⁴C measurements obtained on tree rings (R = 0.81). In particular, it is easy to identify periods of maximal ¹⁴C/¹²C which correspond to solar activity minima centred at about 1060, 1320 (Wolf), 1500 (Spörer), 1690 (Maunder) and 1820 (Dalton) yr A.D. Cross-correlation calculations suggest that there is no significant lag between the ¹⁰Be-based ¹⁴C and the tree-ring ¹⁴C records. Our study strongly suggests the dominance of the solar modulation on the cosmonuclide production variations during the last millennium.     

Using SPIRAL (Single Pollen Isotope Ratio AnaLysis) to estimate C3- and C4-grass abundance in the paleorecord

C₃ and C₄ grasses differ greatly in their responses to environmental controls and influences on biogeochemical processes (e.g. water, carbon, and nutrient cycling). Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. Stable carbon isotopic analysis of individual grains of grass pollen using a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer holds promise for improving C₃ and C₄ grass reconstructions. This technique, SPIRAL (Single Pollen Isotope Ratio AnaLysis), has only been evaluated using pollen of known C₃ and C₄ grasses. To test the ability of SPIRAL to reproduce the abundance of C₃ and C₄ grasses on the landscape, we measured δ¹³C values of > 1500 individual grains of grass pollen isolated from the surface sediments of ten lakes in areas that span a large gradient of C₃- and C₄-grass abundance, as determined from vegetation surveys. Results indicate a strong positive correlation between the δ¹³C-based estimates of % C₄-grass pollen and the abundance of C₄ grasses on the landscape. The % C₄-grass pollen slightly underestimates the actual abundance of C₄ grasses at sites with high proportions of C₄ grasses, which can be corrected using regression analysis. Comparison of the % C₄-grass pollen with C/N and δ¹³C measurements of bulk organic matter illustrates the distinct advantages of grass-pollen δ¹³C as a proxy for distinguishing C₃ and C₄ shifts within the grass family. Thus SPIRAL promises to advance our understanding of grassland ecology and evolution.     

Accretion, core formation, H and C evolution of the Earth and Mars

Recent understandings of planetary accretion have suggested that accumulation of a small number of large planetesimals dominates intermediate to final growth stages of the terrestrial planets, with impact velocity high enough to induce extensive melting of the planetesimal and target materials, resulting in formation of a large molten region in which gravitational segregation of silicate and metal, that is, core formation proceeds. In case of homogeneous accretion, volatiles contained in each planetesimal are likely subjected to partitioning among gas, silicate melt, and molten metallic iron at significantly high temperatures and pressures in such a massive molten region. Each phase would subsequently form the proto-atmosphere, -mantle, or-core, respectively. Such chemical reprocessing of H and C associated with core formation, which is followed by both degassing from mantle and atmospheric escape, may result in a diverse range of H₂O/CO₂ in planetary surface environments, which mainly depends on the H and C content relative to metallic iron in planetary building stones. This may explain inferred difference in volatile distribution between the Earth's (relatively H₂O-rich, CO₂-poor) and the martian (H₂O-poor, CO₂-rich) surface environments. Such volatile redistribution may be systematically described by using the retentivity of H₂O, ξ, defined as follows: ξ = 1 − ([CO]⁰ + 2[CH₄]⁰ + 2[C(gr)]⁰)/[H₂O]⁰, where [i]⁰ represents mol number of species i partitioned into non-metallic phases, that is, gas and silicate melt in impact-induced molten region. When ξ > 0.5, relatively H₂O-rich and CO₂-poor surface environment may eventually evolve, although a small portion of H₂O partitioned into the NON=metallic phases are possibly consumed by subsequent chemical reactions with reduced C-species with producing CO₂ and H₂. When ξ< 0.5, on the contrary, H₂O consumption by the above reactions and selective loss of H₂ to space may result in relative H₂O-depleted and CO₂-rich surface environment. Given the building stone composition by the two-component model by Ringwood (1977) and Wänke (1981), ξ is found to decrease with increasing the mixing fraction of the volatile-rich component: ξ > 0.5 for the mixing fraction smaller than about 15–20% and ξ < 0 for the mixing fraction larger than about 20–30%. This is not significantly dependent on temperature and pressure in molten region and H/C ratio in the building stone. The estimated mixing fraction of the volatile-rich component, about 10% for the Earth and 35% for Mars, is consistent with the observed difference in volatile distribution between the surfaces of both planets.     

Ice core record of Be over the past millennium from Dome Fuji, Antarctica: A new proxy record of past solar activity and a powerful tool for stratigraphic dating

The cosmogenic nuclide ¹⁰Be was analyzed by using accelerator mass spectrometry on an ice core drilled at the Dome Fuji station, inland Antarctica, for 700–1900 yr CE. The measured concentration of ¹⁰Be in the Dome Fuji ice core and the derived ¹⁰Be flux show similar fluctuations, with both increasing at known solar-activity minima over the last millennium in agreement with earlier observations of ¹⁰Be and ¹⁴C. Based on the similar nature of the ¹⁰Be flux to the reconstructed ¹⁴C production rate patterns, a ¹⁰Be–¹⁴C correlation age model for the Dome Fuji ice core was successfully constructed. This age model agrees well with the initial version of the tephrochronology of the core. The ¹⁰Be-flux record contains information on variability in the amount of cosmic radiation incident on the atmosphere, which is mainly attributable to high-frequency change in solar activity and low-frequency background intensity adjustment of the geomagnetic field. High-resolution ¹⁰Be analyses of the Dome Fuji ice cores promise to provide potentially important information on the history of cosmic radiation intensity over the past several hundred thousand years.     

Variation in water use efficiency and δC levels in Eucalyptus grandis clones

This study aimed to determine whether the δ¹³C levels in the foliage and twigs of four Eucalyptus grandis clones were related to their water use efficiency (WUE). This relationship has previously been demonstrated in a number of herbaceous species but not in mature trees. The study involved accurate measurements of tree trunk growth and water use over a period of 4 months, with subsequent isotopic analysis of mature foliage from the north and south side of the canopy, and young leaves from the top of the canopy.

The water use efficiencies were found to vary from 5.97 × 10⁻³ to 12.3 × 10⁻³ m³ m⁻³. Significant differences were observed between clonal-mean water use efficiencies averaged over six sampling periods. The average δ¹³C of the mature and young foliage was found to be significantly correlated with WUE. However, the correlation was weak, suggesting that the relationship between δ¹³C and WUE is more complex in trees than suggested in the literature on crop plants. It is suggested that differences between sample trees in carbon allocation and leaf-to-air vapour pressure deficits may account for the poor correlation between δ¹³C and WUE in the four E. grandis clones studied.     

Groundwater recharge and palaeoclimate in the Sirte and Kufra basins, Libya

Stable and radio-isotope results (C, H, O) for groundwaters from the Sirte and northern Kufra basins are used to determine the recharge history during the Holocene and late Pleistocene. Radiocarbon ages have been corrected on the basis of their stable carbon isotope ratios and on environmental samples from the areas, and two groups may be recognised: (1) low ¹⁴C activity groundwaters (13000–34000 yr. BP) with δ ¹³C-5.6 to −11.7‰; and (2) higher ¹⁴C activity groundwaters (5000–7800 yr. BP) enriched in ¹³C up to δ ¹³C = −3.2‰. There is a general correlation of age with depth.

A well defined freshwater (< 50 mg/l Cl⁻) channel can be traced within the aquifer for some 130 km through the region, which is considered to represent recharge from a former wadi. This water with an age of ± 7800 yr. BP is chemically and isotopically distinct from the regional groundwaters and provides direct evidence of a significant recharge event during the Holocene.

The stable isotope (O and H) composition of groundwater from the Kufra and Sirte basins are all related by an evaporative line with slope δ D = 4.5δ ¹³O − 35 with an intercept on the meteoric line of -11‰. This suggests a recharge source continuing into the Holocene from air masses, analogous to current heavy monsoon rain derived from south of the Sahara. The spatial and temporal distribution of groundwaters in relation to the evaporative line suggests a progressive change in character of the recharge which is controlled by a shift towards strongly convective rainfall during the Holocene.

The direct hydrogeological and geochemical evidence supports climatic models proposed by several workers in which discrete humid episodes during the Holocene are inferred.     

Organic carbon isotope geochemistry of clayey deposits and their associated porewaters, southern Alberta

The organic carbon cycle of slowly permeable, clayey glacial till deposits in the Western Interior Great Plains, southern Alberta, was investigated by examining the relationship between solid organic matter (SOM) in the till sediments and dissolved organic carbon (DOC) in the till porewaters. Geochemically, the tills can be divided into two distinct zones: an upper oxidized (low SOM) till zone, and a lower unoxidized (high SOM) till zone. Till porewaters in both zones are characterized by high DOC contents. Radiocarbon dating and comparison of SOM and DOC fractions suggest DOC in the deep unoxidized zone originated during deglaciation, and is probably representative of groundwater ages in this till zone. In the oxidized zone, DOC originates from variable mixtures of soluble organic matter emplaced during deglaciation, and Cretaceous age coal fragments in this till zone. SOM in the upper till zone was mainly oxidized to CO₂ gas during lowered water table conditions of the Altithermal climatic period. The subsurface production of fossil CO₂ gas has serious implications for using the conventional dissolved inorganic carbon (DIC) ¹⁴C groundwater dating method in these clayey till porewaters.     

Accurate chronological construction for two young stalagmites from the tropical South Pacific

Modern to Holocene tropical Pacific stalagmites are commonly difficult to date with the U-series, the most commonly used dating method for speleothems. When U-series does not provide robust age models, due to multiple sources of ²³⁰Th or little U, radiocarbon is, potentially, the best alternative. The ¹⁴C content of two stalagmites (Pu17 and Nu16) collected from Pouatea and Nurau caves in the Cook Island Archipelago of the South Pacific were measured to obtain accurate chronology for their most modern parts. The bomb-pulse soil continuum modelling indicates that bomb radiocarbon in Pu17 onsets in 1956 and reaches its maximum in 1966 CE, suggesting a fast transfer of atmospheric carbon to the stalagmite of <1 year. The modelling for Pu17 suggests a 20% contribution from C₁ - an instantaneous carbon source, which renders possible an immediate transfer of atmospheric signal into the cave. Nu16 shows a slower transfer of atmospheric carbon to the stalagmite than Pu17, with bomb radiocarbon onsetting in 1957 CE and peaking in 1972 CE. The less negative δ¹³C values in Nu16 than Pu17, and also the modelling corroborated this, which points out no contribution from the instantaneous carbon source. The radiocarbon age models and laminae counting age models were then spliced to achieve a single master chronology for the top part of each stalagmite. This study is an example of ¹⁴C age modelling combined with visible physical and chemical laminae counting and how it can improve the accuracy and precision of dating for otherwise hard-to-date tropical Pacific speleothems. Such accurate and precise age models pave the way to obtain sub-annually resolved paleoclimate records by further improving the calibration of climate proxy data with the current and instrumental weather parameters.     

The influence of particle composition on thorium scavenging in the NE Atlantic ocean (POMME experiment)

²³⁰Th, ²³²Th and ²³⁴Th were analyzed in sinking particles collected by moored and drifting sediment traps in the NE Atlantic Ocean (POMME experiment) in order to constrain the phase(s) carrying Th isotopes in the water column. It reveals a contrasted behaviour between ²³⁴Th and ²³⁰Th. ²³⁴Th is correlated to the particulate organic carbon suggesting that it is primarily scavenged by organic compounds in the surface waters. ²³⁰Th_xs is correlated with Mn, Ba and the lithogenic fraction that are enriched in small suspended particles and incorporated in the sinking particulate flux throughout the water column. The lack of correlation between ²³⁰Th_xs and CaCO₃ or biogenic silica (bSi) indicates that CaCO₃ and bSi are not responsible for ²³⁰Th scavenging in the deep waters of this oceanic region. ²³⁰Th is generally correlated with the lithogenic content of the trapped material but this correlation disappears in winter during strong atmospheric dust inputs suggesting that lithogenic matter is not directly responsible for ²³⁰Th scavenging in the deep waters or that sufficient time is required to achieve particle–solution equilibration. MnO₂ could be the prevalent ²³⁰Th_xs-bearing phase. The narrow range of K_{d_MnO2}^Th obtained for very contrasted oceanic environments supports a global control of ²³⁰Th_xs scavenging by MnO₂ and raises the possibility that the ²³⁰Th–²³¹Pa fractionation is controlled by the amount of colloidal MnO₂ in seawater.     

Mid-Holocene variability in the marine C reservoir age for northern coastal Papua New Guinea

Changes in oceanic radiocarbon (¹⁴C) reservoir ages through the deglaciation and Holocene can provide important information on ocean circulation as Earth's climate warmed. Here, we present reservoir ages for the western tropical Pacific that span the mid-Holocene transition from less to more frequent El Niño events. Reservoir ages were calculated using paired U–Th and conventional ¹⁴C dating of eight individual fossil coral samples from Koil and Muschu Islands, northern coastal Papua New Guinea (PNG). AMS ¹⁴C and MC-ICPMS U–Th dating of additional samples from six of the fossil corals were used to confirm the TIMS U–Th and conventional ¹⁴C ages. The combined results show average reservoir ages of 185±30 ¹⁴C yr (n=4) for 7220–5850 yr BP compared to 420 ¹⁴C yr for a modern coral from Muschu Island. From 5850 to 5420 yr BP reservoir ages increase to modern values. The relatively young reservoir ages from 7220 to 5850 yr BP are best explained by greater influx of well-equilibrated sub-tropical water from the southern branch of the South Equatorial Current (SEC). This is consistent with strengthening trade winds (facilitating air–sea exchange) and a more northerly position of the Intertropical Convergence Zone thought to have occurred at this time. The transition to more modern-like reservoir ages from 5850 to 5420 yr BP suggests modern oceanic circulation patterns were established during this interval. The onset of modern El Niño activity around this time would have served to enhance the intrusion of ¹⁴C-depleted equatorial waters via the south equatorial branch of the SEC. Overall, the changes in reservoir age presented here for the western tropical Pacific suggest that Holocene changes in the El Niño–Southern Oscillation state of the tropical Pacific resulted in reorganisation of oceanic circulation in this region.     

Quantifying CO2 fluxes from soil surfaces to the atmosphere

Measurements of CO₂ fluxes from ground surface of the atmosphere (soil respiration) are needed to quantify biotic and abiotic reaction rates in unsaturated zones and to gain insight into the importance of these processes on global warming. The use of three techniques (dynamic closed chambers, static chambers, and gradient calculations) to determine soil respiration was assessed by measuring fluxes of microbially produced CO₂ from an unsaturated mesocosm (2.4 m dia.×3.2 m thick) and two unsaturated minicosms (0.58 m dia.×1.2 m thick), one maintained at 18–23 °C (HT) and the other at 5 °C (LT). By injecting known and constant CO₂ fluxes into the bottom of the HT minicosm and measuring the resulting fluxes, it was shown that the dynamic closed chamber (DCCS) technique yielded accurate measurements of fluxes over the range observed from natural unsaturated media. Over this same range, results showed that the concentration gradient method yielded reasonable estimates of fluxes but its accuracy was limited by uncertainties in both the concentration gradient and the gaseous diffusion coefficient in the soil atmosphere. The static chamber method underestimated the actual flux at higher CO₂ fluxes and when adsorption times of >24 h were used.     

Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa

Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO₃²⁻], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO₃, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO₃ export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δ_sed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δ_sed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.