Hilary J. Sloane

The oxygen isotope relationship between the phosphate and structural carbonate fractions of human bioapatite

RATIONALE Oxygen isotope analysis of archaeological human dental enamel is widely used as a proxy for the drinking water composition (δ(18)O(DW)) of the individual and thus can be used as an indicator of their childhood place of origin. In this paper we demonstrate the robustness of structural carbonate oxygen isotope values (δ(18)O(C)) in bioapatite to preserve the life signal of human tooth enamel by comparing it with phosphate oxygen isotope values (δ(18)O(P)) derived from the same archaeological human tooth enamel samples. METHODS δ(18)O(C) analysis was undertaken on 51 archaeological tooth enamel samples previously analysed for δ(18)O(P) values and strontium isotopes. δ(18)O(C) values were determined on a GV IsoPrime dual inlet mass spectrometer, following a series of methodological tests to assess: (1) The reaction time needed to ensure complete release of CO(2) from structural carbonate in the enamel; (2) The effect of an early pre-treatment with dilute acetic acid to remove diagenetic carbonate; (3) Analytical error; (4) Intra-tooth variation; and (5) Diagenetic alteration. RESULTS This study establishes a direct relationship between δ(18)O(C) and δ(18)O(P) values from human tooth enamel (δ(18)O(P) =  1.0322 × δ(18)O(C) - 9.6849). We have combined this equation with the drinking water equation of Daux et al. (J. Hum. Evol. 2008, 55, 1138) to allow direct calculation of δ(18)O(DW) values from human bioapatite δ(18)O(C) (δ(18)O(DW)  =  1.590 × δ(18)O(C) - 48.634). CONCLUSIONS This is the first comprehensive study of the relationship between the ionic forms of oxygen (phosphate oxygen and structural carbonate) in archaeological human dental enamel. The new equation will allow direct comparison of data produced by the different methods and allow drinking water values to be calculated from structural carbonate data with confidence.

Oxygen and sulfur isotopic composition of volcanic sulfate aerosol at the point of emission

Volcanic sulfate aerosol is emitted from the vents of many active volcanoes, but its origin has not yet been explained. We report the first measurements of the isotopic compositions of near-vent volcanic aerosol sulfate and use the combined sulfur and oxygen isotope systematics of the aerosol and magma at Masaya volcano, Nicaragua, to draw preliminary conclusions about the production mechanism of near-source volcanic sulfate. The sulfate aerosol does not display a significant mass-independent oxygen or sulfur isotopic signature, which suggests that primary volcanic aerosol does not contribute to the larger mass-independent anomalies found in some ambient atmospheric aerosols and as preserved in ice cores. The oxygen isotope composition of the sulfate appeared to become heavier on the particle filters with increasing amount of sample collected and suggests that the δ 18O value of the sulfate aerosol is <8‰. The sulfur isotopic composition of the sulfate did not vary with sample loading on the filters and had a mean δ 34S value of 7.7 ± 0.8‰, similar to that of the magma (6.6 ± 0.2‰). The low Δ17O value, the δ 18O value of the magma (6.6 ± 0.3‰) and the high δ 18O value of atmospheric oxygen (23.5‰) suggest that known atmospheric oxidation pathways at ambient temperatures are not the major routes of production for this sulfate. Instead, the isotopic systematics of aerosol and magma are consistent with sulfate production either by high-temperature equilibration of the magmatic gas mixture with small amounts of atmospheric oxygen or by direct emission of SO4 2− from the magma.

Diatom δ18O evidence for the development of the modern halocline system in the subarctic northwest Pacific at the onset of major Northern Hemisphere glaciation

Establishing a time frame for the development of the modern halocline and stratified water column in the subarctic North Pacific has significant paleoclimatic implications. Here we present a d18O(diatom) record consisting of only two species that represents autumn/winter conditions in the region across the onset of major Northern Hemisphere glaciation boundary. At circa 2.73 Ma a decrease in d18O(diatom) of 4.6% occurs, whereas previously published d18O(foram) results show a 2.6% increase. The d18O(diatom) and Uk37 sea surface reconstructions indicate both a significant freshening of 2–4 practical salinity units and an increase in surface temperatures in the summer to early winter period from circa 2.73 Ma onward. In contrast, the concomitant increase in d18O(foram) is likely to be reflective of conditions beneath the mesothermal structure and/or spring conditions when warmer sea surface temperatures are not present in the region. These results are consistent with the development of the modern halocline system at 2.73 Ma with year-round stratification of the water column and a strengthened seasonal thermocline during the summer to early winter period, resulting in one of the largest summer to winter temperature gradients in the open ocean. The onset of stratification would also have led to a warm pool of surface water from circa 2.73 Ma, which may have provided a potential source of extra moisture needed to supply the growing North American ice sheets at this time.

Seasonality in equatorial climate over the past 25 k.y. revealed by oxygen isotope records from Mount Kilimanjaro

Multiproxy analysis of a well-dated 25 ka lake sediment sequence from Lake Challa, on the eastern flank of Mount Kilimanjaro (East Africa), reveals the climatic controls that govern both the lakes paleohydrology and the climate-proxy record contained in the mountains receding ice cap. The oxygen isotope record extracted from diatom silica (δ18Odiatom) in Lake Challa sediments captured dry conditions during the last glacial period and a wet late-glacial transition to the Holocene interrupted by Younger Dryas drought. Further, it faithfully traced gradual weakening of the southeastern monsoon during the Holocene. Overall, δ18Odiatom matches the branched isoprenoid tetraether (BIT) index of rainfall-induced soil runoff, except during 25–22 ka and the past 5 k.y. when insolation forcing due to orbital precession enhanced the northeastern monsoon. This pattern arises because during these two periods, a weakened southeastern monsoon reduced the amount of rainfall during the long rainy season and enhanced the opposing effect of evaporation intensity and/or length of the austral winter dry season. Importantly, our lake-based reconstruction of moisture-balance seasonality in equatorial East Africa also helps us understand the oxygen isotope record contained in Mount Kilimanjaro ice. Negative correlation between ice core δ18O and Lake Challa δ18Odiatom implies that moisture balance is not the primary climate control on the long-term trend in ice core δ18O.

Diatom oxygen isotopes : evidence of a species effect in the sediment record

Diatom oxygen isotope measurements are commonly made on bulk mixed species assemblages due to the difficulty in purifying and separating individual taxa. As such, it is essential to understand processes in diatoms which may lead to isotope offsets both between and within individual species. Existing studies have suggested that mechanisms which may lead to isotopes offset in diatoms, such as vital effects, are either nonexistent or negligible. Here, we present a suite of diatom oxygen isotope data from the onset of major Northern Hemisphere Glaciation at ODP site 882 in the northwest Pacific Ocean which display large offsets ( mean = 1.23 parts per thousand, max = 3.51 parts per thousand, error = 0.84 parts per thousand) between two different size fractions ( 75 - 150 mu m and > 150 mu m) that are dominated by only two species: Coscinodiscus marginatus and Coscinodiscus radiatus. These offsets are most likely size related, although additional interspecies and intraspecies effects may also be important in determining the exact magnitude of the offsets. Consequently, considerable care is needed when interpreting bulk diatom oxygen isotope data in relation to paleoenvironmental change, especially when the amount of stratigraphical change within the isotopes is small.

Silicon isotopes in Antarctic sponges : an interlaboratory comparison

Abstract Cycling of deepwater silicon (Si) within the Southern Ocean, and its transport into other ocean basins, may be an important player in the uptake of atmospheric carbon, and global climate. Recent work has shown that the Si isotope (denoted by δ29Si or δ30Si) composition of deep sea sponges reflects the availability of dissolved Si during growth, and is a potential proxy for past deep and intermediate water silicic acid concentrations. As with any geochemical tool, it is essential to ensure analytical precision and accuracy, and consistency between methodologies and laboratories. Analytical bias may exist between laboratories, and sponge material may have matrix effects leading to offsets between samples and standards. Here, we report an interlaboratory evaluation of Si isotopes in Antarctic and sub-Antarctic sponges. We review independent methods for measuring Si isotopes in sponge spicules. Our results show that separate subsamples of non-homogenized sponges measured by three methods yield isotopic values within analytical error for over 80% of specimens. The relationship between δ29Si and δ30Si in sponges is consistent with kinetic fractionation during biomineralization. Sponge Si isotope analyses show potential as palaeoceaongraphic archives, and we suggest Southern Ocean sponge material would form a useful additional reference standard for future spicule analyses.

Atlantic overturning circulation and Agulhas leakage influences on southeast Atlantic upper ocean hydrography during marine isotope stage 11

Climate dynamics during the marine isotope stage (MIS) 11 interglacial may provide information about how the climate system will evolve under the conditions of low-amplitude orbital forcing that are also found during the late Holocene. New stable isotope and alkenone data are presented from southeast Atlantic Ocean Drilling Program Site 1085, providing detailed information on interglacial climate evolution and the impacts of Atlantic meridional overturning circulation (MOC) and Agulhas leakage on the regional upper ocean hydrography. The data suggest that although warm surface ocean conditions were maintained at approximate Holocene levels for 40,000 years during MIS 11, subsurface temperature and salinity recorded by deeper-dwelling planktonic foraminifera species were maintained at their highest values for only 7000–8000 years. Surface water temperature and salinity data suggest that the interocean exchange of warm, salty waters into the southeast Atlantic Ocean was directly related to changes in the activity of the MOC during the study interval. Specifically, transient regional warming events during periods of weakened overturning circulation may have been amplified by the continuous interocean exchange of warm, salty Indian Ocean waters that primed the MOC for abrupt resumptions into a vigorous mode of operation. Conversely, a peak in interocean exchange at the end of the MIS 11 interglacial optimum may reflect enhanced trade wind forcing of surface waters whose export to the North Atlantic Ocean could have contributed to renewed ice sheet buildup during the MIS 11 to 10 glacial inception.

Mid-Holocene sea surface conditions and riverine influence on the inshore Great Barrier Reef

We present measurements of Sr/Ca, δ18O, and spectral luminescence ratios (G/B) from a mid-Holocene Porites sp. microatoll recovered from the nearshore Great Barrier Reef (GBR). These records were used as proxies to reconstruct sea surface temperature (SST), the δ18O of surrounding seawater (δ18Osw), and riverine influence, respectively, and compared with records from a modern Porites sp. microatoll growing in the same environment. Strong riverine influence in the mid-Holocene record is indicated by (1) an increased annual δ18Osw range in the mid-Holocene record, (2) negative peaks in δ18O characteristic of flood events, and (3) a higher G/B luminescence ratio. Seasonal cycles in G/B suggest that humic acid inputs were elevated for a longer portion of the year during the mid-Holocene. The seasonal cycle of δ18Osw peaked earlier in the year in the mid-Holocene record relative to the modern, while mean δ18Osw values from the mid-Holocene record were similar to modern values. These records provide an insight into the oceanographic conditions the nearshore GBR experienced during mid-Holocene climatic shifts and are consistent with a strong Australian–Indonesian Summer Monsoon (AISM) system at ~ 4700 cal. yr BP.

Effects of active silicon uptake by rice on 29Si fractionation in various plant parts

Rice (Oryza sativa L.) accumulates large amounts of silicon which improves its growth and health due to enhanced resistance to biotic and abiotic stresses. Silicon uptake and loading to xylem in rice are predominantly active processes performed by transporters encoded by the recently identified genes Lsi1 (Si influx transporter gene) and Lsi2 (Si efflux transporter gene). Silicon deposition in rice during translocation to upper plant tissues is known to discriminate against the heavier isotopes (29)Si and (30)Si, resulting in isotope fractionation within the plant. We analyzed straw and husk samples of rice mutants defective in Lsi1, Lsi2 or both for silicon content and delta(29)Si using isotope ratio mass spectrometry (IRMS) and compared these results with those for the corresponding wild-type varieties (WT). The silicon content was higher in husk than in straw. All the mutant rice lines showed clearly lower silicon content than the WT lines (4-23% Si of WT). The delta(29)Si was lower in straw and husk for the uptake defective mutant (lsi1) than for WT, albeit delta(29)Si was 0.3 per thousand higher in husk than in straw in both lines. The effect of defective efflux (lsi2) differed for straw and husk with higher delta(29)Si in straw, but lower delta(29)Si in husk while WT showed similar delta(29)Si in both fractions. These initial results show the potential of Si isotopes to enlighten the influence of active uptake on translocation and deposition processes in the plant.

Oxygen isotope analysis of carbonates in the calcite‐dolomite‐magnesite solid‐solution by high‐temperature pyrolysis: initial results

Accurate and efficient measurement of the oxygen isotope composition of carbonates (delta(C) (18)O) based on the mass spectrometric analysis of CO(2) produced by reacting carbonate samples with H(3)PO(4) is compromised by: (1) uncertainties associated with fractionation factors (alpha(CO)(2)C) used to correct measured oxygen isotope values of CO(2)(delta(CO(2)(18)O) to delta(C) (18)O; and (2) the slow reaction rates of many carbonates of geological and environmental interest with H(3)PO(4). In contrast, determination of delta(C) (18)O from analysis of CO produced by high-temperature (>1400 degrees C) pyrolytic reduction, using an elemental analyser coupled to continuous-flow isotope-ratio mass spectrometry (TC/EA CF-IRMS), offers a potentially efficient alternative that measures the isotopic composition of total carbonate oxygen and should, therefore, theoretically be free of fractionation effects. The utility of the TC/EA CF-IRMS technique was tested by analysis of carbonates in the calcite-dolomite-magnesite solid-solution and comparing the results with delta(C) (18)O measured by conventional thermal decomposition/fluorination (TDF) on the same materials. Initial results show that CO yields are dependent on both the chemical composition of the carbonate and the specific pyrolysis conditions. Low gas yields (<100% of predicted yield) are associated with positive (>+0.2 per thousand) deviations in delta(C(TC/EA) (18)O compared with delta(C(TDF) (18)O. At a pyrolysis temperature of 1420 degrees C the difference between delta(C) (18)O measured by TC/EA CF-IRMS and TDF (Delta(C(TC/EA,TDF) (18)O) was found to be negatively correlated with gas yield (r = -0.785) and this suggests that delta(C) (18)O values (with an estimated combined standard uncertainty of +/-0.38 per thousand) could be derived by applying a yield-dependent correction. Increasing the pyrolysis temperature to 1500 degrees C also resulted in a statistically significant correlation with gas yield (r = -0.601), indicating that delta(C) (18)O values (with an estimated uncertainty of +/-0.43 per thousand) could again be corrected using a yield-dependent procedure. Despite significant uncertainty associated with TC/EA CF-IRMS analysis, the magnitude of the uncertainty is similar to that associated with the application of poorly defined values of alpha(CO)(2), (C) used to derive delta(C) (18)O from delta(CO(2) (18)O measured by the H(3)PO(4) method for most common carbonate phases. Consequently, TC/EA CF-IRMS could provide a rapid alternative for the analysis of these phases without any effective deterioration in relative accuracy, while analytical precision could be improved by increasing the number of replicate analyses for both calibration standards and samples. Although automated gas preparation techniques based on the H(3)PO(4) method (ISOCARB, Kiel device, Gas-Bench systems) have the potential to measure delta(CO)(2) (18)O efficiently for specific, slowly reacting phases (e.g. dolomite), problems associated with poorly defined alpha(CO)(2), (C) remain. The application of the Principle of Identical Treatment is not a solution to the analysis of these phases because it assumes that a single fractionation factor may be defined for each phase within a solid-solution regardless of its precise chemical composition. This assumption has yet to be tested adequately.