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Here, we report new estimates of local marine radiocarbon reservoir ages from northwestern Luzon Island in the Philippines, on the east side of the South China Sea. Data for two periods, through the 1940’s and the mid-Holocene, were derived from modern and fossil corals. Our results from Luzon Island show variable ΔR values, from −39 ± 25 to 337 ± 27 14C yr over the past 6000 years and highlight the importance of understanding temporal ΔR changes to obtain accurate radiocarbon dates for mid-Holocene samples. An abrupt shift in ΔR at ∼5.5 ka BP, in the east side of the South China Sea, can be attributed to changes in the intensity of the upwelling, in the eastern Pacific, and to the East Asian Monsoon. Additional reservoir age data from the Pacific is likely to reveal details of oceanographic and climate changes at this time.

Globally, rivers supply uranium to the oceans with excess 234 U relative to secular equilibrium and 234 U taken-up by corals can be used for dating. In addition, the 234 U abundance in sea water, at the time the coral was growing, can be measured independently. The veracity of U-series ages used in determining past sea-level variations is dependent on selecting pristine corals free from diagenetic alteration. A quantitative test for alteration assumes invariant 234 U abundances in the oceans for at least the past half a million years and results from samples outside of a narrow range in modern ocean 234 U abundance are excluded from data sets. Here, we have used previously published data to show that 234 U in the oceans appears to be variable and directly related to changes in sea-level, not only over long glacial–interglacial timescales but also at very short, centennial timescales. Most of the previously discarded data can be used to provide valuable additional sea-level information. The process permits a unique insight into the interplay between sources and sinks of uranium in the oceans mediated by sea-level changes at rates far faster than previously thought possible. Similar, rapid sea-level, forcing of other trace element abundances in the oceans is likely.

Radiocarbon calibration beyond the extent of tree-ring records depends on U-series dating of fossil corals or speleothem, both of which can provide independent calendar ages. Less direct methods rely on layer counting and comparison with other well-dated records. In spite of considerable effort to provide a reliable radiocarbon calibration curve beyond 25,000 years, the majority of the data show large atmospheric radiocarbon peaks which are inconsistent both in magnitude and timing between different determinations. The results of the most recent work [Chiu, T.-C., Fairbanks, R.G., Mortlock, R.A., Bloom, A.L., 2005. Extending the radiocarbon calibration beyond 26,000 years before present using fossil corals. Quaternary Science Reviews 24 (16–17), 1797–1808], from Araki Island fossil corals, indicate a monotonic variation from about 33 to 49 ka, with no radiocarbon peaks, but with some gaps in the data. The difference between this and previous results, from fossil corals, has been attributed to selection of better-quality samples and rigorous analytical methods. However, previous results from Huon Peninsula [Yokoyama, Y., Esat, T.M., Lambeck, K., Fifield, L.K., 2000. Last ice age millennial scale climate changes recorded in Huon Peninsula corals. Radiocarbon 42 (3), 383–401; Cutler, K.B., Gray, S.C., Burr, G.S., Edwards, R.L., Taylor, F.W., Cabioch, G., Beck, J.W., Cheng, H., Moore, J., 2004. Radiocarbon calibration and comparison to 50 kyr BP with paired 14 C and 230 Th dating of corals from Vanuatu and Papua New Guinea. Radiocarbon 46 (3), 1127–1160] show radiocarbon peaks exclusively located within the gaps in the Araki data. The timing of the gaps are not random, but appear to be related to severe climate and sea-level variations associated with Heinrich events initiated in the North Atlantic. We propose that the Huon and Araki data sets are complementary rather than exclusive and that the absence of coral growth at Araki Island during Heinrich events presumably reflect local adverse conditions for coral growth.

At Huon Peninsula, Papua New Guinea, prolific coral growth during the last-glacial was episodic and in response to a series of sea-level rises. The resultant step-like coral terraces are currently situated from 20 m up to 140 m above sea-level due to continuous tectonic uplift of the Peninsula. The sea-level rises were in response to periodic partial disintegration of Northern Hemisphere ice sheets associated with severe climate swings and occurred within decadal timescales. The relatively rapid 15 m to 35 m rise in sea-levels exposed new head-room for corals to colonize. The resulting terrace structures contain individual corals that do not appear to have grown sequentially in time and with elevation. Additionally, following the peak, sea level fell relatively slowly over several thousand years and corals grew and filled in the flanks of the terrace such that younger corals now occupy lower elevations. We have labeled these structures “pack-up” reefs. This is in contrast to coral terraces formed during major sea-level rises from glacial to interglacial or glacial to interstadial transitions where the rate of sea level rise is commensurate with coral growth rates and corals can keep up with sea-level rise by growing on top of each other in a time orderly sequence. Deriving sea-level information from pack-up terraces is difficult and is likely to be ambiguous. The periodic fluctuations in climate were associated with atmospheric radiocarbon swings that seem to have varied smoothly with time. The same corals that show a scatter in stratigraphic temporal ordering appear regularly distributed in time and with radiocarbon content attesting to the veracity of the age measurements and at the same time confirm the disordered distribution of corals in “pack-up” type reefs.

Uranium-series mass spectrometric analyses of corals from the uplifted last glacial terraces at Huon Peninsula, Papua New Guinea, that grew from 50,000 years ago to 30,000 years ago show systematically low values of 234U/238U, at the time of coral growth, compared with modern corals. When combined with coral data from other studies a systematic trend emerges indicating shifts in the 234U/238U ratio at times of major glacial–interglacial transitions that involve large variations in sea-levels. From last glacial to Holocene, the rate of change in δ234U is approximately 1‰ per thousand years. The variations in the U budget of the oceans appear to be due to accumulation of excess 234U in near shore areas in anoxic and suboxic sediments, in salt marshes and mangroves, in estuaries, and in continental margins during periods of warm climate and high sea-levels. These near-shore areas are exposed during periods of low sea level resulting in rapid oxidation of U into highly soluble phases. The subsequent release of 234U-enriched uranium into the oceans occurs over a sustained period, in step with rising sea-levels.

Initial 187Os/188Os isotopic compositions for geochronologically and geologically well -constrained 3.8-Ga spinel peridotites from the Itsaq Gneiss Complex of southern West Greenland and chromite separates from 3.46-Ga komatiites from the Pilbara region of Western Australia have been determined to investigate the osmium isotopic evolution of the early terrestrial mantle. The measured compositions of 187Os/188Os(0) = 0.10262 ± 2, from an olivine separate, and 0.10329 ± 3, for a spinel separate from ∼3.8-Ga peridotite G93/42, are the lowest yet reported from any terrestrial sample. The corrections for in situ decay over 3.8 Ga for these low Re/Os phases are minimal and change the isotopic compositions by only 0.5 and 2.2% for the spinel and the olivine, respectively, resulting in 187Os/188Os(3.8 Ga) = 0.1021 ± 0.0002 and 0.1009 ± 0.0002, respectively. These data extend direct measurement of Os isotopic compositions to much earlier periods of Earth history than previously documented and provide the best constraints on the Os isotopic composition of the early Archean terrestrial mantle. Analyses of Pilbara chromites yield 3.46-Ga mantle compositions of 0.1042 ± 0.0002 and 0.1051 ± 0.0002. These new data, combined with published initial Os isotopic compositions from late Archean and early Proterozoic samples, are compatible with the mantle, or at least portions of it, evolving from a solar system initially defined by meteorites to a modern composition of 187Os/188Os(0) = 0.1296 ± 0.0008 as previously suggested from peridotite xenolith data ( Meisel et al., 2001); the associated 187Re/188Os(0) = 0.435 ± 0.005. Thus, chondritic 187Os/188Os compositions were a feature of the upper mantle for at least 3.8 billion years, requiring chondritic Re/Os ratios to have been a characteristic of the very early terrestrial mantle. In contrast, nonchondritic initial compositions of some Archean komatiites demonstrate that Os isotopic heterogeneity is an ancient feature of plume materials, reflecting the development of variable Re/Os mantle sources early in Earth history. The lower average 187Os/188Os = 0.1247 for abyssal peridotites (Snow and Reisberg, 1995) indicate that not all regions of the modern mantle have evolved with the same Re/Os ratio. The relative sizes of the various reservoirs are unknown, although mass balance considerations can provide some general constraints. For example, if the unradiogenic 187Os/188Os modern abyssal peridotite compositions reflect the prevalent upper mantle composition, then the complementary high Re/Os basaltic reservoir must represent 20 to 40% by mass of the upper mantle (taken here as 50% of the entire mantle), depending on the mean storage age. The difficulties associated with efficient long-term storage of such large volumes of subducted basalt suggest that the majority of the upper mantle is not significantly Re-depleted. Rather, abyssal peridotites sample anomalous mantle regions. The existence of 3.8-Ga mantle peridotites with chondritic 187Os/188Os compositions and with Os concentrations similar to the mean abundances measured in modern peridotites places an upper limit on the timing of a late accretionary veneer. These observations require that any highly siderophile element -rich component must have been added to the Earth and transported into and grossly homogenized within the mantle by 3.8 Ga. Either large-scale mixing of impact materials occurred on very short (0–100 myr) timescales or (the interpretation preferred here) the late veneer of highly siderophile elements is unrelated to the lunar terminal cataclysm estimated to have occurred at ∼3.8 to 3.9 Ga.

Huon Peninsula, Papua New Guinea, is a tectonically unstable, uplifting shoreline ringed by emergent coral terraces. The terraces were formed during episodes of rapid sea-level rise when corals constructed large, discrete coral platforms that were subsequently uplifted. Uranium series ages of four prominent Huon Peninsula last glacial (OIS 3) coral terraces coincide with the timing of major North Atlantic climate reversals at intervals of 6000–7000 yr between 30 000 yr and 60 000 yr ago. Terrace elevations, when combined with uplift, indicate 10–15-m high sea-level excursions at these times. We attribute the growth of the terraces directly to sea-level rises arising from ice-calving episodes from major North Atlantic ice-sheets and the Antarctic ice-sheet that precipitated extremes of cold climate called Heinrich events. These periods are associated with major discharges of land-based ice and enhanced concentrations of ice-rafted debris in deep-sea cores. Sea-levels at this time were 60–90 m lower than present.

The rise and fall of the Last Interglacial (LI) sea levels and sea surface temperatures (SSTs) are evaluated using U-series dating combined with Sr/Ca ratios in corals from both stable and tectonically uplifted sites. Along the stable coastal margin of Western Australia, an extensive series of LI coral reefs occur at heights of 2–3 m above present-day sea level. These corals have a very tight cluster of 234U–230Th ages ranging from 129±1 to 119±1 ka, as well as a narrow range of initial δ234U values of 150±5, similar to modern seawater. Bahamas, which is also a stable site, has an essentially identical pattern of U-series ages from 130±1 to 120±1 ka. Barbados and Huon Peninsula are tectonically active sites where the LI terraces are found at elevations of >50 and >200 m, respectively. U-series ages from corals exposed in the lower footwall of these uplifted reefs, allow better constraints to be placed on the rate of sea level rise which initiated the LI. Corals from the Huon Peninsula constrain sea level at −80±10 m at 131±2 ka, and from Barbados, at −30±5 m at 129±1 ka. Combined with constraints from stable sites, these observations require an exceedingly rapid rise in sea level of 30–50 m per 1000 years at 130±1 ka. This indicates that large-scale catastrophic melting of the once massive continental ice sheets occurred in phase with the rapidly increasing northern hemisphere (NH) summer insolation, consistent with the orbital forcing being the main driver of glacial–interglacial climate change. There is also some evidence from Huon Peninsula, although still not conclusive, for a precursor oscillation in sea level during the penultimate deglaciation, that may have been within ∼−20 m of present-day levels at ∼135 ka. SSTs for the LI Porites corals from the Huon Peninsula and Western Australia have mean annual temperatures and seasonal ranges that are remarkably similar to present-day patterns. The tropical site of Huon Peninsula has SSTs of 29±1°C, which is indistinguishable from the SSTs given by modern corals. At Ningaloo Reef in Western Australia, similar mean annual (∼24°C) and summer maximum SSTs of 27–29°C are found in both LI and modern corals. The only significant difference is the ∼1°C cooler winter minimum SSTs of ∼21°C for the LI compared to present-day minimums of ∼22°C. LI SSTs from these southern hemisphere (SH) sites were thus very similar, or at most, only slightly cooler than today, despite sea levels being up to 4 m higher. This maybe indicative of asymmetric warming of the Earth, with the increased NH insolation during the LI period being responsible for the extensive melting of the mainly NH-based ice sheets, and hence, higher global sea levels. The observation of relatively high sea levels in the LI, together with the rapid pulses of sea level rise, indicates that the potential now exists for greenhouse warming to initiate increases in sea level of at least several metres on relatively short time-scales (102 years).

We report new mass spectrometric U-series ages for eight Last Interglacial fossil reefs along the continental margin of Western Australia. Corals were selected in growth position from localities that are characterized by apparently low levels of diagenesis and relative tectonic stability so that the fossil reefs provide critical information on Last Interglacial sea-levels without requiring corrections for tectonic movements. In addition, we have improved the constraint on the timing of onset of reef growth by recovering drill core coral from the base of the reefs. Uranium and thorium isotopes were measured with high levels of precision, leading to improvements in age resolution and allowing samples which have undergone diagenetic exchange of uranium and thorium to be more easily identified and discarded. These data supplement our previous results for Rottnest Island and Leander Point, leading to more than seventy mass spectrometric U-series ages from which constraints can be placed on the timing, duration and character of the Last Interglacial sea-level highstand. Reliable ages show that reef growth started contemporaneously at 128 ± 1 ka along the entire Western Australian coastline, while relative sea-levels were at least 3 m above the present level. Because Western Australia is located far from the former Penultimate Glacial Maximum ice sheets and are not significantly effected by glacial unloading, these data constrain the timing of onset of the Last Interglacial period to 128 ± 1 ka, assuming reef growth started soon after sea-level approached interglacial levels. A unique regressive reef sequence at Mangrove Bay constrains the timing of termination of the Last Interglacial period to 116 ± 1 ka. The major episode of reef building, however, both globally and locally along the Western Australian coast, is restricted to a very narrow interval occurring from ∼128 ka and ∼121 ka, suggesting that global ocean surface temperatures were warm and/or sea-levels were stable enough to allow prolific reef growth only during the earlier part of the Last Interglacial.

The ReOs systematics of a suite of spinel peridotite xenoliths from southeast Australia provide insight into the effects of melt extraction and metasomatism on Re and Os and place strong constraints on the evolution and long-term stability of post-Archean lithospheric mantle in a tectonically complex region. Data from variably melt-depleted and non-modally metasomatised xenoliths demonstrate that Re abundances are largely controlled by melt extraction, with Re similarly distributed to Os. Ratios of ReOs correlate strongly with indices of melt extraction (e.g. Al2O3, Ni and Yb), and with the calculated bulk partition coefficient of Re, comparable to that of Yb over a large range of melt extraction (∼ 4–20%). Hence, if Re is controlled by sulfide phases, sulfur:clinopyroxene ratios should remain essentially constant over large degrees of melt extraction. Eight of the 24 samples analysed were wehrlites or apatite-bearing peridoties, representing residual peridotite which has interacted with a carbonatitic melt. In comparison with the non-modally metasomatised xenoliths, these samples show no evidence for disturbance of Os isotopic composition, or addition of Re or Os during metasomatism. The entire suite provides a 220 km long, WNW-ESE lithospheric mantle transect, east of, and perpendicular to, the presumed Australian Precambrian shield margin. The Os model ages indicate at least three episodes of mantle depletion: ca. 1960 Ma, 800–1000 Ma and < 500 Ma. The older age is found only in the two westernmost localities where a subset of four samples define a ReOs age of 1959 ± 100 Ma, with an initial γOs = +0.2. Although the oldest exposed rocks in the region are of Cambrian age, and the presence of early Proterozoic basement is highly contentious, the Os isotopic data require that early Proterozoic basement extends some 400 km further east than the easternmost exposed early Proterozoic crust. Model ages of 800–1000 Ma are common to all but one locality, indicating at least two melt extraction events in the western localities. Paleozoic ages are only identified in the eastern localities, suggesting the lithospheric mantle becomes younger to the east. Importantly, this and other ReOs isotopic studies provide increasing evidence for the long-term stability and persistence of lithospheric mantle of Proterozoic as well as of Archean age.

High-precision measurements of SrCa ratios are reported for Porites corals from the uplifted Holocene coral terraces at Huon Peninsula, Papua New Guinea. The early Holocene Porites have UTh mass spectrometric ages of 8920 ± 60 yr and 7370 ± 50 yr, and δ234U(t) values of 145 ± 2, similar to modern seawater. The SrCa coral records provide 5–6 year high resolution (near weekly) time windows into early Holocene sea surface temperatures. Seasonal temperature fluctuations are generally in the range of ± 1°C, with occasional excursions of ± 2°C, which may indicate the more frequent recurrence of very strong ENSO (El Nino-Southern Oscillation) events. Mean annual SrCa temperatures of 24.2 ± 1.1°C and 22.9 ± 0.8°C have been obtained, which are ∼ 2–3°C cooler than that exhibited by a modern Porites. These results indicate that, during the early Holocene, the equatorial western Pacific ocean was at least several degrees cooler than present-day temperatures. This is consistent with late glacial coral records from the Caribbean that indicate lower (∼ 6°C) sea surface temperatures for the equatorial oceans. The Huon Peninsula corals also indicate that SSTs were several degrees cooler than those in the Caribbean during the early Holocene. Thus, although the northern hemisphere summer radiation maximum occurred at ∼ 10 ka, there appears to have been a significant lag in the response of the equatorial western Pacific ocean to this warming. Cooler early Holocene sea surface temperatures in the western Pacific may have been due to changing patterns of ocean-atmosphere circulation, resulting from the exposure of large areas of continental shelf in the southeast Asia region, a consequence of lower glacial sea levels. It is likely that ocean temperatures in the Huon Peninsula were influenced by the opening at ∼ 7 ka of the Torres Strait, that now separates New Guinea from the Australian mainland.

The determination of thorium isotope ratios using a new technique suitable for low intensity ion beams has resulted in significant improvement in analytical precision. A capacitor was substituted in place of the usual high-value resistor at the feedback loop of an electrometer. Charge collected in a Faraday cup accumulates on the capacitor, resulting in a time-varying voltage proportional to the ion current. Electrometer noise levels are reduced by a factor of up to 500, and immunity to temperature fluctuations is improved by a factor of more than 10. Charge collection thermal ion mass spectrometry bridges the gap between the measurement range for resistive feedback electrometers and electron multiplier devices. Standard design Faraday cup arrays and electrometers equipped with capacitive feedback elements can be used for simultaneous data collection in multiple channels. Maximum working range, for unit mass separation in adjacent Faraday cups, is uncompromised. The charge collection method was tested with thorium ion beams. Filaments loaded with 15 pg of 230Th produce intensities up to 6 × 1−14 A over 1 h. The ionization efficiency is 4% and analytical errors for a single run are better than ±0.6‰; these results are superior to those reported for other techniques. Charge collection mass spectrometry will be most useful in cases where large ion beams cannot easily be obtained or where the concentration of the element of interest in geological materials is very low.

U-series ages using methods of thermal ionisation mass spectrometry (TIMS) are reported for Last Interglacial fossil reefs along the stable coastal margin of Western Australia. Thorium isotope ratios were measured with superior precision using methods of charge collection. High levels of precision in the measurement of both uranium and thorium isotopes has reduced the age uncertainty due to analytical errors, excluding the uncertainty in the decay constants, by a factor of four over the precisions reported by many earlier TIMS workers. Uncertainties in δ234U(T), determined from both 230Th/238U and 234U/238U, are also significantly smaller than previously reported, allowing samples which have undergone diagenetic exchange of uranium and thorium to be more easily identified. Strict criteria were adopted to screen the new Western Australian data. Reliable ages range from 127 to 122 ka. Published TIMS observations from other localities have been assessed using the same strict criteria. When these are combined with glacio-hydro isostatic sea-level models they indicate that the Last Interglacial period occurred from at least 130 to 117 ka. However, these age constraints are largely determined from single data points and need to be verified with additional ages before considering them to be robust estimates for the timing of onset and termination of the Last Interglacial. Globally, the main episode of reef growth appears to be confined to a narrow interval occurring from 127 to 122 ka, in direct agreement with the narrow range in ages obtained from the Western Australian sites. This may indicate that the Last Interglacial was of short duration, extending from 127 to 122 ka only. Alternatively, this interval may reflect a major reef-building event in the middle of a longer duration (130-117 ka) interglacial interval.

New Ca- and Ti-isotopic analyses of DH-H1, 7-404, and 7-971, and Mg-isotopic analyses on DH-H1 and 7-404 are reported. O-isotopic analyses of HAL, 7-404, 7-971, and a variety of other refractory inclusions from Murchison were made in order to establish the presence or absence of FUN O-isotopic systematics. A higonite-rich residue produced by the evaporation of kaersutite was analyzed for its trace-element and isotopic abundances to see if any of the characteristics of FUN hibonite inclusions can be produced by distillation in the laboratory. These data are then used to evaluate for all four inclusions the HAL-type formation models originally proposed by Allen et al. (1980) and Lee et al. (1980). The four inclusions were found to have very similar chemical and isotopic features. All are characterized by large Ce depletions and very low Mg, Ti, and V concentrations compared to other meteoritic hibonites. All four inclusions have delta(C-48) within error of -5 per mil. Ca-, Ti-, and O-isotopic compositions are fractionated with enrichments of the heavy isotopes, and the Ti-isotopic mass fractionation is inversely correlated with Ti concentration. It is concluded that the inclusions formed primarily as distillation residues in accord with the early conclusions.

Isotopic composition of refractory elements can be modified, by physical processes such as distillation and sputtering, in unexpected patterns. Distillation enriches the heavy isotopes in the residue and the light isotopes in the vapor. However, current models appear to be inadequate to describe the detailed mass dependence, in particular for large fractionations. Coarse- and fine-grained inclusions from the Allende meteorite exhibit correlated isotope effects in Mg both as mass-dependent fractionation and residual anomalies. This isotope pattern can be duplicated by high temperature distillation in the laboratory. A ubiquitous property of meteoritic inclusions for Mg as well as for most of the other elements, where measurements exist, is mass-dependent fractionation. In contrast, terrestrial materials such as microtektites, tektite buttons as well as lunar orange and green glass spheres have normal Mg isotopic composition. A subset of interplanetary dust particles labelled as chondritic aggregates exhibit excesses in {sup 26}Mg and deuterium anomalies. Sputtering is expected to be a dominant mechanism in the destruction of grains within interstellar dust clouds. An active proto-sun as well as the present solar-wind and solar-flare flux are of sufficient intensity to sputter significant amounts of material. Laboratory experiments in Mg show widespread isotope effects including residual {supmore » 26}Mg excesses and mass dependent fractionation. It is possible that the {sup 26}Mg excesses in interplanetary dust is related to sputtering by energetic solar-wind particles. The implication if the laboratory distillation and sputtering effects are discussed and contrasted with the anomalies in meteoritic inclusions the other extraterrestrial materials the authors have access to.« less

The Mg isotopic compositions of olivine, spinel, and hibonite from the Murchison carbonaceous chondrite have been determined by secondary ion mass spectrometry. The olivines exhibit only marginal effects. They have no detectable intrinsic mass fractionation; however, after correcting for mass fractionation, the mean residual 26Mg24Mg for the five grains is slightly in excess of the terrestrial value. Blue spinel, which often contains inclusions of hibonite and perovskite, is characterised by positive fractionation (enriched in heavier isotopes) ranging from +1 to +46 permil/amu, and with a roughly constant residual of +1.04 ± 0.25 (2σm) permil. These characteristics can be derived from an initial terrestrial Mg isotopic composition through varying degrees of mass fractionation, and the addition of 26Mg from 26Al decay. The hibonites show both positive and negative fractionation and residuals. Three deep-blue granular hibonites show large fractionation from +10 to + 17 permil/amu with residuals ranging from −1.8 to +9.7 permil. The remaining five colourless hibonites are closer to the terrestrial composition. The fractionation for these grains varies from −5 to +3 permil/amu and the residual from −7.0 to +2.5 permil. There is a hint of a correlation between fractionation and residual effects.