Raexcess/Ba growth rates and U-Th-Ra-Ba systematic of Baltic Mn/Fe crusts

We analyzed ²³⁸U, ²³⁴U, ²³²Th, ²³⁰Th, and ²²⁶Ra by thermal ionization mass spectrometry (TIMS) and Ba by inductively coupled plasma optical emission spectrometry (ICP-OES) on eight Mn/Fe crusts from the Mecklenburg Bay (SW Baltic) and on one from the Bothnian Bay (N Baltic) to test the ²²⁶Ra_ex/Ba ratio as potential geochronometer. ²²⁶Ra_ex/Ba ratios decrease as a function of depth within the concretions in all analyzed profiles. Calculated diffusion coefficients are relatively low (∼9 · 10⁻⁷ cm²/yr for Ra and 5 · 10⁻⁷ cm²/yr for Ba) and suggest that diffusion is negligible for the Ra and Ba record. In addition, ²²⁶Ra_ex/Ba ages are consistent and independent from the growth rate and growth direction within a crust. Thus, the decline in ²²⁶Ra_ex/Ba ratio is most likely due to radioactive decay of ²²⁶Ra_ex, although the influence of varying oxic conditions has still to be evaluated. ²²⁶Ra_ex/Ba growth rates range from 0.021 to 0.0017 mm/yr and tend to be lower than those calculated and based on stratigraphic methods (1 to 0.013 mm/yr). ²²⁶Ra_ex/Ba ages of concretions from shallow water environment (20 m depth, Mecklenburg Bay/SW Baltic) cover a time interval from 990 ± 140 yr to 4310 ± 310 yr BP corresponding to the stabilization of the sea level close to the present position about 5500 to 4500 yr ago. One sample from greater depth (70 m, Bothnian Bay-/N Baltic) showed a higher ²²⁶Ra_ex/Ba age of 6460 ± 520 yr BP.     

Ra/Ra and Ra/Ba ratios in the Western Mediterranean Sea: Barite formation and transport in the water column

²²⁶Ra, ²²⁸Ra and Ba distributions as well as ²²⁸Ra/²²⁶Ra and ²²⁶Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the ²²⁸Ra_ex/²²⁶Ra_ex ratios (Ra_ex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Ba_ex (Ba_ex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high ²²⁸Ra/²²⁶Ra ratio) and formed in the mesopelagic layer (with a low ²²⁸Ra/²²⁶Ra ratio). ²²⁸Ra_ex/²²⁶Ra_ex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High ²²⁶Ra_ex/Ba_ex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in ²²⁶Ra may thus contribute to the decrease in the dissolved ²²⁶Ra activity and ²²⁶Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.     

Ra/Ra and Ra/Ba ratios to track barite formation and transport in the water column

We measured ²²⁸Ra_ex/²²⁶Ra_ex and ²²⁶Ra_ex/Ba_ex ratios in suspended and sinking particles collected at the Oceanic Flux Program (OFP) time-series site in the western Sargasso Sea and compared them to seawater ratios to provide information on the origin and transport of barite (BaSO₄) in the water column. The ²²⁸Ra_ex/²²⁶Ra_ex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth. These ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer. The ²²⁸Ra_ex/²²⁶Ra_ex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0.1 and 0.2, which is intermediate between the seawater ratio at these depths (<0.03) and the seawater ratios found in the upper 250 m (0.31-0.42). This suggests that excess Ba (i.e., Ba_ex = Ba_total − Ba_lithogenic), considered to be mainly barite, present in the sinking flux is a mixture of crystals formed recently in the upper water column, formed several years earlier in the upper water column, or formed recently in deeper waters. We observe a sizeable temporal variability in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles, which indicates temporal variability in the relative proportion of barite crystals originating from surface (with a high ²²⁸Ra_ex/²²⁶Ra_ex ratio) and mesopelagic (with a low ²²⁸Ra_ex/²²⁶Ra_ex ratio) sources. However, we could not discern a clear pattern that would elucidate the factors that control this variability. The ²²⁶Ra/Ba ratios measured in seawater are consistent with the value reported from the GEOSECS expeditions (2.3 dpm μmol⁻¹) below 500 m depth, but are significantly lower in the upper 500 m. High ²²⁶Ra_ex/Ba_ex ratios and elevated Sr concentrations in suspended particles from the upper water column suggest preferential uptake of ²²⁶Ra over Ba during formation of SrSO₄ skeletons by acantharians, which must contribute to barite formation in shallow waters. Deeper in the water column the ²²⁶Ra_ex/Ba_ex ratios of suspended particles are lower than those of seawater. Since ²²⁸Ra_ex/²²⁶Ra_ex ratios demonstrate that suspended barite at these depths has been produced recently and in situ, their low ²²⁶Ra_ex/Ba_ex ratios indicate preferential uptake of Ba over Ra in barite formed in mesopelagic water.     

Ba, Ra, Th, and U in marine mollusc shells and the potential of Ra/Ba dating of Holocene marine carbonate shells

The geochemistry of Ba, Ra, Th, and U and the potential of using ²²⁶Ra/Ba ratios as an alternative dating method are explored in modern and Holocene marine mollusc shells. Five modern shells of the Antarctic scallop Adamussium colbecki collected from the present day beach and six radiocarbon dated specimens from Holocene beach terraces of the Ross Sea region (Antarctic) between 700 and 6100 calibrated yr BP old have been analysed by mass spectrometry. In clean shells ²²⁶Ra concentrations and ²²⁶Ra/Ba ratios show a clear decrease with increasing age, suggesting the possibility of ²²⁶Ra dating. Limiting factors for such dating are Ba and ²²⁶Ra present in surface contaminants, and ingrowth of ²²⁶Ra from U present within the shell. Surface contamination is difficult to clean off entirely, but moderate levels of residual contamination can be corrected using ²³²Th. Sub-samples from the same shell with different proportions of contamination form a mixing line in a ²²⁶Ra/Ba-²³²Th/Ba graph, and the ²²⁶Ra/Ba of the pure shell can be derived from the intercept on the ²²⁶Ra/Ba axis. Contaminant corrected ²²⁶Ra/Ba ratios of late-Holocene ¹⁴C-dated samples fall close to that expected from simple ²²⁶Ra excess decay from seawater ²²⁶Ra/Ba values. ²²⁶Ra ingrowth from U incorporated into the shell during the lifetime of the mollusc can be corrected for. However, the unknown timing of post mortem U uptake into the shell makes a correction for ²²⁶Ra ingrowth from secondary U difficult to achieve. In the A. colbecki shells, ²²⁶Ra ingrowth from such secondary U becomes significant only when ages exceed ∼2500 yr. In younger shells, ²²⁶Ra/Ba ratios corrected for surface contamination provide chronological information. If evidence for a constant oceanic relationship between ²²⁶Ra and Ba in the ocean can be confirmed for that time scale, the ²²⁶Ra/Ba chronometer may enable the reconstruction of variability in sea surface ¹⁴C reservoir ages from mollusc shells and allow its use as a paleoceanographic tracer.     

Factors controlling the groundwater transport of U, Th, Ra, and Rn

A model for the groundwater transport of naturally occurring U, Th, Ra, and Rn nuclides in the²³⁸U and²³²Th decay series is discussed. The model developed here takes into account transport by advection and the physico-chemical processes of weathering, decay, α-recoil, and sorption at the water-rock interface. It describes the evolution along a flowline of the activities of the²³⁸U and²³²Th decay series nuclides in groundwater. Simple sets of relationships governing the activities of the various species in solution are derived, and these can be used both to calculate effective retardation factors and to interpret groundwater data. For the activities of each nuclide, a general solution to the transport equation has been obtained, which shows that the activities reach a constant value after a distance ϰ_i, characteristic of each nuclide. Where ϰ_i is much longer than the aquifer length, (for²³⁸U,²³⁴U, and²³²Th), the activities grow linearly with distance. Where gKⁱ is short compared to the aquifer length, (for²³⁴Th,²³⁰Th,²²⁸Th,²²⁸Ra, and²²⁴Ra), the activities rapidly reach a constant or quasi-constant activity value. For²²⁶Ra and²²²Rn, the limiting activity is reached after 1 km. High δ²³⁴U values (proportional to the ratio^ɛ234Th/^W238U) can be obtained through high recoil fraction and/or low weathering rates. The activity ratios²³⁰Th/²³²Th,²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra have been considered in the cases where either weathering or recoil is the predominant process of input from the mineral grain. Typical values for weathering rates and recoil fractions for a sandy aquifer indicate that recoil is the dominant process for Th isotopic ratios in the water. Measured data for Ra isotope activity ratios indicate that recoil is the process generally controlling the Ra isotopic composition in water. Higher isotopic ratios can be explained by different desorption kinetics of Ra. However, the model does not provide an explanation for²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra activity ratios less than unity. From the model, the highest²²²Rn emanation equals 2ɛ. This is in agreement with the hypothesis that²²²Rn activity can be used as a first approximation for input by recoil (Krishnaswamiet al 1982). However, high²²²Rn emanation cannot be explained by production from the surface layer as formulated in the model. Other possibilities involve models including surface precipitation, where the surface layer is not in steady-state.     

U-Th chronology and paleoceanographic record in a Fe-Mn crust from the NE Atlantic over the last 700 ka

Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (¹⁰Be, ²³⁰Th_ex, ²³⁰Th_ex/²³²Th, ²³⁴U/²³⁸U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (²³⁰Th_ex), (²³⁰Th_ex/²³²Th), and Be data give very consistent growth rates. In particular, the good match between (²³⁰Th_ex) and (²³⁰Th_ex/²³²Th) data indicates that at the location of crust 121DK, ²³⁰Th and ²³²Th fluxes in the water column change simultaneously and suggests that the normalization of ²³⁰Th_ex to ²³²Th makes (²³⁰Th_ex/²³²Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant ²³⁰Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (²³⁴U/²³⁸U) depth profile, however, was clearly affected by diffusion of ²³⁴U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (²³⁰Th_ex/²³²Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (²³⁰Th/²³²Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.     

Uranium-series disequilibrium in tuffs from Yucca Mountain,Nevada, as evidence of pore-fluid flow over the last million years

Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of ‘bomb’ ³⁶Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios ²³⁴U/²³⁸U, ²³⁰Th /²³⁴U and ²²⁶Ra/²³⁰Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of ²³⁴U (weighted mean ²³⁴U/²³⁸U=0.95±0.01) and a small excess of ²³⁰Th (weighted mean ²³⁰Th/²³⁴U 1.10±0.02). The ²²⁶Ra/²³⁰Th ratios are close to secular equilibrium (weighted mean=0.94±0.07). These data indicate that ²³⁴U has been removed from the rock samples in the last ∼350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that ²²⁶Ra has not been mobilized and removed from the tuff, although there may be some localised ²²⁶Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of ²³⁴U, this indicates that pore fluids are moving equally through fractured and unfractured rock. More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable.     

Geochemical evolution of a shallow magma plumbing system during the last 500 years, Miyakejima volcano, Japan: Constraints from U-Th-Ra systematics

In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469-2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with excess ²³⁸U and ²²⁶Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (²³⁰Th/²³²Th) ratio compared to older Miyakejima eruptives, yielding the youngest ²³⁸U-²³⁰Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram and (2) a positive linear correlation in a (²²⁶Ra/²³⁰Th)₀ − 1/²³⁰Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of ²³⁰Th and ²²⁶Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (²³⁰Th/²³²Th) and (²²⁶Ra/²³⁰Th)₀ ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr-Nd-Pb isotopic systems. In such cases, Th isotopes and (²²⁶Ra/²³⁰Th) ratio are excellent geochemical tracers of magmatic evolution.     

TIMS测定铀矿石样品中^234U/^238U、^230Th/^232Th、^228Ra/^226Ra的方法研究

研究了TIMS测定铀矿石样品中234U/238U、230Th/232Th、228Ra/226Ra的方法。建立了铀矿石密闭混酸一次溶样的方法和采用阴离子、阳离子和Sr特效树脂逐级离子交换分离纯化U、Th和Ra的流程,满足了TIMS测量要求。测定结果表明：100～1000 ng的天然铀中234U/238U,其测量精密度从静态多接收的2.34%提高到动态多接收的0.47%;对230Th与232Th丰度接近、质量为1μg左右的钍,采用三带点样技术和法拉第多接收技术测定230Th/232Th,其内精度平均值为0.0048%,外精度为0.028%;采用单带加钽发射剂,ETP跳峰测定50～100 fg镭-228稀释剂中的228Ra/226Ra,其内精度小于0.10%,外精度小于0.20%。比较TIMS和HR-ICP-MS、α能谱法测定234U/238U、230Th/232Th、228Ra/226Ra结果,三者结果相吻合。TIMS测量法样品用量少、快速、准确、精密度高,是U、Th、Ra同位素比值测定方法的又一补充。     

高分辨电感耦合等离子体质谱法测定铀矿石样品中234U/238U、230Th/232Th和228Ra/226Ra同位素比值 

采用氢氟酸-硝酸-盐酸混合酸密闭消解含铀矿石样品,用阴离子交换树脂、阳离子交换树脂和锶特效树脂逐级分离富集铀、钍和镭。使用高分辨电感耦合等离子体质谱(HR-ICPMS)测定分离纯化液中234U/238U2、30Th/232Th和228Ra/226Ra同位素。比值的测量精密度取决于比值的大小和对应核素浓度的大小。对质量浓度为10 ng/mL天然铀测量液,234U/238U的测量精密度优于1.2%;对230Th质量浓度为0.6ng/mL且230Th和232Th质量浓度接近的测量液,230Th/232Th的测量精密度为1.2%;对228Ra质量浓度为0.48 pg/mL且228Ra和226Ra质量浓度接近的测量液,228Ra/226Ra的测量精密度为4.0%。     

Ra-partitioning between phlogopite and silicate melt and 226Ra/Ba–230Th/Ba isochrons

In this study we experimentally determine phlogopite/melt partition coefficients of Ra and other trace elements in a lamproitic system. This work was achieved using an analytical technique (LA-ICP-MS) with low detection limits (~ 0.01 fg) permitting the measurement of the very low Ra concentrations feasible in experiments (~ 1 ppb). D_Ra^{phlogopite/melt} was determined to 2.28 ± 0.44 and 2.84 ± 0.47 in two experiments, the ratio D_Ra/D_Ba is around 1.6. The compatibility of Ra in phlogopite results from an ionic radius being close to the apex of the lattice strain parabola for earth alkalis in the large XII-coordinated interlayer site of phlogopite. A re-evaluation of D_Ra and D_Ra/D_Ba for magmatic minerals containing appreciable Ra, yields D_Ra^mineral/melt ranging from ~ 2.6 for phlogopite down to 2–3 ? 10^? 5 for pyroxenes, and D_Ra/D_Ba^mineral/melt from ~ 4 for leucite to 2 ? 10^? 2 for orthopyroxene. The influence of melt composition on D_Ra/D_Ba is less than 10%. All investigated minerals have different D_Ra/D_Ba, strongly fractionating Ra from Ba. Thus, for magmatic systems, (²²⁶Ra)/Ba in the various minerals is not constant, these minerals do not form a straight line in the (²²⁶Ra)/Ba–(²³⁰Th)/Ba system at the time of crystallization and thus, there is no (²²⁶Ra)/Ba–(²³⁰Th)/Ba isochron at t₀. ²²⁶Ra–²³⁰Th–Ba mineral dating is thus applicable only to model ages calculated from mineral–glass pairs with known D_Ra.     

U-series disequilibria in Kick’em Jenny submarine volcano lavas: A new view of time-scales of magmatism in convergent margins

We present data for U and its decay series nuclides ²³⁰Th, ²²⁶Ra, ²³¹Pa, and ²¹⁰Po for 14 lavas from Kick’em Jenny (KEJ) submarine volcano to constrain the time-scales and processes of magmatism in the Southern Lesser Antilles, the arc having the globally lowest plate convergence rate. Although these samples are thought to have been erupted in the last century, most have (²²⁶Ra)/(²¹⁰Po) within ±15% of unity. Ten out of 14 samples have significant ²²⁶Ra excesses over ²³⁰Th, with (²²⁶Ra)/(²³⁰Th) up to 2.97, while four samples are in ²²⁶Ra-²³⁰Th equilibrium within error. All KEJ samples have high (²³¹Pa)/(²³⁵U), ranging from 1.56 to 2.64 and high ²³⁸U excesses (up to 43%), providing a global end-member of high ²³⁸U and high ²³¹Pa excesses. Negative correlations between Sr, sensitive to plagioclase fractionation, and Ho/Sm, sensitive to amphibole fractionation, or K/Rb, sensitive to open system behavior, indicate that differentiation at KEJ lavas was dominated by amphibole fractionation and open-system assimilation. While (²³¹Pa)/(²³⁵U) does not correlate with differentiation indices such as Ho/Sm, (²³⁰Th)/(²³⁸U) shows a slight negative correlation, likely due to assimilation of materials with slightly higher (²³⁰Th)/(²³⁸U). Samples with ²²⁶Ra excess have higher Sr/Th and Ba/Th than those in ²²⁶Ra-²³⁰Th equilibrium, forming rough positive correlations of (²²⁶Ra)/(²³⁰Th) with Sr/Th and Ba/Th similar to those observed in many arc settings. We interpret these correlations to reflect a time-dependent magma differentiation process at shallow crustal levels and not the process of recent fluid addition at the slab-wedge interface.The high ²³¹Pa excesses require an in-growth melting process operating at low melting rates and small residual porosity; such a model will also produce significant ²³⁸U-²³⁰Th and ²²⁶Ra-²³⁰Th disequilibrium in erupted lavas, meaning that signatures of recent fluid addition from the slab are unlikely to be preserved in KEJ lavas. We instead propose that most of the ²³⁸U-²³⁰Th, ²²⁶Ra-²³⁰Th, and ²³⁵U-²³¹Pa disequilibria in erupted KEJ lavas reflect the in-growth melting process in the mantle wedge (reflecting variations in U/Th, daughter-parent ratios, fO₂, and thermal structure), followed by modification by magma differentiation at crustal depths. Such a conclusion reconciles the different temporal implications from different U-series parent-daughter pairs and relaxes the time constraint on mass transfer from slab to eruption occurring in less than a few thousand years imposed by models whereby ²²⁶Ra excess is derived from the slab.     

Plume-lithosphere interaction beneath Mt. Cameroon volcano, West Africa: Constraints from U-Th-Ra and Sr-Nd-Pb isotope systematics

Precise measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr-Nd-Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with ²³⁰Th (18-24%) and ²²⁶Ra (9-21%) excesses, and there exists a positive correlation in a (²²⁶Ra/²³⁰Th)-(²³⁰Th/²³⁸U) diagram. The extent of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria is markedly different in lavas of individual eruption ages, although the (²³⁰Th/²³²Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (²³⁰Th/²³⁸U)-(²⁰⁶Pb/²⁰⁴Pb) and (²²⁶Ra/²³⁰Th)-(²⁰⁶Pb/²⁰⁴Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high D_U and D_U/D_Th, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb > 20.47) due to late Mesozoic metasomatism.     

Early diagenesis impact on precise U-series dating of deep-sea corals: Example of a 100-200-year old Lophelia pertusa sample from the northeast Atlantic

Deep-sea coral has proved useful for paleoceanographic reconstructions and for documenting ¹⁴C-ages of water masses using ²³⁰Th-ages. However, for precise and accurate U-series dating, further information on coral-age structure, growth rate and diagenetic evolution is still needed. To document such processes, we used U-Th-²²⁶Ra systematics in a 40 cm diameter, Lophelia pertusa specimen collected in 1912 from the Eastern Atlantic (Sea of the Hebrides). External parts of the specimen are thought to have been alive when collected whereas more internal parts were likely dead. The “live-collected” and “dead” parts of the skeleton were sampled and analyzed for their ²³⁰Th, ²³²Th, ²³⁴U, ²³⁸U, ²²⁶Ra and Ba contents by thermal ionization and multicollector inductively coupled plasma mass spectrometry. ²³⁰Th/²³⁴U ratios in the most recent parts yielded ages of 86 ± 6 a and 92 ± 9 a, in agreement with the date of recovery. The older parts yielded ²³⁰Th ages ranging from 169 ± 15 to 211 ± 10 a (n = 5), but had a 31% higher U content than more recent parts of the skeleton. This raises concerns about the possibility of secondary diagenetic U uptake, although an environmentally controlled U/Ca shift between coral growth stages cannot be ruled out. ²²⁶Ra/Ba measurements were made, and model- ²²⁶Ra/Ba ages averaging 250 ± 12 yr were calculated for the older part, assuming a constant initial ²²⁶Ra/Ba ratio in bottom waters. These ages are slightly older than ²³⁰Th-ages, suggesting either that ²²⁶Ra/Ba ratios of ambient-seawater changed over time or that a diagenetic phenomenon have affected the U-series system, or both. Scanning electron microscope observations revealed bioerosion and secondary biomineralization in the older part of the coral skeleton, supporting the hypothesis that diagenetic processes may have influenced the ages obtained by the U-series toolbox. Modeled U-series ages for such an open system are discussed. However, a comparison between ¹⁴C- and ²³⁰Th-ages performed on both pristine and bioeroded parts of the coral gives coherent values (ca 450 a) for the preindustrial ¹⁴C-reservoir age of North Atlantic waters. It remains to be determined, however, whether diagenesis occurs rapidly over a short period of time, or whether it continues for longer periods. In the latter case, diagenetic processes would hamper paleoceanographic interpretations as well as the precise calculation of ¹⁴C ages of deep-water masses, based on comparative U/Th- and ¹⁴C-chronologies.     

Th/U/U and Pa/U ages from a single fossil coral fragment by multi-collector magnetic-sector inductively coupled plasma mass spectrometry

The ²³⁰Th/²³⁴U/²³⁸U age dating of corals via alpha counting or mass spectrometry has significantly contributed to our understanding of sea level, radiocarbon calibration, rates of ocean and climate change, and timing of El Nino, among many applications. Age dating of corals by mass spectrometry is remarkably precise, but many samples exposed to freshwater yield inaccurate ages. The first indication of open-system ²³⁰Th/²³⁴U/²³⁸U ages is elevated ²³⁴U/²³⁸U_initial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have ²³⁴U/²³⁸U_initial values close to seawater, there is a need for age validation. Redundant ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in a single fossil coral fragment are possible by Multi-Collector Magnetic Sector Inductively Coupled Plasma Mass Spectrometry (MC-MS-ICPMS) and standard anion exchange column chemistry, modified to permit the separation of uranium, thorium, and protactinium isotopes from a single solution. A high-efficiency nebulizer employed for sample introduction permits the determination of both ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in fragments as small as 500 mg. We have obtained excellent agreement between ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in Barbados corals (30 ka) and suggest that the methods described in this paper can be used to test the ²³⁰Th/²³⁴U/²³⁸U age accuracy.Separate fractions of U, Th, and Pa are measured by employing a multi-dynamic procedure, whereby ²³⁸U is measured on a Faraday cup simultaneously with all minor isotopes measured with a Daly ion counting detector. The multi-dynamic procedure also permits correcting for both the Daly to Faraday gain and for mass discrimination during sample analyses. The analytical precision of ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U dates is generally better than ±0.3% and ±1.5%, respectively (2 Relative Standard deviation [RSD]). Additional errors resulting from uncertainties in the decay constant for ²³¹Pa and from undetermined sources currently limit the ²³¹Pa/²³⁵U age uncertainty to about ±2.5%. U isotope data and ²³⁰Th/²³⁴U/²³⁸U ages agree with National Institute of Standards and Technology (NIST) reference materials and with measurements made by Thermal Ionization Mass Spectrometry (TIMS) in our laboratory.     

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria, Sr-Nd-Pb-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr-Nd-Pb-Hf isotopes (⁸⁷Sr/⁸⁶Sr = 0.70319-0.70322; ¹⁴³Nd/¹⁴⁴Nd = 0.51302-0.51305; ²⁰⁶Pb/²⁰⁴Pb = 19.04-19.06; ²⁰⁷Pb/²⁰⁴Pb = 15.53-15.54; ²⁰⁸Pb/²⁰⁴Pb = 38.61-38.65; ¹⁷⁶Hf/¹⁷⁷Hf = 0.28311-0.28312). All the samples possess (²³⁰Th/²³⁸U) disequilibrium with ²³⁰Th excesses, and they show systematic variations in (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) ratios. The highest ²²⁶Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (²²⁶Ra/²³⁰Th) ratio that are close to equilibrium. The ²³⁸U-²³⁰Th-²²⁶Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of ²³⁰Th and ²²⁶Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in ²³⁰Th-²³⁸U and ²²⁶Ra-²³⁰Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.     

中国东部全新世火山的镭-钍同位素年代学

活火山是指1万年来有过喷发历史的全新世火山。火山的高分辨年代学对火山灾害评估和火山分类具有重要意义。对于缺乏历史记载的全新世火山,直接对火山岩进行同位素定年很困难。本文利用具有高时间分辨率的镭-钍-铀非平衡确定中国东部年轻火山的年龄。根据镭-钍-铀同位素,海南岛的马鞍岭和雷虎岭是全新世火山(马鞍岭:4.3ka;雷虎岭:4.7ka);镜泊湖火山(4.9ka)也是全新世火山;龙岗火山存在晚更新世和全新世活动(7.0ka,15.0ka);大兴安岭阿尔山和诺敏河Ra/Th非平衡消失但~(230)Th/~(238)U非平衡显著,属于晚更新世喷发(阿尔山:63ka;诺敏河:71ka)。海南岛的马鞍岭火山、雷虎岭火山和东北地区的龙岗火山、镜泊湖火山,是4座活火山。至于东北地区的阿尔山和诺敏河火山是否是活火山,有待测试更多样品的Ra/Th同位素。五大连池老黑山和火烧山有历史喷发记录,这与它们都存在显著Ra/Th非平衡一致。五大连池老黑山和火烧山的岩浆滞留年龄分别小于4.2ka和3.2ka,岩浆上升速率 18～23m/y。     

Chemical and isotopic constraints on the generation and transport of magma beneath the East Pacific Rise

Interpretation of U-series disequilibria in midocean ridge basalts is highly dependent on the bulk partition coefficients for U and Th and therefore the mineralogy of the mantle source. Distinguishing between the effect of melting processes and variable source compositions on measured disequilibria (²³⁸U-²³⁰Th-²²⁶Ra and ²³⁵U-²³¹Pa) requires measurement of the radiogenic isotopes Hf, Nd, Sr, and Pb. Here, we report measurements of ²³⁸U-²³⁰Th-²²⁶Ra and ²³⁵U-²³¹Pa disequilibria; Hf, Nd, Sr, and Pb isotopic; and major and trace element compositions for a suite of 20 young midocean ridge basalts from the East Pacific Rise axis between 9°28′ and 9°52′N. All of the samples were collected within the axial summit trough using the submersible Alvin. The geological setting and observational data collected during sampling operations indicate that all the rocks are likely to have been erupted from 1991 to 1992 or within a few decades of that time. In these samples, ²³⁰Th excesses and ²²⁶Ra excesses are variable and inversely correlated. Because the eruption ages of the samples are much less than the half-life of ²²⁶Ra, this inverse correlation between ²³⁰Th and ²²⁶Ra excesses can be considered a primary feature of these lavas. For the lava suite analyzed in this study, ²²⁶Ra and ²³⁰Th excesses also vary with lava composition: ²²⁶Ra excesses are negatively correlated with Na₈ and La/Yb and positively correlated with Mg#. Conversely, ²³⁰Th excesses are positively correlated with Na₈ and La/Yb and negatively correlated with Mg#. Th/U, ²³⁰Th/²³²Th, and ²³⁰Th excesses are also variable and correlated to one another. ²³¹Pa excesses are large but relatively constant and independent of Mg#, La/Yb, Th/U, and Na₈. The isotope ratios ¹⁴³Nd/¹⁴⁴Nd, ¹⁷⁶Hf/¹⁷⁷Hf, ⁸⁷Sr/⁸⁶Sr, and ²⁰⁸Pb/²⁰⁶Pb are constant within analytical uncertainty, indicating that they were derived from a common source. The source is homogeneous with respect to parent/daughter ratios Lu/Hf, Sm/Nd, Rb/Sr, and Th/U; therefore, the measured variations of Th/U, ²³⁰Th, and ²²⁶Ra excesses and major and trace element compositions in these samples are best explained by polybaric melting of a homogeneous source, not by mixing of compositionally distinct sources.     

Uranium geochemistry and dating of Pacific island apatite

Uranium-series disequilibrium dating of island phosphate deposits is evaluated in terms of known associated coral ages, uranium geochemistry, and stratigraphic sequences as well as the concordance between the geochronometers ²³⁴U/²³⁸U, ²³⁰Th/²³⁴U and ²²⁶Ra/²³⁸U. U(VI) is the predominant oxidation state of uranium in island phosphorites and by analogy to the youngest surficial deposits, most of the uranium initially bound is in the form of U(VI) sorbed by surfaces from seawater. Insular deposits contain more organic matter than even very young ocean floor samples and this leads to a greater probability of reduction of available recoil uranium than occurs in marine deposits. As a consequence, R(VI) ? R(T) ? R(VI), where R represents the ²³⁴U/²³⁸U activity ratio. This situation is completely opposite from that observed for marine-origin phosphorites. We determined that a fraction of U(VI) in ancient insular phosphorites is very labile and lost to alkaline carbonate solutions with a uranium activity ratio even more depleted in ²³⁴U than the bulk R(VI).Most younger samples appear to have no more discordance between ²³⁴U/²³⁸U, ²³⁰Th/²³⁴U and ²²⁶Ra/²³⁸U than marine phosphorites of similar apparent age. Young, surficial atoll-rim apatite cements and unconsolidated phosphorites date in the range of 1500–8000 years B.P., consistent with the concept of partial submergence of low-lying coral islands prior to 2000 years B.P. Sub-surficial samples in the same environment date older at about 20,000 years B.P. Violation of the closed system assumption occurs in at least 6 out of 13 ancient (> 800,000 year) samples. Uranium-series disequilibrium dating of insular apatite shows some promise as a recorder of climatic/sea level events, but the assumptions necessary for valid ages must be carefully evaluated for each occurrence.     

The effect of assimilation, fractional crystallization, and ageing on U-series disequilibria in subduction zone lavas

Although most arc lavas have experienced significant magma differentiation, the effect of the differentiation process on U-series disequilibria is still poorly understood. Here we present a numerical model for simulating the effect of time-dependent magma differentiation processes on U-series disequilibria in lavas from convergent margins. Our model shows that, in a closed system with fractional crystallization, the ageing effect can decrease U-series disequilibria via radioactive decay while in an open system, both ageing and bulk assimilation of old crustal material serve to reduce the primary U-series disequilibria. In contrast, with recharge of refresh magma, significant ²²⁶Ra excess in erupted lavas can be maintained even if the average residence time is longer than 8000 years.The positive correlations of (²²⁶Ra/²³⁰Th) between Sr/Th or Ba/Th in young lavas from convergent margins have been widely used as evidence of fluid addition generating the observed ²²⁶Ra excess in subduction zones. We assess to what extent the positive correlations of (²²⁶Ra/²³⁰Th) with Sr/Th and Ba/Th observed in the Tonga arc could reflect AFC process. Results of our model show that these positive correlations can be produced during time-dependent magma differentiation at shallow crustal levels. Specifically, fractional crystallization of plagioclase and amphibole coupled with contemporaneous decay of ²²⁶Ra can produce positive correlations between (²²⁶Ra/²³⁰Th) and Sr/Th or Ba/Th (to a lesser extent). Therefore, the correlations of (²²⁶Ra/²³⁰Th) with Sr/Th and Ba/Th cannot be used to unambiguously support the fluid addition model, and the strength of previous conclusions regarding recent fluid addition and ultra-fast ascent rates of arc magmas is significantly lessened.