Estimating the uncertainty of coral isochron U–Th ages

Recently, alternative models to estimate the age of diagenetically altered fossil reef corals have been presented based on either redistribution of U or its immediate daughters ²³⁴Th and ²³⁰Th. Here, we present three methods to estimate the uncertainty of ages derived using an amended version of our coral isochron method [Scholz et al., 2004. U-series dating of diagenetically altered fossil reef corals. Earth and Planetary Science Letters 218, 163–178], which is based on addition/loss of U. The obtained uncertainties are substantially larger than those previously published and should, in general, be more reliable. The isochron method yields larger uncertainties than alternative models based on Th redistribution due to -recoil processes. However, comparison of model open-system ages based on such redistribution of U-series daughters for different sub-samples from an individual coral specimen shows that the smaller errors derived with these models cannot account for the observed variability. We recognise that none of the available models is applicable to all corals, probably reflecting different diagenetic processes even in different sub-samples from one coral specimen. To better understand the diagenetic processes and precisely constrain the uncertainties of the ages derived from diagenetically altered corals, the application of all available models is recommended.     

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.     

Relative importance of dissolved and food pathways for lead contamination in shrimp

The relative importance of dissolved and food pathways and the influence of food type in the bioaccumulation and retention of lead in the shrimp Palaemonetes varians were examined using a radiotracer method. Shrimp were exposed to ²¹⁰Pb-labelled seawater or fed two types of ²¹⁰Pb-labelled food, viz. mussels or worms. The amount of radiotracer accumulated by shrimp was examined over a 7-day period, followed by a 1-month and a 7-day depuration period for the dissolved and food source, respectively. Steady state in the uptake was reached after 2 days exposure to dissolved lead, with a resultant estimated concentration factor of 98 ± 3. Transfer factors following ingestion of contaminated mussels and worms were lower than unity for both food types, with lead transfer from worms being significantly higher than that from mussels. Accumulation of dissolved Pb by shrimp was found to occur mainly through adsorption on the exoskeleton with a minor accumulation in the internal tissues probably resulting from the intake of seawater for osmoregulation. In contrast, lead taken up from contaminated food was readily absorbed and bound in the internal tissues of P. varians. Although the transfer of lead to P. varians through the ingestion of contaminated food was low (TF < 1%), it still represented 4 to 8% of the lead content in the prey which is a significant additional contribution of lead to the shrimp body burden. Independent of food type, following ingestion of contaminated food, approximately 23–27% of total lead accumulated in shrimp was located in the edible parts (e.g. muscle). Therefore, the food pathway is suggested to be a significant contributor to the lead transfer to humans through ingestion of contaminated shrimp. After exposure to contaminated food, lead loss kinetics were described by a two-component model, whereas Pb loss following direct uptake from seawater was best described by a three-component model. The additional compartment representing 64% of total Pb retained and characterized by a turnover < 10 min, corresponded to lead weakly adsorbed on the exoskeleton and incorporated in the hepatopancreas. Nevertheless, a significant fraction of lead accumulated from the dissolved (2%) and food (52–57%) pathways remained irreversibly retained in the tissues, suggesting that this organism could also serve as an effective long-term bioindicator of lead contamination in marine waters.     

Evaluation of selected cobalt-60 complexes as tracers of groundwater

A series of Co-60 compounds, considered as potentially useful tracers of groundwater movement, were prepared and evaluated in soil column and batch studies. The compounds were: potassium hexacyanocobaltate (III), K₃Co(CN)₆; potassium ethylenediamminetetraacetato-cobaltate (III), KCo(EDTA); ammonium 12-tungstodicobaltoate (III), (NH₄)₈[Co(II)Co(II)W₁₂O₄₂] · 20 H₂O; chloraquotetrammine cobalt (III) chloride, [Co(NH₃)₄(H₂O)Cl]Cl₂; and sodium hexanitrocobaltate (III), Na₃Co(NO₂)₆. The performance of K₃ ⁶⁰Co(CN)₆ and K ⁶⁰Co EDTA were dependent on their environment and more especially on the type and amount of clay present. The EDTA cobalt complex cannot be used in soils that are basic or where a large fraction of the clay is saturated with Na⁺ and/or Ca⁺⁺. Of the other radioactive tracers tested, none were suitable for groundwater tracing because of instability in aqueous solution (Na₃Co(NO₂)₆), variable anionic structure under acid conditions ((NH₃)₈[Co(II)Co(II)W₁₂O₄₂] · 20 H₂O), or preferential uptake by the clay fraction ([Co(NH₃)₄(H₂O)Cl]Cl₂).     

In situ cosmogenic Be in olivines and pyroxenes

This study proposes an efficient new cleaning procedure for measuring in situ cosmogenic ¹⁰Be in olivines and pyroxenes. This chemical routine is specially designed to decontaminate the abundant meteoric ¹⁰Be from these minerals. The method was tested on mafic minerals from basaltic flows of Mt. Etna volcano and from Hawaiian flows and moraines. A sequential dissolution test shows that ¹⁰Be concentrations decrease with the number of cleaning steps until reaching a constant value. This is a necessary condition to demonstrate the efficiency of the method in properly decontaminating samples of meteoric ¹⁰Be. Moreover, cross-calibration with cosmogenic ³He measured within the same samples yielded a sea level high-latitude production rate of 4.5±0.4 at g⁻¹ a⁻¹ for cosmogenic ¹⁰Be in mafic minerals. This rate is within 1σ uncertainty of empirically or model-derived rates for ¹⁰Be on the same targets. Such concordance supports the consistency of the new method.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

Dating earthquakes with high-precision thorium-230 ages of very young corals

Mass spectrometric techniques have recently yielded significant increases in precision and sensitivity over previous methods for measuring²³⁰Th abundance in corals. To assess the accuracy of²³⁰Th ages, three corals from Vanuatu, whose ages were known from counting annual growth bands, were analyzed. For each sample, the date of growth determined by²³⁰Th analysis (A.D.1969 ± 3, 1932 ± 5,and1806 ± 5; 2σ uncertainties based on analytical error) was indistinguishable from the date determined by counting bands (A.D. 1971–1973, 1935–1937, and 1804–1810), indicating that the²³⁰Th dates are accurate.²³⁰Th dates were also determined for two adjacent emerged heads from Santo Is., Vanuatu, which were thought to have died when they were raised above sea level during coseismic uplift. The dates (A.D.1864 ± 4, 1866 ± 4) were the same, indicating that the heads died at the same time and consistent with the idea that they were killed by coseismic emergence around A.D. 1865. The difference between this date and the date of the only major historically documented earthquake that caused uplift (A.D. 1973,M_s = 7.5), suggests a seismic recurrence interval of108 ± 4y for Santo. Analogous emerged corals from Malekula Is., Vanuatu yielded²³⁰Th dates that were similar to each other (A.D.1729 ± 3, 1718 ± 5) and are inferred to have died during coseismic emergence around A.D. 1729. In conjunction with the date of the only large historically documented earthquake that caused uplift (A.D. 1965,M_s = 7.5), the recurrence interval for Malekula is236 ± 3y. If similar emerged corals can be found, this appraoch may be extended back in time and to other localities because it appears that such features can now be dated both accurately and precisely.     

Temporal–compositional trends over short and long time-scales in basalts of the Big Pine Volcanic Field, California

Primitive basaltic single eruptions in the Big Pine Volcanic Field (BPVF) of Owens Valley, California show systematic temporal–compositional variation that cannot be described by simple models of fractional crystallization, partial melting of a single source, or crustal contamination. We targeted five monogenetic eruption sequences in the BPVF for detailed chemical and isotopic measurements and ⁴⁰Ar/³⁹Ar dating, focusing primarily on the Papoose Canyon sequence. The vent of the primitive (Mg# = 69) Papoose Canyon sequence (760.8 ± 22.8 ka) produced magmas with systematically decreasing (up to a factor of two) incompatible element concentrations, at roughly constant MgO (9.8 ± 0.3 (1σ) wt.%) and Na₂O. SiO₂ and compatible elements (Cr and Ni) show systematic increases, while ⁸⁷Sr/⁸⁶Sr systematically decreases (0.7063–0.7055) and ε_Nd increases (− 3.4 to − 1.1). ¹⁸⁷Os/¹⁸⁸Os is highly radiogenic (0.20–0.31), but variations among four samples do not correlate with other chemical or isotopic indices, are not systematic with respect to eruption order, and thus the Os system appears to be decoupled from the dominant trends. The single eruption trends likely result from coupled melting and mixing of two isotopically distinct sources, either through melt-rock interaction or melting of a lithologically heterogeneous source. The other four sequences, Jalopy Cone (469.4 ± 9.2 ka), Quarry Cone (90.5 ±17.6 ka), Volcanic Bomb Cone (61.6 ± 23.4 ka), and Goodale Bee Cone (31.8 ± 12.1 ka) show similar systematic temporal decreases in incompatible elements. Monogenetic volcanic fields are often used to decipher tectonic changes on the order of 10⁵–10⁶ yr through long-term changes in lava chemistry. However, the systematic variation found in Papoose Canyon (10⁰–10² yr) nearly spans that of the entire volcanic field, and straddles cutoffs for models of changing tectonic regime over much longer time-scales. Moreover, ten new ⁴⁰Ar/³⁹Ar ages combined with chemistry from all BPVF single eruption sequences show the long-term trend of BPVF evolution comprises the overlapping, temporal–compositional trends of the monogenetic vents. This suggests that the single eruption sequences contain the bulk of the systematic chemical variation, whereas their aggregate compositions define the long-term trend of volcanic field evolution.     

A critical evaluation of young (near-zero) K–Ar ages

An evaluation of the precision and resolution of the unspiked K–Ar dating method is presented with particular regard to the statistical significance of ages that are measured near or at the detection limit of the technique. Near-zero (historical) ages can be measured by the unspiked K–Ar technique with a precision that is essentially controlled by the precision with which the ⁴⁰Ar/³⁶Ar of the sample can be resolved from the present-day atmospheric value of 295.5. The best analytical precision on the isotopic ratio is ±0.05% (1σ) by this technique, which currently limits the lower detection limit of unspiked K–Ar ages to samples featuring at least 0.14% of radiogenic ⁴⁰Ar. The corresponding youngest resolvable K–Ar age depends on the K content and atmospheric contamination of the sample. Total-fusion analysis of high-K refractory minerals like sanidine is not practicable via K–Ar, and the lowest resolvable age for medium-K samples more amenable to complete fusion is around 1.5 ka (on a single-run basis). It is argued that near-zero age measured with a probability density straddling or narrowing the time-origin cannot be handled without accounting for the non-negativity constraint imposed by the physical requirement of a positive age. The pertinent equations are derived both for the single-run case and for the case of independent replicates made on a single sample. We show that pooled K–Ar replicates can theoretically reduce the nominal uncertainty of individual unspiked ages (typically ±1.5 ka, 2σ) to a value that is close to the smallest ⁴⁰Ar/³⁹Ar isochron age uncertainty achievable on sanidine in the 0–2 ka range (±0.2 ka, 2σ). However, this performance is obtained at the cost of prohibitively large-sample statistics (n≥15) for medium-K feldspars datable via K–Ar. Coupled with the inability of the K–Ar approach to obviate the problems of excess/fractionated ⁴⁰Ar and/or xenocrystic contamination, this makes the ⁴⁰Ar/³⁹Ar technique the method of choice for dating historical events by the K–Ar scheme.     

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.     

Organic pollutants in sediment cores of NE-Germany: comparison of the marine Arkona Basin with freshwater sediments

During a contamination survey in NE-Germany sediment cores were sampled at 5 locations with freeze-coring devices and conventional box-coring systems. In total more than 40 samples were analysed for several organic compounds (136 PCDD/F, 33 PCB, 39 PAH, 10 DDX, 4 HCH, 4 CB), sedimentological parameters (TOC, TC, TIC, LOI), some total trace metals (Pb, Cd, Cr, Cu, Zn) and dated by measurement of the ²¹⁰Pb and ¹³⁷Cs activity. The deepest segment of the cores from the Arkona Basin and the freshwater lakes were dated back to the end of the 19th century. A comparison of marine versus freshwater data is presented. The contamination levels of Arkona Basin were often lower than anthropogenically influenced freshwater sediments and more similar to a freshwater sediment core only influenced by deposition, with an additional Oder River inflow. Differences in patterns and contamination levels are discussed.     

Issues in radiocarbon and U-series dating of corals from the last glacial period

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 ¹⁴C and ²³⁰Th 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.     

Influence of temperature on the accumulation and retention of 11 radionuclides by the marine alga Fucus vesiculosus (L.)

Accumulation of the radionuclides ²⁴¹Am, ^110mAg, ¹³³Ba, ¹⁰⁹Cd, ⁵⁷Co-cobalamine, ⁶⁰Co, ¹³⁴Cs, ¹⁵²Eu, ⁵⁴Mn, ¹⁰⁶Ru and ⁶⁵Zn in the brown macroalga Fucus vesiculosus (L.) Phaeophyceae, was compared at 2°C and 12°C in a series of laboratory radiotracer experiments. Concentration factors in the thallus were temperature-dependent and significantly decreased at 2°C for ^110mAg, ¹⁰⁹Cd, ⁶⁰Co, ⁵⁴Mn and ⁶⁵Zn (CF = 439, 51, 101, 92 and 162, respectively) but not for ²⁴¹Am, ¹³³Ba, ¹³⁴Cs, ¹⁵²Eu and organic ⁵⁷Co (CF = 329, 210, 3.3, 470 and 214, respectively); hence, for these last isotopes concentration factors in this species derived from temperate latitude (12°C) studies can probably be applied to radiological assessments made under Arctic conditions. Between 2 and 14 days of depuration, the radionuclides, except ¹³³Ba and ¹³⁴Cs, remained tightly bound to the alga. Our results suggest that: 1. temperature must be considered when modelling the radiological impact of radioactive waste dumping in the Arctic Seas; and 2. Fucus spp. would be excellent bioindicators of radionuclide contamination and dispersion in the Barents and Kara Seas.     

An assessment of the effect of chemical scavenging within submarine hydrothermal plumes upon ocean geochemistry

Profiles of ²¹⁰Pb over the Endeavour and North Cleft Segments of the Juan de Fuca Ridge are used to model a time scale for the scavenging, by hydrothermal plumes, of reactive elements in seawater. The hydrothermal plumes above these ridge segments are sites of intense scavenging removal of ²¹⁰Pb. At Endeavour, the total ²¹⁰Pb activities within the plume are as low as 8 dpm/100 l and dissolved activities are as low as 3 dpm/100 l. At the North Cleft, which is characterized by higher particulate Fe concentrations, the total ²¹⁰Pb activities are 4.5 dpm/100 l, the dissolved activities are 1–2 dpm/100 l and the ²¹⁰Pb activities are deficient with respect to the activity of the ²¹⁰Po daughter. These are perhaps the lowest ²¹⁰Pb activities ever measured in the deep sea. The large gradient of ²¹⁰Pb between the plume and surrounding deep water suggests that scavenging is focused into the plumes through horizontal transport. The implication, therefore, is that this process might impact the ocean on a scale larger than that local to the ridge crest. By coupling published measurements of particle flux from Endeavour with ²¹⁰Pb activities on particles trapped at that site, the total volume of seawater stripped of ²¹⁰Pb per year for that site was calculated to be 7.4 × 10¹² l/y. Globally, the extrapolated volume flux of seawater stripped of reactive constituents is 5.7 × 10¹⁵ l/y, such that the entire ocean is processed in this manner in 2.4×10⁵ y. The geochemical cycle of elements with ocean residence times much shorter than this (e.g., Pb and Th) will not be greatly affected by hydrothermal scavenging. On the other hand, this process holds significance for the geochemistry of other elements scavenged by hydrothermal plumes, such as P and V, whose ocean residence times are > 10⁴ y.     

Melting rates beneath Hawaii: Evidence from uranium series isotopes in recent lavas

²³⁸U, ²³²Th, ²³⁰Th and ²²⁶Ra abundances have been measured in six samples of recent Hawaiian basalt by high precision mass spectrometry, in an attempt to compare the melting process in plumes and at spreading ridges. The data reveal a very small range in (²³⁰Th/²³⁸U) activity ratio up to a maximum value of 1.02 ± 0.01, and (²²⁶Ra/²³⁰Th) activity ratios which lie between 1.10 ± 0.015 and 1.19 ± 0.02. UTh and RaTh abundances are linearly correlated demonstrating that the disequilibria predate crystallisation and differentiation. Using recently published estimates for the bulk partition coefficients of U and Th, the results are consistent with melting rates > 10⁻³ kg m⁻³ a⁻¹ at porosities < 10⁻³ for dynamic fractional melting in the garnet stability field.     

Noble gas systematics of deep rift zone glasses from Loihi Seamount, Hawaii

We report new noble gas fusion and crushing data for six pillow rim glasses, recovered between 3 and 5 km water depth on the south rift zone of Loihi Seamount, Hawaii. Helium abundances of the glasses vary from 0.3 to 2.3 μcc/g, with ⁴He/³He ratios between 30000 and 27000 (24–27 R_A), similar to previously reported values. The neon data form a correlation line which is similar to the Loihi-Kilauea line reported by Honda et al. [1], but extends to much higher ratios, up to 12.9 and 0.0382 for the ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios, respectively. This provides conclusive evidence for the suggestion that the Hawaiian plume, thought to originate in the lower mantle, has a solar-like ²⁰Ne/²²Ne composition [1], but a slightly higher ²¹Ne/²²Ne ratio. ⁴⁰Ar/³⁶Ar ratios of the deep rift-zone glasses are as high as 2600, and show a positive correlation with neon isotopic ratios. In contrast to neon and argon, all xenon isotopic compositions are isotopically indistinguishable from air, which either suggests preferential atmospheric contamination of xenon, or could indicate an atmospheric xenon isotopic composition for the lower mantle.     

Atmospheric noble gases in volcanic glasses from the southern Lau Basin: origin from the subducting slab?

Noble gas concentrations and isotopic compositions have been determined for four submarine volcanic glasses from the Valu Fa Ridge (VFR) in the southern Lau Basin. The samples are the least differentiated ones from this area, and they display enrichments in fluid-mobile elements similar to the nearby island arc. ³He/⁴He ratios are slightly below average MORB (6.8–7.8 times atmospheric), whereas Ne, Ar, Kr, and Xe have isotopic compositions very similar to air. Together with previously published data from the Valu Fa Ridge and other spreading segments in the Lau Basin, our data show a systematic latitudinal variation of increasing Ne, Ar, Kr, and Xe abundances from north to south as well as Ne and Ar isotopic compositions changing from MORB-like to atmosphere-like in the same direction. Moreover, isotopic compositions and noble gas abundances of the lavas correlate strongly with Ba/Nb ratios and H₂O concentrations. Based on these observations and mass balance arguments, we propose that the atmospheric noble gases come from the subducting oceanic crust and are not due to shallow contamination with air dissolved in seawater or assimilation of old crust. Our data suggest that the noble gases released from the subducting slab are atmospheric and thus contain little or no solar He and Ne. In addition to the fact that ratios of He to heavy noble gases are small in aged ocean crust, He has possibly fractionated from the other noble gases due to its higher diffusivity, and thus He transport from the subducting slab into the mantle wedge is probably insignificant. We propose that the ³He/⁴He ratios lower than MORB observed in the VFR lavas result from radiogenic ingrowth of He in a highly depleted, and hence degassed, mantle wedge after the enrichment of U and Th released from the downgoing slab.     

Radionuclide fluxes in the Arabian Sea: the role of particle composition

We investigated the influence of the composition of the vertical particle flux on the removal of particle reactive natural radionuclides (²³⁰Th and ²³¹Pa) from the water column to the sediments. Radionuclide concentrations determined in sediment traps moored in the western, central and eastern Arabian Sea were related to the major components (carbonate, particulate organic matter (POC), opal, lithogenic material) of the particle flux. These data were combined with sediment trap data previously published from the Southern Ocean, Equatorial Pacific and North Atlantic [Z. Chase, R.F. Anderson, M.Q. Fleisher, P.W. Kubik, The influence of particle composition and particle flux on scavenging of Th, Pa and Be in the ocean, Earth Planet. Sci. Lett. 204 (2002) 215–229; J.C. Scholten, F. Fietzke, S. Vogler, M. Rutgers van der Loeff, A. Mangini, W. Koeve, J. Waniek, P. Stoffers, A. Antia, J. Kuss, Trapping efficiencies of sediment traps from the deep eastern North Atlantic: The ²³⁰Th calibration, Deep Sea Research II 48 (2001) 2383–2408]. The correlations observed between the particle-dissolved distribution coefficients (K_d) of ²³⁰Th and ²³¹Pa and the concentrations of the particle types depend on the sediment trap data set used. This result suggests that scavenging affinities of the nuclides differ between oceanic regions. Several factors (K_d values, reactive surface areas of particles, inter-correlations in closed data set) can, however, influence the observed relationships and thus hamper the interpretation of these correlation coefficients as a measure of relative scavenging affinities of the nuclides to the particle types investigated. The mean fractionation factor (F(Pa/Th)=K_d(Pa)/K_d(Th)) from the Equatorial Pacific (F=0.11±0.03) is similar to that from the North Atlantic (F(Pa/Th)=0.077±0.026), and both are lower than the factors from the Arabian Sea (F(Pa/Th)=0.35±0.12) and from the Southern Ocean (F(Pa/Th)=0.87±0.4). For opal concentrations exceeding 60%, an increase in the fractionation factors is observed causing a higher mean fractionation factor for the Southern Ocean trap data set. For the other areas investigated, differences in the mean fractionation factors cannot be related to the particles types considered. In the Arabian Sea, seasonally variable ²³¹Pa_ex/²³⁰Th_ex ratios observed in the sediment traps as well as differences of the ratios between recently deposited phytodetritus (fluff) and normal surface sediments indicate seasonal changes in scavenging processes which the generally accepted reversible scavenging models do not envisage. We assume that variable sinking rates of particles, and/or particles not considered in this study (e.g. colloids, manganese oxides, transparent exopolymer particles) may play an important but as yet unexplored role in deep-water scavenging processes.     

Osmium-strontium-neodymium-lead isotopic covariations in mid-ocean ridge basalt glasses and the heterogeneity of the upper mantle

Osmium, strontium, neodymium, and lead isotopic data have been obtained for 30 hand picked samples of basaltic glass from the Pacific, Atlantic and Indian mid-oceanic ridges. Large variations in Os isotopic ratios exist in the glasses, from abyssal peridotite-like values to radiogenic compositions similar to oceanic island basalts (¹⁸⁷Os/¹⁸⁶Os and ¹⁸⁷Os/¹⁸⁸Os ratios range from 1.06 to 1.36 and from 0.128 to 0.163, respectively). Os isotopic and elemental data suggest the existence of mixing correlations. This relationship might be ascribed to secondary contamination processes; however, such a hypothesis cannot account for the negative correlation observed between Os and Nd isotopes and the existence of complementary covariations between Os and SrPb isotopes. In this case, OsSrNdPb isotopic variations are unrelated to late post-eruption or shallow level contamination. These relationships provide strong evidence that the Os isotopic composition of the samples are derived from the mantle and thus implies a global chemical heterogeneity of the oceanic upper mantle. The results are consistent with the presence of recycled oceanic crust in the mantle sources of mid-ocean ridge basalts, and indicate that the unique composition of the upper mantle below the Indian ocean results from its contamination by a mantle component characterized by radiogenic Os and particularly unradiogenic Nd and Pb isotopic compositions.     

Pu, Cs and excess Pb in Russian Arctic sediments

The activity ratios of Pu and radiocesium isotopes have been used to delineate the major sources (such as global and close-in (debris) fallout, nuclear fuel reprocessing and fabrication plant effluents) in the environment. We have measured ²³⁸Pu, ^239,240Pu, ¹³⁷Cs, and excess ²¹⁰Pb concentrations in 107 surficial sediments as well as in 5 sediment cores collected in the summer months of 1993 and 1994 from the Ob and Yenisey Rivers (Russia) and the Kara sea. A comparison of the sediment core inventories of ^239,240Pu and ¹³⁷Cs, along with the ²³⁸Pu/^239,240Pu activity ratios, with those expected from global fallout allows us to estimate the relative amounts, if any, of reactor-derived ²³⁸Pu and ^239,240Pu from the dumped reactor sites in the study area.

In surficial sediment samples collected in 1993 and 1994, the ^239,240Pu concentrations varied between 4.2 and 856 mBq kg⁻¹, with a mean of 239 mBq kg⁻¹. In samples with a measurable ²³⁸Pu, the ²³⁸Pu/^239,240Pu activity ratios varied between 0.010 and 0.069, with an average value of 0.035 ± 0.014. This range can be compared to the average ²³⁸Pu/^239,240Pu activity ratio of 0.030 for the year 1993 from nuclear weapons testing and SNAP fallout obtained from soil studies, indicating very little (≤ 5%) additional sources of ²³⁸Pu to the sediments in the study area. The inventories of Pu in the 5 sediment cores from the study area varied between 2.67 ± 0.67 and 24.5 ± 2.2 Bq m⁻² with a mean value of 8.83 Bq m⁻². The ¹³⁷Cs concentrations in the upper 3 cm of the sediments varied between below detection limit to 71.4 Bq kg⁻¹, with a mean of 14.9 Bq kg⁻¹. The ¹³⁷Cs inventories in the 5 sediment cores varied between 156.7 ± 28.3 and 1600 ± 153.3 Bq m⁻², with a mean value of 583.3 Bq m⁻². The mean ratio of inventories of Pu to that of ¹³⁷Cs, 0.015, is comparable to the values in other places in the Arctic region. There is a significant correlation between total organic carbon and concentrations of ¹³⁷Cs, ^239,240Pu and ²¹⁰Pb, suggesting that organic matter-enriched fine particles are a likely carrier phase for these nuclides. The ratio of ¹³⁷Cs/^239,240Pu also suggests that most of these nuclides are derived from global fallout.