210Pb in the ocean: A pilot tracer for modeling particle reactive elements

We discuss the basic requirements for a successful modeling of²¹⁰Pb in the ocean as a test tracer for at least other lead isotopes, but also of other elements that behave similarly to lead. With the aid of realistic models of the oceanic circulation and the major biogeochemical cycles in it, the result is a dynamically consistent model of lead cycling that reproduces observed profiles within 10%.     

Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study

The Emarat deposit, with a total proved reserve of 10 Mt ore grading 6% Zn and 2.26% Pb, is one of the largest Zn–Pb deposits in the Malayer–Esfahan belt. The mineralization is stratabound and restricted to Early Cretaceous limestones and dolomites. The ore consists mainly of sphalerite and galena with small amounts of pyrite, chalcopyrite, calcite, quartz, and dolomite. Textural evidence shows that the ore has replaced the host rocks and thus is epigenetic.Sulfur isotopes indicate that the sulfur in sphalerite and galena has been derived from Cretaceous seawater through thermochemical sulfate reduction. Sulfur isotope compositions of four apparently coprecipitated sphalerite–galena pairs suggest their precipitation was under equilibrium conditions. The sulfur isotopic fractionation observed for the sphalerite–galena pairs corresponds to formation temperatures between 77 °C and 168 °C, which agree with homogenization temperatures of fluid inclusions.Lead-isotope studies indicate that the lead in galena has been derived from heterogeneous sources including orogenic and crustal reservoirs with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios. Ages derived from the Pb-isotope model give meaningless ages, ranging from Early Carboniferous to future. It is probable that the Pb-isotope model ages that point to an earlier origin than the Early Cretaceous host rocks are derived from older reservoirs in the underlying Carboniferous or Jurassic units, either from the host rocks or from earlier-formed ore deposits within these units.This research and other available data show that the Emarat Zn–Pb deposit has many important features of Mississippi Valley-type (MVT) lead–zinc deposits and thus we argue that it is an MVT-type ore deposit.     

210Pb, 226Ra and 32Si in Pavin lake (Massif Central,France)

Measurements of cosmogenic ³²Si and the U-decay series' nuclides ²¹⁰Pb and ²²⁶Ra in waters and sediments of lake Pavin are reported. Both ²¹⁰Pb and ²²⁶Ra are enriched in the anoxic deep waters compared to the oxic surface waters, respectively by a factor of 4 and 10, whereas ³²Si is depleted by a factor of2. Redox conditions in the lake appear to have no marked effect on the ³²Si. Using a steady-state box model it is shown that the deep-water ³²Si concentration is controlled by the underground lacustrine springs. The residence times of ²¹⁰Pb, ³²Si and ²²⁶Ra are1,10 and80 a, respectively. In the case of ³²Si, where more data are available, the assessed inventory data from the overhead atmospheric fallout and that measured in the sediments agree very well as expected. The ²¹⁰Pb- and ³²Si-based deposition rates during the past100 a ranged from 0.8 to 1.9 mm a⁻¹, earlier these were a factor of3–5 faster. The geochemistry of ³²Si and ²¹⁰Pb in lake Pavin in many ways resembles that in the ocean, only the time scales of the processes involved are faster.     

Concentrations,physico-chemical states and mean residence times of 210Pb and 210Po in marine and estuarine waters

The concentrations and physico-chemical states of ²¹⁰Pb have been measured in Bikini Atoll and Washington State coastal waters, and ²¹⁰Po in Washington coastal waters. Lead-210 concentrations of 113–133 dpm · m^?3 were found in surface water collections near Bikini Atoll and 29–153 dpm · m^?3 in Bikini Lagoon. The concentrations of ²¹⁰Pb in near Bikini and in Washington State waters increased with depth in the upper 150m at a rate of 0.35–0.45dpm·m^?3 · m^?1. In the North Equatorial Current waters near Bikini Atoll ²¹⁰Pb was found associated predominantly with the soluble (colloidal) fraction, but in Washington coastal waters ²¹⁰Pb and ²¹⁰Po were found associated with the paniculate (> 0.3 μm) fraction. The mean residence times of ²¹⁰Pb, calculated from the atmospheric input to marine waters from precipitation and the concentrations measured in surface water, were consistent with the physico-chemical states of ²¹⁰Pb found in samples collected in deep ocean and coastal waters. Approximate values of the mean residence times were calculated, for the upper 50 m, to be as follows: 58 days in the Strait of Juan de Fuca, 128 days at the 5-mile (8 km) station off Cape Flattery (Washington), 163 days at the 12-mile (19 km) station off Cape Flattery, and 2.6 yr near Bikini Atoll. It appears that ²¹⁰Pb and ²¹⁰Po can be used to trace particle removal rates in the upper layers of marine waters.     

210Pb balance in Long Island Sound

A material balance is constructed for excess ²¹⁰Pb (relative to ²²⁶Ra) as a test of the retentivity of Long Island Sound for a reactive heavy metal. Excess ²¹⁰Pb is supplied to Long Island Sound chiefly by direct atmospheric deposition [1 ± 0.2(dis·min^?1)cm^?2·yr^?1]. Rivers supply less than 20% of the atmospheric flux, and other inputs, from open ocean waters, ²²⁶Ra decay, groundwater seepage, and sewage discharge, appear to be negligible. The total input of excess ²¹⁰Pb represents approximately the flux required to maintain the inventory of excess ²¹⁰Pb measured in sediment cores from central Long Island Sound; that is, excess ²¹⁰Pb is lost from Long Island Sound chiefly by radioactive decay. The retention of excess ²¹⁰Pb within Long Island Sound is achieved in two steps: a rapid removal of soluble ²¹⁰Pb onto suspended particles and the ongoing entrapment of particles in the basin by the residual bottom-water influx from the east.     

High-precision Pb isotope analysis by multicollector-ICP-mass-spectrometry using 205Tl/203Tl normalization: Optimization and calibration of the method for the studies of Pb isotope variations

The development of the MC-ICP-MS method, which was launched about one decade ago and was largely stimulated by the need to solve geological problems, has opened a new avenue in isotope mass spectrometry. One of the advantages of this method is the possibility of applying a newly developed approach to the correction of analytical results for the effect of mass discrimination by normalizing the measured isotope ratios of an element to a reference (standard) isotope ratio of another element. This makes it possible to overcome the main disadvantage of conventional thermal ionization mass spectrometry (TIMS), in which the effect of mass discrimination cannot be fully taken into account during isotope analysis, and thus to implement a highly accurate method for the analysis of Pb-isotope composition. In application to the capability of the NEPTUNE MC-ICP mass spectrometer, we optimized and calibrated a method for high-accuracy Pb isotope analysis in solutions spiked with Tl, with all currently measured Pb-isotope ratios normalized to the standard ²⁰⁵Tl/²⁰³Tl ratio (TLN-MC-ICP-MS). The factors affecting the random and systematic analytical errors were examined, and the optimal operating regime and analytical conditions were determined. Much attention was paid to the correlation of the measurement results and the mass discrimination effect determined from the ²⁰⁵Tl/²⁰³Tl ratio. The value of the ²⁰⁵Tl/²⁰³Tl normalizing ratio was analytically determined through isotope analyses of the NIST SRM 981, and SRM 982 standard samples of Pb-isotope composition. The data obtained for two mixtures Tl + Pb (SRM 982) and Tl + Pb (SRM 981) in ten replicate analyses were 2.38898 ± 12 and 2.38883 ± 20, respectively. These results are in good mutual agreement, and their general mean ²⁰⁵Tl/²⁰³Tl = 2.3889 ± 1 coincides (within the error) with the recently published values of 2.3887 ± 7 [Collerson et al., 2002] and 2.3889 ± 1 [Thirlwall, 2002]. The precision of the method (±2SD), which was assayed by the long-term reproducibility of the results of replicate analyses of SRM 981 and seven galena samples (90 analyses) was 0.016–0.018% for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios and 0.005 and 0.009% for the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios, respectively. The precision of the isotope analysis of common Pb was significantly improved (by factors of 6–10 for various isotope ratios) compared with the precision of TIMS techniques acceptable in isotope studies during three decades. The described method was applied to examine the Pb-isotope composition of approximately 250 samples of galena, scheelite, and pyrite from a number of well known (including large) gold, sulfied, and base-metal deposits. The precision of the method (0.01–0.02%) makes it possible to study small inter-and intra-phase differences in Pb-isotope ratios in hydrothermal and magmatic rocks, to assay the scale of regional and variations in the isotope composition of ore Pb, and to correlate the Pb-isotope composition of rocks and ores and reveal its evolutionary trends.     

A biogeochemical mass balance of 210Po and 210Pb in an oligotrophic lake with seasonally anoxic hypolimnion

The mass balances of ²¹⁰Po and ²¹⁰Pb were determined for Bickford Pond, Massachusetts. Activities of these nuclides at various depths within the water column, in sediments, in streams flowing into and out of the lake and in precipitation were measured at approximately monthly intervals for a period of one year. Streamwater contained about 10 dpm/100 kg of ²¹⁰Pb, mostly filtrable and showed little variation with changing flow. ²¹⁰Pb in the streams is believed to be derived mostly from ²²²Rn that enters groundwater via alpha-recoil from aquifer matrix materials. It is therefore not meteoric in origin and represents a local source to the lake. Surface inflow was equally important as precipitation as a source of ²¹⁰Pb to the lake. Only half of total ²¹⁰Pb input was trapped in sediments; the rest was lost from the lake as outflow. The ²¹⁰Pb removal times via scavenging and sedimentation both averaged close to 40 days and ²¹⁰Pb scavenging was almost an order of magnitude greater than that of ²¹⁰Po.     

Annual fallout of32Si,210Pb,22Na,35S and7Be in rains in India

The concentration of radioisotopes⁷Be,³⁵S were measured in Bombay since 1956 and²²Na,²¹⁰Pb,³²Si since 1963. In Khandala and other stations such measurements have been made at irregular periods since 1961. In addition several measurements especially that of³²Si were made in 1970. Data available todate from Indian stations is summarised and critically analysed. We conclude that appreciable amounts of³⁵S,²²Na and³²Si, over and above their production by cosmic rays, were produced during the high yield Russian tests as evidenced by their fallout between 1962–66. Based on the bomb produced excess the half period for their removal from the stratosphere is deduced to be less than 1 year. The ‘excess’ contribution of³²Si due to bombs is, however, small; about 1% of its inventory in the oceans. The present study shows that for stations where orogeny is the principal mechanism of precipitation, the annual fallout is independent of the annual rainfall.     

Budgets and behaviors of uranium and thorium series isotopes in Santa Monica Basin sediments

Nine natural decay-series isotopes were measured in six box cores collected from a transect across the Santa Monica Basin. The ²¹⁰Pb-derived sedimentation rate decreases from ~80 mg/cm²-yr at the slope to ~20 mg/cm²-yr in the deep central basin. Sediment mixing prevails in sites underlying oxic waters, but is subdued in the anoxic deep basin below the sill depth. Uranium contents in sediments are controlled by levels of authigenic U, which are higher in the more reduced condition in the deep basin. Most of the authigenic U results from precipitation within the sediments.The ²³²Th-²²⁸Th disequilibrium in sediments indicates that ²²⁸Ra is lost from the sediments from a depth of ~ 10 cm upward. Modelling the distribution of excess ²²⁸Th and ²³⁴Th in the surficial layers of the deep basin sediments results in a mean sediment mixing coefficient of 0.2 cm²/yr and a sedimentation rate close to that based on ²¹⁰Pb. There is no evidence of changing sedimentation rate in the central basin during the past century. Fluxes of excess ²¹⁰Pb, ²³⁰Th and ²³¹Pa to the central Santa Monica Basin sediments are much higher than what can be predicted from local supply. Advective input of open ocean waters coupled with enhanced scavenging of these reactive nuclides at the ocean margin is considered to be the primary cause.     

Seasonal variations of 210Pb and 210Po concentrations in an oligotrophic lake

The vertical distribution of ²¹⁰Pb and ²¹⁰Po in the dissolved (<0.4 μm) and the paniculate (>0.4 μm) phases was measured in Crystal Lake, Wisconsin, to examine the spatial and temporal variability during the seasonal cycle of this oligotrophic lake. The concentration of unsupported ²¹⁰Pb in the water column is maintained principally by atmospheric input. However, most of the ²¹⁰Po in Crystal Lake is produced in situ from radioactive decay of ²¹⁰Pb.Mass balance considerations indicated that the removal rates of ²¹⁰Pb and ²¹⁰Po from the water column to the sediment varied temporally by nearly an order of magnitude. During transient periods of high biological productivity, a large net flux of these nuclides into the sediment occurred. In addition, ²¹⁰Pb was rapidly stripped from the water column during fall turnover. It was during these short-lived events that most of the annual net removal of ²¹⁰Pb and ²¹⁰Po occurred. The mean removal residence time was estimated to be 0.095 yr for ²¹⁰Pb and 0.26 yr for ²¹⁰Po. These residence times suggest that there is a difference between ²¹⁰Pb and ²¹⁰Po in the extent of their recycling in the water column. Calculations indicated that there was a cyclic response of the water column ²¹⁰Po inventory corresponding to successive time periods where there was a net loss or net gain. This cycling is attributed to rapid biological removal and subsequent release from the sediment of freshly deposited ²¹⁰Po. For ²¹⁰Pb, replenishment of the water column appeared to occur mainly from atmospheric input.     

Distribution and sources of pre-anthropogenic lead isotopes in deep ocean water from FeMn crusts

The lead isotope composition of ocean water is not well constrained due to contamination by anthropogenic lead. Here the global distribution of lead isotopes in deep ocean water is presented as derived from dated (ca. 100 ka) surface layers of hydrogenetic Fe-Mn crusts. The results indicate that the radiogenic lead in North Atlantic deep water is probably supplied from the continents by river particulates, and that lead in Pacific deep water is similar to that characteristic of island and continental volcanic arcs. Despite a short residence time in deep water (80–100 a), the isotopes of lead appear to be exceedingly well mixed in the Pacific basin. There is no evidence for the import of North Atlantic deep water-derived lead into the Pacific ocean, nor into the North Indian Ocean. This implies that the short residence time of lead in deep water prohibits advection over such long distances. Consequently, any climate-induced changes in deep-water flow are not expected to result in major changes in the seawater Pb-isotope record of the Pacific Ocean.     

210Pb activities in and fluxes to sediments of the Washington continental slope and shelf

Surface sediments of the Washington coast have ²¹⁰Pb activites which average 104 ± 48dpm/g for submarine canyon and slope regimes and 18 ± 12dpm/g for the continental shelf regime. ²¹⁰Pb sedimentary fluxes are also higher in canyons, averaging 18 ± 13dpm/cm² per yr, compared to 5.2 ± 3.1 dpm/cm² per yr for slope and 4.8 ± 1.8dpm/cm² per year for shelf regions. These ²¹⁰Pb activities and fluxes are 2–7 times greater than those reported for other coastal regions. Inputs from the atmosphere and the Columbia River are not sufficient to supply the ²¹⁰Pb, but advection of seawater containing dissolved ²¹⁰Pb produced in situ from ²²⁶Ra provides an input several times larger than the sedimentary fluxes. The sedimentary ²¹⁰Pb flux is limited by scavenging reactions rather than by supply of dissolved ²¹⁰Pb.Calculations of maximum biological uptake and fluxes of ²¹⁰Pb and ‘selective’ chemical leaching experiments all show that the primary scavenging processes are due to hydrous Mn and Fe oxides rather than biological phases. The pattern of higher ²¹⁰Pb depositional fluxes in canyons than in nearby open slope areas of comparable water depth is most reasonably explained by enhanced scavenging of dissolved ²¹⁰Pb near the sea floor, rather than by processes operating throughout the water column. Relatively rapid removal of dissolved ²¹⁰Pb from the near bottom nepheloid layer to slope and canyon sediments is shown by its mean residence time of less than two years in this layer.     

The relationship of soil Po and Pb geochemical dispersion patterns to uranium mineralization

²¹⁰Po and ²¹⁰Pb measurements of soils delineated uranium anomalies at three out of four test sites in Ontario, Canada. Measurements were made of ²¹⁰Po in solutions produced by both complete digestion and partial leaching of soil samples. Direct plating of ²¹⁰Po onto metal plates was followed by measuring the alpha activity. Subsequent plating of ²¹⁰Po in-grown from ²¹⁰Pb in solution several months later confirmed the anomalies.The ²¹⁰Po and ²¹⁰Pb anomalies at three of the test sites coincided with ²²⁶Ra and ²²²Rn anomalies. Samples from the fourth uranium occurrence associated with a known ²²²Rn anomaly failed to show either a ²²⁶Ra anomaly on the one hand, or ²¹⁰Po or ²¹⁰Pb anomalies on the other. This suggests that the ²¹⁰Po and ²¹⁰Pb anomalies were probably produced by the decay of ²²⁶Ra contained within secondary dispersion haloes.Although anomalies due to the ²¹⁰Po and ²¹⁰Pb products of ²²²Rn have now been documented, prospecting methods based on their use as direct tracers of the migration paths of ²²²Rn require much further development.     

Atmospheric supply of osmium to the oceans

Supply of Os to the oceans via atmospheric transport is assessed by means of aerosol analyses and tracking with ²¹⁰Pb. Although the inferred continental Os flux at a coastal site (New Haven, Connecticut) was found to be large, this flux is not representative of the global atmospheric flux to the oceans. This conclusion is based on the observed ²¹⁰Pb atmospheric flux pattern across the Pacific Ocean and the constancy of the ¹⁸⁷Os/¹⁸⁸Os in the oceans. The ²¹⁰Pb-based flux of Os to Pacific islands based on a measure of the leachable Os in stream sediments and the measured Al flux to these islands is assessed. By means of this approach, 0.8 mol of Os per year of atmospherically transported Os to the world oceans is obtained. This value is considerably smaller than the value of ∼1500 mol of Os per year assigned to delivery by streams. However, there may be an additional flux of Os to the oceans from the release from coastal aerosols, although the amount is uncertain.     

The relationship of soil 210Po and 210Pb geochemical dispersion patterns to uranium mineralization

²¹⁰Po and ²¹⁰Pb measurements of soils delineated uranium anomalies at three out of four test sites in Ontario, Canada. Measurements were made of ²¹⁰Po in solutions produced by both complete digestion and partial leaching of soil samples. Direct plating of ²¹⁰Po onto metal plates was followed by measuring the alpha activity. Subsequent plating of ²¹⁰Po in-grown from ²¹⁰Pb in solution several months later confirmed the anomalies.The ²¹⁰Po and ²¹⁰Pb anomalies at three of the test sites coincided with ²²⁶Ra and ²²²Rn anomalies. Samples from the fourth uranium occurrence associated with a known ²²²Rn anomaly failed to show either a ²²⁶Ra anomaly on the one hand, or ²¹⁰Po or ²¹⁰Pb anomalies on the other. This suggests that the ²¹⁰Po and ²¹⁰Pb anomalies were probably produced by the decay of ²²⁶Ra contained within secondary dispersion haloes.Although anomalies due to the ²¹⁰Po and ²¹⁰Pb products of ²²²Rn have now been documented, prospecting methods based on their use as direct tracers of the migration paths of ²²²Rn require much further development.     

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε_Nd and ε_Hf both decrease with water depth. Similarly, ε_Nd and ε_Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.     

K-Ar ages and Pb,Sr isotopic characteristics of Cenozoic volcanic rocks in Shandong Province,China

28 samples of Cenozoic volcanic rocks collected from Shandong Province have been dated by K-Ar method. They are mainly Neogene with an age range of 4–19 m. y. The basalts from Linqu and Yishui in west Shandong Province are Miocene and those from Penglai and Qixia in east Shandong Province are Miocene and Pliocene in age. The basalts from Wudi in north Shandong Province are Middle-Early Pleistocene in age. In each area the duration of volcanic eruption was estimated at about 2–3 m. y. Pb and Sr isotopic compositions and U, Th, Pb, Rb, Sr, and major elements in most of the samples were determined. The isotopic compositions are:²⁰⁶Pb/²⁰⁴Pb—16.92-18.48,²⁰⁷Pb/²⁰⁴Pb—15.30-15.59,²⁰⁸Pb/²⁰⁴Pb—37.83-38.54, and (⁸⁷Sr/⁸⁶Sr)_i—0.70327-0.70632. There are some positive or negative linear correlations between²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb, Pb isotopes and Pb content, Pb isotopes and Sr isotopes, and Sr isotopes and other elements. The basaltic rocks from east and west Shandong Province have somewhat differences in isotopic composition and element content. The basalts probably are products of multi-stage evolution of the mantle. They have preserved the primary features of the source, although they were influenced, to some extent, by the contamination of crustal materials.     

Determination of recent deposition rates in Lake Constance with radioisotopic methods

Sedimentation rates were determined with the ²¹⁰Pb method in eight sediment cores from Lake Constance. The rate of deposition in the main basin (Obersee) varies from about 0.06 g cm^?2 y^?1 in the central part to 0.13 g cm^?2 y^?1 in the eastern part of the lake and then increases rapidly towards the Rhine delta. In the central lake area the rate of deposition has been approximately constant since 1900, and dating with the ²¹⁰Pb method is in good agreement with sedimentological observations. In the Konstanzer Trichter area, the deposition rate has been increasing since about 1955 as a result of eutrophication and subsequent high carbonate production. Dating with ¹³⁷Cs is fairly accurate for sediments deposited at a high rate, but is questionable for slowly accumulating ones. A positive correlation of ²¹⁰Pb fluxes and sedimentation rates indicates that ²¹⁰Pb flux into sediments follows the distribution pattern of solids. ²¹⁰Pb profiles in four sediment cores interpreted in terms of a constant flux model display synchronous fluctuations of the sedimentation rate; however, their relation to long-range particulate input variations remains to be proved. Sedimentation rates determined with the ²¹⁰Pb method were used to calculate recent nutrient and heavy metal fluxes. Anthropogenic fluxes of Zn and Pb are in the same range of magnitude as in other polluted areas in Europe and America.     

Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl-Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε²⁰⁵Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε²⁰⁵Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε²⁰⁵Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε²⁰⁵Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.     

The temporal evolution of fluid flow through the Tahiti barrier reef traced by Sr isotopes and pore water chemistry

The internal fluid circulation of the Tahiti barrier reef has been studied with Sr isotopes and pore water chemistry. The study is based on 15 sample series recovered over 2 years from a 150-m deep core drilled through the entire barrier reef down to the volcanic basement.Temperature data suggest that the interstitial fluids originate from seawater that penetrated the volcanic basement to at least 200 m depth on the ocean-sided slope below the barrier reef. Subsequently, the fluids migrated upward driven by buoyancy through the entire reef.Chemical evolution of the interstitial fluids is mainly controlled by basalt–seawater interaction and by admixture of seawater from the open ocean during upward migration. These processes are monitored with ⁸⁷Sr/⁸⁶Sr isotope ratios, H₄SiO₄ concentrations and alkalinity to give a picture of the evolution of interstitial fluid flow over 2 years. The results indicate that the internal circulation patterns change through time. The modifications concern mainly the residence time of the fluids within the volcanics and the intensity and localization of lateral seawater admixture within the karstified Pleistocene reef.