The water column distributions of thorium isotopes in the western North Pacific

Four vertical profiles of²³⁰Th and²²⁸Th were determined using large volume water samples in the western North Pacific. An almost linear increase of²³⁰Th with depth was observed for all of the profiles for which the unidirectional first order scavenging model was difficult to explain. We developed a model which included a dissolved-particulate transformation as well as parameters of the scavenging model. Application of the model to the vertical distributions of total and the GEOSECS particulate Th isotopes (²³⁰Th and²³⁴Th) yielded the residence time of dissolved Th with respect to adsorption to particles and the turnover time of particulate Th to be 235 days and 57 days, respectively. The Th isotopes appeared to be carried down the water column by fine particles with a mean settling velocity of 1 m/day which continually release Th into sea water as well as pick up Th from the water along their journey to the bottom.For²²⁸Th, a large excess over²³²Th was observed throughout the water column with pronounced high concentrations in surface and bottom waters, suggesting that the²²⁸Th was derived from²²⁸Ra diffused out of sediments. The vertical distributions of²²⁸Th seemed to be significantly influenced by lateral mixing along isopycnals.     

Stable calcium isotopic composition of meteorites and rocky planets

New measurements of mass-dependent calcium isotope effects in meteorites, lunar and terrestrial samples show that Earth, Moon, Mars, and differentiated asteroids (e.g., 4-Vesta and the angrite and aubrite parent bodies) are indistinguishable from primitive ordinary chondritic meteorites at our current analytical resolution (± 0.07‰ SD for the ⁴⁴Ca/⁴⁰Ca ratio). In contrast, enstatite chondritic meteorites are slightly enriched in heavier calcium isotopes (ca. + 0.5‰) and primitive carbonaceous chondritic meteorites are depleted in heavier calcium isotopes (ca. ? 0.5‰). The calcium isotope effects cannot be easily ascribed to evaporation or intraplanetary differentiation processes. The isotopic variations probably survive from the earliest stages of nebular condensation, and indicate that condensation occurred under non-equilibrium (undercooled nebular gas) conditions. Some of this early high-temperature calcium isotope heterogeneity is recorded by refractory inclusions (Niederer and Papanastassiou, 1984) and survived in planetesimals, but virtually none of it survived through terrestrial planet accretion. The new calcium isotope data suggest that ordinary chondrites are representative of the bulk of the refractory materials that formed the terrestrial planets; enstatite and carbonaceous chondrites are not. The enrichment of light calcium isotopes in bulk carbonaceous chondrites implies that their compositions are not fully representative of the solar nebula condensable fraction.     

Fluxes of uranium and thorium series isotopes in the Santa Barbara Basin

Samples from the MANOP Santa Barbara Basin sediment trap intercomparison were analyzed for the isotopes of uranium, thorium, radium, lead, and polonium. All of the traps showed approximately the same compositions and isotopic ratios, indicating that they trapped similar materials. The²³⁴Th flux via falling particles was very close to the flux predicted from the production and scavenging rates of²³⁴Th from the water column. The²¹⁰Pb content of the trapped particles and the surface sediments were the same, however, the measured flux of²¹⁰Pb was seven times greater than the predicted flux. Predicted and measured fluxes of²²⁸Th and²¹⁰Po were similarly out of balance. To explain this apparent inconsistency, we suggest (as others have done) that the Santa Barbara Basin is an area where scavenging from the water column is intensified and where sediments deposited initially on the margins may be physically remobilized on a short time scale. These two effects increase the apparent area from which the basin derives the longer-lived isotopes but does not increase significantly the supply of the short-lived²³⁴Th.     

Transport ofBe andBe in the ocean

Beryllium isotopes (¹⁰Be and⁹Be) have been measured in suspended particles of < 1 mm size collected by mid-water sediment traps deployed in the eastern Pacific at MANOP sites H (6°32′N, 92°50′W, water depth 3600 m) and M (8°50′N, 104°00′W, 3100 m). For comparison, surface sediments from box cores taken from the two sites were also studied. The concentrations of¹⁰Be and⁹Be in sediment-trap particles are about an order of magnitude smaller than those in the bottom sediments which contain about 8 × 10⁹ and 6 × 10¹⁶ atoms g⁻¹ of¹⁰Be and⁹Be, respectively. The sediment trap samples collected from 50 m off the bottom showed significant (26–63%) contributions from resuspended bottom sediments. The¹⁰Be/⁹Be ratio in trap samples varies from 3 to 20 × 10⁻⁸. The variation may partly result from varied proportion of authigenic/detrital material. The fluxes of both isotopes exhibit a very strong seasonality. The fluxes of¹⁰Be into the traps at about 1500 m are estimated as 9 × 10⁵ and 4 × 10⁵ atoms cm⁻² a⁻¹ at sites H and M respectively. These values are to be compared with the fluxes into the sediments of 4–5 × 10⁵ atoms cm⁻² a⁻¹ at both locations. Good correlations exist between¹⁰Be,⁹Be and²⁷Al indicating that the primary carrier phase(s) for the beryllium isotopes in the water column may be aluminosilicates.     

Excess protactinium in phosphate nodules from a coastal upwelling zone

Measurements of²³¹Pa/²³⁵U and²³⁰Th/²³⁴U activity ratios have been made for a suite of Quaternary age phosphate nodules from the upwelling zone off Peru and Chile. Many of these samples contain more²³¹Pa than would be predicted based on closed-system²³⁰Th/²³⁴U ages unlike samples from non-upwelling environments which have been shown to have concordant²³¹Pa and²³⁰Th ages. Peru/Chile phosphate nodules apparently pick up²³¹Pa preferentially to²³⁰Th. This is most likely a result of prior fractionation of protactinium and thorium in the open ocean. Highly productive coastal upwelling zones may be added to the growing list of localities where fractionation between thorium and protactinium isotopes has been observed in marine sediments.     

Rare gases in a phlogopite nodule and a phlogopite-bearing peridotite in South African kimberlites

Rare gas isotopes in a phlogopite nodule and a phlogopite-bearing peridotite nodule in South African kimberlites were studied to examine the state of rare gases in the deep interior of the kimberlite region.Within the experimental error of 1 ～ 2%, rare gas isotopic compositions are atmospheric except for radiogenic⁴He and⁴⁰Ar. No excess¹²⁹Xe was observed.In phlogopite, Ne is more depleted, whereas the heavier rare gases are more enriched than the atmospheric rare gases relative to³⁶Ar.Together with other data these results suggest that the state of rare gases in the upper mantle of the South African kimberlite region might have been changed from the typical primitive mantle by a process such as mixing of crustal materials.     

The thorium isotope content of ocean water

²³²Th concentrations of surface and deep Pacific Ocean waters are 0.01–0.02 dpm/1000 kg (60 pgm/kg). The²³⁰Th activity is 0.03–0.13 dpm/1000 kg in surface waters and 0.3–2.7 dpm/1000 kg in deep waters. Chemical residence times based on in situ production from parent isotopes are about the same for²³⁰Th and²²⁸Th in surface waters (1–5 years) but are ten times greater for²³⁰Th in deep waters (10–100 years). Apparently there are additional sources of²³⁰Th into deep waters. At MANOP site S manganese nodule tops are enriched in Th isotopes by adsorption of Th from seawater and not by incorporation of Th-rich particulates.     

Sr isotope evolution during chemical weathering of granites —Impact of relative weathering rates of minerals

The Sr isotopic systematics in the weathering profiles of biotite granite and granite porphyry in southern Jiangxi Province were investigated. The results showed that during the chemical weathering of granites, remarked fractionation occurred between Rb and Sr. During the early stages of chemical weathering of granites, the released Sr/Si and Sr/Ca ratios are larger than those of the parent rocks, and the leaching rate of Sr is higher than those of Si, Ca, K, Rb, etc. Dynamic variations in relative weathering rates of the main Sr-contributing minerals led to fluctuation with time in⁸⁷Sr/⁸⁶Sr ratios of inherent and released Sr in the weathering crust of granite. Successive weathering of biotite, plagioclase and K-feldspar made⁸⁷Sr/⁸⁶Sr ratios in the weathering residues show such a fluctuation trend as to decrease first, increase, and then decrease again till they maintain stable. This work further indicates that when Sr isotopes are used to trace biogeochemical processes on both the catchment and global scales, one must seriously take account of the preferential release of Sr from dissolving solid phase and the fluctuation of⁸⁷Sr/⁸⁶Sr ratios caused by the variations of relative weathering rates of Sr-contributing minerals.     

Temporal variation of228Ra in the near-surface Gulf of Mexico

The Mn-fiber technique for extracting radium from seawater has proved useful for studying the marine geochemistry of²²⁸Ra. In the Gulf of Mexico, this technique was used to measure the surface and near-surface distribution of²²⁶Ra and²²⁸Ra. The observed surface distribution of²²⁸Ra, and particularly the radium activity ratio (228/226) can be explained by known circulation patterns, or, when local surface currents are not well understood, may provide insight into their general characteristics.The radium activity ratio has increased from 0.5 in 1968 to 0.7 in 1973 in the surface Gulf of Mexico. This observed increase cannot be attributed to known anthropogenic or natural source perturbations within the Caribbean Sea-Gulf of Mexico system. Possible causes include a change in the residence time for near-surface water, or variations in the relative dominance of the two sources for water entering the eastern Caribbean; the North Equatorial Current and the Guiana Current.The temporal distribution of²²⁸Ra is unstable and naturally variable over a time period less than or equal to five years in the Gulf of Mexico and by extrapolation, the Caribbean Sea. Therefore, its usefulness in calculations of eddy diffusion coefficients for these regions is greatly diminished.     

Uranium and thorium series nuclides in oriented ferromanganese nodules: growth rates,turnover times and nuclide behavior

Three ferromanganese nodules handpicked from the tops of 2500 cm² area box cores taken from the north equatorial Pacific have been analysed for their U-Th series nuclides.²³⁰Th_exc concentrations in the surface 1–2 mm of the top side of the nodules indicate growth rates of 1.8–4.6 mm/10⁶ yr. In two of the nodules a significant discontinuity in the²³⁰Th_exc depth profile has been observed at ～0.3 m.y. ago, suggesting that the nodule growth has been episodic. The concentration profiles of²³¹Pa_exc (measured via²²⁷Th) yield growth rates similar to the²³⁰Th_exc data. The bottom sides of the nodules display exponential decrease of²³⁰Th_exc/²³²Th activity ratio with depth, yielding growth rates of 1.5–3.3 mm/10⁶ yr.The²³⁰Th_exc and²³¹Pa_exc concentrations in the outermost layer of the bottom face are significantly lower than in the outermost layer of the top face. Comparison of the extrapolated²³⁰Th_exc/²³²Th and²³⁰Th_exc/²³¹Pa_exc activity ratios for the top and bottom surfaces yields an “age” of (5?15) × 10⁴ yr for the bottom relative to the top. This “age” most probably represents the time elapsed since the nodules have attained the present orientation.The²¹⁰Pb concentration in the surface ～0.1 mm of the top side is in large excess over its parent²²⁶Ra. Elsewhere in the nodule, up to ～1 mm depth in both top and bottom sides,²¹⁰Pb is deficient relative to²²⁶Ra, probably due to²²²Rn loss. The absence of²¹⁰Pb_exc below the outermost layer of the top face rules out the possibility of a sampling artifact as the cause of the observed exponentially decreasing²³⁰Th_exc and²³¹Pa_exc concentration profiles. The flux of²¹⁰Pb_exc to the nodules ranges between 0.31 and 0.58 dpm/cm² yr. The exhalation rate of²²²Rn, estimated from the²²⁶Ra-²¹⁰Pb disequilibrium is ～570 dpm/cm² yr from the top side and >2000 dpm/cm² yr from the bottom side.²²⁶Ra is deficient in the top side relative to²³⁰Th up to ～0.5–1 mm and is in large excess throughout the bottom. The data indicate a net gain of²²⁶Ra into the nodule, corresponding to a flux of (24?46) × 10^?3 dpm/cm² yr. On a total area basis the gain of²²⁶Ra into the nodules is <20% of the²²⁶Ra escaping from the sediments. A similar gain of²²⁸Ra into the bottom side of the nodules is reflected by the high²²⁸Th/²³²Th activity ratios observed in the outermost layer in contact with sediments.     

Removal of234Th from a coastal sea: Funka Bay,Japan

In Funka Bay of Hokkaido, Japan, seawater, suspended matter and settling matter were collected once every month in the summer of 1974. These samples were analyzed for²³⁴Th, a short-lived daughter of dissolved²³⁸U. A pronounced disequilibrium between²³⁴Th and²³⁸U, and a highly variable concentration of²³⁴Th were found. Positive correlation, however, exist among the deficiency of²³⁴Th relative to²³⁸U in seawater, the concentration of particulate²³⁴Th, the fraction of particulate²³⁴Th to total²³⁴Th in seawater, the total dry weight of suspended matter, and the primary productivity during the month previous to sampling. The specific activity of²³⁴Th for the settling particles (620 ± 170 dpm/g) was nearly equal to that for suspended particles (720 ± 600 dpm/g) but much greater than that for plankton (47 ± 24 dpm/g). These facts suggest that suspended particles are somehow closely related to the removal of heavy metals from seawater, in spite of the negligibly small settling flux of suspended matter. The residence time of thorium in Funka Bay (mean depth: 60 m) is found to be about 60 days, which is nearly equal to those of²¹⁰Pb and²¹⁰Po.     

Terrestrial,meteoritic, and lunar titanium isotopic ratios revaluated: evidence for correlated variations

Variations in the titanium isotopic ratios of various solar system materials have been reported by three laboratories. In this work we compare these data (including some new Allende inclusion values reported here) on a common basis. The data of all three groups for terrestrial samples have been found to be consistent within about ten parts per ten thousand for all ratios. The considerable disagreement in reported titanium isotopic anomalies for Allende materials has been investigated by renormalization of all published high-precision titanium isotopic ratio data to various bases in order to assess the nature, number, and loci of possible anomalies. On this basis, variations appear to be present in⁴⁶Ti and⁴⁷Ti, as well as in⁵⁰Ti. All materials reported to date can be divided into two main groups, with the only exceptions being about 10% of Allende inclusions. All but one of the materials reported to date are interpretable as mixtures of a material similar to C-1 and varying amounts (up to about 0.5% of⁵⁰Ti) of a material characterized by⁵⁰Ti/⁴⁶Ti?6 and⁴⁶Ti?⁴⁷Ti+⁴⁸Ti+⁴⁹Ti. Inclusion EK 1-4-1 requires a further component (up to about 0.5%⁴⁶Ti) characterized by⁴⁶Ti/⁴⁷Ti? 1.3and⁴⁷Ti?⁴⁸Ti+⁴⁹Ti+⁵⁰Ti.     

The behaviour of short-lived radiogenic lead isotopes (214Pb and212Pb) in groundwaters and laboratory leaching experiments

The concentrations of²¹⁴Pb (half-life=26.4minutes) and²²Rn (half-life=3.84days) have been measured in deep groundwaters of Gujarat, India. The results show that the abundance of²¹⁴Pb in the water is only ～25% of that expected from its production through the radioactive decay of dissolved²²²Rn. This deficiency if modelled in terms of a first-order removal, yields a residence time of ～10 minutes for²¹⁴Pb in these waters. The estimated residence time for²¹⁴Pb is the shortest observed for any nuclide in natural water systems and suggests that reactive nuclides lead like could be removed from aqueous phases to adjoining solid surfaces on extremely short time scales. Results of laboratory experiments using the²¹²Pb-²²⁴Ra pair are compatible with the observed fast removal of²¹⁴Pb from groundwaters.Re-evaluation of²³⁴Th residence times in these waters using a model with a recoil flux of²³⁴Th into aqueous phase, the same as that of²²²Rn, yields values in the range of 23 to<176 minutes, very similar to that of²¹⁴Pb. This “concordancy” in the residence times seems to suggest that the geochemical behaviour of²³⁴Th and²¹⁴Pb in these waters is quite similar.     

Plutonium,radiocesium and radiocobalt in sediments of the Hudson River estuary

Anthropogenic radionuclides have reached the Hudson estuary as global fallout from nuclear weapons testing and through local releases from commercial nuclear reactors. Significant activities of²³⁸Pu and^239,240Pu (fallout-derived),¹³⁴Cs and⁶⁰Co (reactor-released), and¹³⁷Cs (derived from both sources), have accumulated in the sediments throughout the estuary, with the primary zone of accumulation near the downstream end of the system in New York harbor. The estuary appears to have trapped nearly all of the^239,240Pu delivered as fallout, and consequently, ocean dumping of dredged harbor sediment is currently the primary means for the net transport of these nuclides to coastal waters. In contrast, only 10–30% of the¹³⁷Cs,¹³⁴Cs and⁶⁰Co delivered to the estuary have been retained on the fine particles which accumulate at a rapid rate in the harbor.The primary factors which have governed the distribution of anthropogenic radionuclides in Hudson sediments are: (1) spread of fine particles labeled with both fallout and reactor nuclides throughout the axis of the estuary, (2) differences in timing of the peak fallout years (1962–1964) and years of maximum reactor releases (1971–1972), (3) large variations in sediment accumulation rates, ranging from a few millimeters per year or less to many tens of centimeters per year, (4) appreciable desorption of¹³⁷Cs and¹³⁴Cs from particles at higher salinities, and (5) possible enhanced desorption of⁶⁰Co at higher salinities (relative to¹³⁴Cs and¹³⁷Cs) which may be associated with the release of reduced manganese from the harbor sediments.     

The effects of alteration and the interpretation of heat flow and radioactivity data—a reply to R.U.M. Rao

The first²²⁴Ra (t_1/2 = 3.64days) measurements from mixing zones of estuarine systems are presented for the Pee Dee River-Winyah Bay and Delaware Bay Estuaries. High-resolution gamma-ray spectrometry was used to determine²²⁴Ra,²²⁸Ra (t_1/2 = 5.7years), and²²⁶Ra (t_1/2 = 1622years) activity ratios. Desorption and diffusion from suspended and bottom sediments contributes to the non-conservative increases of the three isotopes in each systems. In Delaware Bay²²⁴Ra concentrations were nearly constant over the 2.5‰ to 15‰ salinity range where two turbidity maximum zones are located.²²⁸Th scavenging onto the suspended particles in the turbid zones may supply a regenerative source of²²⁴Ra in this system. Samples collected on the ebb and flood tide from a salt marsh along Delaware Bay have a 5-fold increase in²²⁴Ra from flood to ebb and 3- and 2-fold increases for²²⁸Ra and²²⁶Ra respectively, indicating salt marshes are another source of radium to estuarine waters.     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

Minor element and Ca isotope composition of calcareous dinoflagellate cysts of cultured Thoracosphaera heimii

We investigated the influences of temperature, salinity and pH on the calcium isotope as well as trace and minor element (uranium, strontium, magnesium) to Ca ratios on calcium carbonate cysts of the calcareous dinoflagellate species Thoracosphaera heimii grown in laboratory cultures. The natural habitat of this species is the photic zone (preferentially at the chlorophyll maximum depth) of temperate to tropical oceans, and it is abundant in deep-sea sediments over the entire Cenozoic. In our experiments, temperatures ranged from 12 to 30 °C, salinity from 36.5 to 38.8 and pH from 7.9 to 8.4. The δ^44/40Ca of T. heimii cysts resembles that of other marine calcifiers, including coccolithophores, foraminifers and corals. However, its temperature sensitivity is considerably smaller and statistically insignificant, and T. heimii might serve as a recorder of changes in seawater δ^44/40Ca over geologic time. The Sr/Ca ratios of T. heimii cysts show a pronounced temperature sensitivity (0.016 mmol/mol °C^? 1) and have the potential to serve as a palaeo-sea surface temperature proxy. No clear temperature- and pH-dependences were observed for Mg/Ca. U/Ca seems to be influenced by temperature and pH, but the correlations change sign at 23 °C and pH 8.2, respectively.     

Evidence for a secular variation in the13C/12C ratio of carbon implanted in lunar soils

A plot of δ¹³C against δ¹⁵N for all lunar soils and breccias for which both values are available indicates that the 30% change in δ¹⁵N previously observed is accompanied by a change in δ¹³C about one-tenth as large. The correlation remains when the data are broken down into sub-sets according to soil maturity. The correlation therefore is not due to maturation effects or non-selective sample contamination and must represent concurrent changes in the isotope ratios of both elements at their source. A rough calculation of the relative production rates of¹³C and¹⁵N indicates that spallation reactions in the sun could lead to the observed ratio of the δ¹³C to δ¹⁵N variations.     

The distribution of 210Pb and 210Po in the surface waters of the Pacific Ocean

By modelling the observed distribution of²¹⁰Pb and²¹⁰Po in surface waters of the Pacific, residence times relative to particulate removal are determined. For the center of the North Pacific gyre these are τ_Po = 0.6years andτ_Pb = 1.7years. The surface ocean τ_Pb is determined by particulate transport rather than plankton settling. The fact that it is about two orders of magnitude smaller than τ_Pb for the deep ocean implies a sharp change in the adsorptive quality of particles during descent through the water column.