Natural and anthropogenic radionuclide distributions in the northwest Atlantic Ocean

We have used in-situ pumps which filter large volumes of sea water through a 1 μm cartridge prefilter and two MnO₂-coated cartridges to obtain information on dissolved and particulate radionuclide distributions in the oceans. Two sites in the northwest Atlantic show subsurface maxima of the fallout radionuclides¹³⁷Cs,^239,240Pu and²⁴¹Am. Although the processes of scavenging onto sinking particles and release at depth may contribute to the tracer distributions, comparison of predicted and measured water column inventories suggests that at least 35–50% of the Pu and²⁴¹Am are supplied to the deep water by advection.The depth distributions of the naturally occurring radionuclides²³²Th,²²⁸Th and²³⁰Th reflect their sources to the oceans.²³²Th shows high dissolved concentrations in surface waters, presumably as a result of atmospheric or riverine supply. Activities of²³²Th decrease with depth to values 0.01 dpm/1000 l.²²⁸Th shows high activities in near surface and near bottom water, due to the distribution of its parent,²²⁸Ra. Dissolved²³⁰Th, produced throughout the water column from²³⁴U decay, increases with depth to 3000 m. Values in the deep water (> 3000 m) are nearly constant ( 0.6–0.7 dpm/1000 l), and the distribution of this tracer (and perhaps other long-lived particle-reactive tracers as well) may be affected by the advection inferred from Pu and²⁴¹Am data.The ratio of particulate to dissolved activity for both²³⁰Th and²²⁸Th is 0.15–0.20. This similarity precludes the calculation of sorption rate constants using a simple model of reversible sorption equilibrium. Moreover, in mid-depths²²⁸Th tends to have a higher particulate/dissolved ratio than²³⁰Th, suggesting uptake and release of²³⁰Th and²²⁸Th by different processes. This could occur if²²⁸Th, produced in surface water, were incorporated into biogenic particles formed there and released as those particles dissolved or decomposed during sinking.²³⁰Th, produced throughout the water column, may more closely approach a sorption equilibrium at all depths.²³⁰Th,²⁴¹Am and^239,240Pu are partitioned onto particles in the sequence Th > Am > Pu with 15% of the²³⁰Th on particles compared with 7% for Am and 1% for Pu. Distribution coefficients (K_d) are 1.3–1.6 × 10⁷ for Th, 5–6 × 10⁶ for Am and 7–10 × 10⁵ for Pu. The lower reactivity for Pu is consistent with analyses of Pu oxidation states which show 85% oxidized (V + VI) Pu. However, theK_d value for Pu may be an upper limit because Pu, like²²⁸Th, may be incorporated into particles in surface waters and released at depth only by destruction of the carrier phase.     

Chemical and radiochemical investigations of surface and deep particles of the Indian Ocean

The distribution of “ash” (the non-combustible fraction of marine suspended matter) and concentrations of particulate Al, Ca, Fe, Cr, Ni, Cu, Sr and²³⁴Th in surface waters and of²¹⁰Pb,²³⁰Th and²³⁴Th in two vertical profiles (385–4400 m) of the Indian Ocean are reported.The ash concentrations in surface waters follow the primary productivity pattern, with higher abundances in samples south of 40°S and lower concentrations in the equatorial and subtropical regions. Opaline silica and CaCO₃ are the dominant components of the ash in samples from >40°S and from 7°N to 39°S, respectively. Aluminosilicates are only a minor constituent of the surface particulate matter. The metal/Al ratios in the surface particles are significantly higher compared to their corresponding crustal ratios for all the metals analyzed in this work. Comparison of enrichment factors between marine aerosols, plankton and surface oceanic particles, seem to indicate that this high metal/Al ratio in surface particles most likely arises from their involvement in marine biogeochemical cycles. Particulate²³⁴Th activity in surface waters parallels the ash abundance implying that its scavenging efficiency from surface waters depends on the particulate concentration.The particulate²³⁰Th and²¹⁰Pb concentration profiles increase monotonously with depth. It is difficult to ascribe this increase to a process other than the in-situ vertical scavenging of²³⁰Th and²¹⁰Pb from the water column by settling particles. The mean settling velocities of particles calculated from the particulate²³⁰Th data using a one-dimensional settling model is about 2 × 10^?3 cm/s. The settling velocity computed from the particulate²³⁰Th profiles does not appear to be compatible with the particulate²¹⁰Pb depth profiles; one possible explanation to account for the disparity would be that²³⁰Th and²¹⁰Pb are scavenged by different size populations of particles.On the whole, the geographic distribution of particulate matter, their composition and settling velocities in the Atlantic, Pacific and Indian Oceans are similar indicating that they are controlled by quite similar processes in the marine hydrosphere.     

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.     

Natural radionuclides in the water of Narragansett Bay

The concentrations of radionuclides of the U-Th series (²³⁸U,²³⁴Th,²³⁴U,²³⁰Th,²²⁶Ra,²¹⁰Pb,²¹⁰Po, and²³²Th,²²⁸Ra,²²⁸Th) in the water of Narragansett Bay are reported. Analysis of the total, particulate, dissolved and colloidal forms of Th isotopes reveal a consistent removal behavior which is controlled mainly by the particulate matter concentration and the sediment resuspension rate. Half-removal times of Th from solution onto particles range from 1.5 to 15 days, and settling velocities of Th containing particles range generally between 1 and 11 m/day.²¹⁰Pb and²¹⁰Po concentrations are seasonally dependent, with higher concentrations and slower removal during the early summer (half-removal times from solution onto particles of 1–5 days in winter and up to 2 months in early summer).     

Removal of230Th and231Pa from the open ocean

Concentrations of²³⁰Th and²³¹Pa were measured in particulate matter collected by sediment traps deployed in the Sargasso Sea (Site S₂), the north equatorial Atlantic (site E), and the north equatorial Pacific (Site P) as well as in particles collected by in situ filtration at Site E. Concentrations of dissolved Th and Pa were determined by extraction onto manganese dioxide adsorbers at Site P and at a second site in the Sargasso Sea (site D).Dissolved²³⁰Th/²³¹Pa activity ratios were 3–6 at Sites P and D. In contrast, for all sediment trap samples from greater than 2000 m, unsupported²³⁰Th/²³¹Pa ratios were 22–35 (average 29.7). Ratios were lower in particulate matter sampled at shallower depths. Particles filtered at 3600 m and 5000 m at Site E had ratios of 50 and 40. Results show that suspended particulate matter in the open ocean preferentially scavenges Th relative to Pa. Most of the²³⁰Th produced by decay of²³⁴U in the open ocean is removed by adsorption to settling particulate matter. In contrast, less than 50% of the²³¹Pa produced by decay of²³⁵U is removed from the water column by this mechanism. Mixing processes transport the remainder to other sinks.     

The removal rates of234Th and228Th from waters of the New York Bight

The mean residence time (τ) of thorium with respect to non-radioactive removal from water was determined as a function of location in three traverses of the New York Bight using both²³⁴Th/²³⁸U and²²⁸Th/²²⁸Ra. τ correlates well with salinity increasing from about ten days near shore to 70 days at the shelf break. It shows a much weaker correlation with suspended matter concentrations both because suspended matter varies in its scavenging efficiency and because salinity is a longer-term integrator of scavenging potential.τ's computed from²²⁸Th/²²⁸Ra were often higher than those computed from²³⁴Th/²³⁸U either because of the detrital matter present as reflected in the²³²Th concentrations or because the water parcels had recently arrived from environments of lower scavenging efficiency.Anomalous isotopic concentrations found in three adjacent samples can best be explained as the result of an episodic release of²²⁸Ra from bottom sediments at a rate 200 times the normal one.     

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.     

230Th,226Ra and222Rn in abyssal sediments

A model that predicts the flux of²²²Rn out of deep-sea sediment is presented. The radon is ultimately generated by²³⁰Th which is stripped from the overlying water into the sediment. Data from many authors are compared with the model predictions. It is shown that the continental contribution of ionium is not significant, and that at low sedimentation rates, biological mixing and erosional processes strongly affect the surface concentration of the ionium. Two cores from areas of slow sediment accumulation, one from a manganese nodule region of the central Pacific and one from the Rio Grande Rise in the Atlantic were analyzed at closely spaced intervals for²³⁰Th,²²⁶Ra, and²¹⁰Pb. The Pacific core displayed evidence of biological mixing down to 12 cm and had a sedimentation rate of only 0.04 cm/kyr. The Atlantic core seemed to be mixed to 8 cm and had a sedimentation rate of 0.07 cm/kyr. Both cores had less total excess²³⁰Th than predicted.Radium sediment profiles are generated from the²³⁰Th model. Adsorbed, dissolved, and solid-phase radium is considered. According to the model, diffusional losses of radium are especially important at low sedimentation rates. Any particulate, or excess radium input is ignored in this model. The model fits the two analyzed cores if the fraction of total radium available for adsorption-desorption is about 0.5–0.7, and ifK, the distribution coefficient, is about 1000.Finally, the flux of radon out of the sediments is derived from the model-generated radium profiles. It is shown that the resulting standing crop of²²²Rn in the overlying water may be considered as an added constraint in budgeting²³⁰Th and²²⁶Ra in deep-sea 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.     

210Pb/226Ra disequilibrium in the Santa Barbara Basin

The vertical distributions of²¹⁰Pb and²²⁶Ra in the Santa Barbara Basin have been measured. The²¹⁰Pb/²²⁶Ra activity ratio is close to unity in surface water, but ranges from 0.2 to 0.6 in deep water with a mean value of 0.3 (d > 250m), suggesting rapid removal of²¹⁰Pb from the water column. The²¹⁰Pb concentrations in the particulate phase at different water depths indicate that the removal of²¹⁰Pb is due to adsorption on settling particles.It is estimated that the particulate²¹⁰Pb contributes about 50–70% of the total²¹⁰Pb measured on unfiltered water samples of the Santa Barbara Basin. The fate of²¹⁰Pb (and Pb) in the water column is thus strongly controlled by the settling particles, which have a mean residence time of one year or less in the basin. Material balance calculation for²¹⁰Pb in the basin suggests that there is an external source supplying about 70–80% of the²¹⁰Pb observed in particulate material or sediments. This excess²¹⁰Pb is most likely provided by particles entering the basin loaded already with²¹⁰Pb.     

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.     

210Pb and226Ra distributions in the Circumpolar waters

²¹⁰Pb and²²⁶Ra profiles have been measured at five GEOSECS stations in the Circumpolar region. These profiles show that²²⁶Ra is quite uniformly distributed throughout the Circumpolar region, with slightly lower activities in surface waters, while²¹⁰Pb varies with depth as well as location or area. There is a subsurface²¹⁰Pb maximum which matches the oxygen minimum in depth and roughly correlates with the temperature and salinity maxima. This²¹⁰Pb maximum has its highest concentrations in the Atlantic sector and appears to originate near the South Sandwich Islands northeast of the Weddell Sea. Concentrations in this maximum decrease toward the Indian Ocean sector and then become fairly constant along the easterly Circumpolar Current.Relative to²²⁶Ra, the activity of²¹⁰Pb is deficient in the entire water column of the Circumpolar waters. The deficiency increases from the depth of the²¹⁰Pb maximum toward the bottom, and the²¹⁰Pb/²²⁶Ra activity ratio is lowest in the Antarctic Bottom Water, indicating a rapid removal of Pb by particulate scavenging in the bottom layer and/or a short mean residence time of the Antarctic Bottom Water in the Circumpolar region.²²⁶Ra is essentially linearly correlated with silica and barium in the Circumpolar waters. However, close examination of the vertical profiles reveals that Ba and Si are more variable than²²⁶Ra in this region.     

Importance of vertical geochemical processes in controlling the oceanic profiles of dissolved rare earth elements in the northeastern Indian Ocean

Vertical profiles of dissolved rare earth elements (REEs) were obtained in the Bay of Bengal and the Andaman Sea. The REE concentrations at various depths in the Bay of Bengal are the highest in the Indian Ocean. This is attributable ultimately to the large outflow of the Ganges–Brahmaputra and Irrawaddy rivers, but the dissolved REE flux to surface waters alone cannot explain the large and near-constant REE enrichment throughout the entire water column. The underlying fan sediments serve as not a source but a sink for dissolved REE(III)s. Absence of excess ²²⁸Ra in the deep waters suggests that lateral input of dissolved REEs from slope sediments is also small in these regions. Partial (<0.3%) dissolution of detrital particles, which are carried by the rivers and lateral surface currents and subsequently settle through the water column, appears to be a predominant source for the dissolved REEs. Vertical profiles showing an almost linear increase with depth are common features for the light and middle REEs everywhere, but their concentration levels are variable from basin to basin and from element to element. This suggests that their oceanic distributions respond quickly to the variation of particle flux and its REE composition through reversible exchange equilibrium with suspended and sinking particles much like the case for Th. The relative importance of the vertical geochemical processes of reversible scavenging over the horizontal basin-scale ocean circulation with passive regeneration like nutrients decreases systematically from the light to the heavy REEs. Using a model, the mean oceanic residence times of REEs in the Bay of Bengal are estimated to range from 37 years for Ce to 140–1510 years for the strictly trivalent REEs. In the deep water of the Andaman Sea, isolated from the Bay of Bengal by the Andaman–Nicobar Ridge (maximum sill depth of ∼1800 m), the REE concentrations are almost uniform presumably due to rapid vertical mixing. The REE(III) concentrations are similar to that of ∼1250 m depth water in the Bay of Bengal, consistent with other oceanographic properties. However, the REE composition of the deep water appears to be altered slightly by preferential scavenging of the light REE(III) at the bottom boundary of the basin.     

Excess228Th in the airborne dust: an indicator of continental dust from the East Asian deserts

Thorium isotopes in the airborne dust collected at Tsukuba Science City in Japan from January 1981 to December 1982 show clear seasonal variations. Especially²²⁸Th in the airborne particles have a typical maximum cincentration between February and April, which is about an order of magnitude higher than during the remainder of the year. According to the result of size distribution of thorium isotope-bearing particles in the air, about 53% of²²⁸Th is associated with the particles less than 1.6 μm aerodynamic diameter. These results reveal that²²⁸Th in the airborne particles is present in fine soily matters originating from the East Asian deserts.     

Pb and Th in settling particles in the western Northwest Pacific Ocean: Particle flux and scavenging

A mooring of three conical time-series sediment traps was deployed at two sites in the western Northwest Pacific Ocean for 9 months. Total mass fluxes and activities of ²¹⁰Pb and ²³⁰Th were determined for the settling particles to elucidate their scavenging and transport processes. Sediment samples also were analyzed for ²¹⁰Pb activities. Total mass fluxes, ²¹⁰Pb fluxes and ²³⁰Th fluxes showed large seasonal variations and their weighted mean fluxes tended to increase with depth, with an especially large increase near-bottom. The ratios of the observed ²¹⁰Pb fluxes to the ²¹⁰Pb deficiency fluxes in the upper traps at the two sites were only 0.02 and 0.12, and were attributable to advective export of ²¹⁰Pb from the surface waters. Those ratios in the near-bottom traps ranged between 1.22 and 2.63. This suggests that these high ratios are due to effective particle scavenging, large lateral ²¹⁰Pb import and input of resuspended particles that have not become incorporated into the sediments. The mean total ²³⁰Th fluxes at the near-bottom traps were 4.2–6.7 times higher than that expected from production in the overlying water column. The ²¹⁰Pb activities in the surficial sediments were much lower than those in the near-bottom traps. The ²¹⁰Pb accumulation rates estimated from the excess ²¹⁰Pb inventory in the sediment column were 40–70% higher than the mean ²¹⁰Pb fluxes at the near-bottom traps. The ratios of the ²¹⁰Pb accumulation rates to the ²¹⁰Pb deficiency fluxes at the near-bottom traps ranged between 2.0 and 3.7. The high fluxes of particulate ²¹⁰Pb and ²³⁰Th at the near-bottom traps reflected a combination of enhanced scavenging of dissolved nuclides and the lateral redistribution of particulate matter by downslope and alongshore transports. However, it was not possible to discriminate among the various processes contributing to high nuclide fluxes.     

226Ra, 210Pb and 210Po disequilibria in the Western North Pacific

²²⁶Ra,²¹⁰Pb and²¹⁰Po were measured in oceanic profiles at two stations near the Bonin and Kurile trenches.²¹⁰Po is depleted by 50% on average relative to²¹⁰Pb in the surface water. In the deep water,²¹⁰Pb is about 25% deficient relative to²²⁶Ra. Based on the deficiency,²¹⁰Pb residence time with respect to removal by particulate matter was estimated to be less than 96 years in the deep water.²¹⁰Pb deficiency in the bottom water was significantly greater than that of the adjacent deep water, indicating more effective removal near or at the bottom interface.²¹⁰Pb,²¹⁰Po and Th appear to have similar overall rate constants of particulate removal throughout the water column.     

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.     

Particulate and soluble210Pb activities in the deep sea

Particulate and soluble,²¹⁰Pb activities have been measured by filtration of large-volume water samples at two stations in the South Atlantic. Particulate phase²¹⁰Pb (caught by a 0.4-μm filter) varies from 0.3% of total²¹⁰Pb in equatorial surface water to 15% in the bottom water. The “absolute activity” of²¹⁰Pb per unit mass of particulate matter is about 10⁷ times the activity of soluble²¹⁰Pb per unit mass of water, but because the mass ratio of particulate matter to water is about 10^?8, the particulate phase carries only about 10% of the total activity. In Antarctic surface water the particulate phase carries 40% of the total²¹⁰Pb activity; the absolute activity of this material is about the same as in other water masses and the higher fraction is due to the much larger concentration of suspended matter in surface water in this region.In the equatorial Atlantic the particulate phase²¹⁰Pb activity increases with depth, by a factor of 40 from surface to bottom, and by a factor of 4 from the Antarctic Intermediate Water core to the Antarctic Bottom Water. This increase with depth is predicted by our previously proposed particulate scavenging model which indicated a scavenging residence time of 50 years for²¹⁰Pb in the deep sea. A scavenging experiment showed that red clay sediment removes all the²¹⁰Pb from seawater in less than a week. The Antarctic particulate profile shows little or no evidence of scavenging in this region, which may be due to the siliceous nature of the particulate phase in circumpolar waters. Our previous observation that the²¹⁰Pb/²²⁶Ra activity ratio is of the order of 0.5 in the deep water is further confirmed by the two South Atlantic profiles analyzed in the present work.