Thorium concentration and the activity ratios230Th/232Th and228Th/232Th in sea water in the western North Pacific

The concentration of thorium isotopes and the activity ratios of²³⁰Th/²³²Th and²²⁸Th/²³²Th in sea water collected in the Kuroshio region, the mixing area of Oyashio and Kuroshio, the Japan Sea and the East China Sea in the western North Pacific were determined. Thorium isotopes were analyzed by α-ray spectrometry after separating them with an anion exchange resin. The average content of thorium (²³²Th) of 2.2×10⁻⁹ g/l was obtained in the open Pacific waters. The ratio of²³⁰Th/²³²Th is in accord with that of the top layer of the sediment in the same area. The high values of²²⁸Th/²³²Th ratio up to 36 were observed in sea water. The excess²²⁸Th in sea water may be due to the migration of²²⁸Ra through the water-sediment interface. Thorium content in suspended matter was 10 to 20% of the total thorium content in the Pacific water.     

Th isotopes in the Santa Monica basin: Temporal variation,long-term mass balance and model rate constants

Distribution and flux of²³⁴Th,²³²Th and²³⁰Th in the water column of central Santa Monica basin observed over a period of seven years show seasonal and interannual variabilities. A steady-state model is applied to the integrated data to calculate long term average flux and model rate constants of Th isotopes. Mass balance calculations show that the basin acts like a closed system for short-lived²³⁴Th, but not for the long-lived isotopes²³⁰Th and²³²Th. Most²³⁰Th in the basin is transported from elsewhere. Of the incoming Th, 40–55% of the²³⁰Th and 14–26% of the²³²Th enter the surface water in dissolved form. In the upper 100 m, the residence time of dissolved Th with respect to adsorption onto suspended particulates, 70–80 days, is about one order of magnitude higher than the residence time of suspended particles with respect to aggregation into sinking particles, 7–10 days.     

Content of plutonium,thorium and protactinium in sea water and recent coral in the North Pacific

The contents of plutonium isotopes (²³⁹Pu and²³⁸Pu), thorium isotopes (²³²Th,²³⁰Th and²²⁸Th) and protactinium-231 in sea water collected in the North Pacific, the East China Sea and the Japan Sea were determined. These nuclides were sequentially analyzed byα-ray spectrometry after separating them mainly with solvent extraction technique. The contents of²³⁹Pu in surface sea water ranged from 0.6 to 1.6 pCi/10001,²³⁸Pu/²³⁹Pu activity ratios being 0.2～0.7. The²²⁸Th/²³²Th activity ratios for the North Pacific waters varied between 7.6 and 30, whereas the sample from the East China Sea showed the very high value, 65. The contents of²³¹Pa are less than 6 percent of that in equilibrium with its parent²³⁵U. Furthermore, the analysis of plutonium isotopes in recent coral from Yoron Island was carried out and it was confirmed that plutonium isotopes have concentrated in recent coral with the concentration factor of about 1～2×10³.     

Determination of thorium isotopes in seawater by moored MnO2-fiber method

A method is described for the determination of Th isotopes (²³²Th,²³⁰Th,²²⁸Th and²²⁷Th) in seawater through analysis of Th adsorbed on MnO₂-impregnated fiber that has been moored in the deep sea for up to 10 months. Since the MnO₂-fiber adsorbs Th from seawater at a constant rate, natural²³⁴Th can be used as a yield monitor by making a correction for its decay during the period of deployment. The results obtained by the method showed good reproducibility and accuracy. The method has the advantage over the chemical coprecipitation method that the time and labor for sampling and processing a large-volume of seawater is reduced.     

Sinking fluxes of particulate U-Th radionuclides in the East Sea (Sea of Japan)

A record of radionuclide fluxes at a deep marginal sea of the Northwest Pacific Ocean (39°40′N 132°24′ E, Japan Basin, East Sea/Sea of Japan) was obtained from analysis of a 1-year continuous collection of sediment-trap samples. The trap was placed at a depth of 2800 m, 500 m above the sea floor, and the samples were recovered at the end of one year. Concentrations of ²³⁸U, ²³⁴U, ²³²Th, ²³⁰Th and ²²⁸Th were measured in the trapped material. All of the radionuclide fluxes showed seasonal variations that were in phase with the variations in total particle flux, which were shown in earlier work to be closely tied to the primary production in the surface water. The formation of authigenic ²³⁸U appears to be less than in other open ocean regimes. The residence time of particulate thorium isotopes were of the order of a year, resulting in an average settling rate of a meter per day. Comparison of the measured ²³⁰Th_ex flux with that of the theoretical production in the overlying water column yielded about 40% surplus of ²³⁰Th, indicating that lateral advection contributes ²³⁰Th to this sampling site.     

Thorium isotopes as tracers of particles dynamics and deep water circulation in the Indian sector of the Southern Ocean (ANTARES IV)

Dissolved and particulate samples were collected to study the distribution of thorium isotopes (²³⁴Th, ²³²Th and ²³⁰Th) in the water column of the Indian sector of the Southern Ocean (from 42°S to 47°S and from 60°E to 66°E, north of the Polar Front) during Austral summer 1999. Vertical profiles of excess ²³⁰Th (²³⁰Th_xs) increases linearly with depth in surface water (0–100 m) and a model was applied to estimate a residence time relative to the thorium scavenging (τ_scav). Low τ_scav in the Polar Front Zone (PFZ) are found, compared to those estimated in the Subtropical Front Zone (STZ). Changes in particle composition between the PFZ and STZ could influence the ²³⁰Th_xs scavenging efficiency and explain this difference. An innovative coupling between ²³⁴Th and ²³⁰Th_xs was then used to simultaneously constrain the settling velocities of small (0.6–60 μm) and large (above 60 μm) particles. Although the different hydrological and biogeochemical regimes visited during the ANTARES IV cruise did not explain the spatial variation of sinking velocity estimates, our results indicate that less particles may reach the seafloor north (60 ± 2 m d^− 1, station 8) than south of the Agulhas Return Current (119 ± 23 and 130 ± 5 m d^− 1 at stations 3 and 7, respectively). This information is essential for understanding particle transport and by extension, carbon export. In the deep water column, the ²³⁰Th_xs concentrations did not increase linearly with depth, probably due to lateral transport of North Atlantic Deep Water (NADW) from the Atlantic to the Indian sector, which renews the deep waters and decreases the ²³⁰Th_xs concentrations. A specific ²³⁰Th_xs transport model is applied in the deep water column and allows us to assess a “travel time” of NADW ranging from 2 to 15 years.     

Impact of the Mediterranean Outflow Water on particle dynamics in intermediate waters of the Northeast Atlantic, as revealed by Th and Th

Over the last decade ²³⁴Th has become increasingly used to study particle transport in the ocean on a timescale of weeks. The application of ²³⁴Th is mainly focused on the determination of particle and associated carbon fluxes from oceanic surface water. However, ²³⁴Th is also suitable for investigating particle dynamic from the upper ocean down to interface sediments, as illustrated by the present work which reports unexpected behavior of ²³⁴Th in intermediate waters associated with the Mediterranean Outflow Water (MOW). Concentration profiles of dissolved ²³⁸U and ²²⁸Ra, and dissolved and particulate ²³⁴Th and ²²⁸Th were measured in the Mediterranean Outflow Water (MOW) near the Gibraltar Straits and at two sites (36°30′N–15°35′W, Nicole; 36°27′N–10°35′W, Yseult) which had hydrographic characteristics of Meddies, i.e. MOW that propagates as eddies in the Northeastern Atlantic at intermediate depths.There are marked differences in the distribution of thorium between MOW and the surrounding Atlantic waters. At the youngest Meddy Nicole salinity maximum at 1000 m depth, ²³⁴Th(total) : ²³⁸U and ²²⁸Th(total) : ²²⁸Ra activity ratios are significantly lower than radioactive equilibrium, indicating an unusual deficit of short half-life thorium nuclides. This implies an export of thorium, presumably on particles, from intermediate Meddy Nicole waters. This process is supported by an increase of particulate thorium fluxes measured in sediment traps deployed for two weeks above and within Meddy Nicole. In contrast, offshore Meddy Yseult has more typical profiles of both thorium nuclides that are nearly in equilibrium with their parents. These results indicate that at intermediate depths, the presence of MOW affects the exchange of reactive elements between particles and dissolved forms and enhances the downward flux of particles from intermediate waters in the Northeast Atlantic.     

Temporal variations of dissolved and particulate Th at a coastal station of the northern Adriatic Sea

Water–particle interactions, particle behaviour and short-time scale variability were assessed at a coastal station adjacent to the Emilia Romagna Region (Adriatic Sea) using dissolved and particulate ²³⁴Th analyses. The water column was sampled six times between March and September 1997. Measurements showed that ²³⁴Th is actively scavenged by particles but the dissolved fraction is always prevalent. Changes in hydrological conditions affect to some degree thorium activities and residence times. Dissolved thorium inventories slowly increased from May to July, then decreased in August, and increased again in September. In July, the formation of a sharp pycnocline associated with low productivity led to high dissolved and very low particulate ²³⁴Th activities due to inefficient scavenging. The presence of mucilaginous aggregates, observed in both August and September, may have played a role in scavenging of thorium. In September at 16 m depth, the highest ²³⁴Th particulate activity of the study period was measured, probably due to the presence of mucilage. However, the thorium deficit was scarce, due to the small sinking velocity of these aggregates. Both steady-state and non-steady state models were used to calculate residence times for the whole water column and its topmost part (10 m) obtaining strictly comparable results. Residence times in the whole water column are small, ranging from 15 to 45 and from 0.5 to 24 d for dissolved and particulate thorium, respectively.     

Th and Pa isotopes in the waters of the western margin of the pacific near Japan: Evidence for release of228Ra and227Ac from slope sediments

Using the moored MnO₂-fiber method, we have obtained 38 determinations of Th and Pa isotope concentrations from 18 sites along the margin of the western North Pacific near Japan, from water depths of 1,330 to 5,873 m. From our data, we are able to show that (1)²²⁸Ra and²²⁷Ac are being supplied to the seawater from the slope sediments of Honshu, Japan, (2) our²³⁰Th and²³¹Pa concentrations match those obtained byin situ pumping with a MnO₂-fiber adsorber in the Japan and Izu-Ogasawara trenches but are significantly higher than those from the Panama and Guatemala basins, and (3) our²³²Th concentrations show a similar systematic decrease with depth as do those of trace metals like Mn, Al, Te and Bi whose concentrations are strongly controlled by particulate matter scavenging.In contrast, our data fail to show (1) that enhanced removal of²³⁰Th and²³¹Pa by scavenging from the water column is taking place near the western margins and (2) that²³¹Pa is being removed in preference to²³⁰Th from the water column to the marginal sediments. This is probably due to rapid mixing of the deep waters as compared to the scavenging rates of²³⁰Th and²³¹Pa in the water column and at the sediment/seawater interface.     

Radiochemical studies of deep-sea manganese nodules

Five manganese nodules collected from the Northern Mid - Pacific have been analysed for their U and Th isotopes.lt is found that the enrichment of thorium compared to uranium is universal in deep- sea manganese, nodules and in the top sides of the nodules there are large excesses of Th and Pa decreasing exponentially with depth. For each of the nodules, the concordant growth rates are obtained from three different methods: 230Thex 230Thex/232Th and 231Paex.The growth rates of manganese nodules are closely related to the chemical compositions of the nodules and the types of the underlying sediments. The growth rates of five nodules are determined to be in the range of 0.79-7.4 mm/106a, in agreement with those predicted from the chemical compositions of the nodules. By the comparison of the extrapolated 230Thex,230Thex/232 Th and 231PaeX data from the top and bottom surfaces of the nodule from Site M21 yields, the nodule turnover time is (9.83-13.7)×104a.     

A practical method for the simultaneous determination of234Th,226Ra,210Pb and210Po in seawater

A practical method has been developed for the simultaneous determination of²²⁶Ra,²³⁴Th,²¹⁰Pb and²¹⁰Po in seawater. In the method, the samples are spiked with²²⁸Ra,²³⁰Th,²⁰⁸Po and common lead to determine chemical yield. These nuclides are coprecipitated with calcium carbonate and ferric hydroxide from 20 to 50 l of seawater and separated from one another by using coprecipitation and ion exchange techniques. Counting sources of Ra and the other nuclides are prepared by electrodeposition onto silver discs. Their radioactivities are counted with an-spectrometer and a low background-counter. This method gives a standard deviation of about 5% for replicate determination of²²⁶Ra and the other nuclides.     

沉积物中钍同位素分析样品的处理方法比较研究

分别用HCl浸取和HF全溶法分析研究沉积物中的同位素^232Th、^230Th、^228Th，并对所分析的结果进行全面的对照比较，盐酸浓度、温度及样品的矿物组分都能影响这3种同位素的酸浸取效率，对于一种确定的沉积物来说，在相同的浸取条件下，^228Th的酸浸取效率总是高于^232Th，这是由于α辐射子体同位素的反冲作用造成的，与HCl浸取法比较，HF全溶法更可靠、更准确。     

Measuring low concentrations of Th in water and sediment

²³⁴Th/²³⁸U disequilibria have been used extensively in studies of particle dynamics and the fate and transport of particle-reactive matter in marine environments. Similar work in low salinity, estuarine, and freshwater systems has not occurred primarily because the lower concentrations of both parent and daughter nuclides that are typical of these systems often render established methods for the analysis of ²³⁴Th inadequate. The application of this radionuclide tracer technique to these systems, however, has great potential. To this end, we present a method for measuring low activities of ²³⁴Th in relatively small samples (<200 l) using low background gas-flow proportional counters, a ²²⁹Th yield monitor, and empirical corrections for the interferences from real and apparent betas that are emitted by other thorium isotopes and their progeny. For samples with low ²³⁴Th/²²⁸Th activity ratios, we improve upon current beta counting methodologies that rely on immediate sample counting, weak beta absorption, or multiple beta counts so that, using the analytical approach outlined here, it should be possible to measure ²³⁴Th activities (i) as low as 1.5 dpm/total sample, (ii) up to 2 weeks after radiochemical purification of thorium, and (iii) with only one sample count for alpha and beta activity.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

Thorium speciation in seawater

Since the 1960s, thorium isotopes occupy a special place in the oceanographer's toolbox as tracers for determining rates and mechanisms of oceanic scavenging, particle dynamics, and carbon fluxes. Due to their unique and constant production rates from soluble parent nuclides of uranium and radium, their disequilibrium can be used to calculate rates and time scales of sinking particles. In addition, by ratio-ing particulate ²³⁴Th (as well, in principle, other Th-nuclides) to carbon (and other elements), and linking this ratio to the parent–daughter disequilibrium in the water column, it is possible to calculate fluxes of carbon and other elements. Most of these applications are possible with little knowledge of the dissolved chemical properties of thorium, other than its oxidation state (IV) and tendency to strongly sorb to surfaces, i.e., its “particle- or surface-activity”. However, the use of any tracer is hindered by a lack of knowledge of its chemical properties. Recent observations in the variability of carbon to ²³⁴Th ratios in different particle types, as well as of associations of Th(IV) with various marine organic biomolecules has led to the need for a review of current knowledge and what future endeavors should be taken to understand the marine chemistry of thorium.     

Organic carbon to Th ratios of marine organic matter

Uncertainties in the determinations of particulate organic carbon flux from measurements of the disequilibrium between ²³⁴Th and its mother isotope uranium depend largely on the determination of the organic carbon to ²³⁴thorium (OC : ²³⁴Th) ratio. The variability of the OC : ²³⁴Th ratio in different size fractions of suspended matter, ranging from the truly dissolved (< 3 or 10 kDa) fraction to several millimeter sized marine snow, as well as from sediment trap material was assessed during an eight-day cruise off the coast of California in Spring 1997. The affinity of polysaccharide particles called TEP (transparent exopolymer particles) and inorganic clays to ²³⁴Th was investigated through correlations. The observed decrease in the OC : ²³⁴Th ratio with size, within the truly dissolved to small particle size range, is consistent with concepts of irreversible colloidal aggregation of non-porous nano-aggregates. No consistent trend in the OC : ²³⁴Th ratio was observed for particles between 1 or 10 to 6000 μm. Origin and fate of marine particles belonging to this size range are diverse and interactions with ²³⁴Th too complex to expect a consistent relationship between OC : ²³⁴Th ratio and size, if all categories of particles are included. The relationship between OC and ²³⁴Th was significant when data from the truly dissolved fraction were excluded. However, variability was very large, implying that OC flux calculations using different collection methods (e.g. sediment trap, Niskin bottles or pumps) would differ significantly. Therefore a large uncertainty in OC flux calculations based on the ²³⁴Th method exist due to individual decisions as to which types or size classes of particles best represent sinking material in a specific area. Preferential binding of ²³⁴Th to specific substance classes could explain the high variability in the relationship between OC and ²³⁴Th. At 15 m, in the absence of lithogenic material, the OC : ²³⁴Th ratio was a function of the fraction of TEP or TEP-precursors in OC, confirming that acidic polysaccharides have a high affinity for ²³⁴Th and that TEP carry a ligand for ²³⁴Th. Preferential binding to TEP might change distribution patterns of ²³⁴Th considerably, as TEP may sink when included in large aggregates, or remain suspended or even ascend when existing as individual particles or microaggregates. In the presence of lithogenic matter, at depths below 30 m, the ratio between ²³⁴Th and OC was linearly related to the ratio between alumino silicates and C. The affinity of inorganic substances to ²³⁴Th is known to be relatively low, suggesting that a coating of acidic polysaccharides was responsible for the apparently high affinity between ²³⁴Th and lithogenic material. Overall, OC : ²³⁴Th ratios of all material collected during this investigation can best be explained by differential binding of ²³⁴Th to both TEP and TEP-precursors, as well as to lithogenic minerals, which were very abundant in an intermediate nepheloid layer between 50 and 90 m.     

Sediment trap experiments in the water column off southwestern Taiwan:234Th fluxes

The activity of²³⁴Th (t _1/2=24.1 days) in dissolved, particulate and sediment trap samples was determined in the water column off southwestern Taiwan during 2–4 October, 1993. Vertical²³⁴Th fluxes measured by the free-floating sediment traps ranged from 363 to 2290 dpm m^–2 d^–1 in the upper 450 m. Th-234 fluxes predicted from the irreversible scavenging model concur with those measured by the sediment traps. Comparison of the residence times of particulate²³⁴Th and particulate organic carbon showed that their respective values differ by a factor of approximately 23, which suggests organic carbon is preferentially recycled relative to²³⁴Th in the euphotic zone.     

错流超滤技术在海水胶体态铀、钍、镭同位素和有机碳研究中的应用

建立了由预过滤装置、蠕动泵、中空纤维超滤膜(AmiconH10P10-20,标称截留分子量10KDa)和连接管组成的错流超滤系统,利用荧光标记的40KDa葡聚糖和已知放射性活度的234Th示踪剂评估了超滤膜的截留和吸附性质,探讨了234Th在超滤过程中的渗透行为,考查了该系统用于实际海水样品时铀、钍、镭同位素和有机碳的质量平衡状况.结果表明,10Kda中空纤维超滤膜对40Kda葡聚糖具有良好的截留效率(85%),而吸附损失率为18%.铀、钍、镭同位素和有机碳在超滤过程中均达到极佳的质量平衡,回收率R=95%～98%,优于大多数文献报道的值.234Th在超滤过程中的渗透行为可以很好地用渗透模型加以描述.研究组分胶体态含量占“溶解”态含量的份额大小顺序如下:钍同位素、有机碳、镭同位素约等于铀同位素,这与钍为强颗粒活性元素、铀和镭为水溶性元素的地球化学性质相吻合.     

Spatial variation of234Th scavenging in the surface water of the Bashi Channel and the Luzon Strait

Activities of dissolved and particulate²³⁴Th were measured to study the spatial variation of scavenging phenomena in the surface water of the Bashi Channel and the Luzon Strait. Using an irreversible scavenging model, the residence times for total, dissolved, and particulate²³⁴Th are 28–613, 8–156, and 7–306 days, respectively. Along the PR21 transect of the WOCE project, three major domains can be identified based on the hydrography and the²³⁴Th data: the Bashi Channel, the Northern Luzon Strait, and the Southern Luzon Strait. Tight correlation between the scavenging constant and the suspended particle matter (TSM) concentration in the surface water of the Northern Luzon Strait implies that TSM concentration is an important parameter in studying thorium scavenging.     

Fluxes of234Th,210Po and210Pb determined by sediment trap experiments in pelagic oceans

Sediment trap experiments were carried out in two oceans, the eastern Pacific Ocean and the Antarctic Ocean, which have very different biological productivities. The natural radionuclides,²³⁴Th,²¹⁰Po and²¹⁰Pb were used as tracers of reactive metals. Larger particulate fluxes of these radionuclides were found in the seas where total mass fluxes were larger, although the concentrations of these radionuclides in the settling particles were somewhat smaller. The concentrations of²³⁴Th in the settling particles varied widely and irregularly with depth, whereas the concentrations of²¹⁰Po and²¹⁰Pb in the settling particles steadily increased with increasing water depth. The ratios of²¹⁰Po/²¹⁰Pb in the settling particulates were larger than unity which the ratio of²³⁴Th/excess²¹⁰Po as larger than²³⁴Th/²¹⁰Po in the deep water. These results suggest that, when the particles sink through the water column, these radionuclides are being absorbed by settling particles in the order²³⁴Th>²¹⁰Po>²¹⁰Pb. The observed particulate fluxes of²¹⁰Pb are about one eighth of those calculated from the disequilibria between²²⁶Ra and²¹⁰Pb at the stations in the subtropical eastern Pacific, although the observed fluxes are the same as the calculated ones in the northern North Pacific and the Antarctic Ocean. Thus, there must be a horizontal flow carrying these reactive metals from the oligotorophic ocean to the biologically productive ocean where the metals are removed by settling particles even in deep water.