Seasonal variation in the Ra/Ra ratio of coastal water within the Sea of Japan: Implications for the origin and circulation patterns of the Tsushima Coastal Branch Current

In the current study, low-background γ-spectrometry was employed to determine the ²²⁸Ra/²²⁶Ra activity ratio and ¹³⁷Cs activity of 84 coastal water samples collected at six sites along the main island of Japan (Honshu Island) within the Sea of Japan, including the Tsushima Strait, and two other representative sites on Honshu Island (a Pacific shore and the Tsugaru Strait) at 1-month intervals in 2006.The ²²⁸Ra/²²⁶Ra ratio of coastal waters in the Sea of Japan exhibited similar patterns of seasonal variation, with minimum values during early summer (²²⁸Ra/²²⁶Ra = 0.6–0.8), maximum values during autumn (²²⁸Ra/²²⁶Ra = 1.5–3), and a time lag in their temporal changes ( 2.5 months and over  1300 km distance). However, the 2 other sites represented no clear periodic variation.In contrast to the positive correlation between ¹³⁷Cs activity (0.6–1.7 mBq/L) and salinity (15–35), the ²²⁸Ra/²²⁶Ra ratio of coastal water samples from the Sea of Japan was not observed to correlate with salinity, and the increase in the ²²⁸Ra/²²⁶Ra ratio was not as marked (0.5–1; May–June 2004 and 2005) during the migration along Honshu Island. The input of land-derived water and/or the diffusion of radium from coastal sediments is unlikely to have affected the wide seasonal variation in the ²²⁸Ra/²²⁶Ra ratio observed in these water samples.The seasonal variation in the ²²⁸Ra/²²⁶Ra ratio recorded for the coastal waters of the Sea of Japan is considered to be mainly controlled by the remarkable changes in the mixing ratio of the ²²⁸Ra-poor Kuroshio and the ²²⁸Ra-rich continental shelf waters within the East China Sea (ECS). After passing through the Tsushima Strait, this water mass moves northeast along the coastline of the Sea of Japan as the Tsushima Coastal Branch Current (TCBC).     

228Ra, 226Ra, 224Ra and 223Ra in potential sources and sinks of land-derived material in the German Bight of the North Sea: implications for the use of radium as a tracer

Activities of the naturally occurring radium nuclides ²²⁸Ra, ²²⁶Ra, ²²⁴Ra and ²²³Ra were determined in waters of the open German Bight and adjacent nearshore areas in the North Sea, in order to explore the potential use of radium isotopes as natural tracers of land–ocean interaction in an environment characterised by extensive tidal flats, as well as riverine and groundwater influx. Data collected at various tidal phases from the Weser Estuary (²²⁸Ra: 46.3 ± 4.6; ²²⁶Ra: 17.1 ± 1.1; ²²⁴Ra: 26.1 ± 8.2 to 36.5 ± 6.1; ²²³Ra: 1.8 ± 0.1 to 4.0 ± 0.4), tidal flats near Sahlenburg (²²⁸Ra: 39.3 ± 3.8 to 46.0 ± 4.5; ²²⁶Ra: 15.5 ± 1.5 to 16.5 ± 1.7; ²²⁴Ra: 34.3 ± 2.2 to 85.3 ± 6.3; ²²³Ra: 3.6 ± 0.5 to 8.0 ± 1.2), freshwater seeps on tidal flats near Sahlenburg (²²⁸Ra: 42.1 ± 4.1; ²²⁶Ra: 21.3 ± 2.2; ²²⁴Ra: 5.1 ± 0.9; ²²³Ra: 2.6 ± 1.3) and also in permanently inundated parts of the North Sea (²²⁸Ra: 23.0 ± 2.3 to 28.2 ± 2.8; ²²⁶Ra: 8.2 ± 0.8 to 11.8 ± 1.2; ²²⁴Ra: 3.1 ± 1.0 to 10.1 ± 0.9; ²²³Ra: 0.1 ± 0.02 to 0.9 ± 0.05; units: disintegrations per minute per 100 kg water sample) reveal that, except for the fresh groundwater, the potential end-members of nearshore water mass mixing have quite similar radium signatures, excluding a simple discrimination between the sources. However, the decreasing activities of the short-lived ²²⁴Ra and ²²³Ra isotopes recorded towards the island of Helgoland in the central German Bight show a potential to constrain fluxes of land-derived material to the open North Sea. The largest source for all radium isotopes is generally found on the vast tidal flats and in the Weser Estuary. Future work could meaningfully combine this so-called radium quartet approach with investigations of radon activity. Indeed, preliminary data from a tidal flat site with fresh groundwater seepage reveal a ²²²Rn signal that is clearly lower in seawater.     

TIMS measurements of Ra and Ra in the Gulf of Lion, an attempt to quantify submarine groundwater discharge

Submarine groundwater discharge (SGD) is now recognized as an important pathway for water and chemical species fluxes to the coastal ocean. In order to determinate SGD to the Gulf of Lion (France), we measured the activities of ²²⁶Ra and ²²⁸Ra by thermal ionization mass spectrometry (TIMS) in coastal waters and in the deep aquifer waters of the Rhone deltaic plain after pre-concentration of radium by MnO₂. Compared to conventional counting techniques, TIMS requires lower quantities of water for the analyses, and leads to higher analytical precision. Radium isotopes were thus measured on 0.25–2 L water samples containing as little as 20 fg of ²²⁶Ra and 0.2–0.4 fg of ²²⁸Ra with precision equal to 2%. We demonstrate that coastal surface waters samples are enriched in ²²⁶Ra and ²²⁸Ra compared to the samples further offshore. The high precision radium measurements display a small but significant ²²⁶Ra and ²²⁸Ra enrichment within a strip of circa 30 km from the coast. Radium activities decrease beyond this region, entrained in the northern current along the shelf break or controlled by eddy diffusion. The radium excess in the first 30 km cannot be accounted for by the river nor by the early diagenesis. The primary source of the radium enrichment must therefore be ascribed to the discharge of submarine groundwater. Using a mass-balance model, we estimated the advective fluxes of ²²⁶Ra and ²²⁸Ra through SGD to be 5.2 × 10¹⁰ and 21 × 10¹⁰ dpm/d respectively. The ²²⁶Ra activities measured in the groundwater from the Rhone deltaic plain aquifer are comparable to those from other coastal groundwater studies throughout the world. By contrast, ²²⁸Ra activities are higher by up to one order of magnitude. Taking those groundwater radium activities as typical of the submarine groundwater end-member, a minimum volume of 0.24–4.5 × 10¹⁰ l/d is required to support the excess radium isotopes on the inner shelf. This has to be compared with the average rivers water runoff of 15.4 × 10¹⁰ l/d during the study period (1.6 to 29% of the river flow).     

Ra/226Ra activity ratio in oceanic settling particles: implications regarding the use of barium as a proxy for paleoproductivity reconstruction

Activities of the natural radionuclides ²²⁶Ra (T1/2 =1602 years) and 22sRa (T1/2 =5.75 years) in particulate matter are reported from sediment traps deployed in the tropical northeast Atlantic. ²²⁸Ra/²²⁶Ra activity ratios in settling particles are compared to those found in the water column in order to specify the origin of radium incorporated in particulate matter, and consequently that of barium, since the two elements are known to display close geochemical behaviours in the oceans. Whereas ²²⁸Ra/²²⁶Ra activity ratios in the water column display very large variations with depth, they remain nearly constant in particles, with values close to those found in the upper 250 m. These results clearly demonstrate that particles acquire their radium and, by inference, their barium, in the upper water column and that there is very little exchange with the dissolved phase as they settle to the bottom.     

Ra and Ra in the mixing zones of the Pee Dee River-Winyah Bay, Yangtze River and Delaware Bay Estuaries

²²⁶Ra and ²²⁸Ra have non-conservative excess concentrations in the mixing zones of the Pee Dee River-Winyah Bay estuary, the Yangtze River estuary, and the Delaware Bay estuary. Laboratory experiments, using Pee Dee River sediment, indicate desorption of ²²⁶Ra to increase with increasing salinities up to 20‰. In Winyah Bay desorption from river-borne sediments could contribute almost all of the increases for both isotopes. Desorption adds only a portion of the excess ²²⁸Ra measured in the Yangtse River and adjacent Shelf waters and Delaware Bay. In the Yangtze River the mixing zone extends over a considerable portion of the Continental Shelf where ²²⁸Ra is added to the water column by diffusion from bottom sediments, while ²²⁶Ra concentrations decrease from dilution. Diffusion of ²²⁸Ra from bottom sediments in Delaware Bay primarily occurs in the upper part of the bay (< 22‰ water) where fine grained sediments predominate. A diffusive flux for ²²⁸Ra of 0·33 dpm cm⁻² year was determined for Delaware Bay.     

Incorporation rate measurements of <Superscript>10</Superscript>Be, <Superscript>230</Superscript>Th, <Superscript>231</Superscript>Pa,and <Superscript>239,240</Superscript>Pu radionuclides in manganese crust in the Pacific Ocean: A search for extraterrestrial material

In order to estimate the deposition rate of extraterrestrial material onto a manganese crust in a search for supernova debris, we analyzed the contents of ¹⁰Be, ²³⁰Th, ²³¹Pa, and ^239,240Pu in a sample of manganese crust collected from the North Pacific Ocean. On the basis of the depth profile of ¹⁰Be, the growth rate of the manganese crust was determined to be 2.3 mm Myr⁻¹. The uptake rates of ¹⁰Be, ²³⁰Th, and ²³¹Pa onto the manganese crust were estimated to be 0.22–0.44%, 0.11–0.73%, and 1.4–4.5%, respectively, as compared to the deposition rates onto the deep-sea sediments near the sampling station, while that for ^239,240Pu was 0.14% as compared to the total inventory of seawater and sediment column. Assuming that sinking particles represent 0.11–4.5% of the uptake rates, the deposition rate of extraterrestrial material onto the manganese crust was estimated to be 2–800 μg cm⁻²Myr⁻¹ according to the uptake of ¹⁰Be onto the manganese crust. Further, our estimate is similar to the value of 9–90 μg cm^{− 2}Myr⁻¹ obtained using the integrated global production rate of ¹⁰Be and the deposition rate of ¹⁰Be onto the manganese crust.     

Seasonal changes in submarine groundwater discharge to coastal salt ponds estimated using Ra and Ra as tracers

Submarine groundwater discharge (SGD) to coastal southern Rhode Island was estimated from measurements of the naturally-occurring radioisotopes ²²⁶Ra (t_1/2 = 1600 y) and ²²⁸Ra (t_1/2 = 5.75 y). Surface water and porewater samples were collected quarterly in Winnapaug, Quonochontaug, Ninigret, Green Hill, and Pt. Judith–Potter Ponds, as well as nearly monthly in the surface water of Rhode Island Sound, from January 2002 to August 2003; additional porewater samples were collected in August 2005. Surface water activities ranged from 12–83 dpm 100 L^− 1 (60 dpm = 1 Bq) and 21–256 dpm 100 L^− 1 for ²²⁶Ra and ²²⁸Ra, respectively. Porewater ²²⁶Ra activities ranged from 16–736 dpm 100 L^− 1 (2002–2003) and 95–815 dpm 100 L^− 1 (2005), while porewater ²²⁸Ra activities ranged from 23–1265 dpm 100 L^− 1. Combining these data with a simple box model provided average ²²⁶Ra-based submarine groundwater fluxes ranging from 11–159 L m^− 2 d^− 1 and average ²²⁸Ra-derived fluxes of 15–259 L m^− 2 d^− 1. Seasonal changes in Ra-derived SGD were apparent in all ponds as well as between ponds, with SGD values of 30–472 L m^− 2 d^− 1 (Winnapaug Pond), 6–20 L m^− 2 d^− 1 (Quonochontaug Pond), 36–273 L m^− 2 d^− 1 (Ninigret Pond), 29–76 L m^− 2 d^− 1 (Green Hill Pond), and 19–83 L m^− 2 d^− 1 (Pt. Judith–Potter Pond). These Ra-derived fluxes are up to two orders of magnitude higher than results predicted by a numerical model of groundwater flow, estimates of aquifer recharge for the study period, and values published in previous Ra-based SGD studies in Rhode Island. This disparity may result from differences in the type of flow (recirculated seawater versus fresh groundwater) determined using each technique, as well as variability in porewater Ra activity.     

<Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium and particulate organic carbon export in the northern South China Sea

We utilized ²³⁴Th, a naturally occurring radionuclide, to quantify the particulate organic carbon (POC) export rates in the northern South China Sea (SCS) based on data collected in July 2000 (summer), May 2001 (spring) and November 2002 (autumn). Th-234 deficit was enhanced with depth in the euphotic zone, reaching a subsurface maximum at the Chl-a maximum in most cases, as commonly observed in many oceanic regimes. Th-234 was in general in equilibrium with ²³⁸U at a depth of ∼100 m, the bottom of the euphotic zone. In this study the ²³⁴Th deficit appeared to be less significant in November than in July and May. A surface excess of ²³⁴Th relative to ²³⁸U was found in the summer over the shelf of the northern SCS, most likely due to the accumulation of suspended particles entrapped by a salinity front. Comparison of the ²³⁴Th fluxes from the upper 10 m water column between 2-D and traditional 1-D models revealed agreement within the errors of estimation, suggesting the applicability of the 1-D model to this particular shelf region. 1-D model-based ²³⁴Th fluxes were converted to POC export rates using the ratios of bottle POC to ²³⁴Th. The values ranged from 5.3 to 26.6 mmol C m⁻²d⁻¹ and were slightly higher than those in the southern SCS and other oligotrophic areas. POC export overall showed larger values in spring and summer than in autumn, the seasonality of which was, however, not significant. The highest POC export rate (26.6 mmol C m⁻²d⁻¹) appeared at the shelf break in spring (May), when Chl-a increased and the community structure changed from pico-phytoplankton (<2 μm) dominated to nano-phytoplankton (2–20 μm) and micro-phytoplankton (20–200 μm) dominated.     

Nearshore scavenging phenomenon elucidated by <Superscript>234</Superscript>th/<Superscript>238</Superscript>u disequilibrium in the coastal waters off Western Taiwan

Dissolved and particulate ²³⁴Th activities in surface seawater were determined at 27 stations along the coastline of western Taiwan during 19–23 November 2004. Contrasting scavenging settings were observed between the northern and southern regimes of the nearshore water off western Taiwan, separated by the Cho-Shui River. The northern regime is characterized by a large quantity of suspended load contributed by northward transport of a suspension plume from the Cho-Shui River, while the southern regime, low in suspended load and high in chlorophyll concentration, is a system controlled by biological activity. A scavenging model that takes account of the physical transport was used to estimate the ²³⁴Th budget in order to estimate the scavenging and removal rates from the nearshore water. The scavenging and removal rates ranged from 21 to 127 dpm m⁻³d⁻¹ and from 36 to 525 dpm m⁻³d⁻¹, for dissolved and particulate ²³⁴Th, respectively. The removal fluxes of particulate organic carbon (POC) and particulate organic nitrogen (PON) were estimated by multiplying the particulate ²³⁴Th removal flux to the organic carbon/²³⁴Th and nitrogen/²³⁴Th ratios in suspended particles, which ranged from 4.5 to 275.2 mmol-C m⁻²d⁻¹ and from 1.3 to 50.1 mmol-N m⁻²d⁻¹, respectively. These fluxes resulted in residence times of 1∼20 days for the POC in the surface water of nearshore water off western Taiwan.     

East-west distribution of POC fluxes estimated from <Superscript>234</Superscript>Th in the northern North Pacific in autumn

Observations of primary productivity, ²³⁴Th, and particulate organic carbon (POC) were made from west to east across the northern North Pacific Ocean (from station K2 to Ocean Station Papa) during September–October 2005. Primary productivities in this region varied longitudinally from approximately 236 to 444 mgC m⁻²d⁻¹ and clearly indicate the West High East Low (WHEL) trend. We estimated east-west variations in the POC flux from the surface layer (0–100 m) by using ²³⁴Th as a tracer. POC fluxes in the western region (44–53 mgC m⁻²d⁻¹) were higher than those in the eastern region (21–34 mgC m⁻²d⁻¹). However, the export ratios (e-ratios) ranged from approximately 8% to 16% and did not show the WHEL trend. Contrary to our expectation, no relation between POC flux (or e-ratio) and diatom biomass (or dominance) was apparent in autumn in the northern North Pacific.     

High-precision measurement of oceanic 226Ra

A system capable of oceanic ²²⁶Ra measurements with a precision of ±1% is described, which represents an improvement of approximately a factor of three over existing techniques. ²²²Rn grown-in from ²²⁶Ra decay in 14-l seawater samples is quantitatively transferred to, and measured in, proportional gas counters. Errors other than counting statistics are estimated not to exceed ±0.5%, which is consistent with repeated ²²⁶Ra measurements on the same samples. A NE Atlantic ²²⁶Ra depth profile (2000–5000 m) is reported as an example. It is found that with the precision reported here, certain hitherto unresolved features of the ²²⁶Ra distribution in deep water become apparent.     

Radium and radon radioisotopes in regional groundwater, intertidal groundwater, and seawater in the Adelaide Coastal Waters Study area: Implications for the evaluation of submarine groundwater discharge

The input of groundwater-borne nutrients to Adelaide's (South Australia) coastal zone is not well known but could contribute to the ongoing decline of seagrass in the area. As a component of the Adelaide Coastal Waters Study (ACWS), the potential for using the radium quartet (²²³Ra, ²²⁴Ra, ²²⁶Ra and ²²⁸Ra) and ²²²Rn to evaluate submarine groundwater discharge (SGD) was evaluated. Potential isotopic signatures for SGD were assessed by sampling groundwater from three regional aquifers potentially contributing SGD to the ACWS area. In addition, intertidal groundwater was sampled at two sand beach sites. In general, the regional groundwaters were enriched in long-lived Ra isotopes (²²⁶Ra and ²²⁸Ra) and in ²²²Rn relative to intertidal groundwater. Radium activity (but not ²²²Rn activity) was positively correlated to salinity in groundwater from one of the regional aquifers and in intertidal groundwater. Radium isotope ratios (²²³Ra/²²⁶Ra, ²²⁴Ra/²²⁶Ra and ²²⁸Ra/²²⁶Ra) were less variable than individual Ra isotope activities within potential SGD sources. Recirculated seawater (estimated from the intertidal groundwater samples with seawater-like salinities) also had distinctly higher Ra isotope ratios than the regional groundwaters. The activities for all radioisotopes were relatively low in seawater. The activity of the short-lived ²²³Ra and ²²⁴Ra were highest at the shoreline and declined exponentially with distance offshore. In contrast, ²²⁸Ra and ²²⁶Ra activities had a weak linear declining trend with distance offshore. Rn-222 activity was at or near background in all seawater samples. The pattern of enrichment in short-lived Ra isotopes and the lack of ²²²Rn in seawater suggest that seawater recirculation is the main contributor to SGD in the ACWS area. Preliminary modeling of the offshore flux of ²²⁸Ra and ²²⁶Ra suggest that the SGD flux to the ACWS area ranges between 0.2 and 3 · 10^− 3 m³ (m of shoreline)^− 1 s^− 1.     

228Ra in surface water of the Seto Inland Sea

The concentrations of²²⁸Ra in surface waters of the Seto Inland Sea were determined. Surface waters from the central region of the Seto Inland Sea, Hiuchi Nada and Bingo Nada, contained concentrations of²²⁸Ra of 655–811 dpm/1000 l which were 100 times higher than those obtained in the Pacific Ocean. These high concentrations of²²⁸Ra must be supported by a²²⁸Ra flux from the bottom sediment. The lower limit of this flux was estimated to be more than 0.16 dpm cm^–2 y^–1. The²²⁸Ra concentrations decreased markedly from central regions of the Seto Inland Sea to about 18 dpm/1000 l in the Kii and the Bungo Channels as salinity increased. Using a box model and the²²⁸Ra data, the mean residence time of sea water in the Seto Inland Sea with respect to the exchange with the open ocean water was estimated to be less than 10 y, and the most probable value is the order of several years.     

白令海峡水团来源的镭同位素示踪

对白令海峡64.3°N纬向断面镭同位素的研究表明,水体中226Ra比活度、228Ra比活度和228Ra/226Ra)A.R.存在明显的纬向变化,反映出太平洋与北冰洋水体交换的多种路径.根据温度、盐度和镭同位素的水平与垂直分布,太平洋水进入北冰洋的路径可能主要有3支,分别为白令海峡西侧的阿拉德水、白令海峡东侧的阿拉斯加沿...     

Uncertainties associated with Ra and Ra measurements in water via a Delayed Coincidence Counter (RaDeCC)

The short-lived radium isotopes, ²²³Ra (T_1/2 = 11.4 days) and ²²⁴Ra (T_1/2 = 3.66 days), have been successfully used as tracers of several environmental processes, e.g., submarine groundwater discharge, coastal mixing processes, and water residence times. In this paper, the uncertainties associated with ²²³Ra and ²²⁴Ra measurements using a Radium Delayed Coincidence Counter are determined on a detailed error propagation basis with a confidence interval of 1σ. From the data analyses of several groups of coastal water samples, the calculated relative uncertainties averaged 12% for the ²²³Ra and 7% for the ²²⁴Ra. These uncertainties can decrease for radium-enriched groundwater samples although asymptotic limits have been found at 7% relative uncertainty for ²²³Ra and 4% for ²²⁴Ra. In this paper, the influence of sampling and measurement parameters on the final radium uncertainties is evaluated in order to provide guidance to optimize these factors and obtain more reliable results.     

北黄海水体的226Ra和228Ra

用锰纤维富集-射气法测定了北黄海海水中的镭同位素226Ra和228Ra,研究了该海域水体中镭同位素的含量和分布.研究结果表明北黄海水体夏季226Ra的比活度为1.80～4.35 Bq/m3,平均值为3.06 Bq/m3;冬季226Ra的比活度为2.08～5.20 Bq/m3,平均值为3.28 Bq/m3.北黄海夏季228Ra的比活度为3.85～25.60 Bq/m3,平均值为10.60 Bq/m3;冬季228Ra的比活度为3.14～15.60Bq/m3,平均值为7.66 Bq/m3.该数据范围和中国近海其他海域、孟加拉湾、泰国昭披耶河口、濑户内海等海域相近.北黄海东北部海域,渤海海峡靠近山东半岛的海区和中北部海区表层镭同位素活度较高.C1断面镭同位素的分布特征从镭同位素的方面证实了渤海海峡水交换表现为北进南出特征这一结论的正确性.226Ra和228Ra的垂直分布较为复杂,大部分站位呈现出底层活度变高的趋势,其他少数站位呈现出中间层活度高的分布特征,不同来源的镭同位素输入至该海域形成了这样的分布特征.     

High 226Ra and 228Ra activities in Nueces Bay,Texas indicate large submarine saline discharges

We have investigated submarine groundwater discharge to Nueces Bay (Texas) using naturally occurring Ra isotopes. Dissolved Ra activities in Nueces Bay are among the highest observed in coastal estuaries; as great as 2600 dpm m^− 3 for ²²⁸Ra and 1000 dpm m^− 3 for ²²⁶Ra. Using a combination of salt and Ra mass balances, we demonstrate that river discharge and bay bottom sediments cannot supply the Ra needed to balance tidal export. In the case of ²²⁶Ra there is an additional source of 218 × 10⁶ ± 105% dpm day^− 1 which is 9 times the maximum supply from bay bottom sediments and 50 times the Ra supplied by the Nueces River. A groundwater flux of 310,000 m³ day^− 1 is required to supply the needed ²²⁶Ra, based on the measured maximum Ra activity of local groundwater. Though as little as 10% of this flux may be advecting terrestrial groundwater this would still represent 160% of the Nueces River discharge. This makes it unlikely that groundwater discharge alone is supplying all of the additional ²²⁶Ra. Oil-field brine could potentially account for the remainder. Leakage of 6290 m³ day^− 1 of oil-field brine from the submerged petroleum wells and pipelines within the bay could supply all of the needed ²²⁶Ra. Such large fluxes of brackish groundwater and oil-field brine could significantly affect bay nitrogen budgets, salinities, and dissolved oxygen concentrations and should be considered when determining the freshwater inflow requirements for Nueces Bay and similar estuaries.     

Seasonal export fluxes of particulate organic carbon from <Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium measurements in the Ulleung Basin<Superscript>1</Superscript> (Tsushima Basin) of the East Sea<Superscript>1</Superscript> (Sea of Japan)

Export fluxes of particulate organic carbon (POC) were estimated from the ²³⁴Th/²³⁸U disequilibrium in the Ulleung Basin¹ (UB) of the East/Japan Sea¹ (EJS) over four seasons. The fluxes were calculated by multiplying the average POC/²³⁴Th ratio of sinking particles larger than 0.7 μm at 100- and 200-m water depths to ²³⁴Th fluxes by the integrated ²³⁴Th/²³⁸U disequilibrium from the surface to 100-m water depth. In spring, the ²³⁴Th profiles changed dramatically with sampling time, and hence a non-steady-state ²³⁴Th model was used to estimate the ²³⁴Th fluxes. The ²³⁴Th flux estimated from the non-steady-state model was an order of magnitude higher than that estimated from the steady-state model. The ²³⁴Th fluxes estimated using the steady-state model showed distinct seasonal variation, with high values in summer and winter and low values in autumn. In spring, the phytoplankton biomass had the highest value, and primary production was higher than in summer and autumn, but the ²³⁴Th fluxes were moderate. However, these values might have been significantly underestimated, as the ²³⁴Th fluxes were estimated using the steady-state model. The POC export fluxes estimated in autumn were about four times lower than those in other seasons when they were rather similar. The annually averaged POC flux was estimated to be 161 ± 76 mgC m⁻² day⁻¹, which was somewhat lower than that in highly productive coastal areas, and higher than that in oligotrophic regions. The export/primary production (ThE) ratios ranged from 7.0 to 56.1%, with higher values in spring and summer and lower values in autumn and winter. In summer, a high ThE ratio of 48.4 ± 7.0% was measured. This may be attributed to the mass diatom sinking event following nitrate depletion. In the UB¹, the annually averaged ThE ratio was estimated to be 34.4 ± 12.9%, much higher than that in oligotrophic oceans. The high ThE ratio may have contributed to the high organic carbon accumulation in the UB¹.     

Comparison of techniques for pre-concentrating radium from seawater

In the framework of the KEOPS project (KErguelen: compared study of the Ocean and the Plateau in Surface water), we aimed to provide information on the water mass pathways and vertical mixing on the Kerguelen Plateau, Southern Ocean, based on ²²⁸Ra profiles. Because ²²⁸Ra activities are extremely low in this area (~ 0.1 dpm/100 kg or ~ 2.10^− 18 g kg^− 1), the filtration of large volumes of seawater was required in order to be able to detect it with minimal uncertainty. This challenging study was an opportunity for us to test and compare methods aimed at removing efficiently radium isotopes from seawater. We used Mn-fiber that retains radium and that allows the measurement of all four radium isotopes (²²⁶Ra, ²²⁸Ra, ²²³Ra, ²²⁴Ra). First, we used Niskin bottles or the ship's seawater intake to collect large volumes of seawater that were passed onto Mn-fiber in the laboratory. Second, we filled cartridges with Mn-fiber that we placed in tandem on in situ pumps. Finally, we fixed nylon nets filled with Mn-fiber on the frame of in situ pumps to allow the passive filtration of seawater during the pump deployment.Yields of radium fixation on the cartridges filled with Mn-fiber and placed on in situ pumps are ca. 30% when combining the two cartridges. Because large volumes of seawater can be filtered with these pumps, this yields to effective volumes of 177–280 kg (that is, higher than that recovered from fourteen 12-l Niskin bottles). Finally, the effective volume of seawater that passed through Mn-fiber placed in nylon nets and deployed during 4 h ranged between 125 and 364 kg. Consequently, the two techniques that separate Ra isotopes in situ are good alternatives for pre-concentrating radium from seawater. They can save ship-time by avoiding repeated CTD casts to obtain the large volumes of seawater. This is especially true when in situ pumps are deployed to collect suspended particles. However, both methods only provide ²²⁸Ra/²²⁶Ra ratios. The determination of the ²²⁸Ra specific activity is obtained by multiplying this ratio by the ²²⁶Ra activity measured in a discrete sample collected at the same water depth.     

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.