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.     

POC export from ocean surface waters by means of 234Th/238U and 210Po/210Pb disequilibria: A review of the use of two radiotracer pairs

²³⁴Th (T_1/2=24.1 d) and ²¹⁰Po (T_1/2=138.4 d) are particle reactive radioisotopes that are used as tracers for particle cycling in the upper ocean. Particulate organic carbon (POC) export has frequently been estimated using ²³⁴Th/²³⁸U disequilibrium. Recent evidence suggests that ²¹⁰Po/²¹⁰Pb disequilibrium may be used as an additional tool to examine particle export, given the direct biological uptake of ²¹⁰Po into cellular material. Differences in these two radioisotope pairs with regard to their half-lives, particle reactivity and scavenging affinity in seawater should provide complementary information to be obtained on the processes occurring in the water column. Here, we review eight different studies that have simultaneously used both approaches to estimate POC export fluxes from the surface ocean. Our aim is to provide a complete “dataset” of all the existing POC flux data derived from the coupled use of both ²³⁴Th and ²¹⁰Po and to evaluate the advantages and limitations of each tracer pair. Our analysis suggests that the simultaneous use of both radiotracers provides more useful comparative data than can be derived from the use of a single tracer alone. The difference in half-lives of ²³⁴Th and ²¹⁰Po enables the study of export production rates over different time scales. In addition, their different biogeochemical behaviour and preferred affinity for specific types of particles leads to the conclusion that ²³⁴Th is a better tracer of total mass flux, whereas ²¹⁰Po tracks POC export more specifically. The synthesis presented here is also intended to provide a basis for planning future sampling strategies and promoting further work in this field to help reveal the more specific application of each tracer under specific water column biogeochemistries.     

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.     

南海与厦门湾海水中210Po和210Pb的粒级分布

对南海和厦门湾表层水中210Po和210Pb的粒级分布特征进行了研究.结果表明,南海海水中210Po和210Pb在不同粒级颗粒物中的体积比活度高低顺序为:(＜0.4μm)＞(0.4～2.0 μm)＞(2.0～10 μm)＞(＞10μm).210Po、210Pb主要存在于＜2.0 μm粒级颗粒物中.厦门湾210Po体积比活度高低顺序为:(2.0～10 μm)＞(＜1.2μm)＞(＞10μm)＞(1.2～2.0 μm),210Po主要存在于＞2.0μm粒级颗粒物中.南海不同粒级颗粒物中210Pb的质量比活度差异不大,0.4～2.0 μm和2.0～10 μm粒级210Po质量比活度约为10μm粒级210Po比活度的3倍.厦门湾210Po的质量比活度比南海相应粒级210Po低约1个数量级,且各粒级间差异不大,表明不同粒径颗粒物在210Po和210Pb清除过程中的作用不同.210Po和210Pb的固-液分配系数(Kd)及分馏因子(α)进一步证实南海0.4～2.0 μm粒级颗粒物对210Po的清除能力比其它粒级颗粒物更强,而＞10μm粒级颗粒物对210Pb的清除能力比其它粒级颗粒物更强.不同粒级颗粒物中210Po与210Pb之间的不平衡状况揭示了不同粒级颗粒物不同的来源,为210Po/210Pb不平衡示踪颗粒物来源提供了依据.     

Scavenging,cycling and removal fluxes of 210Po and 210Pb at the Bermuda time-series study site

Quantifying relative affinities of Po and Pb in different populations of marine particulate matter is of great importance in utilizing ²¹⁰Po as a tracer for carbon cycling. We collected and analyzed water samples for the concentrations of dissolved and total ²¹⁰Po and ²¹⁰Pb from the upper 600 m of the water column at Bermuda Time-series Study site (September 1999–September 2000) to investigate their seasonality of concentrations and their activity ratio (²¹⁰Po/²¹⁰Pb activity ratio, AR). Sinking particles collected in sediment traps at depths of 500 m, 1500 m, and 3200 m from the Oceanic Flux Program (OFP) time-series sediment traps were analyzed over a period of 12 months (May 1999–May 2000). The objective was to compare the deficiencies of ²¹⁰Po with respect to ²¹⁰Pb in the water column to that measured in the sediment traps and to assess the relative affinities of Po and Pb with different particle pools.Inventories of ²¹⁰Po in the upper 500 m water column varied by a factor of 2, indicating seasonal variations of particulate flux dominated the removal of ²¹⁰Po. The ²¹⁰Po/²¹⁰Pb ARs in the dissolved phase were generally less than the secular equilibrium value (1.0) in the upper 600 m, while were generally greater than 1.0 in the particulate phase, indicating higher removal rates of ²¹⁰Po relative to ²¹⁰Pb by particulate matter. The measured fluxes of ²¹⁰Po and ²¹⁰Pb in the 500 m, 1500 m, and 3200 m traps increased with depth, while the ²¹⁰Po/²¹⁰Pb ARs decreased with depth except from May–August 1999. From the measured fluxes of ²¹⁰Po and ²¹⁰Pb at these three traps and the concentrations of ²¹⁰Po and ²¹⁰Pb in the water column, this region appears to be a sink for ²¹⁰Pb which is likely brought-in by lateral advection.     

海水中228Th、234Th、228Ra的联合富集与测定

采用大体积现场泵方法同时采集不同粒级的^228Th、^234Th及溶解态的^228Th、^234Th、^228Ra．以小体积MnO2共沉淀-β计数法测定海水中的总^234Th活度（A＇TTh）；用Goflo采水器采集6～10dm^3海水，继而过滤收集颗粒物质并测定其^234Th的活度（A’PTh）；以α能谱测定分离纯化后的^228Th；对^228Ra则是采用测定其子体^228Ac的β放射性方法．采用此流程分析了南海2004年2月航次A1站住的样品，获得了较好的结果．     

厦门近岸210Po和210Pb的大气沉降通量

为揭示中国东南沿海地区210Po和210Pb的大气沉降时空变化特征,探讨该地区气溶胶的停留时间,于2013年1月至2014年12月对厦门地区210Po和210Pb的大气沉降通量进行了时间序列研究。结果发现,210Po和210Pb的平均日沉降通量分别为（65.38±4.79） mBq/（m2·d）（n=54）和（0.78±0.09） Bq/（m2·d）（n=54）,表现出明显的周年变化。东北季风期间,210Po和210Pb的沉降通量较高,而西南季风期间其通量较低。2013年和2014年,210Po的年沉降通量分别为19.29 Bq/（m2·a）和9.25 Bq/（m2·a）,210Pb的年沉降通量分别为159.2 Bq/（m2·a）和189.6 Bq/（m2·a）。两核素的年沉降通量表现出不同程度的年际差异。210Po与210Pb沉降通量之间存在显著的线性正相关关系,揭示了大气中210Po和210Pb具有相同的迁出机制,降雨和大气中核素含量是影响210Po和210Pb沉降通量的主要因素。该研究结果可以为探求台湾海峡海水中210Po与210Pb的收支平衡提供大气来源项。     

Vertical transport of organic materials in the northern North Pacific as determined by sediment trap experiment

Sediment traps were deployed at 5 depths of 100 through 5,250 m to collect suspended sediments in the northern North Pacific (47°51.1'N; 176°20.6'E, 5,300 m deep) in the summer of 1978. Fatty acid composition was determined in the samples of phytoplankton, particulate matter, trap sediment and bottom sediment.Fatty acid composition of the trap sediments revealed no significant vertical trend throughout the water column from depths of 100 to 5,250 m, and were also similar to those of the phytoplankton and the particulate matter from the euphotic layer. However, a marked difference in the fatty acid composition was observed between the trap sediments and the particulate matter from deep waters. Therefore, it can be concluded that the source of fatty acids in the trap sediments is the particulate matter from the euphotic layer but not from deep waters.Unsaturated fatty acids highly susceptible to biological agents were rather abundant in the trap sediments as well as in the phytoplankton and particulate matter from the euphotic layer, however no unsaturated fatty acid was found in the particulate matter from deep waters. From these findings, it is clear that the particulate matter of the euphotic layer is transported to deep waters very rapidly. As the sinking rate of fecal pellets produced by zooplankton is in the range of ten to hundreds of meters a day, fecal pellets are assumed to be the most likely carrier of rapid-transport of organic matter including fatty acids from the euphotic layer to deep waters.     

Calibration of sediment traps and particulate organic carbon export using 234Th in the Barents Sea

Profiles of particulate and dissolved ²³⁴Th (t_1/2=24.1 days) in seawater and particulate ²³⁴Th collected in drifting traps were analyzed in the Barents Sea at five stations during the ALV3 cruise (from June 28 to July 12, 1999) along a transect from 78°15′N–34°09′E to 73°49′N–31°43′E. ²³⁴Th/²³⁸U disequilibrium was observed at all locations. ²³⁴Th data measured in suspended and trapped particles were used to calibrate the catchment efficiency of the sediment traps. Model-derived ²³⁴Th fluxes were similar to ²³⁴Th fluxes measured in sediment traps based on a steady-state ²³⁴Th model. This suggests that the sediment traps were not subject to large trapping efficiency problems (collection efficiency ranges from 70% to 100% for four traps). The export flux of particulate organic carbon (POC) can be calculated from the model-derived export flux of ²³⁴Th and the POC/²³⁴Th ratio. POC/²³⁴Th ratios measured in suspended and trapped particles were very different (52.0±9.9 and 5.3±2.2 μmol dpm⁻¹, respectively). The agreement between calculated and measured POC fluxes when the POC/²³⁴Th ratio of trapped particles was used confirms that the POC/²³⁴Th ratio in trap particles is representative of sinking particles. Large discrepancies were observed between calculated and measured POC fluxes when the POC/²³⁴Th ratio of suspended particles was used. In the Barents Sea, vertical POC fluxes are higher than POC fluxes estimated in the central Arctic Ocean and the Beaufort Sea and lower than those calculated in the Northeast Water Polynya and the Chukchi Sea. We suggest that the latter fluxes may have been strongly overestimated, because they were based on high POC/²³⁴Th ratios measured on suspended particles. It seems that POC fluxes cannot be reliably derived from thorium budgets without measuring the POC/²³⁴Th ratio of sediment trap material or of large filtered particles.     

Accumulation rates and sources of sediments and organic carbon on the Palos Verdes shelf based on radioisotopic tracers (137Cs, 239,240Pu, 210Pb, 234Th, 238U and 14C)

We report here bioturbation and sediment accumulation rates determined from replicate sediment cores at four different sampling sites on the Palos Verdes shelf, Southern California, using bomb fallout and natural radionuclides (¹³⁷Cs, ^239,240Pu, ²¹⁰Pb, ²³⁴Th, and ¹⁴C), along with supporting measurements of organic carbon (OC), porosity and granulometry. Present-day particle reworking, on time scales of several months, is restricted to the upper 3 cm, with rates ranging from 13 to 200 cm²/year, as deduced from ²³⁴Th_xs profiles. There is little evidence that particle reworking reached depths significantly greater than 5 cm. Post-1963 (or post-1971) sediment accumulation rates ranged from 0.7 to 1.4 g/cm²/year (equivalent to 1.1–1.8 cm/year for surficial sediments), as calculated from Pu and Cs isotope profiles, with little change over time or distance from the outfall. Lateral transport of older sediment and multiple sediment sources on the Palos Verdes shelf is suggested from radiocarbon measurements on foraminifera and bulk sedimentary organic matter at two sampling sites, which showed variable, old and refractory sources of OC. Pre-1953 sediments accumulated at rates that were at least 0.4 g/cm²/year (≥0.3 cm/year), based on ²¹⁰Pb_xs dating. Given the abundance of sediment sources to the Palos Verdes shelf, the high sedimentation rates, and shallow particle mixed layers, contaminant-enriched layers should continue to move deeper into the sediments.     

Time-series measurements of Th in water column and sediment trap samples from the northwestern Mediterranean Sea

Disequilibrium between ²³⁴Th and ²³⁸U in water column profiles has been used to estimate the settling flux of Th (and, by proxy, of particulate organic carbon); yet potentially major non-steady-state influences on ²³⁴Th profiles are often not able to be considered in estimations of flux. We have compared temporal series of ²³⁴Th distributions in the upper water column at both coastal and deep-water sites in the northwestern Mediterranean Sea to coeval sediment trap records at the same sites. We have used sediment trap records of ²³⁴Th fluxes to predict temporal changes in water column ²³⁴Th deficits and have compared the predicted deficits to those measured to determine whether the time-evolution of the two coincide. At the coastal site (327 m water depth), trends in the two estimates of water column ²³⁴Th deficits are in fairly close agreement over the 1-month deployment during the spring bloom in 1999. In contrast, the pattern of water column ²³⁴Th deficits is poorly predicted by sediment trap records at the deep-water site (DYFAMED, 2300 m water depth) in both 2003 and 2005. In particular, the transition from a mesotrophic to an oligotrophic system, clearly seen in trap fluxes, is not evident in water column ²³⁴Th profiles, which show high-frequency variability. Allowing trapping efficiencies to vary from 100% does not reconcile the differences between trap and water column deficit observations; we conclude that substantial lateral and vertical advective influences must be invoked to account for the differences.Advective influences are potentially greater on ²³⁴Th fluxes derived from water column deficits relative to those obtained from traps because the calculation of deficits in open-ocean settings is dominated by the magnitude of the “dissolved” ²³⁴Th fraction. For observed current velocities of 5–20 cm s⁻¹, in one radioactive mean-life of ²³⁴Th, the water column at the DYFAMED site can reflect ²³⁴Th scavenging produced tens to hundreds of kilometers away. In contrast, most of the ²³⁴Th flux collected in shallow sediment traps at the DFYFAMED site was in the fraction settling >200 m d⁻¹; in effect the sediment trap can integrate the ²³⁴Th flux over distances 40-fold less than water column ²³⁴Th distributions. In some sense, sediment trap and water column sampling for ²³⁴Th provide complementary pictures of ²³⁴Th export. However, because the two methods can be dominated by different processes and are subject to different biases, their comparison must be treated with caution.     

Vertical flux of particulate Al,Fe, Pb,and Ba from the upper ocean estimated from 234Th/238U disequilibria

The vertical sinking flux of particulate Al, Fe, Pb, and Ba from the upper 250 m of the Labrador Sea has been estimated from measurements of ²³⁴Th/²³⁸U disequilibrium and the respective metal/²³⁴Th ratios in >53 μm size particles. ²³⁴Th-derived particulate metal fluxes include in situ scavenged metals, labile lithogenic metals, and metals derived from external input (e.g., atmospheric supply). In contrast to the POC/²³⁴Th ratio, particle size-fractionated (0.4–10 μm, 10–53 μm, and >53 μm) Al/²³⁴Th, Fe/²³⁴Th and Pb/²³⁴Th, and Ba/²³⁴Th ratios generally increase with depth and exhibit no systematic change with particle diameter. Sinking fluxes of particulate Al (2.47–22.3 μmol m⁻² d⁻¹), Fe (2.69–16.3 μmol m⁻² d⁻¹), Pb (2.85–70 nmol m⁻² d⁻¹), and Ba (0.13–2.1 μmol m⁻² d⁻¹) at 50 m (base of the euphotic zone) and 100 m (base of the mixed layer) are largely within the range of previous sediment trap results from other ocean basins. Estimates of the upper ocean residence time of Al (0.07–0.28 yr) and Pb (0.8–2.9 yr) are short compared to previously reported values. The settling rate of >53 μm particles calculated from the ²³⁴Th data ranges from 14 to 38 m d⁻¹.     

Quantitative evaluation of bioturbation rates in deep ocean sediments. II. Comparison of rates determined by 210Pb and 239,240Pu

Excess ²¹⁰Pb was determined in six abyssal cores from the Eastern Atlantic, Hatteras Abyssal Plain, and Puerto Rico Trench. A bioturbation rate for each core was evaluated using the mixing model of Guinasso and Schink. The rates were compared to mixing rates evaluated for the same cores using ^239,240Pu. In all cases, the excess ²¹⁰Pb-derived mixing rates were lower than the plutonium-derived mixing rates. ^239,240Pu was also present at greater depths than excess ²¹⁰Pb. One possible explanation for these observations is the association of plutonium with particles of greater food value which are bioturbated at faster rates.     

海水中234Th的超低水平液闪谱仪测定

本文提出了利用超低水平液闪谱仪测定海水中234Th的方法.海水经氢氧化铁吸附共沉淀富集后,接着用阴离子交换和TBP/煤油萃取进行Th同位素的分离与纯化.对一系列测定条件进行了详细的研究,提出了测定海水中234Th的适宜程序,即在含有234Th和产额示踪剂230Th的纯化后的5mol/dm3HNO3溶液中加入TBP/煤油进行萃取,然后用0.1mol/dm3HNO3反萃取,后者是先用契伦柯夫计数法测量234Th(通过234mPa),后加入闪烁液Hisafe 3用α/β模式测量α放射体230Th.对于α和β放射体液闪谱仪的计数效率分别为100%和55.7%±2.7%.234Th的化学回收率和总探测效率分别为70%～80%和30%～45%.该法测定海水中的234Th快速、简便和高效.     

Sediment trap and in-situ pump size-fractionated POC/234Th ratios in the Mediterranean Sea and Northwest Atlantic: Implications for POC export

Measurements of particle size-fractionated POC/²³⁴Th ratios and ²³⁴Th and POC fluxes were conducted using surface-tethered, free-floating, sediment traps and large-volume in-situ pumps during four cruises in 2004 and 2005 to the oligotrophic eastern Mediterranean Sea and the seasonally productive western Mediterranean and northwest Atlantic. Analysis of POC/²³⁴Th ratios in sediment trap material and 10, 20, 53, 70, and 100 μm size-fractionated particles indicate, for most stations, decreasing ratios with depth, a weak dependence on particle size, and ratios that converge to ～1–5 μmol dpm^?1 below the euphotic zone (～100–150 m) throughout the contrasting biogeochemical regimes. In the oligotrophic waters of the Aegean Sea, ²³⁴Th and POC fluxes estimated using sediment traps were consistently higher than respective fluxes estimated from water-column ²³⁴Th–²³⁸U disequilibrium, observations that are attributed to terrigenous particle scavenging of ²³⁴Th. In the more productive western Mediterranean and northwest Atlantic, ²³⁴Th and POC fluxes measured by sediment trap and ²³⁴Th–²³⁸U disequilibrium agreed within a factor of 2–4 throughout the water column. An implication of these results is that estimates of POC export by sediment traps and ²³⁴Th–²³⁸U disequilibrium can be biased differently because of differential settling speeds of POC and ²³⁴Th-carrying particles.     

POC export from ocean surface waters by means of Th/U and Po/Pb disequilibria: A review of the use of two radiotracer pairs

²³⁴Th (T_1/2=24.1 d) and ²¹⁰Po (T_1/2=138.4 d) are particle reactive radioisotopes that are used as tracers for particle cycling in the upper ocean. Particulate organic carbon (POC) export has frequently been estimated using ²³⁴Th/²³⁸U disequilibrium. Recent evidence suggests that ²¹⁰Po/²¹⁰Pb disequilibrium may be used as an additional tool to examine particle export, given the direct biological uptake of ²¹⁰Po into cellular material. Differences in these two radioisotope pairs with regard to their half-lives, particle reactivity and scavenging affinity in seawater should provide complementary information to be obtained on the processes occurring in the water column. Here, we review eight different studies that have simultaneously used both approaches to estimate POC export fluxes from the surface ocean. Our aim is to provide a complete “dataset” of all the existing POC flux data derived from the coupled use of both ²³⁴Th and ²¹⁰Po and to evaluate the advantages and limitations of each tracer pair. Our analysis suggests that the simultaneous use of both radiotracers provides more useful comparative data than can be derived from the use of a single tracer alone. The difference in half-lives of ²³⁴Th and ²¹⁰Po enables the study of export production rates over different time scales. In addition, their different biogeochemical behaviour and preferred affinity for specific types of particles leads to the conclusion that ²³⁴Th is a better tracer of total mass flux, whereas ²¹⁰Po tracks POC export more specifically. The synthesis presented here is also intended to provide a basis for planning future sampling strategies and promoting further work in this field to help reveal the more specific application of each tracer under specific water column biogeochemistries.     

Regeneration of chemical elements from settling particles collected by sediment trap in Funka Bay,Japan

Sediment trap experiments were carried out 39 times during the years from 1977 to 1981 in Funka Bay, Hokkaido, Japan. The observed total particulate flux varies seasonally, that is, the particulate fluxes in winter and spring are larger than those in summer. The fluxes in all seasons increased with depth. Major components of settling particles are aluminosilicate in winter, biogenic silicate in spring and organic matter and terrestrial material in summer, respectively. The fluxes of each chemical component observed with sediment traps are normalized to that of Al by assuming that the actual flux of Al is equal to the accumulation rate onto the sediment surface. Vertical changes of the normalized flux of each chemical component indicate the following: Fe was not regenerated from the settling particles in the water column. Mn was regenerated from the settling particles in the lower layer exclusively between 80 m depth and the sediment surface. Cd was actively regenerated in the upper layer above 80 m depth. Phosphate was regenerated in the upper layer, while biogenic silicate was in the lower layer. The silicate regeneration, therefore, occurs after phosphate regeneration. The material decomposing in the water column below 40 m has an atomic ratio of P ∶ Si ∶ C = 1 ∶ 52 ∶ 128.