Thorium-234 as a tracer of spatial,temporal and vertical variability in particle flux in the North Pacific

An extensive ²³⁴Th data set was collected at two sites in the North Pacific: ALOHA, an oligotrophic site near Hawaii, and K2, a mesotrophic HNLC site in the NW Pacific as part of the VERTIGO (VERtical Transport In the Global Ocean) study. Total ²³⁴Th:²³⁸U activity ratios near 1.0 indicated low particle fluxes at ALOHA, while ²³⁴Th:²³⁸U ～0.6 in the euphotic zone at K2 indicated higher particle export. However, spatial variability was large at both sites—even greater than seasonal variability as reported in prior studies. This variability in space and time confounds the use of single profiles of ²³⁴Th for sediment trap calibration purposes. At K2, there was a decrease in export flux and increase in ²³⁴Th activities over time associated with the declining phase of a summer diatom bloom, which required the use of non-steady state models for flux predictions. This variability in space and time confounds the use of single profiles of ²³⁴Th for sediment trap calibration purposes. High vertical resolution profiles show narrow layers (20–30 m) of excess ²³⁴Th below the deep chlorophyll maximum at K2 associated with particle remineralization resulting in a decrease in flux at depth that may be missed with standard sampling for ²³⁴Th and/or with sediment traps. Also, the application of ²³⁴Th as POC flux tracer relies on accurate sampling of particulate POC/²³⁴Th ratios and here the ratio is similar on sinking particles and mid-sized particles collected by in-situ filtration (>10–50 μm at ALOHA and >5–350 μm at K2). To further address variability in particle fluxes at K2, a simple model of the drawdown of ²³⁴Th and nutrients is used to demonstrate that while coupled during export, their ratios in the water column will vary with time and depth after export. Overall these ²³⁴Th data provide a detailed view into particle flux and remineralization in the North Pacific over time and space scales that are varying over days to weeks, and 10's–100's km at a resolution that is difficult to obtain with other methods.     

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.     

Particulate organic carbon export fluxes and size-fractionated POC/234Th ratios in the Ligurian,Tyrrhenian and Aegean Seas

Measurements of ²³⁴Th/²³⁸U disequilibria and particle size-fractionated (1, 10, 20, 53, 70, 100 μm) organic C and ²³⁴Th were made to constrain estimates of the export flux of particulate organic C (POC) from the surface waters of the Ligurian, Tyrrhenian and Aegean Seas in March–June 2004. POC exported from the surface waters (75–100 m depth) averaged 9.2 mmol m⁻² d⁻¹ in the Ligurian and Tyrrhenian Seas (2.3±0.5–14.9±3.0 mmol m⁻² d⁻¹) and 0.9 mmol m⁻² d⁻¹ in the Aegean Sea. These results are comparable to previous measurements of ²³⁴Th-derived and sediment-trap POC fluxes from the upper 200 m in the Mediterranean Sea. Depth variations in the POC/²³⁴Th ratio suggest two possible controls. First, decreasing POC/²³⁴Th ratios with depth were attributed to preferential remineralization of organic C. Second, the occurrence of maxima or minima in the POC/²³⁴Th ratio near the DCM suggests influence by phytoplankton dynamics. To assess the accuracy of these data, the empirical ²³⁴Th-method was evaluated by quantifying the extent to which the ²³⁴Th-based estimate of POC flux, P_POC, deviates from the true flux, F_POC, defined as the p-ratio (p-ratio=P_POC/F_POC=S_Th/S_POC, where S=particle sinking rate). Estimates of the p-ratio made using Stokes’ Law and the particle size distributions of organic C and ²³⁴Th yield values ranging from 0.93–1.45. The proximity of the p-ratio to unity implies that differences in the sinking rates of POC- and ²³⁴Th-carrying particles did not bias ²³⁴Th-normalized POC fluxes by more than a factor of two.     

An in-situ analysis and measurement of thorium-234, uranium isotopes in seawater

A low-level β counting-α spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium-228 simultaneously and an easy operating procedure for the enrichment, radiochemical separating, sampling and measurement of thorium-234 and uranium-238 in the ocean are developed based on the requirements of analyzing export productivity in the euphotic zone via thorium-234-uranium-238 radioactivity disequilibrium. The detecting efficiency both of β and α radiation is higher than 20%. The background of β radiation is less than 0.5 min-1, and the energy resolution of α detector is better than 1%. Total recycle ratio of thorium-234 is about 75%. Using the above apparatus and procedure, the radioactivities of dissolved thorium-234 and uranium-238, particle thorium-234 and uranium-238 in seawater of the South China Sea, the Southern Ocean and the Arctic Ocean were analyzed.     

Binding of thorium(IV) to carboxylate, phosphate and sulfate functional groups from marine exopolymeric substances (EPS)

Th(IV) isotopes are important proxies in oceanographic investigations, and are used as tracers of particle dynamics and particulate organic matter (POC) fluxes out of the euphotic zone through the use of ²³⁴Th/POC ratios. These approaches rely on empirically determined and variable POC to ²³⁴Th ratios, which might be controlled, in parts, by the abundance of exopolymeric substances (EPS). EPS contain acidic polysaccharides (APS) and are excreted by both phytoplankton and bacteria. To this end, radiotracer experiments with EPS from microbial cultures were conducted to determine the binding environment of ²³⁴Th(IV)-binding ligands in colloids and suspended particles in marine systems. In these experiments, the ²³⁴Th distribution during isoelectric focusing (IEF) and polyacrylamide gel electrophoresis (PAGE) was related to the functional group composition of EPS and of colloidal organic matter (COM) isolated from the Gulf of Mexico (GOM) using cross-flow ultrafiltration. EPS was extracted from phytoplankton (Emiliania huxleyi and Synechococcus elongatus) and bacteria (Sagittula stellata and Roseobacter gallaeciensis) cultures by repeated alcohol precipitation. Phosphate and sulfate concentrations were determined using ion chromatography (IC). IEF profiles indicated that 49% to 65% of the ²³⁴Th-labeled EPS from plankton and bacteria as well as COM samples from the GOM was found concentrated below pH of 4, near an isoelectric point, pH_IEP, of about 2. The carboxylic acid maxima for extracted EPS and COM samples appeared close to the pH_IEF of ²³⁴Th(IV). The phosphate maximum appeared at the same pH_IEF as ²³⁴Th(IV) for EPS from R. gallaeciensis and S. elongatus. The sulfate maximum was found at the same pH_IEF as ²³⁴Th(IV) for EPS from S. elongatus and COM. The molecular weight (MW) of the strongly Th(IV)-binding ligand varied from 1 to 14 kDa, depending on the species, but was about 10 kDa in COM. Thus, depending on the species of plankton or bacteria, the MW and specific functional group composition of the strongly ²³⁴Th(IV)-binding amphiphilic biomolecule can vary. Therefore, different acidic functional groups can, at times, contribute to the binding of Th(IV) to the EPS chelating ligand, which can also have different MWs. This implies that the binding environment for Th(IV), which is present at total concentrations at least a million times lower than the acid functional groups, consists of strong polydentate chelate complexes in clustered structures of carboxylate, sulfates and/or phosphates. The combination of strongly chelating groups and amphiphilicity gives this biomolecule the unique properties of a “sticky” ligand.     

Short-lived thorium isotopes (Th, Th) as indicators of POC export and particle cycling in the Ross Sea, Southern Ocean

Repeated measurements of depth profiles of ²³⁴Th (dissolved, 1–70 and >70 μm particulate) at three stations (Orca, Minke, Sei) in the Ross Sea have been used to estimate the export of Th and particulate organic carbon (POC) from the euphotic zone. Sampling was carried out on three JGOFS cruises covering the period from October 1996 (austral early spring) to April 1997 (austral fall). Deficiencies of ²³⁴Th relative to its parent ²³⁸U in the upper 100 m are small during the early spring cruise, increase to maximum values during the summer, and decrease over the course of the fall. Application of a non-steady-state model to the ²³⁴Th data shows that the flux of Th from the euphotic zone occurs principally during the summer cruise and in the interval between summer and fall. Station Minke in the southwestern Ross Sea appears to sustain significant ²³⁴Th removal for a longer period than is evident at Orca or Sei. Particulate ²³⁴Th activities and POC are greater in the 1–70 μm size fraction, except late in the summer cruise, when the >70 μm POC fraction exceeds that of the 1–70 μm fraction. The POC/²³⁴Th ratio in the >70 μm fraction exceeds that in the 1–70 μm fraction, likely due in part to the greater availability of surface sites for Th adsorption in the latter. Particulate ²³⁴Th fluxes are converted to POC fluxes by multiplying by the POC/²³⁴Th ratio of the >70 μm fraction (assumed to be representative of sinking particles). POC fluxes calculated from a steady-state Th scavenging model range from 7 to 91 mmol C m⁻² d⁻¹ during late January–early February, with the greatest flux observed at station Minke late in the cruise. Fluxes estimated with a non-steady-state Th model are 85 mmol C m⁻² d⁻¹ at Minke (1/13–2/1/97) and 50 mmol C m⁻² d⁻¹ at Orca (1/19–2/1/97). The decline in POC inventories (0–100 m) is most rapid in the southern Ross Sea during the austral summer cruise (Smith et al., 2000. The seasonal cycle of phytoplankton biomass and primary productivity in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3119–3140. Gardner et al., 2000. Seasonal patterns of water column particulate organic carbon and fluxes in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3423–3449), and the ²³⁴Th-derived POC fluxes indicate that the sinking flux of POC is 30–50% of the POC decrease, depending on whether steady-state or non-steady-state Th fluxes are used. Rate constants for particle POC aggregation and disaggregation rates are calculated at station Orca by coupling particulate ²³⁴Th data with ²²⁸Th data on the same samples. Late in the early spring cruise, as well as during the summer cruise, POC aggregation rates are highest in near-surface waters and decrease with depth. POC disaggregation rates during the same time generally increase to a maximum and are low at depth (>200 m). Subsurface aggregation rates increase to high values late in the summer, while disaggregation rates decrease. This trend helps explain higher values of POC in the >70 m fraction relative to the 1–70 m fraction late in the summer cruise. Increases in disaggregation rate below 100 m transfer POC from the large to small size fraction and may attenuate the flux of POC sinking out of the euphotic zone.     

南大洋普里兹湾基于234Th/238U不平衡法的POC输出通量研究

中国第22次南极科学考察(2005年11月至2006年3月)期间,测定了南极普里兹湾海域5个站位的从表层至150 m水深的不同层位水样中溶解态和颗粒态234Th,238U的放射性比活度以及颗粒有机碳.利用234Th/238U在上层水体中的不平衡,计算了南极普里兹湾上层水体中234Th的平均停留时间和输出通量.结果显示,随着纬度的增加,上层水体中颗粒态和溶解态234Th的平均停留时间总体趋向减小,并在中纬度站位出现了最低值,分别为1~8和29~48 d,而颗粒态和溶解态234Th的输出通量则在中纬度站位出现了最大值,分别为21~38和26~39 dpm/(m3·d).运用箱型清除模式,利用两种不同的方法估算了各水柱中从真光层底部输出的POC通量,平均值分别达到104.7 mmol/(m2·d)(E法)和120.6 mmol/(m2·d)(B法),表明南极普里兹湾夏季存在很高的新生产力,它将会对该海域碳的生物泵过程产生重要作用.     

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.     

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.     

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.     

不同潮时对厦门湾水体中234Th/238U不平衡的影响

厦门湾水体中2 3 4 Th 2 3 8U不平衡的时间序列数据表明 ,无论是溶解态、颗粒态2 3 4 Th还是总2 3 4 Th ,相对于母体2 3 8U均严重亏损 ,呈现出与开阔大洋水明显不同的特征。溶解态、颗粒态2 3 4 Th的停留时间介于 0 .5— 41d之间 ,其中低潮时停留时间比高潮时小 2— 4倍 ,证实近岸海域具有强烈的清除、迁出作用 ,且潮汐变化对海域颗粒动力学特征有重要影响。2 3 4 Th停留时间与总悬浮颗粒物浓度 (TSM)、Chl.a的关系则表明 ,近岸海域元素的清除、迁出作用主要受陆源颗粒物输送的影响 ,与生物活动关系并不密切。此外 ,非稳态与稳态清除模型结果的对比证明 ,稳态模型对于具有强烈清除、迁出作用的近岸海域是适用的     

The investigation on particulate organic carbon fluxes with disequilibria between thorium-234 and uranium-238 in the Prydz Bay, the Southern Ocean

Dissolved and particulate thorium-234, particulate organic carbon in the upper 150 m of water columns from five stations in the Prydz Bay, the Southern Ocean were determined during the 22nd Chinese National Antarctic Research Expedition （from November 2005 to March 2006 ）. The disequilibria between thorium-234 and its parent uranium-238 in upper layer was used to derive the averaged residence time of thorium-234, which decreased along with the latitude to the south and a minimum value, 1 - 8 d for particulate thorium-234 and 29 - 48 d for dissolved thorium-234, appeared at the medium latitude station, and the export fluxes of thorium-234 were calculated too and ＇a maximum value, 0. 35 -0. 63 Bq/（m^3 · d） for the particulate thorium-234 and 0. 44 -0. 65 Bq/ （m^3 ·d） for the dissolved thorium-234, appeared at the same station. The export fluxes of particulate organic carbon at different water columns were derived by two methods with irreversible scavenging model, and the averaged values were 104. 7 mmol/ （ m2 · d ） （ E method） and 120. 6 mmol/（ m2·d ） （ B method ）, respectively, indicating that a relatively high new production would exist in summer in the Prydz Bay where it will play a potential significant role in sequestering the absorption CO2 to deeper ocean.     

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

Contrasting behaviors of 210Po, 210Pb and 234Th in the East China Sea during a severe red tide: Enhanced scavenging and promoted fractionation

210Po, 210Pb, and 234Th were determined in water columns of the East China Sea (ECS) to investigate their biogeochemical behaviors during a severe red tide event. Dissolved 210Po, 210Pb, and 234Th accounted for large fractions of the total phases. The abnormally high concentrations of dissolved 210Pb were observed. Partition behaviors of these radionuclides were influenced by particle content effect and particle composition based on distribution coefficient (K_d) vs. total suspended matter (TSM) content and K_d vs. ratios of particulate organic carbon and total suspended matter contents (POC/TSM content ratios). The peaks of mass specific activities of 210Po, 210Pb, and 234Th indicated that degraded particles could have an intensified enrichment ability for radionuclides compared with the surficial suspended matters. Fractionation factor of 210Po and 210Pb (F_Po/Pb) (>1) and fractionation factor of 210Po and 234Th (F_Po/Th) (>1) were much higher at algal blooming regions than that at non-blooming stations, indicating that algal blooms promoted the fractionation of 210Po against 210Pb and 234Th, and proving that 210Po exhibited a stronger affinity for biogenic particles than 210Pb and 234Th when POC content increased in the sea. POC/210Po, POC/210Pb and POC/234Th ratios (content/activity ratios) sharply decreased with depth in both algal bloom and non-bloom stations. The outbreak of algal bloom promoted the complexity of suspended particles and increased the variability of POC/tracer ratios (content/activity ratios) in the different depth of the shallow seas. More considerations should be taken to the difficulty of the selection of export interface and the suitable tracers when algal blooming occurs.     

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.     

An assessment of particulate organic carbon to thorium-234 ratios in the ocean and their impact on the application of Th as a POC flux proxy

Thorium-234 is increasingly used as a tracer of ocean particle flux, primarily as a means to estimate particulate organic carbon export from the surface ocean. This requires determination of both the ²³⁴Th activity distribution (in order to calculate ²³⁴Th fluxes) and an estimate of the C / ²³⁴Th ratio on sinking particles, to empirically derive C fluxes. In reviewing C / ²³⁴Th variability, results obtained using a single sampling method show the most predictable behavior. For example, in most studies that employ in situ pumps to collect size fractionated particles, C / ²³⁴Th either increases or is relatively invariant with increasing particle size (size classes > 1 to 100s μm). Observations also suggest that C / ²³⁴Th decreases with depth and can vary significantly between regions (highest in blooms of large diatoms and highly productive coastal settings). Comparisons of C fluxes derived from ²³⁴Th show good agreement with independent estimates of C flux, including mass balances of C and nutrients over appropriate space and time scales (within factors of 2–3). We recommend sampling for C / ²³⁴Th from a standard depth of 100 m, or at least one depth below the mixed layer using either large volume size fractionated filtration to capture the rarer large particles, or a sediment trap or other device to collect sinking particles. We also recommend collection of multiple ²³⁴Th profiles and C / ²³⁴Th samples during the course of longer observation periods to better sample temporal variations in both ²³⁴Th flux and the characteristic of sinking particles. We are encouraged by new technologies which are optimized to more reliably sample truly settling particles, and expect the utility of this tracer to increase, not just for upper ocean C fluxes but for other elements and processes deeper in the water column.     

Sensitivity of 234Th export to physical processes in the central equatorial Pacific

We determined the sensitivity of the calculated sinking flux of ²³⁴Th in the central equatorial Pacific to physical processes and scavenging mechanisms by imposing a meridional and vertical advection and diffusion field on a simple dissolved and particulate ²³⁴Th cycle. We used the model to estimate the efficiency with which the ²³⁴Th deficiency relative to ²³⁸U reflected the predicted sinking flux of ²³⁴Th on particles and compared our results with ²³⁴Th data taken during the JGOFS-EqPac 1992 Survey II Cruise. ²³⁴Th deficiencies near the equator were strongly affected by both vertical advection and horizontal diffusion. The model ²³⁴Th deficiency at the equator underestimated the model ²³⁴Th sinking flux by 144% in neglecting advection and diffusion in the presence of strong upwelling at the equator. The model ²³⁴Th deficiency at the equator corrected for advection overestimated the sinking flux of ²³⁴Th by 33% in neglecting horizontal diffusion. Analysis of the scavenging mechanism suggests that, during situations of export governed by rapidly sinking particles, ²³⁴Th-based estimates of particle export are only half as sensitive to advection compared to situations of export governed by slowly sinking particles. Given that results using the mechanism of slowly sinking particles compare better with the observed ²³⁴Th deficiency and calculated meridional ²³⁴Th fluxes at the equator than the mechanism of rapidly sinking particles, we consider the mechanism of slowly sinking particle more appropriate for this region. In agreement with previous studies based on observed ²³⁴Th gradients, this study supports the incorporation of vertical advection terms in the ²³⁴Th balance to estimate particulate carbon export at the equator but suggests that this method may have overestimated the sinking flux at the equator during EqPac Survey II by 0–63% due to the role of horizontal diffusion.     

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.     

A review of present techniques and methodological advances in analyzing Th in aquatic systems

The short-lived thorium isotope ²³⁴Th (half-life 24.1 days) has been used as a tracer for a variety of transport processes in aquatic systems. Its use as a tracer of oceanic export via sinking particles has stimulated a rapidly increasing number of studies that require analyses of ²³⁴Th in both marine and freshwater systems. The original ²³⁴Th method is labor intensive. Thus, there has been a quest for simpler techniques that require smaller sample volumes. Here, we review current methodologies in the collection and analysis of ²³⁴Th from the water column, discuss their individual strengths and weaknesses, and provide an outlook on possible further improvements and future challenges. Also included in this review are recommendations on calibration procedures and the production of standard reference materials as well as a flow chart designed to help researchers find the most appropriate ²³⁴Th analytical technique for a specific aquatic regime and known sampling constraints.     

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.