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.     

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.     

Flocculation and phytoplankton cell size can alter Th-based estimates of the vertical flux of particulate organic carbon in the sea

The deficit of ²³⁴Th relative to its radioactive parent ²³⁸U in the surface ocean can yield reliable estimates of vertical Particulate Organic Carbon (POC) fluxes to deeper waters, but only when coupled with an accurate ratio of POC concentration to activity of ²³⁴Th on sinking matter. Assuming a simple partitioning of suspended phytoplankton mass between single cells and flocs, we calculate the ratio of the POC flux estimated from ²³⁴Th deficit to the actual POC flux (p ratio, Smith, J.N., Moran, S.B., Speicher, E.A., in press. The p-ratio: a new diagnostic for evaluating the accuracy of upper ocean particulate organic carbon export fluxes estimated from ²³⁴Th/²³⁸U disequilibrium. Deep-Sea Research I.). The p ratios are calculated under the assumption that particle surface area is correlated with ²³⁴Th activity and particle volume is correlated with POC concentration. The value of the p ratio depends on the relative contributions of single cells and flocs to the vertical flux. When large single cells make up a significant fraction of the vertical flux, p ratios are less than one, meaning POC fluxes estimated from ²³⁴Th deficits underestimate actual POC fluxes. When large single cells are abundant but do not sink fast enough to contribute to vertical POC flux, p ratios are greater than one (up to 3 × overestimate). Factor analysis of the model indicates that altering the extent of flocculation in suspension and changing the density and maximum size of phytoplankton cells have the greatest effects on the p ratio. Failure to measure the properties of flocs when characterizing the ratio of POC to thorium on sinking matter potentially leads to large overestimation of the POC flux (over 20 ×). Failure to characterize the POC to thorium ratio of large particles, by, for example, destruction of phytoplankton cells in pumps, can lead to underestimation of POC flux. Estimates of POC flux should be most reliable in highly flocculated suspensions populated by small cells and rapidly sinking flocs. These conditions are often associated with intense phytoplankton blooms.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

The POC / Th ratio of settling particles isolated using split flow-thin cell fractionation (SPLITT)

The common assumption that the ratio between particulate organic carbon (POC) and particulate ²³⁴Th obtained from shallow sediment traps and filterable particles are representative of the ratio in the total particle settling flux should be treated with caution in view of well-known biases associated with tethered shallow sediment traps and the decoupling between size and settling velocity of many natural particle regimes. To make progress toward reliably constraining the POC / ²³⁴Th ratio on truly settling particles, we have tested here a settling collection technique designed to remove any hydrodynamic bias; split flow-thin cell fractionation (SPLITT). These first results from a North Sea fjord and an open Baltic Sea time-series station indicates that the POC / ²³⁴Th ratio on the more complete particle-settling spectrum, isolated with SPLITT, was higher than the POC / ²³⁴Th ratio obtained simultaneously from tethered shallow sediment traps in seven out of seven parallel deployments with an average factor of 210%. The POC / ²³⁴Th ratio from the SPLITT was either in the same range or higher than that obtained on filtered “bulk” particles. To explain this novel data we hypothesize that the slowest settling fraction is organic-matter rich and does not strongly complex ²³⁴Th (i.e., high POC / ²³⁴Th). We suggest that this ultra-slow sinking fraction is better collected by SPLITT than with tethered sediment traps because of minimized hydrodynamic bias.This was tested using the ratio of POC / Al as a tracer of detrital mineral-ballast influenced settling velocity. The higher POC / Al ratios in SPLITT samples relative to in traps is consistent with the hypothesis that SPLITT is better suited for collecting also the slow-settling component of sinking particles. This important slow-settling component appears to here consist primarily of non-APS/TEP components of plankton exudates or other less-strongly ²³⁴Th-complexing organic matter. Further applications of the SPLITT technique are likely to return increasingly new insights on the composition (including “truly settling” POC / ²³⁴Th) of the total spectrum of particles settling out of the upper ocean.     

Particulate organic carbon–Th relationships in particles separated by settling velocity in the northwest Mediterranean Sea

In order to better understand the relationship between the natural radionuclide ²³⁴Th and particulate organic carbon (POC), marine particles were collected in the northwestern Mediterranean Sea (spring/summer, 2003 and 2005) by sediment traps that separated them according to their in situ settling velocities. Particles also were collected in time-series sediment traps. Particles settling at rates of >100 m d⁻¹ carried 50% and 60% of the POC and ²³⁴Th fluxes, respectively, in both sampling years. The POC flux decreased with depth for all particle settling velocity intervals, with the greatest decrease (factor of 2.3) in the slowly settling intervals (0.68–49 m d⁻¹) over trap depths of 524–1918 m, likely due to dissolution and decomposition of material. In contrast the flux of ²³⁴Th associated with the slowly settling particles remained constant with depth, while ²³⁴Th fluxes on the rapidly settling particles increased. Taking into account decay of ²³⁴Th on the settling particles, the patterns of ²³⁴Th flux with depth suggest that either both slow and fast settling particles scavenge additional ²³⁴Th during their descent or there is significant exchange between the particle classes. The observed changes in POC and ²³⁴Th flux produce a general decrease in POC/²³⁴Th of the settling particles with depth. There is no consistent trend in POC/²³⁴Th with settling velocity, such as might be expected from surface area and volume considerations. Good correlations are observed between ²³⁴Th and POC, lithogenic material and CaCO₃ for all settling velocity intervals. Pseudo-K_ds calculated for ²³⁴Th in the shallow traps (2005) are ranked as lithogenic material opal <calcium carbonate <organic carbon. Organic carbon contributes 33% to the bulk K_d, and for lithogenic material, opal and CaCO₃, the fraction is 22% each. Decreases in POC/²³⁴Th with depth are accompanied by increases in the ratio of ²³⁴Th to lithogenic material and opal. No change in the relationship between ²³⁴Th and CaCO₃ was evident with depth. These patterns are consistent with loss of POC through decomposition, opal through dissolution and additional scavenging of ²³⁴Th onto lithogenic material as the particles sink.     

Seasonal deposition and reworking at the sediment-water interface on the northwestern Iberian margin

Seabed distributions of ²³⁴Th excess (Th_xs) were determined in the upper centimetres of 38 sediment cores from the north-western Iberian Margin, sampled from 41–44°N and from 9–12°E during five OMEX II cruises. Three main areas, a northern, and at 42°38 and 42°N, were investigated during representative seasons (winter, spring and summer). Low ²³⁴Th_xs activities in summer 1998 (18–252 Bq per kg) were similar to those measured in summer 1997. In winter ²³⁴Th also showed moderate excess. The highest values were observed in spring with surface ²³⁴Th_xs values up to 402 Bq kg⁻¹. Maximum penetration depths of ²³⁴Th_xs ranged from a few mm to 3 cm. ²³⁴Th_xs activities always showed a smooth decrease with depth, without any evidence of non-local mixing. Thus particle mixing on a short time scale can be described as an eddy diffusive process, and bioturbation rates, calculated on this basis, range from 0.02 to 3.07 cm² per year. Data (activities, inventories, bioturbation rates) are discussed in order to relate the observed surface and down-core variations to spatial and seasonal trends. Using ²³⁴Th_xs data in sediment as a substitute for sediment trap estimates, particle fluxes were calculated from ²³⁴Th_xs inventories. The range of ²³⁴Th-derived particle fluxes for the north-western Iberian Margin is 16–1418 mg.m⁻².d⁻¹. Mean values indicate a gradual decrease of mass fluxes from the shelf to the open ocean. On a 100-day scale, the northern area (43–44°N) represents a low sedimentation regime. Further south, around 42°–43°N, particle inputs are more important. On the middle slope, around 1000 to 2000 m depth, high inventories and bioturbation rates indicate enhanced, and probably organic-rich, particle fluxes to the seafloor, particularly in spring.     

234Th/238U disequilibrium and particulate organic carbon export in the northwestern South China Sea

234 Th was utilized as a tracer of particulate organic carbon (POC) export in the northwestern South China Sea (SCS) on the basis of the data collected at four stations during a spring cruise.Depth profiles of dissolved and particulate 234 Th activities were measured in the upper 60 m,showing a significant deficit relative to 238 U over the investigated stations.A stratified structure of 234 Th-238 U disequilibrium was in general observed in the upper 60 m water column,indicating that the euphotic zone of t...     

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.     

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.     

A single vs. double spike approach to improve the accuracy of Th measurements in small-volume seawater samples

²³⁴Th is a particle-reactive radionuclide widely used to trace biogeochemical oceanic processes occurring over short timescales. During the last few years, small-volume techniques based on the co-precipitation of ²³⁴Th with MnO₂ coupled with beta-counting have been developed as an alternative to large volume gamma-spectrometric techniques. Here a procedure has been developed to enhance quantitative measurement of ²³⁴Th in MnO₂ precipitates. The main objectives were to obtain a purified Th fraction for beta-counting and to determine the chemical recovery of ²³⁴Th using Th spikes and alpha-spectrometry as an alternative to ICP-MS based methods. Two variations of the procedure are presented. In the first “1 spike” method a ²³⁰Th tracer is added to the sample prior to precipitation of MnO₂, and UTEVA® extraction chromatography is used to obtain a NdF₃(Th) purified source that can be used for both beta-counting of ²³⁴Th and alpha-spectrometry of ²³⁰Th. In the “2 spike” method a ²³⁰Th spike is added and the MnO₂(Th) precipitate is directly beta-counted for ²³⁴Th and subsequently spiked with ²²⁸Th or ²²⁹Th prior to UTEVA® purification and alpha-spectrometry. The results confirm the need to process small-volume seawater samples for ²³⁴Th measurement in presence of a yield tracer, and show that both the 1 spike and 2 spike methods allow an accurate and precise determination of ²³⁴Th (relative percent difference, RPD, between expected and mean measured value < 1%; CV between replicate samples < 3%). Our work also suggests that, although the combined analytical uncertainty on total ²³⁴Th measurements accomplished with both versions of the NdF₃ procedure is promising (6% for 2-L samples), the precision of the ²³⁴Th flux estimation will ultimately depend on the degree of disequilibrium between ²³⁴Th and ²³⁸U.