Particle fluxes associated with mesoscale eddies in the Sargasso Sea

We examined the impact of a cyclonic eddy and mode-water eddy on particle flux in the Sargasso Sea. The primary method used to quantify flux was based on measurements of the natural radionuclide, ²³⁴Th, and these flux estimates were compared to results from sediment traps in both eddies, and a ²¹⁰Po/²¹⁰Pb flux method in the mode-water eddy. Particulate organic carbon (POC) fluxes at 150 m ranged 1–4 mmol C m⁻² d⁻¹ and were comparable between methods, especially considering differences in integration times scales of each approach. Our main conclusion is that relative to summer mean conditions at the Bermuda Atlantic Time-series Study (BATS) site, eddy-driven changes in biogeochemistry did not enhance local POC fluxes during this later, more mature stage of the eddy life cycle (>6 months old). The absence of an enhancement in POC flux puts a constraint on the timing of higher POC flux events, which are thought to have caused the local O₂ minima below each eddy, and must have taken place >2 months prior to our arrival. The mode-water eddy did enhance preferentially diatom biomass in its center, where we estimated a factor of three times higher biogenic Si flux than the BATS summer average. An unexpected finding in the highly depth-resolved ²³⁴Th data sets is narrow layers of particle export and remineralization within the eddy. In particular, a strong excess ²³⁴Th signal is seen below the deep chlorophyll maxima, which we attribute to remineralization of ²³⁴Th-bearing particles. At this depth below the euphotic zone, de novo particle production in the euphotic zone has stopped, yet particle remineralization continues via consumption of labile sinking material by bacteria and/or zooplankton. These data suggest that further study of processes in ocean layers is warranted not only within, but below the euphotic zone.     

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.     

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.     

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.     

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-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.     

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.     

Controls of 234Th removal from the oligotrophic ocean by polyuronic acids and modification by microbial activity

To gain new insights into the variability of particulate organic carbon (POC) fluxes and to better understand the factors controlling the POC/²³⁴Th ratios in suspended and sinking particulate matter, we investigated the relationships between POC/²³⁴Th ratios and biochemical composition (uronic acids, URA; total carbohydrates, TCHO; acid polysaccharides, APS; and POC) of suspended and sinking matter from the Gulf of Mexico in 2005 and 2006. Our data show that URA/POC in sediment traps (STs), APS/POC in the suspended particles, and turnover times of particulate ²³⁴Th in the water column and those of bacteria in STs inside eddies usually increased with depth, whereas particulate POC/²³⁴Th (10–50 μm) and the sediment-trap parameters (POC flux, POC/²³⁴Th ratio, bacterial biomass, and bacterial production) decreased with depth. However, this trend was not the case for most biological parameters (e.g., phytoplankton and bacterial biomass) or for the other parameters at the edges of eddies or at coastal-upwelling sites.In general, the following relationships were observed: 1) ²³⁴Th/POC ratios in STs were correlated with APS flux, and these ratios in the 10–50 μm suspended particles also correlated with URA/POC ratios; 2) neither URA fluxes nor URA/POC ratios were significantly related to bacterial biomass; 3) the sum of two uronic acids (G2, glucuronic, and galacturonic acid, which composed most of the URA pool) was positively related to bacterial biomass; and 4) the POC/²³⁴Th ratios in intermediate-sized particles (10–50 μm) were close to those in sinking particles but much lower than those in > 50 μm particles. The results indicate that acid polysaccharides, though a minor fraction (~ 1%) of the organic carbon, act more likely as proxy compound classes that might contain the more refractory ²³⁴Th-binding biopolymer, rather than acting as the original ²³⁴Th “scavenger” compound. Moreover, these acid polysaccharides, which might first be produced by phytoplankton and then modified by bacteria, also influence the on-and-off “piggy-back” processes of organic matter and ²³⁴Th, thus causing additional variability of the POC/²³⁴Th in particles of different sizes.     

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.     

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.     

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.     

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.     

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.     

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.     

The influence of a mature cyclonic eddy on particle export in the lee of Hawaii

Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using ²³⁴Th–²³⁸U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. ²³⁴Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the ²³⁴Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day⁻¹ yielded the best fit to sediment-trap data. These ²³⁴Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m⁻² day⁻¹, 27±3 to 114±12 μmol N m⁻² day⁻¹, and 33±20 to 309±73 μmol Si m⁻² day⁻¹. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO₂ fluxes within the eddy core were three times higher. Detailed analyses of ²³⁴Th depth profiles consistently showed excess ²³⁴Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.     

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.     

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.     

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.     

Exploring the connection between 210Po and organic matter in the northwestern Mediterranean

The disequilibrium between ²¹⁰Po and its grandparent ²¹⁰Pb has been proposed as a tracer of the vertical flux of sinking particulate organic matter in the ocean. The mechanism of association between ²¹⁰Po and organic matter is, however, still unclear. To investigate this association we measured trace metals, minerals, organic carbon, nitrogen, and the natural radioisotopes ²³⁴Th, ²²⁸Th, ²¹⁰Po, and ²¹⁰Pb in sinking particles collected in sediment traps at 200 m in the northwestern Mediterranean. Pigments, fatty acids, and amino acids were used to identify the types and sources of particulate organic matter. Multivariate analyses were used to determine which components of sinking particulate matter are traced by ²¹⁰Po and/or by the ²¹⁰Po/²¹⁰Pb ratio. Statistical analysis of the results indicates that the distribution of polonium in sinking marine particles is influenced by fresh phytoplankton-derived, nitrogen-rich organic matter as well as sulfur-containing amino acids. These findings are consistent with previous laboratory observations that the distribution of ²¹⁰Po in biota parallels the distributions of both sulfur and protein, and indicate that these associations persist as material sinks through the water column. While this research generally supports the use of ²¹⁰Po as a specific tracer of the flux of organic matter, the signals traced by ²¹⁰Po/²¹⁰Pb and ²³⁴Th/²³⁸U are not as distinct in the field as in laboratory experiments. Further work is needed to determine more precisely what ²¹⁰Po/²¹⁰Pb traces in order to increase the correspondence of ²¹⁰Po/²¹⁰Pb measurements to biogeochemically important rates and quantities.     

A time-series study of particulate matter export in the North Pacific Subtropical Gyre based on Th : U disequilibrium

Depth profiles of total ²³⁴Th (dissolved+particulate) were collected at Station ALOHA (22°45N, 158°00W) in the North Pacific Subtropical Gyre during 9 cruises from April 1999 to March 2000. Samples were collected and processed by a new 2 L technique that enables more detailed depth resolution then previous ²³⁴Th studies. Significant zones of particle export (²³⁴Th deficiency) and particle remineralization (²³⁴Th excess) were measured both temporally and with depth. ²³⁴Th derived particulate carbon (PC) and nitrogen (PN) fluxes were determined with steady-state and non-steady-state models and PC/²³⁴Th and PN/²³⁴Th ratios measured with both in situ pumps and free-drifting particle interceptor traps deployed at 150 m. ²³⁴Th based export estimates of 4.0±2.3 mmol C m⁻² d⁻¹ and 0.53±0.19 mmol N m⁻² d⁻¹, were approximately 60% higher than those measured in PIT style sediment traps from the same time period, 2.4±0.2 mmol C m⁻² d⁻¹ and 0.32±0.08 mmol N m⁻² d⁻¹. Most of this difference is attributable to two large export events that occurred during October and December 1999, when traps undercollected for ²³⁴Th by a factor of 2 to 4. ²³⁴Th export (ThE) ratios based on ²³⁴Th derived PC flux/¹⁴C based primary production ranged from 4% to 22% (average=8.8%). Our results confirm the recent estimates of C export by Emerson et al. (Nature 389 (1997) 951) and Sonnerup et al. (Deep-Sea Research I 46 (1999) 777) and indicate that C export from the oligotrophic ocean must be considered when discussing C sequestration in global climate change.