Recycling of manganese in the coastal sea,Funka Bay,Japan

The downward flux of Mn through the water column was directly measured using sediment traps. The Mn flux from the bottom sediment to the water column, and the removal rate of Mn in the bottom water were estimated from Mn gradients in the bottom water. The sediment traps were deployed more than ten times at the same station in Funka Bay, Japan. The trapped settling matter and filtered suspended matter samples were analyzed for Mn, Fe, Al and ignition loss. The observed downward flux of Mn through the water column in winter (1.3–2.8 μg/cm² /day) was generally an order of magnitude larger than that in summer (0.13–0.45 μg/cm² /day), and the Mn fluxes for both seasons were also greater than the accumulation rate of Mn in the bottom sediments (0.10 μg/cm ²/day). More Al was contained in the trapped settling matter than in the suspended matter, while Mn showed the opposite behavior. The Fe/Mn ratio of the residual fraction (obtained by subtracting the sediment component of the settling matter) was rather well correlated with the corresponding ratio in suspended matter. Settling particles are expected to scavenge suspended matter during their passage through the water column. The flux of Mn across the sediment—water interface was estimated from its vertical profiles in the water column to be 0.1–0.3 μg/cm² day. The residence time of Mn in bottom water was about one to several months. These results suggest that Mn is actively recycled between the water column and the sediments of the coastal sea.     

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.     

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.     

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.     

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 study of particle exchange at the sediment–water interface in the Benguela upwelling area based on 234Th/238U disequilibrium

The natural isotope ²³⁴Th is used in a small-scale survey of particle transport and exchange processes at the sediment–water interface in the Benguela upwelling area. Results from water and suspended particulate matter (SPM) samples from the uppermost and lowermost water column as well as the underlying sediment of three stations are compared. The stations are situated in different sedimentological environments at 1200–1350 m water depth at the continental slope off Namibia. Highly differing extent and particle content of the bottom nepheloid layer (BNL) are determined from transmissometer data. Three models are presented, all explaining the ²³⁴Th depletion of the BNL and ²³⁴Th excess of the surface sediment that were observed. While the first model is based solely on local resuspension of surface sediment particles, the second evaluates the influence of vertical particle settling from the surface waters on the ²³⁴Th budget in the BNL. The third model explains ²³⁴Th depletion in the BNL by sedimentation of particles that were suspended in the BNL during long-range transport. Particle inventory of the BNL is highest at a depocenter of organic matter at 25.5°S, where strong deposition is presently taking place and lateral particle transport is suggested to predominate sediment accumulation. This is supported by the high settling flux of particles out of the BNL into the sediments of the depocenter, exceeding the vertical particle flux into sediment traps at intermediate depth in the same area by up to an order of magnitude. High particle residence/removal times in the BNL above the depocenter in the range of 5–9 weeks support this interpretation. Comparison with carbon mineralization rates that are known from the area reveals that, notwithstanding the large fraction of advected particles, organic carbon flux into the surface sediment is remineralized to a large extent. The deployment of a bottom water sampler served as an in situ resuspension experiment and provided the first data of ²³⁴Th activity on in situ resuspended particles. We found a mean specific activity of 86 disintegrations per minute (dpm) g⁻¹ (39–339 dpm g⁻¹), intermediate between the high values for suspended particles (in situ pump: 580–760 dpm g⁻¹; CTD rosette: 870–1560 dpm g⁻¹) and the low values measured at the sediment surface (26–37 dpm g⁻¹). This represents essential information for the modeling of ²³⁴Th exchange processes at the sediment–water interface.     

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

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

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.     

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

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

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.     

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.     

A comparison of the quantity and composition of material caught in a neutrally buoyant versus surface-tethered sediment trap

The flux and composition of material caught using two different upper ocean sediment trap designs was compared at the Bermuda Atlantic Time-series Study site (BATS). The standard surface-tethered trap array at BATS was compared to a newly designed neutrally buoyant sediment trap (NBST). Both traps used identical cylindrical collection tubes. Of particular concern was the effect of horizontal flow on trap collection efficiency. In one experiment, mass, particulate organic carbon (POC) and particulate organic nitrogen (PON) fluxes were slightly lower (20–30%) in the NBST than in the standard BATS trap. In contrast, ²³⁴Th and fecal pellet fluxes were up to a factor of two to three lower in the NBST. In a second experiment, mass and POC fluxes decreased significantly with depth in the BATS surface-tethered trap, but not in the NBST. Different brine treatments had no measurable effect on collection efficiencies. A striking observation was that the swimmer “flux” was much larger in the standard BATS traps than in the NBST. Overall, these results show that different components of the sinking flux can be collected with differing efficiencies, depending upon how traps are deployed in the ambient environment.     

Distribution of 210Po and export of organic carbon from the euphotic zone in the southwestern East Sea (Sea of Japan)

The distribution of the natural radionuclide ²¹⁰Po in the water column along a horizontal transect of the continental shelf, slope and deep basin regions of the East Sea (Sea of Japan), a marginal sea of the Northwest Pacific Ocean, was investigated, and its behavior is described here. The settling fluxes of particulate ²¹⁰Po in the deep basin along with ²¹⁰Pb, ²³⁴Th and biogenic matter were also determined. ²¹⁰Po inventories in the water column were observed to decrease from winter to summer in all stations, probably due to increased influx of ²¹⁰Po-poor Kuroshio Water of the Northwest Pacific Ocean during summer. Vertical profiles of dissolved and particulate ²¹⁰Po along with the settling fluxes of particulate ²¹⁰Po in the deep basin station have enabled us to evaluate temporal variations and residence times of ²¹⁰Po. In the slope and basin, activities of dissolved ²¹⁰Po generally decreased from the surface to the bottom water, with maximum activity just below the subsurface chlorophyll a maximum at 50–75 m depth in spring and summer. These subsurface peaks of dissolved ²¹⁰Po activity were attributed to the release of ²¹⁰Po from the decomposition of ²¹⁰Po-laden biogenic particulate organic matter. In the deep basin, despite the decrease in total mass flux, the sinking flux of particulate ²¹⁰Po was higher in the deeper trap (2000 m) than in the shallower one (1000 m), probably due to scavenging of dissolved ²¹⁰Po from the water column during particle descent and/or break-down of ²¹⁰Po-depleted particulate matter between 1,000 m and 2,000 m depths. In general, the ratios of the particulate phase to the dissolved phase of ²¹⁰Po (K_d) increased with depth in the slope and basin stations. ²¹⁰Po removal from the water column appears to depend on the primary productivity in the upper waters. There is an inverse relationship between K_d and suspended particulate matter (SPM) concentration in the water column. From the ²¹⁰Po activity/chlorophyll a concentration ratios, it appears that sinking particles arriving at 1000 m depth were similar to those in the surface waters.     

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.     

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.     

Th isotopes in the Santa Monica basin: Temporal variation,long-term mass balance and model rate constants

Distribution and flux of²³⁴Th,²³²Th and²³⁰Th in the water column of central Santa Monica basin observed over a period of seven years show seasonal and interannual variabilities. A steady-state model is applied to the integrated data to calculate long term average flux and model rate constants of Th isotopes. Mass balance calculations show that the basin acts like a closed system for short-lived²³⁴Th, but not for the long-lived isotopes²³⁰Th and²³²Th. Most²³⁰Th in the basin is transported from elsewhere. Of the incoming Th, 40–55% of the²³⁰Th and 14–26% of the²³²Th enter the surface water in dissolved form. In the upper 100 m, the residence time of dissolved Th with respect to adsorption onto suspended particulates, 70–80 days, is about one order of magnitude higher than the residence time of suspended particles with respect to aggregation into sinking particles, 7–10 days.     

Electron microprobe analysis of suspended matter in the Angola Basin

Electron microprobe analysis of suspended-matter samples collected at different water depths at ten stations in the Angola Basin indicated that at each station, from top to bottom, the elementary composition of the suspended matter was very similar and differed from the composition of the suspended matter at the adjacent stations. This indicates that the downward settling of the suspended matter is much faster than the horizontal transport and mixing by the currents. Assuming that the suspended matter settles in the form of flocs, or is scavenged by settling flocs, the suspended matter can indeed reach the bottom in a shorter period than needed for the currents to cover the distance between adjacent stations. Comparison with sediment trap data from the literature shows that also lateral transports and/or deep water gyres have to be invoked to further increase residence times of suspended matter in the water column.     

Temporal variations in the concentration and settling flux of carbon and phytoplankton pigments in a deep fjordlike estuary

The weekly mass flux of C and phytoplankton pigments at five depths in the main basin of Puget Sound, a deep (200 m) fjordlike estuary, was sampled for a year with moored sequentially-sampling sediment traps. Flux measurements were compared with weekly samples of suspended pigments in the euphotic zone and bi-monthly samples of total suspended matter and particulate C throughout the water column at the mooring site.Seasonal changes in the total mass flux at all depths were small; instead, physical (river runoff, bottom resuspension) and biological (phytoplankton blooms) events caused occasional sharp increases on a weekly scale. The dry weight concentration of pigments in the trap samples mirrored the concentration of pigments in the euphotic zone suspended matter, increasing from 0·01% in winter to a maximum of 0·65% in late summer. Bloom-induced changes in the pigment concentration were observed almost simultaneously in the euphotic zone and in the traps to a depth of 160 m, indicating a rapid vertical transfer of surface-originating particles by organic aggregates. In contrast to the strong seasonal signal in the pigment concentration, C concentration varied by only a factor of three during the year.The seasonal trend of C/pigment ratios in the C flux arises from at least two sources: (1) a balance between terrestrial sources of C during the high-runoff winter season and in-situ primary production in spring and summer, and (2) cycling of C through the zooplankton population. Budget calculations suggest that the loss of primary-produced C and pigment from the euphotic zone by settling is 5% regardless of season. On an annual basis, this C flux (16 g m⁻²) is sufficient to support previously measured values of benthic aerobic respiration at the mooring site. To account for other C sinks such as burial, predation and chemical oxidation, however, terrestrial C sources and alternate transport pathways, such as vertical advection and sediment movement down the steep basin walls, are necessary.     

Particulate organic carbon export flux by 234Th/238U disequilibrium in the continental slope of the East China Sea

234Th is widely used to quantify the magnitude of upper ocean particulate organic carbon(POC)export in oceans.In the present work,the rates of particulate organic carbon export were measured based on the distribution patterns of234Th/238U disequilibrium in the water column within the continental slope of the East China Sea(ECS)during May 2011.The profiles of particulate and dissolved234Th activities at all three stations showed a relative deficit with respect to238U in the upper 100 m of the water column.The dissolved234Th scavenging rates and the particulate234Th removal rates and their residence times were calculated by a one-dimensional steady state model.The results showed that the dissolved234Th scavenging rates and the particulate234Th removal rates ranged from 12.4–61.4 dpm/(m3·d)andfrom3.8–21.8 dpm/(m3·d),respectively.The residence times of dissolved and particulate234Th were in the range of 3.4–158 d and 63.7–96.5 d,respectively.Combined with the measurement of POC/234Th ratios of suspended particles,POC export flux(calculated by carbon)from the euphotic zone was estimated in the study region,which ranged from 4.14–14.7 mmol/(m2·d),withanaverageof8.21mmol/(m2·d),occupying35%oftheprimeproductivity in the study area.The results of this study can provide new information for better understanding the carbon biogeochemical cycle within the continental slope of the ECS.     

Downward fluxes of settling particles in the deep Cretan Sea (NE Mediterranean)

During the CINCS project (Pelagic–benthic Coupling IN the oligotrophic Cretan Sea—NE Mediterranean), a single mooring with two sediment traps (at 200 and 1515m water depth) and two current meters was deployed in the southern Cretan Sea margin at a depth of 1550 m. A second mooring deployed at the 500 m station was lost, as a result of fishing activities. The duration of the study was 12 months (November 1994 to November 1995) with sampling intervals of 15 or 16 days. The traps were retrieved, serviced and the sedimented material was collected every 6 months. In total, 48 samples were collected (24 from each trap) throughout the study period and fluxes of total particulate mass, opal, organic matter, carbonates, and lithogenic component were measured. Natural radionuclides (²¹⁰Po and ²¹⁰Pb) were determined for all trap samples. Total mass flux and the fluxes of four major constituents increased with depth, the total mass flux reaching values of nearly 550 mg m⁻² d⁻¹ at 1515 m and 187 mg m⁻² d⁻¹ at 200 m depth, following the same patterns observed in other experiments (ECOMARGE, SEEP-I, SEEP-II). The mean annual mass fluxes were 209 and 49.8 mg m⁻² d⁻¹ at the near bottom and near surface trap respectively. This suggests that lateral transport of particulate matter is of importance in the area. Total mass fluxes at the two depths were characterized by different seasonal fluctuations, although a general decreasing trend was observed from the I (winter) to the II (summer) deployment at both depths. This was mainly a result of reductions in aluminosilicate inputs during the summer dry period. At 200 m depth carbonates were more important during winter, because of a large carbonate input consisting mainly of coccoliths of Emiliania huxleyi, while during the summer decreased fluxes of carbonates and aluminosilicates resulted in a reduction of the mass flux. In contrast, at 1515 m depth the lithogenic component was the dominant component during the winter deployment, indicating a terrigenous input. During the summer period the decrease in mass flux was strongly effected by the decrease in aluminosilicates. There was a diminution in the organic carbon content with a concomitant increase in total mass flux, which, together with the almost negligible increase in the annual ²¹⁰Pb activity with depth and the increase of ²¹⁰Po activity with depth could be interpreted as indicating a contribution of resuspended material to the input at 1515 m. The complex mesoscale circulation of the Cretan Sea, consisting of a cyclone (east)–anticyclone (west) system, controls particle transfer in the area. This hydrodynamic system seems to move water masses towards the southern Cretan Sea margin, and consequently carry materials from the open sea to the upper slope and shelf.