<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.     

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.     

Strong seasonality in particle dynamics of north-western Mediterranean surface waters as revealed by 234Th/238U

²³⁴Th was used to quantify sinking fluxes and residence times of particles in surface waters of the north-western Mediterranean Sea. Measurements of dissolved and particulate ²³⁴Th were made at the DYFAMED station (43°25′N–7°51′E, JGOFS-France program). Sampling covered 1 year on four cruises in 1994 (February 9, April 29, June 3, October 1) and focused on a transition period in mid-spring with six repeated profiles collected during May 1995. ²³⁴Th was nearly in equilibrium with its parent ²³⁸U most of the year, except in spring. The intensive sampling in May shows a rapid evolution throughout the month from a moderate ²³⁴Th deficit to near-equilibrium values. The time-series of ²³⁴Th were treated with steady-state and non-steady-state models. ²³⁴Th particulate fluxes clearly indicate large variability in export, with the highest values observed in spring. Particle residence times in the upper 40 m range from <10 to >250 days, and could increase by a factor of 10 within 2 weeks. POC fluxes from the upper 40 m and export ratios (ThE: ratio of ²³⁴Th-derived POC export to primary production), derived from the ²³⁴Th/²³⁸U disequilibrium in the water column and POC/²³⁴Th ratio on trapped material, decrease from about 9.5 mmol C m⁻² d⁻¹ and >22% in early May to less than 5 mmol C m⁻² d⁻¹ and 15% after mid-May. The ²³⁴Th-derived information is in agreement with the annual variations in Mediterranean Sea productivity.     

East-west distribution of POC fluxes estimated from <Superscript>234</Superscript>Th in the northern North Pacific in autumn

Observations of primary productivity, ²³⁴Th, and particulate organic carbon (POC) were made from west to east across the northern North Pacific Ocean (from station K2 to Ocean Station Papa) during September–October 2005. Primary productivities in this region varied longitudinally from approximately 236 to 444 mgC m⁻²d⁻¹ and clearly indicate the West High East Low (WHEL) trend. We estimated east-west variations in the POC flux from the surface layer (0–100 m) by using ²³⁴Th as a tracer. POC fluxes in the western region (44–53 mgC m⁻²d⁻¹) were higher than those in the eastern region (21–34 mgC m⁻²d⁻¹). However, the export ratios (e-ratios) ranged from approximately 8% to 16% and did not show the WHEL trend. Contrary to our expectation, no relation between POC flux (or e-ratio) and diatom biomass (or dominance) was apparent in autumn in the northern North Pacific.     

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.     

Time-series observation of POC fluxes estimated from 234Th in the northwestern North Pacific

Time-series measurements of ²³⁴Th activities and particulate organic carbon (POC) concentrations were made at time-series stations (K1, K2, K3, and KNOT) in the northwestern North Pacific from October 2002 to August 2004. Seasonal changes in POC export fluxes from the surface layer (∼100 m) were estimated using ²³⁴Th as a tracer. POC fluxes varied seasonally from approximately 0 to 180 mg C m⁻² d⁻¹ and were higher in spring–summer than in autumn–winter. The export ratio (e-ratio) ranged from 6% to 55% and was also higher in spring–summer. Annual POC fluxes were estimated to be 31 g C m⁻² y⁻¹ in the subarctic region (station K2) and 23 g C m⁻² y⁻¹ in the region between the subarctic and subtropical gyres (station K3). POC fluxes and e-ratios in the northwestern North Pacific were much higher than those in most other oceans. The annual POC flux corresponded to 69% of annual new production estimated from the seasonal difference of the nutrient in the Western Subarctic Gyre (45 g C m⁻² y⁻¹). These results indicate that much of the organic carbon assimilated in the surface layer of the northwestern North Pacific is transferred to the deep ocean in particulate form. Our conclusions support previous reports that diatoms play an important role in the biological pump.     

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.     

Export fluxes of particulate organic carbon in the Chukchi Sea: A comparative study using 234Th/238U disequilibria and drifting sediment traps

Large-volume sampling of ²³⁴Th and drifting sediment trap deployments were conducted as part of the 2004 Western Arctic Shelf–Basin Interactions (SBI) spring (May 15–June 23) and summer (July 17–August 26) process cruises in the Chukchi Sea. Measurements of ²³⁴Th and particulate organic carbon (POC) export fluxes were obtained at five stations during the spring cruise and four stations during the summer cruise along Barrow Canyon (BC) and along a parallel shelf-to-basin transect from East Hanna Shoal (EHS) to the Canada Basin. ²³⁴Th and POC fluxes obtained with in situ pumps and drifting sediment traps agreed to within a factor of 2 for 70% of the measurements. POC export fluxes measured with in situ pumps at 50 m along BC were similar in spring and summer (average = 14.0 ± 8.0 mmol C m^− 2 day^− 1 and 16.5 ± 6.5 mmol C m^− 2 day^− 1, respectively), but increased from spring to summer at the EHS transect (average = 1.9 ± 1.1 mmol C m^− 2 day^− 1 and 19.5 ± 3.3 mmol C m^− 2 day^− 1, respectively). POC fluxes measured with sediment traps at 50 m along BC were also similar in both seasons (31.3 ± 9.3 mmol C m^− 2 day^− 1 and 29.1 ± 14.2 mmol C m^− 2 day^− 1, respectively), but were approximately twice as high as POC fluxes measured with in situ pumps. Sediment trap POC fluxes measured along the EHS transect also increased from spring to summer (3.0 ± 1.9 mmol C m^− 2 day^− 1 and 13.0 ± 6.4 mmol C m^− 2 day^− 1, respectively), and these fluxes were similar to the POC fluxes obtained with in situ pumps. Discrepancies in POC export fluxes measured using in situ pumps and sediment traps may be reasonably explained by differences in the estimated POC/²³⁴Th ratios that arise from differences between the techniques, such as time-scale of measurement and size and composition of the collected particles. Despite this variability, in situ pump and sediment trap-derived POC fluxes were only significantly different at a highly productive station in BC during the spring.     

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.     

厦门湾水体中颗粒有机碳的垂向输出通量:234Th/238U不平衡的应用

对厦门湾塔角附近海域某站位叶绿素 a、POC、初级生产力、234Th/238U不平衡进行的周日变化研究表明,POC含量介于14.4～34.6 mmol/m3之间,其中碎屑有机碳与活体有机碳所占份额分别为74%～92%和8%～26%.POC垂直分布呈现由表及底降低的趋势,且白昼期间POC含量高于晚间,说明研究海域POC含量与生物过程具有密切联系.初级生产力水平在1d之中变化达5倍,垂直分布亦随深度增加而降低,与叶绿素a的变化相对应.短时间(2h)培养获得的初级生产力水平明显高于长时间培养(24 h)的结果,证实部分新固定的碳被优先呼吸排出.结合234Th/238U不平衡法获得的颗粒态234Th输出通量及输出界面颗粒物中的POC/P_Th比值,可计算出真光层 POC的垂向输出通量为16.0mmol/(m2·d),其中碎屑有机碳与活体有机碳贡献的数量分别为13.3和2.7mmol/(m2·d).POC输出通量与初级生产力的比值(ThE比值)平均为0.31,真光层POC停留时间平均为11d.上述结果与Aksnes和Wassmann[1]的模型计算结果相吻合,但与其他大多数模型的结果仍存在一定的差异.     

Seasonal changes in thorium scavenging and particle aggregation in the western Arctic Ocean

Seasonal changes in Th scavenging and particle aggregation were determined along two shelf-basin transects in the western Arctic Ocean during the spring (May–June) and summer (July–August) of 2002 and 2004. Measurements of dissolved and particulate ²³⁴Th and ²²⁸Th activities were used to quantify Th residence times and reversible rates of Th sorption and particle aggregation. Prior to the spring bloom in 2002, ²³⁴Th and ²²⁸Th residence times were equal and Th scavenging was concordant, indicating predominately steady-state conditions. In contrast, scavenging of ²³⁴Th and ²²⁸Th in the summer of 2002 and the spring and summer of 2004 was discordant, indicating a departure in scavenging rates from steady-state conditions during periods of seasonally high biological activity and particle export. Rates of particle aggregation and disaggregation were calculated using a one-dimensional reversible exchange model and ²³⁴Th and ²²⁸Th activities in small (1–53 μm) and large (>53 μm) particles. Maximum rates were determined coincident with the chlorophyll maximum (25–100 m) and increased by an order of magnitude between periods of low and high productivity. These Th measurements provide evidence that seasonally enhanced rates of particle aggregation might increase the magnitude of the particulate organic carbon (POC) flux in this Arctic regime.     

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.     

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.     

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.     

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...     

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.     

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.     

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 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.     

Regional estimates of POC export flux derived from thorium-234 in the western Arctic Ocean

1Introduction CarboncyclingintheArcticOceanplaysanim- portantroletoglobalchange.Traditionally,marine productivityintheArcticOceanisthoughttobevery low,andthussomebiogeochemicalprocessessuchas particleexportandcyclingofnutrientsarenotsoac- tivebecauseofthembeingcoveredperenniallybyice, lowtemperatureandshorttimeofphotosynthesis (PlattandRao,1975).Afewpreviousestimatesof particulateorganiccarbon(POC)exportindicateda neglectablemagnitudeinthecentralArcticOcean (Baconetal.,1989).However,recen…