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.     

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

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

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...     

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 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.     

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.     

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.     

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.     

On the accuracy of upper ocean particulate organic carbon export fluxes estimated from 234Th/238U disequilibrium

An analysis of the ²³⁴Th method for determining the export flux of particulate organic carbon (P_POC) from the upper ocean using in situ pumps or water bottles shows that the accuracy of the method (the ratio of the experimental value of P_POC divided by the true POC flux, F_POC), defined as the p-ratio, is equal to the mean settling velocity of particulate ²³⁴Th divided by that of POC. Therefore, P_POC is equivalent to the true POC flux (F_POC) and the p-ratio is equal to unity if, and only if, POC and particulate ²³⁴Th have the same mean sinking velocities. A simple particle settling model is discussed that invokes Stokes’ Law settling velocities, volume:surface area (V:SA) fractionation of C:²³⁴Th and two assemblages of particles having different sizes and densities. The model is used to illustrate the ranges of parameter values that conform to values of the p-ratio sufficiently close to unity that the experimentally determined POC flux can be considered to be an accurate representation of the true POC flux.Despite the over-simplification of real systems implicit in the model, the results suggest that p-ratios<1, equivalent to an under-estimate of the POC flux, are representative of single particle settling regimes in which the larger particles dominate the vertical flux. This follows from the assumption that the ratio of C/²³⁴Th on particles is governed by the volume to surface area (V:SA) ratio of the particles. This results in a greater proportion of ²³⁴Th compared to C being associated with the smaller, more slowly settling particles and, as a result, normalization of the POC flux to the ²³⁴Th flux provides an under-estimate of the former quantity. However, when the smaller particle assemblage dominates the vertical flux, as could occur in open ocean regimes having high aeolian inputs of dense, rapidly settling, inorganic particles, then the p-ratio could exceed unity (p-ratio >1) resulting in an over-estimate of the POC flux using the ²³⁴Th method. High levels of flocculation associated with phytoplankton blooms in productive regions of the ocean are likely to produce p-ratios approaching unity, because flocs would tend to preserve the V:SA partitioning of the original particle size distribution and thereby minimize differences in the mean settling speeds of POC and particulate ²³⁴Th (Waite, A.W., Hill, P.S., 2006. Flocculation, phytoplankton and the accuracy of ²³⁴Th-based estimates of the vertical flux of particulate organic carbon in the sea. Marine Chemistry in press). Selective sampling of the large particle fraction using, for example, 53-μm screens can produce a more accurate estimate of the true POC flux, but may not entirely shift the p-ratio to a value of unity.     

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.     

Calibration of sediment traps and particulate organic carbon export using 234Th in the Barents Sea

Profiles of particulate and dissolved ²³⁴Th (t_1/2=24.1 days) in seawater and particulate ²³⁴Th collected in drifting traps were analyzed in the Barents Sea at five stations during the ALV3 cruise (from June 28 to July 12, 1999) along a transect from 78°15′N–34°09′E to 73°49′N–31°43′E. ²³⁴Th/²³⁸U disequilibrium was observed at all locations. ²³⁴Th data measured in suspended and trapped particles were used to calibrate the catchment efficiency of the sediment traps. Model-derived ²³⁴Th fluxes were similar to ²³⁴Th fluxes measured in sediment traps based on a steady-state ²³⁴Th model. This suggests that the sediment traps were not subject to large trapping efficiency problems (collection efficiency ranges from 70% to 100% for four traps). The export flux of particulate organic carbon (POC) can be calculated from the model-derived export flux of ²³⁴Th and the POC/²³⁴Th ratio. POC/²³⁴Th ratios measured in suspended and trapped particles were very different (52.0±9.9 and 5.3±2.2 μmol dpm⁻¹, respectively). The agreement between calculated and measured POC fluxes when the POC/²³⁴Th ratio of trapped particles was used confirms that the POC/²³⁴Th ratio in trap particles is representative of sinking particles. Large discrepancies were observed between calculated and measured POC fluxes when the POC/²³⁴Th ratio of suspended particles was used. In the Barents Sea, vertical POC fluxes are higher than POC fluxes estimated in the central Arctic Ocean and the Beaufort Sea and lower than those calculated in the Northeast Water Polynya and the Chukchi Sea. We suggest that the latter fluxes may have been strongly overestimated, because they were based on high POC/²³⁴Th ratios measured on suspended particles. It seems that POC fluxes cannot be reliably derived from thorium budgets without measuring the POC/²³⁴Th ratio of sediment trap material or of large filtered particles.     

Seasonal POC fluxes at BATS estimated from 210Po deficits

In this study at the Bermuda Atlantic Time-series Study (BATS) site we demonstrate that the polonium–lead disequilibrium system may perform better as a tracer of organic carbon export under low-flux conditions (in this case, <2.5 mmol C m^?2 d^?1) than under bloom conditions in an oligotrophic setting. With very few exceptions, the POC flux predictions calculated from the water-column ²¹⁰Po deficit were within a factor of 2 of the POC flux caught in surface-tethered sediment traps. However, we found higher correlation between size-fractionated particulate ²¹⁰Po activity and POC concentration in November 2006 (r=0.93) than in January (r=0.79) and during the spring bloom in March 2007 (r=0.80). We suggest that this is due to the ability of polonium to distinguish between bulk mass flux and organic carbon export under oligotrophic and lithogenic-driven flux regimes. Further, we found that the POC/Po ratio on particles was largely independent of size class between 10 and 100 μm (P=0.13) during each season, supporting the notion that export in this oligotrophic system is driven by sinking aggregates of smaller cells and not by large, individual cells.     

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

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

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.     

真光层的颗粒动力学──Ⅵ.南海东北部海域上层水体颗粒动力学的示踪研究

利用234Th－238U不平衡研究南海东北部海域3个站位上层水体中的颗粒动力学性质，测定了水往中溶解态及颗粒态234Th的比活度，具体讨论各相中234Th／238U）AR（放射性活度比）比值的垂直分布情况及其与水化学要素间的关系。运用稿态箱式模型计算出各站位不同水层中溶解态234Th相对于清除至颗粒物的平均停留时间和颗粒态234Th相对于迁出作用的停留时间。由模型得出的参数表明3个站位的真光层具有两种不同的层化图像，这一情形与我们在南沙群岛海域得到的结果相一致。结合POC／PTh比值，估算出3个站位从真光层输出的颗粒有机碳（POC）通量分别为4.025.0和5．4mmolC·m－3－d-1。文中进一步讨论了234Th与POC两者停留时间的关系。     

Biogeochemical responses to late-winter storms in the Sargasso Sea,III—Estimates of export production using 234Th:238U disequilibria and sediment traps

Direct measurements of new production and carbon export in the subtropical North Atlantic Ocean appear to be too low when compared to geochemical-based estimates. It has been hypothesized that episodic inputs of new nutrients into surface water via the passage of mesoscale eddies or winter storms may resolve at least some of this discrepancy. Here, we investigated particulate organic carbon (POC), particulate organic nitrogen (PON), and biogenic silica (BSiO₂) export using a combination of water column ²³⁴Th:²³⁸U disequilibria and free-floating sediment traps during and immediately following two weather systems encountered in February and March 2004. While these storms resulted in a 2–4-fold increase in mixed layer NO₃ inventories, total chlorophyll a and an increase in diatom biomass, the systems were dominated by generally low ²³⁴Th:²³⁸U disequilibria, suggesting limited particle export. Several ²³⁴Th models were tested, with only those including non-steady state and vertical upwelling processes able to describe the observed ²³⁴Th activities. Although upwelling velocities were not measured directly in this study, the ²³⁴Th model suggests reasonable rates of 2.2–3.7 m d^?1.Given the uncertainties associated with ²³⁴Th derived particle export rates and sediment traps, both were used to provide a range in sinking particle fluxes from the upper ocean during the study. ²³⁴Th particle fluxes were determined applying the more commonly used steady state, one-dimensional model with element/²³⁴Th ratios measured in sediment traps. Export fluxes at 200 m ranged from 1.91±0.20 to 4.92±1.22 mmol C m^?2 d^?1, 0.25±0.08 to 0.54±0.09 mmol N m^?2 d^?1, and 0.22±0.04 to 0.50±0.06 mmol Si m^?2 d^?1. POC export efficiencies (Primary Production/Export) were not significantly different from the annual average or from time periods without storms, although absolute POC fluxes were elevated by 1–11%. This increase was not sufficient, however, to resolve the discrepancy between our observations and geochemical-based estimates of particle export. Comparison of PON export rates with simultaneous measurements of NO₃^? uptake derived new production rates suggest that only a fraction, <35%, of new production was exported as particles to deep waters during these events. Measured bSiO₂ export rates were more than a factor of two higher (p<0.01) than the annual average, with storm events contributing as much as 50% of annual bSiO₂ export in the Sargasso Sea. Furthermore it appears that 65–95% (average 86±14%) of the total POC export measured in this study was due to diatoms.Combined these results suggest that winter storms do not significantly increase POC and PON export to depth. Rather, these storms may play a role in the export of bSiO₂ to deep waters. Given the slower remineralization rates of bSiO₂ relative to POC and PON, this transport may, over time, slowly decrease water column silicate inventories, and further drive the Sargasso Sea towards increasing silica limitation. These storm events may further affect the quality of the POC and PON exported, given the large association of this material with diatoms during these periods.     

Fluxes of234Th,210Po and210Pb determined by sediment trap experiments in pelagic oceans

Sediment trap experiments were carried out in two oceans, the eastern Pacific Ocean and the Antarctic Ocean, which have very different biological productivities. The natural radionuclides,²³⁴Th,²¹⁰Po and²¹⁰Pb were used as tracers of reactive metals. Larger particulate fluxes of these radionuclides were found in the seas where total mass fluxes were larger, although the concentrations of these radionuclides in the settling particles were somewhat smaller. The concentrations of²³⁴Th in the settling particles varied widely and irregularly with depth, whereas the concentrations of²¹⁰Po and²¹⁰Pb in the settling particles steadily increased with increasing water depth. The ratios of²¹⁰Po/²¹⁰Pb in the settling particulates were larger than unity which the ratio of²³⁴Th/excess²¹⁰Po as larger than²³⁴Th/²¹⁰Po in the deep water. These results suggest that, when the particles sink through the water column, these radionuclides are being absorbed by settling particles in the order²³⁴Th>²¹⁰Po>²¹⁰Pb. The observed particulate fluxes of²¹⁰Pb are about one eighth of those calculated from the disequilibria between²²⁶Ra and²¹⁰Pb at the stations in the subtropical eastern Pacific, although the observed fluxes are the same as the calculated ones in the northern North Pacific and the Antarctic Ocean. Thus, there must be a horizontal flow carrying these reactive metals from the oligotorophic ocean to the biologically productive ocean where the metals are removed by settling particles even in deep water.     

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

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

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.     

<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.