234Th Ratios Research Articles

Carbon and silica fluxes during a declining North Atlantic spring bloom as part of the EXPORTS program

The goal of NASA's EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) project is to develop a predictive understanding of the fate of global ocean primary productivity and export of carbon from the surface to the deep ocean. Thorium-234 (234Th, t1/2 = 24.1 d) was used to measure sinking particle export from an anticyclonic eddy during the EXPORTS North Atlantic cruise (May 2021) at the Porcupine Abyssal Plain. The four-week sampling period was broken into three time periods (“epochs”) where 800 234Th seawater samples were collected from over 50 CTD casts with high depth resolution over the upper 500 m. Size-fractioned particulate samples were collected to determine particulate organic carbon (POC) and biogenic silica (bSi) to 234Th ratios using in situ McLane pumps. A 234Th non-steady state model shows an eddy center epoch average progression of increasing 234Th export (∼2800 ± 300 (Epoch 1; standard deviation) to 4500 ± 700 (Epoch 3) dpm m−2 d−1) out of the top 110 m of the water column over the course of the cruise (29 d). This translates into an epoch average progression of ∼11 ± 1 to 14 ± 2 mmol C m−2 d−1 of sinking POC flux, and ∼ 3 ± 1 to 6 ± 1 mmol bSi m−2 d−1 of sinking bSi flux to deeper waters at 110 m. The overall efficiency of the biological carbon pump (amount of net primary production reaching 100 m below the euphotic zone) increases from ∼10% to ∼30% throughout the sampling period. The temporal trends discussed extensively in this paper show that POC and bSi export increase during diatom bloom evolution.

Revisiting five decades of <sup>234</sup>Th data: a comprehensive global oceanic compilation

Abstract. We present here a global oceanic compilation of 234Th measurements that collects results from researchers and laboratories over a period exceeding 50 years. The origin of the 234Th sampling in the ocean goes back to 1967, when Bhat et al. (1969) initially studied 234Th distribution relative to its parent 238U in the Indian Ocean. However, it was the seminal work of Buesseler et al. (1992) – which proposed an empirical method to estimate export fluxes from 234Th distributions – that drove the extensive use of the 234Th–238U radioactive pair to evaluate the organic carbon export out of the surface ocean by means of the biological carbon pump. Since then, a large number of 234Th depth profiles have been collected using a variety of sampling instruments and strategies that have changed during the past 50 years. The present compilation is made of a total 223 data sets: 214 from studies published in either articles in refereed journals, PhD theses, or repositories, as well as 9 unpublished data sets. The data were compiled from over 5000 locations spanning all the oceans for total 234Th profiles, dissolved and particulate 234Th activity concentrations (in dpm L−1), and POC:234Th ratios (in µmol dpm−1) from both sediment traps and filtration methods. A total of 379 oceanographic expeditions and more than 56 600 234Th data points have been gathered in a single open-access, long-term, and dynamic repository. This paper introduces the dataset along with informative and descriptive graphics. Appropriate metadata have been compiled, including geographic location, date, and sample depth, among others. When available, we also include water temperature, salinity, 238U data (over 18 200 data points), and particulate organic nitrogen data. Data source and method information (including 238U and 234Th) is also detailed along with valuable information for future data analysis such as bloom stage and steady-/non-steady-state conditions at the sampling moment. The data are archived on the PANGAEA repository, with the dataset DOI https://doi.org/10.1594/PANGAEA.918125 (Ceballos-Romero et al., 2021). This provides a valuable resource to better understand and quantify how the contemporary oceanic carbon uptake functions and how it will change in future.

Seasonal variability in carbon:234thorium ratios of suspended and sinking particles in coastal Antarctic waters: Field data and modeling synthesis

238U–234Th disequilibrium is a powerful tool for investigating particle cycling and carbon export associated with the ocean's biological carbon pump. However, the interpretation of this method is complicated by multiple processes that can modify carbon:thorium ratios over small spatial scales. We investigated seasonal variability in the thorium and carbon cycles at a coastal site in the Western Antarctic Peninsula. Throughout the ice-free summer season, we quantified carbon and 234Th vertical flux, total water column 234Th, particulate 234Th, and the C:234Th ratios of sinking material and bulk suspended material. Simultaneous identification and separation of fecal pellets from sinking material showed that fecal pellets (primarily from krill) contributed 56% of carbon flux and that as a result of lower C:234Th ratios than suspended particles, these fecal pellets were primary drivers of variability in the C:234Th ratios of sinking material. Bulk suspended particles had highly variable C:234Th ratios and were consistently elevated in the euphotic zone relative to deeper waters. The fraction of 234Th adsorbed onto particles was positively correlated with chlorophyll and particulate organic carbon (POC) concentrations. The C:234Th ratios of suspended particles were positively correlated with POC, although during the spring diatom bloom C:234Th ratios were lower than would have been predicted based on POC concentrations alone. We hypothesize that diatom production of transparent exopolymers may have led to enhanced rates of thorium adsorption during the bloom, thus decreasing the C:234Th ratios. We used a Bayesian model selection approach to develop and parameterize mechanistic models to simulate thorium sorption dynamics. The best model incorporated one slowly-sinking POC pool and rapidly-sinking fecal pellets, with second-order sorption kinetics. The model accurately simulated temporal patterns in the C:234Th ratios of sinking and suspended particles and the fraction of 234Th adsorbed to particles. However, it slightly over-estimated C:234Th ratios during the spring (diatom-dominated) bloom and underestimated C:234Th ratios during the fall (mixed-assemblage) bloom. Optimized model parameters for thorium sorption and desorption were 0.0047 ± 0.0002 m3 mmol C−1 d−1 and 0.017 ± 0.008 d−1, respectively. Our results highlight the important role that specific taxa can play in modifying the C:234Th ratio of sinking and suspended particles and provide guidance for future studies that use 234Th measurements to investigate the functional relationships driving the efficiency of the biological pump.

High-resolution spatial and temporal measurements of particulate organic carbon flux using thorium-234 in the northeast Pacific Ocean during the EXport Processes in the Ocean from RemoTe Sensing field campaign

The EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) program of National Aeronautics and Space Administration focuses on linking remotely sensed properties from satellites to the mechanisms that control the transfer of carbon from surface waters to depth. Here, the naturally occurring radionuclide thorium-234 was used as a tracer of sinking particle flux. More than 950 234Th measurements were made during August–September 2018 at Ocean Station Papa in the northeast Pacific Ocean. High-resolution vertical sampling enabled observations of the spatial and temporal evolution of particle flux in Lagrangian fashion. Thorium-234 profiles were remarkably consistent, with steady-state (SS) 234Th fluxes reaching 1,450 ± 300 dpm m−2 d−1 at 100 m. Nonetheless, 234Th increased by 6%–10% in the upper 60 m during the cruise, leading to consideration of a non-steady-state (NSS) model and/or horizontal transport, with NSS having the largest impact by decreasing SS 234Th fluxes by 30%. Below 100 m, NSS and SS models overlapped. Particulate organic carbon (POC)/234Th ratios decreased with depth in small (1–5 μm) and mid-sized (5–51 μm) particles, while large particle (>51 μm) ratios remained relatively constant, likely influenced by swimmer contamination. Using an average SS and NSS 234Th flux and the POC/234Th ratio of mid-sized particles, we determined a best estimate of POC flux. Maximum POC flux was 5.5 ± 1.7 mmol C m−2 d−1 at 50 m, decreasing by 70% at the base of the primary production zone (117 m). These results support earlier studies that this site is characterized by a modest biological carbon pump, with an export efficiency of 13% ± 5% (POC flux/net primary production at 120 m) and 39% flux attenuation in the subsequent 100 m (POC flux 220 m/POC flux 120m). This work sets the foundation for understanding controls on the biological carbon pump during this EXPORTS campaign.

High-resolution spatial and temporal measurements of particulate organic carbon flux using thorium-234 in the northeast Pacific Ocean during the EXport Processes in the Ocean from RemoTe Sensing field campaign

The EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) program of National Aeronautics and Space Administration focuses on linking remotely sensed properties from satellites to the mechanisms that control the transfer of carbon from surface waters to depth. Here, the naturally occurring radionuclide thorium-234 was used as a tracer of sinking particle flux. More than 950 234Th measurements were made during August–September 2018 at Ocean Station Papa in the northeast Pacific Ocean. High-resolution vertical sampling enabled observations of the spatial and temporal evolution of particle flux in Lagrangian fashion. Thorium-234 profiles were remarkably consistent, with steady-state (SS) 234Th fluxes reaching 1,450 ± 300 dpm m−2 d−1 at 100 m. Nonetheless, 234Th increased by 6%–10% in the upper 60 m during the cruise, leading to consideration of a non-steady-state (NSS) model and/or horizontal transport, with NSS having the largest impact by decreasing SS 234Th fluxes by 30%. Below 100 m, NSS and SS models overlapped. Particulate organic carbon (POC)/234Th ratios decreased with depth in small (1–5 μm) and mid-sized (5–51 μm) particles, while large particle (>51 μm) ratios remained relatively constant, likely influenced by swimmer contamination. Using an average SS and NSS 234Th flux and the POC/234Th ratio of mid-sized particles, we determined a best estimate of POC flux. Maximum POC flux was 5.5 ± 1.7 mmol C m−2 d−1 at 50 m, decreasing by 70% at the base of the primary production zone (117 m). These results support earlier studies that this site is characterized by a modest biological carbon pump, with an export efficiency of 13% ± 5% (POC flux/net primary production at 120 m) and 39% flux attenuation in the subsequent 100 m (POC flux 220 m/POC flux 120m). This work sets the foundation for understanding controls on the biological carbon pump during this EXPORTS campaign.

Global database of ratios of particulate organic carbon to thorium-234 in the ocean: improving estimates of the biological carbon pump

Abstract. The ocean's biological carbon pump (BCP) plays a major role in the global carbon cycle. A fraction of the photosynthetically fixed organic carbon produced in surface waters is exported below the sunlit layer as settling particles (e.g., marine snow). Since the seminal works on the BCP, global estimates of the global strength of the BCP have improved but large uncertainties remain (from 5 to 20 Gt C yr−1 exported below the euphotic zone or mixed-layer depth). The 234Th technique is widely used to measure the downward export of particulate organic carbon (POC). This technique has the advantage of allowing a downward flux to be determined by integrating the deficit of 234Th in the upper water column and coupling it to the POC∕234Th ratio in sinking particles. However, the factors controlling the regional, temporal, and depth variations of POC∕234Th ratios are poorly understood. We present a database of 9318 measurements of the POC∕234Th ratio in the ocean, from the surface down to >5500 m, sampled on three size fractions (∼>0.7 µm, ∼1–50 µm, ∼>50 µm), collected with in situ pumps and bottles, and also from bulk particles collected with sediment traps. The dataset is archived in the data repository PANGAEA® under https://doi.org/10.1594/PANGAEA.911424 (Puigcorbé, 2019). The samples presented in this dataset were collected between 1989 and 2018, and the data have been obtained from published papers and open datasets available online. Unpublished data have also been included. Multiple measurements can be found in most of the open ocean provinces. However, there is an uneven distribution of the data, with some areas highly sampled (e.g., China Sea, Bermuda Atlantic Time Series station) compared to some others that are not well represented, such as the southeastern Atlantic, the south Pacific, and the south Indian oceans. Some coastal areas, although in a much smaller number, are also included in this global compilation. Globally, based on different depth horizons and climate zones, the median POC∕234Th ratios have a wide range, from 0.6 to 18 µmol dpm−1.

Are all sediment traps created equal? An intercomparison study of carbon export methodologies at the PAP-SO site

Sinking particulate flux out of the upper ocean is a key observation of the ocean’s biological carbon cycle. Particle flux in the upper mesopelagic is often determined using sediment traps but there is no absolute standard for the measurement. Prior to this study, differing neutrally-buoyant sediment trap designs have not been deployed simultaneously, which precludes meaningful comparisons between flux data collected using these designs.The aim of the study was to compare a suite of modern methods for measuring sinking carbon flux out of the surface ocean. This study compared samples from two neutrally buoyant drifting sediment trap designs, and a surface tethered drifting sediment trap, which collected sinking particles alongside other methods for sampling particle properties, including in situ pumps and 234Th radionuclide measurements. Samples were collected at the Porcupine Abyssal Plain Sustained Observatory (PAP-SO) site in the Northeast Atlantic Ocean (49°N, 16.5°W).Neutrally-buoyant conical traps appeared to collect lower absolute fluxes than neutrally-buoyant, or surface-tethered cylindrical traps, but compositional ratios of sinking particles indicated collection of similar material when comparing the conical and cylindrical traps. In situ pump POC:234Th ratios generally agreed with trap ratios but conical trap samples were somewhat depleted in 234Th, which along with sinking particle size distribution data determined from gel traps, may imply under-sampling of small particles. Cylindrical trap POC fluxes were of similar magnitude to 234Th-derived POC fluxes while conical POC fluxes were lower. Further comparisons are needed to distinguish if differences in particle flux magnitude are due to conical versus cylindrical trap designs. Parallel analytical determinations, conducted by different laboratories, of replicate samples for elemental fluxes and gel trap particle size distributions were comparable. This study highlights that the magnitude of particle fluxes and size spectra may be more sensitive than the chemical composition of particle fluxes to the instrumentation used. Only two deployments were possible during this study so caution should be taken when applying these findings to other regions and export regimes. We recommend that multiple methodologies to measure carbon export should be employed in field studies, to better account for each method’s merits and uncertainties. These discrepancies need further study to allow carbon export fluxes to be compared with confidence across laboratory, region and time and to achieve an improved global understanding of processes driving and controlling carbon export.

An Estimate of Thorium 234 Partition Coefficients Through Global Inverse Modeling

AbstractThorium‐234 (234Th), an insoluble radioisotope scavenged by marine particles, can be used as a proxy of the biological carbon pump. Thorium‐234 observations can constrain biogeochemical models, but a necessary first step is to estimate the poorly known partition coefficients between particulate and dissolved phases. In this study, the 234Th partition coefficients for five particle types, differing in size and chemical composition, are estimated by fitting a global 3‐D 234Th model based on the coupled ocean general circulation‐biogeochemistry model NEMO‐PISCES (at a resolution of 2°) to a global 234Th data set (including GEOTRACES data). Surface partition coefficients are estimated between 0.79 and 16.7×106. Biogenic silica has the smallest partition coefficients. Small particulate organic carbon and lithogenic dust have the largest. Thorium‐234 observations at depth cannot be recovered without allowing partition coefficients to increase by one order of magnitude from surface to 1,000 m deep. In our time‐dependent global 3‐D model, the biases introduced by three common assumptions made in biological carbon pump studies can be quantified. First, using the C:234Th ratio of large particles alone leads to an overestimation of carbon export at the base of the euphotic layer, by up to a factor 2. Furthermore, assuming steady state and neglecting transport by advection and diffusion can bias fluxes by as much as 50%, especially at high latitudes and in upwellings, with a sign and intensity depending on the season.

The carbon: 234Thorium ratios of sinking particles in the California current ecosystem 2: Examination of a thorium sorption, desorption, and particle transport model

Thorium-234 (234Th) is a powerful tracer of particle dynamics and the biological pump in the surface ocean; however, variability in carbon: thorium ratios of sinking particles adds substantial uncertainty to estimates of organic carbon export. We coupled a mechanistic thorium sorption and desorption model to a one-dimensional particle sinking model that uses realistic particle settling velocity spectra. The model generates estimates of 238U234Th disequilibrium, particulate organic carbon concentration, and the C:234Th ratio of sinking particles, which are then compared to in situ measurements from quasi-Lagrangian studies conducted on six cruises in the California Current Ecosystem. Broad patterns observed in in situ measurements, including decreasing C:234Th ratios with depth and a strong correlation between sinking C:234Th and the ratio of vertically-integrated particulate organic carbon (POC) to vertically-integrated total water column 234Th, were accurately recovered by models assuming either a power law distribution of sinking speeds or a double log normal distribution of sinking speeds. Simulations suggested that the observed decrease in C:234Th with depth may be driven by preferential remineralization of carbon by particle-attached microbes. However, an alternate model structure featuring complete consumption and/or disaggregation of particles by mesozooplankton (e.g. no preferential remineralization of carbon) was also able to simulate decreasing C:234Th with depth (although the decrease was weaker), driven by 234Th adsorption onto slowly sinking particles. Model results also suggest that during bloom decays C:234Th ratios of sinking particles should be higher than expected (based on contemporaneous water column POC), because high settling velocities minimize carbon remineralization during sinking.

The Carbon:234Thorium ratios of sinking particles in the California current ecosystem 1: relationships with plankton ecosystem dynamics

We investigated variability in the C:234Th ratio of sinking particles and its relationship to changing water column characteristics and plankton ecological dynamics during 29 Lagrangian experiments conducted on six cruises of the California Current Ecosystem Long-Term Ecological Research (CCE-LTER) Program. C:234Th ratios of sinking particles collected by a surface-tethered sediment trap (C:234ThST) varied from 2.3 to 20.5 μmol C dpm−1 over a depth range of 47–150 m. C:234ThST was significantly greater (by a factor of 1.8) than C:234Th ratios of suspended >51-μm particles collected in the same water parcels with in situ pumps. C:234Th ratios of large (>200-μm) sinking particles also exceeded those of smaller sinking particles. C:234ThST decreased with depth from the base of the euphotic zone through the upper twilight zone. C:234ThST was positively correlated with several indices of ecosystem productivity including particulate organic carbon (POC) and chlorophyll (Chl) concentrations, mesozooplankton biomass, and the fraction of Chl >20-μm. Principal component analysis and multiple linear regression suggested that decaying phytoplankton blooms exhibited higher C:234ThST than actively growing blooms at similar biomass levels. C:234ThST was positively correlated with indices of the fractional contribution of fecal pellets in sediment traps when the proportion of fecal pellets was low in the traps, likely because of a correlation between mesozooplankton biomass and other indices of ecosystem productivity. However, when fecal pellets were a more important component of sinking material, C:234ThST decreased with increasing fecal pellet content. C:234ThST was also positively correlated with the Si:C ratio of sinking particles. Across the dataset (and across depths) a strong correlation was found between C:234ThST and the ratio of vertically-integrated POC to vertically-integrated total water column 234Th (vC:234Thtot). A mechanistic one-layer, two-box model of thorium sorption and desorption was invoked to explain this correlation. Two empirical models (one using vC:234Thtot; one using depth and vertically-integrated Chl) were developed to predict C:234Th ratios in this coastal upwelling biome. The former regression (log10(C:234ThST) = 0.43 × log10(vC:234Thtot) + 0.53) was found to also be a reasonable predictor for C:234ThST from diverse regions including the Southern Ocean, Sargasso Sea, Subarctic North Pacific, and Eastern Tropical North Pacific.

Does adsorption of dissolved organic carbon and thorium onto membrane filters affect the carbon to thorium ratios, a primary parameter in estimating export carbon flux?

The particulate organic carbon (POC) to 234Th ratio, or POC/234Th, is crucial to constrain the 234Th-derived downward export flux. Marine particles for 234Th based export studies are typically collected via two sampling modes: filtration of Niskin or GO-FLO bottle water samples and filtration of in situ pumped samples. Large discrepancies have been frequently observed between these bottle and pump filtration methods and attributed to the difference in adsorption of dissolved material. We noted however, that simultaneous measurements of carbon and 234Th have not been made to evaluate such a putative effect on the POC/234Th ratio. In this study, we adopted a “two filters in-line” approach method with one stacked on another and we measured both carbon and 234Th to compare their adsorption behavior in bottle and pump sampling modes. We proposed that the 234Th and carbon on the second filter (filter-B) might be attributable to direct adsorption from the dissolved phase (including the partial capture from the submicron particles) and/or breakdown of particles initially collected on the first filter (filter-A). The relative importance of these two processes differed between the two filtration modes. For bottle sampling, we observed significantly positive correlation (R2=0.54) between the 234Th recorded on the second filter and dissolved 234Th activities, suggesting that adsorption was the dominant contributor to the second filter. The overestimation due to adsorption (filter-B/filter-A) is estimated to be 22±7% for POC and 25±17% for particulate 234Th. The effect of adsorption on the POC/234Th, on the other hand, would be negligible since the adsorption-corrected and -uncorrected POC/234Th on filter-A were similar. For the large volume pumping mode, the absorbed 234Th on the filters appeared to reach the saturation state as evidenced by the fact that the amount of particulate 234Th (dpmcm−2) on filter-B was independent of the filtered sample volume. We justified that the saturation amount should be >0.21dpmcm−2 which was the highest unsaturated value from the bottle sample, but <0.31dpmcm−2 which was the upper value on filter-B taken from pump samples. The calculated adsorption still dominated for 234Th on filter-B and particle breakdown might be important in the euphotic zone. The collected POC on filter-B tended to increase with the filtration volume which implied that DOC adsorption remained under-saturated. Similar to bottle filtration, the corrected POC/234Th was comparable to the uncorrected POC/234Th on filter-A. We thus conclude that adsorption did not appear to influence the POC/234Th ratio in either sampling mode. We suggested that the positive offset in POC/234Th between bottle and pump sampling, if any, cannot be caused by adsorption. Other mechanisms such as zooplankton invasion and/or artificial particle formation need to be examined in order to resolve the discrepancy.

Chemical composition and relative hydrophobicity of microbial exopolymeric substances (EPS) isolated by anion exchange chromatography and their actinide-binding affinities

Understanding the chemical and physical properties of microbially produced, actinide-carrying biopolymers is essential for the prediction of their relative binding affinities and particle-interaction propensities that are affecting the transport of actinide elements. In addition, they form the basis for their oceanographic applications, such as using POC/ 234Th ratios to determine organic carbon fluxes and for tracing upper ocean particle dynamics. Furthermore, environmental applications of bioflocculation and bioremediation can benefit from such improved understanding. Exopolymeric substances (EPS) in “attached” and “non-attached” forms, produced by two bacteria and one alga, were extracted and purified using improved procedures. These biopolymers produced by the two bacteria, which were previously shown to contain strong 234Th complexing ligands, were further fractionated by semi-preparative HPLC-anion exchange chromatography in order to relate Th(IV)-binding ability to chemical composition. Eluted fractions were further characterized at both semi-molecular and molecular levels. It was found that the EPS consisted of more than one biopolymer, with distinct monosaccharide and amino acid compositions, but very similar molecular weight (~ 25 kDa). 234Th binding strength was correlated to their uronic acid to organic carbon ratios, suggesting that uronic acids are the actual binding agents of 234Th, or more likely, proxy compounds for the actual macromolecular 234Th binding ligands. These compounds were, however, not pure uronic acids, but rather amphiphilic glycoproteins or proteoglycans. Hydrophobic contact areas (HCA) of “attached” EPS, as measures of their relative hydrophobicity and amphiphilicity, were higher than those of “non-attached” EPS, and all were highly correlated to the ratios of the FTIR areas of amide-I bands from proteins to those of C O C bands from carbohydrates. This suggests that the relative hydrophobicity of the carrier biopolymers, which can be responsible for gel formation, particle aggregation and bioflocculation, was mainly regulated by their relative protein to polysaccharide contents.

234Th in surface waters: Distribution of particle export flux across the Antarctic Circumpolar Current and in the Weddell Sea during the GEOTRACES expedition ZERO and DRAKE

As part of the GEOTRACES Polarstern expedition ANTXXIV/3 (ZERO and DRAKE) we have measured the vertical distribution of 234Th on sections through the Antarctic Circumpolar Current along the zero meridian and in Drake Passage and on an EW section through the Weddell Sea. Steady state export fluxes of 234Th from the upper 100 m, derived from the depletion of 234Th with respect to its parent 238U, ranged from 621±105 to 1773±90 dpm m −2 d −1. This 234Th flux was converted into an export flux of organic carbon ranging from 3.1 to 13.2 mmol C m −2 d −1 (2.1–9.0 mmol C m −2 d −1) using POC/ 234Th ratio of bulk (respectively >50 μm) suspended particles at the export depth (100 m). Non-steady state fluxes assuming zero flux under ice cover were up to 23% higher. In addition, particulate and dissolved 234Th were measured underway in high resolution in the surface water with a semi-automated procedure. Particulate 234Th in surface waters is inversely correlated with light transmission and pCO 2 and positively with fluorescence and optical backscatter and is interpreted as a proxy for algal biomass. High resolution underway mapping of particulate and dissolved 234Th in surface water shows clearly where trace elements are absorbed by plankton and where they are exported to depth. Quantitative determination of the export flux requires the full 234Th profile since surface depletion and export flux become decoupled through changes in wind mixed layer depth and in contribution to export from subsurface layers. In a zone of very low algal abundance (54–58°S at the zero meridian), confirmed by satellite Chl-a data, the lowest carbon export of the ACC was observed, allowing Fe and Mn to maintain their highest surface concentrations. An ice-edge bloom that had developed in December/January in the zone 60–65°S as studied during the previous leg had caused a high export flux at 64.5°S when we visited the area 2 months later (February/March). The ice-edge bloom had then shifted south to 65–69°S evident from uptake of CO 2 and dissolved Fe, Mn and 234Th, without causing export yet. In this way, the parallel analysis of 234Th can help to explain the scavenging behavior of other trace elements.

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.

Insights into particle formation and remineralization using the short‐lived radionuclide, Thoruim‐234

Simple mass balance models are applied to a high resolution 234Th profile from the northwest Pacific to examine the magnitude, rate, and depth distribution of particle remineralization processes below the euphotic zone (Ez). Here, excess 234Th (234Th &gt; 238U) below the Ez is attributed to fragmentation processes that result in the conversion of sinking to non‐sinking particles. By considering particulate organic carbon (POC) to 234Th ratios on particles, we show that POC flux attenuation is larger than for 234Th, which we attribute to bacterial and zooplankton consumption of sinking POC. Three case studies are used to demonstrate how different combinations of particle fragmentation and POC respiration impact flux attenuation below the Ez. When sampled with high vertical resolution and precision, 234Th and POC/234Th ratios provide insights into both export from the Ez and the extent to which sinking particle fluxes and associated minerals are attenuated with depth.

POC/ 234Th ratios in particles collected in sediment traps in the northern South China Sea

234Th has been increasingly used as a tracer to estimate particulate organic carbon (POC) flux, based on calculation of the product of the POC/ 234Th ratio in sinking particles and the 234Th flux. Large (>50 μm) pump-collected particles are assumed to be representative of sinking particles for determining POC/ 234Th ratios, but the basis of this assumption has not been extensively investigated. Here we present POC and 234Th data for various particle size classes (1–10, 10–50, 50–150 and >150 μm) from trap-collected particles in the northern South China Sea (SCS, a subtropical region). Within the trap-collected POC pool the 1–10 μm fraction contained the largest proportion of POC (26–35%), followed by the 10–50 μm (25–29%), 50–150 μm (19–24%), and >150 μm (17–23%) fractions. The distribution pattern of 234Th in the trap-collected particles was analogous to that of POC, with the smallest (1–10 μm) particles representing the largest proportion (37–54%) of the 234Th flux. Our preliminary results indicate that trap-collected particles <50 μm carry most of the POC and 234Th flux in the northern SCS, suggesting that the contribution of particles smaller than 50 μm to the settling flux is larger than previously thought. The results indicate that it may be necessary to simultaneously measure POC/ 234Th ratios on size-fractionated trap- and pump-collected materials from different marine regions, including tropical and high latitude locations.

Comparative evaluation of sediment trap and 234Th-derived POC fluxes from the upper oligotrophic waters of the Gulf of Mexico and the subtropical northwestern Pacific Ocean

To better understand the inter-relationships between particulate organic carbon (POC) fluxes and phytoplankton and bacteria biomass and production, we compared POC fluxes determined in sediment traps and approaches based on size-fractionated (1–10, 10–50, 50–150 and > 150 μm) suspended particulate 234Th and POC concentrations in oligotrophic sections of the Gulf of Mexico during August 2005 and May 2006 and in the oligotrophic northwestern Pacific Ocean during 2009. In 2005, the sediment trap POC flux near the bottom of the euphotic zone (120 m) ranged from 71 to 94 mg C m − 2 day − 1 , while 234Th-derived POC fluxes using POC/ 234Th ratios in the 10–50 µm and 50–150 µm varied from 71 to 150 mg C m − 2 day − 1 . In 2006, the sediment trap POC flux at 120 m ranged from 24 to 67 mg C m − 2 day − 1 , while the 234Th-derived POC fluxes in the 10–50 µm fraction were comparable or somewhat higher, ranging from 71 to 119 mg C m − 2 day − 1 . The POC fluxes in 2006, calculated by using POC/ 234Th ratios in the 1–10 µm and the 50–150 µm fractions were much higher, ranging from 847 to 1369 mg C m − 2 day − 1 . Correlations with biological and chemical parameters support a likely mechanism of sinking aggregates of haptophytes (0.2–20 µm) of higher density held together by Th-complexing and uronic acid containing exopolymeric substances. The observations that 234Th (and POC) is mainly associated with medium-sized (10–15 µm) suspended particles rather than larger (50–150 µm) ones may be caused by the use of a one-filter method and standard filtration and processing procedures that were applied here for collecting suspended particles. This then raises the question of what constitutes representative material from the ocean that settles on the characteristic time scale of 234Th. As a comparison, size-fractionated trap-collected particles in the oligotrophic northwestern Pacific Ocean showed that the 10–50 μm fraction contained the largest proportion of POC (22–41%), followed by the 50–150 μm (22–37%), the > 150 μm (15–27%), and the 1–10 μm (17–23%) fraction. The partitioning of 234Th in trap-collected particles was slightly different from that of POC, with the 1–10 μm fraction representing the largest proportion (27–48%) of 234Th flux. Together, the < 50 μm particles contributed, on average, 52 ± 6% of POC, which suggests that the POC/ 234Th ratios traditionally derived from large (> 50 µm) pump-collected particles may not accurately reflect the majority of sinking particles. Therefore, estimated POC fluxes may be significantly biased using a conventional 234Th based approach, i.e., using POC/ 234Th ratios from a single filter obtained from large (> 50 µm) pump-collected particles.

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.

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 (BSiO 2) 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 NO 3 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 NO 3 − 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 bSiO 2 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 bSiO 2 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 bSiO 2 to deep waters. Given the slower remineralization rates of bSiO 2 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.

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.