An intercomparison of small- and large-volume techniques for thorium-234 in seawater

In this paper, an intercomparison of methods for the determination of ²³⁴Th in seawater is discussed. Samples were collected either from a shore-based 600 m water source, or from standard bottle casts in deep waters off Hawaii and the Southern Ocean. We compared large-volume techniques, which rely upon Mn cartridges for the collection of dissolved ²³⁴Th and its detection via gamma counting (>200-l samples), with small volume methods that employed either direct beta counting, or beta counting after radiochemical purification (2–20-l samples). Unique to this study is the presentation of small volume (2 and 5 l) ²³⁴Th methods. This new technique is an adaptation of 20-l methods that are based on the coprecipitation of thorium with Mn oxides followed by direct beta counting of the precipitate. The small volume Mn coprecipitation methods were found to be superior to other methods due to ease of sample collection, processing and low overall analytical uncertainties.     

A review of present techniques and methodological advances in analyzing Th in aquatic systems

The short-lived thorium isotope ²³⁴Th (half-life 24.1 days) has been used as a tracer for a variety of transport processes in aquatic systems. Its use as a tracer of oceanic export via sinking particles has stimulated a rapidly increasing number of studies that require analyses of ²³⁴Th in both marine and freshwater systems. The original ²³⁴Th method is labor intensive. Thus, there has been a quest for simpler techniques that require smaller sample volumes. Here, we review current methodologies in the collection and analysis of ²³⁴Th from the water column, discuss their individual strengths and weaknesses, and provide an outlook on possible further improvements and future challenges. Also included in this review are recommendations on calibration procedures and the production of standard reference materials as well as a flow chart designed to help researchers find the most appropriate ²³⁴Th analytical technique for a specific aquatic regime and known sampling constraints.     

Temporal variations of dissolved and particulate Th at a coastal station of the northern Adriatic Sea

Water–particle interactions, particle behaviour and short-time scale variability were assessed at a coastal station adjacent to the Emilia Romagna Region (Adriatic Sea) using dissolved and particulate ²³⁴Th analyses. The water column was sampled six times between March and September 1997. Measurements showed that ²³⁴Th is actively scavenged by particles but the dissolved fraction is always prevalent. Changes in hydrological conditions affect to some degree thorium activities and residence times. Dissolved thorium inventories slowly increased from May to July, then decreased in August, and increased again in September. In July, the formation of a sharp pycnocline associated with low productivity led to high dissolved and very low particulate ²³⁴Th activities due to inefficient scavenging. The presence of mucilaginous aggregates, observed in both August and September, may have played a role in scavenging of thorium. In September at 16 m depth, the highest ²³⁴Th particulate activity of the study period was measured, probably due to the presence of mucilage. However, the thorium deficit was scarce, due to the small sinking velocity of these aggregates. Both steady-state and non-steady state models were used to calculate residence times for the whole water column and its topmost part (10 m) obtaining strictly comparable results. Residence times in the whole water column are small, ranging from 15 to 45 and from 0.5 to 24 d for dissolved and particulate thorium, respectively.     

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.     

Organic carbon to Th ratios of marine organic matter

Uncertainties in the determinations of particulate organic carbon flux from measurements of the disequilibrium between ²³⁴Th and its mother isotope uranium depend largely on the determination of the organic carbon to ²³⁴thorium (OC : ²³⁴Th) ratio. The variability of the OC : ²³⁴Th ratio in different size fractions of suspended matter, ranging from the truly dissolved (< 3 or 10 kDa) fraction to several millimeter sized marine snow, as well as from sediment trap material was assessed during an eight-day cruise off the coast of California in Spring 1997. The affinity of polysaccharide particles called TEP (transparent exopolymer particles) and inorganic clays to ²³⁴Th was investigated through correlations. The observed decrease in the OC : ²³⁴Th ratio with size, within the truly dissolved to small particle size range, is consistent with concepts of irreversible colloidal aggregation of non-porous nano-aggregates. No consistent trend in the OC : ²³⁴Th ratio was observed for particles between 1 or 10 to 6000 μm. Origin and fate of marine particles belonging to this size range are diverse and interactions with ²³⁴Th too complex to expect a consistent relationship between OC : ²³⁴Th ratio and size, if all categories of particles are included. The relationship between OC and ²³⁴Th was significant when data from the truly dissolved fraction were excluded. However, variability was very large, implying that OC flux calculations using different collection methods (e.g. sediment trap, Niskin bottles or pumps) would differ significantly. Therefore a large uncertainty in OC flux calculations based on the ²³⁴Th method exist due to individual decisions as to which types or size classes of particles best represent sinking material in a specific area. Preferential binding of ²³⁴Th to specific substance classes could explain the high variability in the relationship between OC and ²³⁴Th. At 15 m, in the absence of lithogenic material, the OC : ²³⁴Th ratio was a function of the fraction of TEP or TEP-precursors in OC, confirming that acidic polysaccharides have a high affinity for ²³⁴Th and that TEP carry a ligand for ²³⁴Th. Preferential binding to TEP might change distribution patterns of ²³⁴Th considerably, as TEP may sink when included in large aggregates, or remain suspended or even ascend when existing as individual particles or microaggregates. In the presence of lithogenic matter, at depths below 30 m, the ratio between ²³⁴Th and OC was linearly related to the ratio between alumino silicates and C. The affinity of inorganic substances to ²³⁴Th is known to be relatively low, suggesting that a coating of acidic polysaccharides was responsible for the apparently high affinity between ²³⁴Th and lithogenic material. Overall, OC : ²³⁴Th ratios of all material collected during this investigation can best be explained by differential binding of ²³⁴Th to both TEP and TEP-precursors, as well as to lithogenic minerals, which were very abundant in an intermediate nepheloid layer between 50 and 90 m.     

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

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

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

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.     

MnO2共沉淀直接β计数测定小体积海水中的234Th

探讨了MnO₂共沉淀直接β计数测定小体积海水中234Th方法在固体闪烁α/β计数仪上实现的可能性,对实验流程空白、流程化学回收率、仪器探测效率、MnO₂共沉淀量对全程回收率的影响以及检测核素的特征性等进行了研究.结果表明,该方法具有稳定的流程空白和全程回收率、高的探测效率和化学回收率,且所检测核素与234Th的理论半衰期基本吻合.将该流程应用于亚热带北太平洋表层水中234Th的分析也得到了令人满意的结果.与传统方法相比,该方法具有流程简单、所用水样体积小、快速获得结果等特点,适合于船载分析,由此可实现高时空分辨率数据的获取,为海洋颗粒有机碳输出通量以及颗粒物迁移速率的研究提供了更好的分析手段.     

An introduction to the application and future use of Th in aquatic systems

²³⁴Th is an extremely useful radiotracer of particle dynamics in aquatic systems. Its utility, however, has yet to be realized by many within the aquatic science community. The reasons for this may in part be due to a lack of knowledge of how this nuclide has been used in the past as well as how and where ²³⁴Th might be profitably applied in future research. The purpose of this paper, then, is to examine the variety of ²³⁴Th applications that have been used to understand natural aquatic processes in four major areas: vertical transport, particle cycling, horizontal transport, and sediment dynamics. We provide a general overview of the possible applications of ²³⁴Th in the hopes of provoking an increased interest in the inherent potential and future application of ²³⁴Th in these systems. We end this paper with a discussion of future research avenues in the context of three specific regimes: (i) the upper 1000 m of the open ocean, (ii) coastal sediment/water processes and (iii) large freshwater lakes.     

Determination of cosmogenic 32P and 33P in environmental samples

Understanding phosphorus dynamics in marine environment is of great importance, and appropriate tracers for phosphorus cycling in oceans are invaluable. In this study, two methods were developed for extraction, purification, and determination of naturally occurring 32P and 33P in rainwater, marine plankton and sediments using both a low-level beta counter (LBC) and an ultra-low-level liquid scintillation spectrometer (LSS). Blanks, chemical yields and counting efficiencies were quantified for both methods. The chemical purification of 32P and 33P separated by both procedures was validated by their decay curves. The absorber thickness of aluminum for LBC was assessed as 39.2 mg/cm 2 . 32P and 33P specific activities in some rain samples were determined by both methods and showed good consistent results. The advantage of the LSS over the LBC is apparent in its high counting efficiency and in determining samples with high concentration of stable phosphorus. However, when measuring environmental samples with low concentration of stable phosphorus, such as rainwater, both methods can be used and each has its distinct advantage.     

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...     

Analysis of Ac in seawater by delayed coincidence counting

The activity of ²²⁷Ac in seawater was determined using a delayed coincidence counting technique based on the measurement of the short-lived daughter ²²³Ra (half-life of 11 days). Two 180-l aliquots of Ac free seawater from surface waters of the California borderlands were spiked with Harwell Uraninite standard and the added Ac and Ra were extracted on Mn-fibers. The measured activities on the fibers agreed to within 5% of the equilibrium Ac activity of the spike addition, well within the 2σ counting error of 7% for the measurements. Thus, any recovery error was indistinguishable from counting error. Large volume samples were collected from the water column of the Eastern North Pacific in December of 1998 and processed through Mn-fiber columns. The ²²³Ra activities on the fibers were measured four or more times over a period of 2 months by the technique of [J. Geophys. Res. 101 (1996) 1321] to determine if the activity of ²²³Ra was wholly supported by ²²⁷Ac. In most cases, no significant differences in ²²³Ra activity were observed during repeated counting of the same sample, again implying that ²²³Ra was supported wholly by ²²⁷Ac. In samples where unsupported ²²³Ra were present, samples were counted beyond five half live of the ²²³Ra (>60 days). Two depth profiles of ²²⁷Ac in the Eastern North Pacific showed similar shape and activity to profiles in the Western and Central Pacific measured with alpha-spectrometry by [Nature 310 (1984) 486). Surface waters of the Southern Ocean were relatively enriched in ²²⁷Ac compared to Eastern North Pacific waters, possibly indicating export of the parent ²³¹Pa from Atlantic surface waters or upwelling.     

Different partitioning among thorium isotopes in seawater of the Northern North pacific

Each about 400 l of seawater sample was collected in the northern North Pacific and filtered through a membrane filter. Four radioisotopes of thorium,²³²Th,²³⁰Th,²²⁸Th and²³⁴Th, were determined for the two FractionsF (filtrate) andP (particles on the filter). In the percentages of FractionP in the subsurface water,²³⁰Th was significantly larger than other 3 isotopes, and²³²Th was significantly smaller than other 3 isotopes. The former finding can be explained by the slower rates in the reversible change between the FractionsF andP. The latter one, however, cannot be explained if thorium isotopes in the FractionF are truly dissolved with the same chemical form. This suggests that major part of the FractionF of²³²Th is not identical with those of other radiogenic thorium isotopes, and it should not be composed of simple dissolved ions. The removal of radiogenic²³⁴Th was related to the biological activity, but there was a deviation, between the FractionP and radioactivity deficiency of²³⁴Th in their vertical profiles. The deviation was similar to that between the chlorophylla and phaeo-pigments contents including their maximum depths.     

Impact of the Mediterranean Outflow Water on particle dynamics in intermediate waters of the Northeast Atlantic, as revealed by Th and Th

Over the last decade ²³⁴Th has become increasingly used to study particle transport in the ocean on a timescale of weeks. The application of ²³⁴Th is mainly focused on the determination of particle and associated carbon fluxes from oceanic surface water. However, ²³⁴Th is also suitable for investigating particle dynamic from the upper ocean down to interface sediments, as illustrated by the present work which reports unexpected behavior of ²³⁴Th in intermediate waters associated with the Mediterranean Outflow Water (MOW). Concentration profiles of dissolved ²³⁸U and ²²⁸Ra, and dissolved and particulate ²³⁴Th and ²²⁸Th were measured in the Mediterranean Outflow Water (MOW) near the Gibraltar Straits and at two sites (36°30′N–15°35′W, Nicole; 36°27′N–10°35′W, Yseult) which had hydrographic characteristics of Meddies, i.e. MOW that propagates as eddies in the Northeastern Atlantic at intermediate depths.There are marked differences in the distribution of thorium between MOW and the surrounding Atlantic waters. At the youngest Meddy Nicole salinity maximum at 1000 m depth, ²³⁴Th(total) : ²³⁸U and ²²⁸Th(total) : ²²⁸Ra activity ratios are significantly lower than radioactive equilibrium, indicating an unusual deficit of short half-life thorium nuclides. This implies an export of thorium, presumably on particles, from intermediate Meddy Nicole waters. This process is supported by an increase of particulate thorium fluxes measured in sediment traps deployed for two weeks above and within Meddy Nicole. In contrast, offshore Meddy Yseult has more typical profiles of both thorium nuclides that are nearly in equilibrium with their parents. These results indicate that at intermediate depths, the presence of MOW affects the exchange of reactive elements between particles and dissolved forms and enhances the downward flux of particles from intermediate waters in the Northeast Atlantic.     

<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.     

不平衡铀系和钍系核素的γ谱测定

求解初始时刻子体活度不为零时两个子体级连衰变动力学方程,给出γ谱分析测量不平衡铀系和钍系核素活度的计算公式.作为应用测量了两个沉积物样品中的238U,234Th,226Ra,222Rn,228Ra,228Th,224Ra,212Pb,210Pb和40K的活度.     

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 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.     

An assessment of particulate organic carbon to thorium-234 ratios in the ocean and their impact on the application of Th as a POC flux proxy

Thorium-234 is increasingly used as a tracer of ocean particle flux, primarily as a means to estimate particulate organic carbon export from the surface ocean. This requires determination of both the ²³⁴Th activity distribution (in order to calculate ²³⁴Th fluxes) and an estimate of the C / ²³⁴Th ratio on sinking particles, to empirically derive C fluxes. In reviewing C / ²³⁴Th variability, results obtained using a single sampling method show the most predictable behavior. For example, in most studies that employ in situ pumps to collect size fractionated particles, C / ²³⁴Th either increases or is relatively invariant with increasing particle size (size classes > 1 to 100s μm). Observations also suggest that C / ²³⁴Th decreases with depth and can vary significantly between regions (highest in blooms of large diatoms and highly productive coastal settings). Comparisons of C fluxes derived from ²³⁴Th show good agreement with independent estimates of C flux, including mass balances of C and nutrients over appropriate space and time scales (within factors of 2–3). We recommend sampling for C / ²³⁴Th from a standard depth of 100 m, or at least one depth below the mixed layer using either large volume size fractionated filtration to capture the rarer large particles, or a sediment trap or other device to collect sinking particles. We also recommend collection of multiple ²³⁴Th profiles and C / ²³⁴Th samples during the course of longer observation periods to better sample temporal variations in both ²³⁴Th flux and the characteristic of sinking particles. We are encouraged by new technologies which are optimized to more reliably sample truly settling particles, and expect the utility of this tracer to increase, not just for upper ocean C fluxes but for other elements and processes deeper in the water column.