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.     

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.     

Measuring low concentrations of Th in water and sediment

²³⁴Th/²³⁸U disequilibria have been used extensively in studies of particle dynamics and the fate and transport of particle-reactive matter in marine environments. Similar work in low salinity, estuarine, and freshwater systems has not occurred primarily because the lower concentrations of both parent and daughter nuclides that are typical of these systems often render established methods for the analysis of ²³⁴Th inadequate. The application of this radionuclide tracer technique to these systems, however, has great potential. To this end, we present a method for measuring low activities of ²³⁴Th in relatively small samples (<200 l) using low background gas-flow proportional counters, a ²²⁹Th yield monitor, and empirical corrections for the interferences from real and apparent betas that are emitted by other thorium isotopes and their progeny. For samples with low ²³⁴Th/²²⁸Th activity ratios, we improve upon current beta counting methodologies that rely on immediate sample counting, weak beta absorption, or multiple beta counts so that, using the analytical approach outlined here, it should be possible to measure ²³⁴Th activities (i) as low as 1.5 dpm/total sample, (ii) up to 2 weeks after radiochemical purification of thorium, and (iii) with only one sample count for alpha and beta activity.     

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.     

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...     

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.     

<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.     

POC export from ocean surface waters by means of Th/U and Po/Pb 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.     

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.     

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.     

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

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

Flocculation and phytoplankton cell size can alter Th-based estimates of the vertical flux of particulate organic carbon in the sea

The deficit of ²³⁴Th relative to its radioactive parent ²³⁸U in the surface ocean can yield reliable estimates of vertical Particulate Organic Carbon (POC) fluxes to deeper waters, but only when coupled with an accurate ratio of POC concentration to activity of ²³⁴Th on sinking matter. Assuming a simple partitioning of suspended phytoplankton mass between single cells and flocs, we calculate the ratio of the POC flux estimated from ²³⁴Th deficit to the actual POC flux (p ratio, Smith, J.N., Moran, S.B., Speicher, E.A., in press. The p-ratio: a new diagnostic for evaluating the accuracy of upper ocean particulate organic carbon export fluxes estimated from ²³⁴Th/²³⁸U disequilibrium. Deep-Sea Research I.). The p ratios are calculated under the assumption that particle surface area is correlated with ²³⁴Th activity and particle volume is correlated with POC concentration. The value of the p ratio depends on the relative contributions of single cells and flocs to the vertical flux. When large single cells make up a significant fraction of the vertical flux, p ratios are less than one, meaning POC fluxes estimated from ²³⁴Th deficits underestimate actual POC fluxes. When large single cells are abundant but do not sink fast enough to contribute to vertical POC flux, p ratios are greater than one (up to 3 × overestimate). Factor analysis of the model indicates that altering the extent of flocculation in suspension and changing the density and maximum size of phytoplankton cells have the greatest effects on the p ratio. Failure to measure the properties of flocs when characterizing the ratio of POC to thorium on sinking matter potentially leads to large overestimation of the POC flux (over 20 ×). Failure to characterize the POC to thorium ratio of large particles, by, for example, destruction of phytoplankton cells in pumps, can lead to underestimation of POC flux. Estimates of POC flux should be most reliable in highly flocculated suspensions populated by small cells and rapidly sinking flocs. These conditions are often associated with intense phytoplankton blooms.     

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.     

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.     

Do bottom mixed layers influence 234Th dynamics in the abyssal near-bottom water column?

Dynamics of the natural radioactive particle tracer ²³⁴Th (half-life: 24.1 days) within the abyssal water column up to 1000 m above bottom and within surface sediments of the northeast Atlantic (Porcupine Abyssal Plain; depth: ≈4845 m) were investigated. Distributions of transmissometer voltages and potential temperature indicated a subdivision of the near-bottom water column into a benthic mixed layer (BML; thickness: ≈10–65 m) and the layer above the BML up to the upper boundary of the bottom nepheloid layer (BNL; thickness: ≈1000 m). Comparison of ²³⁴Th fluxes (dpm m⁻²d⁻¹) in sediment traps, vertical fluxes derived from ²³⁴Th/²³⁸U-disequilibrium in the near-bottom water column and excess ²³⁴Th inventories in the surface sediment provided evidence for lateral advection of ²³⁴Th-depleted water and a ‘missing sink’ for ²³⁴Th. A simple one-dimensional steady-state box-model approach was applied to investigate ²³⁴Th dynamics. Estimated residence times suggest the BML and the resuspension zone of the surface sediment to be highly dynamic systems with respect to particle cycling and sorptive reactions on a time scale of weeks. Model results indicate that, through the chemical forcing of changing particle concentration, a thickening BML results in (1) increasing residence times of particulate ²³⁴Th in the BML with respect to the net fluxes across the upper boundary of the BML and into the surface sediment; (2) declining adsorption rate constants in the BML; (3) increasing desorptive fluxes in the BML resulting in (4) enhanced ²³⁴Th decay in the BML; (5) decreasing net fluxes of particulate ²³⁴Th from the BML to the upper BNL above the BML and to the sediment. Potential consequences for carbon cycling in the water column of the deep ocean are discussed.     

An improvement in the small-volume technique for determining thorium-234 in seawater

The recently developed 2–5 L small-volume MnO₂ coprecipitation method for determining ²³⁴Th in seawater has provided a new way to substantially increase, both temporally and spatially, the sampling resolution of ²³⁴Th and ²³⁴Th-based particulate organic carbon export estimates in the upper ocean. In this study, we further optimize the technique by reducing reagent quantities and the use of an additional water bath heating step. This optimization allows the filtration of the MnO₂ precipitate onto a 25-mm diameter, 1.0 μm pore size QMA filter to be completed within < 30 min for unfiltered waters from the South China Sea. In addition, we have modified the MnO₂ purification procedure to allow for alpha spectrometric measurements of ²³⁴Th recoveries. Results from recovery experiments suggest that reagent amounts can be reduced to 0.0375 mg KMnO₄ and 0.1 mg MnCl₂·4H₂O per liter of sample, while still maintaining high ²³⁴Th recovery. This study further confirms that the addition of a yield monitor is necessary for the application of the small-volume method.     

Sensitivity of 234Th export to physical processes in the central equatorial Pacific

We determined the sensitivity of the calculated sinking flux of ²³⁴Th in the central equatorial Pacific to physical processes and scavenging mechanisms by imposing a meridional and vertical advection and diffusion field on a simple dissolved and particulate ²³⁴Th cycle. We used the model to estimate the efficiency with which the ²³⁴Th deficiency relative to ²³⁸U reflected the predicted sinking flux of ²³⁴Th on particles and compared our results with ²³⁴Th data taken during the JGOFS-EqPac 1992 Survey II Cruise. ²³⁴Th deficiencies near the equator were strongly affected by both vertical advection and horizontal diffusion. The model ²³⁴Th deficiency at the equator underestimated the model ²³⁴Th sinking flux by 144% in neglecting advection and diffusion in the presence of strong upwelling at the equator. The model ²³⁴Th deficiency at the equator corrected for advection overestimated the sinking flux of ²³⁴Th by 33% in neglecting horizontal diffusion. Analysis of the scavenging mechanism suggests that, during situations of export governed by rapidly sinking particles, ²³⁴Th-based estimates of particle export are only half as sensitive to advection compared to situations of export governed by slowly sinking particles. Given that results using the mechanism of slowly sinking particles compare better with the observed ²³⁴Th deficiency and calculated meridional ²³⁴Th fluxes at the equator than the mechanism of rapidly sinking particles, we consider the mechanism of slowly sinking particle more appropriate for this region. In agreement with previous studies based on observed ²³⁴Th gradients, this study supports the incorporation of vertical advection terms in the ²³⁴Th balance to estimate particulate carbon export at the equator but suggests that this method may have overestimated the sinking flux at the equator during EqPac Survey II by 0–63% due to the role of horizontal diffusion.     

生物固氮速率测定中15N2同位素示踪剂的引入

生物固氮作用是一个重要的海洋新氮来源,在海洋生物地球化学循环中扮演着不可替代的角色。基于稳定同位素（15N₂）示踪吸收法,是目前直接测定海洋生物固氮速率最有效的手段。其中,高效、洁净地将15N₂引入海水培养体系,并准确定量培养体系底物的同位素示踪水平,是同位素示踪吸收法准确获取固氮速率的关键。本研究针对15N₂同位素示踪剂引入这一关键环节进行了探讨,确认改进气泡法是将15N₂引入海水培养体系的首选操作。在对培养体系造成的较小扰动的情况下,可将培养体系氮气底物的15N原子丰度提升至10%以上,相对于另一种导入同位素示踪剂的手段——预溶解海水法,改进气泡法将培养瓶中氮气底物的15N原子丰度提升了近200%。此外,改进气泡法还具有最小化痕量金属沾污、操作简便等优点。将改进气泡法结合与稳定同位素比值质谱测定结合,是准确测定水体生物固氮速率的推荐方法。     

The POC / Th ratio of settling particles isolated using split flow-thin cell fractionation (SPLITT)

The common assumption that the ratio between particulate organic carbon (POC) and particulate ²³⁴Th obtained from shallow sediment traps and filterable particles are representative of the ratio in the total particle settling flux should be treated with caution in view of well-known biases associated with tethered shallow sediment traps and the decoupling between size and settling velocity of many natural particle regimes. To make progress toward reliably constraining the POC / ²³⁴Th ratio on truly settling particles, we have tested here a settling collection technique designed to remove any hydrodynamic bias; split flow-thin cell fractionation (SPLITT). These first results from a North Sea fjord and an open Baltic Sea time-series station indicates that the POC / ²³⁴Th ratio on the more complete particle-settling spectrum, isolated with SPLITT, was higher than the POC / ²³⁴Th ratio obtained simultaneously from tethered shallow sediment traps in seven out of seven parallel deployments with an average factor of 210%. The POC / ²³⁴Th ratio from the SPLITT was either in the same range or higher than that obtained on filtered “bulk” particles. To explain this novel data we hypothesize that the slowest settling fraction is organic-matter rich and does not strongly complex ²³⁴Th (i.e., high POC / ²³⁴Th). We suggest that this ultra-slow sinking fraction is better collected by SPLITT than with tethered sediment traps because of minimized hydrodynamic bias.This was tested using the ratio of POC / Al as a tracer of detrital mineral-ballast influenced settling velocity. The higher POC / Al ratios in SPLITT samples relative to in traps is consistent with the hypothesis that SPLITT is better suited for collecting also the slow-settling component of sinking particles. This important slow-settling component appears to here consist primarily of non-APS/TEP components of plankton exudates or other less-strongly ²³⁴Th-complexing organic matter. Further applications of the SPLITT technique are likely to return increasingly new insights on the composition (including “truly settling” POC / ²³⁴Th) of the total spectrum of particles settling out of the upper ocean.     

Thorium speciation in seawater

Since the 1960s, thorium isotopes occupy a special place in the oceanographer's toolbox as tracers for determining rates and mechanisms of oceanic scavenging, particle dynamics, and carbon fluxes. Due to their unique and constant production rates from soluble parent nuclides of uranium and radium, their disequilibrium can be used to calculate rates and time scales of sinking particles. In addition, by ratio-ing particulate ²³⁴Th (as well, in principle, other Th-nuclides) to carbon (and other elements), and linking this ratio to the parent–daughter disequilibrium in the water column, it is possible to calculate fluxes of carbon and other elements. Most of these applications are possible with little knowledge of the dissolved chemical properties of thorium, other than its oxidation state (IV) and tendency to strongly sorb to surfaces, i.e., its “particle- or surface-activity”. However, the use of any tracer is hindered by a lack of knowledge of its chemical properties. Recent observations in the variability of carbon to ²³⁴Th ratios in different particle types, as well as of associations of Th(IV) with various marine organic biomolecules has led to the need for a review of current knowledge and what future endeavors should be taken to understand the marine chemistry of thorium.