Particle-reactive Radionuclides Research Articles

222Rn, 210Pb and 210Po in coastal zone groundwater: Activities, geochemical behaviors, consideration of seawater intrusion effect, and the potential radiation human-health risk

Groundwater quality in human-influenced coastal landscapes is receiving novel attention. Radionuclides have been recognized as another important monitoring indicator in many developed countries due to the discovery of extremely high level of natural 210Po (up to 10,000 Bq/m3) and radium and radon isotopes. This study aims to evaluate the groundwater quality in the Beibu Bulf-Guangxi coast from radiological point of view. 210Po, 210Pb and 222Rn activities in 20 wells ranged from 0.24 ± 0.05 to 6.96 ± 1.62 Bq/m3, 2.17 ± 0.12 to 13.08 ± 0.74 Bq/m3 and 1500 ± 200 to 31,800 ± 900 Bq/m3, respectively. Compared with research data of other countries, groundwaters in this area have 210Po, 210Pb and 222Rn activity within low levels. The large deficiencies of 210Po and 210Pb relative to 222Rn in groundwaters implied that 210Po and 210Pb are strong particle-reactive radionuclides and they might be controlled by similar scavenging processes in groundwaters due to a good positive correlation between 210Pb and 210Po (R2 = 0.67, p < 0.01). The concentrations of 210Po and 210Pb decreased with increasing pH values and salinity, which indicated that geochemical behaviors of 210Po and 210Pb in groundwater were influenced by seawater intrusion and pH changing. Groundwater 222Rn activity concentrations decreased with increasing salinity in coastal zone, which may be caused by dilution due to seawater intrusion or intensified 222Rn escaping from well-developed pores in coastal zone. The estimated annual ingestion doses for infants, children and adults were well below the recommended reference dose level (RDL) of 0.2–0.8 mSv/a, suggesting that consumption of analyzed groundwaters is safe from radiological point of view.

Distribution of Pu isotopes and 210Pb in the Bohai Sea and Yellow Sea: Implications for provenance and transportation

Particle-reactive radionuclides are useful for tracing sediment dynamics in marginal seas. We collected a suite of surface sediment samples in May 2014 from the Bohai Sea (BS) and Northern Yellow Sea (NYS) to observe the spatial distribution of Plutonium (Pu) isotopes and 210Pb activities. 239+240Pu activities ranged from 0.001 to 0.288 and 0.040–0.269 Bq kg−1 in BS and NYS surface sediments, respectively. 210Pbex shows a significant correlation with 239+240Pu (r = 0.84, p < 0.01) that suggested these two nuclides were scavenged to the same grade. 240Pu/239Pu atom ratios in BS (0.173–0.256) and NYS (0.196–0.275) were slightly higher than the global fallout value of 0.18 and lower than the Pacific Proving Ground (PPG) value of 0.36, indicating that some fraction of Pu originating from the PPG was capable of being transported to the BS and NYS. Mass balance results showed that 41% of 239+240Pu (8.9 × 109 Bq yr−1) and 18% of 210Pb (2.4 × 1012 Bq yr−1) in the NYS originated in the oceanic input. In the BS, 63% of 210Pb originated from atmospheric deposition and 84% of 239+240Pu originated from riverine input. Using Pu and 210Pb as tracers, we estimate that (1.8–2.6) × 108 t yr−1 and (3.6–3.8) × 108 t yr−1 of sedimentary particles could be transported from the BS to the NYS and from the NYS to the Southern Yellow Sea, respectively. Furthermore, the 226Ra/238U activity ratio distribution suggested that sedimentary particles derived from the Yellow River could be transported to the middle of the BS and coastal areas of the NYS.

Molecular Nature of Marine Particulate Organic Iron-Carrying Moieties Revealed by Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS)

Marine sinking particulate organic matter (POM), acting as a link between surface primary production and burial of organic matter in marine sediments, undergoes a variety of physical and biochemical alterations on its way to the deep ocean, resulting in an increase in its un-characterizable proportion with diagenesis. Further, the binding ligands in POM for iron, an essential nutrient to marine life and tightly coupled with organic matter, has rarely been studied. In the current study, we employed an approach combining sequential extraction with ultrahigh resolution mass spectrometry (ESI-FTICRMS), in order to explore and unravel the chemical characteristics of organic matter compounds relevant to marine particle flux within the mesopelagic and deep ocean, with a focus on the potential iron-carrying molecules. With increasing depth, POM increases in aliphaticity, and decreases in intensity-normalized O/C ratios, aromatics, and carboxylic-rich alicyclic molecules (CRAM)-like compounds. The potential iron-carrying molecules account for ~14% of total identified molecules, and appear to have been incorporated into the marine particles via ion complexation, hydrophobic interaction, and/or interlayered ‘occlusion’. The relative abundance of iron-binding organic molecules in these three operationally-defined categories changes with depth: “surficially-complexed” fraction decreases with depth, the “interlayered-occluded” fraction increases to a comparable extent and “hydrophobic interaction” fraction occurs at all depths. Collectively, the potential iron-carrying organic molecules exhibit a set of unique molecular characteristics: a relatively lower average H/C ratio and a higher O/C ratio compared to bulk POM, a dominance of aromatics, black carbon-like compounds and CRAM-like compounds, and minor amounts of aliphatics. These molecules exhibit partial similar molecular features as precursors formed from photochemical reactions in the surface ocean, but they have been greatly modified by flux processes. Noticeably, a minor fraction of these iron-carrying molecules (<1%) was identified to contain hydroxamate-like moieties (N(OH)-COOH), the key functionality of one of the strongest iron-binding ligands in the dissolved phase. This agrees with improved spectrophotometric results and corroborates their presence in the POM. These hydroxamate-like moieties play an important role in controlling the distributions and fluxes of Fe and particle-reactive radionuclides with similar chemical complexing properties as Fe (e.g., thorium) in the ocean.

The Critical Role of Bioturbation for Particle Dynamics, Priming Potential, and Organic C Remineralization in Marine Sediments: Local and Basin Scales

Bioturbation promotes priming and total remineralization of sedimentary organic matter (Corg) in multiple ways. A primary local mode is the injection of reactive Corg from the water column, surface sediment, and mucus secretions into deposits. During feeding, burrowing, and construction activities by benthic fauna, labile substrates are brought into close association with more refractory material over a wide range of time scales, geometries, and depths, enhancing decomposition of the less reactive components (priming). One measure of these local interactions is the particle mixing coefficient, DB, which can be estimated from the averaged penetration of particle-reactive radionuclides into deposits. Patterns of DB in Long Island Sound, an estuarine system with well-defined sources of naturally-occurring radionuclides, show consistent positive correlations between DB and total inventories of 234Th (t1/2 = 24 d) and 210Pb (t1/2 = 22 yr) at local and basin scales. These correlations, maintained seasonally in the case of 234Th, demonstrate not only the penetration of plankton-derived, reactive Corg into deeper regions of deposits during bioturbation over monthly (~ 5 – 10 cm) to decadal timescales (~ 20 – 100 cm) but also the enhanced capture of labile substrates from the water column across basin scales into bioturbated patches as the intensity of reworking increases. In Long Island Sound, sedimentary Chl-a distributions and benthic nutrient regeneration (e.g., NH4+ fluxes) reflect these particle exchange processes. Basin and regional scale capture of labile substrates into bioturbated deposits can be generally demonstrated, for example, along the highly productive Cape Hatteras continental margin. Thus, total and net remineralization necessarily increase with the biogenic enhancement of the quantity of labile particulate substrate in deposits. This capture, intermixing, and close association of reactive and refractory substrates (reductant mixing), and thus the optimization of priming potential, represent important, often overlooked, pathways by which bioturbation generates biogeochemical conditions conducive to maximum efficiency of remineralization.

Thorium and protactinium isotopes as tracers of marine particle fluxes and deep water circulation in the Mediterranean Sea

Abstract 231Pa, 230Th and 232 Th were analyzed in unfiltered seawater samples (n = 66) and suspended particles (n = 19) collected in the Mediterranean Sea during the MedSeA-GA04-S cruise along the GEOTRACES section GA04S and used to investigate mechanisms controlling the distribution and fractionation of Pa and Th in an ocean margin environment. 231Pa and 230 Th are particle reactive radionuclides and are often used as tracers of processes such as boundary scavenging, particle transport and ocean circulation. The depth profiles of total 231Pa and 230Th concentrations in the Mediterranean Sea displayed non-linear shapes. Higher total 232Th concentrations were observed at the straits and in deep waters pointing at lithogenic sources. Fractionation factors FTh/Pa ranged from 1.4 to 9. Application of a box-model illustrated that 94% of the 231Pa and almost all of the 230Th (99.9%) produced in the Mediterranean Sea is removed to the sediment by scavenging. The negligible export of 230Th to the Atlantic Ocean, leads to a reevaluation of the mean settling speed of the filtered particles, which is now estimated to 500–1000 m/y. The low FTh/Pa fractionation factors are attributed to the efficient scavenging and lack of transport of 231Pa to the Atlantic Ocean.

The removal of particle-reactive radionuclides in shallow water: Bottom scavenging versus particle settling of iodine-131 and beryllium-7

In pelagic waters, the removal of particle-reactive radionuclides is controlled by nuclide sorption to particles and subsequent settling by gravity. However, in shallow nearshore waters, the dominant mechanism of nuclide scavenging is not so clear. Understanding how particle-reactive radionuclides are scavenged from the water column is critical if these tracers are to be used as proxies of particle flux in shallow aquatic systems. In this study, we present evidence that the removal of particle-reactive radionuclides in nearshore and turbulent waters is primarily controlled by bottom scavenging. Specifically, we measured both water column and bottom sediment activities of sewage-sourced iodine-131 (131I, t ½ = 8.02 days) and atmospherically-sourced beryllium-7 (7Be, t ½ = 53.3 days) in a semi-enclosed harbor. We show that the water column 7Be/131I flux ratio that is required to sustain observed harbor bottom inventories of both nuclides is incongruent with 7Be/131I activity ratios on water column particles, and (2) 131I and 7Be derived mass fluxes of particulate matter to the harbor bottom are in concordance with each other and independently made estimates of river sediment loading to the harbor only when bottom scavenging of both particle-bound and dissolved (<0.7 μm) nuclide fractions are considered.

Continuous transport of Pacific-derived anthropogenic radionuclides towards the Indian Ocean

Unusually high concentrations of americium and plutonium have been observed in a sediment core collected from the eastern Lombok Basin between Sumba and Sumbawa Islands in the Indonesian Archipelago. Gamma spectrometry and accelerator mass spectrometry data together with radiometric dating of the core provide a high-resolution record of ongoing deposition of anthropogenic radionuclides. A plutonium signature characteristic of the Pacific Proving Grounds (PPG) dominates in the first two decades after the start of the high yield atmospheric tests in 1950’s. Approximately 40–70% of plutonium at this site in the post 1970 period originates from the PPG. This sediment record of transuranic isotopes deposition over the last 55 years provides evidence for the continuous long-distance transport of particle-reactive radionuclides from the Pacific Ocean towards the Indian Ocean.

The sediment budget of an urban coastal lagoon (Jamaica Bay, NY) determined using 234Th and 210Pb

The sediment budget of Jamaica Bay (New York, USA) has been determined using the natural particle-reactive radionuclides 234Th and 210Pb. Inventories of excess thorium-234 (234Thxs, half-life = 24.1 d) were measured in bottom sediments of the Bay during four cruises from September 2004 to July 2006. The mean bay-wide inventory for the four sampling periods ranged from 3.5 to 5.0 dpm cm−2, four to six times that expected from 234Th production in the overlying water column. The presence of dissolved 234Th and a high specific activity of 234Thxs on particles at the bay inlet (∼30 dpm g−1) indicated that both dissolved and particulate 234Th could be imported into the bay from the ocean. Based on these observations, a mass balance of 234Th yields an annual input of ∼39 ± 14 × 1010 g sediment into the bay. Mass accumulation rates determined from profiles of excess 210Pb (half-life = 22.3 y) in sediment cores require annual sediment import of 7.4 ± 4.5 × 1010 g. Both radionuclides indicate that there is considerable marine-derived sediment import to Jamaica Bay, consistent with earlier work using 210Pb. Such sediment input may be important in sustaining longer-term accretion rates of salt marshes in the bay.

Activity of 210Po and 210Pb in the riverine environs of coastal Kerala on the southwest coast of India

The paper presents the systematic investigations on the activity concentrations of 210Po and 210Pb in the riverine environs of Bharathapuzha, Periyar and Kallada, the three major rivers of coastal Kerala. The radionuclides 210Po and 210Pb in sediment and water samples were separated using radiochemical methods and activity was counted using scintillation based alpha counting system. The mean value of 210Po activity in sediment samples was found to be 3.4 Bq kg−1, 40.0 Bq kg−1 and 22.5 Bq kg−1 in Bharathapuzha, Periyar and Kallada river respectively. The mean value of 210Pb activity was found to be 13.5 Bq kg−1, 88.7 Bq kg−1 and 60.8 Bq kg−1 in the sediment samples of Bharathapuzha, Periyar and Kallada river respectively. The activity ratio 210Po/210Pb shows that the radionuclides 210Po and 210Pb are not in equilibrium in the riverine environs and the accumulation of 210Pb in sediment is greater than that of 210Po. The disequilibrium between 210Po and 210Pb and the higher activity of 210Pb indicates the presence of unsupported 210Pb in the sediments. A significant correlation was observed between the concentrations of these radionuclides and organic matter content and clay minerals of the sediment samples. The low activity of 210Po and 210Pb was observed in the dissolved phase due to the removal of these particle reactive radionuclides from solution to particle. High Kd value for 210Po and 210Pb in water column indicates that there is a strong adsorption of these radionuclides on to the suspended particles in the aquatic environment, where suspended particulate matter acts as a carrier to transport and removal of 210Po and 210Pb from their site of production.

Important role of biomolecules from diatoms in the scavenging of particle‐reactive radionuclides of thorium, protactinium, lead, polonium, and beryllium in the ocean: A case study with Phaeodactylum tricornutum

Laboratory studies were conducted to examine the sorption of selected radionuclides (234Th, 233Pa, 210Po, 210Pb, and 7Be) onto inorganic (pure silica and acid‐cleaned diatom frustules) and organic (diatom cells with or without silica frustules) particles in natural seawater and the role of templating biomolecules and exopolymeric substances (EPS) extracted from the same species of diatom, Phaeodactylum tricornutum, in the sorption process. The range of partition coefficients (Kd, reported as logKd) of radionuclides between water and the different particle types was 4.78–6.69 for 234Th, 5.23–6.71 for 233Pa, 4.44–5.86 for 210Pb, 4.47–4.92 for 210Po, and 4.93–7.23 for 7Be, similar to values reported for lab and field determinations. The sorption of all radionuclides was significantly enhanced in the presence of organic matter associated with particles, resulting in Kd one to two orders of magnitude higher than for inorganic particles only, with highest values for 7Be (logKd of 7.2). Results further indicate that EPS and frustule‐embedded biomolecules in diatom cells are responsible for the sorption enhancement rather than the silica shell itself. By separating radiolabeled EPS via isoelectric focusing, we found that isoelectric points are radionuclide specific, suggesting that each radionuclide binds to specific biopolymeric functional groups, with the most efficient binding sites likely occurring in acid polysaccharides, iron hydroxides, and proteins. Further progress in evaluating the effects of diatom frustule—related biopolymers on binding, scavenging, and fractionation of radionuclides would require the application of molecular‐level characterization techniques.

Recent sediment transport and deposition in the Cap-Ferret Canyon, South-East margin of Bay of Biscay

The Cap-Ferret Canyon (CFC), a major morphologic feature of the eastern margin of the Bay of Biscay, occupies a deep structural depression that opens about 60km southwest of the Gironde Estuary. Detailed depth profiles of the particle-reactive radionuclides 234Th and 210Pb in interface sediments were used to characterise the present sedimentation (bioturbation, sediment mass accumulation, and focusing) in the CFC region. Two bathymetric transects were sampled along the CFC axis and the southern adjacent margin. Particle fluxes were recorded from the nearby Landes Plateau by means of sediment traps in 2006 and 2007. This dataset provides a new and comprehensive view of particulate matter transfer in the Cap-Ferret Canyon region, through a direct comparison of the canyon with the adjacent southern margin. Radionuclide profiles (234Th and 210Pb) and mass fluxes demonstrate that significant particle dynamics occur on the SE Aquitanian margin in comparison with nearby margins. The results also suggest show three distinct areas in terms of sedimentary activity. In the upper canyon (<500m), there is little net sediment accumulation, suggesting a by-pass area. Sediment focusing is apparent at the middle canyon (500–1500m), that therefore acts as a depocenter for particles from the shelf and the upper canyon. The lower canyon (>2000m) can be considered inactive at annual or decadal scales. In contrast with the slow and continuous accumulation of relatively fresh material that characterises the middle canyon, the lower canyon receives pulses of sediment via gravity flows on longer time scales. At decadal scale, the CFC can be considered as a relatively quiescent canyon. The disconnection of the CFC from major sources of sediment delivery seems to limit its efficiency in particle transfer from coastal areas to the adjacent ocean basin.

Evaluation of processes occurring in the bottom nepheloid layer (BNL) of an eastern Mediterranean area using 234Th/238U disequilibria

Particle-reactive radionuclide (234)Th and its ratios with the conservative (238)U were used to trace the marine processes occurring over short timescales in the bottom nepheloid layer (BNL) of seven stations in the Saronikos Gulf and the Elefsis Bay (Greece) during three seasons (summer 2008, autumn 2008 and winter 2009). Summer was considered as a steady season where low physical processes occur and stratification is well established, autumn as a commutative period and winter as period of extensive trawling and physical activities. The obtained ratio profiles showed excess of (234)Th relative to (238)U in the BNL of the sampling area during summer, caused by the dissolved fraction of (234)Th. During autumn, the situation was different with large (234)Th deficit throughout the water column leading to large export fluxes of particles from the water column. Finally, during winter the ratios showed that predominant phenomenon in the area was likely resuspension of bottom sediments. The resuspension signature was additionally evaluated by total suspended matter (TSM) inventories in the BNL. Despite the intense resuspension, small scavenging of dissolved (234)Th was recorded in the BNL resulting in high residence times of dissolved (234)Th. A 1 order of magnitude difference between dissolved and particulate (234)Th residence times was observed indicating that scavenging from dissolved to particulate (234)Th could be highly variable and, as a result, the Saronikos Gulf is a highly dynamic environment, in terms of temporal and spatial particle uptake and removal. Comparing these values to literature ones consistent results were obtained. The possibility of sediment resuspension in the BNL during winter was amplified by the bloom of phytoplankton resulting in even decreased residence times of particulate (234)Th (average values). In contrast, the respective residence times of the dissolved fraction of (234)Th in the BNL were higher showing a maximum in winter at the stations where resuspension concluded. Nevertheless, (234)Th cycling in the area is not controlled by TSM, probably due to the presence of colloids, which could play an essential role in (234)Th scavenging.

Atmospheric fluxes of 7Be and 210Pb on monthly time-scales and during rainfall events at Stony Brook, New York (USA)

The particle-reactive radionuclides 7Be and 210Pb have been employed extensively as tracers and chronometers for a variety of aquatic and terrestrial processes. Both radionuclides are delivered to the Earth's surface from the atmosphere, and in order to use them effectively as natural tracers, an understanding of variations in atmospheric fluxes of these radionuclides due to latitudinal differences and storm events is required. The monthly atmospheric fluxes of 7Be and 210Pb, measured from April-2008 to December-2009 at Stony Brook, NY, ranged from 67 to 385 Bq m−2 and 6.7 to 16.7 Bq m−2, respectively. Composite annual atmospheric fluxes over the sampling period were 3110 ± 1200 Bq m−2 y−1 for 7Be and 146 ± 50 Bq m−2 y−1 for 210Pb and were similar to geographically comparable sites. The monthly atmospheric fluxes of 7Be and 210Pb were significantly correlated with rainfall. The 7Be/210Pb ratio in the monthly samples varied seasonally, with values of ∼10–11 during the winter months and ∼20–28 during the spring – fall. The pattern of seasonal variation in 7Be fluxes and 7Be/210Pb ratios is most consistent with that observed in surface air at continental sites in which more frequent deep convective storms occur during the summer and therefore result in an increased transport of 7Be from the upper troposphere to the Earth's surface. An additional factor may be that the winds at Stony Brook were dominantly from the northwest during the winter of 2009 and so were characterized by low 7Be/210Pb ratios while in the spring, winds from the southwest brought marine air with higher 7Be/210Pb ratios to the sampling site. Fluxes of 7Be and 210Pb also were measured over two long (16–24 h) and two short (∼1 h) intense periods of rainfall in June and July 2009. Fluxes of 7Be and 210Pb continued throughout the short events, but the two radionuclides showed different patterns during the long events. While the entirety of the 210Pb flux accumulated during the first ∼1 h, 7Be continued to be accumulated over the course of both long events. The 7Be/210Pb ratio ranged from 20 to ∼300 during the events and, in general, was considerably greater than the ratios measured in the monthly samples. Radar image snapshots taken during the events show cloud heights of 7–10.5 km, and the 7Be/210Pb ratios measured in the precipitation are consistent with previous model estimates of 7Be/210Pb ratios in aerosols at altitudes of 5–10 km (latitude 40°N). The data suggest that 210Pb can be effectively stripped from the lower troposphere early in a rainfall event, but intense convective mixing and scavenging of 7Be from the upper troposphere results in a continuous flux of 7Be and elevated 7Be/210Pb ratios as the event progresses.

234Th in different size classes of sediment trap collected particles from the Northwestern Pacific Ocean

234Th, a surface area specific particle-reactive radionuclide has been used to estimate particulate organic carbon (POC) export fluxes, based on the POC/234Th ratio of sinking particles and the 234Th flux, in the ocean. The POC/234Th ratios from large particles (>50μm) are conventionally considered to represent sinking particles (collected by sediment traps), but this assumption has not been thoroughly tested. More recently, Hung and Gong (2010) separated sinking particles from the northern South China Sea (where diatoms are the most dominant group) using different Nitex screens and found that small (<50μm) sinking particles dominate the bulk 234Th and POC flux. However, the size distribution of sinking particles has seldom been measured in picoplankton-dominated oligotrophic and upwelling conditions. Here we used Nitex screens to separate sinking particles in oligotrophic and upwelling regions. Additionally, images of selected bulk sinking particles (not subject to sequential filtration) were directly taken by scanning electron microscopy (SEM) to determine the size distribution of sinking particles. Within the trap-collected 234Th pool in the upwelling area, the 1–10 and 10–50μm fractions had, on average, the highest amounts of 234Th, while POC did not show significant variations among the different size fractions. In the oligotrophic region, the 10–50 and 1–10μm fractions had, on average, the highest amounts of 234Th, while the >150 and 10–50μm had elevated shares of POC. Results thus demonstrate that 234Th was mainly carried by the smaller (<50μm) sinking particles (∼70–80% of the total). SEM images of bulk sinking particles demonstrate that sinking particles contained abundant diatom cells, fecal pellets, detritus and small particle aggregates, mostly smaller than 50μm. These images show that particles smaller than 50μm indeed can account for a major fraction of the bulk sinking particles in open ocean regions. While the sequentially size-fractionated filtration might have influenced the original size distribution of sinking particles to some extent, the results provide new and consistent data which suggest that the contribution of particles smaller than 50μm to the sinking 234Th flux can be a major fraction of the total sinking flux of this isotope, and thus, particles smaller than 50μm cannot be ignored because the POC/234Th ratio that is often used is that of large (>50μm) particles obtained from pump systems, not traps.

Distribution patterns of particle-reactive radionuclides in sediments off eastern Hainan Island, China: Implications for source and transport pathways

The study of sediment sources and transport processes from land to ocean can help in predicting the fate of the pollutants released from land or the potential change in sediment delivery to coastal areas and/or open oceans. The activities of 7Be, excess 210Pb (210Pbxs), excess 234Th (234Thxs) and 137Cs in surface sediments collected offshore of eastern Hainan Island, China, in August of 2008 were measured by an HPGe γ-spectrometer to evaluate the sediment source and transport processes. The results showed that all the surface sediments were silt or sand, and the mean grain sizes of the northern locations were higher than those in the other regions. The ranges of activities of 7Be, 210Pbxs, 234Thxs and 137Cs in surface sediment were 0.14–12.7, 37.4–199, 2.24–176 and 0.02–1.06Bqkg−1, with averages of 3.78±4.77, 110±8.1, 66.7±8.9 and 0.52±0.22Bqkg−1, respectively. The activities of the radionuclides increased from coast to offshore in the northern section. The upwelling may cause high particle fluxes with high activities of 210Pbxs and 234Thxs. A comparison of the source and transport of the suspended sediments with river discharge along the coast shows that the coastal current and offshore upwelling are the dominant factors for the transport and sources of surface sediment in the study region. The sediment was transported from south to north by the coastal current, and sediments with a large grain size may be deposited via the north loop current. The ratios of the nuclide activities indicated that the suspended particles need approximately one year to be removed from the water column into the seabed and that the main source of the sediments off eastern Hainan Island in the study regions was terrigenous deposits.

Modelling the reworking effects of bioturbation on the incorporation of radionuclides into the sediment column: implications for the fate of particle-reactive radionuclides in Irish Sea sediments

A microcosm laboratory experiment was conducted to determine the impact of biological reworking by the ragworm Nereis diversicolor on the redistribution of particle-bound radionuclides deposited at the sediment–water interface. Over the course of the 40-day experiment, as much as 35% of a 137Cs-labelled particulate tracer deposited on the sediment surface was redistributed to depths of up to 11 cm by the polychaete. Three different reworking models were employed to model the profiles and quantify the biodiffusion and biotransport coefficients: a gallery-diffuser model, a continuous sub-surface egestion model and a biodiffusion model. Although the biodiffusion coefficients obtained for each model were quite similar, the continuous sub-surface egestion model provided the best fit to the data. The average biodiffusion coefficient, at 1.8 ± 0.9 cm 2 y −1, is in good agreement with the values quoted by other workers on the bioturbation effects of this polychaete species. The corresponding value for the biotransport coefficient was found to be 0.9 ± 0.4 cm y −1. The effects of non-local mixing were incorporated in a model to describe the temporal evolution of measured 99Tc and 60Co radionuclide sediment profiles in the eastern Irish Sea, influenced by radioactive waste discharged from the Sellafield reprocessing plant. Reworking conditions in the sediment column were simulated by considering an upper mixed layer, an exponentially decreasing diffusion coefficient, and appropriate biotransport coefficients to account for non-local mixing. The diffusion coefficients calculated from the 99Tc and 60Co cores were in the range 2–14 cm 2 y −1, which are consistent with the values found by other workers in the same marine area, while the biotransport coefficients were similar to those obtained for a variety of macrobenthic organisms in controlled laboratories and field studies.

Hydrochemistry and weathering rates on Corumbataí River basin, São Paulo State, Brazil

This work was held at the Corumbataí River basin that is inserted within the giant Paraná sedimentary basin (Paleozoic–Cenozoic) in South America. The Corumbataí River is the major river draining the area and its water is extensively used by water supply systems in the basin. Its surface waters were collected at two sampling points, upstream and downstream from Rio Claro city, the principal municipality within the basin. We report chemical and radionuclides (222Rn and 210Po) analyses for rainwater and river water samples in order to estimate chemical weathering fluxes. All major chemical data indicated poorer conditions of the water quality in Corumbataí River after reaching Rio Claro city. However, one very important finding was that the weighted mean of the 210Po activity concentration is the same (0.21 dpm/L) upstream and downstream from Rio Claro city, indicating that 210Po is a conservative nuclide. The net output flux in Corumbataí River basin estimated from the difference between the total discharge flux and the input flux based on wet precipitation yielded a negative value for polonium as it is a very particle-reactive radionuclide, tending to accumulate into fluvial sediments. The chemical weathering rate (removed material quantity) corresponded to 76.5 t/km2 yr when Po data in sediments and rocks were utilized in the calculations. This rate is compatible with others determined elsewhere, indicating the usefulness of Po in studies of weathering processes, even in areas characterized by anthropogenic inputs.

The importance of tides for sediment dynamics in the deep sea—Evidence from the particulate-matter tracer 234Th in deep-sea environments with different tidal forcing

Key aspects of deep-ocean fluid dynamics such as basin-scale (residual) and tidal flow are believed to have changed over glacial/interglacial cycles, with potential relevance for climatic change. To constrain the mechanistic links, magnitudes and temporal succession of events analyses of sedimentary paleo-records are of great importance. Efforts have been underway for some time to reconstruct residual-flow patterns from sedimentary records. Attempts to reconstruct tidal flow characteristics from deep-sea sediment deposits, however, are at a very early stage and first require a better understanding of the reflection of modern tides in sediment dynamics. In this context internal (baroclinic) tides, which are formed by the surface (barotropic) tide interacting with seafloor obstacles, are believed to play a particularly important role. Here we compare two modern deep-sea environments with respect to the effect of tides on sediment dynamics. Both environments are influenced by kilometre-scale topographic features but with vastly different tidal forcing: (1) two sites in the Northeast Atlantic (NEA) being surrounded by, or located downstream of, fields of short seamounts (maximum barotropic tidal current velocities ∼5 cm s −1); and (2) a site next to the Anaximenes seamount in the Eastern Mediterranean (EMed) (maximum barotropic tidal current velocities ∼0.5 cm s −1). With respect to other key fluid-dynamical parameters both environments are very similar. Signals of sedimentary particle dynamics, as influenced by processes taking place in the bottom boundary layer, were traced by the vertical water-column distribution of radioactive disequilibria (daughter/parent activity ratios≠1) between the naturally occurring, short-lived (half-life: 24.1 d) particulate-matter tracer 234Th relative to its very long-lived and non-particle-reactive parent nuclide 238U. Activity ratios of 234Th/ 238U<1 in water samples collected near the seafloor indicate fast 234Th scavenging onto particles followed by fast settling of these particles from the sampled parcel of water and, therefore, imply active sediment resuspension and dynamics on time scales of up to several weeks. In the Northeast Atlantic study region tides (in particular internal tides) are very likely to locally push total current velocities near the seafloor across the critical current velocity threshold for sediment erosion or resuspension whereas in the Eastern Mediterranean the tides are much too weak for this to happen. This difference in tidal forcing is reflected in a difference of the frequency of the occurrence of radioactive disequilibria <1 between total 234Th and 238U: In the near-bottom water column of the Northeast Atlantic region 59% of samples had detectable 234Th/ 238U disequilibria whereas at the Eastern Mediterranean site this fraction was only 7% (including a few disequilibria >1). The results of this study, therefore, add to the evidence suggesting that tides in the deep sea of the open oceans are more important for sediment dynamics than previously thought. It is hypothesised that (a) tide/seamount interactions in the deep open ocean control the local distribution of erosivity proxies (e.g., distributions of sediment grain sizes, heavy minerals and particle-reactive radionuclides) in sedimentary deposits and (b) the aforementioned topographically controlled sedimentary imprints of (internal) tides are useful in the reconstruction of past changes of tidal forcing in the deep sea.

Constraints on the utility of MnO2 cartridge method for the extraction of radionuclides: A case study using 234Th

Large volume (102–103 L) seawater samples are routinely processed to investigate the partitioning of particle reactive radionuclides and Ra between solution and size‐fractionated suspended particulate matter. One of the most frequently used methods to preconcentrate these nuclides from such large volumes involves extraction onto three filter cartridges (a prefilter for particulate species and two MnO2‐coated filters for dissolved species) connected in series. This method assumes that the extraction efficiency is uniform for both MnO2‐coated cartridges, that no dissolved species are removed by the prefilter, and that any adsorbed radionuclides are not desorbed from the MnO2‐coated cartridges during filtration. In this study, we utilized 234Th‐spiked coastal seawater and deionized water to address the removal of dissolved Th onto prefilters and MnO2‐coated filter cartridges. Experimental results provide the first data that indicate (1) a small fraction of dissolved Th (&lt;6%) can be removed by the prefilter cartridge; (2) a small fraction of dissolved Th (&lt;5%) retained by the MnO2 surface can also be desorbed, which undermines the assumption of uniform extraction efficiency for Th; and (3) the absolute and relative extraction efficiencies can vary widely. These experiments provide insight on the variability of the extraction efficiency of MnO2‐coated filter cartridges by comparing the relative and absolute efficiencies and recommend the use of a constant efficiency on the combined activity from two filter cartridges connected in series for future studies of dissolved 234Th and other radionuclides in natural waters using sequential filtration/extraction methods.

Advection and scavenging: Effects on 230Th and 231Pa distribution off Southwest Africa

We investigated the controls of hydrography and of scavenging on the distribution of the particle reactive radionuclides 231Pa and 230Th in the water column and in surface sediments off Southwest Africa (Angola and Cape basins). Based on a vertical section of total 230Th ex concentrations in the water column we show that small differences in the salinity between the North Atlantic Deep Water (NADW) in the Angola Basin and the NADW in the Cape Basin as well as the advection of NADW associated with the Namib Col Current are reflected in total 230Th ex concentrations. These variable total concentrations are believed to reflect the flow path and mixing history of NADW with the NADW in the Angola Basin being relatively older and 230Th enriched compared to the NADW in the Cape Basin. In the area investigated we found high 231Pa ex/ 230Th ex ratios ( 231Pa ex/ 230Th ex > 0.093) in surface sediments at the continental margin and lower ones ( 231Pa ex/ 230Th ex < 0.093) in the open ocean. Such a distribution is normally interpreted to result from high particle flux at ocean margins (boundary scavenging). However, the lack of any significant depletion of dissolved 230Th and 231Pa in the water column does not indicate extensive scavenging at the continental margin. High 231Pa ex/ 230Th ex ratios are constrained to shallow waters depths (< 2000 m) only and coincide with low fractionation between 231Pa and 230Th indicating that preferential scavenging of 231Pa on opal may have caused high 231Pa ex/ 230Th ex ratios in the sediments. The observed close negative correlation ( r 2 = 0.82) between 231Pa ex/ 230Th ex ratios in sediments and water depths is believed to reflect changes in the particle composition, i.e. a decrease in opal content with water depth. In the Angola and Cape basins the total 231Pa ex concentrations in NADW were the highest observed so far in the Atlantic Ocean, and they are attributed to the meridional export of 231Pa from the North Atlantic. This caused the average dissolved 231Pa/ 230Th in the Southeast Atlantic to be about a factor 2 higher when compared to the North Atlantic (Labrador Sea). These differences in the dissolved 231Pa/ 230Th were not reflected in 231Pa/ 230Th ratios of surface sediments because the fractionation is lower in the Labrador Sea compared to the Southeast Atlantic, i.e. fractionation counteracts changes in the dissolved 231Pa/ 230Th. This suggests that fractionation is more important for the determination of 231Pa ex/ 230Th ex ratios in sediments than the meridional export of 231Pa from the North Atlantic.