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This study provides dissolved and particulate 230Th and 232Th results as well as particulate 234Th data collected during expeditions to the central Arctic Ocean (GEOTRACES, an international project to identify processes and quantify fluxes that control the distributions of trace elements; sections GN04 and GIPY11). Constructing a time series of dissolved 230Th from 1991 to 2015 enables the identification of processes that control the temporal development of 230Th distributions in the Amundsen Basin. After 2007, 230Th concentrations decreased significantly over the entire water column, particularly between 300 and 1500 m. This decrease is accompanied by a circulation change, evidenced by a concomitant increase in salinity. A potentially increased inflow of water of Atlantic origin with low dissolved 230Th concentrations leads to the observed depletion in dissolved 230Th in the central Arctic. Because atmospherically derived tracers (chlorofluorocarbon (CFC), sulfur hexafluoride (SF6)) do not reveal an increase in ventilation rate, it is suggested that these interior waters have undergone enhanced scavenging of Th during transit from Fram Strait and the Barents Sea to the central Amundsen Basin. The 230Th depletion propagates downward in the water column by settling particles and reversible scavenging.

Since the 1980–1990s, international research efforts have augmented our knowledge of the physical and chemical properties of the Arctic Ocean water masses, and recent studies have documented changes. Understanding the processes responsible for these changes is necessary to be able to forecast the local and global consequences of these property evolutions on climate. The present work investigates the distributions of geochemical tracers of particle fluxes and circulation in the Amerasian Basin and their temporal evolution over the last three decades (from stations visited between 1983 and 2015). Profiles of 230‐thorium (230Th) and 231‐protactinium (231Pa) concentrations and neodymium isotopes (expressed as εNd) measured in the Amerasian Basin prior to 2000 are compared to a new, post‐2000s data set. The comparison shows a large scale decrease in dissolved 230Th and 231Pa concentrations, suggesting intensification of scavenging by particle flux, especially in coastal areas. Higher productivity and sediment resuspension from the shelves appear responsible for the concentration decrease along the margins. In the basin interior, increased lateral exchanges with the boundary circulation also contribute to the decrease in concentration. This study illustrates how dissolved 230Th and 231Pa, with εNd support, can provide unique insights not only into changes in particle flux but also into the evolution of ocean circulation and mixing., Key Points Concentration decreases of 230Thd and 231Pad suggest an enhancement of particulate scavenging since the 2000s in the Amerasian BasinParticulate scavenging results from higher productivity and sediment resuspension from the shelvesPost‐2000s changes in intermediate and deep layers suggest enhanced lateral mixing between the margins and central areas of the basins

This study provides dissolved and particulate 230Th and 232Th results as well as particulate 234Th data collected during expeditions to the central Arctic Ocean on ARK-XXIX/3 (2015) and ARK-XXII/2 (2007) (GEOTRACES sections GN04 and GIPY11, respectively). Constructing a time-series of dissolved 230Th from 1991 to 2015 enables the identification of processes that control the temporal development of 230Th distributions in the Amundsen Basin. After 2007, 230Th concentrations decreased significantly over the entire water column, particularly between 300 m and 1500 m. This decrease is accompanied by a circulation change, evidenced by a concomitant increase in salinity. Potentially increased inflow of water of Atlantic origin with low dissolved 230Th concentrations leads to the observed depletion in dissolved 230Th in the central Arctic. Because atmospherically derived tracers (CFC, 3He/3H) do not reveal an increase in ventilation rate, it is suggested that these interior waters have undergone enhanced scavenging of Th during transit from the Fram Strait and the Barents Sea to the central Amundsen Basin. The 230Th depletion propagates downward in the water column by settling particles and reversible scavenging. Taken together, the temporal evolution of Th distributions point to significant changes in the large-scale circulation of the Amundsen Basin.

The measurable supply of 232Th to the ocean can be used to derive the supply of other elements, which is more difficult to quantify directly. The measured inventory of an element divided by the derived supply yields a replacement time estimate, which in special circumstances is related to a residence time. As a proof of concept, Th-based supply rates imply a range in the replacement times of the rare earth elements (REEs) in the North Atlantic that is consistent with the chemical reactivity of REEs related to their ionic charge density. Similar estimates of replacement times for the bioactive trace elements (Fe, Mn, Zn, Cd, Cu and Co), ranging from 50,000 years, demonstrate the broad range of elemental reactivity in the ocean. Here, we discuss how variations in source composition, fractional solubility ratios or non continental sources such as hydrothermal vents lead to uncertainties in Th-based replacement time estimates. We show that the constraints on oceanic replacement time provided by the Th-based calculations are broadly applicable in predicting how elements are distributed in the ocean and for some elements, such as Fe, may inform us on how the carbon cycle may be impacted by trace element supply and removal.

The natural radionuclides 231Pa and 230Th are incorporated into the marine sediment record by scavenging, or adsorption to various particle types, via chemical reactions that are not fully understood. Because these isotopes have potential value in tracing several oceanographic processes, we investigate the nature of scavenging using trans-Atlantic measurements of dissolved (

Rare earth element (REE) concentrations were analyzed in surface water and submarine groundwater within the Pettaquamscutt Estuary, located on the western edge of Narragansett Bay in Rhode Island. These water samples were collected along the salinity gradient of the estuary. Rare earth element concentrations in the majority of the groundwater samples are substantially higher than their concentrations in the surface waters. In particular, Nd concentrations in groundwater range from 0.43 nmol kg − 1 up to 198 nmol kg − 1 (mean ± SD = 42.1 ± 87.2 nmol kg − 1 ), whereas Nd concentrations range between 259 pmol kg − 1 and 649 pmol kg − 1 (mean ± SD = 421 ± 149 pmol kg − 1 ) in surface waters from the estuary, which is, on average, 100 fold lower than Nd in the groundwaters. Groundwater samples all exhibit broadly similar middle REE (MREE) enriched shale-normalized REE patterns, despite the wide variation in pH of these natural waters (4.87 ≤ pH ≤ 8.13). The similarity of the shale-normalized REE patterns across the observed pH range suggests that weathering of accessory minerals, such as apatite, and/or precipitation of LREE enriched secondary phosphate minerals controls groundwater REE concentrations and fractionation patterns. More specifically, geochemical mixing models suggest that the REE fractionation patterns of the surface waters may be controlled by REE phosphate mineral precipitation during the mixing of groundwater and stream water with incoming water from the Rhode Island Sound. The estimated SGD (Submarine Groundwater Discharge) of Nd to the Pettaquamscutt Estuary is 26 ± 11 mmol Nd day − 1 , which is in reasonable agreement with the Nd flux of the primary surface water source to the estuary, the Gilbert Stuart Stream (i.e., 36 mmol day − 1 ), and of the same order of magnitude for a site in Florida.

Depth profiles of 210 Po and 210 Pb activity and phytoplankton and zooplankton abundance were collected during two cruises along the Canadian time-series Line P in the Northeast Subarctic Pacific (ranging from 48o39 N to 50o00 N and 126o40 W to 145o00 W) in August 2010 and February 2011 to evaluate connections between the planktonic community and distributions of these radionuclides in the upper 500 m of the water column. Statistical analysis indicates that 210 Po is more effectively removed from the surface ocean when large (>0.1 mg ind � 1 dry wt) zooplankton dominate, and is less effectively scavenged when the picoplankton Synechococcus is present at high concentrations (>1 � 10 5 cells ml � 1 ). While the zooplankton field data are consistent with previous lab studies and field observations, the phytoplankton results seem to conflict with recent evidence that small cells may contribute significantly to export in other oligotrophic regions. Differences in ecosystem mechanisms between the Subarctic Pacific and other oligotrophic systems that limit the contribution of small cells to sinking flux remain to be identified. 2014 Published by Elsevier Ltd.

Marshes in the urban Jamaica Bay Estuary, New York, USA are disappearing at an average rate of 13 ha/yr, and multiple stressors (e.g., wastewater inputs, dredging activities, groundwater removal, and global warming) may be contributing to marsh losses. Among these stressors, wastewater nutrients are suspected to be an important contributing cause of marsh deterioration. We used census data, radiometric dating, stable nitrogen isotopes, and soil surveys to examine the temporal relationships between human population growth and soil nitrogen; and we evaluated soil structure with computer-aided tomography, surface elevation and sediment accretion trends, carbon dioxide emissions, and soil shear strength to examine differences among disappearing (Black Bank and Big Egg) and stable marshes (JoCo). Radiometric dating and nitrogen isotope analyses suggested a rapid increase in human wastewater nutrients beginning in the late 1840s, and a tapering off beginning in the 1930s when wastewater treatment plants (WWTPs) were first installed. Current WWTPs nutrient loads to Jamaica Bay are approximately 13 995 kg N/d and 2767 kg P/d. At Black Bank, the biomass and abundance of roots and rhizomes and percentage of organic matter on soil were significantly lower, rhizomes larger in diameter, carbon dioxide emission rates and peat particle density significantly greater, and soil strength significantly lower compared to the stable JoCo Marsh, suggesting Black Bank has elevated decomposition rates, more decomposed peat, and highly waterlogged peat. Despite these differences, the rates of accretion and surface elevation change were similar for both marshes, and the rates of elevation change approximated the long-term relative rate of sea level rise estimated from tide gauge data at nearby Sandy Hook, New Jersey. We hypothesize that Black Bank marsh kept pace with sea level rise by the accretion of material on the marsh surface, and the maintenance of soil volume through production of larger diameter rhizomes and swelling (dilation) of waterlogged peat. JoCo Marsh kept pace with sea-level rise through surface accretion and soil organic matter accumulation. Understanding the effects of multiple stressors, including nutrient enrichment, on soil structure, organic matter accumulation, and elevation change will better inform management decisions aimed at maintaining and restoring coastal marshes.

Intercomparision of 234 Th measurements in both water and particulate samples was carried out between 15 laboratories worldwide, as a part of GEOTRACES inter-calibration program. Particulate samples from four dif ferent stations namely BATS (both shallow and deep) and shelf station (shallow) in Atlantic and SAFE (both shallow and deep) and Santa Barbara station (shallow) in Pacific were used in the effort. Particulate intercali bration results indicate good agreement between all the participating labs with data from all labs falling with in the 95% confidence interval around the mean for most instances. Filter type experiments indicate no signif icant differences in 234 Th activities between filter types and pore sizes (0.2‐0.8 µm). The only exception are the

Nineteen labs representing nine nations participated in the GEOTRACES intercalibration initiative that determined concentrations of 232Th, 230Th, 231Pa or 10Be in seawater, suspended particles or sediments. Results generally demonstrated good agreement among labs that analyzed marine sediments. Two sets of seawater samples, aliquots of particulate material filtered in situ, and/or aliquots of biogenic sediments were distributed to participating labs. Internal consistency among participating labs improved substantially between the first and second set of seawater samples. Contamination was a serious problem for 232Th. Standard Niskin™ bottles introduced no detectable contamination, whereas sample containers, reagents and labware were implicated as sources of contamination. No detectable differences in concentrations of dissolved 232Th, 230Th or 231Pa were observed among samples of seawater filtered through Nuclepore ™, Supor ™ or QMA™ (quartz) filters with pore diameters ranging between 0.4 and 1.0 μm. Isotope yield monitors equilibrate with dissolved Th in seawater on a time scale of much less than one day. Samples of filtered seawater acidified to a pH between 1.7 and 1.8 experienced no detectable loss of dissolved Th or Pa during storage for up to three years. The Bermuda Atlantic Time Series station will serve as a GEOTRACES baseline station for future intercalibration of 232Th and 230Th concentrations in seawater. Efforts to improve blanks and standard calibration are ongoing, as is the development of methods to determine concentrations of particulate nuclides, tests of different filtration methods, and an increasing awareness of the need to define protocols for reporting uncertainties.

In order to assess the current state of net community production (NCP) in the southeastern Bering Sea, we measured the spatio-temporal distribution and controls on dissolved inorganic carbon (DIC) concentrations in spring and summer of 2008 across six shelf domains defined by differing biogeochemical characteristics. DIC concentrations were tightly coupled to salinity in spring and ranged from ~1900 μmoles kg−1 over the inner shelf to ~2400 μmoles kg−1 in the deeper waters of the Bering Sea. In summer, DIC concentrations were lower due to dilution from sea ice melt, terrestrial inputs, and primary production. Concentrations were found to be as low ~1800 μmoles kg−1 over the inner shelf. We found that DIC concentrations were drawn down 30–150 μmoles kg−1 in the upper 30 m of the water column due to primary production and calcium carbonate formation between the spring and summer occupations. Using the seasonal drawdown of DIC, estimated rates of NCP on the inner, middle, and outer shelf averaged 28 ± 9 mmoles C m−2 d−1. However, higher rates of NCP (40–47 mmoles C m−2 d−1) were observed in the "Green Belt" where the greatest confluence of nutrient-rich basin water and iron-rich shelf water occurs. We estimated that in 2008, total NCP across the shelf was on the order of ~96 Tg C yr−1. Due to the paucity of consistent, comparable productivity data, it is impossible at this time to quantify whether the system is becoming more or less productive. However, as changing climate continues to modify the character of the Bering Sea, we have shown that NCP can be an important indicator of how the ecosystem is functioning.

The large discharge of radioactivity into the northwest Pacific Ocean from the 2011 Fukushima Dai-ichi nuclear reactor accident has generated considerable concern about the spread of this material across the ocean to North America. We report here the first systematic study to our knowledge of the transport of the Fukushima marine radioactivity signal to the eastern North Pacific. Time series measurements of (134)Cs and (137)Cs in seawater revealed the initial arrival of the Fukushima signal by ocean current transport at a location 1,500 km west of British Columbia, Canada, in June 2012, about 1.3 y after the accident. By June 2013, the Fukushima signal had spread onto the Canadian continental shelf, and by February 2014, it had increased to a value of 2 Bq/m(3) throughout the upper 150 m of the water column, resulting in an overall doubling of the fallout background from atmospheric nuclear weapons tests. Ocean circulation model estimates that are in reasonable agreement with our measured values indicate that future total levels of (137)Cs (Fukushima-derived plus fallout (137)Cs) off the North American coast will likely attain maximum values in the 3-5 Bq/m(3) range by 2015-2016 before declining to levels closer to the fallout background of about 1 Bq/m(3) by 2021. The increase in (137)Cs levels in the eastern North Pacific from Fukushima inputs will probably return eastern North Pacific concentrations to the fallout levels that prevailed during the 1980s but does not represent a threat to human health or the environment.

The long-lived uranium decay products 230Th and 231Pa are widely used as quantitative tracers of adsorption to sinking particles (scavenging) in the ocean by exploiting the principles of radioactive disequilibria. Because of their preservation in the Pleistocene sediment record and through largely untested assumptions about their chemical behavior in the water column, the two radionuclides have also been used as proxies for a variety of chemical fluxes in the past ocean. This includes the vertical flux of particulate matter to the seafloor, the lateral flux of insoluble elements to continental margins (boundary scavenging), and the southward flux of water out of the deep North Atlantic. In a section of unprecedented vertical and zonal resolution, the distributions of 230Th and 231Pa across the North Atlantic shed light on the marine cycling of these radionuclides and further inform their use as tracers of chemical flux. Enhanced scavenging intensities are observed in benthic layers of resuspended sediments on the eastern and western margins and in a hydrothermal plume emanating from the Mid-Atlantic Ridge. Boundary scavenging is clearly expressed in the water column along a transect between Mauritania and Cape Verde which is used to quantify a bias in sediment fluxes calculated using 230Th-normalization and to demonstrate enhanced 231Pa removal from the deep North Atlantic by this mechanism. The influence of deep ocean ventilation that leads to the southward export of 231Pa is apparent. The 231Pa/230Th ratio, however, predominantly reflects spatial variability in scavenging intensity, complicating its applicability as a proxy for the Atlantic meridional overturning circulation.

The naturally occurring radionuclide 234Th (t1/2 = 24.1 days) was used to examine the organic carbon cycle in the Gulf of Maine. A seasonal study (March, June, and September 1995) was conducted in the central Gulf of Maine in Wilkinson and Jordan Basins, and a regional survey, which included the Scotian Shelf, was conducted during August-September 1997. Particulate organic carbon (POC) export (particulate export production) was estimated from a three-dimensional steady state model of 234Th flux combined with measurements of the POC/234Th ratio on >53-μm particles. The POC export for this region was seasonally variable; average values ranged from 15 to 34 mmol C m−2 d−1, between 11% and 25% of the regionally integrated primary production. The Gulf of Maine was a net source (to the Mid-Atlantic Bight) of dissolved organic carbon (2.4 mmol C m−2 d−1) amounting to ∼2% of carbon uptake rates. Organic carbon burial in the sediments was a minor fraction of the primary production, averaging 1.6 mmol C m−2 d−1. Though only a fraction of total export production was buried in the sediments, these estimates close the budget for organic carbon in the Gulf of Maine. An implication is that off-shelf export may not be as important as previously estimated in this shelf region.

[1] Time series measurements of the nuclear fuel reprocessing tracers, 129I and 137Cs, and ventilation tracer, CFC-11, were used to determine circulation time scales for Atlantic Water (AW) in the Arctic Ocean. Measurements in surface water are consistent with an advection model and transit times from the North Sea of 1–4 years to the Barents Sea, 3–6 years to the Kara Sea, and 9–12 years to the North Pole. Tracer ages for intermediate waters do not support an advection model because they vary with time. The tracer relationships were employed to determine transit time distributions (TTD), using inverse Gaussian functions, that implicitly incorporate the effects of mixing in simulating fluid flow. Tracer concentrations were used to constrain the ratio of the width, Δ, of the TTD to the mean age, Γ, a measure of the relative importance of mixing, giving values for most intermediate water regimes of Δ/Γ ≤ 1. These results are in contrast to values, Δ/Γ 1 typical of the North Atlantic, indicating the greater relative importance of advection compared to mixing in the Arctic Ocean. Mean ages for AW increase from 12–20 years in the southern Makarov Basin to 30–40 years near the Arctic outflow north of Greenland. A decline in Δ/Γ with distance along the direction of AW boundary flow from the Makarov into the Canada Basin may indicate relatively stronger mixing in regimes upstream of the Makarov Basin but also implies that TTDs may differ from inverse Gaussian functions for flow in the Arctic domain.

Particle-reactive, naturally occurring radionuclides are useful tracers of the sinking flux of organic matter from the surface to the deep ocean. Since the Joint Global Ocean Flux Study (JGOFS) began in 1987, the disequilibrium between (234)Th and its parent (238)U has become widely used as a technique to measure particle export fluxes from surface ocean waters. Another radionuclide pair, (210)Po and (210)Pb, can be used for the same purpose but has not been as widely adopted due to difficulty with accurately constraining the (210)Po/(210)Pb radiochemical balance in the ocean and because of the more time-consuming radiochemical procedures. Direct comparison of particle flux estimated in different ocean regions using these short-lived radionuclides is important in evaluating their utility and accuracy as tracers of particle flux. In this paper, we present paired (234)Th/(238)U and (210)Po/(210)Pb data from oligotrophic surface waters of the subtropical Northwest Atlantic and discuss their advantages and limitations. Vertical profiles of total and particle size-fractionated (210)Po and (234)Th activities, together with particulate organic carbon (POC) concentrations, were measured during three seasons at the Bermuda Atlantic Time-series Study (BATS) site. Both (210)Po and (234)Th reasonably predict sinking POC flux caught in sediment traps, and each tracer provides unique information about the magnitude and efficiency of the ocean's biological pump.

The Canadian Basin of the Arctic Ocean, largely ice covered and isolated from deep contact with the more dynamic Eurasian Basin by the Lomonosov Ridge, has historically been considered an area of low productivity and particle flux and sluggish circulation. High-sensitivity mass-spectrometric measurements of the naturally occurring radionuclides protactinium-231 and thorium-230 in the deep Canada Basin and on the adjacent shelf indicate high particle fluxes and scavenging rates in this region. The thorium-232 data suggest that offshore advection of particulate material from the shelves contributes to scavenging of reactive materials in areas of permanent ice cover.

[1] The Arctic Ocean and adjacent continental shelf seas such as the Chukchi and Beaufort Seas are particularly sensitive to long-term change and low-frequency modes of atmosphere-ocean-sea-ice forcing. The cold, low salinity surface waters of the Canada Basin of the Arctic Ocean are undersaturated with respect to CO2 in the atmosphere and the region has the potential to take up atmospheric CO2, although presently suppressed by sea-ice cover. Undersaturated seawater CO2 conditions of the Arctic Ocean are maintained by export of water with low dissolved inorganic carbon content and modified by intense seasonal shelf primary production. Sea-ice extent and volume in the Arctic Ocean has decreased over the last few decades, and we estimate that the Arctic Ocean sink for CO2 has tripled over the last 3 decades (24 Tg yr 1 to 66 Tg yr 1 ) due to sea-ice retreat with future sea-ice melting enhancing air-to-sea CO2 flux by 28% per decade. Citation: Bates, N. R., S. B. Moran, D. A. Hansell, and J. T. Mathis (2006), An increasing CO2 sink in the Arctic Ocean due to sea-ice loss, Geophys. Res. Lett., 33, L23609, doi:10.1029/2006GL027028.

The naturally occurring radionuclide 226Ra (t1/2 = 1600 years) was used as a tracer to determine ground water input to Point Judith, Potter, Green Hill and Ninigret ponds in southern Rhode Island. Measurements of 226Ra activity were made in samples collected from salt ponds, pore waters, sediments, and local ground water wells during June-August, 1997. These results were combined with a simple box model to derive ground water input fluxes of 0.1-0.3 cm3 cm-2 d-1 (2-5 x 10(7) L d-1), which are comparable to previous estimates of ground water input to these ponds.

RECENT observations of abundant, nonliving, submicrometre particles in the upper ocean1–3 and new measurements of 'dissolved9organic carbon4–7 have fuelled speculation concerning the role of colloidal matter in ocean chemistry and biology. Colloids may act as reactive intermediates in the marine geochemistry of trace metals8–12, and a biologically labile pool of colloidal matter would affect models of ocean carbon cycling13–16. Here we report the use of naturally occurring 234Th as an in situ tracer to estimate the residence time of colloidal matter in the surface waters near Bermuda. The 234Th activity of colloidal matter (size range 10,000 nominal molecular weight to 0.2 μm) is similar to that of small particles (0.2–53 μm). Modelling of our results indicates a mean residence time of colloidal 234Th with respect to aggregation into small particles of 10 days, which is roughly the same as for small-particle 234Th, yet a factor of ∼6 less than for the dissolved pool. These results suggest that, more generally, macromolecular colloidal matter has a short residence time and hence a rapid turnover rate in the upper open ocean.

The marine geochemical cycle of aluminium is relevant to such oceanographic processes as the diagenesis of aluminosilicate material1 and tracing atmospheric dust inputs to oceanic surface waters2–6; Al has also been used as a non-transient water mass tracer7. The principal inputs of aluminium to the oceans are from the atmosphere and rivers, and have been reasonably well quantified8–13. Processes controlling its removal from the water column are, however, not well understood and in the past they have been inferred only from measurements of its oceanic distribution2–6,12 and unrealistic laboratory culture experiments14. Here we report the results of a more realistic and controlled temporal study, using a 10-m mesocosm tank, of changes in dissolved aluminium levels and particulate aluminium flux during a diatom bloom. We find that rapid removal of dissolved aluminium occurs by a surface adsorption mechanism and/or incorporation into soft tissues of diatoms. These observations represent the first direct demonstration of the influence and mechanism of biogenic particle removal of aluminium.