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Marine particles play a central role in controlling the transport, cycling, and inventories of many major elements and trace elements and isotopes throughout the oceans. Studies seeking to elucidate the biogeochemical roles of marine particles often require reliable ways to collect them from the ocean. Here, we review the oceanographic toolbox of techniques and instrumentation that are employed to collect both suspended and sinking particles. With these tools, it is possible to determine both the concentrations and vertical fluxes of important elements and individual particle types. We describe the various methods for quantifying the concentrations of particulate matter with in situ pumps, towed sampling devices, bottle collectors, and large volume capture devices. The uses of various types of flux collection platforms are discussed including surface tethered, neutrally buoyant, and bottom moored devices. We address the issues of sediment trap collection biases and the apparent inconsistencies that can arise due to differences in the temporal and spatial scales sampled by the various methodologies. Special attention is given to collection considerations made for the analysis of trace metals and isotopes, as these methodologies are of high importance to the ongoing GEOTRACES program which seeks to identify the processes and quantify fluxes that control the distributions of key trace elements and isotopes in the ocean. With the emergence of new particle collection methodologies and the continued reliance on traditional collection methods, it is imperative that we combine these multiple approaches in ways that will help improve their accuracy and precision while enhancing their utility in advancing understanding of the biogeochemical and ecological roles of marine particles.

We present a synthesis of the rates of gross, new, net and primary production along with particulate organic carbon (POC) flux at 100 m from four cruises along 170°W in the Southern Ocean. Concurrent satellite pigment data, a primary productivity model, and a nitrate mass balance are used to extrapolate daily production estimates in space and time to seasonal and annual rates. From this analysis, we gain a better understanding of the timing, magnitude and impact of the phytoplankton blooms in this region. One of the dominant features with respect to plankton biomass is the association of high chlorophyll levels with the retreat of the sea ice which begins in October just south of the Polar Front. Our primary production model and satellite pigment data suggest higher production and flux levels characterize the marginal ice zone than previous estimates. Elevated rates of new production in ice impacted regions are restricted to relatively short periods following retreat of the ice edge. Export is found to lag the onset of production by up to 1 month. The ratio of POC flux at 100 m to primary production when averaged over the entire season is quite high, increasing from 15% to 25% in the Subantarctic zones to 35-40% near the Polar Front and as high as 50-65% in the southernmost stations, just north of the Ross Sea gyre. Comparisons of phytoplankton community structure and Fe stress indicators suggest that blooms at the Polar Front are initially dominated by large centric diatoms, but are replaced by smaller pennate diatom and non-diatom species as Fe levels decrease. Further south, where Fe levels are never as high and large diatoms are not found, we still observe relatively high biomass and elevated production rates and POC fluxes during the short growing season. © 2003 Elsevier Science Ltd. All rights reserved.

A deep-sea coral was studied to determine its growth rate and to reconstruct time histories of isotope distributions in the deep ocean. The specimen was collected at a depth of 600 m off Little Bahama Banks using the Deep Submergence Vehicle (DSV) Alvin. The growth rate of the calcitic coral trunk was determined using excess 210Pb measured in concentric bands. Excess 210Pb was found in the outer half of the coral's radius, and a growth rate of 0.11 ± 0.02 mm/a is calculated. Assuming a constant growth rate during formation of the entire trunk, an age of 180 ± 40 a is estimated for the coral. The decrease observed in radiocarbon activities measured on the same bands (Griffin and Druffel, 1989) concurred with the growth rate estimated from excess 210Pb activity. 239,240pu activities measured by mass spectrometry were also detected in the outer two bands of the coral, as expected from the 210Pb chronology. Stable oxygen and carbon isotopes measured in samples collected by a variety of techniques are positively correlated. This is evidence of a variable kinetic isotope effect most likely caused by variations in the skeletal growth rate. Long-lived corals such as this specimen have the potential for serving as integrators of seawater chemistry in the deep-sea over several century timescales. © 1990.

Sinking or floating is the natural state of planktonic organisms and particles in the ocean. Simulating these conditions is critical when making measurements, such as respirometry, because they allow the natural exchange of substrates and products between sinking particles and water flowing around them and prevent organisms that are accustomed to motion from changing their metabolism. We developed a rotating incubator, the RotoBOD (named after its capability to rotate and determine biological oxygen demand, BOD), that uniquely enables automated oxygen measurements in small volumes while keeping the samples in their natural state of suspension. This allows highly sensitive rate measurements of oxygen utilization and subsequent characterization of single particles or small planktonic organisms, such as copepods, jellyfish, or protists. As this approach is nondestructive, it can be combined with several further measurements during and after the incubation, such as stable isotope additions and molecular analyses. This makes the instrument useful for ecologists, biogeochemists, and potentially other user groups such as aquaculture facilities. Here, we present the technical background of our newly developed apparatus and provide examples of how it can be utilized to determine oxygen production and consumption in small organisms and particles.

To better quantify the ocean's biological carbon pump, we resolved the diversity of sinking particles that transport carbon into the ocean's interior, their contribution to carbon export, and their attenuation with depth. Sinking particles collected in sediment trap gel layers from four distinct ocean ecosystems were imaged, measured, and classified. The size and identity of particles was used to model their contribution to particulate organic carbon (POC) flux. Measured POC fluxes were reasonably predicted by particle images. Nine particle types were identified, and most of the compositional variability was driven by the relative contribution of aggregates, long cylindrical fecal pellets, and salp fecal pellets. While particle composition varied across locations and seasons, the entire range of compositions was measured at a single well-observed location in the subarctic North Pacific over one month, across 500 m of depth. The magnitude of POC flux was not consistently associated with a dominant particle class, but particle classes did influence flux attenuation. Long fecal pellets attenuated most rapidly with depth whereas certain other classes attenuated little or not at all with depth. Small particles (<100 μm) consistently contributed ∼5% to total POC flux in samples with higher magnitude fluxes. The relative importance of these small particle classes (spherical mini pellets, short oval fecal pellets, and dense detritus) increased in low flux environments (up to 46% of total POC flux). Imaging approaches that resolve large variations in particle composition across ocean basins, depth, and time will help to better parameterize biological carbon pump models., Competing Interests: The authors declare no conflicts of interest relevant to this study., (© 2021 The Authors.)

The short-lived radionuclide 234 Th is widely used to study particle scavenging and transport from the upper ocean to deeper waters. This manuscript optimizes, reviews and validates the collection, processing and analyses of total 234 Th in seawater and suggests areas of further improvements. The standard 234 Th protocol method consists of scavenging 234 Th from seawater via a MnO 2 precipitate, beta counting, and using chemical recoveries determined by adding 230 Th. The revised protocol decreases sample volumes to 2 L, shortens wait times between steps, and simplifies the chemical recovery process, expanding the ability to more rapidly and safely apply the 234 Th method., Competing Interests: Conflict of interestThe authors have no relevant financial or non-financial interests to disclose., (© The Author(s) 2021.)

The ocean's biological carbon pump (BCP) sequesters carbon from the surface to the deep ocean and seabed, constituting one of Earth's most valuable ecosystem services. Significant uncertainty exists surrounding the amounts and rates of organic carbon sequestered in the oceans, however. With improved understanding of BCP sequestration, especially its scale, world policymakers would be positioned to make more informed decisions regarding the mitigation of carbon emissions. Here, an analytical model of the economic effects of global carbon emissions-including scientific uncertainty about BCP sequestration-was developed to estimate the value of marine scientific research concerning sequestration. The discounted net economic benefit of a putative 20-year scientific research program to narrow the range of uncertainty around the amount of carbon sequestered in the ocean is on the order of $0.5 trillion (USD), depending upon the accuracy of predictions, the convexities of climate damage and economic output functions, and the initial range of uncertainty., Competing Interests: Declaration of competing interest The authors whose names are listed immediately below certify that they have NO affiliations with or involvement in any organization or entity with any financial interest (such as honoraria; educational grants; participation in speakers' bureaus; membership, employment, consultancies, stock ownership, or other equity interest; and expert testimony or patent-licensing arrangements), or non-financial interest (such as personal or professional relationships, affiliations, knowledge or beliefs) in the subject matter or materials discussed in this manuscript. Author names: Di Jin, Porter Hoagland, Ken O. Buesseler., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

The Fukushima Dai-ichi Nuclear Power Plants (FDNPPs) accident in 2011 led to an unprecedented release of radionuclides into the environment. Particularly important are 90 Sr and 137 Cs due to their known health detriments and long half-lives ( T 1/2 ≈ 30 y) relative to ecological systems. These radionuclides can be combined with the longer-lived 129 I ( T 1/2 = 15.7 My) to trace hydrologic, atmospheric, oceanic, and geochemical processes. This study seeks to evaluate 137 Cs, 90 Sr, and 129 I concentrations in seawater off the coast of Japan, reconcile the sources of contaminated waters, and assess the application of 137 Cs/ 90 Sr, 129 I/ 137 Cs, and 129 I/ 90 Sr as oceanic tracers. We present new data from October 2015 and November 2016 off the coast of Japan, with observed concentrations reaching up to 198 ± 4 Bq·m -3 for 137 Cs, 9.1 ± 0.7 Bq·m -3 for 90 Sr, and (114 ± 2) × 10 -5 Bq·m -3 for 129 I. The utilization of activity ratios suggests a variety of sources, including sporadic and independent releases of radiocontaminants. Though overall concentrations are decreasing, concentrations are still elevated compared to pre-accident levels. In addition, Japan's Environment Minister has suggested that stored water from the FDNPPs may be released into the environment and thus continued efforts to understand the fate and distribution of these radionuclides is warranted.

The biological carbon pump (BCP) comprises wide-ranging processes that set carbon supply, consumption, and storage in the oceans' interior. It is becoming increasingly evident that small changes in the efficiency of the BCP can significantly alter ocean carbon sequestration and, thus, atmospheric CO 2 and climate, as well as the functioning of midwater ecosystems. Earth system models, including those used by the United Nation's Intergovernmental Panel on Climate Change, most often assess POC (particulate organic carbon) flux into the ocean interior at a fixed reference depth. The extrapolation of these fluxes to other depths, which defines the BCP efficiencies, is often executed using an idealized and empirically based flux-vs.-depth relationship, often referred to as the "Martin curve." We use a new compilation of POC fluxes in the upper ocean to reveal very different patterns in BCP efficiencies depending upon whether the fluxes are assessed at a fixed reference depth or relative to the depth of the sunlit euphotic zone (Ez). We find that the fixed-depth approach underestimates BCP efficiencies when the Ez is shallow, and vice versa. This adjustment alters regional assessments of BCP efficiencies as well as global carbon budgets and the interpretation of prior BCP studies. With several international studies recently underway to study the ocean BCP, there are new and unique opportunities to improve our understanding of the mechanistic controls on BCP efficiencies. However, we will only be able to compare results between studies if we use a common set of Ez-based metrics., Competing Interests: The authors declare no competing interest., (Copyright © 2020 the Author(s). Published by PNAS.)

Beach sand samples were collected along a coastal area 32 km south of the Fukushima Daiichi Nuclear Power Plant (FDNPP) in Fukushima Prefecture, Japan, 5 years after the FDNPP accident. Desorption experiments were performed on the sand samples using seawater in a batch experimental system to understand the forms of existence of radiocesium in sand and their desorption behavior in a coastal environment. The percentage of radiocesium desorption decreased exponentially with an increase in the number of desorption experiments for the four sand samples, with 137 Cs radioactivity from 16 to 1077 Bq kg -1 at surface and deeper layers from three sites. Total desorption percentage ranged from 19 to 58% in 12 desorption experiments. The results indicate that the weak adsorption varies with the sampling sites and their depth layer. To understand the desorption behavior of radiocesium in the sand samples, the desorption experiments were performed for a sand sample by using natural and artificial seawater, and NaCl solution in the presence and absence of KCl. The 137 Cs desorption from the sand collected at a depth of 100 - 105 cm from the ground surface ( 137 Cs radioactivity 1052 ± 25 Bq kg -1 ) was 0.1% by ultrapure water, 3.7% by 1/4 seawater and 7.1% by 1/2 seawater, 2.2% by 470 mM NaCl solution (corresponding to a similar concentration of seawater) and 10 - 12% by seawater, artificial seawater and 470 mM NaCl + 8 mM KCl solution. These results indicate that about 10% of radiocesium adsorbed on the sand is mainly desorbed by ion exchange of potassium ion in seawater, though the concentration of major cation, or sodium ion, in seawater makes a small contribution on 137 Cs desorption from the sand samples.

Amidoxime-based adsorbents have become highly promising for seawater uranium extraction. However, current deployment schemes are stand-alone, intermittent operation systems that have significant practical and economic challenges. This paper presents two 1:10 scale prototypes of a Symbiotic Machine for Ocean uRanium Extraction (SMORE) which pairs with an existing offshore structure. This pairing reduces mooring and deployment costs while enabling continuous, autonomous uranium extraction. Utilizing a shell enclosure to decouple the mechanical and chemical requirements of the adsorbent, one design concept prototyped continuously moves the shells through the water while the other keeps them stationary. Water flow in the shells on each prototype was determined using the measurement of radium adsorbed by MnO 2 impregnated acrylic fibers contained within each enclosure. The results from a nine-week ocean trial show that while movement of the shells through the water may not have an effect on uranium adsorption by the fibers encased, it could help reduce biofouling if above a certain threshold speed (resulting in increased uptake), while also allowing for the incorporation of design elements to further mitigate biofouling such as bristle brushes and UV lamps. The trace metal uptake by the AI8 adsorbents in this trial also varied greatly from previous marine deployments, suggesting that uranium uptake may depend greatly upon the seawater concentrations of other elements such as vanadium and copper. The results from this study will be used to inform future work on the seawater uranium production cost from a full-scale SMORE system.

We made an assessment of the levels of radionuclides in the ocean waters, seafloor and groundwater at Bikini and Enewetak Atolls where the US conducted nuclear weapons tests in the 1940's and 50's. This included the first estimates of submarine groundwater discharge (SGD) derived from radium isotopes that can be used here to calculate radionuclide fluxes in to the lagoon waters. While there is significant variability between sites and sample types, levels of plutonium ( 239,240 Pu) remain several orders of magnitude higher in lagoon seawater and sediments than what is found in rest of the world's oceans. In contrast, levels of cesium-137 ( 137 Cs) while relatively elevated in brackish groundwater are only slightly higher in the lagoon water relative to North Pacific surface waters. Of special interest was the Runit dome, a nuclear waste repository created in the 1970's within the Enewetak Atoll. Low seawater ratios of 240 Pu/ 239 Pu suggest that this area is the source of about half of the Pu in the Enewetak lagoon water column, yet radium isotopes suggest that SGD from below the dome is not a significant Pu source. SGD fluxes of Pu and Cs at Bikini were also relatively low. Thus radioactivity associated with seafloor sediments remains the largest source and long term repository for radioactive contamination. Overall, Bikini and Enewetak Atolls are an ongoing source of Pu and Cs to the North Pacific, but at annual rates that are orders of magnitude smaller than delivered via close-in fallout to the same area., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

This paper focuses on how a community of researchers under the COMET (CO-ordination and iMplementation of a pan European projecT for radioecology) project has improved the capacity of marine radioecology to understand at the process level the behaviour of radionuclides in the marine environment, uptake by organisms and the resulting doses after the Fukushima Dai-ichi nuclear accident occurred in 2011. We present new radioecological understanding of the processes involved, such as the interaction of waterborne radionuclides with suspended particles and sediments or the biological uptake and turnover of radionuclides, which have been better quantified and mathematically described. We demonstrate that biokinetic models can better represent radionuclide transfer to biota in non-equilibrium situations, bringing more realism to predictions, especially when combining physical, chemical and biological interactions that occur in such an open and dynamic environment as the ocean. As a result, we are readier now than we were before the FDNPP accident in terms of having models that can be applied to dynamic situations. The paper concludes with our vision for marine radioecology as a fundamental research discipline and we present a strategy for our discipline at the European and international levels. The lessons learned are presented along with their possible applicability to assess/reduce the environmental consequences of future accidents to the marine environment and guidance for future research, as well as to assure the sustainability of marine radioecology. This guidance necessarily reflects on why and where further research funding is needed, signalling the way for future investigations., (Copyright © 2017 Elsevier B.V. All rights reserved.)

There are 440 operational nuclear reactors in the world, with approximately one-half situated along the coastline. This includes the Fukushima Dai-ichi Nuclear Power Plant (FDNPP), which experienced multiple reactor meltdowns in March 2011 followed by the release of radioactivity to the marine environment. While surface inputs to the ocean via atmospheric deposition and rivers are usually well monitored after a nuclear accident, no study has focused on subterranean pathways. During our study period, we found the highest cesium-137 ( 137 Cs) levels (up to 23,000 Bq⋅m -3 ) outside of the FDNPP site not in the ocean, rivers, or potable groundwater, but in groundwater beneath sand beaches over tens of kilometers away from the FDNPP. Here, we present evidence of a previously unknown, ongoing source of Fukushima-derived 137 Cs to the coastal ocean. We postulate that these beach sands were contaminated in 2011 through wave- and tide-driven exchange and sorption of highly radioactive Cs from seawater. Subsequent desorption of 137 Cs and fluid exchange from the beach sands was quantified using naturally occurring radium isotopes. This estimated ocean 137 Cs source (0.6 TBq⋅y -1 ) is of similar magnitude as the ongoing releases of 137 Cs from the FDNPP site for 2013-2016, as well as the input of Fukushima-derived dissolved 137 Cs via rivers. Although this ongoing source is not at present a public health issue for Japan, the release of Cs of this type and scale needs to be considered in nuclear power plant monitoring and scenarios involving future accidents., Competing Interests: Conflict of interest statement: K.O.B. has served in a consulting capacity related to radionuclides in Japanese fisheries products.

The large inventory of radioactivity released during the March, 2011 Fukushima Dai-ichi nuclear reactor accident in Japan spread rapidly across the North Pacific Ocean and was first observed at the westernmost station on Line P, an oceanographic sampling line extending 1500 km westward of British Columbia (BC), Canada in June 2012. Here, time series measurements of 134 Cs and 137 Cs in seawater on Line P and on the CLIVAR-P16N 152°W line reveal the recent transport history of the Fukushima radioactivity tracer plume through the northeast Pacific Ocean. During 2013 and 2014 the Fukushima plume spread onto the Canadian continental shelf and by 2015 and early 2016 it reached 137 Cs values of 6-8 Bq/m 3 in surface water along Line P. Ocean circulation model simulations that are consistent with the time series measurements of Fukushima 137 Cs indicate that the 2015-2016 results represent maximum tracer levels on Line P and that they will begin to decline in 2017-2018. The current elevated Fukushima 137 Cs levels in seawater in the eastern North Pacific are equivalent to fallout background levels of 137 Cs that prevailed during the 1970s and do not represent a radiological threat to human health or the environment.

After the Fukushima Dai-ichi nuclear accident, many efforts were put into the determination of the presence of 137 Cs, 134 Cs, 131 I, and other gamma-emitting radionuclides in the ocean, but minor work was done regarding the monitoring of less volatile radionuclides, pure beta-ray emitters or simply radionuclides with very long half-lives. In this study we document the temporal evolution of 129 I, 236 U, and Pu isotopes ( 239 Pu and 240 Pu) in seawater sampled during four different cruises performed 2, 3, and 4 years after the accident, and we compare the results to 137 Cs collected at the same stations and depths. Our results show that concentrations of 129 I are systematically above the nuclear weapon test levels at stations located close to the FDNPP, with a maximum value of 790 × 10 7 at·kg -1 , that exceeds all previously reported 129 I concentrations in the Pacific Ocean. Yet, the total amount of 129 I released after the accident in the time 2011-2015 was calculated from the 129 I/ 137 Cs ratio of the ongoing 137 Cs releases and estimated to be about 100 g (which adds to the 1 kg released during the accident in 2011). No clear evidence of Fukushima-derived 236 U and Pu isotopes has been found in this study, although further monitoring is encouraged to elucidate the origin of the highest 240 Pu/ 239 Pu atom ratio of 0.293 ± 0.028 we found close to FDNPP.

The years following the Fukushima Dai-ichi nuclear power plant (FDNPP) accident, the distribution of (90)Sr in seawater in the coast off Japan has received limited attention. However, (90)Sr is a major contaminant in waters accumulated within the nuclear facility and in the storage tanks. Seawater samples collected off the FDNPP in September 2013 showed radioactive levels significantly higher than pre-Fukushima levels within 6 km off the FDNPP. These samples, with up to 8.9 ± 0.4 Bq·m(-3) for (90)Sr, 124 ± 3 Bq·m(-3) for (137)Cs, and 54 ± 1 Bq·m(-3) for (134)Cs, appear to be influenced by ongoing releases from the FDNPP, with a characteristic (137)Cs/(90)Sr activity ratio of 3.5 ± 0.2. Beach surface water and groundwater collected in Sendai Bay had (137)Cs concentrations of up to 43 ± 1 Bq·m(-3), while (90)Sr was close to pre-Fukushima levels (1-2 Bq·m(-3)). These samples appear to be influenced by freshwater inputs carrying a (137)Cs/(90)Sr activity ratio closer to that of the FDNPP fallout deposited on land in the spring of 2011. Ongoing inputs of (90)Sr from FDNPP releases would be on the order of 2.3-8.5 GBq·d(-1) in September 2013, likely exceeding river inputs by 2-3 orders of magnitude. These results strongly suggest that a continuous surveillance of artificial radionuclides in the Pacific Ocean is still required.

A three year time-series of particle fluxes is presented from sediment traps deployed at 500 and 1000 m at a site 115 km southeast of Fukushima Daiichi Nuclear Power Plant (FDNPP). Results show a high fraction of lithogenic material and mass flux peaks that do not align between the trap depths, suggesting a lateral source of sediments. Fukushima cesium-137 and cesium-134 were enhanced in flux peaks that, given variations in trap (137)Cs/(210)Pbex ratios, are characteristic of material derived from shelf and slope sediments found from <120 to >500 m. These lateral flux peaks are possibly triggered by passing typhoons. The Cs fluxes are an order of magnitude higher than were previously reported for the trap located 100 km due east of FDNPP. We attribute this large difference to the position of our trap under the southeasterly currents that carry contaminated waters and resuspended sediments away from FDNPP and into the Pacific. These higher Cs sedimentary fluxes offshore are still small relative to the inventory of Cs currently buried nearshore. Consequently, we do not expect them to effect any rapid decrease in Cs levels for the coastal sediments near FDNPP that have been linked to enhanced Cs in demersal fish.

The Tōhoku earthquake and tsunami of March 11, 2011, resulted in unprecedented radioactivity releases from the Fukushima Dai-ichi nuclear power plants to the Northwest Pacific Ocean. Results are presented here from an international study of radionuclide contaminants in surface and subsurface waters, as well as in zooplankton and fish, off Japan in June 2011. A major finding is detection of Fukushima-derived (134)Cs and (137)Cs throughout waters 30-600 km offshore, with the highest activities associated with near-shore eddies and the Kuroshio Current acting as a southern boundary for transport. Fukushima-derived Cs isotopes were also detected in zooplankton and mesopelagic fish, and unique to this study we also find (110 m)Ag in zooplankton. Vertical profiles are used to calculate a total inventory of ~2 PBq (137)Cs in an ocean area of 150,000 km(2). Our results can only be understood in the context of our drifter data and an oceanographic model that shows rapid advection of contaminants further out in the Pacific. Importantly, our data are consistent with higher estimates of the magnitude of Fukushima fallout and direct releases [Stohl et al. (2011) Atmos Chem Phys Discuss 11:28319-28394; Bailly du Bois et al. (2011) J Environ Radioact, 10.1016/j.jenvrad.2011.11.015]. We address risks to public health and marine biota by showing that though Cs isotopes are elevated 10-1,000× over prior levels in waters off Japan, radiation risks due to these radionuclides are below those generally considered harmful to marine animals and human consumers, and even below those from naturally occurring radionuclides.

Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

Episodic eddy-driven upwelling may supply a significant fraction of the nutrients required to sustain primary productivity of the subtropical ocean. New observations in the northwest Atlantic reveal that, although plankton blooms occur in both cyclones and mode-water eddies, the biological responses differ. Mode-water eddies can generate extraordinary diatom biomass and primary production at depth, relative to the time series near Bermuda. These blooms are sustained by eddy/wind interactions, which amplify the eddy-induced upwelling. In contrast, eddy/wind interactions dampen eddy-induced upwelling in cyclones. Carbon export inferred from oxygen anomalies in eddy cores is one to three times as much as annual new production for the region.

The oceanic biological pump drives sequestration of carbon dioxide in the deep sea via sinking particles. Rapid biological consumption and remineralization of carbon in the "twilight zone" (depths between the euphotic zone and 1000 meters) reduce the efficiency of sequestration. By using neutrally buoyant sediment traps to sample this chronically understudied realm, we measured a transfer efficiency of sinking particulate organic carbon between 150 and 500 meters of 20 and 50% at two contrasting sites. This large variability in transfer efficiency is poorly represented in biogeochemical models. If applied globally, this is equivalent to a difference in carbon sequestration of more than 3 petagrams of carbon per year.

Since the mid-1980s, our understanding of nutrient limitation of oceanic primary production has radically changed. Mesoscale iron addition experiments (FeAXs) have unequivocally shown that iron supply limits production in one-third of the world ocean, where surface macronutrient concentrations are perennially high. The findings of these 12 FeAXs also reveal that iron supply exerts controls on the dynamics of plankton blooms, which in turn affect the biogeochemical cycles of carbon, nitrogen, silicon, and sulfur and ultimately influence the Earth climate system. However, extrapolation of the key results of FeAXs to regional and seasonal scales in some cases is limited because of differing modes of iron supply in FeAXs and in the modern and paleo-oceans. New research directions include quantification of the coupling of oceanic iron and carbon biogeochemistry.

A suboxic groundwater from a sandy coastal aquifer was sampled using a new air free, large volume sampling method. Subsequent processing for size fractionation was completed with a modified cross-flow ultrafiltration (CFF) system equipped with a 1 kDa CFF membrane. By purging the CFF system with nitrogen, no oxygen was able to reach the sample. With this optimization, the sample was processed with higher than 90% recovery in terms of both iron and phosphate. Only about 4% of iron and 20% of phosphate in the filtered (0.2 microm) groundwater sample was found to be in colloidal form in the groundwater. In contrast, if no care was taken to maintain the suboxic environment of the original sample, iron was rapidly and completely oxidized and subsequently adsorbed to the CFF membrane. Other elements, such as phosphorus, were also lost to the CFF membrane to a substantial degree, and the mechanism is most likely coprecipitation with iron oxides. This study thus strongly supports the importance of maintaining ambient redox conditions during sampling and fractionation, especially for the determinations of colloid abundances in groundwater.

We examined the concentration, size distribution, redox state and isotopic composition of plutonium (Pu) in groundwater at the 100K-Area at the U.S. Department of Energy's (DOE) Hanford Site. Total concentrations of Pu isotopes were extremely low (10(-4) to 10(-6) pCi/kg, approximately 10(4) to 10(6) atoms/kg) but measurable for the first time in the 100K-Area wells using mass spectrometric analyses that are much more sensitive than alpha spectroscopy methods used previously. Size fractionation data from two wells suggest that 7-29% of the Pu is associated with colloids, operationally defined here as particles between 1 kDa-0.2 microm in size. These colloids were collected using a 1 kDa cross-flow ultrafiltration (CFF) system developed specifically for groundwater actinide studies to include careful controls both in the field and during processing to ensure in situ geochemical conditions are maintained and size separations can be well characterized. Pu in this colloidal fraction was exclusively in the more reduced Pu(III/IV) form, consistent with the higher affinity of Pu in the lower oxidation states for particle surfaces. While the overall concentrations of Pu were low, the Pu isotopic composition suggests at least two local sources of groundwater Pu, namely, local Hanford reactor operations at the 100K-Area and spent nuclear fuel from the N-reactor, which was stored in concrete pools at this site. Differences between this site and the Savannah River Site (SRS) are noted, since groundwater Pu at the F-Area seepage basin at SRS has been found using these same methods, to be characterized by lower colloidal abundances and higher oxidation states. This difference is not directly attributable to groundwater redox potential or geochemical conditions, but rather the physical-chemical difference in Pu sources, which at SRS appear to be dominated downstream from the seepage basins by decay of 244Cm, resulting in more oxidized forms of 240Pu. There is no clear evidence for colloid facilitated transport of Pu in groundwater at the Hanford Site, since downstream wells have both an order of magnitude lower concentrations of Pu and a lower fractional colloidal distribution.

Under an IAEA's Co-ordinated Research Project "Worldwide Marine Radioactivity Studies (WOMARS)" 90Sr, 137Cs and (239,240)Pu concentration surface water time series in the Pacific and Indian Oceans have been investigated. The Pacific and Indian Oceans were divided into 17 latitudinal boxes according to ocean circulation, global fallout patterns and the location of nuclear weapons test sites. The present levels and time trends in radionuclide concentrations in surface water for each box were studied and the corresponding effective half-lives were estimated. For the year 2000, the estimated average 90Sr, 137Cs and (239,240)Pu concentrations in surface waters of the Pacific and Indian Oceans varied from 0.1 to 1.5 mBq/L, 0.1 to 2.8 mBq/L, and 0.1 to 5.2 microBq/L, respectively. The mean effective half-lives for 90Sr and 137Cs in surface water were 12+/-1 years for the North, 20+/-1 years for the South and 21+/-2 years for the Equatorial Pacific. For (239,240)Pu the corresponding mean effective half-lives were 7+/-1 years for the North, 12+/-4 years for the South and 10+/-2 years for the Equatorial Pacific. For the Indian Ocean the mean effective half-lives of 137Cs and (239,240)Pu were 21+/-2 years and 9+/-1 years, respectively. There is evidence that fallout removal rates before 1970 were faster than those observed during recent decades. The estimated surface water concentrations of 90Sr, 137Cs and (239,240)Pu in latitudinal belts of the Pacific and Indian Oceans for the year 2000 may be used as the average levels so that any new contribution from nuclear facilities, nuclear weapons test sites, radioactive waste dumping sites and from possible nuclear accidents can be identified.

The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide.

An unresolved issue in ocean and climate sciences is whether changes to the surface ocean input of the micronutrient iron can alter the flux of carbon to the deep ocean. During the Southern Ocean Iron Experiment, we measured an increase in the flux of particulate carbon from the surface mixed layer, as well as changes in particle cycling below the iron-fertilized patch. The flux of carbon was similar in magnitude to that of natural blooms in the Southern Ocean and thus small relative to global carbon budgets and proposed geoengineering plans to sequester atmospheric carbon dioxide in the deep sea.

The isotopic composition, size distribution, and redox speciation of plutonium (Pu) in the groundwater in the vicinity of the F-area seepage basins at the U.S. Department of Energy Savannah River Site (SRS) were examined. A low 240Pu/239Pu ratio in the upstream control well signifies a Pu source otherthan global fallout and indicates reactor-produced Pu. Elevated 240Pu/239Pu atom ratios downstream from the seepage basins are due to the decay of transplutonium isotopes, mainly 244Cm to 240Pu, which were generated at the SRS. Evidence suggests that the migration of basin-released Pu isotopes is minor. Rather, it is the transplutonium isotopes that migrate preferentially downstream and in the process decay to yield progeny Pu isotopes. Size fractionation studies with cross-flow ultrafiltration show that <4% of the 239Pu or 240Pu is found in the colloidal fraction, a finding that is consistent with the higher Pu oxidation states observed in the SRS groundwater. The observation of a low abundance of colloid-associated Pu in SRS groundwater cannot be extrapolated to all sites, but is in contrast to the conclusions of prior groundwater Pu studies at the SRS and elsewhere. This work is unique in its application of a novel combination of sampling and processing protocols as well as its use of thermal ionization mass spectrometry for the detection of Pu isotopes. This allows quantification of the Pu source terms and better determination of the ambient Pu size and redox speciation representative of in situ conditions.

We have examined the distribution of individual Pu isotopes (239Pu, 240Pu, and 241Pu) in seawater from the Gulf of Maine (GOM). Samples were size-fractionated with a 1 kD cross-flow ultrafiltration (CFF) membrane. Subfractioned samples were radiochemically purified and Pu isotopes were analyzed using a three-stage thermal ionization mass spectrometer (TIMS). To our knowledge, this is the first time that both size class and Pu isotopic data have been obtained for seawater samples. Within measurement uncertainties a single 240Pu/239Pu atom ratio of 0.18 was found for all sample collection depths and sample size fractions. This signifies a current, single Pu source in GOM waters, namely global fallout, and suggests that no measurable isotopic fractionation occurred during CFF processing. The majority of Pu was found in the low molecular weight fraction (< 1 kD). Colloidal Pu varied from 8% of the total in surface waters to < 1% in the deepest (250 m) seawater sample. Evidence suggests that the vertical distribution of Pu in GOM is primarily controlled by conservative mixing processes. The high Pu fraction found in the low molecular size fraction implies that most of the Pu is in the non-particle-reactive oxidized fraction, and is consistent with the conservative Pu behavior. The activity levels are in agreement with other studies which show a slow decrease in Pu with time due to continued mixing and relatively slow particle removal.

Changes in iron supply to oceanic plankton are thought to have a significant effect on concentrations of atmospheric carbon dioxide by altering rates of carbon sequestration, a theory known as the 'iron hypothesis'. For this reason, it is important to understand the response of pelagic biota to increased iron supply. Here we report the results of a mesoscale iron fertilization experiment in the polar Southern Ocean, where the potential to sequester iron-elevated algal carbon is probably greatest. Increased iron supply led to elevated phytoplankton biomass and rates of photosynthesis in surface waters, causing a large drawdown of carbon dioxide and macronutrients, and elevated dimethyl sulphide levels after 13 days. This drawdown was mostly due to the proliferation of diatom stocks. But downward export of biogenic carbon was not increased. Moreover, satellite observations of this massive bloom 30 days later, suggest that a sufficient proportion of the added iron was retained in surface waters. Our findings demonstrate that iron supply controls phytoplankton growth and community composition during summer in these polar Southern Ocean waters, but the fate of algal carbon remains unknown and depends on the interplay between the processes controlling export, remineralisation and timescales of water mass subduction.

We have developed a new method for the collection, purification, and measurement of natural levels of (32)P and (33)P in rain, marine particulates, and dissolved constituents of seawater. (32)P and (33)P activities were measured using a recently developed ultra-low-level liquid scintillation counter. Measurement by liquid scintillation counting allows, for the first time, simultaneous measurement of both (32)P and (33)P. Furthermore, (33)P activities are measured with high efficiency (>50%), regardless of the amount of stable phosphorus in the sample. Liquid scintillation also produces energy specific β spectra which has enabled us to identify previously unrecognized β-emitting contaminants in natural samples. In order to remove these contaminants, new methods of purification have been developed which utilize a series of precipitations and anion and cation exchange columns. Rainwater and dissolved seawater samples were extracted from large volumes of rain- and seawater, 5-20 and >5000 L, respectively, using iron-impregnated polypropylene filters. On these filters, it was possible to load between 25 and 30% Fe(OH)(3) by weight, over twice that loaded on previously utilized materials. Using our collection, purification, and liquid scintillation counting techniques, it was possible to obtain specific (32)P and (33)P activities with less than 10% error (2σ) in rainwater and 20% error (2σ) in seawater.

The Chernobyl nuclear power station accident released large quantities of vaporized radionuclides, and, to a lesser extent, mechanically released small (less than 1-10 micron) aerosol particles. The total release of radioactivity is estimated to be out of the order of 1-2 x 10(18) Bq (3-5 x 10(7) Ci) not allowing for releases of the xenon and krypton gases. The 137Cs releases of 3.8 x 10(16) Bq from Chernobyl can be compared to 1.3 x 10(18) Bq 137Cs released due to atmospheric nuclear weapons testing. Chernobyl-derived radionuclides can be used as transient tracers to study physical and biogeochemical processes. Initial measurements of fallout Chernobyl radionuclides from a time-series sediment trap at 1,071 m during June-September 1986 in the southern Black Sea are presented. The specific activities of 137Cs, 144Ce and 106Ru in the trap samples (0.5-2, 4-12 and 6-13 Bq g-1) are independent of the particle flux while their relative activities reflect their rates of scavenging in the order Ce greater than Ru greater than Cs.