On the Fractional Solubillity of Copper in Marine Aerosols: Toxicity of Aeolian Copper Revisited

Paytan et al. (2009) argue that the atmospheric deposition of aerosols lead to copper concentrations that are potentially toxic to marine phytoplankton in a large area of tropical and subtropical North Atlantic Ocean. A key assumption in their model is that all marine aerosols (mineral dust and anthropogenic particles) have a high (40%) fractional solubility of copper. Our data show that the fractional solubility of copper for Saharan dust over the Sargasso Sea and Bermuda is significantly lower (1-7%). In contrast, anthropogenic aerosols with non-Saharan sources have significantly higher values (10-100%). Hence, the potential Cu toxicity in the tropical and subtropical North Atlantic should be re-estimated, given the low fractional solubility of Cu in the Saharan dust that dominates aerosol deposition to this region

Development of an autonomous aerosol sampler for ocean buoys and land sites

The authors have successfully designed, built and tested an aerosol sampler which is capable of collecting, in an unattended manner, a time-series set of aerosol samples (aerosol-embedded filters) from moored ocean buoys and remote areas on land. Research on aerosols, in particular, and atmospheric chemistry, in general, has not been previously attempted from buoys. Aerosols entering and leaving the ocean play an important role in climate change, ocean productivity, pollutant transport and atmospheric optics. This report discusses (1) the scientific applications of a buoy-mounted aerosol sampler, (2) the advantages of using buoys as research platforms and (3) the authors' new instrument. Also discussed are the results of a four month test of the aerosol sampler on the AEROCE (Atmosphere/Ocean Chemistry Experiment) tower in Bermuda and the results of a three month test on a buoy moored in Vineyard Sound off Woods Hole, MA USA. The direct comparison between WHOI filters and AEROCE filters from the Bermuda tower is very encouraging as the Fe concentrations of aerosols compare to within 10-15% over a wide range of values. Aerosol sampling from a buoy moored in coastal waters was successfully tested under a variety of atmospheric and oceanic conditions.Funding was provided by the National Science Foundation through Grant No. OCE-943212

Atmospheric trace metal concentrations, solubility and deposition fluxes in remote marine air over the south-east Atlantic

Total and soluble trace metal concentrations were determined in atmospheric aerosol and rainwater samples collected during seven cruises in the south-east Atlantic. Back trajectories indicated the samples all represented remote marine air masses, consistent with climatological expectations. Aerosol trace metal loadings were similar to previous measurements in clean, marine air masses. Median total Fe, Al, Mn, V, Co and Zn concentrations were 206, 346, 5, 3, 0.7 and 11 pmol m-3 respectively. Solubility was operationally defined as the fraction extractable using a pH4.7 ammonium acetate leach. Median soluble Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb concentrations were 6, 55, 1, 0.7, 0.06, 24, 2, 1, 0.05 and 0.3 pmol m-3 respectively. Large ranges in fractional solubility were observed for all elements except Co; median solubility values for Fe, Al and Mn were below 20% while the median for Zn was 74%. Volume weighted mean rainwater concentrations were 704, 792, 32, 10, 3, 686, 25, 0.02, 0.3 and 10 nmol L-1 for Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb respectively (n = 6). Wet deposition fluxes calculated from these values suggest rain makes a significant contribution to total deposition in the study area for all elements except perhaps Ni

Trace element cycling in a subterranean estuary : part 2. Geochemistry of the pore water

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 70 (2006): 811-826, doi:10.1016/j.gca.2005.10.019.Submarine groundwater discharge (SGD) is an important source of dissolved elements to the ocean, yet little is known regarding the chemical reactions that control their flux from sandy coastal aquifers. The net flux of elements from SGD to the coastal ocean is dependent on biogeochemical reactions in the groundwater-seawater mixing zone, recently termed the "subterranean estuary". This paper is the second in a two part series on the biogeochemistry of the Waquoit Bay coastal aquifer/subterranean estuary. The first paper addressed the biogeochemistry of Fe, Mn, P, Ba, U, and Th from the perspective of the sediment composition of cores (Charette et al., 2005). This paper uses pore water data from the subterranean estuary, along with Bay surface water data, to establish a more detailed view into the estuarine chemistry and the chemical diagenesis of Fe, Mn, U, Ba and Sr in coastal aquifers. Nine high-resolution pore water (groundwater) profiles were collected from the head of the bay during July 2002. There were non-conservative additions of both Ba and Sr in the salinity transition zone of the subterranean estuary. However, the extent of Sr release was significantly less than that of its alkaline earth neighbor Ba. Pore water Ba concentrations approached 3000 nM compared with 25-50 nM in the surface waters of the bay; the pore water Sr-salinity distribution suggests a 26% elevation in the amount of Sr added to the subterranean estuary. The release of dissolved Ba to the mixing zone of surface estuaries is frequently attributed to an ion-exchange process whereby seawater cations react with Ba from river suspended clay mineral particles at low to intermediate salinity. Results presented here suggest that reductive dissolution of Mn oxides, in conjunction with changes in salinity, may also be an important process in maintaining high concentrations of Ba in the pore water of subterranean estuaries. In contrast, pore water U was significantly depleted in the subterranean estuary, a result of SGD-driven circulation of seawater through reducing permeable sediments. This finding is supported by surface water concentrations of U in the bay, which were significantly depleted in U compared with adjacent coastal waters. Using a global estimate of SGD, we calculate U removal in subterranean estuaries at 20 x 106 mol U y-1, which is the same order of magnitude as the other major U sinks for the ocean. Our results suggest a need to revisit and reevaluate the oceanic budgets for elements that are likely influenced by SGD-associated processes.This research was supported by the National Science Foundation (OCE-0095384) to M.A.C. and E.R.S., and a WHOI Coastal Ocean Institute Fellowship to M.A.C

Evidence for intense REE scavenging at cold seeps from the Niger Delta margin

International audienceFor many trace elements, continental margins are the location of intense exchange processes between sediment and seawater, which control their distribution in the water column, but have yet to be fully understood. In this study, we have investigated the impact of fluid seepage at cold seeps on the marine cycle of neodymium. We determined dissolved and total dissolvable (TD) concentrations for REE and well-established tracers of fluid seepage (CH4, TDFe, TDMn), and Nd isotopic compositions in seawater samples collected above cold seeps and a reference site (i.e. away from any fluid venting area) from the Niger Delta margin. We also analyzed cold seep authigenic phases and various core-top sediment fractions (pore water, detrital component, easily leachable phases, uncleaned foraminifera) recovered near the hydrocast stations. Methane, TDFe and TDMn concentrations clearly indicate active fluid venting at the studied seeps, with plumes rising up to about 100 m above the seafloor. Depth profiles show pronounced REE enrichments in the non-filtered samples (TD concentrations) within plumes, whereas filtered samples (dissolved concentrations) exhibit slight REE depletion in plumes relative to the overlying water column and display typical seawater REE patterns. These results suggest that the net flux of REE emitted into seawater at cold seeps is controlled by the presence of particulate phases, most probably Fe-Mn oxyhydroxides associated to resuspended sediments. At the reference site, however, our data reveal significant enrichment for dissolved REE in bottom waters, that clearly relates to diffusive benthic fluxes from surface sediments. Neodymium isotopic ratios measured in the water column range from εNd ~−15.7 to − 10.4. Evidence that the εNd values for Antarctic Intermediate waters (AAIW) differed from those reported for the same water mass at open ocean settings shows that sediment/water interactions take place in the Gulf of Guinea. At each site, however, the bottom water εNd signature generally differs from that for cold seep minerals, easily leachable sediment phases, and detrital fractions from local sediments, ruling out the possibility that seepage of methane-rich fluids and sediment dissolution act as a substantial source of dissolved Nd to seawater in the Gulf of Guinea. Taken together, our data hence suggest that co-precipitation of Fe-Mn oxyhydroxide phases in sub-surface sediments leads to quantitative scavenging of dissolved REE at cold seeps, preventing their emission into bottom waters. Most probably, it is likely that diffusion from suboxic surface sediments dominates the exchange processes affecting the marine Nd cycle at the Niger Delta margin

Iron isotope systematics in estuaries : the case of North River, Massachusetts (USA)

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 4045-4059, doi:10.1016/j.gca.2009.04.026.Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ56Fe values (with an average of 0.43 ± 0.04 ‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ56Fe values vary from -0.09‰ at no flocculation to ~ 0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ56Fe composition of rivers can also be characterized by more positive δ56Fe values (up to 0.3 per mil) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe isotopes during continental run-off.This study was supported by the National Science Foundation (OCE 0550066) to O. Rouxel and Edward Sholkovitz

Assessment of groundwater discharges into West Neck Bay, New York, via natural tracers

Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Continental Shelf Research 29 (2006): 1971-1983, doi:10.1016/j.csr.2006.07.011.A field experiment to compare methods of assessing submarine groundwater discharge (SGD) was held on Shelter Island, NY, in May 2002. We evaluated the use of radon, radium isotopes, and methane to assess SGD rates and dynamics from a glacial aquifer in the coastal zone. Fluxes of radon across the sediment-water interface were calculated from changes in measured surface water inventories following evaluation and correction for tidal effects, atmospheric evasion, and mixing with offshore waters. These fluxes were then converted to SGD rates using the measured radon concentration in the groundwater. We used the short-lived radium isotopes to calculate a horizontal mixing coefficient to assess radon loss by mixing between nearshore and offshore waters. We also made an independent calculation of SGD using the Ra-derived mixing coefficient and the long-lived 226Ra concentration gradient in the bay. Seepage rates were calculated to range between 0 and 34 cm.day-1 using the radon measurements and 15 cm.day-1 as indicated by the radium isotopes. The radiotracer results were consistent and comparable to SGD rates measured directly with vented benthic chambers (seepage meters) deployed during this experiment. These meters indicated rates between 2 and 200 cm.day-1 depending on their location. Both the calculated radon fluxes and rates measured directly by the automated seepage meters revealed a clear reproducible pattern of higher fluxes during low tides. Considering that the two techniques are completely independent, the agreement in the SGD dynamics is significant. Methane concentration in groundwater was very low (~30 nM) and not suitable as SGD tracer at this study site.The SGD intercomparison experiment was partially funded by SCOR, LOICZ, and UNESCO (IOC and IHP). W. C. Burnett acknowledges support from CICEET (Grant# 1368-810-41) and ONR (Grant# 1368-769-27). J. P. Chanton acknowledges support from Seagrant (R\C-E-44). The WHOI researchers acknowledge funding from CICEET (#NA07OR0351, NA17OZ2507)

Iron isotope fractionation in subterranean estuaries

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 3413-3430, doi:10.1016/j.gca.2008.05.001.Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redoxstratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ56Fe values between 0.3 and –1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ56Fe values down to –5‰. These low δ56Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Feoxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe values between –2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ56Fe values relative to river values.This study was supported by the National Science Foundation (OCE 0550066) to OR and ES , (OCE 0095384) to MC and ES and NASA Astrobiology Institute - Cycle 3 CAN-02-OSS-02 to KJE

Online preconcentration ICP-MS analysis of rare earth elements in seawater

The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (∼pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available “seaFAST” system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2σ) of the technique to be estimated at <23% for all REEs and <15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired

Reactivity of neodymium carriers in deep sea sediments: Implications for boundary exchange and paleoceanography

The dissolved neodymium (Nd) isotopic distribution in the deep oceans is determined by continental weathering inputs, water mass advection, and boundary exchange between particulate and dissolved fractions. Reconstructions of past Nd isotopic variability may therefore provide evidence on temporal changes in continental weathering inputs and/or ocean circulation patterns over a range of timescales. However, such an approach is limited by uncertainty in the mechanisms and importance of the boundary exchange process, and the challenge in reliably recovering past seawater Nd isotopic composition (εNd) from deep sea sediments. This study addresses these questions by investigating the processes involved in particulate–solution interactions and their impact on Nd isotopes. A better understanding of boundary exchange also has wider implications for the oceanic cycling and budgets of other particle-reactive elements. Sequential acid-reductive leaching experiments at pH ∼2–5 on deep sea sediments from the western Indian Ocean enable us to investigate natural boundary exchange processes over a timescale appropriate to laboratory experiments. We provide evidence that both the dissolution of solid phases and exchange processes influence the εNd of leachates, which suggests that both processes may contribute to boundary exchange. We use major element and rare earth element (REE) data to investigate the pools of Nd that are accessed and demonstrate that sediment leachate εNd values cannot always be explained by admixture between an authigenic component and the bulk detrital component. For example, in core WIND 24B, acid-reductive leaching generates εNd values between −11 and −6 as a function of solution/solid ratios and leaching times, whereas the authigenic components have εNd ≈ −11 and the bulk detrital component has εNd ≈ −15. We infer that leaching in the Mascarene Basin accesses authigenic components and a minor radiogenic volcanic component that is more reactive than Madagascan-derived clays. The preferential mobilisation of such a minor component demonstrates that the Nd released by boundary exchange could often have a significantly different εNd composition than the bulk detrital sediment. These experiments further demonstrate certain limitations on the use of acid-reductive leaching to extract the εNd composition of the authigenic fraction of bulk deep sea sediments. For example, the detrital component may contain a reactive fraction which is also acid-extractible, while the incongruent nature of this dissolution suggests that it is often inappropriate to use the bulk detrital sediment elemental chemistry and/or εNd composition when assessing possible detrital contamination of leachates. Based on the highly systematic controls observed, and evidence from REE patterns on the phases extracted, we suggest two approaches that lead to the most reliable extraction of the authigenic εNd component and good agreement with foraminiferal-based approaches; either (i) leaching of sediments without a prior decarbonation step, or (ii) the use of short leaching times and low solution/solid ratios throughout