Jay T. Cullen

Developing standards for dissolved iron in seawater

In nearly a dozen open- ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters. However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well- known dissolved iron (Fe) concentrations similar to open- ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002]. The Sampling and Analysis of Fe (SAFe) cruise was staged from Honolulu, Hawaii, to San Diego, Calif., between 15 October and 8 November 2004 to collect data and samples that were later used to provide this reference material. Here we provide a brief report on the cruise results, which have produced a tenfold improvement in the variability of iron measurements, and announce the availability of the SAFe dissolved Fe in seawater standards.

Modulation of cadmium uptake in phytoplankton by seawater CO2 concentration

The vertical distribution of cadmium in the ocean is characteristic of an algal nutrient, although an underlying physiological basis remains undiscovered. The strong correlation between dissolved cadmium and phosphorus concentrations in sea water has nevertheless been exploited for reconstructing past nutrient distributions in the ocean. In culture experiments, the addition of cadmium accelerates the growth of some marine phytoplankton and increases the activity of carbonic anhydrase, normally a zinc-based metalloenzyme that is involved in inorganic carbon acquisition. Here we show that the concentration of a Cd-carbonic-anhydrase—distinct from Zn-carbonic-anhydrases—in a marine diatom is regulated by the CO2 partial pressure (pCO2) as well as by the zinc concentration. Field studies in intensely productive coastal waters off central California demonstrate that cadmium content in natural phytoplankton populations similarly increases as surface-water pCO2 decreases. Incubation experiments confirm that cadmium uptake by natural phytoplankton is inversely related to seawater pCO2 and zinc concentration. We thus propose that biological removal of cadmium from ocean surface waters is related to its utilization in carbonic anhydrase, and is regulated by dissolved CO2 and zinc concentrations. The dissolved seawater Cd/P ratio would therefore vary with atmospheric pCO2, complicating the use of cadmium as a tracer of past nutrient concentrations in the upper ocean.

Direct determination of 10 trace metals in 50 µL samples of coastal seawater using desolvating micronebulization sector field ICP-MS

Understanding the trace metal marine geochemistry of temporally variable coastal systems requires intensive sampling programs with attendant analytical burdens. Most established techniques for multi-element trace metal determinations are slow, require a skilled chemist, and are not easily automated. Advances in sample introduction systems and ICP-MS instrumentation now provide marine chemists with the sensitivity and mass resolution necessary to determine many trace metals at natural concentrations in coastal seawater. A new method has been developed for the rapid (10 samples h –1 ) determination of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in diluted seawater, requiring just 50 µL of seawater and no reagents other than pure nitric acid. A sensitivity of 800 000-1 200 000 cps ppb –1 86 Sr in a 10% sea water matrix is obtained when microconcentric desolvating nebulization is combined with a shielded torch and hot plasma high resolution ICP-MS. Analyses are standardized by a matrix-matched external calibration curve with variations in sensitivity corrected by normalizing to the natural internal standard Sr, a conservative ion in seawater. The method thus depends on mass bias stability for each analyte relative to Sr, which was examined as a function of forward power and matrix and found to be optimized at 1100-1350 W. Precision and accuracy are limited by appropriate correction for blanks, which derive mainly from the ICP-MS introduction system, and are equivalent to about 10% of typical coastal seawater concentrations for these metals. Preliminary evaluation of a new low-flow nebulizer (µFlow, Elemental Scientific, Omaha, NE, USA) suggested lower blanks and compatibility with solutions high in total dissolved solids compared with standard microconcentric designs. Determination of dissolved concentrations in reference seawater (CASS-3) demonstrate very good agreement with certified values (within 95% confidence limit) and a precision of 3-12% (1σ) for all elements except Cr (15%). The utility of the method is demonstrated by the determination of spatial trends for these metals in a transect of seawater samples from shelf waters off southern New Jersey, USA. The new technique is sufficiently sensitive to determine some of these metals in open ocean seawater and, with minor modifications, should be applicable to a larger suite of analytes in a wide variety of natural waters.

Techniques for determination of trace metals in small samples of size-fractionated particulate matter: phytoplankton metals off central California

The oceanic biogeochemical cycles of many trace elements are dominated by their association with the growth, death, consumption and sinking of phytoplankton. The trace element content of marine phytoplankton reflects nutritional status, species composition, surface area to volume ratios, and interactions with bioactive and toxic elements in the ambient seawater. Despite the ecological and environmental importance of trace element assimilation by autotrophs, there are few modern measurements of trace elements in phytoplankton assemblages from the natural environment. Here we introduce a new method for collection and analysis of size-fractionated particulate samples from practical seawater volumes. We pay particular attention to accurate determination of trace element filter blanks which are typically the limiting factor for analysis of such samples. Metals were determined at very low detection limits by high resolution inductively coupled plasma mass . spectrometry HR-ICP-MS for 11 elements Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, U, Zn and P, which is used as a biomass . . . normalizer in three types of polymer filters 0.45, 5.0, and 53 mm pore size and a quartz fiber filter 0.8 mm pore size . To place these new determinations in a practical context, results are presented for a vertical profile of samples filtered from 1-4 . l of coastal seawater 0.3-1.0 mg total solid dry weight at a station off central California. The results demonstrate that the blanks of the evaluated filter types, precleaned appropriately, are sufficiently low to allow accurate determination of the trace . metal content of three size-classes of phytoplankton. At the Pacific station, measured phytoplankton Zn content as Zn rP agrees with values predicted from single-species culture studies growing at seawater Zn concentrations expected for coastal waters. The new method has utility as a generally applicable and simple size fractionation technique, and allows determination of natural and pollutant elements in small samples of phytoplankton and particles in coastal, estuarine and offshore marine regimes. q 1999 Elsevier Science B.V. All rights reserved.

Undocumented water column sink for cadmium in open ocean oxygen-deficient zones

Significance Cadmium (Cd), a trace nutrient for marine algae, has a marine distribution that closely matches the macronutrients nitrate and phosphate. Sedimentary microfossil records of Cd provide reconstructions of past ocean nutrient distributions that facilitate understanding the role of the oceans in the carbon cycle and climate change. However, incomplete knowledge of processes that control the addition and removal of Cd in the ocean, and Cd’s variability relative to major nutrients, limit use of the paleoceanographic proxy. We present coupled data of Cd concentration and isotopic composition in seawater and suspended marine particles, indicating direct removal of Cd via coprecipitation with sulfide in oxygen-deficient waters. Thus, the marine Cd cycle may be highly sensitive to the extent of global oceanic oxygen depletion. Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals.

Biogeochemistry of cadmium and its release to the environment.

Cadmium is at the end of the 4d-transition series, it is relatively mobile and acutely toxic to almost all forms of life. In this review we present a summary of information describing cadmiums physical and chemical properties, its distribution in crustal materials, and the processes, both natural and anthropogenic, that contribute to the metals mobilization in the biosphere. The relatively high volatility of Cd metal, its large ionic radius, and its chemical speciation in aquatic systems makes Cd particularly susceptible to mobilization by anthropogenic and natural processes. The biogeochemical cycle of Cd is observed to be significantly altered by anthropogenic inputs, especially since the beginning of the industrial revolution drove increases in fossil fuel burning and non-ferrous metal extraction. Estimates of the flux of Cd to the atmosphere, its deposition and processing in soils and freshwater systems are presented. Finally, the basin scale distribution of dissolved Cd in the ocean, the ultimate receptacle of Cd, is interpreted in light of the chemical speciation and biogeochemical cycling of Cd in seawater. Paradoxically, Cd behaves as a nutrient in the ocean and its cycling and fate is intimately tied to uptake by photosynthetic microbes, their death, sinking and remineralization in the ocean interior. Proximate controls on the incorporation of Cd into biomass are discussed to explain the regional specificity of the relationship between dissolved Cd and the algal nutrient phosphate (PO[Formula: see text]) in oceanic surface waters and nutriclines. Understanding variability in the Cd/PO[Formula: see text] is of primary interest to paleoceanographers developing a proxy to probe the links between nutrient utilization in oceanic surface waters and atmospheric CO(2) levels. An ongoing international survey of trace elements and their isotopes in seawater will undoubtedly increase our understanding of the deposition, biogeochemical cycling and fate of this enigmatic, sometimes toxic, sometimes beneficial heavy metal.

Did natural reactors form as a consequence of the emergence of oxygenic photosynthesis during the Archean

The advent of oxygenic photosynthesis changed Earth’s surface environment in numerous ways, perhaps most notably by making possible the evolution of large and complex life-forms. Current models suggest that organisms that can perform oxygenic photosynthesis first took hold in isolated marine and freshwater basins, producing local oxygen oases. Here we present calculations that suggest that uranium deposits could have formed at the margins of these basins due to the strong local reductionoxidation gradients. Because of the high abundance of 235 U at this time, these uranium deposits could have formed widespread, near-surface, critical natural fission reactors. These natural reactors would have represented point sources of heat, ionizing radiation, and free radicals. Additionally, they would have far-field effects through the production of mobile short- and long-lived radioactive daughter isotopes and toxic byproducts. It is possible that these fission products pro vided a negative feedback, helping to limit the proliferation of the cyanobacteria in the Archean environment. Secular decreases in the abundance of 235 U in

Processes controlling the distributions of Cd and PO4 in the ocean

Depth profiles of dissolved Cd and PO4 from a global data compilation were used to derive the Cd/P of particles exported from the surface layer, and the results indicate lowest values in the North Atlantic (0.17 ± 0.05), highest in the Southern (0.56 ± 0.24), and intermediate in the South Indian (0.31 ± 0.14) and North Pacific (0.36 ± 0.08) Ocean basins. The Cd/P of exported particles in high nutrient-low chlorophyll (HNLC) regions is twice that for particles exported in non-HNLC regions as is the fractionation effect during biological uptake of Cd and PO4, and these trends primarily determine the spatial trends of dissolved Cd/PO4 observed in the surface ocean. In deep waters the lowest dissolved Cd/PO4 of 0.23 ± 0.07 is found in the North Atlantic Ocean and the result primarily of low Cd/PO4 of North Atlantic Deep Water (0.23). In contrast, deep waters in the Southern Ocean have significantly higher dissolved Cd/PO4 (0.30 ± 0.06), which is a result of the Cd/PO4 of upwelled deep water from the South Pacific and South Indian (0.28) and the high Cd/P of degrading particles. A multibox model that accounts for the impacts of particle degradation and thermohaline circulation in the deep sea yields dissolved Cd and PO4 interbasin trends close to observations. Model experiments illustrate the dependence of the dissolved Cd/PO4 of the deep sea on the extent of HNLC conditions in the Southern Ocean and the impact on reconstructing paleo PO4 concentrations from a Cd proxy.

The Common Oceanographer: Crowdsourcing the Collection of Oceanographic Data

We live on a vast, underexplored planet that is largely ocean. Despite modern technology, Global Positioning System (GPS) navigation, and advanced engineering of ocean vessels, the ocean is unforgiving, especially in rough weather. Coastal ocean navigation, with risks of running aground and inconsistent weather and sea patterns, can also be challenging and hazardous. In 2012, more than 100 international incidents of ships sinking, foundering, grounding, or being lost at sea were reported (http://en.wikipedia.org/wiki/List_of_shipwrecks_in_2012). Even a modern jetliner can disappear in the ocean with little or no trace [1], and the current costs and uncertainty associated with search and rescue make the prospects of finding an object in the middle of the ocean daunting [2]. Notwithstanding satellite constellations, autonomous vehicles, and more than 300 research vessels worldwide (www.wikipedia.org/wiki/List_of_research_vessels_by_country), we lack fundamental data relating to our oceans. These missing data hamper our ability to make basic predictions about ocean weather, narrow the trajectories of floating objects, or estimate the impact of ocean acidification and other physical, biological, and chemical characteristics of the worlds oceans. To cope with this problem, scientists make probabilistic inferences by synthesizing models with incomplete data. Probabilistic modeling works well for certain questions of interest to the scientific community, but it is difficult to extract unambiguous policy recommendations from this approach. The models can answer important questions about trends and tendencies among large numbers of events but often cannot offer much insight into specific events. For example, probabilistic models can tell us with some precision the extent to which storm activity will be intensified by global climate change but cannot yet attribute the severity of a particular storm to climate change. Probabilistic modeling can provide important insights into the global traffic patterns of floating debris but is not of much help to search-and-rescue personnel struggling to learn the likely trajectory of a particular piece of debris left by a wreck. Oceanographic data are incomplete because it is financially and logistically impractical to sample everywhere. Scientists typically sample over time, floating with the currents and observing their temporal evolution (the Langrangian approach), or they sample across space to cover a gradient of conditions—such as temperature or nutrients (the Eulerian approach). These observational paradigms have various strengths and weaknesses, but their fundamental weakness is cost. A modern ocean research vessel typically costs more than US

Structural Characterization of S100A15 Reveals a Novel Zinc Coordination Site Among S100 Proteins and Altered Surface Chemistry with Functional Implications for Receptor Binding.

30,000 per day to operate—excluding the full cost of scientists, engineers, and the cost of the research itself. Even an aggressive expansion of oceanographic research budgets would not do much to improve the precision of our probabilistic models, let alone to quickly and more accurately locate missing objects in the huge, moving, three-dimensional seascape. Emerging autonomous technologies such as underwater gliders and in situ biological samplers (e.g., environmental sample processors) help fill gaps but are cost prohibitive to scale up. Similarly, drifters (e.g., the highly successful Argo floats program) have proven very useful for better defining currents, but unless retrieved after their operational lifetime, they become floating trash, adding to a growing problem. Long-term sampling efforts such as the continuous plankton recorder in the North Sea and North Atlantic [3] provide valuable data on decadal trends and leveraged English Channel ferries to accomplish much of the sampling. Modernizing and expanding this approach is a goal of citizen science initiatives. How do we leverage cost-effective technologies and economies of scale given shrinking federal research budgets?