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1.
Laboratory experiments were carried out to assess the role of photochemical reactions upon the dissolution of 239 + 240pu and 241Am from marine sediment in sea water. Supplementary information was obtained by comparing their behaviour with that of 54Mn under similar experimental conditions. Irradiation from natural sunlight resulted in more than a ten-fold increase in the extent of 239 + 240Pu desorption relative to that observed in the dark. Remobilisation of 54Mn from sediment was also enhanced by natural sunlight, albeit to a lesser extent than 239 + 240Pu, whilst the behaviour of 241Am was largely unaffected. Data for concentrations of dissolved 239 + 240Pu(IV) and 239 + 240Pu(V) species showed that only the oxidised form was significantly affected by irradiation, indicating remobilisation occurs as a result of photooxidation reactions. Further experiments were carried out using artificial light sources to establish the influence of wavelength. Data from these investigations indicated 239 + 240Pu photooxidation (hence desorption) was a function of both light intensity and wavelength. Remobilisation decreased concomitant with light intensity but increased as the wavelength decreased. Similar trends were observed for photoreduction of 54Mn, although differences were less pronounced than those observed for 239 + 240Pu.  相似文献   

2.
Bivalve shells offer several advantages over tissues for the monitoring of heavy metal pollutants in the marine environment. They are easier to handle and to store. The problem of whether to depurate the animals before analyses is avoided. The shells appear to be more sensitive to environmental heavy metals levels over the long term than do the soft parts. Of the substances examined (Cd, Cu, Zn, Pb, Ag, Ni, 238Pu and 239 + 240Pu) only Pb and Pu displayed a strong covariance between soft tissue and shell concentrations. There were strong correlations between metals in the shell but not in the soft tissues in general. The byssal threads, because of their enrichment of transuranic elements and of their ease in handling, may be useful in monitoring these metals. A very weak discharge of 238Pu to marine waters adjacent to a nuclear reactor was detected in the byssal threads of mussels.  相似文献   

3.
241Am is a useful tracer for understanding biogeochemical processes in the marine environment. 241Am also poses a potential radiation threat to human health due to the continuous increase of its concentration in the global environment. We report a rapid analytical method for determining 241Am in marine sediments using isotope dilution sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) combined with a high-efficiency sample introduction system (APEX-Q). A selective CaF2 co-precipitation procedure followed by TRU extraction chromatography was employed to effectively remove the major sediment matrix and to pre-concentrate 241Am. We achieved an extremely low detection limit of 0.32 fg/g or 0.041 mBq/g (for 1 gram sediment), which is better than that of alpha spectrometry, and it allowed the accurate determination of 241Am in low-level marine sediment samples. The accuracy and precision of the developed analytical method was evaluated using a laboratory prepared Am isotope standard solution and Ocean Sediment reference material (IAEA-368). The results were satisfactory. For sediment samples, overall chemical recoveries varied from 60–90%. The developed method was applied to the study of 241Am depth distribution in Sagami Bay, Japan, where we observed different depth profiles between 241Am activity and 239+240Pu activity.  相似文献   

4.
We report here thermal ionization mass spectrometry measurements of 239Pu, 240Pu, 241Pu, 242Pu, and 237Np isolated from oceanic, estuarine, and riverine sediments from the Arctic Ocean Basin. 238Pu/239+240Pu activity ratios are also reported for alpha spectrometric analyses undertaken on a subset of these samples. Our results indicate that the Pu in sediments on the Alaskan shelf and slope, as well as that in the deep basins (Amerasian and Eurasian) of the Arctic Ocean, has its origin in stratospheric and tropospheric fallout. Sediments from the Ob and Yenisei Rivers show isotopic Pu signatures that are distinctly different from those of northern-hemisphere stratospheric fallout and indicate the presence of weapons-grade Pu originating from nuclear fuel reprocessing wastes generated at Russian facilities within these river catchments. Consequently, sediments of the Eurasian Arctic Ocean, particularly those in the Barents and Kara Seas, probably contain a mixture of Pu from stratospheric fallout, tropospheric fallout, and fuel-reprocessing wastes of riverine origin. In particular, the 241Pu/239Pu ratios observed in these sediments are inconsistent with significant contributions of Pu to the arctic sediments studied from western European reprocessing facilities, principally Sellafield in the UK. Several other potential sources of Pu to arctic sediments can also be excluded as significant based upon the transuranic isotope ratios presented.  相似文献   

5.
《Marine Geology》2005,216(4):249-263
Bottom sediments collected in the Northwest (NW) Pacific Ocean in 1997 were analysed for 90Sr, 137Cs, 239,240Pu and 241Am contents to determine their distribution patterns, inventories and sources. Enhanced inventories of 239,240Pu and 241Am were observed in the latitudinal belts of 10–20°N and 30–40°N, which correspond to major areas of local (tropospheric) and global (stratospheric) fallout (with a contribution from local fallout), respectively. The sediment inventory of 239,240Pu near the Bikini Atoll exceeded its overlying water inventory, however, in the mid-latitudes, more than 70% of 239,240Pu still remains in the water column. 241Am inventories in sediments exceeded that of the water column for the entire NW Pacific Ocean. Higher 137Cs and 90Sr sediment inventories in the latitudinal belt of 30–40°N are due to global fallout, and they account for about 10% and less than 5% of the water column inventories, respectively. The observed activity ratios of 137Cs/90Sr, 238Pu/239,240Pu and 241Am/239,240Pu in sediment were at some stations higher than the global fallout ratios due to contributions from local fallout and due to specific processes in the water column. Two end-member mixing model based on the 240Pu/239Pu atom ratios observed in global and local fallout yielded ∼60% contribution of the local fallout in the bottom sediments near the Bikini Atoll. The upward decrease in the 240Pu/239Pu atom ratios in the sediment column indicates a decrease in the contribution of local fallout to the Pu inventory with time. 241Am and 241Pu dating of sediment layers was utilized to explain a hiatus in sediment accumulation in the deep seafloor.  相似文献   

6.
The results of the U.S. Mussel Watch Monitoring Program for the period 1976–1978 for trace metals and artificial radionuclides in bivalves are presented. The substances analysed included Ag, Cu, Zn, Cd, Ni, Pb, 238Pu, 239+240Pu and 241Am. The analyses of organic substances will be presented elsewhere. The concentrations of these substances in the bivalves may reflect upwelling processes, anthropogenic inputs or natural levels. Off the California coast, mussels show markedly elevated Pu and Cd concentrations in coastal areas adjacent to the most intensive upwelling zones. Elevated levels of Pb, for example, are found in organisms living adjacent to highly urbanized places. The general patterns of distribution repeat themselves year after year at a given site. Thus, it is concluded that annual monitoring activities may not be necessary and that a frequency of sampling of several or so years may be more appropriate to identify pollution problems. Finally, national or regional baselines for metal concentrations in bivalves from unpolluted waters are proposed. National baselines for Pb in the west coast mussels of 1·0 parts 10?6 and for Ag in east coast mussels of 0·05 parts 10?6 are suggested.  相似文献   

7.
Radionuclide measurements have been conducted on sediment cores collected in 1992 in the south-eastern region of the Barents Sea, known as the Pechora Sea. Cesium-137 and 239,24OPu activities in surface sediments are generally less than 30 Bq/kg, with the highest levels being measured in sediments off the southwestern coastline of the island of Novaya Zemlya. High correlations between both 137Cs and 239,24OPu and the concentration of fine (< 63 μm) particles in surface sediments indicate that much of the variance in radionuclide concentrations throughout the Pechora Sea can be explained by particle size fractionation. However, elevated activities of 137Cs (138 Bq/kg), 60Co (92 Bq/kg), 241Am (433 Bq/kg), and especially 239,24OPu (8.47 × 103 Bq/kg) were measured in one surface sediment sample from the fjord of Chernaya Bay on the southern coast of Novaya Zemlya. The source of radioactive contamination is two underwater nuclear tests conducted in Chernaya Bay in 1955 and 1957.The 238Pu/239,240Vu activity ratio of 0.0245 in Chernaya Bay is equivalent to values measured in global fallout. The 240Pu/239Pu atom ratio (0.0304), measured by mass spectrometry, is much lower than values (0.18) typical of global fallout, but is consistent with ratios measured for fallout from the early (1951–1955) series of weapons tests at the Nevada Test Site. The timing of the Chernaya Bay source term, estimated from the 241Am/241Pu ratio, is consistent with the timing of the 1955 and 1957 underwater nuclear tests. Relatively low initial yields of 241Pu (241Pu/239Pu atom RATIO = 0.00 123) in these tests have resulted in relatively low 241Am/239,240Pu activity ratios (0.05) in recent sediments in Chernaya Bay.Radionuclide tracer profiles in cores from the Pechora Sea can be simulated using a two-layer biodiffusion model with rapid, near-homogeneous mixing in the surface mixed layer and reduced mixing in the deep layer. Lead-210 profiles are consistent with a wide range of sedimentation and mixing rates in the deep sediment layer. However, the 137Cs and 239,240Pu results further constrain the model parameters and indicate that the downward transport of radionuclides in the sediments is governed primarily by sediment mixing, with sediment burial playing a secondary role.  相似文献   

8.
Anthropogenic 90Sr, 239,240Pu and 241Am were used as tracers of water mass circulation in the Crozet Basin of the South Indian Ocean, represented by three main water fronts—Agulhas (AF), Subtropical (STF) and Subantarctic (SAF). Higher 90Sr concentrations observed north of 43°S were due to the influence of AF and STF, which are associated with the south branch of the Subtropical gyre, which acts as a reservoir of radionuclides transported from the North to the South Indian Ocean. On the other hand, the region south of 43°S has been influenced by SAF, bringing to the Crozet Basin Antarctic waters with lower radionuclide concentrations. The 238Pu/239,240Pu activity ratios observed in water and zooplankton samples indicated that, even 35 years after the injection of 238Pu to the Indian Ocean from the burn-up of the SNAP-9A satellite, the increased levels of 238Pu in surface water and zooplankton are still well visible. The radionuclide concentrations in seawater and their availability to zooplankton are responsible for the observed 210Po, 239,240Pu and 241Am levels in zooplankton.  相似文献   

9.
Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19 μmol site mg−1 C, and a log K′ of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu–FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC50 of 58.9 μg l−1. However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC50 ranging from 55.6 μg l−1 in the no-FA control to 137.4 μg l−1 in the 20 mg l−1 FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu–FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.  相似文献   

10.
The accumulation and retention of 241Am by the pelagic tunicate Oikopleura dioica were examined using laboratory cultures and radiotracer methodology. Animals (i.e., trunks and tails) and discarded empty houses accumulated Am from seawater, giving volume/volume concentration factors of 59±8 and 10±1, respectively. The half-time for retention of Am in empty labelled houses transferred to non-contaminated seawater was 29 h; the retention half-time of Am in houses discarded by larvaceans feeding on Am-labelled diatoms was 219 h; the half-time of Am in fecal pellets produced by animals feeding on a monospecific diet of diatoms was 134 h, and 247 h for fecal pellets from animals fed a mixed diet. Approximately 30% of filtered cells remained in houses after the houses were discarded. Sinking rates of discarded houses and fecal pellets were found to vary with temperature and size, ranging from 26–157 m day?1 (house) and from 25–166 m day?1 (fecal pellets). The ubiquity and abundance of appendicularians, together with their prodigious production of houses (e.g., 10±2 houses day?1 at 17°C for each experimental animal) point to their potential significance in the vertical transport of Am, and probably other reactive metals, to intermediate depths in the ocean.  相似文献   

11.
Species-specific photosynthetic responses to stress were detected in mixed phytoplankton assemblages using autoradiography. In laboratory experiments subjecting a mixture of the diatom Phaeodactylum and the flagellate Pseudoisochrysis to control and transient thermal stress treatments of +5, +10, +15 and +20°C, both species responded negatively with Phaeodactylum appearing more sensitive. Whole community measures of stress (14C uptake and DCMU-fluorescence) showed alterations in the photosynthetic response of the two-species mixtures with increasing ΔT, but did not sort out species-specific differences. In two field trials at an estuarine power plant, after entrainment through the plant's cooling system, the photosynthetic rate of a diatom, Cyclotella sp., was reduced whereas the photosynthetic rate of a thecate dinoflagellate, Prorocentrum minimum, was enhanced. Field DCMU-fluorescence measurements of stress failed to detect the observed species-specific entrainment effects.  相似文献   

12.
The water masses of the central and western equatorial Pacific can be divided into two parts: the Western Pacific Warm Pool (WPWP) and the Equatorial Upwelling Region (EUR). The behavior of the WPWP plays a significant role in global climate changes such as the El Niño-Southern Oscillation (ENSO), and it drastically modifies the oceanographic conditions in the area every few years. It is important to evaluate changes in time-series diatom fluxes during both the El Niño and the La Niña events. As a part of the Global Carbon Cycle and Related Mapping based on Satellite Imagery (GCMAPS) Program, time-series sediment trap moorings were deployed and recovered along the Equator at seven stations (Sites MT1–MT7) during five R/V Mirai cruises in the central and western Pacific during January 1999–January 2003. The entire length of this study is divided into two phases depending on the oceanographic conditions: the La Niña event (1999 and 2000); and the El Niño event (2002). Site MT3 was located in the WPWP and Sites MT5–MT7 were in the EUR. Annual means of total diatom fluxes increased towards the east in each year. The fluxes observed at Sites MT4–MT6 decreased from the La Niña event to the El Niño event. However, the fluxes observed at Site MT3 in 2001 and 2002 were higher than those in 2000. Total diatom fluxes showed different seasonal patterns at all sites. The diatom assemblages in the WPWP differed from those of the EUR. Pennate diatoms (e.g., Nitzschia bicapitata, Thalassionema nitzschioides) dominated in the WPWP, while the relative abundances of centric diatoms (e.g., Rhizosolenia bergonii, Azpeitia spp., Thalassiosira spp.) were higher than those of pennate diatoms in the EUR. The diatom fluxes during the La Niña event reflected seasonal oscillation of the WPWP in spatial extent. At Site MT3 during El Niño, terrestrial materials appeared to have been transported by subsurface currents, which might be a secondary influence on total diatom fluxes. The spatial extent of the WPWP reached Site MT7 in 2002, when total diatom fluxes decreased in the sediment traps located in the eastern region including Site MT7. Therefore, we conclude that the relationships between the ENSO and diatoms fluxes in the western and central equatorial Pacific can be explained by the geographic (west–east) expansion or contraction of the WPWP.  相似文献   

13.
We examine the diatom flux collected between November 1996 and April 1998, and between January and October 1999 at the time-series study site in the Cariaco Basin, off Venezuela. The temporal dynamics of the total diatom flux mainly reflect seasonal, trade wind-driven changes in surface hydrographic conditions, including changes associated with the El Niño/Southern Oscillation (ENSO). Highest diatom fluxes (>1.8×107 valves m?2 d?1) coincided with the upwelling season in boreal winters 1997 and 1999. Changes in the composition of the diverse diatom community reflect variations in hydrographic and atmospheric conditions, as well as nutrient availability. Cyclotella litoralis, a neritic diatom typical of nutrient-rich waters, along with resting spores of several Chaetoceros spp., dominate during periods of high diatom flux, following trade wind-driven upwelling. During the boreal summers of 1997 and 1999, nutrient-depleted surface waters resulted in low diatom fluxes (<5.2×106 valves m?2 d?1). The seasonal pattern of high diatom production was altered from July 1997 through April 1998, when the ENSO affected the Caribbean Sea. The occurrence of ENSO during boreal winter 1997–1998 caused a major change in the qualitative composition of the diatom assemblage: the highly diverse diatom assemblage was composed of a mixture of pelagic (Nitzschia bicapitata, Thalassionema nitzschioides var. inflata, T. nitzschioides var. parva, Azpeitia tabularis) and coastal species (C. litoralis, resting spores of Chaetoceros, T. nitzschioides var. nitzschioides). The simultaneous occurrence of neritic and open-ocean diatoms during boreal summers reflects the fact that the Cariaco Basin is influenced by both offshore and coastal waters, with considerable short-term variability in hydrographic conditions and nutrient availability.  相似文献   

14.
Natural colloids are abundant in seawater and are an intermediary in the fate, transport and bioavailability of many trace elements. Knowledge of the pathways and mechanisms of the biological uptake of colloidal Fe and other Fe species is of paramount importance in understanding Fe limitation on marine phytoplankton and thus carbon sequestration in the ocean. Whether the natural colloids serve as a source for the biological Fe requirements of marine phytoplankton, or just as a sink for particle-reactive metals in the oceans remains largely unknown. This study examined the bioavailability of Fe bound with colloids from different regions to a coastal diatom (Thalassiosira pseudonana). Natural colloids were isolated by cross-flow ultrafiltration and radiolabeled with 59Fe before being exposed to phytoplankton. Control experiments were conducted to ensure that 59Fe radiolabeled onto the colloids remained mostly in the colloidal phase. Both the natural oceanic and coastal colloidal organic matter complexed Fe (1 nm–0.2 μm) can be biologically available to the marine diatom even though its uptake was lower than the low molecular weight counterparts. By comparing the measured Fe internalization fluxes and the calculated maximum diffusive uptake fluxes, it is evident that ligand exchange kinetics on the cell surface may control the internalization of macromolecular Fe. The calculated concentration factors under dark and light conditions were generally comparable. Colloidal Fe, as an important intermediary phase, can be actively involved in the planktonic food web transfer through biological uptake and regeneration processes. The bioavailable fraction of Fe may be substantially underestimated by only considering the truly dissolved Fe or overestimated when using the external fluxes, such as aerosol Fe, as the bioavailable fraction.  相似文献   

15.
The effects of cresols on the photosynthesis and growth of natural marine phytoplankton assemblages from the Scripps Pier at La Jolla, California, USA were measured. In two experiments, in which dinoflagellates were the dominant algae, photosynthesis (measured by 14C uptake) was inhibited at concentrations > 100 μg litre?1 and the concentration giving half-maximal photosynthesis was 10,000 μg litre?1. In a third experiment, in which diatoms were dominant, photosynthesis was not inhibited until levels > 10,000 μg litre?1 were reached and the half-maximal concentration was 20,000 μg litre?1. These experiments suggested that dinoflagellates were more sensitive to cresols than diatoms. However, the reverse was true in an experiment using cultures. In a long-term growth experiment (natural assemblages from the Scripps Pier), only a level of 88,000 μg litre?1 completely inhibited growth. There was a two-day lag in growth at 8500 μg litre?1, but the algae recovered and grew as well as the controls which contained no cresols. This experiment was started with a mixed diatom-dinoflagellate-microflagellate population but only the diatoms grew. High concentrations of cresols (> 900 μg litre?1) resulted in a decrease in the diatom Skeletonema costatum, compared with the controls. Otherwise there was no selection for resistant species. In these experiments, cresols were measured by extraction with methylene chloride from seawater followed by measurement by UV absorption. In all experiments cresol levels decreased with time. This was attributed to uptake by phytoplankton and bacterial degradation.  相似文献   

16.
Results of the radiochemical determination of 239+240Pu and 238Pu in seawater, plankton, marine organisms and sediment are reported. The samples were collected in the Taranto Gulf, and the data are compared with those obtained from other stations in the Mediterranean Sea. The vertical distribution of plutonium isotopes in sediments is also presented and discussed.  相似文献   

17.
Thermodynamic considerations based on existing data from various laboratory studies of plutonium species in aqueous solution are used to predict the speciation of this radioactive pollutant in seawater. Oxidation-reduction data for plutonium suggest that Pu(VI) should be very dominant in seawater solution compared to Pu(IV), and that Pu(III) and Pu(V) should be absent. The disproportionation reactions and the alpha reduction mechanism are probably of no consequence to the oxidation state in seawater. However, the irreversible hydrolysis of Pu4+ and the associated formation of polymeric Pu(OH)4 colloids are important mechanisms of speciation control and plutonium removal to sediments, by adsorption onto suspended matter. Stability constants for plutonium complexation with inorganic ligands in seawater suggest that Pu(VI) dissolved in seawater will be dominantly PuO2CO3OH−.The theoretical predictions of plutonium speciation and behaviour in seawater are compared to the only available data on plutonium speciation in seawater (Nelson and Lovett, 1978). Good agreement between the predictions and field observations was obtained, within the limitations imposed by the scarcity of data on this subject.  相似文献   

18.
Interannual variability of nutrients and plankton cycles were studied at the time-series station KERFIX (50°40′S, 68°25′E) using a 1-D coupled physical-biogeochemical model that is descended from that of Pondaven et al. (1998). At KERFIX, a high half saturation constant for silicic acid uptake (KSi) and a high Si/N uptake ratio are required to reproduce the Si and N cycles. Although very high in comparison with most data from temperate systems, these values are consistent with KSi and Si/N uptake ratios measured in the Indian sector of the Southern Ocean. Past and recent finding on the role of light and iron limitation on nutrient consumption ratios might explain these “unusual” silicon uptake kinetic parameters. Comparison of model results with observations show that the model correctly reproduces the observed interannual variability of nutrients and plankton cycles at KERFIX between 1992 and 1995. Characteristic features of this region are a spring phytoplankton bloom of 1.0–1.5 mg Chlorophyll a m−3 and a net excess of silicic acid utilisation over that of nitrate. This high silicic acid utilisation leads to low Si concentrations in late summer and subsequent Si limitation of diatom growth. The interannual variability of production of silicon and nitrogen predicted by the model is 1.93±0.04 mol Si m−2 yr−1 and 1.35±0.07 mol N m−2 yr−1 (±SD). In parallel, the predicted export is 1.12±0.04 mol Si m−2 yr−1 and 0.06±0.01 mol N m−2 yr−1. It is shown that diatoms may contribute significantly to export if diatom sinking is taken into account. An interannual variability of the predicted Si and N cycles is detected. This variability is associated with changes in the mixed layer properties, which have been documented to be linked to the Pacific El Niño Southern Oscillation or displacement of the Polar Front.  相似文献   

19.
Several are the hypotheses proposed to explain the occurrence of Ethmodiscus oozes in tropical sediments representative of some glacial periods. In this paper, a review of those hypotheses within a paleoclimatic perspective is presented. Flux records of Ethmodiscus fragments found in site M16772 (1°21′ S, 11°58′ W) during the last 190 ka are compared to the other marine and freshwater diatom accumulation rates (AR) and diatom assemblages composition. Ethmodiscus is present all along the core, but Ethmodiscus-rich levels are found at 185–170 and 150–140 ka (stages 6.6 and 6.4), and at 70–60 ka (stage 4.2), levels where a concomitant increase in the flux of the other marine diatoms, and in the contribution to the assemblage of diatom species related to equatorial and coastal upwelling, and river plume waters is also observed. Climatic conditions favouring simultaneous occurrence of strong equatorial upwelling, coincident with increased advection of waters from coastal upwelling areas and important river run-off are proposed as the explanation for these Ethmodiscus-rich levels.  相似文献   

20.
《Marine Chemistry》2001,76(3):175-187
Iron (Fe) is an essential element for the biochemical and physiological functioning of terrestrial and oceanic organisms, including phytoplankton, which are responsible for the primary productivity in the world's oceans. However, due to the low solubility of Fe in seawater, phytoplankton are often limited by their inability to incorporate enough Fe to allow for optimal growth rates in regions with dissolved Fe concentrations below 1 nM. It has been postulated that certain phytoplankton may produce compounds to facilitate the uptake of Fe from seawater to overcome this limitation. Dissolved Fe in the oceans is overwhelmingly complexed (>99%) by strong organic ligands that may control the uptake of Fe by microbiota; however, the identity, origin, and chemical characteristics of these organic chelates are largely unknown. Although it has been implied that some components of natural Fe-binding ligands are siderophores, no direct analyses of such compounds from natural seawater have been conducted. Here, we present a simple solid-phase extraction technique employing Biobeads SM-2 and Amberlite XAD-16 resins for concentrating naturally occurring dissolved iron-binding compounds from large volumes (>200 l) of seawater. Additionally, we report on the first successful determination of molecular weight size classes and preliminary iron-binding functional group characterization within those size classes for isolates collected from the surface and below the photic zone (150 m) in the central California coastal upwelling system. Electrochemical analyses using competitive ligand equilibration/adsorptive cathodic stripping voltammetry (CLE-ACSV) showed that isolated compounds had conditional Fe-binding affinities (with respect to inorganic iron—Fe′) of KFeL,Fe′cond=1011.5–1011.9 M−1, similar to purified marine siderophores produced in laboratory cultures and to the ambient Fe-binding ligands observed in seawater. In addition, 63% of the extracted compounds from surface-collected samples fall within the defined size range of siderophores (300–1000 Da). Hydroxamate or catecholate Fe-binding functional groups were present in each compound for which Fe binding was detected. These results illustrate that the functional groups previously shown to be present in marine and terrestrial siderophores extracted and purified from laboratory cultures are also present in the natural marine environment. These data provide evidence that a significant fraction of the organic Fe-binding compounds we collected contain Fe-binding functional groups consistent with biologically produced siderophores. These results provide further insight into characteristics of the Fe-binding ligands that are thought to be important in controlling the biological availability of Fe in the oceans.  相似文献   

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