Metal partitioning between colloidal and dissolved phases and its relation with bioavailability to American oysters

Kinetics and the extent of metal partitioning between colloidal and dissolved phases and coagulation of metals associated with colloids were examined to determine their effects on the bioavailability of selected metals (Cd, Co, Hg, Ag, Fe, and Zn) to American oysters (Crassostrea virginica) using radiotracer and short term exposure experiments. After dispersion of radiolabeled colloids into low molecular weight (LMW, < 1 kDa) seawater, metal partitioning between dissolved (<1 kDa) and colloidal (1 kDa-0.2 microm) phases resulted in a consistent pattern, with a relatively constant percentage in the colloidal phase for each metal. On average, about 90% of Hg and Fe, approximately 60% of Ag and approximately 40% of Zn, Co, and Cd were measured in the colloidal fraction during a short term exposure experiment, consistent with their partitioning in natural waters. Controlled laboratory experiments carried out in parallel using radioactively tagged colloids showed that coagulation of colloidal species, quantified as the fraction retained by a 0.2 microm filter, was insignificant for most metals under the conditions and time periods of the uptake experiments. The bioavailability of colloidally complexed metals, measured in terms of dry weight concentration factor (DCF, ml g(-1)) and uptake rate constant (ml g(-1) h(-1)), was somewhat depressed compared with their counterpart in the LMW treatment, but could be well predicted from the results of the LMW treatment and metal partitioning. Both DCF values and uptake rate constants were higher in the LMW treatment than in the colloidal treatment. In addition, B-type metals, such as Ag, Hg, and Zn, all had higher values of DCF and uptake rate constants, regardless of treatments, except for Cd which had a lower DCF and uptake rate constant. In contrast, Co and Fe had significantly lower DCF values and uptake rate constants. Most of Hg and Ag (60-80%) were measured in the soft tissue of oysters in both LMW and colloidal treatments. In contrast, 80% of Fe, 75% of Co, and approximately 60% of Cd were observed on the shell, while Zn was found evenly distributed between shell and soft tissue of oysters. These results agree well with the variation pattern of both DCF value and uptake rate constant for these two groups of metals.     

The Uptake of Colloidal Melanin from Seawater by Marine Bivalves

Abstract. A number of coastal organisms ( e.g ., bivalves) are known as important consumers of particulate organic carbon (POC) in the sea. In this paper we present new evidence that they are also important consumers of dissolved organic carbon (DOC) in the colloidal size range down to about 0.2 μm in diameter. Those colloids play an important role in the global flux of carbon in the seas.
We compare the uptake of colloidal DOC by marine bivalves of the North Sea and of the western Indian ocean.
To measure this uptake we made use of colloidal melanin as an alternative way to measure the uptake of colloidal DOC.     

Importance of intracellular Fe pools on growth of marine diatoms by using unialgal cultures and on the Oyashio region phytoplankton community during spring

We report on the ability for luxury Fe uptake and the potential for growth utilizing intracellular Fe pools for 4 coastal centric diatom isolates and in situ phytoplankton assemblages, mainly composed of diatoms. Iron uptake of the diatom isolates and natural phytoplankton assemblages in the Oyashio region during spring blooms were prevented by adding hydroxamate siderophore desferrioxamine B (DFB). After the addition of DFB, intracellular Fe in the diatom isolates supported 2.4–4.2 cell divisions with 1.2–2.6 Chl a doublings. The intracellular Fe was primarily used for cell generation rather than Chl a production, leading to a reduction in the Chl a cell quota in the Fe-starved cells with time. The metabolic properties of the Fe-starved cells with their cell morphologies were different among species or genera. An on-deck incubation experiment also exhibited 1.9 cell divisions and 0.81 Chl a doublings of phytoplankton after the addition of DFB, also indicating the preference of cell generation over Chl a production. A decrease in the level of cellular Chl a, a main light-harvesting pigment in Fe-starved diatoms, may become a superior survival strategy to protect the cells from high irradiance that can cause photo-oxidative damages through photosynthesis. Such relatively low-Fe with high-light conditions could often occur in surface waters of the Oyashio region from spring to summer.     

Exopolysaccharides produced by bacteria isolated from the pelagic Southern Ocean — Role in Fe binding,chemical reactivity,and bioavailability

As a result of ubiquitous excretion by micro-organisms, extracellular polymeric substances are reported in high concentrations in marine systems. The majority of this material is exopolysaccharide (EPS). Despite previous studies showing that EPS can affect carbon as well as trace metal cycling, little is known about the effect on Fe – a critical nutrient limiting primary productivity in up to 40% of the ocean. Here, we have characterised an EPS purified from bacteria isolated from the pelagic Southern Ocean (Pseudoalteromonas sp.) and investigated its role in Fe chemical speciation, solubility, as well as bioavailability for two keystone Southern Ocean phytoplankton strains. This EPS has an average molecular weight of 4.6 MDa, exhibiting mainly –OH, COO– and –NH₂ functional groups. An asymmetrical flow field-flow fractionation coupled online with UV-spectrophotometer, differential refractive index, and multiangle laser light scattering (aFlFFF-UV-DRI-MALS) demonstrates that this EPS is polydisperse with three, not well resolved, size populations having molar masses in the range from 0.57 to 15.8 MDa. Fe was exclusively associated with the medium size fraction of this EPS and was the most abundant trace metal with 2.2 nM Fe per nM EPS. Only a third of this Fe was chemically labile, and the strength of Fe-EPS complexes increased with equilibration time. 1 nM EPS is efficient to retain Fe in solution, mainly in the colloidal phase (0.02–0.2 μm). Fe bound to the EPS was highly bioavailable (25% as much as for inorganic Fe). Due to combined effect of EPS on Fe solubility and bioavailability, it can increase the residence time of bioavailable Fe in the euphotic zone, therefore possibly sustaining and controlling primary productivity in sensitive oceanic regions, such as the Southern Ocean.     

Nickel utilization in phytoplankton assemblages from contrasting oceanic regimes

In most oceanic environments, dissolved nickel (Ni) concentrations are drawn down in surface waters with increasing concentrations at depth, implying a role for biology in the geochemical distribution of Ni. Studies with phytoplankton isolates from the surface ocean have established the biochemical roles of Ni in the assimilation of urea and oxidative defense. To determine if these requirements are relevant in natural marine planktonic assemblages, bottle-based fertilization experiments were used to test the effects of low-level additions of Ni, urea, or both Ni and urea to surface waters at several locations offshore of Peru and California, as well as in the Gulf of California. Urea and Ni+urea additions consistently promoted phytoplankton growth relative to control and +Ni treatments, except in a coastal upwelling site and Peruvian water. No effect was observed in the upwelling site, but in Peruvian waters urea additions resulted in increased phytoplankton pigments and phosphate drawdown only when Ni was added concurrently, suggesting a biochemically dependent Ni–urea colimitation. In the Gulf of California, Ni additions without urea resulted in increased abundances of cyanobacteria, picoeukaryotes, and the corresponding pigments. As urea additions showed the overall phytoplankton community was also urea-limited, it appears that the cyanobacteria and potentially the picoeukaryotes were colimited by Ni and urea in a biochemically independent fashion. In parallel, radiotracer-based uptake experiments were used to study the kinetics and spatial variation of biological Ni assimilation. In these experiments, the added radiotracer rarely equilibrated with the natural Ni present, precluding estimates a determination of in situ Ni uptake rates and suggesting that much of the natural Ni was not bioavailable. The lack of equilibration likely did not preclude the measurement of community Ni uptake kinetics, nor the comparison of measured rates between locations. The highest V_maxK_ρ^?1 values, which reflect a competitive advantage in Ni acquisition at low concentrations, were observed in stratified nitrogen-deplete communities, potentially linking Ni and nitrogen biogeochemistry in a manner consistent with the biochemical utilization of Ni. Overall, uptake rates were higher in the euphotic rather than non-euphotic zone communities, directly reconciling the nutrient-like depth profile of Ni. The Ni uptake rates observed at the nitrate-replete Fe-deplete Peru stations were an order of magnitude lower than the other sites. This result agrees with calculations suggesting that saturation of the cell surface with Ni and iron (Fe) transporters may limit uptake rates in low Fe waters.     

Collection and detection of natural iron-binding ligands from seawater

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 K_FeL,Fe′^cond=10^11.5–10^11.9 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.     

Iron speciation in coastal rainwater: concentration and deposition to seawater

More than half of the dissolved iron in rain collected in Wilmington, NC, USA, occurred as Fe(II)(aq). More than 80% of the dissolved iron in marine rain from several marine storms in both North Carolina and New Zealand was Fe(II)(aq). In almost all rain events Fe(II)(aq) was in excess of Fe(III)(aq). Rainwater is a significant source of iron to surface seawater and contributes approximately 10¹⁰ mol year⁻¹ of dissolved plus particulate iron to surface seawater on a global scale, which is more than 30 times the amount of iron resident in the surface 10 m of seawater. The length of time atmospherically deposited dissolved iron remains in surface seawater is critical to its role as a phytoplankton nutrient because it is predominately the soluble form of Fe that is bioavailable. Earlier studies have demonstrated that Fe(II)(aq) oxidizes rapidly in seawater. Our experiments utilizing authentic rainwater with ambient concentrations and speciation of iron clearly demonstrate, however, that rainwater Fe(II)(aq) is stabilized against oxidation for more than 4 h in seawater and rainwater Fe(III)(aq) is protected against rapid precipitation when added to coastal or oligotrophic seawater. These results are significant because they show rainwater deposited Fe does not behave as previously thought based on earlier kinetic work on non-rainwater Fe(II) oxidation in seawater. Rainwater, therefore, is an important source of soluble, stable Fe(II)(aq) to surface seawater.     

Iron regeneration and organic iron(III)-binding ligand production during in situ zooplankton grazing experiment

To elucidate iron regeneration and organic iron(III)-binding ligand formation during microzooplankton and copepod grazing on phytoplankton, incubation experiments were conducted in the western subarctic Pacific. During 8 days of dark incubation of ambient water and that amended with plankton concentrate, dissolved iron and organic iron(III)-binding ligands accumulated, approximately proportionally to the decrease in chlorophyll a. The observed increases in dissolved iron concentration were much greater than those expected from the consumption of phytoplankton biomass and previously reported Fe:C value of cultured algal cells, suggesting resolution from colloidal or particulate iron adsorbed onto the algal cell surface. When copepods were added to the ambient water, organic iron(III)-binding ligands accumulated more rapidly than in the control receiving no copepod addition, although consumed phytoplankton biomass was comparable between the two treatments. Bioassay experiment using filtrates collected from the incubation experiment showed that organic ligands formed during microzooplankton grazing reduced the iron bioavailability to phytoplankton and suppressed their growth. Moreover, picoplankton Synechococcus sp. and Micromonas pusilla were more suppressed by the organic ligands than the diatom Thalassiosira weissflogii. In conclusion, through microzooplankton and copepod grazing on phytoplankton, organic iron(III)-binding ligands as well as regenerated iron are released into the ambient seawater. Because the ligands lower iron bioavailability to phytoplankton through complexation and the degree of availability reduction varies among phytoplankton species, grazing by zooplankton can shift phytoplankton community structure in iron-limited waters.     

Interactions of marine plankton with transuranic elements. II. Influence of dissolved organic compounds on americium and plutonium accumulation in a diatom

To assess the significance of naturally occurring dissolved organic matter (DOM) on complexation of transuranic elements in seawater, a series of bioassay experiments was conducted in which the effect of DOM on the accumulation of ²⁴¹ Am, ²³⁷Pu (III–IV), and ²³⁷Pu (V–VI) by the marine diatom Thalassiosira pseudonana was measured. EDTA at 0.3μM complexed both metals substantially, resulting in reduced radio-isotope uptake by the diatom; the greatest effect was on Pu (III–IV). In contrast, there was no apparent complexation of either element by equimolar concentrations of marine fulvic (MFA) or humic acids (MHA), naturally occurring photooxidizable DOM (uncharacterized), or diatom exudates, as none of these materials reduced isotope uptake; on the contrary, there were indications that some of this DOM enhanced transuranic bioaccumulation in the diatom slightly. Subsequent experiments showed this enhancement was probably due to complexation of transition metals by the DOM, leading to fewer ambient ions ‘competing’ for binding sites on the cells; ²⁴¹ Am uptake rates were negatively correlated (r =? 0.846, P < .01) with Σ ASV-labile Cu + Zn + Cd + Pb. These experiments suggest that naturally occurring DOM may not appreciably complex Am or Pu or greatly affect their bioavailability in the sea.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Iron deficiency in micro-sized diatoms in the Oyashio region of the Western subarctic Pacific during spring

In order to detect iron (Fe) stress in micro-sized (20–200 μm) diatoms in the Oyashio region, western subarctic Pacific during spring, immunological ferredoxin/flavodoxin assays were applied to samples collected from the surface layer in May 2005. Concomitantly, the community composition of the micro-sized phytoplankton and hydrographic conditions, including dissolved Fe and macronutrient concentrations, were also examined. Chlorophyll (Chl) a concentrations were <2 mg m⁻³ at all sampling stations, except at a station where the Chl a level was 9.0 mg m⁻³ and a micro-sized diatom bloom occurred. A high abundance of ferredoxin in micro-sized diatoms was detected only at a rather near-shore station where dissolved Fe and macronutrient concentrations were higher, indicating that the micro-sized diatoms did not suffer from iron deficiency. On the other hand, flavodoxin in micro-sized diatoms was often observed at the other stations, including the bloom station, where macronutrients were replete but dissolved Fe concentration was low (0.31 nM). A significant amount of chlorophyllide a, a degradation product of Chl a, was also observed at the bloom station, suggesting a decline of the diatom bloom. The micro-sized phytoplankton species at all the stations were mainly composed of the diatoms Thalassiosira, Chaetoceros, and Fragilariopsis spp. Our study indicates that micro-sized diatoms were stressed by Fe bioavailability during the spring season in the Oyashio region     

Phytoplankton dynamics in the NE subarctic Pacific

Ocean Station Papa (OSP, 50°N 145°W) in the NE subarctic Pacific is characterised as high nitrate low chlorophyll (HNLC). However, little is known about the spatial extent of these HNLC waters or the phytoplankton dynamics on the basin scale. Algal biomass, production and size-structure data are presented from winter, spring and summer between 1992 and 1997 for five stations ranging from coastal to open-ocean conditions. The inshore stations (P04–P16) are characterised by the classical seasonal cycle of spring and late summer blooms (production >3 g C m⁻² d⁻¹), diatoms are not Fe-stressed, and growth rate is probably controlled by macronutrient supply. The fate of the phytoplankton is likely sedimentation by diatom-dominated spring blooms, with a pelagic recycling system predominating at other times. The offshore stations (P20/OSP) display low seasonality in biomass and production (OSP, mean winter production 0.3 g C m⁻² d⁻¹, mean spring/summer production 0.85 g C m⁻² d⁻¹), and are dominated by small algal cells. Low Fe availability prevents the occurrence of diatom blooms observed inshore. The main fate of phytoplankton is probably recycling through the microbial food web, with relatively low sedimentation compared to inshore. However, the supply of macro- and micro-nutrients to the coastal and open ocean, respectively, may vary between years. Variability in macro-nutrient supply to the coastal ocean may result in decreased winter reserve nitrate, summer nitrate limitation, subsequent floristic shifts towards small cells, and reduced primary production. Offshore, higher diatom abundances are occasionally observed, perhaps indicating episodic Fe supply. The two distinct oceanic regimes have different phytoplankton dynamics resulting in different seasonality, community structure and fate of algal carbon. These differences will strongly influence the biogeochemical signatures of the coastal and open-oceanic NE subarctic Pacific.     

海水中腐殖质对溶解态铁的络合及其影响因素

腐殖质(humic substances,简称HS)是地表普遍存在的天然有机物,对海洋中重要的微量营养元素-铁(Fe)的分布及生物地球化学循环具有重要的影响作用。本文对腐殖质的来源、分布及对海水中溶解态铁的迁移转化的影响做了总结,特别论述了其在河口及沿岸水域的行为。大量研究表明河口、沿岸及开放海水中溶解态铁分布的变化可以用腐殖质的浓度及其铁结合能力的变化来解释。腐殖质的络合作用不仅能够阻止溶解态铁(DFe)在河口、沿岸等水域被去除,而且能够通过洋流将DFe迁移至外海及大洋区域,此外还能增加铁的溶解度及对海水中浮游植物的生物可利用性,并且促进铁的氧化还原循环。研究还发现两者之间的络合强度受到盐度、pH等理化因素的影响。盐度是影响HS与DFe配合能力的重要影响因素,盐度增加,导致HS中可以与Fe配合的位点数量降低,配合总量呈现指数降低,而pH的增加可以增加HS与DFe的配合量。另外HS还能影响海水中DFe的氧化还原,并以此影响浮游植物对DFe的吸收利用。因此腐殖质对溶解态铁的有机络合作用是影响其海洋生物地球化学循环的一个重要参数,对进一步研究海水中腐殖质的浓度和分布具有重要的意义。     

Studies of nitrogen assimilation by marine phytoplankton and its implication in the nitrogen cycling in the sea

I present here a review of my work concerning nitrogen assimilation by marine phytoplankton. This opportunity was provided to me as the recipient of the Okada Prize for 1990 from the Oceanographical Society of Japan. Assimilation of nitrogenous nutrients by phytoplankton has received considerable research effort since it is an essential process in organic matter production in the sea surface. The use of¹⁵N technique is necessary for tracing nitrogen assimilation by natural marine phytoplankton, but nitrogen metabolism of heterogenous natural populations significantly complicates flow of isotope. Dilution of¹⁵N isotope by heterotrophic regeneration of ammonium causes underestimates of uptake rates. I made an evaluation of isotope dilution effects in available data sets of¹⁵N-ammonium uptake experiments in literature. Incorporated¹⁵N in particulates might revert back to dissolved organic or inorganic nitrogen. I conducted pulse-chase experiments which can quantify such loss of tracer. From these studies, a short term experiment with sufficient amount of tracer enrichment is found to overwhelm these problems. In such an experiment, however, the elevation of nutrient concentration by tracer addition may likely perturb the uptake process. An initial rapid uptake is expected if the population is nitrogen deficient, but I found that this phenomenon is not common to surface oligotrophic open oceans. Uptake rate from such an experiment, or capacity of nitrogen uptake, was obtained using surface waters from an extended area in the North Pacific, and its regional variability was discussed. In addition to overall¹⁵N uptake, time series analysis of intracellular¹⁵N partitioning between hot ethanol soluble and insoluble fractions was found to be useful. When¹⁵N-ammonium is added to nitrogen deficient cells of phytoplankton,¹⁵N is accumulated in the ethanol soluble fraction. Using cultured strains of marine phytoplankton, this accumulation was proved to be caused by the difference of rates of nitrogen uptake and nitrogenous macromolecule synthesis. Uptake rate per cell is relatively constant irrespective of nutritional status, but macromolecule synthesis decreases with nitrogen deficiency. This accumulation of¹⁵N in the ethanol soluble fraction was used as an index of nutritional status with respect to nitrogen of the natural populations of phytoplankton from the western North Pacific. The uptake capacity of nitrate was observed to be higher than that of ammonium in the regional upwelling around Izu Islands and during the spring bloom in Alaskan coastal water. The¹⁵N partitioning technique revealed that nitrate taken up was rapidly incorporated in the macromolecule fraction. This suggests that ammonium uptake is suppressed to be smaller than intracellular nitrogen assimilation, rather than that nitrate is taken up in excess and accumulates within the cell. Regulation of nitrate uptake by light intensity was also discussed in detail for the Alaskan data. Several other studies currently conducted are also mentioned.     

Trace metal composition of colloidal organic material in marine environments

Marine colloidal material (1 kDa–0.2 μm) was isolated by cross-flow ultrafiltration followed by diafiltration and freeze-drying from surface waters of the Gulf of Mexico and the Middle Atlantic Bight (MAB), as well as from estuarine waters of Galveston Bay. Elemental characterization of isolated colloidal material included organic carbon (OC) and selected trace metal (Cu, Pb, Zn, Cd, Co, Ni, Cr, Be, Fe, Al, Mn, V, Ba, and Ti) determinations. It was found that levels of these metals in marine colloids ranged from <0.1 to 50 μg/g colloidal matter, except for Fe which generally had a concentration >120 μg/g. Most metals (Cu, Pb, Zn, Ni, Al, Mn, V, and Ti) had an average concentration >1 μg/g while concentrations of Cd, Co and Be were usually <1 μg/g. Metal concentrations (μg/g) in isolated colloids were, in general, higher in Galveston Bay than in the Gulf of Mexico, suggesting either high abundance of trace metals in estuarine waters or differences in organic matter composition. Higher colloidal metal concentrations in the MAB than in the Gulf of Mexico might be due to higher terrestrial inputs in the MAB. Colloidal metal concentrations (μg/g) were generally lower than those in average soils, continental crust and suspended particles. However, metal/aluminum ratios (Me/Al) in isolated marine colloids were significantly higher than those for average soils and continental crust. Most importantly, colloids had a metal composition and metal/OC ratio (Me/C) similar to humic substances and marine plankton, suggesting that marine colloids largely originate from planktonic sources and are composed of predominately organic components. The Me/C ratios of Galveston Bay colloids followed the sequence of Cu>Ni, Cr, Zn>Mn>Co>Pb, Cd, which is similar to the Irving–Williams order except for Mn, suggesting that the interaction of metals with marine colloids is determined by the affinity of metals for specific organic ligands.     

The role of organic ligands in iron cycling and primary productivity in the Antarctic Peninsula: A modeling study

Iron (Fe) is the limiting nutrient for primary productivity in the Southern Ocean, with much of the dissolved iron (dFe) bound to organic ligands or colloids. A Fe model for the Southern Ocean (SOFe) is developed to understand the role of bacteria and organic ligands in controlling Fe cycling and productivity. The model resolves the classical food web and microbial loop, including three types of nutrients (N, Si, Fe) and two types of Fe ligands. Simulations of the zero-dimensional (0-D) model are calibrated with detailed results of shipboard grow-out incubation experiments conducted with Antarctic Peninsula phytoplankton communities during winter 2006 to provide the best estimate of key biological parameters. Then a one-dimensional (1-D) model is developed by coupling the biological model with the Regional Oceanic Modeling System (ROMS) for a site on the Antarctic Peninsula shelf, and the model parameters are further calibrated with data collected from two surveys (summer 2004 and winter 2006) in the area. The results of the numerical simulations agree reasonably well with observations. An analysis of the 1-D model results suggests that bacteria and organic ligands may play an important role in Fe cycling, which can be categorized into a relatively fast mode within the euphotic zone dominated by photo-reactions (summer d Fe residence time about 600 days) and complexation and a slow mode below with most of the dFe biologically complexed (summer dFe residence time >10 years). The dFe removal from the euphotic zone is dominated by colloidal formation and further aggregations with additional contribution from biological uptake, and an increase of organic ligands would reduce Fe export. The decrease of Fe removal rate over depth is due to the continuous dissolution and remineralization of particulate Fe. A number of sensitivity experiments are carried out for both 0-D and 1-D models to understand the importance of photo-reactive processes in primary productivity, bacterial activity, Fe speciation, and dFe residence time within the euphotic zone. The bio-availability of ligand-bound Fe (FeL) is critical to modeled high primary productivity, which is consistent with both shipboard measurements and field observations. In addition, model productivity is sensitive to photoreaction rates if FeL is not directly available for phytoplankton uptake.     

An Ecosystem Model Including Nitrogen Isotopes: Perspectives on a Study of the Marine Nitrogen Cycle

We have developed an ecosystem model including two nitrogen isotopes (¹⁴N and ¹⁵N), and validated this model using an actual data set. A study of nitrogen isotopic ratios (δ¹⁵N) using a marine ecosystem model is thought to be most helpful in quantitatively understanding the marine nitrogen cycle. Moreover, the model study may indicate a new potential of δ¹⁵N as a tracer. This model has six compartments: phytoplankton, zooplankton, particulate organic nitrogen, dissolved organic nitrogen, nitrate and ammonium in a two-box model, and has biological processes with/without isotopic fractionation. We have applied this model to the Sea of Okhotsk and successfully reproduced the δ¹⁵N of nitrate measured in seawater and the seasonal variations in δ¹⁵N of sinking particles obtained from sediment trap experiments. Simulated δ¹⁵N of phytoplankton are determined by δ ¹⁵N of nitrate and ammonium, and the nitrogen f-ratio, defined as the ratio of nitrate assimilation by phytoplankton to total nitrogenous nutrient assimilation. Detailed considerations of biological processes in the spring and autumn blooms have demonstrated that there is a significant difference between simulated δ¹⁵N values of phytoplankton, which assimilates only nitrate, and only ammonium, respectively. We suggest that observations of δ ¹⁵N values of phytoplankton, nitrate and ammonium in the spring and autumn blooms may indicate the ratios of nutrient selectivity by phytoplankton. In winter, most of the simulated biogeochemical fluxes decrease rapidly, but nitrification flux decreases much more slowly than the other biogeochemical fluxes. Therefore, simulated δ¹⁵N values and concentrations of ammonium reflect almost only nitrification. We suggest that the nitrification rate can be parameterized with observations of δ¹⁵N of ammonium in winter and a sensitive study varying the parameter of nitrification rate.     

Spatiotemporal development of physical,chemical, and biological characteristics of stormwater plumes in Santa Monica Bay,California (USA)

This study characterized stormwater plume development and associated phytoplankton dynamics in a coastal marine ecosystem through shipboard monitoring. We focused on plumes within Santa Monica Bay, California (USA), a coastal system that is subject to rapid pulses of untreated runoff from the urbanized watershed of Los Angeles during the winter rainy season. The physical, chemical, and biological signatures of stormwater plumes were tracked over time after each of 4 precipitation events ranging in magnitude from 1.5 cm to 9 cm. Low salinity surface plumes persisted in Santa Monica Bay for at least 2 to 5 days over spatial scales of up to 15 km. This is consistent with a 6-day residence time for surface water plume parcels, which was estimated from a drifter trajectory in the bay. Shipboard sampling and salinity measurements in the surf zone showed that plumes often persisted even longer nearshore. Plume waters were generally characterized by higher concentrations of dissolved nitrogen, colored dissolved organic matter, and higher light attenuation than non-plume waters. The magnitude of the effect of stormwater runoff on phytoplankton dynamics was dependent on the size of each storm and subsequent residence time of runoff within the bay. Rain events led to increases in primary productivity, phytoplankton biomass, and specifically, increases in diatom biomass, as measured by concentrations of biogenic silica.     

Seasonal changes in size-fractionated primary production and nutrient concentrations in the temperate neritic water of Funka Bay,Japan

Size-fractionated primary productivity and chlorophylla concentration were studied at two stations in the temperate neritic water of Funka Bay, Japan, from April 1984 to May 1985. Size distributions of phytoplankton were discussed in relation to nutrient availability. In the central part of the bay, 66% of the annual primary production occurred during the spring phytoplankton bloom with 95% of the spring production being accounted for by the greater than 10µm size fraction, which was dominated by diatoms. The increase in this large fraction was enhanced at both stations when nutrient concentrations increased in the bay's upper layer. Under low nutrient concentrations during summer, small phytoplankters (<2µm) accounted for 40 to 75% (average 60%) of the total¹⁴C uptake at the central station, and from 25 to 59% (average, 45%) at the coastal station. However, a sudden nutrient enrichment at the coastal station during the summer triggered the growth of the large size fraction. These seasonal and regional changes in total¹⁴C uptake were attributed to the large size fraction, composed mainly of diatoms. From the decreases in various nutrients during diatom blooms, it was further suggested that the predominance of diatoms was determined, not only by nutrient concentrations, but also by their relative availability.Contribution No. 205 from the Research Institute of North Pacific Fisheries, Faculty of Fisheries, Hokkaido University.     

The behaviour of 59Fe in marine microhabitat

Under the artificial condition the 59Fe morphology in sea water, its concentration in sediment and phytoplankton, its distribution and metabolism in tissue organs of marine animals were studied. The results showed that the morphology of 59Fe was in a particulate state in sea water. The adsorption rule of 59Fe by three kinds of sediments was similar. The concentration ability of 59Fe by phytoplankton was very strong. The critical concentration organs of S9Fe by marine animals were viscera. The gross radioactivity of 59Fe was mainly concentrated in protein. The concentration factor of 59Fe by DNA was the highest one. After excretion experiment, 59Fe of all the tissue organs was not detected. Small part of59Fe remained in the organic acid and protein state. There was a redistribution process in sediment for59Fe.