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1.
Aerosol (soluble and total) iron and water-column dissolved (DFe, < 0.2 μm) and total dissolvable (TDFe, unfiltered) iron concentrations were determined in the Canary Basin and along a transect towards the Strait of Gibraltar, in order to sample across the Saharan dust plume. Cumulative dust deposition fluxes estimated from direct aerosol sampling during our one-month cruise are representative of the estimated deposition fluxes based on near surface water dissolved aluminium concentrations measured on board. Iron inventories in near surface waters combined with flux estimates confirmed the relatively short residence time of DFe in waters influenced by the Saharan dust plume (6–14 months). Enhanced near surface water concentrations of DFe (5.90–6.99 nM) were observed at the Strait of Gibraltar mainly due to inputs from metal-rich rivers. In the Canary Basin and the transect towards Gibraltar, DFe concentrations (0.07–0.76 nM) were typical of concentrations observed in the surface North Atlantic Waters, with the highest concentrations associated with higher atmospheric inputs in the Canary Basin. Depth profiles showed that DFe and TDFe were influenced by atmospheric inputs in this area with an accumulation of aeolian Fe in the surface waters. The sub-surface minimum of both DFe and TDFe suggests that a simple partitioning between dissolved and particulate Fe is not obvious there and that export may occur for both phases. At depths of around 1000–1300 m, both regeneration and Meddies may explain the observed maximum. Our data suggest that, in deep waters, higher particle concentrations likely due to dust storms may increase the scavenging flux and thus decrease DFe concentrations in deep waters.  相似文献   

2.
An iron enrichment experiment, EisenEx, was performed in the Atlantic sector of the Southern Ocean during the Antarctic spring of 2000. Deck incubations of open ocean water were performed to investigate the influence of ultraviolet B (UVB: 280–315 nm) and ultraviolet A (UVA: 315–400 nm) on the speciation of iron in seawater, using an addition of the radioisotopes 59Fe(III) (1.25 nM) or 55Fe(III) (0.5 nM). Seawater was sampled inside and outside the iron-enriched region. The radioisotopic Fe(II) concentration was monitored during daylight under three different light conditions: the full solar spectrum (total), total minus UVB, and total minus UVB+UVA. A distinct diel cycle was observed with a clear distinction between the three different light regimes. A clear linear relationship was found for the concentration of radioisotopic Fe(II) versus irradiance. UVB produced most of the Fe(II) followed by UVA and visible light (VIS: 400–700 nm), respectively. UVB produced 4.89 and 0.69 pM m2 W−1 radioisotopic Fe(II) followed by UVA with 0.33 and 0.10 pM m2 W−1 radioisotopic Fe(II) and VIS with 0.04 and 0.03 pM m2 W−1 radioisotopic Fe(II).  相似文献   

3.
Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 1013 relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.  相似文献   

4.
Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (rs), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (rs=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (rs=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.  相似文献   

5.
We have investigated the chemical forms, reactivities and transformation kinetics of Fe(III) species present in coastal water with ion exchange and filtration methods. To simulate coastal water system, a mixture of ferric iron and fulvic acid was added to filtered seawater and incubated for a minute to a week. At each incubation time, the seawater sample was acidified with hydrochloric acid and then applied to anion exchange resin (AER) to separate negatively charged species (such as fulvic acid, its complexes with iron and iron oxyhydroxide coated with fulvic acid) from positively charged inorganic ferric iron (Fe(III)′). By monitoring the acid-induced Fe(III)′ over an hour, it was found that iron complexed by fulvic acid dissociated rapidly to a large extent (86–92% at pH 2), whereas amorphous ferric oxyhydroxide particles associated with fulvic acid (AFO-L) dissociated very slowly with the first-order dissociation rate constants ranging from 6.1 × 10− 5 for pH 3 to 2.7 × 10− 4 s− 1 for pH 2. Therefore, a brief acidification followed by the AER treatment (acidification/AER method) was likely to be able to determine fulvic acid complexes and thus differentiate the complexes from the AFO-L particles (the dissolution of AFO-L was insignificant during the brief acidification). The acidification/AER method coupled with a simple filtration technique suggested that the iron–fulvic acid complexes exist in both the < 0.02 μm and 0.02–0.45 μm size fractions in our coastal water system. The truly dissolved iron (< 0.02 μm) was relatively long-lived with a life-time of 14 days, probably due to the complexation by strong ligands. Such an acid-labile iron may be an important source of bioavailable iron in coastal environments, as a significant relationship between the chemical lability and bioavailability of iron has been well recognised.  相似文献   

6.
The relationship between total and chemically labile Fe has been studied in estuarine, coastal and shelf waters of the Gulf of Maine, U.S.A. Measurements of the labile fraction of total Fe, defined by complexation with 8-hydroxyquinoline in 1 h, correlate with the availability of Fe to marine phytoplankton and therefore can be used to estimate Fe availability in seawater. The results show that the relative lability (=labile/total) of Fe in seawater varied both spatially and temporally from near-zero to 100%. Although particulate Fe (>0.45 μm) was generally less labile than dissolved Fe (<0.45 μm), the particulate fraction often contributed substantially to labile Fe concentrations overall. Conversely, as much as 75% of ‘dissolved’ Fe was non-labile, and therefore was probably not available to phytoplankton. In seawater/river-water mixing experiments, aggregation diminished the relative lability of Fe by 30%, even though much of it remained in the ‘dissolved’ fraction. Considering phytoplankton nutrition, these results demonstrate that equating dissolved Fe concentrations with ‘available’ metal can be misleading. Furthermore, the large variability observed in the labile proportion of total Fe in seawater indicates that Fe availability to phytoplankton cannot be estimated by applying fixed lability-ratios to total Fe concentrations.  相似文献   

7.
To verify the hypothesis that the growth of phytoplankton in the Western Subarctic Gyre (WSG), which is located in the northwest subarctic Pacific, is suppressed by low iron (Fe) availability, an in situ Fe fertilization experiment was carried out in the summer of 2001. Changes over time in the abundance and community structure of phytoplankton were examined inside and outside an Fe patch using phytoplankton pigment markers analyzed by high-performance liquid chromatography (HPLC) and flow cytometry (FCM). In addition, the abundance of heterotrophic bacteria was also investigated by FCM. The chlorophyll a concentration was initially ca. 0.9 μg l−1 in the surface mixed layer where diatoms and chlorophyll b-containing green algae (prasinophytes and chlorophytes) were predominant in the chlorophyll biomass. After the iron enrichment, the chlorophyll a concentration increased up to 9.1 μg l−1 in the upper 10 m inside the Fe patch on Day 13. At the same time, the concentration of fucoxanthin (a diatom marker) increased 45-fold in the Fe patch, and diatoms accounted for a maximum 69% of the chlorophyll biomass. This result was consistent with a microscopic observation showing that the diatom Chaetoceros debilis had bloomed inside the Fe patch. However, chlorophyllide a concentrations also increased in the Fe patch with time, and reached a maximum of 2.2 μg l−1 at 5 m depth on Day 13, suggesting that a marked abundance of senescent algal cells existed at the end of the experiment. The concentration of peridinin (a dinoflagellate marker) also reached a maximum 24-fold, and dinoflagellates had contributed significantly (>15%) to the chlorophyll biomass inside the Fe patch by the end of the experiment. Concentrations of 19′-hexanoyloxyfucoxanthin (a prymnesiophyte marker), 19′-butanoyloxyfucoxanthin (a pelagophyte marker), and alloxanthin (a cryptophyte marker) were only incremented a few-fold increment inside the Fe patch. On the contrary, chlorophyll b concentration reduced to almost half of the initial level in the upper 10 m water column inside the Fe patch at the end of the experiment. A decrease with time in the abundance of eukaryotic ultraphytoplankton (<ca. 5 μm in size), in which chlorophyll b-containing green algae were possibly included was also observed by FCM. Overall, our results indicate that Fe supply can dramatically alter the abundance and community structure of phytoplankton in the WSG. On the other hand, cell density of heterotrophic bacteria inside the Fe patch was maximum at only ca. 1.5-fold higher than that outside the Fe patch. This indicates that heterotrophic bacteria abundance was little respondent to the Fe enrichment.  相似文献   

8.
Intertidal microphytobenthos (MPB) were investigated monthly from August 2006 to March 2008 at four different sites in the sand flats of Nakdong River estuary, Korea. Samples of surface sediment (ca. 1 cm) were collected, and chlorophyll a was extracted as biomass estimation. Species identification and enumeration were carried out by light microscopy, assisted where necessary by scanning electronic microscopy. Biomass varied between 0.47 and 16.58 μg cm−3, abundance changed from 5.25 to 414.75 × 103 cells cm−3, while the Shannon diversity indexes ranged between 0.69 and 2.35 H′. Thirty-nine MPB taxa were identified, primarily composed of epipelic diatoms, among which Amphora and Navicula were the most abundant genera. Based on the biomass, abundance, species composition and their dynamics, MPB assemblages of sampling sites were grouped into three distinct communities corresponding to their sediment composition characteristics. Multivariate correlation analysis revealed that biomass was positively related to mud and very fine sand, negatively related to fine and medium sand, but not significantly related to environmental factors such as pore water nutrients, light intensity and salinity, which fluctuated rapidly during emersion period. Cluster analysis corroborated the division of MPB communities according to site types on seasonal scales, and also showed seasonality between sites by cluster of all summer groups. Principal component analysis identified that variability in species composition was significantly affected by mud, very fine sand, fine sand, light intensity, and sediment temperature. This study suggests that sediment composition plays an important role in the functioning of intertidal MPB communities in estuarine ecosystems.  相似文献   

9.
In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g−1), Cu (1330 μg g−1) and Cd (12 μg g−1) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (Kd) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   

10.
Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using 59Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 106M−1s−1 and 20 M−1s−1, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)3o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands.  相似文献   

11.
Particle-bound phosphorus along an urbanized coastal plain estuary   总被引：1，自引：0，他引：1  
The distribution of particle-bound phosphorus in the suspended sediment of the Delaware Estuary was examined with a sequential chemical leaching technique. The phosphorus content of particles was highest in the tidal river (140–250 μmol g−1) near major anthropogenic inputs. Despite this enrichment of river particles with phosphorus, suspended particles within the salinity gradient had a phosphorus content more similar to the world's average. Sequential chemical leaches revealed that particulate phosphorus was associated with organic matter, aluminum oxides, iron oxides, and apatite in all areas of the estuary. However, ‘excess’ particle-bound phosphorus in the tidal river was associated mainly with iron oxides (27%), aluminum oxides (23%), and organic matter (50%). Within the salinity gradient, particulate phosphorus associated with iron oxides, aluminum oxides, and apatite all decreased with increasing salinity. Estuarine mixing was simulated to determine whether the observed decreases in particle-bound phosphorus pools in field samples were due to release into solution. During simulated mixing, particulate phosphorus associated with iron and aluminum oxides decreased, but no change was observed in apatite-bound phosphorus. The results of the mixing study combined with the observed particle-bound phosphorus distributions suggest that phosphate concentrations along the Delaware Estuary may be partially ‘buffered’ by aluminum and iron oxide phases.  相似文献   

12.
Laboratory experiments were conducted on the light-induced dissolution of three well defined Fe(III) (hydr)oxide phases (γ-FeOOH, α-FeOOH, and α-Fe2O3) with oxalate as reductant/ligand. Upon irradiation of an aerated γ-FeOOH suspension of pH 3, photooxidation of oxalate and photochemical formation of dissolved Fe(II) occurred according to a 1:1 stoichiometry. This was not observed with aerated α-FeOOH and α-Fe2O3 suspensions of pH 3, where photooxidation of oxalate was not accompanied by formation of appreciable concentrations of dissolved Fe(II). We hypothesize that in aerated α-FeOOH and α-Fe2O3 suspensions, oxidation of surface Fe(II) outcompetes its detachment from the crystal lattice. Also in deaerated suspensions, α-FeOOH and α-Fe2O3 behaved differently from γ-FeOOH with regard to light-induced dissolution. We interpret our results by assuming that light-induced dissolution of α-FeOOH and α-Fe2O3 in deaerated suspensions of pH 3 occurred mainly through Fe(II)-catalyzed thermal dissolution of the solid phases, where Fe(II) was initially formed by photoreductive dissolution and then predominantly via photolysis of dissolved Fe(III) oxalate complexes. With γ-FeOOH, on the other hand, dissolved Fe(II) formation occurred probably mainly through photochemical reductive dissolution under photooxidation of adsorbed oxalate. From our results we conclude that the efficiency of detachment of reduced surface iron is a key parameter of the overall kinetics of photoreductive dissolution of Fe(III) (hydr)oxides in aquatic systems, and that thermodynamically stable phases such as α-FeOOH and α-Fe2O3 are not readily dissolved in the presence of O2, even at low pH-values and in the presence of light and reductants like oxalate. We propose that redox cycling of iron at the surface of crystalline Fe(III) (hydr)oxide phases, i.e. reduction and oxidation of surface iron without transfer into solution, may be an important pathway of transformation of thermodynamically stable atmospheric Fe(III) (hydr)oxides into less stable and thus more soluble phases.  相似文献   

13.
Shelf break systems are highly dynamic environments. However little is known about the influence that benthic interactions and water mass mixing may have on vertical distributions of iron in these systems. Dissolved Fe (< 0.4 μm) concentrations were measured in samples from nine vertical profiles across the upper slope (150–2950 m water depth) at the Atlantic Ocean–Celtic Sea shelf break. Dissolved iron concentrations varied between less than 0.2 and 5.4 nM, and the resulting detailed section showed evidence of a range of processes influencing the Fe distributions. The near sea floor data were interpreted in terms of release and removal processes. The concentrations of dissolved Fe present in near seabed waters were consistent with release of Fe from in situ remineralisation of particulate organic matter at two upper slope stations, and possibly release from pore water upon resuspension on shelf. Lateral transport of dissolved iron was evident from elevated Fe concentrations in an intermediate nepheloid layer and its advection along isopycnals. Surface waters at the shelf break also showed evidence of vertical mixing of deeper iron-rich waters. These waters contained macronutrients that sustained primary productivity in these otherwise nutrient-depleted surface waters. The data also suggest some degree of stabilisation of relatively high concentrations of iron, presumably through ligand association or as colloids. This study supports the view that lateral export of dissolved iron to the interior of the ocean from shelf and coastal zones and may have important implications for the global budget of oceanic iron.  相似文献   

14.
A series of high resolution (10 cm) vertical profiles of iron were determined across the oxic/anoxic boundary in the Lower Pond of the Pettaquamscutt Estuary. Selective chemical treatments and multiple analytical methods were used to detemine the oxidation state and lability of iron across the oxic/anoxic boundary. The vertical distributions of dissolved and total iron were determined by atomic absorption spectroscopy, and dissolved Fe(II) and reducible iron were determined using a modified Ferrozine spectrophotometric method. Well-developed maxima of total dissolved iron ≈7·5 μM occurred within the oxic/anoxic transition zone. Analysis of Fe(II) by the FZ method indicates that more than 95% of the dissolved iron determined by atomic absorption spectroscopy within the maximum is in the form of Fe(II). The concentration of dissolved Fe(II) ranged from <4 nM in oxygenated surface waters to between 7 and 8 μM at the total dissolved iron maximum.Both dissolved and total iron samples were treated with ascorbic acid to quantify the fraction of iron that was reducible in this system. Dissolved iron is quantitatively reduced to Fe(II) by 3·5 m depth, and particulate iron was almost completely dissolved by 6 m. Thermodynamic speciation calculations indicate that the dominant species of Fe(II) in the anoxic waters is the Fe(HS)+complex. In addition, the concentration of Fe(II) in the anoxic zone appears to be controlled by precipitation of a sulfide phase, the ion activity product for waters below 7 m is in good agreement with the solubility product of mackinawite.The vertical distribution of oxidation states of the metals indicates non-equilibrium conditions due to microbiological and chemical processes occurring in the redox transition zone. A one-dimensional vertical, eddy diffusion model is presented that incorporates redox reactions of iron, sulfide and oxygen. The modeling suggests the maximum in Fe(II) can be achieved through inorganic oxidation and reduction reactions, however the depth at which the maximum occurs is sensitive to sulfide oxidation, which appears to be dominated by biological oxidation. The magnitude of the Fe(II) maximum depends on the flux of iron into the basin, and reductive dissolution of particulate iron.  相似文献   

15.
Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O2 takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O2 and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g−1 and 3.1 μmol g−1, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g−1), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g−1 and 1.6 mmol g−1, respectively) and of cracks (5.1 μmol g−1 and 0.47 mmol g−1). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.  相似文献   

16.
Distributions of carbohydrate species in the Gulf of Mexico   总被引：2，自引：0，他引：2  
In order to study the role of polysaccharides in the cycling of marine organic matter and transparent exopolymeric particles (TEP), the concentrations of total carbohydrates (p-TCHO), total uronic acids (URA) and total acid polysaccharides (APS) in suspended and sinking particles, as well as carbohydrates in the filter-passing “dissolved” phase (d-TCHO), were measured in vertical profiles along a N–S transect in the Gulf of Mexico, across a cold core (CCR) and a warm core (WCR) ring (eddy) during both July 2000 and May 2001. The concentrations of d-TCHO in 2000 ranged from 4 to 22 μM C, with a subsurface maximum, which was located slightly above the depth of chl a maximum, amounting to, on average, 34% of DOC in the CCR, and 13% in the WCR. The concentration of particulate carbohydrates (p-TCHO) in different size fractions (0.7–10, 10–53, and >53 μm) ranged from 0.04 to 1.1, 0.005 to 0.40, and 0.006 to 0.26 μM C, respectively, indicating that carbohydrates are mostly concentrated in small particles (0.7–10 μm). URA and APS were similarly concentrated in small particles, in which, on average, URA accounted for 87% and 57% of total URA, and APS for 92% and 88% of total APS in 2000 and 2001, respectively. URA accounted for 3–9% of carbohydrates in suspended particles, suggesting that URA are a minor component of the p-TCHO pool. Due to its surface-reactive nature, URA could play a major role in the coagulation of particles and macromolecules despite its relatively low abundance. While, on average, p-TCHO and total APS were more enriched in suspended particles than in sinking particles in both 2000 and 2001, the opposite was true for URA in both years. The greater contents of URA that are present in settling particles compared to suspended particles could indicate a mass flow in the direction of sinking particles, either caused by coagulation, by bacterial reworking of particulate and colloidal organic matter, or by their more refractory nature.  相似文献   

17.
The redox speciation of dissolved iron in seawater was evaluated at 121 locations in the Pacific Ocean at depths of 15-1000 m, using the method of luminol chemiluminescence. The results indicate that reduced iron, Fe(II), is ubiquitous in surface seawater with a relatively consistent pattern of occurrence. Surface maxima were present in most profiles, with median concentrations of 25-30 pM representing 12-14% of the total dissolved iron. Concentrations decreased monotonically with depth to<12 pM within the upper euphotic zone. This pattern was observed during both day and nighttime sampling events, which suggests that non-photochemical production mechanisms can produce photochemical-like signatures. Further, if theoretical rates of Fe(II) oxidation are applicable to the open ocean, then the employed sampling methods precluded assessment of photochemically-produced Fe(II), regardless of ambient light conditions. For this and other reasons, the concentrations reported here for the upper water column likely represent lower limits of labile iron concentration, and suggest that dissolved iron may be more available for uptake than previously believed. Deeper in the water column, Fe(II) was also frequently detected, though it constituted a small fraction of the total dissolved iron. Possible source mechanisms at these depths include thermal (dark) reduction of Fe(III) organic complexes or remineralization of sinking biogenic particles containing Fe(II). In the northern Philippine Sea between the Japanese coast and the Izu-Bonin volcanic arc system, Fe(II) concentrations were found to be atypically high, possibly because of high atmospheric dust deposition near the surface and transport of sediment-derived iron at depth.  相似文献   

18.
Dynamics of transparent exopolymer particles (TEP) was studied during the first in situ iron-enrichment experiment conducted in the western subarctic Pacific in July–August 2001, with the goal of evaluating the contribution of TEP to vertical flux as a result of increased primary production following iron enrichment in open ocean ecosystems. Subsequent to the enhancement of phytoplankton production, we observed increase in TEP concentration in the surface layer and sedimentation of organic matter beneath it. Vertical profiles of TEP, chlorophyll a (Chl a) and particulate organic carbon (POC) were obtained from six depths between 5 and 70 m, from a station each located inside and outside the enriched patch. TEP and total mass flux were estimated from the floating sediment traps deployed at 200 m depth. Chl a and TEP concentrations outside the patch varied from 0.2 to 1.9 μg L−1 and 40–60 μg XG equiv. L−1, respectively. Inside the patch, Chl a increased drastically from day 7 reaching the peak of 19.2 μg L−1 on day 13, which coincided with the TEP peak of 189 μg XG equiv. L−1. TEP flux in the sediment trap increased from 41 to 88 mg XG equiv. m−2 d−1, with 8–14% contribution of TEP to total mass flux. This forms the basic data set on ambient concentrations of TEP in the western subarctic Pacific, and evaluation of the effect of iron enrichment on TEP.  相似文献   

19.
Siderophores play an important role in biological iron acquisition in iron-limited aquatic systems. While it is widely accepted that the solubilization of iron-bearing mineral phases is a key function of siderophores, the mechanism of siderophore-promoted mineral dissolution in aquatic systems is largely unknown. In this study, we investigated the effect of siderophores (desferrioxamine B (DFOB) and aerobactin) on light-induced dissolution of goethite and lepidocrocite in the presence or absence of oxalate in aerated and deaerated suspensions at pH 6. For the irradiated two-ligand system (oxalate/siderophore), the experimental results suggest that oxalate acts as the electron donor for the formation of surface Fe(II), and the siderophore acts as an efficient shuttle for the transfer of surface Fe(II) into solution. Furthermore, even in the absence of an electron donor such as oxalate, both DFOB and aerobactin accelerated the light-induced dissolution of lepidocrocite as compared to the thermal dissolution. Experiments with dissolved Fe(III)–DFOB and Fe(III)–aerobactin complexes suggest that this enhancing effect is not due to photolysis of corresponding surface complexes but to efficient transfer of reduced surface Fe(II) into solution, where surface Fe(II) may be formed, e.g., through photolysis of surface Fe(III)–hydroxo groups. Based on this study, we conclude that the interplay of light and siderophores may play a key role in the dissolution of colloidal iron(III) (hydr)oxides in marine systems, particularly in the presence of efficient electron donors.  相似文献   

20.
Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (FeR) in the absence and presence of 2 μM Dp, FeR being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H2O2 and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for FeR. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for FeR, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of FeR ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.  相似文献   

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