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1.
The relationship between sedimentary Fe inputs and net seagrass population growth across a range of Posidonia oceanica meadows growing in carbonate Mediterranean sediments (Balearic Islands, Spain; SE Iberian Peninsula, Spain; Limassol, Cyprus; Sounion, Greece) was examined using comparative analysis. Sedimentary Fe inputs were measured using benthic sediment traps and the net population growth of P. oceanica meadows was assessed using direct census of tagged plants. The meadows examined ranged from meadows undergoing a severe decline to expanding meadows (specific net population growth, from −0.14 yr−1 to 0.05 yr−1). Similarly, Fe inputs to the meadows ranged almost an order of magnitude across meadows (8.6–69.1 mg Fe m−2 d−1). There was a significant, positive relationship between sedimentary iron inputs and seagrass net population growth, accounting for 36% of the variability in population growth across meadows. The relationship obtained suggested that seagrass meadows receiving Fe inputs below 43 mg Fe m−2 d−1 are vulnerable and in risk of decline, confirming the pivotal role of Fe in the control of growth and the stability of seagrass meadows in carbonate sediments.  相似文献   

2.
The results of a 57Fe Mössbauer spectroscopic and X-ray diffraction study of four pelagic clay sediments from the Southwestern Pacific Basin collected at increasing distances from New Zealand, on a New Zealand—Rarotonga transect, are presented. These show that, with increasing distance from New Zealand, the Fe3+/Fe2+ ratio of the sediment increases as a result of the increasing contribution of the X-ray amorphous secondary hydrous iron oxides, notably ferrihydrite, due to the longer sedimentation periods and consequent greater degree of oxidation of the sediments. This increase in the Fe3+/Fe2+ ratio is correlated with the change in colour of the sediments from pale yellowish to dusky brown, as well as a number of other sediment parameters. Apart from a slight increase in the relative abundance of montmorillonite with increasing distance from New Zealand, the abundances of the other clay minerals, illite and kaolinite, and of chlorite in the sediments are approximately equal. Quartz and feldspar with minor augite are the dominant detrital minerals. Calcite is present in minor amounts in some of the sediments.  相似文献   

3.
以富营养化的胶州湾一个柱状沉积物为例,用细化的铁形态分析及量化的铁氧化物还原活性相结合的方法研究了沉积物中铁的成岩作用过程。结果表明,这两种方法相结合的结果能更详细示踪铁的转化并能从多视角提供铁成岩作用的细微差别。这一方法有望应用于其它研究中更好地揭示复杂的铁和硫的生物地球化学循环。铁微生物还原在上部沉积物铁的还原中起重要作用,但12 cm深度以下铁被硫化物的化学还原为主要过程。最具生物活性的无定形铁氧化物是铁微生物还原的主要参与者,然后依次为弱晶态铁氧化物和磁铁矿,晶态铁氧化物几乎不参与铁的成岩循环。沉积物上部铁微生物还原的重要作用主要是活性铁含量高而活性有机质含量低共同作用的结果,且后者也是沉积物中硫酸盐还原速率以及硫化物积累的最终制约因素。对比研究表明,通过还原性溶解动力学方法表征的微生物可还原的铁氧化物主要由无定形和弱晶态铁氧化物组成,其总体活性常数相当于老化的水铁矿,且随深度增加而减低。  相似文献   

4.
Rates of sediment accumulation and microbial mineralization were examined at three Kandelia candel forests spanning the intertidal zone along the south coastline of the heavily urbanized Jiulongljiang Estuary, Fujian Province, China. Mass sediment accumulation rates were rapid (range: 10–62 kg m−2 y−1) but decreased from the low- to the high-intertidal zone. High levels of radionuclides suggest that these sediments originate from erosion of agricultural soils within the catchment. Mineralization of sediment carbon and nitrogen was correspondingly rapid, with total rate of mineralization ranging from 135 to 191 mol C m−2 y−1 and 9 to 11 mol N m−2 y−1; rates were faster in summer than in autumn/winter. Rates of mineralization efficiency (70–93% for C; 69–92% for N) increased, as burial efficiency (7–30% for C; 8–31% for N) decreased, from the low-to the high-intertidal mangroves. Sulphate reduction was the dominant metabolic pathway to a depth of 1 m, with rates (19–281 mmol S m−2 d−1) exceeding those measured in other intertidal deposits. There is some evidence that Fe and Mn reduction-oxidation cycles are coupled to the activities of live roots within the 0–40 cm depth horizon. Oxic respiration accounted for 5–12% of total carbon mineralization. Methane flux was slow and highly variable when detectable (range: 5–66 μmol CH4 m−2 d−1). Nitrous oxide flux was also highly variable, but within the range (1.6–106.5 μmol N2O m−2 d−1) measured in other intertidal sediments. Rates of denitrification were rapid, ranging from 1106 to 3780 μmol N2 m−2 d−1, and equating to 11–20% of total sediment nitrogen inputs. Denitrification was supported by rapid NH4 release within surface deposits (range: 3.6–6.1 mmol m−2 d−1). Our results support the notion that mangrove forests are net accumulation sites for sediment and associated elements within estuaries, especially Kandelia candel forests receiving significant inputs as a direct result of intense human activity along the south China coast.  相似文献   

5.
Natural iron fertilization processes are occurring around the Crozet Islands (46°26′S–52°18′E), thus relieving the water masses from the normally encountered High Nutrients Low Chlorophyll (HNLC) conditions of the Southern Ocean. During austral summers 2004/2005 and 2005/2006, iron and aluminium concentrations were investigated in large particles (> 53 µm) collected from just below the mixed layer at stations under the influence of island inputs, and also in adjacent HNLC waters. These large particles are anticipated to sink out of the mixed layer, and to reflect the net effects of input and cycling of these elements in the overlying mixed layer. Labile and refractory fractions were determined by a two-stage leaching technique. Data showed that water masses downstream of the islands were enriched in total iron and aluminium (0.25–2.68 nmol L− 1 and 0.34–3.28 nmol L− 1 respectively), relative to the southern HNLC control sites (0.15–0.29 nmol L− 1 for Fe and 0.12–0.29 nmol L− 1 for Al), with only a small fraction (typically < 1%) being acid leachable in both environments. Particulate iron predominantly derived from the island system represents a significant fraction of the total water column iron inventory and may complement dissolved Fe inputs that help support the high summer productivity around the Crozet islands.  相似文献   

6.
The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S0, H2S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ34S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ34S (−39‰ to −46‰ vs. V-CDT). A high variability in δ34S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ34S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in 34S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.  相似文献   

7.
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   

8.
Community metabolism and nutrient, iron (Fe) and manganese (Mn) cycling were examined in two intertidal, marine, microbial mat communities during short (4–5 days) incubations in closed, flow-through microcosms. Sediment microcosms were incubated under either light (light–dark cycles) or dark (continuous darkness) conditions to assess the effect(s) of photosynthetic oxygen production and microalgal activity on nutrient, Fe and Mn cycling. The effects of chemical redox reactions between reduced sulphur (S), Fe and Mn cycling were examined by blocking sulphate reduction, and reduced S production, with 25 mM molybdate while incubating under dark conditions.In light-incubated microcosms, negligible fluxes of nutrients (nitrogen and phosphorus) and trace metals were observed. A substantial sediment–water flux of reduced Fe (Fe2+) and Mn (Mn2+) was observed in microcosms incubated under continuous darkness; highest fluxes were observed in molybdate-amended microcosms. At both sites, biologically-mediated redox reactions accounted for a substantial (>50%) portion of the Fe2+and Mn2+flux. Both microbial mat communities exhibited similar rates of gross photosynthetic oxygen (O2) production, but dramatically different rates of net benthic O2flux. Distinct patterns of net O2production and trace metal cycling arose from differences in either trace metal oxide availability or reactivity (mineralogy), organic carbon mineralization rates, or sediment characteristics (porosity). Variations in the microbial community responsible for trace metal cycling could have also contributed to the pattern. The present data illustrate that chemically-mediated redox reactions between metal oxides and reduced S complicate interpretation of Fe and Mn fluxes, underscoring the need to separate chemical and biological reactions when attempting to determine the role of biological trace metal reduction in organic carbon oxidation.  相似文献   

9.
In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L−1 and dissolved manganese reached 25 nmol L−1. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L−1 and dissolved manganese concentrations were less than 5 nmol L−1. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L−1, and dissolvable iron concentrations of 12–20 nmol L−1 in the upper 100 m in the north, compared to 3.5–2 nmol L−1 Mn and 0.6 nmol L−1 Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L−1 dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L−1 dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.  相似文献   

10.
Surface sediments from the Saronikos Gulf were analyzed for their aliphatic hydrocarbon (AHC) and polycyclic aromatic hydrocarbon (PAH) content by gas chromatography – mass spectrometry (GC/MS). The concentrations of Fe, Cr, As, Sb, Co and Sc were also determined by neutron activation analysis (NAA). The survey was performed at the beginning of the operation of Athens’ sewage primary treatment unit and the results can be used to monitor the unit's long-term effects in the area. The composition of aliphatic hydrocarbons indicated a chronic oil-pollution in the Saronikos Gulf sediments. The industrially impacted Elefsis Bay sediments suffered from heavy petroleum pollution, while the sediments near the sewage outfall had a moderate degree of pollution. Mixed source patterns of polycyclic aromatic hydrocarbons with dominant pyrolytic inputs have been identified in the sediments. Total concentrations of Fe, As and Sb along with their Sc normalized values presented elevated values in Elefsis Bay sediments. Chromium was found enriched in the sediments near the Athens sewage outfall. Factor analysis results showed that a part of As and Sb in Elefsis Bay sediments could be associated with organic or sulphidic phases. In addition, the lithogenic fraction of the sediments and the Fe oxides/hydroxides were important trace element carriers. Chromium and PAH inputs from the sewage outfall were also detected. Comparison of PAH and trace element concentrations with internationally-used sediment quality guidelines (SQG) revealed that Elefsis Bay sediments had the greatest potential of causing adverse effects in benthic organisms.  相似文献   

11.
The objective of this study was to investigate the phosphorus distribution in the estuarine sediments of the Daliao river, intensively affected by municipal effluent and agricultural activity for about 50 years. Surface sediment samples were taken at 35 sites in the estuarine area and phosphorus species and contents of total P, Al, Fe, and Ca in the sediments were measured. Results showed that the content of total P in the sediments ranged from 230 to 841 mg kg−1, with an average of 549 mg kg−1. Ca–bound P, residual P, Al–bound P, reductant–soluble P, Fe–bound P, and soluble and loosely bound P were averagely 44.5, 21.6, 13.6, 11.7, 8.9 and 0.2% of total P, respectively. With the gradual increase of total P content, Al–bound P, reductant–soluble P, and Fe–bound P generally increased, while the rest species of P did not. This might indicate that anthropogenic P is bound to Al and Fe oxides. Regression analysis showed that Al–bound P and sum of Fe–bound P and reductant–soluble P were correlated to the contents of total Al and Fe, respectively. On the other hand, Ca–bound P was not correlated to the content of total Ca in the sediment, probably suggesting that Ca–P was mainly from authigenic marine origin. Whereas the content of total P in the estuarine sediments of the Daliao river was within the range of total P content for Chinese and worldwide river estuaries as well as coastal sediments, non-calcium apatite phosphorus content in the estuarine sediments of the Daliao river was relatively higher, indicating higher release risk and bioavailability of P in the sediment. On the other hand, the molar ratio of total Fe to total P was 16–34 in the estuarine sediments of the Daliao river, suggesting that iron oxides/hydroxides in the sediments might be able to sequester more phosphorus. Therefore, the accumulation or release of P in/from the estuarine sediments might be dependent on the external loading of P and the estuarine eutrophication may be sustained by the internal bioavailable P pools following the decrease of the external P loading.  相似文献   

12.
The effect of benthic oxygenic photosynthesis on sediment-water fluxes of manganese and iron was studied for an intertidal sediment. Undisturbed sediments were incubated at an incident surface irradiance of 250 μE m−2 s−1at 26 °C. Oxygenic photosynthesis was selectively inhibited by adding [3-(3,4-dichloro)-1,1-dimethyl-urea] (DCMU). Benthic fluxes were determined experimentally from the change in manganese and iron concentrations in the overlying water, and were predicted from the pore water concentration gradients at the sediment-water interface assuming molecular diffusion as the transport mechanism. The experimental fluxes of manganese and iron in DCMU-treated cores amounted to −0·84 and −0·59 mmol m−2day−1, respectively, and were directed from the sediment towards the overlying water. In the control cores, showing high rates of benthic oxygenic photosynthesis, the fluxes of manganese and iron were directed towards the sediment, 0·06 and 0·01 mmol m−2day−1, respectively. Mass balances for the 0·1–0·14 cm thick oxic zone, calculated from the experimental fluxes and the predicted fluxes, suggest a minimum areal reoxidation of 0·6 mmol m−2day−1for manganese and of 0·48 mmol m−2day−1for iron in cores showing benthic photosynthesis. The estimated turnover times for dissolved Mn2+and dissolved Fe2+in the oxic surface layer during benthic photosynthesis were 0·8 and 0·25 h, respectively. Sediment oxygen microprofiles and the sediment pH profiles suggest that chemical precipitation and reoxidation dominates the retention of manganese and iron during benthic oxygenic photosynthesis in shallow intertidal sediments.  相似文献   

13.
The influence of bioturbation on certain aspects of the biogeochemistry of sulfur and iron was examined in shallow-water sediments of Great Bay Estuary, New Hampshire. A bioturbated (JEL) and non-bioturbated (SQUAM) site were compared. Annual sulfate reduction measured with 35S, was 4·5 times more rapid at JEL. A significant portion of this difference was attributed to rapid rates which occurred throughout the upper 12 cm of sediment at JEL due to infaunal reworking activities. Sulfate reduction decreased rapidly with depth at SQUAM. FeS in the upper 2 cm at JEL increased in concentration from 3 to 45 μmol ml−1 from early May to late July while only increasing from 3 to 8 μmol ml−1 at SQUAM. Infaunal irrigation and reworking activities caused rapid and continous subsurface cycling of iron and sulfur at JEL. This maintained dissolved iron concentrations at 160–170 μM throughout the summer despite rapid sulfide production. Therefore, dissolved sulfide never accumulated in JEL pore waters. Although dissolved organic carbon (DOC) was generated during sulfate reduction, bioturbation during summer caused a net removal of DOC from JEL pore waters. Sulfate reduction rates, decomposition stoichiometry and nutrient concentrations were used to calculate turnover times of nutrients in pore waters. Nutrient turnover varied temporally and increased three-to five-fold during bioturbation. A secondary maximum in the abundance of recoverable sulfate-reducing bacteria occurred at 10 cm in JEL sediments only during periods of active bioturbation, demonstrating the influence of macrofaunal activities on bacterial distributions.  相似文献   

14.
《Oceanologica Acta》1998,21(1):81-86
Measurement of magnetic parameters in combination with the partitioning of iron in various sediment fractions (authigenic-lithogenous) have been used in order to obtain information concerning the fate of iron within the sediment. Through this approach, it is shown that in the Rhône estuary sediments there is a dominance of the lattice-held iron, represented by the abundance of ferrimagnetic minerals. A considerable part (∼ 17 %) of the iron present is authigenic, associated mainly with the oxide-hydroxide forms and originating from direct fluvial inputs and in situ diagenetic processes. Iron oxides and hydroxides are formed in the water column and/or porewaters and are accumulated mainly in the surface layer (0–2 cm) of the sediment column corresponding to the mineral goethite.  相似文献   

15.
The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment.  相似文献   

16.
Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.  相似文献   

17.
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   

18.
A sudden increase in salinity about 7000 years ago caused a shift in the deposited sediments of the Black Sea from limnic to brackish-marine. Due to the development of an anoxic deep water basin and a relatively high sulfate concentration, organic matter is mineralized primarily through sulfate reduction in modern Black Sea sediments. Earlier studies showed that sulfate-reducing bacteria are abundant within the limnic sub-surface sediment in spite of extremely low concentrations of sulfate and organic carbon. A main objective of the present study was therefore to understand the depth distribution of sulfate reduction across the different sediment units, even deep below the sulfate-methane transition. Our study combined experimental measurements of sulfate reduction using 35S radiotracer with analyses of sulfur and iron geochemistry in pore water and sediment. Potential sulfate reduction rates were measured with 35S in sediment samples that were amended with sulfate and organic substrates and incubated in time-series up to 48 h. Sulfate reduction could thereby be detected and quantified at depths where concentrations of sulfate were otherwise too low to enable calculation of the rates. The results demonstrate that sulfate-reducing bacteria are active several meters below the sulfate-methane transition in Black Sea sediments. The cryptic sulfate reduction below the sulfate-methane transition may be driven by sulfate produced from re-oxidation of reduced sulfur species with oxidized iron minerals buried in the deep limnic sediment.  相似文献   

19.
Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron 55Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10− 9 mol/m2 or 1.7 × 10− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log KFe'W = 11.0 ± 0.3 m2/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 −4–10− 5 L/s and rate constants for association in the order of 108 L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.  相似文献   

20.
This paper reports the initial results of a study of groundwater and coastal waters of southern Brazil adjacent to a 240 km barrier spit separating the Patos Lagoon, the largest coastal lagoon in South America, from the South Atlantic Ocean. The objective of this research is to assess the chemical alteration of freshwater and freshwater–seawater mixtures advecting through coastal permeable sands, and the influence of the submarine discharge of these fluids (SGD) on the chemistry of coastal waters. Here we focus on dissolved iron in this system and use radium isotopic tracers to quantify SGD and cross-shelf fluxes. Iron concentrations in groundwaters vary between 0.6 and 180 μM. The influence of the submarine discharge of these fluids into the surf zone produces dissolved Fe concentrations as high as several micromolar in coastal surface waters. The offshore gradient of dissolved Fe, coupled with results for Ra isotopes, is used to quantify the SGD flux of dissolved Fe from this coastline. We estimate the SGD flux to be 2 × 106 mol day− 1 and the cross-shelf flux to be 3.2 × 105 mol day− 1. This latter flux is equal to about 10% of the soluble atmospheric Fe flux to the entire South Atlantic Ocean. We speculate on the importance of this previously unrecognized iron input to regional ocean production and on the potential significance of this source to understanding variations in glacial–interglacial ocean production.  相似文献   

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