Phosphorus recycling and burial in Baltic Sea sediments with contrasting redox conditions

In this study, redox-dependent phosphorus (P) recycling and burial at 6 sites in the Baltic Sea is investigated using a combination of porewater and sediment analyses and sediment age dating (²¹⁰Pb and ¹³⁷Cs). We focus on sites in the Kattegat, Danish Straits and Baltic Proper where present-day bottom water redox conditions range from fully oxygenated and seasonally hypoxic to almost permanently anoxic and sulfidic. Strong surface enrichments of Fe-oxide bound P are observed at oxic and seasonally hypoxic sites but not in the anoxic basins. Reductive dissolution of Fe-oxides and release of the associated P supports higher sediment-water exchange of PO₄ at hypoxic sites (up to ∼800 μmol P m⁻² d⁻¹) than in the anoxic basins. This confirms that Fe-bound P in surface sediments in the Baltic acts as a major internal source of P during seasonal hypoxia, as suggested previously from water column studies. Most burial of P takes place as organic P. We find no evidence for significant authigenic Ca-P formation or biogenic Ca-P burial. The lack of major inorganic P burial sinks makes the Baltic Sea very sensitive to the feedback loop between increased hypoxia, enhanced regeneration of P and increased primary productivity. Historical records of bottom water oxygen at two sites (Bornholm, Northern Gotland) show a decline over the past century and are accompanied by a rise in values for typical sediment proxies for anoxia (total sulfur, molybdenum and organic C/P ratios). While sediment reactive P concentrations in anoxic basins are equal to or higher than at oxic sites, burial rates of P at hypoxic and anoxic sites are up to 20 times lower because of lower sedimentation rates. Nevertheless, burial of reactive P in both hypoxic and anoxic areas is significant because of their large surface area and should be accounted for in budgets and models for the Baltic Sea.     

Co-diagenesis of iron and phosphorus in hydrothermal sediments from the southern East Pacific Rise: Implications for the evaluation of paleoseawater phosphate concentrations

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ∼19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ∼12 m. Molar P/Fe ratios are then relatively constant to a depth of ∼35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.     

沱江沉积物-水界面磷形态垂向分布及时空变化特征

水体中富营养化水平与磷元素的赋存形态密切相关。目前围绕引起富营养化关键因子之一的磷形态的垂向分布特征、各磷形态间的迁移转化行为及其影响因素取得了比较明确的研究进展。为进一步揭示不同磷形态在沉积物-水体系中迁移转化行为随时空的变化特征,本文采用磷钼蓝分光光度法对沱江流域简阳段间隙水中可溶性活性磷(SRP)、可溶性非活性磷(SUP)及总溶解性磷(TDP)进行测定;采用SMT法和改进的沉积物无机磷形态连续提取法对沉积物中总无机磷(TIP)、总磷(TP)、难提取磷(Res-P)、可交换态磷(Exc-P)、铁结合态磷(Fe-P)、铝结合态磷(Al-P)、钙结合态磷(Ca-P)进行提取,磷钼蓝分光光度法进行测定,以揭示沉积物-水体系中磷的赋存形态垂向分布行为特征,并将实验数据与十年前该地区磷的赋存形态结果进行对比,探讨磷赋存形态的变化趋势及影响因素。结果表明:间隙水中SRP、SUP和TDP的含量分别为0.004～0.36mg/L、0.080～3.19mg/L和0.056～3.28mg/L;沉积物中TP、TIP、Res-P、Exc-P、Al-P、Ca-P含量分别为1235.40～1646.94mg/kg、860.00～1318.59mg/kg、130.31～537.13mg/kg、1.35～14.10mg/kg、0.007～0.12mg/kg、743.13～1109.91mg/kg,Fe-P未检出。对比十年前后沉积物-水体系中磷赋存形态的变化可知,由于受到外源磷输入的影响,间隙水中SRP、SUP以及TDP含量虽然在-10cm以上变化不明显,但在-10cm以下明显增大,且导致沉积物中TP、TIP含量增加;偏碱性的沉积环境导致Al-P的释放,其含量明显减小;Exc-P含量的减小与其转化为稳定的Ca-P或Res-P形态有关。研究认为:随着时空的变化,沱江简阳段沉积物呈现外源磷输入和内源磷释放的综合污染。总体而言,由于输入的磷形态大部分以稳定的Ca-P和Res-P形态存在于沉积物中,使得表层间隙水中生物可直接利用的磷含量总体变化不大,该地区富营养化程度不会加重。维持沉积环境的弱碱性,有利于Al-P、Exc-P等向Ca-P的有效转换,抑制河流富营养化。     

Contributions from glacially derived sediment to the global iron (oxyhydr)oxide cycle: Implications for iron delivery to the oceans

Estimates of glacial sediment delivery to the oceans have been derived from fluxes of meltwater runoff and iceberg calving, and their sediment loads. The combined total (2900 Tg yr⁻¹) of the suspended sediment load in meltwaters (1400 Tg yr⁻¹) and the sediment delivered by icebergs (1500 Tg yr⁻¹) are within the range of earlier estimates. High-resolution microscopic observations show that suspended sediments from glacial meltwaters, supraglacial, and proglacial sediments, and sediments in basal ice, from Arctic, Alpine, and Antarctic locations all contain iron (oxyhydr)oxide nanoparticles, which are poorly crystalline, typically ∼5 nm in diameter, and which occur as single grains or aggregates that may be isolated or attached to sediment grains. Nanoparticles with these characteristics are potentially bioavailable. A global model comparing the sources and sinks of iron present as (oxyhydr)oxides indicates that sediment delivered by icebergs is a significant source of iron to the open oceans, beyond the continental shelf. Iceberg delivery of sediment containing iron as (oxyhydr)oxides during the Last Glacial Maximum may have been sufficient to fertilise the increase in oceanic productivity required to drawdown atmospheric CO₂ to the levels observed in ice cores.     

Phosphorus fractions in sediment profiles and their potential contributions to eutrophication in Dianchi Lake

Dianchi Lake is a eutrophic lake in southwestern China. Sediment and the bottom water samples were taken from six sites in the east, west, south, north and center of the lake, respectively, in December 2002. Total phosphorus (TP) concentrations in sediments were high and reached a maximum value of 6.66 g/kg. There was a soluble reactive phosphorus (SRP) concentration gradient at the sediment–water interface. In the present study, sediment P was divided into loosely adsorbed P (NH₄Cl-P), redox-sensitive P (BD-P), metal oxides bound P (NaOH-P), calcium bound P (HCl-P), and organic P (Org-P). At three of the six sites selected, the concentrations of different P forms in sediments followed the order: NaOH-P, Org-P>HCl-P>BD-P>NH₄Cl-P in the profile, and in the southern lake the order was HCl-P>NaOH-P, Org-P>BD-P>NH₄Cl-P in the top 15 cm layers of the sediments. The sediment profiles showed that different forms of P had an increasing trend upward toward the sediment surface. There is a considerable potential for release from the sediment into the overlying water and sediment P could be the dominant factor determining the trophic status of the lake if the external load is reduced. An erratum to this article can be found at     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.     

潮滩沉积物-水界面磷、铁的高分辨率分布特征及生物地球化学行为

为了解潮间带微环境中磷、铁元素的分布和耦合规律及对磷释放的影响,借助薄膜扩散梯度技术（ZrO-Chelex DGT）原位高分辨率获取九龙江口红树林潮滩孔隙水剖面的溶解活性磷（DRP）、Fe2+浓度,并测定沉积物相应的理化参数.研究结果表明:（1）在表层孔隙水中,DRP、Fe2+浓度呈现显著的正相关性,证实了磷、铁元素的耦合关系以及沉积物铁氧化物对磷吸附/解吸附的控制作用;（2）在深部还原带,DRP浓度相对Fe2+浓度具有较大的波动,主要受到沉积物异质性以及红树植物吸收等的影响;（3）根据表层孔隙水中DRP的浓度梯度计算获得磷的分子扩散通量为0.000 64~0.006 00 μg·cm-2·d-1,结果远低于一般湖泊沉积物内源磷的扩散通量,原因是富铁且具较深氧化带的潮滩沉积物中的磷-铁耦合关系有效地抑制了磷的释放.      

Phosphorus burial as a function of paleoproductivity and redox conditions in Arabian Sea sediments

In this study the response of sedimentary phosphorus (P) burial to changes in primary productivity and bottom water oxygen concentrations during the Late Quaternary is investigated, using two sediment cores from the Arabian Sea, one recovered from the continental slope and the other from the deep basin. The average solid-phase P speciation in both cores is similar, authigenic and biogenic (fish debris) apatite make up the bulk of the P inventory (ca. 70%);whereas P adsorbed to iron oxides, organic P, and detrital apatite constitute minor fractions. Postdepositional redistribution has not significantly altered the downcore distribution of total solid-phase P. Phosphorus burial efficiencies are generally lower during periods of increased paleoproductivity. This is caused by (a) partial decoupling of the P export flux, consisting primarily of particulate organic P, and the P burial flux, consisting primarily of biogenic and authigenic apatite; and (b) the lack of increased rates of authigenic CFA formation during periods of higher P deposition. In addition, fluctuations in bottom water oxygen concentrations may have affected P burial in continental slope sediments. The results of this study indicate that higher primary productivity induces more efficient P cycling. On time scales exceeding the oceanic P residence time, this process may induce higher surface water productivity, thus creating a positive feedback loop. In the Arabian Sea, this feedback mechanism may have contributed to changes in sea surface productivity on sub-Milankovitch time scales because P, regenerated on the continental slopes of the Oman and Somalian coastal upwelling zones, is reintroduced into the photic zone relatively fast.     

The Association of Cobalt with Iron and Manganese (Oxyhydr)oxides in Marine Sediment

Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments. We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment, we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulphides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction.     

Phosphorus Cycling in a Freshwater Estuary Impacted by Cyanobacterial Blooms

The availability of reactive phosphorus (P) may promote cyanobacterial blooms, a worldwide increasing phenomenon. Cyanobacteria may also regulate benthic P cycling through labile organic input to sediments, favouring reduced conditions and P release, ultimately acting as self-sustainment mechanism for the phytoplankton blooms. To analyse P–cyanobacteria feedbacks and compare external versus internal loads, we investigated P cycling in the Curonian Lagoon, a freshwater estuary with recurrent summer blooms. At two sites representing the dominant sediment types, we characterised P pools and mobility, via combined pore water analysis, calculation of diffusive exchanges and flux measurements via sediment core incubations. Annual P budgets were also calculated, to analyse the whole lagoon role as net sink or source. Muddy sediments, representing nearly 50 % of the lagoon surface, displayed higher P content if compared with sandy sediments, and most of this pool was reactive. The muddy site had consequently higher pore water dissolved inorganic phosphorus (DIP) concentrations maintaining high diffusive gradients. However, measured fluxes suggested that both sediment types were mostly P sinks except for a large DIP regeneration (nearly 30 μmol m^?2 h^?1) recorded at the muddy site during an intense cyanobacteria bloom. Such internal regeneration had the same order of magnitude as the annual external P load and may offset the net annual DIP sink role of the estuary. It may also prolong the duration of the bloom. Our results suggest that positive feedbacks can regulate N-fixing cyanobacteria blooms and internal P recycling, through either diffusive fluxes or sediment settling and resuspension.     

The anaerobic degradation of organic matter in Danish coastal sediments: iron reduction, manganese reduction, and sulfate reduction

We used a combination of porewater and solid phase analysis, as well as a series of sediment incubations, to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). In the deep portion of the basin, surface Mn enrichments reached 3.5 wt%, and Mn reduction was the only important anaerobic carbon oxidation process in the upper 10 cm of the sediment. In the less Mn-rich sediments from intermediate depths in the basin, Fe reduction ranged from somewhat less, to far more important than sulfate reduction. Most of the Mn reduction in these sediments may have been coupled to the oxidation of acid volatile sulfides (AVS), rather than to dissimilatory reduction. High rates of metal oxide reduction at all sites were driven by active recycling of both Fe and Mn, encouraged by bioturbation. Recycling was so rapid that the residence time of Fe and Mn oxides, with respect to reduction, ranged from 70-250 days. These results require that, on average, an atom of Fe or Mn is oxidized and reduced between 100-300 times before ultimate burial into the sediment. We observed that dissolved Mn2+ was completely removed onto fully oxidized Mn oxides until the oxidation level of the oxides was reduced to about 3.8, presumably reflecting the saturation by Mn2+ of highly reactive surface adsorption sites. Fully oxidized Mn oxides in sediments, then, may act as a cap preventing Mn2+ escape. We speculate that in shallow sediments of the Skagerrak, surface Mn oxides are present in a somewhat reduced oxidation level (< 3.8) allowing Mn2+ to escape, and perhaps providing the Mn2+ which enriches sediments of the deep basin.     

Importance of terrestrially-derived,particulate phosphorus to phosphorus dynamics in a west coast estuary

Allochthonous inputs of suspended particulate matter from freshwater environments to estuaries influence nutrient cycling and ecosystem metabolism. Contributions of different biogeochemical reactions to phosphorus dynamics in Tomales Bay, California, were determined by measuring dissolved inorganic phosphorus exchange between water and suspended particulate matter in response to changes in salinity, pH, and sediment redox. In serum bottle incubations of suspended particulate matter collected from the major tributary to the bay, dissolved inorganic phosphorus release increased with salinity during the initial 8 h; between 1–3 d, however, rates of release were similar among treatments of 0 psu, 16 psu, 24 psu, and 32 psu. Release was variable over the pH range 4–8.5, but dissolved inorganic phosphorus releases from sediments incubated for 24 h at the pH of fresh water (7.3) and seawater (8.1) were similarly small. Under oxidizing conditions, dissolved inorganic phosphorus release was small or dissolved inorganic phosphorus was taken up by particulate matter with total P content <50 μmoles P g^?1; release was greater from suspended particulate matter with total phosphorus content >50 μmoles P g^?1. In contrast, under reducing conditions maintained by addition of free sulfide (HS^?), dissolved inorganic phosphorus was released from particles at all concentrations of total phosphorus in suspended particulate matter, presumably from the reduction of iron oxides. Since extrapolated dissolved inorganic phosphorus release from this abiotic source can account for only 12.5% of the total dissolved inorganic phosphorus flux from Tomales Bay sediments, we conclude most release from particles is due to organic matter oxidation that occurs after estuarine deposition. The abiotic, sedimentary flux of dissolved inorganic phosphorus, however, could contribute up to 30% of the observed net export of dissolved inorganic phosphorus from the entire estuary.     

Geochemistry of surface sediments in the southwestern East/Japan Sea

We analyzed 77 surface sediment samples collected in the southwestern East/Japan Sea from the Korea Strait through the Ulleung Basin and the Korea Plateau for grain size, calcium carbonate, organic carbon, and major (Na, Mg, Al, Fe, K, Ca, and Ti) and trace elements (P, Mn, Sr, Li, Sc, V, Cr, Co, Ni, Zn, Cu, and Pb).The chemical composition of the surface sediments was found to be highly variable spatially. Cluster analysis of surface sediment chemical compositions indicated five major geochemical sedimentary environments: basin, lower slope, coast and upper slope, inner shelf, and outer shelf. Continental-shelf sediments were rich in shell fragments and had relict and coarse-grained characteristics. Recent fine-grained sediments were only distributed in coastal, slope, and basin areas. Concentrations of Al, K, Ca, Ti, Cr, and Sc were highest in the coastal and upper slope areas and decreased with water depth. Elemental ratios using major and trace elements indicated that coastal and upper slope detrital sediments were mixtures of sediments derived from the Changjiang (Yangtze) and Nakdong Rivers. Although the concentrations of organic carbon, P, Mn, V, Co, Ni, Cu, and Pb increased with water depth, their distribution patterns indicated authigenic (V, Cu, and Pb) and diagenetic (Fe, P, Mn, Co, and Ni) origins. The distribution pattern with water depth suggested that the chemical composition of surface sediment was determined by sedimentologic and geochemical processes, such as the supply of detrital and biogenic materials, and authigenic and post-depositional diagenetic processes in sediments.     

Holocene Refreshening and Reoxygenation of a Bothnian Sea Estuary Led to Enhanced Phosphorus Burial

Salinity variations in restricted basins like the Baltic Sea can alter their vulnerability to hypoxia (i.e., bottom water oxygen concentrations <2 mg/l) and can affect the burial of phosphorus (P), a key nutrient for marine organisms. We combine porewater and solid-phase geochemistry, micro-analysis of sieved sediments (including XRD and synchrotron-based XAS), and foraminiferal δ¹⁸O and δ¹³C analyses to reconstruct the bottom water salinity, redox conditions, and P burial in the Ångermanälven estuary, Bothnian Sea. Our sediment records were retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013. We demonstrate that bottom waters in the Ångermanälven estuary became anoxic upon the intrusion of seawater in the early Holocene, like in the central Bothnian Sea. The subsequent refreshening and reoxygenation, which was caused by gradual isostatic uplift, promoted P burial in the sediment in the form of Mn-rich vivianite. Vivianite authigenesis in the surface sediments of the more isolated part of the estuary ultimately ceased, likely due to continued refreshening and an associated decline in productivity and P supply to the sediment. The observed shifts in environmental conditions also created conditions for post-depositional formation of authigenic vivianite, and possibly apatite formation, at ～8 m composite depth. These salinity-related changes in redox conditions and P burial are highly relevant in light of current climate change. The results specifically highlight that increased freshwater input linked to global warming may enhance coastal P retention, thereby contributing to oligotrophication in both coastal and adjacent open waters.     

Pyrite oxidation during sample storage determines phosphorus fractionation in carbonate-poor anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (∼94 Ma) and the Paleocene-Eocene thermal maximum (∼55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO₃ contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO₃ can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.     

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system.The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn₂SiO₄), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn₂SiO₄, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.     

Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.     

沉积物磷原位钝化技术研究进展

水体磷含量是湖泊富营养化最主要的限制因子之一.伴随着湖泊流域工农业发展,外源污染物的长期输入致使沉积物中蓄积了大量的磷及其他污染物.湖泊沉积物一方面是水体磷重要的汇,但另一方面还是水体磷重要的源.在单纯控制湖泊外源污染条件下,沉积物磷的释放仍可导致水体持续富营养化,湖水水质得到明显改善通常需要数十年,因此控制湖泊沉积物内源污染释放是快速恢复湖泊水质必不可少的措施.沉积物内源污染控制技术包括生物修复、环保疏浚以及原位钝化技术.受水深等环境条件限制,生物修复技术和环保疏浚在深水、亚深水型湖泊难以实施.沉积物磷原位钝化技术具有生态、经济、快速和效果稳定等特点,在控制湖泊底泥内源污染中可望发挥重要作用,尤其适合于深水、亚深水型湖泊内源污染控制.系统阐述了不同沉积物原位钝化剂的钝化原理,对比分析了铝盐、铁盐、钙盐和粘度矿物作为磷钝化剂的优缺点和应用条件,概述了国内外沉积物原位钝化技术的应用现状,在此基础上提出了沉积物原位钝化技术未来的重点研究方向:一是研究发展新型钝化剂;二是因地制宜,探索适合不同类型湖泊的底泥原位钝化技术体系;三是加强底泥原位钝化技术与其他技术的联合应用研究与示范;四是加强钝化剂负面影响评价,建立科学的应用技术方案.     

Distribution and sources of phosphorus in tidal river sediments in the Washington, DC, Area

 Sediments in the rivers and basins around Washington, DC, have high concentrations of phosphorus, which, based on geographic distributions, is largely derived from urban runoff and municipal sewage. Dissolved-particulate phosphate exchange reactions and biological uptake of dissolved phosphorus from the water column may be an added source of phosphorus to the sediments. Concentrations of total sedimentary phosphorus ranged from 24 to 56 μm P/g-dw, and were highest in areas near combined sewer outfalls. As a part of this study, sedimentary phosphorus was fractionated into Fe-P, Ca-P, Al-P, and organic phases using a selective-sequential leaching procedure. The distribution of the phases in all sediments analyzed follow the order , Fe-P>Ca-P>Al-P. Spatial variations in the amounts of phosphorus in the different phases is related to the sources of phosphorus to the area. The proportions of occluded Al-P and organic P are 10–20% of the total P, respectively. This suggests that phosphorus from natural sources is small compared to anthropogenic inputs in this area. The high leachable Fe-P and Ca-P in these sediments might contribute a substantial amount of P to the water column under conditions of remobilization. Received: 20 February 1996 · Accepted: 2 April 1996     

Sediment and hydro biogeochemistry of Lake Nainital, Kumaun Himalaya, India

The picturesque Nainital Lake, in the Uttarakhand state of India, is one of the major tourist attractions in the northern part of India. The increasing tourism and population around these lakes are a major concern for the ecology and good sustenance of the lakes. The present study is aimed to understand the behaviour of nutrients and metals in the sediment and their association with chemical forms in the lake. The study was accomplished by studying the water, interstitial water and sediments for major oxides, nutrients and metals in the lake. The different chemical forms of phosphorus and metals in the sediments were done using sequential extraction procedures. The water chemistry (Ca + Mg:Na + K) and the sediment chemistry (CIA and Al₂O₃/K₂O) show that the rocks in the catchment area play an important role in the geochemistry of the lake. The metals in the water also show that the Tallital basin is more polluted than the Mallital basin, may be due to the influence of Bus station. The high concentration of chloride, NH₄, SO₄ and metals in the sediment water interface and the interstitial water shows denitrification, sulfidisation and sulfide oxidation in the anoxic bottom water. The sediment composition shows that the phosphorus in the water is sequestered as carbonate flour apatite, and the metals precipitate as carbonate. The geo- accumulation index shows that the metals zinc, cobalt and nickel show moderate polluted nature than other metals. In general, the lake is less affected by anthropogenic activities. The chemical processes undergoing within the lake, like sulfidisation and sulfide oxidation, oxide dissolution and denitrification and organic matter degradation play an important role in the remobilization of the metals from the lake sediments.