Effects of aluminum,iron, oxygen and nitrate additions on phosphorus release from the sediment of a Danish softwater lake

The effects of oxygen, aluminum, iron and nitrate additions on phosphate release from the sediment were evaluated in the softwater Lake Vedsted, Denmark, by a 34-day experiment with undisturbed sediment cores. Six treatments were applied: (1) Control - O₂ (0–20% saturation), (2) O₂ (100% saturation) (3) Al³⁺ – O₂, (4) Fe³⁺ + O₂, (5) Fe³⁺ – O₂, and (6) NO₃ ^– – O₂. Al₂(SO₄)₃*18 H₂O and FeCl₃*4H₂O were added in amounts that theoretically should immobilize the exchangeable P-pool in the top 5 cm of the sediment, while sodium nitrate concentrations were increased to 5 mg N l^–1. The four treatments with metals or NO₃ ^– reduced the P efflux from the sediment significantly as compared to the suboxic control treatment. Mean accumulated P-release rates for suboxic treatments with Al³⁺, Fe³⁺, and NO₃ ^– were: –0.27 mmol m^–2 (st. dev = 0.02 mmol m^–2, N = 5), 0.58 mmol m^–2 (st. dev = 0.30 mmol m^–2, N = 5) and 1.40 mmol m^–2 (st. dev = 0.14 mmol m^–2, N = 5), respectively. The oxic treatment with Fe³⁺ had a P efflux of 0.36 mmol m^–2 (st. dev = 0.08 mmol m^–2, N = 5). The two highest P-release rates were observed in the control treatment and the treatment with O₂ (14.50 mmol m^–2 (st. dev = 3.90 mmol m^–2, N = 5) and 2.31 mmol m^–2 (st. dev = 0.80 mmol m^–2, N = 5), respectively). In order to identify changes in the P and Fe binding sites in the sediment as caused by the treatments, a sequential P extraction procedure was applied on the sediment before and after the efflux experiment. Addition of O₂, Fe³⁺ and NO₃ ^– to the sediment increased the amounts of oxidized Fe³⁺ and P_BD. Al³⁺ addition resulted in a lower fraction of P_BD but a correspondingly higher fraction of Al-bound P. Addition of Al³⁺ decreased the Fe-efflux from the suboxic sediment as well as the amount of oxidized Fe³⁺ in the sediment. This questions the use of Al compounds that contain sulfate because of the possible formation of FeS, which will restrict upward migration of Fe²⁺ and the formation of new Fe-oxides in the surface sediment. Instead, we suggest the use of AlCl₃ for lake restoration purposes.     

Prevention of sulphide accumulation and phosphate mobilization by the addition of iron(II) chloride to a reduced sediment: an enclosure experiment

1. In an enclosure experiment carried out in a ditch receiving sulphate-enriched seepage water, iron(II) chloride was added to the sediment. In the sediment pore water of the iron-treated enclosures sulphide levels decreased to very low values (<1 μmol 1^?1) immediately after the iron addition while in the control enclosures sulphide reached values up to 500 μmoll^?1. 2. The sulphide levels in the sediment pore water were also strongly correlated with temperature. In summer, phosphate mobilization was observed in the non-treated enclosures while in the iron-treated enclosures phosphate levels remained low. 3. Total phosphate levels increased greatly in the water layer of the non-treated enclosures, coincident with an algal bloom and increased turbidity. It is suggested that phosphate mobilization in summer is caused by the reduction of iron(III) phosphate complexes and in this high sulphate water body probably also by the reduction of iron(III) by sulphide and the consequential precipitation of iron(II) sulphide. 4. Iron addition appeared to prevent sulphide toxicity in Potamogeton acutifolius Link which was planted in the enclosures immediately after iron(II) addition. In the non-iron-treated enclosures P. acutifolius plants decayed within a few weeks probably as a result of sulphide toxicity.     

Singlet Oxygen and Other Reactive Oxygen Species are Involved in Regulation of Release of Iron-Binding Chelators from Scenedesmus cells

Freshly-added iron only slightly affected the growth of iron-sufficient cells of the green alga Scenedesmus incrassatulus Bohl, strain R-83, but induced accumulation of malondialdehyde (MDA) in cells and excretion of MDA in the medium. These effects were stronger in response to Fe²⁺ as compared to Fe³⁺, but Fe³⁺ induced the release of more iron-binding chelators from these cells than Fe²⁺. Fe³⁺ added either in dark or in light induced release of equal concentrations of iron-complexing agents, part of which formed strong chelates with iron in the medium. Exogenously added hydrogen peroxide inhibited iron-induced release of chelators but the effect was removed by addition of the hydroxyl radical scavenger dimethylsulfoxide (DMSO). Malondialdehyde also inhibited the release of chelators. Release of chelators was induced in the absence of iron salts by photoexcited chlorophyll (Chl). The Chl-induced release was efficiently inhibited by singlet oxygen scavengers such as dimethylfuran, -carotene, sodium azide and vitamin B₆, and stimulated in D₂O or DMSO. Exogenously added catalase inhibited the release more than added superoxide dismutase. The Fe³-induced release of chelators was also inhibited by scavengers of singlet oxygen, but was not affected by sodium azide and by ethanol. Hence both H₂O₂ and singlet oxygen were involved in induction of chelator release in the absence of iron in light. The induction of chelator release by iron in dark involved H₂O₂, but not singlet oxygen.     

Phosphorus mobility in interstitial waters of sediments in Lake Kinneret,Israel

Monthly samples of sediment cores from maximum depth ( 42 m) in Lake Kinneret were taken from May 1988 until January 1989. The chemical composition of the interstitial and overlying water was investigated with respect to phosphate, Fe²⁺, Fe³⁺, Ca²⁺, alkalinity and electric conductivity. pH, pH₂S and pe (electron-activity) were measured by microelectrodes inserted directly into the sediment core immediately after sampling.Ion activity products of vivianite, siderite, ironsulfides, Ca-P complexes and Ca-P solid phases were calculated; in addition, Ca/P ratios for the overlying and pore water were obtained by using the potential diagram technique. Despite the fact that anoxic conditions prevail for most of the year, no control of phosphate solubility by a Fe-P relationship could be found. Determination of IAPs, together with calculated molar Ca/P-ratios, suggests that hydroxyapatite as well as surface complexes like dicalciumphosphate are the solubility-controlling species in pore water. For the overlying water a Ca₃(HCO₃)₃PO₄ surface complex is assumed to fix the phosphorus, accompanied by a subsequent transformation of the bound P into apatite.     

Pore water phosphorus and iron concentrations in a shallow,eutrophic lake — indications of bacterial regulation

Peak pore water SRP and iron(II) concentrations were found during summer in surface sediments in the shallow and eutrophic L. Finjasjön, Sweden, and the concentrations generally increased with water depth. The SRP variation in surface sediments (0–2 cm) was correlated with temperature (R² = 0.82–0.95) and iron(II) showed a correlation with sedimentary carbon on all sites (R² = 0.42–0.96). In addition, sedimentary Chla, bacterial abundances and production rates in surface sediments (0–2 cm) varied seasonally, with peaks during spring and fall sedimentation. Bacterial production rates were correlated with phosphorus and carbon in the sediment (R² = 0.90–0.95 and R² = 0.31–0.95, respectively), indicating a coupling with algal sedimentation. A general increase in sediment Chla and bacterial abundances towards sediments at greater water depth was found. Further, data from 1988–90 reveal that TP and TFe concentrations in the lake were significantly correlated during summer (R² = 0.81 and 0.76, in the hypolimnion and epilimnion, respectively). The results indicate that the increase in pore water SRP and Fe(II) in surface sediments during summer is regulated by bacterial activity and the input of organic matter. In addition, spatial and temporal variations in pore water composition are mainly influenced by temperature and water depth and the significant correlation between TP and TFe in the water suggests a coupled release from the sediment. These findings support the theory of anoxic microlayer formation at the sediment-water interface.     

Ability of marine eukaryotic red tide microalgae to utilize insoluble iron

Iron is an essential trace metal and a limiting factor for microalgal growth, but bioavailable dissolved iron concentrations in seawater are low. Microalgal blooms have frequently occurred in coastal areas under such iron limitation accompanied by mass mortalities of fish and bivalves. Their massive growth despite physiological iron-deficiency has long been an enigma, because most of them cannot grow in chemically defined artificial media. We developed a feasible artificial medium for the culture of many species of red tide microalgae modified for investigation of iron utilization. Here, we report on the ability of marine eukaryotic red tide microalgae to utilize insoluble iron. Some microalgal species could utilize particulate FePO₄ and FeS for growth. Particulate FePO₄ was available for the growth of the raphidophyte Heterosigma akashiwo, the dinoflagellate Heterocapsa triquetra and the diatom Ditylum brightwellii. The dinoflagellates Heterocapsa circularisquama and Karenia mikimotoi, and the cryptophyte Rhodomonas ovalis utilized both particulate FePO₄ and particulate FeS for growth. In contrast, particulate FeO(OH) and Fe₂O₃ did not support the growth of any of the red tide microalgae examined. Except for Chattonella species (Raphidophyceae), the growth of red tide microalgae were confirmed in the medium with very easily soluble FeCl₃ added. The order of bioavailability of tested iron-source species were Fe–EDTA > FeCl₃ > FePO₄ > FeS > FeO(OH), Fe₂O₃ for most of microalgae examined, although for H. circularisquama the utilization of FeCl₃ was higher than that of Fe–EDTA. The results suggest that red tide microalgae show different patterns of specific strategies for the utilization of various iron sources. The occurrence of red tides in coastal areas may depend on the combination of microalgal species and insoluble iron species present.     

Alkalinity generation and sediment CO2 uptake influence establishment of Sparganium angustifolium in softwater lakes

1. Softwater lakes are generally dominated by slow growing, small, isoetid plant species that are adapted to the carbon‐ and nutrient‐limited conditions in these lakes. We investigated the strategy of a fast growing species, Sparganium angustifolium, for occupying softwater lakes. A field survey was carried out in Norwegian carbon‐limited Isoëteto‐Lobelietum softwater lakes to compare abiotic conditions at locations with and without S. angustifolium. In addition, long term abiotic changes (1995–2008) related to the sudden establishment of the species on experimentally limed plots were studied. Based on the results, the carbon acquisition mechanism of S. angustifolium was tested in eco‐physiological laboratory experiments. 2. The redox potential was significantly lower at locations with S. angustifolium (220 ± 2.3) compared to locations without S. angustifolium (338.1 ± 13.9). The lower redox potential was accompanied by significantly higher concentrations of HCO₃^?, CO₂ and Fe²⁺ in the sediment pore water, indicating in‐lake alkalinity generation due to higher iron reduction rates in the generally iron‐rich sediments. In addition, the lower redox potential was accompanied by a higher nutrient availability (NH₄⁺ and PO₄^3?) in the sediment pore water. Since there were no differences in water quality between the lakes, the ability of S. angustifolium to grow in softwater lakes very likely depends upon the higher dissolved inorganic carbon (DIC) and nutrient concentrations present in the sediment pore water. 3. Results from the liming experiment revealed that appearance of S. angustifolium on limed plots was related to the dissolution of Ca and Mg carbonates and development of a lower redox potential in the sediment. These processes were accompanied by a sustained increase in the availability of DIC in the sediment pore water. 4. The eco‐physiological experiments indicated that S. angustifolium can increase in biomass and produce floating leaves at a relatively high DIC availability in the root medium. In addition, it appeared that S. angustifolium can take up CO₂ by the roots. As far as we know, the ability to use sediment CO₂ has only been described as an adaptation typical for isoetid plant species. Use of the relatively large sediment CO₂ pools present in these sediment types (>1000 μmol L^?1) to enable development of long floating leaves for additional uptake of atmospheric CO₂ is a very different strategy to colonise softwater lakes as compared to isoetid plant species.     

Interactions of an acid tolerant strain of phosphate solubilizing bacteria with a few acid tolerant crops

Phosphate solubilizing bacteria (PSB) were isolated from sixty soil samples of various soil classes and cropping histories in Himalayan regions of Uttar Pradesh, India by enrichment culture techniques. Phosphate solubilization and acid tolerance of each strain was estimated. A strain (PAS-2) isolated froma pasture and waste land of pH 4.8, organic matter 2.6% available N 265kg ha^-1, available P₂O₅(Bray's II) 2.3kg ha^-1 and available K₂O 353 kg ha^-1 had the highest P-solubilization (45 µg P per mL per day) and also highest acid tolerance rating 42. The strain was identified as Bacillus sp. Seed inoculation of this bacterial strain resulted in significant increases in grain and vegetative yield of fingermillet (Elosine coracana), maize (Zea mays), amaranth (Amaranthus hypochondriacus), buckwheat (Fagopyrium esculentum), frenchbean (Phaseolus vulgaris) with or without added P sources. The significant grain yield (quintol ha^-1) with phosphate and seed inoculation ranged from 33.85 in maize, 26.33 in frenchbean, 22.41 in buckwheat, 20.71 in amaranth and 19.19 in fingermillet as compared to controls. The highest response was observed with frenchbean followed by fingermillet, buckwheat, amaranth and maize. Phosphate use efficiency was highest in frenchbean followed by maize and lowest and almost at par in buckwheat, amaranth and fingermillet. Available phosphate was also highest in frenchbean cultivated plot followed by amaranth, fingermillet, buckwheat and maize. The MPN count of phosphate solubilizing bacteria were also influenced by seed inoculation of strain PAS-2. Frenchbean exerted greaterrhizosphere effect followed by pseudocereals and cereals. Likewise, phosphate nutrition of crops were also improved through seed inoculation irrespective of added P sources. The study thus demonstrated that selection of efficient strain of PSB from acid soil and its seed inoculation in selected crop genotype is beneficial in boosting up crop yield in low productive hill soil. Seed inoculation also created greater rhizosphere effect over uninoculation which improved P-nutrition of crops and also available soil P.     

Effects of iron chelates on the transferrin-free culture of rat dermal fibroblasts through active oxygen generation

Summary Effects of nonchelating and chelating agents at 10 mM on the serum-free culture of rat dermal fibroblasts were investigated. A strong iron-chelating agent, iminodiacetic acid (IDA), and a weak one, dihydroxyethylglycine (DHEG), decreased iron permeation into preconfluent fibroblasts. A weak iron-chelating agent, glycylglycine (GG), a nonchelating agent, N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid (HEPES), and human apotransferrin (10 μg/ml) increased the permeation with time. Iron may be essential for survival of fibroblasts because subconfluent fibroblasts exposed to 100 μM FeSO₄ in combination with transferrin, HEPES, or GG significantly decreased to release lactate dehydrogenase into the medium. Superoxide dismutase and dimethyl sulfoxide blocked the enzyme release, suggesting that superoxide and hydroxyl radical induce cellular damage but hydrogen peroxide (H₂O₂) generated by superoxide dismutation does not. GG significantly reduced H₂O₂ cytotoxicity. DHEG acted as a potent promoter of the iron-stimulated cellular damage if ascorbate or H₂O₂ was added to the medium. FeSO₄ and FeCl₃ (50 to 100 μM) individually combined with IDA maximally promoted fibroblast proliferation. Ascorbate increased formation of thiobarbituric acid-reactive substances from deoxyribose in the medium supplemented with FeSO₄ and either IDA or DHEG. Conversely, ascorbate decreased the formation in the medium with FeSO₄ and with or without other agents. Fibroblast proliferation may thus be stimulated through the active oxygen generation mediated by a redox-cycling between Fe³⁺ and Fe²⁺, which are dissolved in the medium at a high concentration, rather than through delivery of iron into the cells.     

Coordination chemistry of acrylamide 6: Formation and structural characterization of [Fe(O-OC(NH2)CHCH2)6][Fe2OCl6]

The new acrylamide iron(II)/iron(III) complex [Fe(O-OC(NH₂)CHCH₂)₆][Fe₂OCl₆] (1) was obtained by the reaction of a mixture of anhydrous FeCl₂ and anhydrous FeCl₃ with acrylamide (molar ratio 1:2:6) in 98% pure commercial nitromethane under nitrogen atmosphere. According to an X-ray structural analysis, the acrylamide ligands in the cation are coordinated via the amide-oxygen atoms. The formation of the (μ-oxo)bis[trichloroferrate(III)]²⁻ anion presumably resulted from partial hydrolysis of FeCl₃ or [FeCl₄]⁻ by small amounts of water in the nitromethane and/or by the nitromethane itself.     

Benthic oxygen respiration, ammonium and phosphorus regeneration in surficial sediments of the Sacca di Goro (Northern Italy) and two French coastal lagoons: a comparative study

During 1994 net sediment-water fluxes of oxygen, ammonium and inorganic phosphorus as well as sediment profiles of organic matter, nitrogen, phosphorus and iron were determined in three shallow eutrophic environments. Investigations were conducted monthly from March to December at five stations in the Sacca di Goro (Po River Delta, Italy). In the late summer, samples were collected from a single site in the Prévost lagoon (French Mediterranean coast) and three stations in the Bassin d'Arcachon (French Atlantic coast). In the Sacca di Goro, water-sediment exchanges of O₂, NH ₄ ⁺ and PO ₄ ^3– were estimated by means of core incubation in the dark. Benthic fluxes for the French lagoons were in part determined experimentally using benthic chambers and in part from the literature.In general in the Sacca di Goro the highest oxygen uptake and nutrient release rates were found at the central sites, affected by macroalgal growth. At the sampling site adjacent to the freshwater inlet, sediment-water exchanges were principally influenced by tidal activity. In terms of organic matter and nutrient levels, sediments from the Sacca di Goro and from the Prévost lagoon, both colonised by the floating macroalga Ulva rigida C. Agardh, were similar. Sediments from the inner sheltered site in the Bassin d'Arcachon, invaded by the rooted macrophyte Ruppia cirrhosa (Pet.) Grande, showed the highest total N and P content (363 ± 157 µmol N cm^–3 and 15 ± 2 µmol P cm^–3 as average values in the top 10 cm of sediment), but were low in pore water ammonium and orthophosphate probably due to the high sequestering capacity of the system and/or efficient coupling between bacterial nutrient regeneration and assimilation by the plant roots. In addition the outer tidal stations in the Bassin d'Arcachon, invaded by rooted macrophytes, were low in pore water nutrients. A different trend was evident in the Prévost lagoon where the concentrations of exchangeable inorganic phosphorus and ammonium were appreciable (0.28 ± 0.07 µmol P cm^–3 and 2.4 ± 1.4 µmol N cm^–3 as average values in the top 10 cm of sediment). High amounts of dissolved organic nitrogen were found in the pore water at all the sites investigated showing the key role of the organic nitrogen in the recycling of nitrogen in these systems.The hypothesis that iron is a key factor in controlling phosphorus release is discussed since the Sacca di Goro, which is subject to dystrophic crises, is richer in iron than the Bassin d'Arcachon, which is a more buffered system.     

Iron (III) Stimulation of Lipid Hydroperoxide-Dependent Lipid Peroxidation

In an experimental system where both Fe²⁺ autoxidation and generation of reactive oxygen species is negligible, the effect of FeCl₂ and FeCl₃ on the peroxidation of phosphatidylcholine (PC) liposomes containing different amounts of lipid hydroperoxides (LOOH) was studied; Fe²⁺ oxidation, oxygen consumption and oxidation index of the liposomes were measured. No peroxidation was observed at variable FeCl₂/FeCl₃ ratio when PC liposomes deprived of LOOH by triphenyl-phosphine treatment were utilized. By contrast, LOOH containing liposomes were peroxidized by FeCl₂. The FeCl₂ concentration at which Fe²⁺ oxidation was maximal, defined as critical Fe²⁺ concentration [Fe²⁺]*, depended on the LOOH concentration and not on the amount of PC liposomes in the assay. The LOOH-dependent lipid peroxidation was stimulated by FeCl₃, addition; the oxidized form of the metal increased the average length of radical chains, shifted to higher values the [Fe²⁺]* and shortened the latent period. The iron chelator KSCN exerted effects opposite to those exerted by FeCl₃ addition. The experimental data obtained indicate that the kinetics of LOOH-dependent lipid peroxidation depends on the Fe²⁺/Fe³⁺ ratio at each moment during the time course of lipid peroxidation. The results confirm that exogenously added FeCl₃ does not affect the LOOH-independent but the LOOH-deendent lipid peroxidation; and suggest that the Feg, endogenously generated exerts a major role in the control of the LOOH-dependent lipid peroxidation.     

Effect of Iron Hydroxide on Phosphate Removal during Anaerobic Digestion of Activated Sludge

The addition of iron (III) hydroxide during methanogenic digestion of activated sludge by anaerobic sludge displaying an iron-reducing activity resulted in a microbial reduction of iron (III) with the formation of iron (II), capable of precipitating phosphates. The feasibility of eliminating 66.6 to 99.6% of the dissolved phosphate at initial concentrations of 1000 to 3500 mg PO^3- ₄/l by adding 6420 mg/l iron (III) hydroxide into a reactor for anaerobic fermentation of activated sludge was analyzed. The optimal ratio of iron (III) added to dissolved phosphate removed (mg) providing a 95% removal amounted to 2 : 1. These results may be used in new technology for anaerobic wastewater treatment with phosphate removal.     

A new experimental setup for studying the formation of phosphate binding iron oxides in marine sediments. Preliminary results

A new laboratory method is introduced to study theformation of phosphate binding iron(III) oxides at theredox boundary in marine sediments. A sediment core isgiven a very well-defined oxic-anoxic interface byplacing a 0.45 µm filter between the sediment andthe overlying water. After a period of 1 months thefilter is covered with a layer of fresh iron oxides,formed by the oxidation of upward diffusing Fe²⁺from the sediment pore water. The formed iron oxidesare investigated by electron probe X-ray microanalysis(EXPMA). With a sediment core from the brackish BalticSea the average molar composition of 788 formedparticles is Fe_1.00±0.13P_0.55±0.06Ca_0.37±0.04 plus unknown amounts of O, H andC. The results show that the particles have a uniformcomposition, and that calcium plays an important rolein the phosphate binding. The laboratory method is auseful supplement to in situ sampling forstudies of iron oxides.     

Inhibition of cell membrane lipid peroxidation by cadmium- and zinc-metallothioneins

The effects of all-zinc metallothionein (Zn-metallothionein) and predominantly cadmium metallothionein (Cd/Zn-metallothionein) on free radical lipid peroxidation have been investigated, using erythrocyte ghosts as the test system. When treated with xanthine and xanthine oxidase, Zn-metallothionein and Cd/Zn-metallothionein underwent thiolate group oxidation and metal ion release that was catalase-inhibitable, but superoxide dismutase-non-inhibitable. Similar treatment in the presence of ghosts and added Fe(III) resulted in metallothioneen oxidation that was significantly inhibited by superoxide dismutase. Ghosts incubated with xanthine/xanthine oxidase/Fe(III) underwent H₂O₂- and O₂⁻-dependent lipid peroxidation, as measured by thiobarbituric acid reactivity. Neither type of metallothionein had any effect on xanthine oxidase activity, but both strongly inhibited lipid peroxidation when added to the membranes concurrently with xanthine/xanthine oxidase/iron. This inhibition was far greater and more sustained than that caused by dithiothreitol at a concentration equivalent to that of metallothionein thiolate. Significant protection was also afforded when ghosts plus Cd/Zn-metallothionein or Zn/metallothionein were preincubated with H₂O₂ and Fe(III), and then subjected to vigorous peroxidation by the addition of xanthine and xanthine oxidase. These results could be mimicked by using Cd(II) or Zn(II) alone. Previous studies suggested that Zn(II) inhibits xanthine/xanthine oxidase/iron-driven lipid peroxidation in ghosts by interfering with iron binding and redox cycling. Therefore, the primary determinant of metallothionein proteciion appears to be metal release and subsequent uptake by the membranes. These results have important implications concerning the antioxidant role of metallothionein, a protein known to be induced by various prooxidant conditions.     

The relationship between Chironomus plumosus burrows and the spatial distribution of pore-water phosphate, iron and ammonium in lake sediments

1. To study the influence of chironomids on the distribution of pore‐water concentrations of phosphate, iron and ammonium, we conducted a laboratory experiment using mesocosms equipped with two‐dimensional pore‐water samplers, filled with lake sediment and populated with different densities of Chironomus plumosus. 2. Specially designed mesocosms were used in the study. A 6‐mm deep space between the front plate and the pore‐water sampler at the back plate was just thick enough to allow the chironomids to live undisturbed, yet thin enough to force all the burrows into a two‐dimensional plane. 3. The courses of the burrows were observed during the experiment as oxidised zones surrounding them, as well as being identified with an X‐ray image taken at the end of the experiment. 4. We investigated the relationship between C. plumosus burrows and spatial patterns of pore‐water composition. Concentrations of the three ions were significantly less around ventilated burrows (54% to 24%), as bioirrigation caused a convective exchange of pore‐water enriched with dissolved species compared with the overlying water, and also because oxygen imported into the sediment resulting in nitrification of ammonium, oxidation of iron(II) and a co‐precipitation of phosphate with Fe(III) oxyhydroxides. 5. In mesocosms with chironomids, new (redox) interfaces occurred with diffusive pore‐water gradients perpendicular to the course of burrows and the site of major phosphate, ammonium and iron(II) release shifted from the sediment surface to the burrow walls.     

Protein oxidation by the cytochrome P450 mixed-function oxidation system

This mini-review summarizes results of studies on the oxidation of proteins and low-density lipoprotein (LDL) by various mixed-function oxidation (MFO) systems. Oxidation of LDL by the O₂/FeCl₃/H₂O₂/ascorbate MFO system is dependent on all four components and is much greater when reactions are carried out in the presence of a physiological bicarbonate/CO₂ buffer system as compared to phosphate buffer. However, FeCl₃ in this system could be replaced by hemin or the heme-containing protein, hemoglobin, or cytochrome c. Oxidation of LDL by the O₂/cytochrome P450 cytochrome c reductase/NADPH/FeCl₃ MFO system is only slightly higher (25%) in the bicarbonate/CO₂ buffer as compared to phosphate buffer, but is dependent on all components except FeCl₃. Omission of FeCl₃ led to a 60% loss of activity. These results suggest that peroxymonobicarbonate and/or free radical derivatives of bicarbonate ion and/or CO₂ might contribute to LDL oxidation by these MFO systems.     

The impact of Chironomus plumosus larvae on organic matter decay and nutrient (N, P) exchange in a shallow eutrophic lake sediment following a phytoplankton sedimentation

The importance of Chironomus plumosus larvae onbenthic metabolism and nutrient exchange across thesediment–water interface was evaluated in a shalloweutrophic lake (Lake Arreskov, Denmark) following aphytoplankton sedimentation. Chironomus plumosuslarvae were added to laboratory sediment microcosms,corresponding to a density of 2825 larvae m⁻².Non-inhabited microcosms served as controls. Asedimentation pulse of organic matter was simulated byadding fresh algal material (Chlamydomonasreinhardii) to sediment cores (36 g dryweight m⁻²). The mineralization was followed bymeasuring fluxes of O₂, CO₂, dissolvedinorganic nitrogen and phosphate. A rapid clearance ofalgae from the water column in faunated microcosmssuggested that chironomids may be of major importancein controlling phytoplankton concentrations in shalloweutrophic lakes. Chironomids increased the sedimentO₂ uptake ≈ 3 times more than what wouldbe expected from their own respiration, indicating astimulation of microbial activity and decomposition oforganic matter in the sediment. Addition of algaeenhanced the release of CO₂, NH⁺ ₄ ando-P. The excess inorganic C, N and P released inamended non-inhabited sediment after 36 dayscorresponded to 65, 31 and 58% of the C, N and P inthe added algae. In sediment inhabited by Chironomus plumosus the corresponding numbers were147, 45 and 73%, indicating that mineralization oforganic matter also from the indigenous sediment poolwas stimulated by chironomids. This revised version was published online in July 2006 with corrections to the Cover Date.     

Iron prevents ascorbic acid (vitamin C) induced hydrogen peroxide accumulation in copper contaminated drinking water

Ascorbic acid (vitamin C) induced hydrogen peroxide (H₂O₂) formation was measured in household drinking water and metal supplemented Milli-Q water by using the FOX assay. Here we show that ascorbic acid readily induces H₂O₂ formation in Cu(II) supplemented Milli-Q water and poorly buffered household drinking water. In contrast to Cu(II), iron was not capable to support ascorbic acid induced H₂O₂ formation during acidic conditions (pH: 3.5–5). In 12 out of the 48 drinking water samples incubated with 2 mM ascorbic acid, the H₂O₂ concentration exceeded 400 μM. However, when trace amounts of Fe(III) (0.2 mg/l) was present during incubation, the ascorbic acid/Cu(II)-induced H₂O₂ accumulation was totally blocked. Of the other common divalent or trivalent metal ions tested, that are normally present in drinking water (calcium, magnesium, zinc, cobalt, manganese or aluminum), only calcium and magnesium displayed a modest inhibitory activity on the ascorbic acid/Cu(II)-induced H₂O₂ formation. Oxalic acid, one of the degradation products from ascorbic acid, was confirmed to actively participate in the iron induced degradation of H₂O₂. Ascorbic acid/Cu(II)-induced H₂O₂ formation during acidic conditions, as demonstrated here in poorly buffered drinking water, could be of importance in host defense against bacterial infections. In addition, our findings might explain the mechanism for the protective effect of iron against vitamin C induced cell toxicity.     

The importance of sediment phosphorus release in the restoration of very shallow lakes (The Norfolk Broads,England) and implications for biomanipulation

Phosphorus release from the sediments of very shallow lakes, the Norfolk Broads, can be as high as 278 mgP m^-2 d^-1. These high rates are associated with high total sediment Fe:P ratios and occur when sulphide from sulphate reduction removes Fe(II) from the pore water. There is also evidence that bioturbation from benthic chironomids can enhance phosphorus release rates, particularly in sediments low in total iron. The release of phosphorus from the sediments of these lakes is delaying restoration following the control of phosphorus from sewage discharges. Biomanipulation is being used in these lakes to create clear water and re-establish aquatic macrophytes. This removal of fish has allowed larger populations of benthic chironomid larvae to develop which may result in an increase in the rate of phosphorus release and changes to the pore profiles of dissolved phosphorus, soluble iron and free sulphide.