The role of the ironhydroxide-phosphate-sulphide system in the phosphate exchange between sediments and overlying water

The accumulation of inorganic phosphate in lake sediments and a possible following release is due to the adsorption of phosphate onto Fe(OOH) and, especially in hard waters, to the precipitation of apatite. Attempts are made to quantify both processes.For the quantification of the P adsorbed, P_ads, onto Fe(OOH) the Freundlich adsorption isotherm, P_ads=A(o-P)^B, gave good results. The constants A and B could be quantified. Constant A appeared to depend on the pH and the Ca²⁺ and Mg²⁺ concentrations in the water. Constant B appeared to approach 0.333. The full equation becomes then: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGak0dh9WrFfpC0xh9vqqj-hEeeu0xXdbba9frFj0-OqFf% ea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr% 0-vqpWqaaeaabaGaciaacaqabeaadaqaaqaaaOqaaiaadcfadaWgaa% WcbaGaamyyaiaadsgacaWGZbaabeaakiabg2da9iaaikdacaaIZaGa% aGOnaiaaicdacaaIWaGaaiOlaiaacIcacaaIXaGaaGimamaaCaaale% qabaGaaGimaiaac6cacaaI0aacbiGaa8hCaiaa-HeaaaGccaGGPaGa% aiikaiaaikdacaGGUaGaaG4naiaaiEdacqGHsislcaaIXaGaaiOlai% aaiEdacaaI3aGaai4oaiaadwgadaahaaWcbeqaaiabgkHiTiaa-nea% caWFHbaaaOGaaiykamaakeaabaGaam4BaiabgkHiTiaadcfaaSqaai% aaiodaaaaaaa!57AF!\[P_{ads} = 23600.(10^{0.4pH} )(2.77 - 1.77;e^{ - Ca} )\sqrt[3]{{o - P}}\]. with the Ca concentration in mmol l^–1 and the o-P and P_ads concentrations in mg l^–1.For the quantification of the solubility of calcium-bound phosphate the solubility product of apatite being 10^–50, as found in the two hard water rivers Rhine and Rhone, was used. With this solubility product the solubility of o-P can be calculated as function of the Ca²⁺ concentration and the pH. The two equations, for adsorption and precipitation, are put together in a so-called solubility diagramme, which describes the o-P concentration as function of the Fe(OOH) concentration in the sediments, and the pH and the Ca²⁺ concentration in the overlying water.The release of phosphate from the Fe(OOH)P complex under anoxic conditions after adding H₂S in inorganic suspensions was shown to be limited. Only when a large excess of H₂S was added there was some release, but if less than 75% of the Fe(OOH) was converted into FeS, there was no release. The possibility of organic phosphate as the source of phosphate release under anoxic conditions is discussed. For a full understanding of this possibility, fractionation of sediment bound phosphate must be carried out in such a way, that these organic phosphates are not hydrolysed.This article is dedicated to the memory of Dr Kees de Groot, who died on 21 September 1994. He was a young enthusiastic, promising scientist who will be missed by all who have known him.     

Influence of Microbial Composition on the Carbon Storage Capacity of the Mangrove Soil at the Land-ocean Boundary in the Sundarban Mangrove Ecosystem,India

Spatiotemporal assessment of the mangrove soil of Indian Sundarban revealed that decomposition rate of the organic matter was significantly lower in the anoxic condition than that of the oxic condition. Higher degree of enzyme activity in the oxic soil than the anoxic condition suggested that slower biomineralization in anoxic condition would facilitate long-term storage of organic matter in that particular ecosystem. Microbial population of nitrifying bacteria, phosphate solubilizing bacteria, cellulose degrading bacteria and fungi showed significant reduction in anoxic incubation than that in oxic incubation. In contrary, sulfate reducing bacteria and free living N2 fixing bacteria showed higher population in anoxic incubation indicating their preference for anaerobic condition. Soil CO₂ emission rate decreased with the increase in anoxicity and was largely dependent on the soil redox potential, organic carbon and microbial population of the mangrove soil.     

Sedimentary Sulphur:Iron Ratio Indicates Vivianite Occurrence: A Study from Two Contrasting Freshwater Systems

An increasing number of studies constrain the importance of iron for the long-term retention of phosphorus (P) under anoxic conditions, i.e. the formation of reduced iron phosphate minerals such as vivianite (Fe₃(PO₄)₂⋅8H₂O). Much remains unknown about vivianite formation, the factors controlling its occurrence, and its relevance for P burial during early sediment diagenesis. To study the occurrence of vivianite and to assess its relevance for P binding, surface sediments of two hydrologically contrasting waters were analysed by heavy-liquid separation and subsequent powder X-ray diffraction. In Lake Arendsee, vivianite was present in deeper sediment horizons and not in the uppermost layers with a sharp transition between vivianite and non-vivianite bearing layers. In contrast, in lowland river Lower Havel vivianite was present in the upper sediment layers and not in deeper horizons with a gradual transition between non-vivianite and vivianite bearing layers. In both waters, vivianite occurrence was accompanied by the presence of pyrite (FeS₂). Vivianite formation was favoured by an elevated iron availability through a lower degree of sulphidisation and was present at a molar ratio of total sulphur to reactive iron smaller than 1.1, only. A longer lasting burden of sediments by organic matter, i.e. due to eutrophication, favours the release of sulphides, and the formation of insoluble iron sulphides leading to a lack of available iron and to less or no vivianite formation. This weakening in sedimentary P retention, representing a negative feedback mechanism (P release) in terms of water quality, could be partly compensated by harmless Fe amendments.     

Hydrogen peroxide and the evolution of oxygenic photosynthesis

The early atmosphere of the Earth is considered to have been reducing (H₂ rich) or neutral (CO₂-N₂). The present atmosphere by contrast is highly oxidizing (20% O₂). The source of this oxygen is generally agreed to have been oxygenic photosynthesis, whereby organisms use water as the electron donor in the production of organic matter, liberating oxygen into the atmosphere. A major question in the evolution of life is how oxygenic photosynthesis could have evolved under anoxic conditions — and also when this capability evolved. It seems unlikely that water would be employed as the electron donor in anoxic environments that were rich in reducing agents such as ferrous or sulfide ions which could play that role. The abiotic production of atmospheric oxidants could have provided a mechanism by which locally oxidizing conditions were sustained within spatially confined habitats thus removing the available reductants and forcing photosynthetic organisms to utilize water as the electron donor. We suggest that atmospheric H₂O₂ played the key role in inducing oxygenic photosynthesis because as peroxide increased in a local environment, organisms would not only be faced with a loss of reductant, but they would also be pressed to develop the biochemical apparatus (e.g., catalase) that would ultimately be needed to protect against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis while global conditions were still anaerobic.     

Diversity of Culturable Bacteria,from the Anaerobic Zone of the Meromictic Lake Pavin,Able to Perform Dissimilatory-Iron Reduction in Different in Vitro Conditions

A culture-dependent study was performed with the aim of assessing the carbon, electron and Fe(III) sources used for the dissimilatory Fe(III) reduction pathway and the diversity of culturable Fe(III)-reducers in the anoxic zone of the meromictic Lake Pavin. This metabolic pathway was investigated in enrichment cultures inoculated with water samples collected at 70 m depth in the anoxic zone of Lake Pavin. Combinations of different media, organic acids, and incubation gas phases were performed. The potential for Fe(III) reduction in the different growth conditions was assessed by measuring the accumulation of Fe(II) overtime. Bacterial community structure was determined in each growth conditions by Temporal Temperature gradient Gel Electrophoresis (TTGE) profiles of 16S rDNA genes and bands of interest in positive enrichments were sequenced. Comparisons of bacterial community structure between growth conditions revealed that the electron donor, the basal media as well as the Fe(III) source yielded to the selection of different bacterial populations, suggesting that Fe(III) reducers occupy different ecological niches in the anoxic zone of Lake Pavin. Facultative Fe(III) reducers, such as fermentative (e.g., Pseudomonas, Clostridium) and sulphate-reducing (e.g., Desulfovibrio sp.) bacteria, were retrieved in enrichments but well-known obligatory Fe(III) reducers (e.g., Geobacter) were not detected. A greater Fe(III) reduction was noted under H₂:CO₂ gas phase, suggesting that H₂ is used as an electron donor for Fe(III) reduction. Acetate was not used as a precursor for this terminal electron-accepting process, and a high Fe(III) reduction was observed with fumarate provided as the electron donor and carbon sources suggesting that this metabolite may be energetically more beneficial for Fe(III)-reducers.     

The genome of the Gram‐positive metal‐ and sulfate‐reducing bacterium Desulfotomaculum reducens strain MI‐1

Spore‐forming, Gram‐positive sulfate‐reducing bacteria (SRB) represent a group of SRB that dominates the deep subsurface as well as niches in which resistance to oxygen and dessication is an advantage. Desulfotomaculum reducens strain MI‐1 is one of the few cultured representatives of that group with a complete genome sequence available. The metabolic versatility of this organism is reflected in the presence of genes encoding for the oxidation of various electron donors, including three‐ and four‐carbon fatty acids and alcohols. Synteny in genes involved in sulfate reduction across all four sequenced Gram‐positive SRB suggests a distinct sulfate‐reduction mechanism for this group of bacteria. Based on the genomic information obtained for sulfate reduction in D. reducens, the transfer of electrons to the sulfite and APS reductases is proposed to take place via the quinone pool and heterodisulfide reductases respectively. In addition, both H₂‐evolving and H₂‐consuming cytoplasmic hydrogenases were identified in the genome, pointing to potential cytoplasmic H₂ cycling in the bacterium. The mechanism of metal reduction remains unknown.     

Experimental and field evidence of Antarctic foraminiferal tolerance to anoxia and hydrogen sulfide

The common occurrence of foraminifera in strata deposited under anoxic environmental conditions throughout the geologic record raises the question of whether foraminifera actually survive anoxic or reducing conditions. To test this, benthic foraminifera from McMurdo Sound, Antarctica were exposed to anoxic or reducing conditions for 30 days. These Antarctic forms are known to be exposed to anoxic events in their natural environment. An adenosine triphosphate (ATP) assay was used to determine foraminiferal survival, and their ultrastructure was examined using transmission electron microscopy (TEM) to evaluate any possible effect that might have resulted from exposure to anoxic or reducing conditions. The experimental treatments did not have any statistically significant effects upon the foraminifers with regards to survival or average ATP content per individual including the four most common living species. Some ultrastructural evidence for encystment (fibrillar membrane-bound bodies in the cytoplasm of many specimens) was observed. Field data include the observation thatGlobocassidulina cf.G. biora resides in sediments to depths of 7 cm, as evidenced by ultrastructural investigations. A specimen ofGlobocassidulina cf.G. biora collected from sediments containing anoxic pore waters showed numerous bacteria within the confines of the organic lining. The occurrence of cytoplasmic inclusions similar in appearance to car☐ysomes within these bacteria suggest possible affinities to the chemolithotrophicThiobacillus. Bacteria of this type were not observed in specimens collected from oxygenated pore waters. These field and laboratory findings suggest that certain foraminifera may be facultative anaerobes able to withstand reducing conditions.     

Input-output budgets at Langtjern,a small acidified lake in southern Norway

Precipitation and streamwater volume and chemical composition have been measured since 1974 at Langtjern, a small, acid (pH 4.6–4.8) lake on granitic-gneissic bedrock in coniferous forest located ca. 100 km north of Oslo, Norway. The area receives acid precipitation (weighted average pH 4.28). The 7-year input-output budgets for major ions at two terrestrial subcatchments indicate that for Na, K, SO₄ and Cl outputs approximately equal inputs, for H⁺, NH₄ and NO₃ outputs are much less than inputs, and for Ca, Mg and Al outputs greatly exceed inputs. The sulfate budgets (which include estimated dry deposit) indicate that the terrestrial catchment retains about 20% of the incoming sulfate, perhaps due to absorption in the soil, plant uptake, reduction and storage in peaty areas or reduction and release of H₂S to the atmosphere. The budgets for Langtjern lake itself indicate that for most components output equals inputs to within 10%, i.e. these compounds simply pass through the lake. For H⁺, and possibly NH₄ and NO₃, inputs exceed outputs. Because gaseous phases are not measured the N budgets are uncertain. A mechanism that leads to ‘retention’ of both H⁺ and SO₄ is sulfate reduction and incorporation of sulfides in the lake sediments. Such has been documented in the experimentally-acidified Lake 223, Experimental Lakes Area, Ontario, Canada. Although there is no evidence suggesting the development of anoxic bottom waters at Langtjern, such reduction might occur at the water-sediment interface and in the sediments. The budgets for the pollutant components H⁺ and SO₄ at Langtjern differ substantially from those at the relatively unaffected Lake 239, in the Experimental Lakes Area.     

Modeling the carbon cycle in Lake Matano

Lake Matano, Indonesia, is a stratified anoxic lake with iron‐rich waters that has been used as an analogue for the Archean and early Proterozoic oceans. Past studies of Lake Matano report large amounts of methane production, with as much as 80% of primary production degraded via methanogenesis. Low δ¹³C values of DIC in the lake are difficult to reconcile with this notion, as fractionation during methanogenesis produces isotopically heavy CO₂. To help reconcile these observations, we develop a box model of the carbon cycle in ferruginous Lake Matano, Indonesia, that satisfies the constraints of CH₄ and DIC isotopic profiles, sediment composition, and alkalinity. We estimate methane fluxes smaller than originally proposed, with about 9% of organic carbon export to the deep waters degraded via methanogenesis. In addition, despite the abundance of Fe within the waters, anoxic ferric iron respiration of organic matter degrades <3% of organic carbon export, leaving methanogenesis as the largest contributor to anaerobic organic matter remineralization, while indicating a relatively minor role for iron as an electron acceptor. As the majority of carbon exported is buried in the sediments, we suggest that the role of methane in the Archean and early Proterozoic oceans is less significant than presumed in other studies.     

Relation between phosphate and organic matter in fish-pond sediments of the Deroua fish farm (Béni-Mellal, Morocco): implications for pond management

An experimental approach of the phosphate exchange across the water–sediment interface in fish ponds of the Deroua farm (Béni-Mellal, Morocco) is needed to understand the phosphate dynamics in these ponds in relation to their water quality. During this study, we conducted experiments to determine the P-fractions of the different pond sediments and to estimate the release from these sediments of phosphate available for algal uptake. We also determined the amount of phosphate needed to saturate the sediments of two different fish ponds under anoxic and oxic conditions. Phosphate release from sediments comes mainly from Fe(OOH)P and is more important in ponds lined with sheets. The accumulation of organic matter in sediments favours the installation of anoxic conditions and enhances the phosphate release from CaCO₃P, labile in these pond sediments. Under experimental conditions, org-P plays a minor role in the P-release. Oxic conditions, to the contrary, have an inhibitory effect on the P-release from sediments. About 80–98% of the P-adsorbed onto different pond sediments was recovered in the inorg-P-fractions. Aeration induces the oxidation of FeS to Fe(OOH) which can adsorb phosphate from solution. Besides, the presence of bacteria in pond sediments was essential to promote phosphate release under anoxic conditions by controlling the oxidation state of iron and the mineralization of the organic matter. Sheet-lined ponds, when insufficiently dried, accumulate a large quantity of organic matter in their sediments. After a decrease in pH, P is released from CaCO₃P and enhances the phytoplankton productivity responsible for renewed accumulation of organic matter. Org-C concentrations in sediments over 20 mg g^–1 d.w. favour the formation of toxic factors (Fe²⁺, Mn²⁺, NO₂ ^– and H₂S) harmful for carp growth. An extended period of drying efficiently enhances the mineralization of organic matter.     

Reduction and Activation of Phosphate on the Primitive Earth

Electrical discharges in water-saturated N₂ containing 1–10% CH₄ were shown earlier toreduce phosphate to phosphite. This mechanism was suggestedas a possible source of water-soluble phosphorus-containing compounds in volcanic environments on the prebiotic Earth.We have now extended our investigations to gas mixtures inwhich CO₂ and N₂ are the main components, and studied the effect of introducing smallamounts of H₂ and CO.We show that surprisingly high conversions to phosphite occurin reducing mixtures and thatseveral percent reduction of apatite occurs even in thepresence of as little as 1% each of H₂ and CO. We were also able to confirm a previous report ofpolyphosphate production as a result of heating the mineral apatite in the presence of other minerals.     

Biogeochemical processes in the groundwater discharge zone of urban streams

The influence of biogeochemical processes on nitrogen and organic matter transformation and transport was investigated for two urban streams receiving groundwater discharge during the dry summer baseflow period. A multiple lines of evidence approach involving catchment-, and stream reach-scale investigations were undertaken to describe the factors that influence pore water biogeochemical processes. At the catchment-scale gaining stream reaches were identified from water table mapping and groundwater discharge estimated to be between 0.1 and 0.8 m³ m^?2 d^?1 from baseflow analysis. Sediment temperature profiles also suggested that the high groundwater discharge limited stream water infiltration into the sediments. At the stream reach-scale, dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations were higher in stream water than in groundwater. However, DOC and DON concentrations were greatest in sediment pore water. This suggests that biodegradation of sediment organic matter contributes dissolved organic matter (DOM) to the streams along with that delivered with groundwater flow. Pore water ammonium (NH₄ ⁺) was closely associated with areas of high pore water DOM concentrations and evidence of sulfate (SO₄ ^2?) reduction (low concentration and SO₄:Cl ratio). This indicates that anoxic DOM mineralization was occurring associated with SO₄ ^2? reduction. However the distribution of anoxic mineralization was limited to the center of the streambed, and was not constrained by the distribution of sediment organic matter which was higher along the banks. Lower sediment temperatures measured along the banks compared to the center suggests, at least qualitatively, that groundwater discharge is higher along the banks. Based on this evidence anoxic mineralization is influenced by groundwater residence time, and is only measurable along the center of the stream where groundwater flux rates are lower. This study therefore shows that the distribution of biogeochemical processes in stream sediments, such as anoxic mineralization, is strongly influenced by both the biogeochemical conditions and pore water residence time.     

Using modern low-oxygen marine ecosystems to understand the nitrogen cycle of the Paleo- and Mesoproterozoic oceans

During the productive Paleoproterozoic (2.4–1.8 Ga) and less productive Mesoproterozoic (1.8–1.0 Ga), the ocean was suboxic to anoxic and multicellular organisms had not yet evolved. Here, we link geologic information about the Proterozoic ocean to microbial processes in modern low-oxygen systems. High iron concentrations and rates of Fe cycling in the Proterozoic are the largest differences from modern oxygen-deficient zones. In anoxic waters, which composed most of the Paleoproterozoic and ~40% of the Mesoproterozoic ocean, nitrogen cycling dominated. Rates of N₂ production by denitrification and anammox were likely linked to sinking organic matter fluxes and in situ primary productivity under anoxic conditions. Additionally autotrophic denitrifiers could have used reduced iron or methane. 50% of the Mesoproterozoic ocean may have been suboxic, promoting nitrification and metal oxidation in the suboxic water and N₂O and N₂ production by partial and complete denitrification in anoxic zones in organic aggregates. Sulfidic conditions may have composed ~10% of the Mesoproterozoic ocean focused along continental margins. Due to low nitrate concentrations in offshore regions, anammox bacteria likely dominated N₂ production immediately above sulfidic zones, but in coastal regions, higher nitrate concentrations probably promoted complete S-oxidizing autotrophic denitrification at the sulfide interface.     

微生物纳米导线的导电机制及功能

微生物种间直接电子传递是指在厌氧条件下,一种微生物将电子直接传递给另外一种微生物,将两种不同微生物的代谢途径耦合在一起,以达到互养共生的目的。细菌-古菌之间的直接电子传递是其物质转换与能量代谢的新途径和新调控机制,直接参与甲烷的合成以及与硫酸盐还原耦合的厌氧甲烷氧化,在驱动碳和硫的地球化学转化与循环中起着十分重要的作用。目前研究结果认为细菌-古菌之间的直接电子传递主要是由含多个血红素的C型细胞色素介导的,这些细胞色素能形成不间断的胞外电子传递途径,以电子多步跃迁机制在细菌和古菌的细胞质膜之间传递电子。     

Reduction of bromate by biogenic sulfide produced during microbial sulfur disproportionation

Bromate (BrO₃ ⁻) is a carcinogenic contaminant formed during ozonation of waters that contain trace amounts of bromide. Previous research shows that bromate can be microbially reduced to bromide using organic (i.e. acetate, glucose, ethanol) and inorganic (H₂) electron-donating substrates. In this study, the reduction of bromate by a mixed microbial culture was investigated using elemental sulfur (S⁰) as an electron donor. In batch bioassays performed at 30°C, bromate (0.30 mM) was completely converted to bromide after 10 days and no accumulation of intermediates occurred. Bromate was also reduced in cultures supplemented with thiosulfate and hydrogen sulfide as electron donor. Our results demonstrated that S⁰-disproportionating microorganisms were responsible for the reduction of bromate in cultures spiked with S⁰ through an indirect mechanism involving microbial formation of sulfide and subsequent abiotic reduction of bromate by the biogenic sulfide. Confirmation of this mechanism is the fact that bromate was shown to undergo rapid chemical reduction by sulfide (but not S⁰ or thiosulfate) in abiotic experiments. Bromate concentrations above 0.30 mM inhibited sulfide formation by S⁰-disproportionating bacteria, leading to a decrease in the rate of bromate reduction. The results suggest that biological formation of sulfide from by S⁰ disproportionation could support the chemical removal of bromate without having to directly use sulfide as a reagent.     

Sulfate Reduction Based Bioprocesses for the Treatment of Acid Mine Drainage and the Recovery of Metals

Biological sulfate reduction is increasingly replacing chemical unit processes in mining biotechnology. Sulfate reducing bacteria (SRB) can be used for treating ground‐ and surface waters contaminated with acid mine drainage (AMD), and for recovering metals from wastewater and process streams. Biologically produced H₂S precipitates metals as metal sulfides, while biogenic bicarbonate alkalinity neutralizes acidic waters. This paper reviews various passive and active SRB‐based alternatives as well as some process design aspects, such as reactor types, process configurations, and choices of substrates for sulfate reduction. The latest developments of using various low‐cost substrates together with new bioprocess designs are increasing the uses and applications of SRB‐based bioreactors in AMD control and selective metal recovery.     

The labyrinth of nutrient cycles and buffers in wetlands: results based on research in the Camargue (southern France)

Wetlands, especially in the Mediterranean area, are subject to severe eutrophication. This may upset the equilibrium between phytoplankton production in undesirable quantities and a quantitatively desirable macrophyte production. In order to manage this equilibrium, a quantitative knowledge of nutrient input and fluxes is essential and the role of sediments in these processes must be understood. This knowledge can be useful even for agriculture, e.g. rice cultivation, where optimal utilization of fertilizers can lead to an economic benefit.In this article different aspects of nutrient cycles are discussed in view of approaching a sufficiently precise quantification. The nutrient input balance of the Camargue was therefore measured which showed that the input of nutrients with the irrigation water, taken from the river Rhone, roughly equals the quantity of fertilizers added.Phytoplankton growth can be approached reasonably with the Monod model, although there are still many practical problems, such as the influence of the pH on P uptake and the problem of measuring P uptake in the field. The situation is worse for macrophyte growth; quantitative data are scarce and studies have often been carried out with unrealistic nutrient concentrations or without addressing the influence of the sediment. This influence can also include negative factors, such as high concentrations of Fe²⁺, H₂S or FeS, but cannot yet be quantified.The nitrogen cycle in wetlands is dominated by denitrification. Most wetlands have sediments with high concentrations of organic matter, therefore with a large reducing capacity. Besides this process, we have shown that denitrification can also be controlled by FeS. In the Camargue sediments this denitrification is mediated by bacteria from the sulfur cycle; this appeared to be the major pathway. It was shown that a stoicheiometric relation exists between nitrate reduced and sulphate produced. The influence of the temperature was quantified and appeared to be stronger at high organic matter concentrations than at lower ones. Denitrification with FeS means that the bacteria use nitrate also for their N demands, while this is not necessarily the case during denitrification with organic matter.Mineralization of macrophytes is a much slower process than that of phytoplankton, probably because of their high C/N ratio. We could, however, not confirm the general assumption that the addition of nitrogen stimulates this mineralization. On the contrary, we found that two amino acids both with a C/N ratio of 6 had different mineralization rates. The amino acid composition of dead macrophytes and the C/N ratio may be of equal importance.Unlike nitrogen, phosphate is always strongly adsorbed onto sediments. The two mechanisms of the adsorption of inorganic phosphate onto sediments, i.e. the adsorption onto Fe(OOH) and the precipitation of apatite, have been quantified. The adsorption of phosphate onto Fe(OOH) can be satisfactory described with the Freundlich adsorption isotherm: P_ads = A^* (o-P)^B. The adsorption coefficient A depends on the pH of the system and the Ca²⁺ concentration of the overlying water and can be quantified preliminarily by A = a.10(^–0.416*pH).(2.86 – (1.86.e^–Ca2+)). B can be approached by 0.333, which means the cube root of the phosphate concentration. The second mechanism is the solubility of apatite. We found a solubility product of 10^–50 for hard waters. The two mechanisms are combined in solubility diagrams which describe equilibrium situations for specific lakes.The conversion of Fe(OOH) to FeS has a strong influence on phosphate adsorption, although the partial reduction of Fe(OOH) P by H₂S does not release significant quantities of phosphate. Even after complete conversion to FeS only a small part of the bound phosphate was released.Besides the two inorganic phosphate compounds, we established the existence of two organic pools, one soluble after extraction with strong acid (ASOP), the other one with strong alkali. The first pool is probably humic bound phosphate, while the larger part of the second pool was phytate. The ASOP was remineralized during the desiccation of a Camargue marsh; this drying up oxidized FeS, thus improving the phosphate adsorption and decreasing the denitrification capacity. It can, therefore, be an important tool for management. The phytate was strongly adsorbed onto Fe(OOH), which explains the non-bioavailability towards bacteria.The fact that the sediment phosphate concentration can be approached by multiplying the relevant sediment adsorption constant with % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGak0Jf9crFfpeea0xh9v8qiW7rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaOqaaeaaca% WGVbGaeyOeI0IaamiuaaWcbaGaaG4maaaaaaa!3B8D!\[\sqrt[3]{{o - P}}\] concentration has the consequence that much larger quantities of phosphate accumulate in the sediments than in the overlying water. This means that even if the phosphate input is stopped, the eutrophication will only be reversed very slowly, and not at all, if the shallow waters in wetlands have no through flow — as is often the case in many marshes in Mediterranean wetlands.Abbreviations used o-P = dissolved ortho phosphate (or its concentration) - N_part, P_part = particulate N or P - Tot-N_inorg = Total inorganic nitrogen (= NH₃ + NO ₂ ^– + NO ₃ ^– ) This paper, giving an overview of the research in the sediments of the Camargue, was read during the symposium Nutrient Cycles — A Joy Forever, on the occasion of my retirement, 19th of May 1993 at the I.H.E. in Delft (Netherlands).     

Sulfate control of phosphorus availability in lakes

During summer stratification large amounts of phosphorus (P) accumulate in anoxic bottom waters of many lakes due to release of P from underlying sediments. The availability to phytoplankton of this P is inversely related to the Fe:P ratio in bottom waters. Using data from 51 lakes, we tested the hypothesis that sulfate concentration in lake water may be critical in controlling the Fe:P ratio in anoxic bottom waters. Results showed that Fe:P ratios in bottom waters of lakes were significantly (p<0.001) related to surface water sulfate concentrations. The higher Fe:P ratios in low sulfate systems is due not only to higher iron concentrations in anoxic bottom waters but also to lower P concentrations in anoxic waters. Thus, our results suggest that anthropogenically induced increases in sulfate concentrations of waters (e.g. from fossil fuel burning) may have a double effect on P cycling in lakes. Higher sulfate concentrations can both increase the magnitude of P release from sediments as well as increase the availability of P released from sediments into anoxic bottom waters.