Nearshore abundance of dissolved and sedimented forms of phosphorus

Different forms of dissolved and sediment phosphates, both adsorbed and interstitial, were determined in the highly productive coastal waters of the Indian Ocean. Both inorganic and organic phosphate of the above fractions covered in this paper reveal the extent of inter-dependency as well as exemplify the role of sediment based nutrients to influence the biorhythm in the overlying waters. The area of study in the mudbank regions of Kerala coast, (South India) is subjected to seasonal changes in its physics and hydrochemistry variability and is a natural, dynamic situation (compared to a neighbourhood location of relative quietude) exhibiting features of catalysing the release of sediment bound phosphate depending on its utilisation, via bioturbation. The organic phosphate pool plays a crucial role, wherein it acts as a ‘inducer’ in the triggering mechanism of aquatic life in this coastal zone.     

Phosphate fractionation in mud bank sediments from the southwest coast of India

Mud banks are unique, occurring along the southwest coast of India. They are known as ‘Zones of Bio-rhythm’, providing shelter to abundant aquatic life. The cyclic variation of nutrients in this region provides a clue to the continued and enriched presence of a variety of fish. This study reports on the different forms of phosphate in the resuspended sediments collected during the seasons with and without mud banks from the above mentioned coastal zones. Applying sequential and parallel chemical extractions using eight different schemes, the major forms of phosphate namely exchangeable P, anion exchangeable P, carbonate bound P, labile and resistant organic P, Fe-, Al- and Ca bound P and hydrolysable P have been determined. Quantitatively, these fractions vary and exhibit seasonal fluctuations. The concentration of potentially available anion exchange P, together with resistant organic and hydrolysable surplus P, provide an explanation to the existing organic food web supporting the aquatic life. Sediment phosphate fractionation reflects the role of chemical speciation of nutrients in the propagation of mud banks and is indicative of the biogenic processes controlling the pathways of phosphate in these coastal waters. Editorial note: Because of the sudden, regrettable death of the senior author, Dr P. N. K. Nambisan, editing remained unfinished. The guest editor remains responsible for errors left in the text.     

Mixis strategies and resting eeg production of rotifers living in temporally-varying habitats

The organic phosphate pool of some Camargue sediments (South of France) was studied, after removal of inorganic phosphate, with Ca-NTA/dithionite (Fe bound phosphate) and Na-EDTA (Ca bound phosphate). The organic phosphate was divided into an acid soluble organic phosphate fraction (ASOP) and a residual organic phosphate fraction (ROP). The extraction of organic matter with 2.0 M NaOH (90 °C) from ROP yielded considerable quantities of Org-P. In this extract the presence of phytate (inositol hexa phosphate) could be demonstrated using phytase to hydrolyse the phytate. Phytate was shown to account for a considerable part of organic phosphate in sediments of freshwater marsh sediments as well as in the sediment of the brackish/salt water lake ‘Etang de Vaccares’. In laboratory experiments phytate was found to precipitate with all poly-valent cations tested. Furthermore, phytate was found to be strongly adsorbed onto Fe(OOH), which may explain its accumulation and its stability in sediments. Considerable quantities of ASOP were found; the chemical stucture of this pool remains unknown.     

Changes in sediment phosphate composition of seasonal ponds during filling

Most ponds from the Doñana National Park are shallow temporary freshwater bodies on eolian sands. The total phosphate concentration and the fractional P-composition of the sediments from two small ponds were studied before and inmediately after they were filled (autumn, 1996). Total phosphorus concentration was measured in 2 different size fractions: 2–0.1 mm (coarse) and <0.1 mm (fine). In both ponds, the total phosphorus concentration of the fine sediment increased by 20% at the beginning of the filling period, whereas 5 weeks later it did not increase further. The percentage of organic matter of the fine sediment was relatively high (between 13–18%) and did not change significantly during filling. The concentration of sediment total iron and Fe(OOH) increased significantly in both ponds during filling. The sequential P fractionation of the fine sediment included, besides the determination of two inorganic fractions (Ca-bound P and Fe-bound P), an organic-P fraction extracted with acid, another extracted with alkali, two organic-P fractios from the Ca-EDTA/dithionite and the Na₂-EDTA extracts which contained high concentrations of humic substances. The pond sediments were rich in organic P compounds as the sum of all organic-P fractions ranged between 267 and 320 g g^-1 (68% and 79% of the sum of all fractions). Significant changes (P<0.01) in the fractional P-composition of sediments were found after filling. Acid soluble organic phosphate increased about 30% in both ponds. Iron-bound phosphate increased significantly (about 40%) only in the pond where a higher concentration of Fe(OOH) was measured after filling. An adsorption experiment was carried out for each sediment to simulate P input during filling. Both the iron-bound phosphate and Ca-bound P increased significantly (P<0.01) suggesting that these two fractions were involved in the P-adsorption during the laboratory experiment.     

Influence of the pH and redox potential on phosphate activity in the Parana Medio system

The effect of redox potential and pH on the phosphate mobility in two sediments were investigated using both consolidated and suspended sediments from the area where the Parana Medio long reservoir (Atgentina) is to be built (Smirnov, 1984). In addition to direct chemical sediment analysis, extraction techniques were carried out with a stepwise NH₄Cl-NaOH-HCl shaking method, the latter supposedly separating the weakly bound, the Fe- and Al- bound and the Ca- bound phosphates in the sediments.Phosphate released into water depends upon redox potential and pH, which both were modified in an experimental setup. The source of the phosphate was the fraction of Fe and/or Al bound phosphate present both in the sediment and in the suspended solids.Abbreviations cm centimeter - km kilometer - gg gram - l liter - ¬m micrometer - °C grade centigrades - km² square kilometer - m.s^–1 meter per second - m³.s^–1 cubic meter per second - mg.1¹ miligram per liter     

Sequential fractionation of sediment phosphate

By means of sequential extractions with Ca-NTA and EDTA, a separation was performed between Fe(OOH) P and CaC0₃P in a few sediments; the remaining fraction, considered to be organic phosphate, was quantified as well. We found that with the commonly used method of extraction with NaOH and H₂S0₄, less Fe(OOH) P and much more CaC0₃ P was found than with the chelating extractants. The organic phosphate pool in live and dead algal material and in some mud samples was partly hydrolysed and therefore recovered as inorganic phosphates with classical extractions. The difference between chelating extractants and the classical ones is discussed.Abbreviations o-P: ortho phosphate (or its concentration) - org-P: organic phosphate - extr-P: extractable sediment bound phosphate - extr-Fe: extractable sediment bound iron - Fe(OOH) P: iron bound, sediment phosphate - CaCO₃ P: calcium bound, sediment phosphate - org-C: organic sediment bound carbon     

Seasonal variations of P compounds and their concentrations in two coastal lagoons (Herault,France)

This article concerns seasonal variations in the phosphate concentrations in two coastal lagoons near Montpellier (Mediterranean coast, France). The o-P concentration in the overlying water is highest during summer. The role of the sediment, particularly that of the different P fractions in the sediment, is discussed. Significant variations, especially in the FeOOH ≈ P fraction, occur. For both Tot-P_sed and the Fe00H≈P fraction a gradient from surface to bottom is observed, as well as a distinct decrease in the FeOOH≈P fraction in the surface sediments during summer and autumn. Variations in the FeOOH≈P fraction appear to be compensated by variations in the CaC0₃≈P fraction. These variations appear to be determined by the ferric hydroxide concentration. This compound represents only a small part (maximally 15%) of the total iron in the sediments and is related to the dissolved oxygen content of the immediately overlying water. Besides the fractions o-P, Fe(OOH)≈P, a large part of the CaC0₃≈P fraction is potentially bioavailable. A large proportion of the Tot-P_sed is therefore bioavailable.[/p]     

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.     

Vertical stratification in sediments from a young oligotrophic South African impoundment: implications in phosphorus cycling

Changes at the mud surface in Midmar Dam, following impoundment, were studied by examining vertical profiles of selected parameters in sediment cores. Distinct stratification in organic carbon, pH and exchangeable Al³⁺ was evident. Phosphate adsorption characteristics in the stratified sediments was quantified using Langmuir adsorption isotherms. The adsorption maxima and bonding energy constants in the surface sediments (0–3 cm) were markedly lower than those below 3 cm, indicating that the surface layers are less efficient at binding phosphate than the deeper layers. Radiotracer experiments indicate that the layers comprising the top 3 cm of sediment predominate in PO₄-P exchange with the overlying water.     

Iron-bound phosphorus in marine sediments as measured by bicarbonate-dithionite extraction

A sequential five-step extraction scheme for phosphorus pools in freshwater sediment was modified for use in marine sediments. In the second step phosphate bound to reducible forms of iron and manganese (iron-bound P) is extracted by a bicarbonate buffered dithionite solution (BD-reagent). The extraction scheme was tested on sediment from 16 m water depth in Aarhus Bay, DK and used in two other marine sediments: Kattegat at 56 m and Skagerrak at 695 m depth. By comparing the BD-extractable P-pool with both the pool of iron in the BD-fraction and the pool of oxidized, amorphous or poorly crystalline iron (am.FeOOH), highly significant correlations (p < 0.001) were observed in all three sediments. Thus, we conclude that the BD-reagent was very specific for iron-bound P. Further evidence for this came from two experiments: 1) Enhanced BD treatment did not result in additional phosphate extraction and 2) by sequential extraction of phosphorus pools in pure cultures of diatoms and cyanobacteria no phosphate was recovered in the BD-fraction. The pool of am.FeOOH was very important for controlling porewater phosphate concentration which was inferred from the significant inverse relationships between the two parameters (p < 0.001) in all sediments studied. Further, an isotopic exchange experiment with ³²PO_f4/^p3– revealed that BD-extractable P was by far the most exchangeable P-pool even deep in the sediment where the pool size was small. Iron-bound P made up 33–45% of total P in the surface sediments. The ratio between iron-bound phosphate and am.FeOOH was 8–11 in Aarhus Bay and Kattegat. In Skagerrak the ratio was 17, which may indicate that the iron mineral extracted from this sediment is less capable of adsorbing phosphate or less saturated with phosphate.     

Spatial and temporal patterns of sediment and nutrient accumulation in shallow lakes of the Upper St. Johns River Basin, Florida

We used paleolimnological methods to investigate spatial and temporal patterns of bulk sediment and nutrient (C, N, P) accumulation in Lakes Hell n Blazes (A = 154 ha, zmax = 240 cm), Sawgrass (A = 195 ha, zmax = 157 cm) and Washington (A = 1766 ha, zmax = 322 cm), in the Upper St. Johns River Basin, Florida. The study was designed to evaluate long-term changes in sedimentation and nutrient storage in the basin, and was one component of a larger project addressing flood control, wetland restoration, and water quality improvement. These three study lakes are wide, shallow waterbodies in the upper reaches of the St. Johns River channel. Sediment mapping indicates soft, organic deposits are distributed uniformly throughout Lakes Hell n Blazes and Sawgrass. In contrast, much of Lake Washington is characterized by sandy bottom, and organic sediment is largely restricted to the north end of the lake. Lakes Hell n Blazes and Sawgrass are effective sediment traps because dense submersed macrophytes and their associated epiphytes reduce flow velocity, intercept suspended particles, and utilize dissolved nutrients. Abundant Hydrilla, combined with short fetch, prevents resuspension and downstream transport of sediments. Larger Lake Washington is probably wind-mixed and resuspended organic sediments are redeposited to downstream sites. 210Pb-dated sediment cores show that organic sediment accumulation began in all three lakes before 1900, but that bulk sediment and nutrient accumulation rates have generally increased since then. The increases are probably attributable, in part, to anthropogenic activities including 1) hydrologic modifications that reduced flow rates in the channel, 2) discharge of nutrient-rich waters from urban, agricultural and ranching areas, and, 3) introduction and periodic herbicide treatment of the exotic macrophytes Eichhornia and Hydrilla.     

Variability of the sediment phosphate composition of a temporary pond (Doñana National Park,SW Spain)

This study reports on the spatial and temporal variability of the phosphate composition in the sediment of a temporary pond over a period of 3 years using the EDTA-method for P-fractionation. Sediment samples were collected at three different sites (open-water, littoral and flood plain) to compare the effect of the length of the wet/dry phase on the sediment phosphate composition, with special emphasis on the potential bioavailability of the P-fractions.Fine sediments (<0.1 mm) were rich in organic matter (9–25%) and contained high mean concentrations of Tot-P (182–655 mg kg^–1 d.w.), especially in the flood plain sediment. The sediment P composition was dominated by P-organic fractions at all sites (64–94%). The average C/N ratios were 8.8, 6.0 and 5.9 for sediments of the flood plain, littoral and open-water sites, respectively. The flood plain sediment was significantly poorer in iron-bound P (FeOOHP), but richer in the P-organic fractions extracted by EDTA than the sediment of the open-water site (P<0.01). The percentage of organic matter increased significantly in the sediment of the open-water site at the end of each dry season (P<0.05), while it decreased in the sediment of the flood plain site (P<0.01). In all sediments, the fraction of Fe(OOH)P decreased at the end of each dry season and some of these changes were significant (P<0.05). The decrease in the fraction of Fe(OOH)P was not related to changes in the sediment redox potential. Although the flood plain site was dry longer than the open-water site during the study period, the differences between the sediment composition of both sites were probably due to the effect of plant growth on the dry sediments of the flood plain site rather than to a direct effect of desiccation.     

The effect of physico-chemical parameters on speciation of trace metals insediments from inland and coastal waters of Ghana

The speciation of cadmium, lead, copper, zinc, manganese and iron into exchangeable, carbonate, reducible and organic bound fractions was studied in sediments from coastal and freshwater environments in Ghana. This was relevant as the species in which metals are stored within specific sediment components is important in determining their impact on the environment. For both coastal and inland sediments, a higher percentage of cadmium was associated with the more available exchangeable and carbonate fractions, while iron, zinc and manganese were mainly associated with the reducible and organic fractions. Lead and copper were found to have the greatest ability to form different species in the samples examined and were more evenly associated with all the fractions. The metals generally showed more ability to form different species in inland freshwaters than in coastal relatively saline waters. However, differences between inland and coastal waters were based more on whether the environments were oxidising or reducing than on whether they were fresh or saline. The metals may be divided into three groups of high mobility consisting of lead and copper; moderate mobility made up of cadmium, manganese and zinc; and low mobility, represented by iron.     

Phosphate in the sediments of the Gulf of Lions (NW Mediterranean Sea), relationship with input by the river Rhone

We investigated P-input by the Rhone river into the Mediterranean Sea taking into account P trapped in the surface sediment of the Gulf of Lions. Total phosphate concentration was determined every cm in the upper 10 cm-layer of sediments sampled at 11 stations in the Gulf of Lions during two cruises (March 1998 and January 1999). Two low downward gradients, one East–West and another North–South, with distance to the Rhone river mouth were found. Except at one station, total phosphate concentration in surface sediments was found to be constant with depth down to 10 cm. Values for individual stations ranged between 400 and 700 g g^–1 with an average value of 547 g g^–1 (st. dev. = 63 g g^–1) for the whole gulf. The low variability in total-P concentration in sediments is in contrast to the large variability in suspended matter load of the river Rhone and suggests the dominance of authigenic P removal mechanisms in P burial. The total P-pool in the upper 10 cm-layer of the sediments in the gulf was estimated at 562 kt, with about 80% trapped into the shelf and 20% into the slope. Annual P-deposition was estimated as 7.2–12.4 kt y^–1, from the P-pool in the sediment and the sedimentation rates. This is equivalent to a previous estimation of the river Rhone input, estimated to be about 6.5–12.2 kt y^–1. As the Rhone is the major river flowing into the Mediterranean Sea, total P in surface sediments of the Gulf of Lions should be taken into account in P-budgets at the scale of the Mediterranean Sea.     

The sediment column as a record of trophic status: examples from Bosherston Lakes,SW Wales

Bosherston Lakes are a series of interconnected, mesotrophic to hypereutrophic, artificially-created coastal marl lakes in Dyfed, South West Wales. Progressive eutrophication of the lake system has been produced by a high external phosphorus loading which includes phosphorus-rich effluent from a sewage treatment works (STW) in the catchment of the Lakes.Cores were taken from four sites of varying eutrophic status within the Lakes. In the surface sediment layer, organic C, N and P concentrations generally correlate directly with trophic status and reflect distance from the source of P input. At one site, sediment stratigraphy records a clear transition at 20–15 cm depth, marked by a sharp upward increase in porosity, organic C, N, and P, and iron-associated-P; decreases in organic matter C/N, C/P and N/P ratios; a sharp decrease in carbonate, and a change in the subfossil diatom assemblage. Lead-210 dating indicates that this change occurred in the period 1919 to 1938.The diatom stratigraphy and sediment geochemistry suggest that this transition reflects an increase in trophic status at this site, probably as a result of the influx of nutrient-rich water. This took place when the management of the Stackpole estate surrounding the lake system, fell into decline during the period 1919–1938.     

Transformations between organic and inorganic sediment phosphorus in Lake Balaton

In order to estimate microbial P content and biological P uptake in sediments, the tungstate precipitation method of Orrett & Karl (1987) was used in sediment extracts. This method allows a simple and rapid separation of organic and inorganic ³²P radioactivity. Either inorganic ³²P (as carrierfree H₃ ³²PO₄) or organic ³²P (as ³²P-labelled algal material) was added to surface sediment suspensions of shallow Lake Balaton. Inorganic ³²P was rapidly transformed into organic ³²P, and this process was completely inhibited by formaline. P content of living benthic microorganisms was estimated from steady state distribution of the radioactivity. Transformation of algal organic P into inorganic P could also be detected.In extremely P limited Lake Balaton benthic microorganisms were shown to supplement their high P requirements by inorganic P uptake. The velocity of the inorganic into organic P transformation, i.e. the rate of microbial P uptake, was comparable to P uptake in the water column. Microbial P uptake contributed significantly to total P fixation by sediments, particularly at low ( 100 µg P l^–1) phosphate additions.     

Particle size-related phosphate binding and P-release at the sediment–water interface in a shallow German lake

Phosphate binding and P-release in the sediment of the eutrophic shallow Lake Bützow are described based on sediment profiles, particle size fractions and incubation experiments. Total phosphorus was about 15% higher in the upper 0.5 cm layer than in the 0.5–1 cm layer. Phosphorus binding varied with sediment depth. Hot P_NaOH and P_HCl were the dominant fractions in all sediment horizons down to 10 cm depth, with values ranging from 20 to 30%. The P_H2O, P_BD, o-P_NaOH and nr-P_NaOH decreased with depth. The P_BD contributed 21% to Tot-P in the horizon 0–0.5 cm and decreased by half in 1–2 cm. The greatest proportion of particles (35%) was found in the 100–200 m fraction. This size fraction also accumulated most of the phosphate. Moreover, P-forms were differently distributed in the various particle sizes of the sediment. Sediment particles <40 m can be resuspended by a wind velocity of 2 m s^–1, whereby 17% of the Tot-P from the topmost sediment were transported into the water column. The proportions of released labile phosphate, organic phosphate and hydrolysable phosphate were higher, with values of 24, 33 and 26%, respectively. Dissolved P was released under oxic and anoxic incubation, but anoxic release was higher. Comparison of the results shows that the P-release under anoxic conditions was equal to the P-release by resuspension, but under anoxic conditions the release of bioavailable P was higher.     

Measuring Bacterial Production in Deep-Sea Sediments using 3H-Thymidine Incorporation: Ecological Significance

Bacteria play a major role in the decomposition of organic matter arriving at the deep-sea floor, and hence there is a need to determine accurate rates of bacterial production associated with sediment particles. However, sediment-based procedures are not well defined and sampling deep-sea sediments is technically difficult, time consuming, and expensive, often only producing relatively small amounts of undisturbed sediment for analysis. We describe and test a small-scale method (requiring 0.25 ml sediment) for the examination of bacterial production in deep-sea calcium carbonate rich sediments. Time course experiments showed variation in the period of linear [3H]thymidine uptake between 1 and 3 hr depending on station depth. The average concentration of natural thymidine in deep-sea sediments was 0.61 nmol per 0.5 ml slurry sample. Isotope dilution was significant, ranging between 26 and 51%. There was substantial small-scale (0.2-1.0 m) variation in deep-sea benthic bacterial [3H]thymidine incorporation rates (39%). Deep-sea surficial sediment bacterial production (assuming zero isotope dilution due to its potential high variability) in surficial sediments of the deep NE Atlantic varied between 0.014 and 0.48 mg C g-1 d-1 (mean = 0.23 mg C g-1 d-1) over 3 locations of depths between 1,092 and 3,572 m and at 3 times. Bacterial biomass varied between 1.1 and 12 mg C g-1 (mean = 6.1 mg C g-1). Bacterial growth rate estimates in these deep-sea sediments varied between 0.003 and 0.13 d-1 (mean = 0.050 d-1) giving doubling times of 5.3-216 d (mean = 44.5 d); which are similar to those of bacteria inhabiting waters in the upper mixed layer (2-<40 m) of the water column (2.6-57.8 d). comparison with shallow and coastal sea sediments (0.13-116 d) indicates that deep-sea sediment bacteria in the NE Atlantic are able to grow at rates similar to those in shallow sediment systems given sufficient food. However, the range is broader for deep-sea sediment bacteria, which may indicate a more "feast" and "fast" life than their counterparts in shallower environments. waters >2,000 m cover 60% of the Earth's surface; thus bacterial production in deep-sea sediments must contribute an important fraction of oceanic and global bacterial production. It is therefore important to establish an accurate method of measuring bacterial production so that the full roles and controls of bacteria from this environment can be determined.     

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).     

Distribution and speciation of phosphorus along a salinity gradient in intertidal marsh sediments

We examined forms of solid phosphorus fractions in intertidal marsh sediments along a salinity (0–22%.) gradient in a river-dominated estuary and in a marine-dominated salt marsh with insignificant freshwater input. Freshwater marsh sediments had the highest ratio of organic N:P of between 28:1 and 47:1 mol:mol, compared to 211 to 311 molmol in the saltmarshes, which is consistent with a trend toward P-limitation of primary production in freshwater and N-limitation in salt marshes. However, total P concentration, 24.7±11.1mol P g dw^–1 (±1 SD) averaged over the upper meter of sediment, was greatest in the freshwater marsh where bioavailablity of P is apparently limited. In the freshwater marsh the greatest fraction of total P (24–51%.) was associated with humic acids, while the importance of humic-P decreased with increasing salinity to 1–23%. in the salt marshes. Inorganic P contributed considerably less to total sediment P in the freshwater marsh (15–40%.) than in the salt marshes (33–85%.). In reduced sediments at all sites, phosphate bound to aluminum oxides and clays was an important inorganic P pool irrespective of salinity. Inorganic P associated with ferric iron [Fe(III)] phases was most abundant in surface sediments of freshwater and brackish marshes, while Ca-bound P dominated inorganic P pools in the salt marshes. Thus, our results showed that particle-bound P in marsh sediments exhibited changes in chemical association along the salinity gradient of an estuarine system, which is a likely consequence of changes in ionic strength and the availability of iron and calcium.