Binding of phosphate in sediment accumulation areas of the eastern Gulf of Finland,Baltic Sea

The relationships between P and components binding P were studied by analysing the concentrations of N, P, Fe, Mn, Ca and Al in sediments and pore water along the estuarine transect of the River Neva in August 1995. The high sediment organic matter concentration resulted in low surface redox potential and high pore-water o-P concentration, whereas the abundance of amphipods resulted in high surface redox potentials and low pore-water o-P concentration. However, despite the variation in sediment organic matter and the abundance of amphipods, very reduced conditions and slightly variable concentrations of Tot-P (0.7–1.1 mg g^–1 DW) were observed in the 10–15 cm sediment depth along the estuarine gradient, indicating that the pools of mobile P were largely depleted within the depth of 0–15 cm. Multiple regression analysis demonstrated that organic matter and Tot-Fe concentration of the sediment were closely related to the variation in Tot-P concentration of the sediments (r ² = 0.817, n=32). In addition, the high total Fe:P ratio suggested that there is enough Fe to bind P in sediments along the estuarine gradient. However, low Fe_diss concentrations in the pore water of reduced sediment (redox-potential <–50 mV) indicated efficient precipitation of FeS (FeS and FeS₂), incapable to efficiently bind P. Consequently, the low Fe_diss:o-P ratio (< 1) recorded in pore water in late summer implied that Fe³⁺ oxides formed by diffusing Fe_diss in the oxic zone of the sediments were insufficient to bind the diffusing o-P completely. The measured high o-P concentrations in the near-bottom water are consistent with this conclusion. However, there was enough Fe_diss in pore water to form Fe³⁺ oxides to bind upwards diffusing P in the oxic sediment layer of the innermost Neva estuary and the areas bioturbated by abundant amphipods.     

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.     

Iron:phosphorus ratio in surface sediment as an indicator of phosphate release from aerobic sediments in shallow lakes

Analysis of Danish lakes showed that both mean winter and mean summer concentrations of lake water total phosphorus in the trophogenic zone correlated negatively with the total iron to total phosphorus ratio (Fe:P) in surface sediments. No correlation was found between the water total phosphorus concentration and either the sediment phosphorus concentration alone or with sediment calcium concentration. The increase in total phosphorus from winter to summer, which is partly a function of net internal P-loading, was lowest in lakes with high Fe:P ratios in the surface sediment.A study of aerobic sediments from fifteen lakes, selected as representative of Danish lakes with respect to the sediment Fe and phosphorus content, showed that the release of soluble reactive phosphorus was negatively correlated with the surface sediment Fe:P ratio. Analysis of phosphate adsorption properties of surface sediment from 12 lakes revealed that the capability of aerobic sediments to buffer phosphate concentration correlated with the Fe:P ratio while the maximum adsorption capacity correlated with total iron. Thus, the Fe:P ratio may provide a measure of free sorption sites for orthophosphate ions on iron hydroxyoxide surfaces.The results indicate that provided the Fe:P ratio is above 15 (by weight) it may be possible to control internal P-loading by keeping the surface sediment oxidized. Since the Fe:P ratio is easy to measure, it may be a useful tool in the management of shallow lakes.     

The influence of catchment characteristics on suspended sediment properties

In order to investigate the influence of catchment characteristics on suspended sediment properties, suspended sediment samples were collected from the outlets of 60 small catchments located throughout Southwest England over a 14-month period. The catchments were selected to provide a representative range of topographic, land use, soil and geological characteristics. The suspended sediment samples were collected using time-integrating trap samplers, emptied at monthly intervals. Laboratory analysis focused on a selection of suspended sediment properties, including particle size composition, cation exchange capacity, and organic carbon, nitrogen, metal, radionuclide and phosphorus content. The results presented show that despite the substantial variability of catchment characteristics associated with the 60 sampling sites, the suspended sediment properties generally fell within a relatively limited range. However, statistical analysis identified significant spatial variability of suspended sediment within Southwest England, which in turn can be linked to catchment characteristics.     

Controlling phosphate release from phosphate-enriched sediments by adding various iron compounds

In a laboratory experiment, different ironsalts (FeCl₂, FeCl₃, FeSO₄) andFe₂O₃ were added to a phosphateenriched silty loam sediment in order to studytheir effect on phosphate mobilisation.Phosphate concentrations in sediment pore waterwere not reduced by the addition ofFe₂O₃. Addition of both ironchlorides, however, resulted in a strongdecrease of phosphate levels in sediment porewater. A similar but less pronounced effect wascaused by the addition of iron as iron(II)sulphate. Sulphate appears to counteract theimmobilisation of phosphate brought about byiron(II). Phosphate release from the sedimentappeared to be determined by the iron/phosphateratio in the sediment pore water. The additionof Fe₂O₃ barely affected thephosphate release from the sediment whereas theaddition of iron salts was effective inpreventing phosphate release. Increased amountsof iron added to the sediment resulted in adecreased phosphate release.     

The influence of chironomus plumosus larvae on the exchange of dissolved substances between sediment and water

4th instar Chironomus plumosus larvae (about 1000·m^–2) were added to tubes containing sediment and overlying water. At a temperature of 20°C the larvae greatly increased the trasnport of silica, phosphorus and iron from the sediment to the water. Oxygen concentrations did not influence the exchange of silica. For two non-calcareous sediments the exchange of phosphorus and iron was much higher under anaerobic than under aerobic conditions while the difference was small for sediment from a hardwater lake. Exchange of inorganic nitrogen was little influenced by added chironomid larvae.     

Effect of pH and aluminum on surface properties of barley roots as determined from water vapor adsorption

Water vapor adsorption isotherms were used for the estimation of surface areas and adsorption energy distribution functions of roots of barley grown at different pH levels and at a toxic Al level (10 mg·dm⁻³), induced at tillering and shooting stages of plants growth. Values of surface area as well as energy distributions were the same for the roots grown at all pH values studied: 2, 4 and 7 and not dependent on the age of the plants indicating that the protons do not alter the physicochemical build-up of the surface of roots. However, significant changes of the root surface properties under the influence of aluminum: increase of surface area, average adsorption energy and amount of highly energetic adsorption sites together with a decrease of low energetic sites were observed.     

Temporal changes in the metal and phosphorus content of suspended sediment transported by Yorkshire rivers,U.K. over the last 100 years,as recorded by overbank floodplain deposits

Cores of overbank deposits were collected from locations along the Rivers Swale and Aire in Yorkshire, U.K. The middle and lower reaches of the River Aire drain heavily industrialized and urbanized areas, whereas the River Swale drains a predominantly rural catchment, although Pb and Zn mining in the headwater areas in the 19th century introduced contaminated sediment. Downcore changes in the heavy and trace metal (Al, Cr, Cu, K, Pb, Sr and Zn) and phosphorus (P) content of the floodplain sediment were used to provide evidence of temporal changes in the contaminant content of the fine-grained sediment transported by the study rivers over the last ca. 100 years. The core collected from the downstream site on the River Aire shows upcore increases in P content, which reflects the expansion of the urban area during this period. Variations in the metal content of the deposited sediment over the period represented by the core reflect changes in the extent and type of industrial activity in the catchment. For the cores from the River Swale, there are no major upcore changes in the P content of the sediment, but there was a period characterized by increased levels of Pb and Zn which can be linked to metal mining activities.     

The role of suspended matter in the distribution of dissolved inorganic phosphate,iron and aluminium in the Ems estuary

In winter 1992/1993, a persistent local maximum in fluorescence, dissolved iron, dissolved aluminium and dissolved inorganic phosphate was found, upstream of the turbidity maximum in the freshwater zone of the Ems estuary (The Netherlands — Federal Republic Germany; western Europe). Upstream of this local maximum values ranged from 6 to 9 rel. units fluorescence, 0.9 to 2.4 μmol dm⁻³ iron, 0.5 to 0.7 μmol dm⁻³ aluminium and 0.6 to 2.3 μmol dm⁻³ dissolved inorganic phosphate. Within the maximum peak values of 24 rel. units fluorescence, 5.8 μmol dm⁻³ iron, 1.4 μmol dm⁻³ aluminium and 8.3 μmol dm⁻³ dissolved inorganic phosphate were observed. Downstream, fluorescence (indicator of dissolved organic carbon) showed conservative mixing with sea water, whereas dissolved iron, aluminium and dissolved inorganic phosphate did not. Dissolved aluminium and iron were quickly removed from solution to reach values of ∼100 nmol dm⁻³ aluminium and ∼0.3 μmol·dm⁻³ Fe at salinities of approximately 7 PSU. Further seaward iron concentrations gradually decreased to levels below 0.04 μmol dm⁻³. Dissolved aluminium first decreased to ∼20 nmol dm⁻³ at 29 PSU and increased again to concentrations of 30–44 nmol dm⁻³ at higher salinities. Dissolved inorganic phosphate, however, first decreased to upstream concentrations before reaching a secondary peak in the mid-estuarine reaches. At salinities >25 PSU dissolved inorganic phosphate mixed conservatively with sea water. It is hypothesized that adsorption-desorption equilibria are responsible for the local maximum values of fluorescence (DOC), iron, aluminium and dissolved inorganic phosphate. The similarity between the observed curves suggests a common underlying process, possibly related to the adjustment of new equilibria between suspended matter of marine and riverine origin.     

Phosphorus Limitation in Boreal Forests: Effects of Aluminum and Iron Accumulation in the Humus Layer

Plant growth in boreal forests is generally considered to be predominantly nitrogen (N) limited, but forested groundwater discharge areas may be exceptions. In this study, we conducted tests to determine whether highly productive forested groundwater discharge areas generally differ from adjacent groundwater recharge areas in terms of humus chemistry and the availability of phosphorus (P) and N to plants. We investigated six forested sites, divided into groundwater discharge and adjacent groundwater recharge areas, in northern Sweden. The humus layers of the forested groundwater discharge areas were clearly distinguished from the adjacent groundwater recharge areas by having higher acid-digestible calcium (Ca) and/or aluminium (Al) and iron (Fe) content and higher organic P and N content. Soil solution inorganic N (NH₄ ⁺ and NO₃ ⁻) and pH were higher in the groundwater discharge areas than in the groundwater recharge areas. The organic P content showed a positive linear relationship to the Al and Fe content in the humus layer, indicating that organic P is associated with Al and Fe compounds in the humus. A plant bioassay using humus substrate from one groundwater discharge area and the adjacent groundwater recharge area found that plants grown in groundwater discharge area humus (with a high P-fixation capacity) increased their biomass upon P fertilization, whereas no growth response was found for N additions. By contrast, plants grown in humus from the groundwater recharge area did not respond to added P unless N was added too. This study suggests that groundwater discharge can affect the nutrient availability of N and P both directly, via increased P fixation due to the redistribution of Al and Fe, and indirectly, via the inflow of groundwater high in Ca and alkalinity, maintaining a high pH in the humus layer that favors in situ N turnover processes. Received 2 March 2001; Accepted 9 November 2001.     

Nutrient fluxes and microbial activity in sediment enriched with settled seston

The chemical and microbiological responses of profundal surface sediment were monitored in sediment enriched with natural settled material collected in May, July or August, and with diatom or cyanobacteria cultures. The activation of the sediment microbial community was clearest after the addition of settled seston collected in May which was richer in organic matter than those collected later in the summer. N was released when the sediment was enriched with settled seston which had been collected in July and August and had C:N ratios lower than 10:1. The diatom-rich May-material enhanced the release of P to the interstitial water, obviously because of chemical competition between P and diatom-derived Si at the sediment surface. The July- and August-materials did not release P, nor did the diatom and cyanobacteria cultures. The results thus indicate that the seasonal variations in the quality and quantity of the settling phytoplankton affect the P dynamics at the sediment surface, both chemically and biologically.     

Variable rates of phosphate uptake by shallow marine carbonate sediments: Mechanisms and ecological significance

We determined phosphate uptake by calcareous sediments at two locations within a shallow lagoon in Bermuda that varied in trophic status, with one site being mesotrophic and the other being more eutrophic. Phosphate adsorption over a six hour period was significantly faster in sediments from the mesotrophic site. Uptake at both sites was significantly less than that reported for a similar experiment on calcareous sediments in an oligotrophic lagoon in the Bahamas. The difference in phosphorus adsorption between our sites did not appear to be related to sediment characteristics often cited as important, such as differences in surface area (as inferred from grain size distributions), total organic matter content, or iron content. However, the sediment total phosphorus contents were inversely related to phosphorus uptake at our sites in Bermuda, and at the previously studied Bahamas site.We hypothesize that phosphate uptake in these calcareous sediments is a multi-step process, as previously described for fluvial sediments or pure calcium carbonate solids, with rapid initial surface chemisorption followed by a slower incorporation into the carbonate solid-phase matrix. Accordingly, sediments already richer in solid phase phosphorus take up additional phosphate more slowly since the slower incorporation of surface-adsorbed phosphate into the carbonate matrix limits the rate of renewal of surface-reactive adsorption sites.Although carbonate sediments are a sink for phosphate, and thereby reduce the availability of phosphorus for benthic macrophytes and phytoplankton in the shallow overlying water, phosphate uptake by these sediments appears to decrease along a gradient from oligotrophic to eutrophic sites. If our result is general, it implies a positive feedback in phosphorus availability, with a proportionately greater percentage of phosphorus loading being biologically available longer as phosphorus loading increases. This pattern is supported by the significantly higher tissue phosphorus content of the seagrass,Thalassia testudinum, collected from the eutrophic inner bay site. Over time, this effect may tend to cause a shift from phosphorus to nitrogen limitation in some calcareous marine environments.     

Manganese adsorption by sediment in Wadi Tafna,Algeria

The removal of manganese from aqueous solution by sediment in Wadi Tafna, north-western Algeria, was investigated under batch conditions in 2003. Kinetic data equilibrium removal isotherms were measured at 20 °C. The influence of different experimental parameters, such as contact time, manganese concentration and sediment mass on the removal kinetics of manganese was studied. The content of carbonate in sediment increased the adsorption rate, indicating the active phase towards manganese cations. The process followed pseudo-second-order kinetics. Manganese uptake by sediment was quantitatively evaluated using sorption isotherms. In order to describe the adsorption isotherm mathematically, the experimental data of the removal equilibrium were analysed with Langmuir and Freundlich models revealing that the equilibrium data were perfectly represented using both isotherms.     

Influence of bacterial density on the exchange of phosphate between sediment and overlying water

Fluxes of phosphate across the sediment–water interface have been measured using inhibitors of bacterial activity sterilization and chloramphenicol and a control in order to quantify the influence of bacterial abundance on them. Results show that phosphate concentration in the interstitial water decreased when bacteria were present, in relation to treated aquaria. The measured (Jo) and theoretical fluxes (Jd) of phosphate also were higher when bacterial activity was suppressed. Mass balance calculated for Carbon, Nitrogen and Phosphorus in the sediment revealed a loss of theses compounds when bacterial activity was suppressed, and a net accumulation of Carbon and Phosphorus, and loss of Nitrogen under natural conditions.     

Regeneration of inorganic phosphorus and nitrogen from decomposition of seston in a freshwater sediment

The mineralization of phosphorus and nitrogen from seston was studied in consolidated sediment from the shallow Lake Arreskov (July and November) and in suspensions without sediment (July). In the suspension experiment, phosphorus and nitrogen were mineralized in the same proportions as they occurred in the seston. During the 30 days suspension experiment, 47 and 43% of the particulate phosphorus and nitrogen, respectively, was mineralized with constant rates.Addition of seston to the sediment had an immediate enhancing effect on oxygen uptake, phosphate and ammonia release, whereas nitrate release decreased due to denitrification. The enhanced rates lasted for 2–5 weeks, while the decrease in nitrate release persisted throughout the experiment. The increase in oxygen uptake (equivalent to 21% of the seston carbon) was, however, only observed in the July experiment. The release of phosphorus and nitrogen from seston decomposing on the sediment surface differed from the suspension experiments. Thus, between 91 and 111% of the phosphorus in the seston was released during the experiments. Due to opposite directed effects on ammonium and nitrate release, the resulting net release of nitrogen was relatively low.A comparison of C/N/P ratios in seston, sediment and flux rates indicated that nitrogen was mineralized faster than phosphorus and carbon. Some of this nitrogen was lost through denitrification and therefore not measurable in the flux of inorganic nitrogen ions. This investigation also suggests that decomposition of newly settled organic matter in sediments have indirect effects on sediment-water exchanges (e.g. by changing of redox potentials and stimulation of denitrification) that modifies the release of mineralized phosphate and nitrogen from the sediment.     

Effects of different macrophyte growth forms on sediment and P resuspension in a shallow lake

The effects of floating-leaved, submerged and emergent macrophytes on sediment resuspension and internal phosphorus loading were studied in the shallow Kirkkojärvi basin by placing sedimentation traps among different plant beds and adjacent open water and by sediment and water samples. All the three life forms considerably reduced sediment resuspension compared with non-vegetated areas. Both among submerged (Ceratophyllum demersum, Potamogeton obtusifolius, Ranunculus circinatus) and emergent (Typha angustifolia) plants, resuspension rate was on average 43% of that in the adjacent open water, while within floating-leaved plants (Nuphar lutea) the corresponding value was 87%. The effects of submerged and emergent vegetation increased in the course of the growing season together with increasing plant density. Among floating-leaved vegetation, such seasonal trend in resuspension effects was not observed. Compared with the non-vegetated area, floating-leaved, submerged and emergent plants reduced internal phosphorus loading on average by 21, 12 and 26 mg m⁻² d⁻¹, respectively. The effects of floating-leaved plants on resuspension-mediated internal phosphosrus loading were thus comparable to the effects of the other two life forms.     

The influence of light and nutrient addition upon the sediment chemistry of iron in an arctic lake

The geochemical response of sediments to increased nutrient input to an Alaskan, arctic lake was examined using direct measurements of sediment-water chemical fluxes. An unexpected increase in Fe flux occurred when sediments were exposed to high incident radiation and nutrient concentrations. Correlation between light and acid-soluble Fe concentrations suggests that photoreduction of Fe(III) oxides may occur, but nutrient addition enhanced the effect indicating that primary productivity was also important. The processes controlling the flux of Fe from sediments in this lake were complex and included the redox potential (dissolved oxygen concentration) of the water, quality of organic matter present in the sediment, light, and nutrients supplied from the sediments and/or water column. These four factors together with the possibility of direct uptake of Fe by phytoplankton and the possible release of algal reductants may contribute to Fe cycling in this lake.     

The change of sediment composition during recovery of two Finnish lakes induced by waste water purification and lake oxygenation

Total oxygen deficit occurred regularly during stagnation periods in the deepest part of Lake Kallavesi in the period 1973–1986. The sediment was black and anaerobic during the first sampling in 1987. After beginning of artificial lake oxygenation and efficient purification of waste waters of a paper board mill in 1986 the oxygen deficit decreased gradually and a light brown oxidized uppermost sediment layer appeared and began to thicken. The following changes in the sediment composition were observed during 1987–1996: loss on ignition, total nitrogen and BOD₇ concentrations decreased in the uppermost sediment layer (0–2 cm) and BOD₇ concentration increased in the next sediment layer beneath (2–10 cm). There were no significant change in phosphorus and iron concentrations.Lake oxygen, total phosphorus and suspended solids concentrations fluctuated in a noticeable degree in Lake Huruslahti depending on waste water input and artificial oxygenation during the years 1980–1993. Oxygen condition was good at times of successful waste water elimination and lake oxygenation while deterioration of either resulted oxygen deficiency as well as increase of total phosphorus and suspended solids concentration. Most of the internal load entered with suspended solids during periods of total oxygen deficiency.An explanation for the findings in Lake Huruslahti could be microbiological. Gas formation inside sediment lift organic material towards top of the sediment and into the water, but after the lake recovery the material retain in the sediment. Also in Lake Kallavesi microbiological gas formation resuspended sediment particles with phosphorus into the overlaying water prior to oxygenation. During oxygenation microbiological processes in uppermost sediment utilize the anaerobic metabolic products, organic acids and methane, and block gas formation. Organic substances remain in the top sediment decomposing gradually in the uppermost layer.     

Differential extraction of sediment phosphates with NTA solutions

An extraction technique is described for the separation of iron- and calcium-bound phosphate. The iron-bound phosphate is extracted with a 0.05 M solution of Ca-NTA under reducing conditions. Iron, also, is brought into solution, which is an advantage over the NaOH extraction. The calcium-bound phosphate is extracted with a 0.05 M solution of Na-NTA. The NTA also extracts humic compounds. Organic phosphate compounds can be measured in the NTA extracts, unlike the NaOH or H₂SO₄ extracts such as are used in the (modified) Jackson procedure.Examples of some test compound extractions and of a calcareous sediment are given.     

Longitudinal Gradients in the Chemical and Microbial Composition of the Bottom Sediment in a Channel Reservoir (Saidenbach R., Saxony)

Saidenbach Reservoir is situated in the Erzgebirge Hills, Saxony, in a catchment with agriculture as the principal use and a high sensitivity to soil erosion. The high elimination of total phosphorus (ca. 70%) mainly results from a) the sedimentation flux of planktonic diatoms and b) the adsorption to and sedimentation with mineral particles rich in iron. At stations with a high sulfide concentration in the 0–5 cm sediment layer (about 0.2%), the P content was likewise high (about 0.3%), probably due to the high iron concentration (more than 2.5% of dry weight). A fractionation procedure showed that the major part of the sediment phosphorus was not sensitive to reductants (dithionite) but has been found only in the following extraction step (NaOH extract).