Relation between algal available phosphate in the sediments of the River Garonne and chemically-determined phosphate fractions

Concentrations of total and inorganic phosphate were measured in forty-seven sediments of the River Garonne (France) using an anion resin, NaOH 0.1 M, Ca-NTA and Na-EDTA. Algal available P was measured using Scenedesmus crassus. The sediments presented a wide range of Tot-P concentrations (226 to 923 μg g⁻¹). Resin P varied between 1.1 to 55.5 μg g⁻¹ and NaOH-P between 3.5 to 262 μg g⁻¹. NTA-P and EDTA-P varied between 13.9 and 178 μg g⁻¹ and between 14.4 to 261 μg g⁻¹ respectively. Algal available P varied between 8.8 to 262 μg g⁻¹/ All forms of P are highly correlated and specially with algal available P (r = 0.70, 0.77, 0.88 and 0.77 for resin-P, NaOH-P, NTA-P and EDTA-P respectively). Nevertheless the partial correlation between EDTA-P and algal available P dropped to 0.05 when the concentration of NTA-P was considered as constant, indicating a spurious correlation with apatitic phosphate (extracted by Na-EDTA). Because of the strongest R ² and the lowest standard error of estimate, phosphate extracted by Ca-NTA can be considered as the best predictor of algal available phosphate.     

Fractional phosphate composition in sediments from a tropical river (Catatumbo River, Venezuela)

The distribution of phosphate species in the Catatumbo River, Venezuela, was studied using a sequential extraction scheme. Extraction was performed using 1.0 M NH₄Cl, 0.1 M Na₂S₂O₄–NaHCO₃, 1.0 M NaOH and 0.5 M HCl. Total phosphate was in the range between 121 and 581 g g^–1 D.W. About 64% of the total phosphate is inorganic and present the following composition: 1% NH₄Cl-P, 10% BD-P, 20% NaOH-P, 33% HCl-P; while org-P is 36%. The main form of P in sediment from the Catatumbo River is calcium bound-P, like apatite. The metal concentrations present in sediment are in the following order: Fe> Al > Ca > Mg > Mn. Relationships between P and Fe, Al and Ca were found. Cluster analysis showed that speciation is not dependent on the inorganic matrix of the sediments. Analysing the influence of NaOH concentration and duration of the extraction invalidated the use of NaOH as extracting agent in P-speciation.     

Modified speciation scheme for inorganic phosphate in lake sediments

Abstract

Speciation schemes for phosphate in soils or sediments tend to yield results which are ‘conditional’ and subject to error. In the proposed modified scheme, secondary phosphate-cation interactions have been minimised by including a cation exchange resin in the extraction system; re-sorption errors have been reduced by using low (1:400) solid to liquid extractant ratios; and slow dissolution rates have been balanced by using longer extraction times (up to 62 h). Variables examined during scheme development included the effect of varying sample weights, extraction time, reagent type, exchanger type, exchanger to sample weight ratios and pH on the amount of phosphate released from a polluted lake sediment. It was found that the amount of inorganic phosphate released by chemical reagents (or by cation exchanger) varied markedly with system pH, being greatest in the pH 2 to 3 region, decreasing to near zero in the pH 4 to 6 zone, and then rising to an intermediate value at pH > 8. Monitoring of the Ca, Mg, Fe and Al released into the various solutions (or transferred into the exchanger phase) indicated that one cannot clearly distinguish between phosphate initially present in association with alkaline earth compounds or iron-rich matrix components. The advantages and limitations of this ‘differential solubility’ scheme have been considered and alternative approaches briefly reviewed.     

Inorganic phosphate in exposed sediments of the River Garonne

Fractionation of inorganic phosphates in sediments of the River Garonne was carried out during a period of low water discharge. Sediments were collected under 5 cm of water (LS), in the dried river bank (MS) and in the riparian forest (RS). Sediments were sampled at two dates, during a period in which the water level fell gradually, causing sediment LS to be air exposed.Sediments were analysed for total phosphate, iron bound phosphate (Fe(OOH)P) using Ca-NTA and Ca bound phosphate (CaCO₃P) using Na-EDTA.Total-P varies from 552 (RS at date 1) to 2072 µg g^–1 (LS at date 2). There are significant differences between sediments and a significant increase from date 1 to date 2 in sediment LS only (1825 to 2072 µg g^–1). Fe(OOH)P varies from 186 (RS at date 1) to 874 µg g^–1 (LS at date 2). The highest values correspond to sediment LS. Moreover, Fe(OOH)P increased significantly between date 1 and 2 in LS (560 to 874 µg g^–1) as well as in sediment MS (248 to 432 µg g^–1). Ca bound P concentrations differed significantly between sediments (75, 112, 235 µg g^–1 for sediments RS, MS and LS respectively) but not between sampling dates.These differences are attributed to the conditions of deposition of the sediments (such as morphology and hydrology of the river) and to the changes in chemical composition during the drying out of the sediments.     

Presence of and phosphate release from polyphosphates or phytate phosphate in lake sediments

NaOH is often used as an extractant for thefractionation of sediment-bound phosphates. Besidesorthophosphate, a certain quantity of phosphate whichis called ‘non-reactive NaOH-extractable phosphate’is also extracted. In recent literature it has beensuggested that this fraction consists of bacterialpolyphosphates and might be responsible for the phosphate release from aquatic sediments under anoxicconditions. In a previous publication we have already shown thatNaOH is not an accurate extractant as both theconcentration of NaOH and the duration of theextraction have an influence on the quantity ofphosphate extracted, due to the hydrolysis of organicphosphates. In this article we show that cold NaOH does not onlyextract iron-bound phosphate but phytate phosphate aswell. Non-reactive phosphate in this extract was notrelated to the presence of polyphosphate, but mainlyto phytate and humic phosphates. As it has been shownthat phytate may disappear from sediments when theybecome anoxic, we suggest that phytate mineralizationmay be an important mechanism for anoxic phosphaterelease from sediments. This revised version was published online in July 2006 with corrections to the Cover Date.     

The evaluation of inorganic phosphate species in salt water lake sediments

Abstract

Surface sediments drawn from 10 shallow bays have been subjected to selective extraction in order to sub-divide the total P content into sub-categories such as water soluble P, Ca-P, Al-P and Fe-P. The reagents selected were similar to systems used in soil analysis, but evaluation of the procedures showed that the species values varied with time of extraction, weight of sediment taken, volume of extradant and chemical nature of the sediment. In water extractions, the P levels appeared to be determined by saturation with a sparingly soluble salt, while in acidic media P extract levels peaked (using different experimental conditions) due to loss of extracted P as a new phase (e.g. CaHPO₄) or through re-adsorption on other components.

The optimum conditions for P speciation in sediments must be determined from a series of preliminary studies because each of the five sediments studied in detail displayed individual characteristic behaviour.     

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.     

Fractionation of phosphate in sediments of four representative mangrove stages (French Guiana)

Phosphate was fractionated in Guianese mangrove sediments. Fe(OOH)P was extracted using a Ca-EDTA + Na-dithionite solution buffered at pH 8. CaCO₃P was extracted using Na₂-EDTA solution at pH 4.5. Next, Acid Soluble Organic Phosphate (ASOP) was extracted by H₂SO₄ 0.5 N. Finally, Residual Organic Phosphate (ROP) was digested with H₂SO₄ + H₂O₂. Four representative mangrove stages have been studied: sea edge pioneer mangroves, mature coastal mangroves, mixed riverine mangroves, and declining to dead mangroves. The sum of the P-fractions varied between 638 to 804 g g^-1 in pioneer and mixed mangroves respectively. In all the stages, the percentage of inorganic phosphate was larger than 50% of the total P. Fe(OOH)P varied between 221 (pioneer mangrove) to 426 g g^-1 (dead mangrove). CaCO₃P varied between 75 to 102 g g^-1 in mixed, dead or mature mangroves and attained 125 g g^-1 in pioneer mangrove. The sum of the concentrations of organic phosphate (ASOP + ROP) increased markedly from the dead mangrove (189 g g^-1) to the mixed mangrove (380 g g^-1). Guianese mangroves, are relatively rich in total phosphate, possibly because they are narrowly related to the 'Amazon dispersal system. Each mangrove stage can be characterised by a prevailing form of phosphate. The concentrations of these different forms were ascribed to the marked relations with the seawater which controls import or export of suspended matters and to the wave action which controls the resuspension of the sediments and subsequently exchange of phosphate between the suspended matter and the water column.     

Trace metal fractionation in water and sediments of an urban river stretch

Abstract

In this study, the fractionation and ecotoxic potential of Cr, Ni, Cu and Pb in water and sediments of the river Yamuna (Delhi stretch) is presented. The river water is used for various purposes such as irrigation, industrial, domestic and drinking. The investigations suggest that the availability of metals in water follows the sequence Ni>Cr>Pb>Cu whereas a different pattern (Pb>Cu>Ni>Cr) is observed in sediments. Statistically significant spatial variations are indicated by two-way ANOVA in different geochemical forms of the metals and physicochemical parameters of water and sediments of the river Yamuna. Principal component analysis (PCA) suggests a similar source for all four metals probably from the sewage from municipal drains. PCA also indicates some independent sources of Cu and Pb. The hot spots were identified using hierarchical cluster analysis considering bioavailable forms of the metals in water and sediments as objects and the sampling sites as variables. Risk assessment code analysis indicates that metals generally pose medium to high risk at different sites. However, at a few locations either Ni or Pb cross the level of very high ecological risk.     

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.     

The distribution of phosphate over iron-bound and calcium-bound phosphate in stratified sediments

Release of phosphate from, and adsorption ontosediments is calculated as a chemical equilibriumbetween dissolved o-phosphate and two solidphosphates, i.e. iron- and calcium-bound phosphate.Organic phosphates play a minor role, if any at all.Using chemical equilibrium equations, the distributionof the two solid inorganic phosphates is calculatedfrom the accumulated phosphate quantity as function oftime and depth in sediment layers of shallow lakes orwetlands. It is shown that this distribution dependson water depth, pH, Ca²⁺ concentration in thewater, Fe(OOH) concentration in the sediments andmaximal binding capacity of the sediments. Bycomparing values of dissolved phosphate at differentpH values, it is shown that acidification, whichusually takes place in hypolimnia, will cause releaseof phosphate, which is not necessarily dependent onthe redox potential. The release does depend on pH,Ca²⁺ concentration in the water, CaCO₃concentration in the sediments and the saturationstage of the two P-pools in the surface layers ofthese sediments. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Determination of available phosphorus for phytoplankton populations in lakes and rivers of southeastern Norway

A biotest method with diluted phytoplankton populations was used to determine external concentrations of available phosphorus in water samples with high concentrations of inorganic seston from River Rømua. RP (total molybdate reactive P measured on unfiltered samples) was approximately the P fraction available for Synedra cf. acus, Asterionella formosa and Oscillatoria agardhii. In filtered samples RP_F was the available concentration of P.The ratio RP:RP_F may give valuable information on the ratio between total available P (including available P in seston) and available P in filtered water. Different filter types may give different RP: RP_F ratios. The ratio RP:RP_F was often high during spring and autumn in River Rømua and the lakes studied. During the period June–September RP:RP_F 1 in most of the lakes and periodically in River Rømua.     

Transport of mercury by the Katun river,West Siberia

Some results of a 2-year study of mercury pollution of the Katun river (Siberia) are summarised. Measurements of water flow, sediment transport and mercury concentrations were made and used to calculate the amount of mercury transported by the river. The distribution of transport between water phase and suspended material is calculated. It is concluded that suspended sediments play the main role in this process. The significance of different fractions of suspended sediment is also discussed.     

The mineralization of chloroform in river sediments

The formation of¹⁴CO₂ from 3 μg l⁻¹ labelled chloroform was studied in anaerobic Dutch river sediments. All incubations were performed under anaerobic conditions. The observed first order mineralization kinetics showed half-lives of 2–37 days at 20°C in 12 muddy sediments. In contrast most of the sandy sediment samples did not show a mineralization of chloroform. Most probable number analysis revealed about 3.10⁴ chloroform mineralizing bacteria per g of dry sediment in a muddy sediment and 1–2.10³ chloroform mineralizing bacteria per g of dry sediment in a sandy sediment. Therefore the persistence of chloroform in sandy sediments is not caused by the absence of chloroform mineralizing bacteria but by the inactivity of these bacteria. This inactivity of the sandy sediments might allow chloroform from infiltrating river water to reach the groundwater. Mud samples from a relatively unpolluted site showed a similar chloroform mineralization rate compared with the polluted sediments from the rivers Rhine and Meuse. The data indicate that the reductive dechlorination of aliphatic compounds is not influenced at the polluted sites.     

南淝河沉积物中半挥发性有机污染物分析

采用GC/MS对南淝河沉积物中半挥发性有机污染物进行了分析,共检测出包括多环芳烃和酞酸酯在内的有机化合物有54种,沉积物中有机污染物种类多。对EPA优先控制污染物中的16种多环芳烃（PAHs）进行了定量监测,结果表明多环芳烃的总量已达到30.61mg/Kg。与国外生态风险评价标准对比表明有多种多环芳烃化合物的含量超过风险评价指标的低值,有的甚至超过高值,已有可能对生态环境产生了影响,为较高生态风险区,PAHs污染比较严重。     

An elementary,structural analysis of river phytoplankton

Summary A structural analysis of river phytoplankton has been carried out based upon published studies on 67 rivers. When available on a yearly basis to account for seasonal variability, five structural features have been chosen: species composition, species richness, species dominance, diversity and biomass (total and per taxonomic groups). Despite the high number of reported studies, most of them cover only some of the aforementioned features. As a result of the low amount of studies, tropical rivers are underepresented. No size distribution studies have been carried out on river phytoplankton. The average species richness amounts to 126, being higher in temperate rivers. Roughly one half of each flora is comprised of sporadic species. No statistically significant relationship between species richness and latitude has been found despite the fact that tropical rivers appear to house fewer species than temperate rivers. Also, one half of the support in the floras are either benthic or tychoplanktonic. Diatoms comprise the majority of species numbers in the whole data set but are substituted by desmids in tropical rivers and by green algae when benthic species are not taken into account. There appears to be lower biomass in river phytoplankton than in lakes. Diatoms are also the major taxonomic group comprising total biomass in rivers but they share clearly a lower fraction in tropical rivers. On an average basis, diatoms appear to be more dominant in rivers than in lakes. The time course of diatom dominance occurs close to the summer solstice in tropical rivers whereas is much more lagged in temperate sites. The diversity of river phytoplankton is highly scattered (0.40–4.40 bits ind^–1).     

Development and application of a technique for estimating nutrient deficiency in soft sediments

A diffusion enrichment technique is presented which allows for chemical enrichment of soft surficial and shallow subsurface sediments and subsequent measurement of O₂ production. The sediment is enriched by inserting a perforated tube containing dialysis tubing filled with a nutrient/agar mixture. O₂ production by surficial sediment is measured using an inverted, translucent, polyethylene chamber over the sediment. The inside of the chamber contains a collapsible bag connected to the water outside the chamber. When water overlying the sediment is withdrawn from a sampling port, it is displaced with water from outside the chamber, thus preventing contamination of water samples with pore water from below. The technique was tested by enriching near-shore sediments in a large oligotrophic lake with inorganic N and P. NHinf4/^p+ additions significantly stimulated benthic primary production as measured by 0₂ production, whereas enrichment with POinf4/^3- had no effect.     

淮河安徽段水及沉积物中重金属的研究

对采集淮河安徽段水及沉积物样品,利用ICP-AES进行重金属分析,结果表明砷、铅、铬超标,在沉积物中的含量最多。研究区域的重金属开始富集于生物体内,已对水生态系统及水产品安全产生影响,应进一步加强检测工作,以便及时采取相应防治对策。     

Bacterial enzyme activity and metal speciation in urban river sediments

The effects of stormwater and combined sewer overflows on receiving waters were investigated using measurements of bacterial enzyme activity and metal speciation in the sediments of five urban rivers. Free flowing urban rivers had high enzyme activity and low metal concentration in sediments, indicating a lack of contribution by stormwater sediments. More stagnant urban rivers, which tended to trap sewer-discharged sediments, were characterised by inhibited enzyme activity and high ammonium acetate- and EDTA-extractable metal concentrations. Profiles along two urban rivers showed a direct inhibition of enzyme activity at sites of stormwater and industrial discharge. Deposited sewage, from combined sewer overflows, was indicated by highly elevated enzyme activity and metal concentrations.The results of this study demonstrate that the ecologically relevant enzyme activity measurement may be a useful complement to metal speciation analysis when investigating the effects of stormwater discharges on urban rivers.