Selection and evaluation of sequential extraction procedures for the determination of phosphorus forms in lake sediment

In order to achieve comparable measurements in the determination of phosphate forms in freshwater sediments, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has launched a project the first step of which was to select and evaluate collaboratively existing extraction procedures. This was carried out through expert consultations and a literature survey, and was followed by the organisation of a first interlaboratory study for the evaluation of four sequential extraction schemes, one of which was selected as the most promising method for achieving comparability. This scheme, a modified version of the Williams protocol, was further tested in a second interlaboratory study. The so-called SMT extraction scheme seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration. It will be particularly helpful in estimating the stock of P potentially available, hence the risk of eutrophication due to internal P release.     

SMT法测定沉积物标准样品有机磷形态分析方法探究

目前水体沉积物中磷的分级提取没有统一的方法,不同的提取方法分析沉积物中的磷形态结果可能会有很大差异。SMT法因操作简单、重复性好而被广泛应用于沉积物磷形态分析,但是在实际操作中连续提取过程比较复杂,尤其是有机磷(OP)提取步骤比较繁琐,中间转移过程较多,分析人员人为操作等因素都会导致实验出现较大误差,通过多次实验研究发现,在此基础上还存在另外一种改进的OP提取方法。为了验证改进法是否具有合理可行性,以水系沉积物标准样品GSD-9和GSD-12为标样,同时以野外采集的沉积物样品为实际样品,采用标准SMT法和改进法重复测定(n=30)沉积物中OP含量。结果表明:标准SMT法提取沉积物标准样品GSD-9和GSD-12测得的OP含量分别占其总磷(TP)含量的9.33%和23.03%;改进法测得的OP含量分别占其TP含量的10.44%和23.13%,两种OP提取方法测得结果有着极高的相似性。结果表明,改进的OP提取方法具有可行性,对于沉积物OP分析提取方法的合理选择具有指导意义。     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

Effects of Flooding on Lead and Cadmium Speciation in Sediments from a Drinking Water Reservoir

Římov water reservoir on the river Malše is the main source of drinking water for the town of České Budějovice and for the majority of inhabitants in the South Bohemian region, Czech Republic. Changes in cadmium and lead contents in bottom sediments before and after an extensive flood on the river Malše in August, 2002 were therefore determined. A five-step sequential extraction procedure was used in order to obtain more detailed information about the influence of the flood on heavy metal retention. In order to determine the mobility of lead and cadmium, the mobility factor (MF) for these heavy metals was calculated. The mobility factor of cadmium showed a significant decrease in the upper parts of the sediment profiles after the flood (e.g., from 59.4% to 49.1%) caused by a release of cadmium especially from the exchangeable fraction. There were no significant changes in the lead mobility factor after the flood, but a decrease of lead concentration in the exchangeable fraction was observed. Presented results show that the flood led to a leaching of the heavy metals present in bottom sediments into the environment.     

The effect of humic acids on the sequential extraction of metals in soils and sediments using ICP-AES and chemometric analysis

The effect of humic acids on the sequential extraction of metals from various soils and sediments has been studied. A new multi-element extraction method optimised via experimental design has been employed. The method uses centrifugation to pass the extractant solution, at varying pH, through the sediment sample. The sequential leaches were collected and analysed by ICP-AES. Chemometric data processing was utilised to identify the composition of the physico-chemical components in order to characterise the sample. A sediment sample collected from Carnon River (Cornwall, UK) and a reference material (NIST 2711 agricultural soil) were spiked with humic acids and the sequential extraction scheme was used to monitor the changes in metal distribution. The method has proved a quick and reliable way to evaluate different sediment samples, and has potential as a new tool for environmental geochemistry analysis.     

Chemical sequential extraction for metal partitioning in environmental solid samples

A comprehensive review of the sequential extraction schemes for metal fractionation in environmental samples (ie., sediment, soil, sewage sludge, fly ash, etc.) is presented. The review contains more than 400 references and covers principally the literature published over the last decade. The use of each reagent involved in these schemes is looked at critically, and guidelines for their selectivity and extraction capacity are given. The operational character of these schemes is emphasised. Topics such as comparability between sequential extraction schemes of widespread use, harmonisation, acceleration, validation, etc. are addressed and future developments outlined.     

Accelerated fractionation of heavy metals in contaminated soils and sediments using rotating coiled columns

A new approach to performing an accelerated sequential extraction of trace elements from solid samples has been proposed. It has been shown that rotating coiled columns (RCC) earlier used in counter-current chromatography can be successfully applied to the dynamic leaching of heavy metals from soils and sediments. A solid sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents (aqueous solutions of complexing reagents, mineral salts and acids) were continuously pumped through. The procedure developed is time saving and requires only 4-5 h instead of the several days needed for traditional sequential extraction (TSE), complete automation being possible. Losses of solid sample are minimal. In most cases the recoveries of readily bioavailable and leachable forms of Pb, Zn, and Cd are higher, if a dynamic extraction in RCC is used. Since naturally occurring processes are always dynamic, continuous extraction in RCC may help to estimate the contents of leachable forms and their potential risk for the environment more correctly than batch TSE. The Kersten-Foerstner and McLaren-Crawford leaching schemes have been compared, the former has been found to be preferable.     

Mobility of Different Phosphorus Pools in the Sediment of Lake Dianchi during Cyanobacterial Blooms

By the method of P fractionation, we examined sedimentary P fractions in Lake Dianchi before and during cyanobacterial blooms, namely in April 2004 and August 2004, respectively. In this study, the whole lake is divided into four areas to discuss P fractions in sediment and the relationship between them and water quality or the nutrient status. The results show that where the water body was much more eutrophic (higher levels of total phosphorus, total nitrogen, chlorophyll and trophic status index) in Lake Dianchi, there can be more potentially available phosphorus (BD–P and NaOH–P) and less no available phosphorus (HCl–P and residual P) in the corresponding sediments. Statistical analysis and statistical plots are used to compare the distribution of every P fraction during cyanobacterial blooms with that before cyanobacterial blooms, and the results indicate that the different P fractions had the different mobility. HCl–P and residual P were relatively stable, while NaOH–P, BD–P and NH4Cl–P were more mobile. BD–P can intensively be released from sediment to water and consequently promote cyanobacterial blooms, and at the same time the NaOH–P concentration increased in sediment, which can result from that BD–P released can be partly immobilized to NaOH–P. During cyanobacterial blooms BD–P can be as a source, but NaOH–P as a sink. Besides, total phosphorus in sediment had no significant differences between two samplings.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

Pollution and potential mobility of Cd, Ni and Pb in the sediments of a wastewater-receiving river in Hanoi, Vietnam

Large quantities of untreated industrial and domestic wastewater are discharged from the city of Hanoi into urban rivers. Sediment samples from three sites in the To Lich River in Hanoi were assessed with respect to the concentrations and potential mobility of cadmium (Cd), nickel (Ni) and lead (Pb). Due to very high Cd concentrations up to 700 mg kg^?1 at one site, the sediment was considered highly unsuitable for any types of land use if dredged and disposed of on land. Chemical sequential extractions of wet and anoxic sediment samples showed that Cd and Pb were largely associated with the redox-sensitive fractions and could thus be mobilised following measures such as resuspension or dredging. To assess the potential mobilisation of heavy metals from the anoxic sediment due to oxidation, the samples were exposed to different oxidants (i.e. atmospheric air and hydrogen peroxide) and afterwards submitted to a leaching test. These experiments showed that although oxidation may increase the equilibrium pore water concentrations of heavy metals in the sediments, other sediment mineral fractions seem to effectively immobilise heavy metals potentially released from the oxidisable fraction.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

Sequential fractionation of phosphorus in sediments of El-Fayum lakes—Egypt

The amounts and forms of potentially mobile phosphorus (P) in surface sediments of Qarun and Wadi El-Rayan lakes were evaluated during winter and summer using a sequential chemical extraction. Five sedimentary P fractions were separately quantified: loosely sorbed P (NH₄Cl-P), iron-associated P (BD-P), calcium- bound P (HCl-P), metal oxide bound P (NaOH-P), and residual P (organic and refractory P). The results indicated that the fractional composition of the examined lakes was different while the total P concentrations were approached. The inorganic P in the surface sediment mainly consisted of Ca-P followed by Fe-P in Qarun Lake, while Al-P took the second order in Wadi El-Rayan lakes. The ranks order of the different P extracts were HCl-P > residual-P ≈ NaOH-P > NH₄Cl-P > BD-P and residual-P > NH₄Cl-P > HCl-P > NaOH-P > BD-P for Qarun and Wadi El-Rayan lakes, respectively.     

Sequential fractionation of phosphorus in lake sediments of Northern Greece

The amounts and forms of potentially mobile P in surface sediments from two lakes, Volvi and Koronia, located in Northern Greece were evaluated using a sequential chemical extraction. Five sedimentary P reservoirs were separately quantified: loosely sorbed P (NH₄Cl-P); iron associated P (BD-P); calcium bound P (HCl-P); metal oxide bound P (NaOH-P) and residual P (organic and refractory P). Samples were taken in two seasons and the average concentration of the fractions of phosphorus were calculated. The results indicated that the TP content and chemically extractable phosphorus in the sediments of Koronia Lake were higher than those of Volvi Lake. Sediment TP was also strongly and positively correlated with sediment Fe. Fine-sized sediments exhibited significantly higher concentrations for both lakes than the sand fraction. The P in the surface sediment mainly consisted of HCl-P and Res-P, while NH₄Cl-P and BD-P only constituted a minor part. The rank order of the different P extracts was the same for the two lakes and was Residual-P > HCl-P > NaOH-P > BD-P > NH₄Cl-P.     

Heavy metal concentration and speciation of seven representative municipal sludges from wastewater treatment plants in Northeast China

The analysis of heavy metals is very important for assessing the feasibility of the agricultural utilization for the municipal sludge. In this paper, a four-step sequential extraction method was applied to extract heavy metals (Cu, Zn, Mn, Cr, and Ni) in municipal sludges from seven individual wastewater treatment plants located in Jilin and Heilongjiang Province, China, for estimating the mobility and bioavailability of the metal ions in the agricultural application. The total concentrations of heavy metals and their chemical fractions after the sequential extraction were determined. Principal component analysis (PCA) was applied to analyze the relations of heavy metals fractions in the municipal sludges. Experimental results indicated that the total concentrations of Cu, Zn, Cr, and Ni in all sludge samples were below the threshold values set out by the Chinese legislation (GB18918-2002). Specially, Zn had a high bioavailability and mobility, Cu and Cr had potential bioavailability, while Mn mainly existed in the residual fraction of municipal sludge. On the other hand, Ni had different mobility in different municipal sludge. PCA results were confirmed by the environmental behavior of heavy metals.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Diagenesis of settling seston: identity and transformations of organic phosphorus

Solution (31)phosphorus NMR spectroscopy and sequential fractionation were used to follow diagenetic changes in phosphorus forms during decomposition of settling seston in Lake Nordborg, a shallow eutrophic lake in Denmark. In a decomposition experiment, seston released >60% of their total phosphorus during ~50 days incubation, although seston collected during summer contained more phosphorus and released it over a longer period compared to seston collected during spring. Seston decomposition increased concentrations of potentially bioavailable polyphosphate and phosphodiesters, but also promoted the formation of refractory phosphorus forms that might be buried permanently in the sediment. Combining these results with in situ measurements of phosphorus concentrations in lake water and sediment traps revealed that the release from settling seston plays only a minor role in the accumulation of phosphorus in the hypolimnion of Lake Nordborg.