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.     

Cadmium partition in river sediments from an area affected by mining activities

In this paper, the cadmium distribution in Certej River sediments in an area seriously affected by intense mining activities has been studied. The main objective of this study was the evaluation of partition of this metal into different operational defined fractions by sequential extractions. Community Bureau of Reference (BCR) sequential extraction was used to isolate different fractions. The sediment quality was assessed both upstream and downstream the pollution input points, along the Certej River, in order to reveal a possible accumulation of cadmium in sediments and the seasonal changes in cadmium concentrations in BCR sediment phases. Our results reveal that most of the cadmium content is divided between both the soluble and iron and manganese hydrated oxide fractions. Based on total cadmium concentrations in sediments, the enrichment factors were estimated using aluminum as normalizing element and the regression curve Cd/Al corresponding to the geochemical background of the studied area.     

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.     

Phytoremediation facilitates removal of nitrogen and phosphorus from eutrophicated water and release from sediment

Phosphorus (P) fractions and the effect of phytoremediation on nitrogen and phosphorus removal from eutrophicated water and release from sediment were investigated in the eco-remediation experiment enclosures installed in the Hua-jia-chi pond (Hangzhou city, Zhejiang province, China). The main P fraction in the sediment was inorganic phosphorus (IP). For the mesotrophic sediments, IP mainly consisted of HCl-extractable P (Ca-P). The annual-average concentration of total nitrogen (TN), total phosphorus (TP) in water and the content of TN, TP in different vertical depth of sediment in the experiment enclosures with hydrophyte were always much lower than those in the control enclosure without hydrophyte and those outside of experiment enclosures. It is suggested that phytoremediation was an effective technology for N and P removal from eutrophicated water and release from sediment.     

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.     

Longitudinal heterogeneity of sediment characteristics during southwest monsoon season in hyper-eutrophic Krishnagiri reservoir,India

Krishnagiri reservoir is a hyper-eutrophicated reservoir located in Krishnagiri district which is one of the drought-prone districts in Tamil Nadu, India. The reservoir water is being used for various purposes such as irrigation, drinking, fish rearing, livestock rearing, and recreation. Since there is no an evidence of investigation on bottom sediments in Krishnagiri reservoir, the present study was carried out during southwest monsoon season in 2008. This study examined the physical and chemical characteristics of the bottom sediments such as composition, redox potential, moisture content, organic carbon, organic matter, total phosphorus, and total iron at 15 locations in the reservoir. Phosphorus fractionation study was carried out to find out different fractions such as loosely adsorbed phosphorous, iron and aluminium-bound phosphorus, calcium-bound phosphorous, and organic phosphorous. Results indicated that there was spatial variation in the composition of sediments and low values of redox potential. The significant positive correlation exists between the organic carbon and organic phosphorus concentration. The lacustrine zone of the reservoir showed high accumulation of total phosphorus and total iron when compared to riverine and transition zones. This study concludes an allogenic origin of majority of inorganic phosphorus in the reservoir during the study period and this might have been derived from the catchment during the erosion process. The high concentration of surface sediment phosphorus clearly indicates a greater threat of eutrophication in Krishnagiri reservoir.     

Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA

In the present study, the BCR (Community Bureau of Reference) sequential procedure has been applied to determine the zinc partition in sediments taken from a river situated in the Southwest of Romania, in a region subject of intense mining activities. The sampling was performed during three sampling expeditions, organized in the spring, summer, and autumn, 2007. The zinc concentration in different fractions was normalized, its concentration being related to the concentrations of some metals (such as Al or Fe) that are naturally present in sediments. The zinc-contaminated sediments from the investigated area have been evaluated by means of combining the analysis data from the BCR sequential extraction with the normalization to the Al content. The most important zinc collector in the samples taken during the three sampling expeditions is the easily soluble fraction, next being amorphous iron and manganese hydrated oxides fraction, followed by organic matter fraction.     

Phosphorus fractionation in different trophic sediments of lakes from different regions, China

The characteristics of organic phosphorus (P(o)) fractions in the sediments of nine lakes from the middle and lower reaches of the Yangtze River region, Yungui Plateau, Qinghai-Tibet Plateau, Northeast China Region, and Mongolia-Xinjiang Plateau, China were investigated and the differences of the different lakes on P fractionation was discussed. The results indicated that organic matter (OM) showed significant positive correlations with P(o) in sediment samples, and the rank order of the P(o) fractions was: residual P(o) > HCl-P(o) > fulvic acid-P(o) > humic acid-P(o) > NaHCO(3)-P(o) with mean relative proportions 7.4 : 3.4 : 2.4 : 1.7 : 1.0. The labile and moderately labile P(o) were the main fractions in the sediments for shallow eutrophic lakes except for Lake Qilu, however, nonlabile P(o) was dominant in the sediments from deep lakes. Labile P(o) was significantly correlated with total phosphorus (TP), inorganic phosphorus (P(i)), P(o), NaHCO(3)-P(i), HCl-P(i) and NaOH-P(i), and the nonlabile P(o) was significantly and positively related to OM, TP, P(o) and NaOH-P(i).     

A regional inventory and monitoring setup to evaluate bark peeling damage by red deer (Cervus elaphus) in coniferous plantations in Southern Belgium

Sediment phosphorus (P) fractions and sorption characteristics and P release from intact sediment cores of Baiyangdian Lake in North China in spring 2009 were investigated. Results of chemical fractionation showed that total P (TP) content in sediment ranged from 443 to 611 mg kg(?-1). Of the P fractions including inorganic P (IP) and organic P (OP), IP was a dominant component of TP and present in the form of P bounded to calcium (Ca-P) while the bioavailable P content bounded to Al, Fe, and Mn oxides and hydroxides (Fe/Al-P) varied from 14 to 102 mg kg(?-1). The batch experiments showed that the sediments had appreciable maximum P adsorption capacity from 141.86 to 377.37 mg kg(?-1). However, the zero P equilibrium concentration (C?(eq))in most sampling sites was larger than the P concentration in water column. Accordingly, the sediments from those sampling sites would release P into the overlying water at the positive P flux rates as a P release source. Significant positive correlation between P flux rates and Fe/Al-P revealed that the sediment P release would mainly originate from the bioavailable P fraction. It is evident that the inherent phosphorus present in lake sediments would be a major threat to the water quality and ecosystem reservation in Baiyangdian lake.     

Pool of mobile and immobile phosphorus in sediments of the large, shallow Lake Peipsi over the last 100?years

Temporal variations in sediment phosphorus (P) composition and mobility were estimated in surface sediments of accumulation (core PS509 44?cm) and erosion (core PS2009 30?cm) areas of the shallow, large Lake Peipsi sensu stricto (s.s.; 2611?km(2), unregulated water level). The P pool in sediments including buried and mobile P is evaluated for the first time, which will provide baseline data for the future modelling of internal loading in L. Peipsi. Five sedimentary P fractions (including inorganic and nonreactive P) were separately quantified: loosely adsorbed and pore-water P (NaCl-P); redox-sensitive fraction P (NaBD-P); P bound to oxides of non-reducible Fe and Al (NaOH-P); calcium-bound P, mainly from apatite minerals (HCl-P) and refractory, mainly organic P (Res-P). Concentrations of P fractions varied during the 100?years with the highest values around 2007-2008 and 1923-1935. The P in "active" layers that are available for bacteria and algae or those undergoing changes and diagenetic transformations in the sediment could follow sediments with the water content of ～88%. Potentially mobile P is not decreased in the sediments deposited 50-100?years ago and makes up ca 63?mg?m(-2)?y(-1) (with range 8.3-23.7% of the total P (TP)) in the accumulation area, and ca 0.047?mg?cm(-3) (with range 1.3-22.4% of TP) in the erosion area. The result shows that 13-60% of TP contained in the surface sediment (from 34 to 398?mg P m(-2) y(-1)) has been remobilised during accumulation and could be exported to the overlying water.     

Phosphate adsorption characteristics at the sediment–water interface and phosphorus fractions in Nansi Lake, China, and its main inflow rivers

Phosphorus fractions and phosphate adsorption characteristics of 16 sediments from a shallow freshwater lake (Nansi Lake, China) and its inflow estuaries were investigated. In the present study, the sediment phosphorus is fractionated into exchangeable P (exch-P), Al-P, Fe-P, Ca-P, organic P (OP), inorganic P (IP) and total P (TP). The results show that the total phosphorus (TP) content in the sediments ranges from 571.67 to 1,113.55 mg kg(-1), and calcium bound phosphorus (Ca-P) is the main fraction of IP. The biologically available phosphorus (BAP) ranges from 32.02 to 229.67 mg kg(-1) in the Nansi Lake sediments. Phosphate adsorption on the sediments mainly occurs within 10 h and is completed within 48 h. The content of native adsorbed phosphorus (omega(NAP)) varies greatly from 6.05 to 194.37 mg kg(-1), showing a significant correlation with the total maximal amount of phosphorus adsorbed (TQ(max)). Adsorption efficiency (m) ranges from 574.79 to 3,220.68 l kg(-1) and zero equilibrium phosphorus concentration (C(EPC)) ranges from 0.010 to 0.157 mg l(-1). After the South-to-North Water Diversion Project, the inherent phosphorus present in sediments will be a major threat to the diverted water quality and be a predominant factor determining the trophic status of the lake even if the external load is reduced.     

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。     

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.     

An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

Fractionation of heavy metals and phosphorus in suspended sediments of the Yamuna river,India

The Yamuna river is the largest tributary of the Ganges river system. It originates in the Himalayas and flows through a varied geological terrain encompassing a large basin area. Metals Fe, Mn, Pb, Zn, Cu in different chemical fractions of suspended sediments such as exchangeable, carbonates, Fe–Mn oxides, organics and residual fractions were studied. Phosphorus associated with different chemical forms are discussed. The metals are mostly associated with residual fractions in the sediments followed by organics, Fe–Mn oxides, exhangeable and carbonates. Intensive use of chemical fertilizers and pesticides in agriculture in the basin affects the high inorganic phosphorus content in sediments.     

Effect of ultrasonic agitation on the release of copper, iron, manganese and zinc from soil and sediment using the BCR three-stage sequential extraction

An ultrasonic bath and an ultrasonic probe have been used to develop rapid versions of the three-stage Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) sequential extraction procedure. The effect of the ultrasonic treatments on the extraction of copper, iron, manganese and zinc from a sewage sludge-amended soil has been assessed. Recoveries similar to those of conventional shaking (i.e., conventional value, +/- 30%) could generally be obtained for copper, manganese and zinc, but not for the important matrix element iron. With the use of compromise sonication conditions, steps 1, 2 and 3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 3, 5 and 1 min, respectively, using the ultrasonic probe, and in 3, 1 and 1 h, respectively, using the bath. The extraction procedures developed using the soil performed well when applied to lake sediment BCR CRM 601. Analyte partitioning was generally similar to that obtained with mechanical shaking, and overall metal recoveries were 84-98% of those obtained with the conventional BCR protocol, except for copper extracted with the probe (74%). Poorer performance (analyte recoveries, 58-104%) was obtained when the methods were applied to an intertidal sediment. This highlights the difficulty of developing a version of the BCR extraction, with ultrasonic assistance, which gives a performance equivalent to conventional shaking when applied to different substrates.     

Evaluation of performance of time-saving extraction devices in the BCR three-step sequential extraction procedure

Two alternative extraction methods--a routine ultrasonic bath and a microwave oven--were developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by the European Standards, Measurements and Testing (S, M & T) Programme, formerly Bureau Communitaire de Reference (BCR), for the operationally defined speciation of Cd, Cr, Cu, Ni and Zn. The conventional BCR three-stage sequential extraction procedure was modified at each stage, applying ultrasonic or microwave devices in order to shorten the required 16 h of shaking in all three steps. The experimental tests and the optimization of the operating parameters were carried out on a highly homogenized estuarine sediment reference material (RM S7) prepared by the Joint Research Centre (JRC) of ISPRA. Extractable metal contents were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the results obtained in each fraction by all three methods were statistically compared for all the studied elements. The conventional and newly developed alternative extraction methods were finally compared by the analysis of BCR 601, which is certified for the three-step BCR sequential extraction procedure. According to the statistical evaluation of the results, the proposed accelerated sequential extraction methods are valid alternatives to conventional shaking, with much shorter extraction times.     

Phosphorus fractions and adsorption characteristics of floodplain sediments in the lower reaches of the Hanjiang River, China

The phosphorus fractions and adsorption characteristics of seven floodplain sediment samples collected in the lower reaches of China’s Hanjiang River were studied. Most phosphorus fractions showed a marked downstream increase in response to point-source inputs from urban areas. Total phosphorus (TP) contents in the sediments ranged from 603.68 to 945.25 mg.kg⁻¹. Inorganic phosphorus (IP) was the major component of TP, and calcium-bound phosphorus (Ca–P) was the major fraction of IP. The distribution characteristics of the phosphorus contents were affected by sediment grain size and hydrodynamic conditions. The maximum phosphorus adsorption capacities (Q _max) and the half-saturation concentration (k) were obtained using an improved Langmuir model. Native adsorbed exchangeable phosphorus content (w _NAP) and the zero-equilibrium phosphorus concentration value (c _EPC0) were subsequently calculated. The effects of sediment grain size, temperature, and disturbance on the phosphorus adsorption isotherms were also studied. The results showed that phosphorus adsorption on floodplain sediments was primarily chemisorption; the particle concentration effect played a more important role at a disturbance intensity of 150 r.min⁻¹ (on a shaker table) than at 100 r.min⁻¹.     

洪泽湖沉积物中磷的形态研究

采用改进的七步连续提取法对洪泽湖9个采样点沉积物中的各形态磷进行了分析,结果表明,所测洪泽湖沉积物中总磷(TP)含量范围为580.7～1 447.7 mg/kg,无机磷(IP)是TP的主要部分,占TP含量的64.32％～88.60％;有机磷(0P)占TP的11.40％～35.68％.受河流注入和人为活动的影响,TP、I...     

Distribution of mercury and organic matter in particle-size classes in sediments contaminated by a waste water treatment plant: Vidy Bay, Lake Geneva, Switzerland

In Lake Geneva, Switzerland, the most Hg-contaminated sediments have been found in the Vidy Bay where high Hg contents largely exceeds the background levels of Lake Geneva sediments. This contamination has been attributed to the discharge of a waste water treatment plant (WWTP). Total Hg (THg) and monomethylmercury (MMHg) were determined in bulk sediment and in three different grain size fractions (i: clay and silt, ii: fine-coarse sand, iii: and very coarse sand and gravel) collected close to the outlet pipe of a WWTP in order to verify whether the standardized procedures of sediment treatment is adequate for this setting and, by extension, for similar contaminated sites. THg was homogeneously distributed in the different grain size fractions and was correlated to organic matter content (R(2) = 0.6). MMHg was homogeneously distributed in the two finer grain fractions (Φ < 0.063 mm; 0.063 mm < Φ <1 mm). The results of this study suggested that the analysis of the bulk sediment seems to be more appropriate for the assessment of the content and spatial distribution of Hg in freshwater sediments contaminated by WWTPs.