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Journal of Hazardous Materials 154 (2008) 9981006

Speciation of heavy metals in sediment by conventional, ultrasound and microwave assisted single extraction methods: A comparison with modied sequential extraction procedure
Muhammad B. Arain 1 , Tasneem G. Kazi , Muhammad K. Jamali 1 , Nusrat Jalbani 1 , Hassan I. Afridi 1 , Jameel A. Baig 1
Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan Received 2 October 2007; received in revised form 1 November 2007; accepted 1 November 2007 Available online 20 December 2007

Abstract Sequential extraction procedure proposed by the European Standards, Measurements and Testing (SM&T) Program, formerly the Community Bureau of Reference (BCR), has been applied for the heavy metals (HMs) partitioning in fresh water lake sediment samples. The results obtained by conventional sequential extraction BCR method (SEB) for Cd, Cu, Cr, Ni, Pb and Zn were compared with those estimated from three alternative single extractions, conventional (CSE), ultrasonic (USE) and microwave assisted (MSE), using identical operating conditions applied in each individual BCR fraction and validated by the CRM BCR 701. Extractable HMs contents obtained by all compared methodologies were measured by atomic absorption spectrometery. With the use of compromised sonication and microwave conditions, steps 13 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3) could be completed between 1530 min using ultrasonic bath, while 60120 s were required for MSE. The total extractable metal contents obtained by three single extractions ranged from 75.1% to 114.0% except Cr in rst step, which was extracted (125.3%) by MSE method as compared to those obtained by SEB procedure. The precision of the proposed BCR single extraction methods (expressed as RSD%) was found in the range of (3.999.6%) for all metals. 2007 Elsevier B.V. All rights reserved.
Keywords: Lake sediment; Metal; Sequential extraction; Single extraction; Microwave; Ultrasonic

1. Introduction The contamination of sediments, soils, and biota by heavy metals (HMs) is of major concern especially in many industrialized countries because of their toxicity, persistence and bioaccumulative nature. Sediment samples have been found as a carrier of most metals and some elements may be recycled through biological and chemical reactions within the water column [1]. Metals and metalloids accumulated in sediments, sludges and soils may therefore pose of an environmental problem concerning possible metal transfer from these samples to aquatic medium and thereby including them in the food chain

Corresponding author. Tel.: +92 22 2771379; fax: +92 22 2771560. E-mail addresses: bilal ku2004@yahoo.com (M.B. Arain), tgkazi@yahoo.com (T.G. Kazi), mkhanjamali@yahoo.com (M.K. Jamali), nusratjalbani 21@yahoo.com (N. Jalbani), hassanimranafridi@yahoo.com (H.I. Afridi), jab mughal@yahoo.com (J.A. Baig). 1 Tel.: +92 22 2771379; fax: +92 22 2771560. 0304-3894/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2007.11.004

[2]. The total metals content in polluted environmental samples is a poor indicator of its bioavailability, mobility or toxicity; these properties basically depend on the different chemical forms of binding between trace metals and solid phases of the sample. Different extraction methods of metals from environmental samples are extensively studied [3]. Metal ions in sediments are partitioned between the different phases, i.e., organic matter, oxyhydroxides of iron, aluminum and manganese, phyllosilicate minerals, carbonates and suldes. In addition, metal ions are retained on these solid phases by different mechanisms (ion exchange, outer- and inner-sphere surface complexation (adsorption), precipitation or co-precipitation) [4]. Although, the separation of various chemical forms of heavy metals is very difcult, the use of sequential extraction methods in this way provides an important approach. The most recent sequential extraction method has been developed by the Community Bureau of Reference (BCR) as an attempt to harmonize different methodologies of the extraction process [5]. This method has also been widely accepted and

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applied to metal fractionation in different environmental samples [6]. The main limitations of sequential extraction procedures are that, they are extremely time-consuming, and are less used for routine analysis. This problem has also been noted and is replacing the conventional procedure by other alternatives, such as microwave (MW) heating and ultrasonic (US) shaking. Davidson and Delevoye have effectively developed a modied BCR sequential extraction with the use of ultrasound energy [7]. It is well known that exposure of solids to ultrasound leads to structural changes in their surface morphology [8]. The impact of the ultrasound jet and its associated shock wave erodes the solid, leading to localized fragmentation of particles [9]; the achieved

results were comparable to what can be achieved with mechanical shaking, while the time required (2030 min per step) was much shorter [10]. The sequential extraction procedure could also be improved by using MW irradiation, recently applied for acceleration of different chemical processes [11], including multi-step sequential extraction methods [12]. So this energy could be introduced to replace the conventional and magnetic shaking in order to shorten the treatment time. Another attractive approach consists of replacing the sequential stepwise extractions by single step extractions with the same reagents and operating conditions as the sequential procedure, but different sub-sample is employed for each extractant. The

Fig. 1. Flow diagram of the modied BCR sequential and single extraction procedures.

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last option has been proved by application of Tessiers [13,14] and modied BCR method on sediment and sewage sludge samples [1517]. The main objective of this work was to compare the results obtained by using the conventional BCR sequential extraction methods with those from single extractions, employing similar operating conditions and using time-saving extraction devices (US bath and MW oven), on sediment samples. Sediment certied reference material BCR 701 was also employed to test the extraction efciency of the accelerated procedures. The contents of Cd, Cu, Cr, Ni, Pb and Zn in the extracts were measured by metal determination that was performed by ame atomic absorption (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). The advantages and disadvantages of the time-saving procedures were considered and evaluated from statistical and environmental points of view. 2. Experimental 2.1. Reagents and glassware Ultrapure water obtained form ELGA labwater system (Bucks, UK), was used throughout the work. The extracting solution as listed in Fig. 1, was prepared from analytical grade reagents and also checked for possible trace metal contamination. CH3 COONH4 was purchased from Sigma (Aldrich, Milwaukee, USA). Acetic acid, Hydrochloric acid, nitric acid, and hydrogen peroxide were analytical reagent grade from Merck (Darmstadt, Germany). Standard solutions of Cd, Cr, Cu, Ni, Pb and Zn were prepared by dilution of 1000 ppm certied standard solutions, Fluka Kamica (Buchs, Switzerland) of corresponding metal ions. The hydroxylammonium chloride solution was prepared prior to use. Recommended modiers, magnesium nitrate and palladium (0.001 mg Pd + 0.0015 mg Mg(NO3 )2 ) for Cd; ammonium phosphates (0.2 mg NH4 H2 PO4 ) for Pb; magnesium nitrate (0.05 mg Mg(NO3 )2 ) for Cr and Ni. The certied reference material BCR 701 was purchased from the bureau of references of European communities. All glassware and plastic material used was previously treated for 24 h in 2 N nitric acid and rinsed with double distilled water and then with ultrapure water. We used 50 mL of acid washed polyethylene centrifuge tubes for extraction, while 50 mL polyethylene vessels Bibby (Sterilin Ltd., UK) were used for storage of extractants. 2.2. Instrumentation The US extractions were carried out with a Sonicor, Model No. SC-121TH, Sonicor Instrument Corporation Copiague (NY, USA) programmable for temperature ranging form 090 C with intensication frequency 35 kHz. WIROWKA Laboratoryjna type WE-1, nr-6933 centrifuge; speeds range 06000 rpm, timer 060 min (Mechanika Phecyzyjna, Poland) used for centrifugation. A WTW pH meter was employed for pH adjustments of the reagents. PM023 domestic programmable MW oven PEL (Japan) used for MW extraction and digestion. The determination of metals

in extracts and digests was carried out by means of a double beam PerkinElmer atomic absorption spectrometer model AA700 (Norwalk, CT, USA) equipped with a graphite furnace HGA-400, pyrocoated graphite tube with integrated platform, an auto sampler AS-800. Hollow cathode lamps were used as radiation sources. Lamp intensity and bandpass width were used according to the manufacturers recommendations. The Cu and Zn were measured under optimized operating conditions by FAAS with airacetylene ame, while the Cd, Cr, Ni and Pb were determined by ETAAS. 2.3. Sample collection and pre-treatment The lake sediment samples were collected in polyethylene containers from Mancher Lake (Sehwen Sindh, Pakistan) (26 3 N; 67 6 E), during 2006 on monthly basis, by holes dug with a motor-driven excavator from different entrance and exit points (5 station). From each station, 1015 samples of sediment (12 kg) were collected randomly. On returning to the laboratory, all the sediment samples were spread on the plastic trays in fuming cupboards and allowed to dry at ambient temperature. Sediment samples after air drying for 8 days were ground in an agate mortar and sieved through nylon-ber sieve to obtain particle size <70 m. Homogenized sediment sample was stored in polyethylene bottles in desiccators at room temperature. 2.4. Operating procedure for sequential extraction BCR scheme (SEB) The modied SEB method [18,19] was applied as shown in Fig. 1. All the extractions were performed by shaking in a mechanical, end-over-end shaker at a speed of 30 rpm at room temperature 3035 C as compared to the other studies, which were working at low temperature because we have high temperature in our laboratories due to warm climate of our country and it reduce the weight of samples and volume of extractants, but the ratio is same as compared to the literature reported [20,21]. 2.5. Single extractions Single extractions were carried out by employing a separate aliquot for each individual reagent, using the same operating conditions listed in Fig. 1, centrifugation and storage of extracts were performed as in the modied sequential extraction scheme. The main advantage of this proposed procedure is that all fractions can be simultaneously extracted except oxidizable fractions. Metals bound to organic matters and sulde cannot directly be leached from the corresponding sub-samples due to the H2 O2 boiling under MW, and it also seems to be inefcient for USE. So the oxidizable fraction alternatively extracted by applying to the residue obtained after its treatment with hydroxylammonium chloride. Single extractions supply faster results than the SEB method. In contrast, a larger sample amount is needed, which does not pose an additional problem when environmental samples are being studied.

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2.5.1. Conventional single extraction (CSE) The CSE was carried out by employing a separate duplicate aliquot of each lake sediment and BCR 701 samples for each individual reagent as described in Fig. 1. 2.5.2. Ultrasonic assisted single extraction (USE) In an US bath of capacity 4 L, several samples can be proceeding at once. As reported by previous work, the duration of US exposure was important [9]. So all these conditions were designed to give maximum extraction in the shortest possible time, while avoiding an increase in the temperature of the samples, as the increase in temperature can change the chemical equilibrium of the extraction solutions. The parameters were modied experiment by experiment; the selection of the parameters was based on the values of HMs obtained by SEB method. It was not possible to identify a single set of conditions optimal for all metals, but in nearly all cases, 35 kHz frequency of US bath, 3035 C and up to 30 min ultrasound exposure, produced acceptable results. For optimization, replicate six experiments were carried out as described in Fig. 1. 2.5.3. Microwave induced single extraction (MSE) Microwave energy has long been used successfully for the acceleration of sample preparation process; its efciency is signicantly expressed by the increase in temperature of the sample [22]. The possibility of exploitation of a MW oven in the single extraction steps of BCR procedure was investigated. As the BCR procedure requires, those extractions are performed at ambient temperature, the optimization of the MW power and extraction time was carried out by carefully controlling the temperature of the extracting solutions. For all three single extraction steps of BCR method, to maintain power of MW and time, where the temperature did not exceed 50 C, and the solutions were never brought to boiling. Experiment details are shown in Fig. 1. Blanks (containing reagent but no samples) were also taken through each complete procedure. In all proposed single extraction procedure, with the exception of the rst fraction (exchangeable metals) of the modied BCR method, the metal content corresponding to each individual fraction was calculated by subtracting the results obtained in two consecutive stages. For example, to estimate the reducible fraction in the BCR method from single extractions, the amounts of metal extracted with step 1 reagent, were subtracted from those extracted with the reagents of step 2 (0.5 M NH2 OHHCl). In all cases, metal recovery was calculated as the following ratio: %Recovery = Metal extracted by proposed single extraction Metal extracted by Sequential BCR 100

3. Results and discussion 3.1. Optimization of proposed procedures 3.1.1. Ultrasonic assisted single extraction (USE) procedure The performance of the US bath assisted single extraction procedure (USE) with respect to modied SEB and CSE was assessed by the extraction of BCR 701 and lake sediment samples. Each stage of US assisted single extraction of BCR procedure was characterized individually. The results obtained for all HMs, at each step of the BCR extraction procedure with the use of ultrasound energy at different time intervals, are summarized in Table 1. The maximum recovery of HMs in all BCR steps was obtained in 15 min except in the case of Pb and Cu, they required 20 min in steps 1 and 3. In all cases the effects of sonication time are found to be signicant. The results obtained by USE are comparable to those obtained by the SEB method. However, a few exceptions to this agreement, such as ultrasound method could extract more heavy metals except Cu in step 1 than those obtained from SEB extraction. 3.1.2. Microwave induced single extraction (MSE) procedure The results obtained from heating the extraction mixture (extractantssample) in a MW oven at 2080% of total power (900 W), at different heating time intervals (20120 s) were compared with those values obtained by SEB method. It was observed that in rst step of BCR protocol the maximum recovery of all HMs was observed at 60 s heating time except when Cu and Pb achieved high recovery after 90 s, longer time up to 120 s, not enhance the recovery of Cd, Cu, Cr, Ni, Pb and Zn. In reducible fraction, the maximum recovery of Ni, Cd, Cr and Zn was observed at 90 s while Cu and Pb required 120 s for optimum values. In oxidizable fraction Ni, Cd, Cr and Zn recover at 70 s, while Cu and Pb recovery were obtained at 90 s. So, it was observed that the Cu and Pb required longer duration for optimum recovery from matrixes. In summary, the most favorable extraction conditions for all three steps of MSE were found at 60120 s and 60% of total power 900 W for BCR 701 and lake sediment samples. The power values of MW at 2040% of nominal power did not release the quantitative amount of HMs. It was observed that at 80% of total power the abrupt change in temperature causes signicant changes on metal extraction and fractionation pattern, but when using 60% of total power, the temperature did not change signicantly, so we select 60% of total power of MW oven for all experiments to release all HMs at optimum levels as compared to those obtained from SEB procedure. 3.2. Comparison between extractable heavy metals from the modied sequential BCR method and single extraction procedures The obtained data against the proposed single extraction procedures could be compared to the SEB procedure, extractable

Before extraction 0.5 g of certied BCR 701 and lake sediment samples were precisely weighed in weighing bottles, and placed in an oven (105 2 C) until constant weight. This treatment produced a 2.5% loss of weight in BCR 701 and different ranged values for lake sediment samples. All subsequent measurements were corrected to take account of these losses.

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Table 1 Overview of modied BCR sequential extraction, using single extraction methods. All values reported as mean S.D. (mg kg1 dried basis) Material (a) Exchangeable fraction (rst step) BCR 701 Certied values [5] BCR 601 SEBa This work BCR 701 CSEb,c USEd MSEe USE CSE MSE MSE USE MSE USE Technique Cd Cr Cu Ni Pb Zn t values (df = 5), t critical = 2.57

Modied BCR scheme

7.34 0.35 4.45 0.67 7.30 0.40 7.74 0.6 7.14 0.5 3.38 0.04 4.22 0.06 NPf 3.46 0.51 3.01 0.34 7.76 0.73 5.70 0.54 3.77 0.28 3.95 0.53

2.26 0.16 0.35 0.08 2.49 0.20 2.84 0.24 3.12 0.3 0.28 0.02 0.32 0.05 NDg 0.23 0.06 0.14 0.02 2.48 0.19 1.22 0.12 45.70 1.7 10.6 0.9 46.7 3.7 45.44 4.3 38.76 2.8 44.83 3.6 5.9 0.2 9.83 0.64 ND

49.3 1.7 10.5 0.8 50.2 2.28 45.08 2.2 45.7 3.0 7.97 0.65 9.8 0.8 22.01 0.58 7.9 1.4 5.9 2.5 33.6 1.9 36.13 8.7 124.0 3 72.8 4.9 123.5 7.6 121.65 5.9 134.62 8.4 132.76 5.3 81.7 6.8 74.6 3.2 214.82 0.65 55.20 3.7 78.6 8.9 55.6 3.4 55.91 2.4 52.31 2.4 41.77 1.9 63.2 5.3 75.6 6.3 256.1 1.9

15.4 0.21 7.82 0.84 16.9 1.22 17.4 0.9 16.3 1.5 3.65 0.18 6.95 0.45 2.89 0.22 8.08 1.2 5.25 0.9 19.45 3.2 10.31 2.8 26.60 3 10.6 1.2 27.8 1.6 27.4 1.4 25.9 2.2 22.0 1.8 6.42 0.46 10.9 0.88 0 0.43 15.30 1.92 6.04 1.3 15.8 0.74 16.4 0.9 15.1 1.09 13.62 0.8 5.40 0.62 6.20 0.43 7.97 0.62

3.18 0.21 2.28 0.44 3.58 0.32 3.96 0.36 3.48 0.3 2.72 0.27 2.65 0.18 ND 2.3 0.13 1.5 0.33 2.60 0.36 2.27 0.21 126.0 3 205 11 117.9 9.5 114.01 10.3 112.24 6.8 110.0 9.5 189 13 198 8 ND

205.0 6 261 13 204.2 10.50 218.49 10.9 209.31 12.8 NP NP 34.12 0.69 184.92 16.4 156.15 49.3 205 19.85 153.7 19.2 114.0 5 266 17 109.8 6.9 105.3 5.27 108.15 6.62 104.86 6.47 NP NP 7.09 0.40 45.7 3.4 106 11 44.30 4.2 47.53 3.86 43.24 2.22 35.6 1.56 NP NP 469.2 2.5 0.20 0.12 0.08 0.05 0.74 0.48 0.00 0.52 0.97

M.B. Arain et al. / Journal of Hazardous Materials 154 (2008) 9981006

Filgueiras et al. [15] Fernandez et al. [17]

BCR 601 BCR 601 Sewage sludge BCR 601

Canepari et al. [16] BCR 701 (b) Reducible fractions (second step) BCR 701 Certied values BCR 601

Modied BCR scheme SEB CSE USE MSE USE CSE MSE

This work

BCR 701

3.83 0.25 3.88 0.34 4.10 0.32 3.80 0.3 4.36 0.39 4.10 0.43 NP

Filgueiras et al. [15] Fernandez et al. [17]

BCR 601 BCR 601 Sewage sludge

(c) Oxidizable fractions (third step) BCR 701 Certied values BCR 601

Modied BCR scheme SEB CSE USE MSE USE CSE MSE

0.27 0.05 1.91 1.40 0.27 0.02 0.26 0.02 0.254 0.01 0.241 0.02 1.89 0.18 1.83 0.12 NP

143.0 7.0 14.4 2.6 145.1 8.3 146.26 9.5 139.3 11.3 141.9 12.9 15.6 0.7 13.6 0.9 7.29 0.42

9.28 1.9 19.7 5.8 11.30 0.8 10.76 0.9 11.56 1.0 10.40 1.0 23.2 1.9 20.9 2.2 14.67 1.0

This work

BCR 701

Filgueiras et al. [15] Fernandez et al. [17]

BCR 601 BCR 601 Sewage sludge

M.B. Arain et al. / Journal of Hazardous Materials 154 (2008) 9981006 is calculated using the ratio: sum of metal contents (rst step + second step + third step) extraction using the accelerated single extraction procedures (CSE, USE, MSE)/sum of metal contents extracted by SEB. a Conventional sequential extraction BCR (SEB). b Conventional single extraction (CSE). c CSE have same values as rst step of SEB d Ultrasonic assisted single extraction (USE). e Microwave induced single extraction (MSE). f NP, not perform. g ND, not detected. t values (df = 5), t critical = 2.57

1003

358.3 13.3 357.0 12.4 99.7 369.9 12.9 103.2 349.8 14.4 97.6 132.8 9.5 128.4 10.3 96.7 127.8 6.9 96.2 123.9 9.6 93.3 60.5 2.14 60.7 2.13 100.5 58.4 2.61 96.6 51.9 2.44 85.92 229.3 8.6 227.8 6.8 99.3 232.0 9.0 101.2 220.2 6.4 96.0 194.3 9.1 194.2 10.4 99.9 180.9 11.7 93.1 190 13.4 97.8 11.4 0.5 11.4 0.5 100.4 12.1 0.68 106.1 11.2 0.58 98.07

NP NP

Cd

7.29 0.4 93.6

Cr

263.3 2.1 90.2

Cu

10.9 0.82 100.4

Ni

14.7 1.0 97.0

Pb

510.4 2.7 89.1

Zn

(d) Sum of metal contents (rst step + second step + third step) and % recovery SEB CSE % recovery* USE BCR 701 This work % recovery MSE % recovery

MSE % recovery

Technique

Fig. 2. Analyte partitioning of Manchar lake sediment by the conventional sequential extraction BCR (SEB), conventional single extraction (CSE), ultrasonic assisted single extraction (USE) and microwave assisted single extraction (mg kg1 ).

Table 1 (Continued )

* Recovery

metal contents in BCR 701 (Table 1) and lake sediment samples applying the SEB and single extractions as shown in Fig. 2. The values of HMs obtained from SEB, were used as reference values for calculating the percentage of HMs recovered by all three single extraction procedures. In all cases data are reported as mean values (mg kg1 ) standard deviation. No signicant differences were observed for p = 0.05 when comparing the values obtained by the proposed single extraction methods and conventional method (SEB) (paired t-test). The relative standard deviation (RSD%) values obtained by all single extractions and SEB procedures were generally comparable. The precision, usually in the range 4.39.5% was achieved for most of the elements analyzed but in some cases the high RSD percentage was observed in USE, Pb in steps 1 and 3, while Cr in step 1, it was expected that elements detected near the limits of detection had much greater uncertainty.

Fernandez et al. [17]

Sewage sludge

Material

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3.2.1. Exchangeable fraction The exchangeable fraction constitutes the step 1 of the SEB method and consequently it is always directly extracted, result shown in Table 1(a). The results obtained by CSE are same, while the results obtained by USE show that the recovery of all HMs is increased except Cu in BCR 701. Thus, the observed increase of metals release can be attributed to the enhancement of the contact interface between metals oxides and extractant. The single extraction induced by MW, shows the lower recovery for Cd, Cu, Ni and Pb (97.8%, 91.0%, 96.4% and 97.2%), respectively, while high recoveries for Cr (125.3%) and Zn (102.5%) were obtained as compared to those by the SEB method. In the case of Cr, the extraction efciency is increased considerably with ultrasound and MW energy, due to short exposure time for extraction that allows lower re-adsorption process in this step [23]. The amount of Cu extracted by MSE is 2% greater than the values obtained by USE; however, the extraction of Cu is 9.8411.35% lesser using USE and MSE methods as compared to Cu extracted by SEB. This could be attributed to the long shaking time used in the conventional method, which is responsible for this difference. It should be noted that the objective of this study was not only to improve the extraction efciency of the conventional single extraction procedures, but also to nd out that USE and MSE yields identically extractable metal contents using shorter treatment time. Filgueiras et al. [15], Canepari et al. [16] and Fernandez et al. [17] have investigated the partitioning of HMs in different certied sediment and real samples, using single extraction procedures based on modied BCR procedure, while Fernandez et al. [17] did not use any certied material. The partitioning pattern of all HMs under current study for step 1 is greater than the results of Filgueiras and Canepari, which are suggesting an over extraction of Cd, Pb, Ni, Cr and Zn except Cu (91.492.7) of certied values. The previous work by Canepari et al. compares the quantities of metals extracted from certied sediment samples (BCR 601 and 701) using US bath and MW assisted extraction, while they only perform rst step of BCR sequential extraction. They declared less metal extracted by US bath and MW induced extraction in the range of 53.9877.6% and 68.3126.3% in 701 while 4067.6% and 65.7103.32% in BCR 601, respectively as compared to certied values. 3.2.2. Reducible fraction The reducible fraction estimated from single extraction methods displayed variability in values of HMs as compared to those obtained by SEB, the recoveries of metals obtained by CSE are varied between 95.998.6% for Zn, Pb, Cr, Cu and Ni, except Cd which was higher (101.3%) than the values obtained by SEB (Table 1(b)). Moreover, negative concentration values of Zn (95.9%) and Pb (96.7%) were found in BCR 701 using the CSE, which means that these elements were poorly extracted when the treatment with NH2 OHHCl was carried out on an individual sub-samples. The single extraction of reducible fraction assisted by ultrasound energy released Cd (107.1%) and Cu (109.0%) as compared to values of both metals obtained by CSE and SEB methods, while for other HMs, the range varied between 83.098.5%. The order of extraction of all these

heavy metals is found, Cd > Cu > Ni > Zn > Pb > Cr. Discrepancies exist between the literature [15], using ultrasound energy for metal partitioning in BCR 601, the range of extracted metals is 55.5112.25%, in the order of Cu > Cd > Pb > Ni > Cr, compared to certied values. The reducible fractions of HMs obtained by MSE, show % recoveries varied between 79.199.2 for all metals, except Cu, the considerably higher amount of Cu (107.5%) was released than those obtained by SEB procedure. The results indicate that in relation to reducible fraction of Cu in CRM 701, the extraction efciency of NH2 OHHCl was increased when US and MW energy were applied, while there was a reverse effect in the case of Ni, 93.1% and 79.1%, respectively. 3.2.3. Oxidizable fraction The oxidizable fraction evaluated by single extraction method showed some discrepancies in extraction efciency of HMs, the metals extracted by CSE procedure were considerably higher than those obtained using the other approaches. To compare the values of HMs released by USE with those obtained by SEB procedure was varied between 94.197.6% except Pb released (102.3%) as compared to those obtained by SEB method. The reproducibility of the USE was also comparable to that of SEB. In the case of MSE, the recovery of all HMs except Cr, was found to be lower as compared with other two proposed single extractions (CSE and USE) as well as SEB procedure. As compared to literature on BCR 601 [15], our results are better and comparable (Table 1(c)). 3.2.4. Total extractable HMs Total extractable HMs contents (step 1 + step 2 + step 3) obtained from the SEB method together with those evaluated by single extractions (CSE, USE and MSE) are shown in Table 1(d). According to the above it can be concluded that some signicant differences were found in the metals fractions by the three proposed extraction methods, and even a different behavior was found for some metals (Pb, Cr, Ni and Cu) in BCR 701. The contents of all HMs extracted by SEB and CSE methods are similar except Pb (96.66%) as compared to those values obtained by SEB. In the case of USE, similar extractable contents of all heavy metals except Cr (93.10%) are compared to those obtained by reference method. In the case of MSE, over all recoveries of HMs are found in the range of 85.9298.07% in decreasing order Cd > Cr > Zn > Cu > Pb > Ni, than the values obtained by SEB method. The percentage recovery of total extractable metal obtained by MSE in the present work was better than the reported work of Fernandez et al. [17] they perform MSE on sewage sludge samples. Results are shown in Table 1(d). 3.3. Application of proposed single extraction methods to natural lake sediment The optimization of all three single and sequential extractions by modied BCR procedure based on the use of an US bath and a MW oven was performed on lake sediment samples. The amount of metals extracted in each step of the sequential

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extraction procedures is given in Fig. 2. Among the metals studied the Cd and Zn were extracted predominantly in the rst step of the sequential extraction, which represents the metal bound to carbonates or sorbed/exchangeable phases [24]. On the other hand, only very small fractions of Pb, and Cr were present as acid exchangeable species in all lake sediment samples. The proportion of the metals in the acetic acid extractable fraction followed the order Zn > Cd > Cu > Ni > Pb > Cr. The major associations of all HMs were observed in reducible phase. The surfaces of Fe and Mn oxides have special afnity with the cations to natural pH. Edwards et al. [25], Dawson and Macklin [26] found that Fe and Mn hydroxides are important scavengers of these elements in sediments. The range of relative percentage of Cd in oxidizable fraction was observed 31.6%, and shows the increase in incoming of this element in the lake, probably due to the input of organic matter from domestic sewage and other human activities, from the villages located close to the banks of Manchar lake. According to the results, it is possible to say that Cd and Zn are the most mobalizable metals in all lake sediment samples. 4. Conclusions The purpose of sequential extraction methods to environmental samples provides relevant information about possible toxicity when they are discharged into the environment. The long treatment time required in these procedures could be shortened by replacing the sequential treatment by single extractions. In the BCR sequential method, the use of single extractions provides similar results to the conventional sequential treatment for Cd, Cr, Ni, Pb and Zn. In relation to Cu, although the results obtained in the reducible fraction were signicantly different, both methods supplied overall equivalent information concerning the mobility and bioavailability of this element under diverse environmental conditions. In the BCR method, all fractions could be simultaneously extracted and consequently the total operation time could be reduced from 51 h to only 16 h. In USE and MSE extraction methods, time could be reduced from 1530 min and 60120 s for all three BCR extraction protocols, although there was some variation in the extraction time from metals to metals. Moreover, when the single extraction method was employed, the washing steps after each sequential extraction stage were also eliminated, which allowed us to accelerate the experimental task. In contrast, a larger amount of sample was needed, which did not pose a signicant problem in the study of environmental samples. Hence, the use of single extractions should allow one to evaluate the extractable metals in sediment samples and might be useful for a fast screening of the possible mobility and bioavailability of metals in the environment. The variances associated with the results of all three time-saving procedures were statistically equivalent to those obtained by the conventional BCR procedures. References
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